CN115321516A - Biomass-based hard carbon material, preparation method thereof and lithium ion battery - Google Patents
Biomass-based hard carbon material, preparation method thereof and lithium ion battery Download PDFInfo
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- CN115321516A CN115321516A CN202211112003.5A CN202211112003A CN115321516A CN 115321516 A CN115321516 A CN 115321516A CN 202211112003 A CN202211112003 A CN 202211112003A CN 115321516 A CN115321516 A CN 115321516A
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- 239000002028 Biomass Substances 0.000 title claims abstract description 81
- 229910021385 hard carbon Inorganic materials 0.000 title claims abstract description 69
- 239000003575 carbonaceous material Substances 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 18
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 18
- 239000002253 acid Substances 0.000 claims abstract description 75
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 65
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 52
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 50
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 42
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 41
- 238000010438 heat treatment Methods 0.000 claims abstract description 28
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 22
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- 238000002156 mixing Methods 0.000 claims abstract description 11
- 239000007789 gas Substances 0.000 claims description 39
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 29
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 26
- 229910052757 nitrogen Inorganic materials 0.000 claims description 24
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- 238000000034 method Methods 0.000 claims description 18
- 238000005406 washing Methods 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 14
- 229910052786 argon Inorganic materials 0.000 claims description 13
- 229910052739 hydrogen Inorganic materials 0.000 claims description 12
- 239000001257 hydrogen Substances 0.000 claims description 11
- 229910021529 ammonia Inorganic materials 0.000 claims description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 9
- 229910052698 phosphorus Inorganic materials 0.000 claims description 7
- 229910052717 sulfur Inorganic materials 0.000 claims description 7
- 229910052734 helium Inorganic materials 0.000 claims description 6
- 239000001307 helium Substances 0.000 claims description 6
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 6
- 235000003222 Helianthus annuus Nutrition 0.000 claims description 5
- 240000006677 Vicia faba Species 0.000 claims description 5
- 235000010749 Vicia faba Nutrition 0.000 claims description 5
- 235000002098 Vicia faba var. major Nutrition 0.000 claims description 5
- 150000007513 acids Chemical class 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 4
- 238000000967 suction filtration Methods 0.000 claims description 4
- 230000003247 decreasing effect Effects 0.000 claims description 2
- 150000002431 hydrogen Chemical class 0.000 claims description 2
- 240000003826 Eichhornia crassipes Species 0.000 claims 1
- 244000020551 Helianthus annuus Species 0.000 claims 1
- 229910001415 sodium ion Inorganic materials 0.000 abstract description 30
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 abstract description 24
- 239000000463 material Substances 0.000 abstract description 17
- 238000006243 chemical reaction Methods 0.000 abstract description 5
- 238000009830 intercalation Methods 0.000 abstract description 5
- 230000002687 intercalation Effects 0.000 abstract description 5
- 238000009831 deintercalation Methods 0.000 abstract description 4
- 239000000243 solution Substances 0.000 description 50
- 239000010453 quartz Substances 0.000 description 13
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- 125000005842 heteroatom Chemical group 0.000 description 10
- 229910052744 lithium Inorganic materials 0.000 description 10
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 8
- 239000010410 layer Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 229910021389 graphene Inorganic materials 0.000 description 7
- 239000002356 single layer Substances 0.000 description 6
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- 241000208818 Helianthus Species 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 239000002243 precursor Substances 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 238000004146 energy storage Methods 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 239000007773 negative electrode material Substances 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 2
- 238000003487 electrochemical reaction Methods 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000003780 insertion Methods 0.000 description 2
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- 230000014759 maintenance of location Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 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 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- YZSKZXUDGLALTQ-UHFFFAOYSA-N [Li][C] Chemical compound [Li][C] YZSKZXUDGLALTQ-UHFFFAOYSA-N 0.000 description 1
- ZMVMBTZRIMAUPN-UHFFFAOYSA-H [Na+].[V+5].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O Chemical compound [Na+].[V+5].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O ZMVMBTZRIMAUPN-UHFFFAOYSA-H 0.000 description 1
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
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- 229910045601 alloy Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
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- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
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- 125000000524 functional group Chemical group 0.000 description 1
- 238000005087 graphitization Methods 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000002296 pyrolytic carbon Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 1
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 230000003313 weakening effect Effects 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical Kinetics & Catalysis (AREA)
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- 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 provides a biomass-based hard carbon material, a preparation method thereof and a lithium ion battery, wherein the preparation method comprises the following steps: mixing biomass carbon with the mixed acid solution, and carrying out heat treatment to obtain a biomass-based hard carbon material; the mixed acid solution includes a combination of at least two of hydrochloric acid, sulfuric acid, nitric acid, and phosphoric acid. According to the invention, the biomass carbon is pretreated by adopting the mixed acid and is subjected to heat treatment, so that the specific surface area of the material is further increased under the condition that the biomass carbon keeps the original carbon skeleton, more active sites are provided for the intercalation/deintercalation reaction of sodium ions on the biomass-based hard carbon material, and the rate capability of the material in a sodium ion battery is improved.
Description
Technical Field
The invention belongs to the technical field of batteries, and relates to a biomass-based hard carbon material, a preparation method thereof and a lithium ion battery.
Background
At present, lithium ion batteries are the first choice for energy storage devices of portable electronic devices and electric vehicles, however, lithium resources are limited, and further production and application of lithium ion batteries face continuous limitations. Sodium metal and lithium metal are located in the same main group of the periodic table of elements, and the physicochemical properties of the sodium metal and the lithium metal are similar, and sodium is more abundant in earth than lithium, so that the sodium-ion battery is also considered as one of candidate devices of a large-scale energy storage system.
The research on sodium ion batteries began early around the eighties of the last century and electrode materials such as MoS designed and developed early 2 、TiS 2 And Na x MO 2 The electrochemical performance of the lithium ion battery is not ideal, and the development is very slow, so that the search for a suitable sodium ion electrode material is one of the keys of the practical application of the sodium ion energy storage battery. Compared with the industrialized mature lithium ion battery, the radius of the sodium ions or the solvated sodium ions is larger than that of the lithium ions or the solvated lithium ions, and the hard carbon, the transition metal and the alloy compound materials of the layered negative electrode material make great progress in the aspects of charge and discharge capacity and cycle stability in the last decade. However, as a hard carbon having a wide application range, the charge/discharge maximum gram capacity is 300mAh/g, and the rate capability is severely polarized at 1C.
The hard carbon material traditionally applied to the negative electrode of the sodium ion battery is pyrolytic carbon obtained by pyrolyzing high molecular polymers, petrochemical products, biomass and the like. The precursor of the hard carbon contains a large amount of heteroatoms such as H, O, N and the like, so that the formation of a crystallization area in the heat treatment process is hindered, and the precursor is difficult to graphitize at the high temperature of more than 2500 ℃. In addition, in the pyrolysis process of the hard carbon, the carbon layer has the tendency of planar growth, but the cross-linked structure in macromolecules hinders the planar growth of the hard carbon, so the carbon layer in the hard carbon cannot extend indefinitely to grow into a graphite-like lamellar structure, a carbon layer stacked structure can only occur in a short distance, and a disordered state exists in a long distance; since a part of the carbon layer is randomly stacked to cause defects and voids, and the other part of the carbon layer has a graphite crystallite structure, and these graphite crystallites are not oriented and are cross-linked with each other, the hard carbon structure is mainly amorphous. Research shows that the molecular weight of the precursor has an influence on the microstructure of the hard carbon formed after pyrolysis, and the graphitization degree of the hard carbon gradually becomes higher and the specific surface area gradually increases with the increase of the molecular weight. The hard carbon has large distance relative to the graphite layer, a plurality of micropores, a plurality of active sites for lithium ion insertion and extraction and lithium storage correspondingly, and larger specific capacity, so the capacity of the hard carbon can be improved by regulating and controlling the molecular weight of the precursor; moreover, the hard carbon has better compatibility with PC electrolyte and is more suitable for working at low temperature.
At present, the lithium storage mechanism of hard carbon is not unified, and researchers propose a structural model of a card house to explain the reason that the hard carbon has higher lithium intercalation capacity. According to the X-ray diffraction technology and electrochemical test characterization results, researchers think that the hard carbon material contains a plurality of nano micropores surrounded by single-layer graphene sheets, the pore diameter of the nano micropores is only about 1.5nm, the single-layer graphene sheets form the configuration of a paper-like house, and Li is + The graphene sheets are adsorbed on the surfaces of the single-layer graphene sheets and can reversibly enter and exit the single-layer graphene sheets, and the lithium insertion capacity of the single-layer graphene sheets is increased along with the increase of the single-layer graphene sheets. Also researchers investigated the hard carbon lithium storage mechanism by HX-PES analysis. It was found that lithium was present between the carbon layers and in the micropores. When state of charge (SOC)<70 percent, and lithium ions are inserted between carbon layers; when state of charge (SOC)>50 percent of lithium particle clusters enter the micropores and are in a semimetal state. The micropores are not of the same size, and the particle clusters are not of uniform size. Through the research, the capacity and rate capability of the hard carbon can be improved.
In the prior art, although the hard carbon structure is improved through various researches to improve the capacity and rate capability of the hard carbon, the rate capability of the hard carbon still needs to be further improved; meanwhile, the large-scale application and industrialization of the sodium ion battery not only require that the anode and cathode materials show good excellent performance in the sodium ion electrolyte, but also require that the production and preparation cost of the materials is further reduced. Therefore, the hard carbon material with good rate performance and low production cost is provided, and has important significance for the research and development of the sodium ion battery.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide a biomass-based hard carbon material, a preparation method thereof and a lithium ion battery. According to the invention, the biomass carbon is pretreated by adopting the mixed acid and is subjected to heat treatment, so that the specific surface area of the material is further increased under the condition that the biomass carbon keeps the original carbon skeleton, more active sites are provided for the intercalation/deintercalation reaction of sodium ions on the biomass-based hard carbon material, and the rate capability of the material in a sodium ion battery is improved.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a method for preparing a biomass-based hard carbon material, the method comprising:
mixing the biomass carbon with the mixed acid solution, and carrying out heat treatment to obtain a biomass-based hard carbon material;
the mixed acid solution comprises a combination of at least two of hydrochloric acid, sulfuric acid, nitric acid and phosphoric acid.
In the present invention, the mixed acid solution includes a combination of at least two of hydrochloric acid, sulfuric acid, nitric acid, and phosphoric acid, and may be, for example, a combination of hydrochloric acid and sulfuric acid, a combination of sulfuric acid and nitric acid, a combination of nitric acid and phosphoric acid, a combination of hydrochloric acid, sulfuric acid, and nitric acid, or a combination of hydrochloric acid, sulfuric acid, nitric acid, and phosphoric acid, or the like.
According to the invention, the biomass carbon is mixed with the mixed acid solution, so that light components such as water in the biomass carbon can be removed, and through the synergistic effect of pretreatment and heat treatment of the mixed acid solution, part of multi-carbon contained in the biomass and heteroatoms on a carbon skeleton, especially impurities of non-degreased biomass carbon which are difficult to remove at high temperature, are removed, under the condition of keeping the original carbon skeleton of the biomass carbon, the specific surface area of the material is further increased, active sites are increased, and the rate capability of the biomass-based hard carbon material in a sodium ion battery is improved; meanwhile, different from singly adopting one acid, the specific mixed acid solution can simultaneously meet the requirements of oxidability and pH value, exerts the synergistic effect with heat treatment, creates more active sites and real specific surface area which can be used for the negative electrode of the sodium ion battery to participate in electrochemical reaction, and can further improve the rate capability of the sodium ion battery on the premise of reducing the production cost of hard carbon.
The concentration of the mixed acid solution is preferably 1 to 14mol/L, and may be, for example, 1mol/L, 2mol/L, 3mol/L, 4mol/L, 5mol/L, 6mol/L, 7mol/L, 8mol/L, 9mol/L, 10mol/L, 11mol/L, 12mol/L, 13mol/L, or 14 mol/L.
Preferably, the mixed acid solution is any two or any three of hydrochloric acid, sulfuric acid, nitric acid and phosphoric acid.
Preferably, the mixed acid solution is a combination of two acids, one of the two acids is nitric acid or sulfuric acid, and the other is hydrochloric acid or phosphoric acid, and for example, the mixture may be a combination of nitric acid and hydrochloric acid, a combination of nitric acid and phosphoric acid, a combination of sulfuric acid and hydrochloric acid, or a combination of sulfuric acid and phosphoric acid, preferably, the mass ratio of the two acids is 1.
The concentration and the components of the mixed acid solution are further optimized, and when the nitric acid and the phosphoric acid with the mass ratio of 1.
Preferably, the mass ratio of the biomass carbon to the mixed acid solution is 1 (9-11), and can be, for example, 1.
The mass ratio of the biomass carbon to the mixed acid solution refers to the mass ratio of the biomass carbon to the entire mixed acid solution, and the entire mixed acid solution includes a solute and a solvent.
Preferably, the biomass carbon comprises any one or a combination of at least two of broad bean shells, water hyacinth stems and sunflower roots, and can be, for example, a combination of broad bean shells and water hyacinth stems, a combination of water hyacinth stems and sunflower roots, or a combination of broad bean shells, water hyacinth stems and sunflower roots, and the like.
Preferably, the mixing temperature is 45 ~ 55 ℃, for example can be 45 degrees, 48 degrees, 50 degrees, 52 degrees or 55 degrees C.
Preferably, the mixing time is 4 to 6 hours, and may be, for example, 4 hours, 4.5 hours, 5 hours, 5.5 hours, 6 hours, or the like.
Preferably, after the mixing and before the heat treatment, the method further comprises the steps of suction filtration and drying.
As a preferable technical scheme of the preparation method, the heat treatment comprises a heating stage, a constant temperature stage and a cooling stage.
Preferably, the temperature of the constant temperature stage is 800-1000 ℃, for example, 800 ℃, 820 ℃, 840 ℃, 860 ℃, 880 ℃, 900 ℃, 920 ℃, 940 ℃, 960 ℃, 980 ℃ or 1000 ℃, etc., and in this temperature range, the method is favorable for the massive decomposition of functional groups such as-CHO and-COOH on the carbon skeleton, thereby generating more holes on the original carbon skeleton and further improving the content of doping sites.
Preferably, the time of the constant temperature stage is 4 to 12 hours, for example, 4 hours, 6 hours, 8 hours, 10 hours or 12 hours, etc.
In a preferred embodiment of the preparation method of the present invention, the gas in the atmosphere of the heat treatment includes a mixed gas and/or a single gas.
Preferably, the mixed gas includes nitrogen, ammonia, a combination of at least two of hydrogen and argon, and may be, for example, a combination of nitrogen and ammonia, a combination of ammonia and hydrogen, a combination of ammonia, hydrogen and argon, or a combination of nitrogen, ammonia, hydrogen and argon, or the like.
Preferably, the single gas comprises nitrogen, helium or argon.
Preferably, the gas in the atmosphere of the temperature increasing stage and the temperature decreasing stage is a single gas, and the gas in the atmosphere of the constant temperature stage is a mixed gas.
In the invention, specific mixed gas is preferably introduced at a constant temperature stage with higher temperature, and single gas components are introduced at a temperature rising stage and a temperature lowering stage to realize the doping of heteroatoms, the doping of the mixed gas at the specific temperature enables elements to be distributed more uniformly, and the mixed gas is more suitable for the doping of a biomass carbon skeleton treated by mixed acid, and the heteroatoms are uniformly deposited on the treated biomass carbon skeleton, so that active sites of sodium ions during the embedding/extracting reaction on hard carbon prepared from biomass carbon can be improved, and the rate capability of a sodium ion battery is further improved.
Preferably, the heat treatment further comprises a step of acid washing, and the surface of the material is activated through acid washing, so that the substances which are not easy to volatilize are dissolved, and the biomass-based hard carbon material with higher purity and better performance is obtained.
Preferably, the acid-washing solution includes any one of hydrochloric acid, sulfuric acid and phosphoric acid or a combination of at least two of them, and may be, for example, a mixed solution of hydrochloric acid and sulfuric acid, a mixed solution of hydrochloric acid and phosphoric acid, or a mixed solution of sulfuric acid and phosphoric acid, and the like, and further preferably 0.1mol/L hydrochloric acid solution.
As a preferable technical scheme of the preparation method of the invention, the preparation method comprises the following steps:
(1) Mixing biomass carbon and a mixed acid solution with the concentration of 1-14 mol/L for 4-6 h at the temperature of 45-55 ℃, and drying after suction filtration, wherein the mixed acid solution comprises the combination of at least two of hydrochloric acid, sulfuric acid, nitric acid and phosphoric acid;
(2) Heating the product obtained after drying in the step (1) under a single gas, keeping the temperature for 4-12 h under the mixed gas after heating to 800-1000 ℃, and then switching back to the single gas for cooling to obtain a carbonized product;
the mixed gas comprises a combination of at least two of nitrogen, ammonia, hydrogen and argon, and the single gas comprises nitrogen, helium or argon;
(3) And (3) carrying out acid washing, washing and drying on the carbonized product obtained in the step (2) to obtain the biomass-based hard carbon material.
In a second aspect, the invention provides a biomass-based hard carbon material, which is prepared by the preparation method of the first aspect.
The biomass-based hard carbon material prepared by the invention has a natural carbon skeleton of biomass carbon, and after the biomass-based hard carbon material is treated by the preparation method, the skeleton has more active sites, and the material has better rate performance.
Preferably, the biomass-based hard carbon material is doped with any one or a combination of at least two of N, P and S, for example, the combination of N and P, the combination of N and S, or the combination of N, P and S, and the like, the heteroatom source comprises biomass carbon itself, mixed gas doping and acid washing doping, and the doping of the heteroatom further increases the active sites and improves the rate capability of the sodium-ion battery.
In a third aspect, the invention provides a lithium ion battery, wherein the biomass-based hard carbon material according to the second aspect is included in a negative electrode of the lithium ion battery.
The lithium ion battery prepared from the biomass-based hard carbon material has excellent rate capability.
Compared with the prior art, the invention has the following beneficial effects:
according to the invention, the biomass carbon is mixed with the mixed acid solution, so that light components such as water in the biomass carbon can be removed, and through the synergistic effect of pretreatment and heat treatment of the mixed acid solution, part of multi-carbon and heteroatoms on a carbon skeleton contained in the biomass are removed, especially impurities of non-degreased biomass carbon which is difficult to remove at high temperature are removed, under the condition of keeping the original carbon skeleton of the biomass carbon, the specific surface area of the material is further increased, active sites are increased, and the rate capability of the biomass-based hard carbon material in a sodium ion battery is improved; meanwhile, different from singly adopting one acid, the specific mixed acid solution can simultaneously meet the requirements of oxidability and pH value, exerts the synergistic effect with heat treatment, creates more active sites and real specific surface area which can be used for the sodium ion battery cathode to participate in electrochemical reaction, and can further improve the rate capability of the sodium ion battery on the premise of reducing the production cost of hard carbon.
Drawings
Fig. 1 is a flow chart of the preparation of biomass-based hard carbon material in one embodiment of the present invention.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Example 1
The embodiment provides a preparation method of a biomass-based hard carbon material, and a flow chart is shown in fig. 1, and the preparation method comprises the following steps:
(1) Putting 80mg of broad bean shells into a 50mL beaker containing a mixed acid solution, wherein the concentration of the mixed acid solution is 8mol/L, the mixed acid solution is a combination of hydrochloric acid and sulfuric acid with the mass ratio of 1;
(2) Putting the product obtained after drying in the step (1) into a sample quartz tube, putting the sample quartz tube into a tube furnace, heating the sample quartz tube under helium, switching the sample quartz tube into a mixed gas of nitrogen and hydrogen for constant temperature treatment for 8 hours after the temperature is raised to 900 ℃, and switching back to the helium to cool the sample quartz tube after the constant temperature is finished to obtain a carbonized product;
(3) And (3) carrying out acid washing on the carbonized product obtained in the step (2) in a hydrochloric acid solution with the concentration of 0.2mol/L, washing and drying to obtain the biomass-based hard carbon material.
The biomass-based hard carbon material of the present example was doped with N, P, and S.
Example 2
The embodiment provides a preparation method of a biomass-based hard carbon material, and a flow chart is shown in fig. 1, and the preparation method comprises the following steps:
(1) Putting 100mg of water hyacinth stems into a 50mL beaker containing a mixed acid solution, wherein the concentration of the mixed acid solution is 10mol/L, the mixed acid solution is a combination of hydrochloric acid and nitric acid with the mass ratio of 1;
(2) Putting the product obtained after drying in the step (1) into a sample quartz tube, putting the sample quartz tube into a tube furnace, heating the sample quartz tube under argon, switching the sample quartz tube into mixed gas of ammonia and hydrogen for constant temperature treatment for 4 hours after the temperature is raised to 1000 ℃, and switching back to the argon again to cool the sample quartz tube after the constant temperature is finished to obtain a carbonized product;
(3) And (3) carrying out acid washing on the carbonized product obtained in the step (2) in a sulfuric acid solution with the concentration of 0.1mol/L, washing and drying to obtain the biomass-based hard carbon material.
The biomass-based hard carbon material of the present example was doped with N, P, and S.
Example 3
The embodiment provides a preparation method of a biomass-based hard carbon material, and a flow chart is shown in fig. 1, and the preparation method comprises the following steps:
(1) Placing 50mg of sunflower roots into a 50mL beaker containing a mixed acid solution, wherein the concentration of the mixed acid solution is 12mol/L, the mixed acid solution is a combination of sulfuric acid and phosphoric acid with the mass ratio of 1;
(2) Putting the product obtained after drying in the step (1) into a sample quartz tube, putting the sample quartz tube into a tube furnace, heating the sample quartz tube under nitrogen, switching to mixed gas of ammonia, hydrogen and argon for constant temperature treatment for 12h after the temperature is raised to 800 ℃, and switching back to nitrogen for cooling after the constant temperature is finished to obtain a carbonized product;
(3) And (3) carrying out acid washing on the carbonized product obtained in the step (2) in a phosphoric acid solution with the concentration of 0.2mol/L, washing and drying to obtain the biomass-based hard carbon material.
The biomass-based hard carbon material of the present example was doped with N, P, and S.
Example 4
The procedure was repeated in the same manner as in example 1 except that the concentration of the mixed acid solution in the step (1) was changed to 0.1 mol/L.
Example 5
The procedure of example 1 was repeated except that the concentration of the mixed acid solution in the step (1) was changed to 15 mol/L.
Example 6
The same procedures as in example 1 were repeated except that the mixed gas of nitrogen and hydrogen in step (2) was replaced with nitrogen.
Example 7
The procedure was as in example 1 except that the temperature maintained in step (2) was changed to 750 ℃.
Example 8
The procedure was as in example 1 except that the temperature maintained in step (2) was changed to 1100 ℃.
Example 9
The procedure of example 1 was repeated except that the mixed acid solution of step (1) was replaced with 8mol/L of nitric acid and sulfuric acid having a mass ratio of 1.
Example 10
The procedure of example 1 was repeated except that the mixed acid solution of step (1) was replaced with 8mol/L of hydrochloric acid, nitric acid and sulfuric acid at a mass ratio of 1.
Comparative example 1
The procedure of example 1 was repeated, except that the biomass carbon was directly charged into the tube furnace without the operation of step (1) to carry out the operation of step (2).
Comparative example 2
The procedure of example 1 was repeated except that the mixed acid solution in step (1) was replaced with a nitric acid solution.
1. Preparation of sodium ion battery
The biomass-based hard carbon materials prepared in examples 1 to 10 and comparative examples 1 to 2 were used as negative active materials to prepare negative electrodes, and the negative electrodes included 94% by mass: 3%:2%:1% of negative electrode active material, conductive agent SP, sodium carboxymethylcellulose and styrene butadiene rubber, and the positive electrode comprises 96% of the following components in percentage by mass: 2%:2 percent of sodium vanadium phosphate, and the electrolyte is 1M LiPF 6 /(EC: DMC = 1), assembling to obtain a sodium ion battery.
2. Rate capability test
The prepared sodium ion battery is charged and discharged at 25 ℃ and a voltage interval of 2.5-4.0V at multiplying power of 0.5C and 1C respectively, the discharge capacity is divided by the charge capacity to obtain data of capacity retention rate, the data are recorded in table 1, the multiplying power performance of the sodium ion battery is represented, and the test result is shown in table 1.
TABLE 1
From the above examples 1 to 10, it can be seen that the biomass carbon is pretreated by using the mixed acid, and is subjected to heat treatment, so that the specific surface area of the material is further increased under the condition that the biomass carbon keeps the original carbon skeleton, and more active sites are provided for the intercalation/deintercalation reaction of sodium ions on the biomass-based hard carbon material, thereby improving the rate capability of the material in the sodium ion battery.
It can be seen from the comparison between example 1 and examples 4-5 that the concentration of the mixed acid solution affects the rate capability of the biomass-based hard carbon material, the concentration of the mixed acid solution in example 4 is too low, which results in incomplete reaction on the surface of the hard carbon material, and the concentration of the mixed acid solution in example 5 is too high, which results in damage to the carbon skeleton in the material and weakening of the capacity retention rate, therefore, the concentration of the mixed acid solution in example 1 is in the most suitable range, the acid treatment effect of the biomass carbon is the best, and the rate capability of the material is higher.
It can be known from the comparison between example 1 and example 6 that the rate capability of the biomass-based hard carbon material can be further improved by performing heteroatom doping with mixed gas at a constant temperature stage at a higher temperature in the present invention, and the number density of active sites generated by doping is smaller by using a single gas in example 6, so that the rate capability of example 1 is higher than that of example 6.
It can be seen from comparison between example 1 and examples 7-8 that the doping of heteroatoms at a suitable temperature according to the present invention can further increase the number density of active sites for sodium ion intercalation/deintercalation on the surface of the biomass-based hard carbon material. The rate performance of example 1 is better because example 7 has a lower temperature, which results in incomplete volatilization of light components and fewer vacancies to which doped heteroatoms are expected to attach, thereby impairing the doping effect, and example 8 has a higher temperature, which results in collapse of the carbon skeleton structure during carbonization of biomass.
As can be seen from comparison between example 1 and examples 9 and 10, the mixed acid solution in the present invention has the most suitable acid combination, i.e., concentration ratio, and the mixed acid solution in example 1 adopts a mixed solution of hydrochloric acid and sulfuric acid with a concentration of 8mol/L and a mass ratio of 1; therefore, the rate capability of the biomass-based hard carbon material prepared in example 1 is better.
As can be seen from the comparison between example 1 and comparative examples 1-2, the biomass carbon of the present invention does not undergo the pretreatment of the mixed acid solution or the treatment with the single acid solution, and thus the effect of effectively improving the rate capability of the material cannot be achieved. In comparative example 1, no mixed acid is added, light components in the biomass carbon cannot be eliminated, the specific surface area of the material is small, the active sites of the material are greatly lower than those in example 1, and the rate capability is obviously inferior to that in example 1. Although the acid solution with the same concentration is added in the comparative example 2, the nitric acid solution in the comparative example 2 cannot simultaneously meet the requirements of oxidation and pH value, cannot fully exert the synergistic effect with the heat treatment, and has rate performance which is obviously inferior to that of the example 1.
The above description is only for the specific embodiment of the present invention, but the protection scope of the present invention is not limited thereto, and it should be understood by those skilled in the art that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are within the protection scope and the disclosure of the present invention.
Claims (10)
1. A preparation method of biomass-based hard carbon material is characterized by comprising the following steps:
mixing the biomass carbon with the mixed acid solution, and carrying out heat treatment to obtain a biomass-based hard carbon material;
the mixed acid solution includes a combination of at least two of hydrochloric acid, sulfuric acid, nitric acid, and phosphoric acid.
2. The preparation method according to claim 1, wherein the concentration of the mixed acid solution is 1 to 14mol/L;
preferably, the mixed acid solution is any two or any three of hydrochloric acid, sulfuric acid, nitric acid and phosphoric acid;
preferably, the mixed acid solution is a combination of two acids, wherein one of the two acids is nitric acid or sulfuric acid, and the other acid is hydrochloric acid or phosphoric acid;
preferably, the mass ratio of the biomass carbon to the mixed acid solution is 1 (9-11);
preferably, the biomass carbon comprises any one or a combination of at least two of broad bean shells, water hyacinth stems and sunflower roots.
3. The method according to claim 1 or 2, wherein the temperature of the mixing is 45 to 55 ℃;
preferably, the mixing time is 4-6 h;
preferably, after the mixing and before the heat treatment, the method further comprises the steps of suction filtration and drying.
4. The production method according to any one of claims 1 to 3, wherein the heat treatment includes a temperature-raising stage, a constant-temperature stage, and a temperature-lowering stage;
preferably, the temperature of the constant temperature stage is 800-1000 ℃;
preferably, the time of the constant temperature stage is 4 to 12 hours.
5. The production method according to any one of claims 1 to 4, wherein the gas in the atmosphere of the heat treatment comprises a mixed gas and/or a single gas;
preferably, the mixed gas includes a combination of at least two of nitrogen, ammonia, hydrogen, and argon;
preferably, the single gas comprises nitrogen, helium or argon;
preferably, the gas in the atmosphere of the temperature increasing stage and the temperature decreasing stage is a single gas, and the gas in the atmosphere of the constant temperature stage is a mixed gas.
6. The method according to any one of claims 1 to 5, characterized by further comprising a step of acid washing after the heat treatment;
preferably, the acid-washing solution comprises any one of hydrochloric acid, sulfuric acid and phosphoric acid or a combination of at least two thereof.
7. The production method according to any one of claims 1 to 6, characterized by comprising:
(1) Mixing biomass carbon and a mixed acid solution with the concentration of 1-14 mol/L for 4-6 h at the temperature of 45-55 ℃, and drying after suction filtration, wherein the mixed acid solution comprises the combination of at least two of hydrochloric acid, sulfuric acid, nitric acid and phosphoric acid;
(2) Heating the product obtained after drying in the step (1) under a single gas, keeping the temperature constant for 4-12 h under a mixed gas after heating to 800-1000 ℃, and then switching back to the single gas for cooling to obtain a carbonized product;
the mixed gas comprises a combination of at least two of nitrogen, ammonia, hydrogen and argon, and the single gas comprises nitrogen, helium or argon;
(3) And (3) carrying out acid washing, washing and drying on the carbonized product obtained in the step (2) to obtain the biomass-based hard carbon material.
8. A biomass-based hard carbon material, characterized in that it is produced by the production method according to any one of claims 1 to 7.
9. The biomass-based hard carbon material according to claim 8, wherein the biomass-based hard carbon material is doped with any one of N, P and S or a combination of at least two thereof.
10. A lithium ion battery, characterized in that the biomass-based hard carbon material according to claim 8 or 9 is included in the negative electrode of the lithium ion battery.
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