GB2619456A - Hard carbon negative electrode material, and preparation method therefor and use thereof - Google Patents
Hard carbon negative electrode material, and preparation method therefor and use thereof Download PDFInfo
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- GB2619456A GB2619456A GB2314132.8A GB202314132A GB2619456A GB 2619456 A GB2619456 A GB 2619456A GB 202314132 A GB202314132 A GB 202314132A GB 2619456 A GB2619456 A GB 2619456A
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- hard carbon
- carbon anode
- anode material
- starch
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- 229910021385 hard carbon Inorganic materials 0.000 title claims abstract description 90
- 239000007773 negative electrode material Substances 0.000 title abstract description 9
- 238000002360 preparation method Methods 0.000 title abstract description 5
- 239000011148 porous material Substances 0.000 claims abstract description 47
- 229920002472 Starch Polymers 0.000 claims abstract description 37
- 239000008107 starch Substances 0.000 claims abstract description 34
- 235000019698 starch Nutrition 0.000 claims abstract description 34
- 239000002994 raw material Substances 0.000 claims abstract description 18
- 229910001415 sodium ion Inorganic materials 0.000 claims abstract description 18
- 239000000758 substrate Substances 0.000 claims abstract description 3
- 239000010405 anode material Substances 0.000 claims description 63
- 229920000642 polymer Polymers 0.000 claims description 38
- 238000000034 method Methods 0.000 claims description 20
- 125000003118 aryl group Chemical group 0.000 claims description 19
- 238000007363 ring formation reaction Methods 0.000 claims description 19
- 239000002243 precursor Substances 0.000 claims description 18
- 239000011734 sodium Substances 0.000 claims description 15
- 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 claims description 13
- 238000003763 carbonization Methods 0.000 claims description 13
- 229910052708 sodium Inorganic materials 0.000 claims description 13
- 229920002261 Corn starch Polymers 0.000 claims description 11
- 239000008120 corn starch Substances 0.000 claims description 11
- 229920000945 Amylopectin Polymers 0.000 claims description 6
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims description 6
- 239000012798 spherical particle Substances 0.000 claims description 6
- 229920001592 potato starch Polymers 0.000 claims description 5
- 229920000856 Amylose Polymers 0.000 claims description 4
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 3
- 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 claims description 3
- 229920003123 carboxymethyl cellulose sodium Polymers 0.000 claims description 3
- 229940063834 carboxymethylcellulose sodium Drugs 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 3
- 229940100445 wheat starch Drugs 0.000 claims description 3
- 244000017020 Ipomoea batatas Species 0.000 claims description 2
- 235000002678 Ipomoea batatas Nutrition 0.000 claims description 2
- 240000003183 Manihot esculenta Species 0.000 claims description 2
- 235000016735 Manihot esculenta subsp esculenta Nutrition 0.000 claims description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- 239000011229 interlayer Substances 0.000 abstract description 12
- 238000009830 intercalation Methods 0.000 abstract description 5
- 230000002687 intercalation Effects 0.000 abstract description 5
- 238000009831 deintercalation Methods 0.000 abstract description 3
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 238000010438 heat treatment Methods 0.000 description 25
- 238000005245 sintering Methods 0.000 description 24
- 239000000047 product Substances 0.000 description 20
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 18
- 229920001030 Polyethylene Glycol 4000 Polymers 0.000 description 18
- 238000004132 cross linking Methods 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 13
- 239000012299 nitrogen atmosphere Substances 0.000 description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 11
- 229910001873 dinitrogen Inorganic materials 0.000 description 11
- 238000001816 cooling Methods 0.000 description 9
- 229920000620 organic polymer Polymers 0.000 description 8
- 239000003575 carbonaceous material Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 239000011261 inert gas Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 229910001416 lithium ion Inorganic materials 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- 229910052744 lithium Inorganic materials 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229940057838 polyethylene glycol 4000 Drugs 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 239000002028 Biomass Substances 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 239000011889 copper foil Substances 0.000 description 3
- 238000004146 energy storage Methods 0.000 description 3
- 239000001307 helium Substances 0.000 description 3
- 229910052734 helium Inorganic materials 0.000 description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000000197 pyrolysis Methods 0.000 description 3
- 230000008439 repair process Effects 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000006258 conductive agent Substances 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000003780 insertion Methods 0.000 description 2
- 230000037431 insertion Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 230000001788 irregular Effects 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-NJFSPNSNSA-N Carbon-14 Chemical compound [14C] OKTJSMMVPCPJKN-NJFSPNSNSA-N 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 241001625808 Trona Species 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000000844 transformation Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- 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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/16—Pore diameter
-
- 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
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
Disclosed in the present invention are a hard carbon negative electrode material, and a preparation method therefor and the use thereof. A substrate of the hard carbon negative electrode material is prepared by taking starch as a raw material; and the diameter of an internal pore of the hard carbon negative electrode material is greater than that of a surface pore thereof. The rational pore diameter and large interlayer spacing of the hard carbon negative electrode material are beneficial to the intercalation/deintercalation of sodium ions.
Description
HARD CARBON NEGATIVE ELECTRODE MATERIAL, AND PREPARATION METHOD THEREFOR AND USE THEREOF
CROSS REFERENCE TO RELATED APPLICATIONS
[0001] This application claims the priority of Chinese Patent Application No. 202111456775.6, filed on December 01, 2021, and the disclosure of which is hereby incorporated by reference.
FIELD
[0002] The present disclosure belongs to the technical field of battery anode materials, specifically relates to a hard carbon anode material, a method for preparing the same thereof and uses thereof
BACKGROUND
[0003] As the increasing reduction of traditional fossil energy source and the increasing environmental pollution, it is particularly important to develop and utilize new energy.
Lithium-ion batteries have become the main energy storage devices in the field of consumer electronics owing to their advantages of high energy density, high voltage, low self-discharge, and excellent cycle performance. However, lithium resources on the earth are scarce and become even more scarce and expensive due to the wide application of lithium-ion batteries, and thus lithium-ion batteries are not suitable for large-scale energy storage applications. Therefore, there is an urgent need to develop new generation of energy storage battery system with excellent comprehensive performance.
[0004] Sodium, being in the same element family with lithium, has similar physicochemical properties to lithium, rich in reserves and cheap (Trona as the basic raw material of sodium is about 30 to 40 times cheaper than lithium carbonate as the raw material of lithium). With an electrode potential (Na'/Na) 0.3 V higher than that of lithium ions (LIE/Li), sodium has more stable electrochemical and safety performance. However, sodium ions have an ionic radius (r=0.113nm) that is at least 35% larger than that of lithium ions (r=0.076), so they are relatively stable in a rigid lattice, and difficult to reversibly (de)intercalation in a regular graphite structure, resulting almost no sodium storage capacity.
SUMMARY
[0005] The first technical problem to be solved by the present disclosure is to provide a hard carbon anode material having reasonable pore diameter and large interlayer spacing, which are conducive to the insertion/extraction of sodium ions.
[0006] The second technical problem to be solved by the present disclosure is to provide a method for preparing the hard carbon anode material.
[0007] The present disclosure further provides a hard carbon anode.
[0008] In order to solve the first technical problem, the present disclosure adopts the following technical solutions.
[0009] A hard carbon anode material, wherein the substrate of the hard carbon anode material is prepared by using starch as a raw material, and the diameter of the inner pores of the hard carbon anode material is larger than the diameter of the surface pores.
[0019] According to an embodiment of the present disclosure, the interlayer spacing of the hard carbon anode material is greater than 0.34nm.
[0011] Since the ionic diameter of a sodium ion is about 0.226nm, the interlayer spacing of the anode material should be at least greater than 0.226nm, so that the sodium ions can theoretically freely intercalate and deintercalate among the negative electrode material layers. In fact, the interlaced layered structure in the negative electrode material will affect the conduction of sodium ions at a certain extent. When the interlayer spacing of an anode material reaches 0 34nm, it is still difficult for sodium ions to freely and reversibly deintercalate. Accordingly, the interlayer spacing of the negative electrode material should be at least greater than 0.34nm.
[0012] According to an embodiment of the present disclosure, the hard carbon anode material has an interlayer spacing about 3.828nm.
[0013] According to an embodiment of the present disclosure, the inner pores have a diameter
_ _
of X, O<X<5nm.
[0014] According to an embodiment of the present disclosure, the inner pores of the hard carbon anode material have a diameter between 0 and 5nm. Within this range, intercalation and deintercalation of sodium ions are favored, so the hard carbon anode material has both sodium storage capacity and cycle stability.
[0015] According to an embodiment of the present disclosure, the diameter of the inner pores of the hard carbon anode material is mainly 2nm.
[0016] According to an embodiment of the present disclosure, the diameter of the surface pores of the hard carbon anode material is smaller than that of inner pores thereof. Since the pore diameter at surface is small, while the sodium ions can pass through the external pores of the hard carbon anode material, it is difficult for substances larger than ions to pass through the external pores, which prevents unwanted impurities from being doped into the hard carbon anode material, thereby ensuring a good sodium storage environment inside the hard carbon anode material. In addition, there are a large number of random pores inside the spherical particles, which can further enhance the sodium storage capacity inside the hard carbon anode material.
[0017] According to an embodiment of the present disclosure, charge/discharge cycle testing is performed on the hard carbon anode material through a blue electric test cabinet. As a result, the obtained average sodium intercalation capacity of the hard carbon anode material was 330mAh/g.
[0018] According to an embodiment of the present disclosure, the starch is amylose and/or amylopectin, and preferably at least one of potato starch, corn starch, wheat starch, sweet potato starch, and tapioca starch.
[0019] According to an embodiment of the present disclosure, the hard carbon anode material is spherical particles of I 5-20tim. The spherical particles are moderate in size.
[0020] In order to solve the second technical problem, the present disclosure adopts the following technical solution.
[0021] A method for preparing the hard carbon anode material comprises the following steps: [0022] mixing a cross-linked starch with a thermally unstable polymer to obtain a precursor; and -3 - [0023] performing aromatic cyclization treatment and carbonization treatment on the precursor, to obtain a hard carbon anode material.
[0024] According to an embodiment of the present disclosure, the polymer is selected from the group consisting of polyethylene glycol, polyvinyl alcohol, carboxy methyl cellulose sodium, 5 N-methylpyrrolidone and a mixture thereof [0025] According to an embodiment of the present disclosure, the polymer may be polymer powder or may be a polymer solution. When the polymer is a solution, the concentration of the polymer in mass percentage is 0.5%-20%.
[0026] The polymers can form a stable segment structure with starch, and further promote the cross-linking of starch. And, subsequently, as the temperature of the reaction system rise, some segments of the polymer in the system will decompose into volatile substances, so that an irregular pore structure is formed inside the hard carbon anode material. As the temperature rise, the hard carbon anode material will undergo self-repairing to repair the surface pores without affecting the formation of the internal pore structure.
[0027] Starch is composed of amylose and amylopectin. During the cross-linking process of starch, due to the poor thermal stability of amylopectin, the hydrogen bonds between amylopectin and amylose will break, and amylopectin will decompose. After the cross-linking treatment with the addition of the polymer, the polymer and starch re-form a stable segment structure, while as the temperature of the reaction system rise, the segments of both starch and polymer move violently and break, and then ether bond is formed between two segments to be repolymerized. This process is equivalent to further promoting the process of starch cross-linking.
[0028] The volatile substances include water vapor, carbon monoxide, carbon dioxide, and alkanes.
[0029] According to an embodiment of the present disclosure, the mass ratio of the polymer and the cross-linked starch is 0.05: 1 -0.5: 1. Within this mass ratio. the hard carbon anode material can be synthesized.
[0030] According to an embodiment of the present disclosure, when the polymer is a liquid, the mass ratio of the polymer and the cross-linked starch is 0.5: 1 -2: 1. When the polymer is powder, the mass ratio of the polymer and the cross-linked starch is 0.05: 1 -0.5: 1. -4 -
[0031] According to an embodiment of the present disclosure, the cross-linking treatment of the starch is under the protection of an inert gas, wherein the inert gas is at least one of nitrogen gas, argon gas, and helium gas. The concentration of oxygen in the cross-linking treatment is below 200ppm.
[0032] According to an embodiment of the present disclosure, the cross-linking treatment is performed at 200-235°C for 8-60h, and at a heating rate of 1-5°C/min After the cross-linking treatment, the resultant is cooled to below 50°C.
[0033] The cross-linked starch forms a spatial network structure. During the cross-linking, a suitable crosslinking agent may be added to promote the hydroxyl reaction of starch molecules, thereby linking multiple starch molecules.
[0034] Uncrosslinked starch swells at mesophilic conditions, which destroys its structure, making pore formation impossible.
[0035] According to an embodiment of the present disclosure, the aromatic cyclization treatment is carried out at a temperature of 300-500°C for a duration of 2-6h, and at a heating rate of 3-5°C/min The aromatic cyclization treatment is carried out under the protection of an inert gas. The inert gas is at least one of nitrogen gas, argon gas, and helium gas.
[0036] During the aromatic cyclization treatment, some segments of the polymer in the system will decompose into volatile substances, so that an irregular pore structure is formed inside the hard carbon anode material.
[0037] The method for making pores by using a polymer can he applied not only to hard carbon material systems, but also to other carbonaceous systems, and has wide applicability.
[0038] According to an embodiment of the present disclosure, the carbonization treatment is carried out at a temperature of 1000-1400°C for a duration of 0.5-3h, at a heating rate of 3-5°C/min. The carbonization treatment is carried out under the protection of an inert gas, wherein the inert gas is at least one of nitrogen gas, argon gas, and helium gas.
[0039] The purpose of the carbonization treatment is to burn out excess organic matter and easily decomposed substances on the one hand, and to make the hard carbon structure more stable on the other hand. When the unstable medium in the material has been decomposed, the _ s _ material repairs itself at the same time, making the material structure more stable.
[0040] By a three-step pyrolysis method, a starch-biomass-based hard carbon material is prepared by step-by-step sintering, whose disordered interlayer structure and large interlayer spacing facilitate insertion/extraction of sodium ions, and exhibits excellent cycling stability.
[0041] Furthermore, another aspect of the present disclosure provides a hard carbon anode which comprises copper foil and a slurry coated on the copper foil, wherein the slurry contains a binder, a conductive agent and said hard carbon anode material.
[0042] Furthermore, yet another aspect of the present disclosure provides a sodium ion battery which comprises a sodium sheet cathode and a hard carbon anode, wherein the hard carbon anode includes said hard carbon anode material.
[0043] According to an embodiment of the present disclosure, the average capacity of hard carbon anode is maintained at 83%, after 100 cycles at a rate of 0.1C.
[0044] One of the technical solutions in the technical solution has at least one of the following advantages or beneficial effects: [0045] 1. The diameter of the surface pores of the hard carbon anode material is smaller than that of inner pores thereof, and the sodium ions can pass through the external pores of the hard carbon anode material. Since the pore diameter at surtUce is small, it is difficult for substances larger than ions to pass through the external pores, which prevents unwanted impurities from being doped into the hard carbon anode material, thereby ensuring a good sodium storage environment inside the hard carbon anode material. In addition, there are a large number of random pores inside the spherical particles, which can further enhance the sodium storage capacity inside the hard carbon anode material.
[0046] 2. By a three-step pyrolysis method, a starch-biomass-based hard carbon material is prepared by step-by-step sintering, whose disordered interlayer structure and large interlayer spacing facilitate intercalation/deintercalation of sodium ions, and exhibits excellent cycling stability.
BRIEF DESCRIPTION OF DRAWINGS
[0047] The accompanying drawings forming a part of the present disclosure are given to aid in further understanding of the present disclosure. The exemplary examples of the present disclosure and their descriptions are given to explain the present disclosure, but not do not constitute an improper limitation of the present invention.
[0048] FIG. 1 is a schematic diagram illustrating the internal structure of the hard carbon anode material in the examples.
[0049] FIG. 2 is a SEM image of the hard carbon anode material in the examples.
DETAILED DESCRIPTION
[0050] Hereinafter the technical solutions of the present disclosure will be described clearly and completely, in conjunction with the accompanying drawings in examples of the present disclosure. Obviously, the described examples are only part of the examples of the present disclosure, rather than all of them. Based on the examples in the present disclosure, all other embodiments obtained by a person having ordinary skill in the art without creative labor should fall within the protection scope of the present invention.
[0051] The hard carbon anodes used in the tests includes a copper foil and a slurry coated on the above-mentioned copper wherein the above-mentioned slurry contains a hinder, a conductive agent and a hard carbon anode material.
[0052] The battery used in the tests is a sodium-ion button half-cell, with a sodium sheet as 20 cathode. and the above-mentioned hard carbon anode as anode.
Examples
[0053] Example 1
[0054] A method for preparing the above-mentioned hard carbon anode material included the following steps: [0055] (1) 50g of PEG-4000 (polyethylene glycol 4000) was dissolved in 1000m1 of deionized water, to prepare a 5% PEG-4000 as an organic polymer pore-forming solution; [0056] (2) Under the protection of nitrogen gas, corn starch was placed in a sintering furnace, and heated to 220°C at a heating rate of PC/min to undergo cross-linking treatment for 30 hours, and then after cooling to 50°C, a first sintered product was obtained; [0057] (3) 100m1 of the 5% PEG-4000 polymer solution from step (1) and 100g of the first sintered product from step (2) were well mixed to obtain a precursor; [0058] (4) The precursor obtained in step (3) was placed in a sintering furnace, and heated to 400°C at a heating rate of 3°C/min under a nitrogen atmosphere to undergo aromatic cyclization treatment for 3 hours to produce a raw material with pores; and [0059] (5) The raw material with pores by aromatic cyclization in step (4) was placed in a sintering furnace, and heated from 400°C to 1100°C at a heating rate of 5°C/min under a nitrogen atmosphere to undergo high temperature carbonization treatment for 2 hours, and then the above-mentioned hard carbon anode material was obtained.
Example 2
[0060] A method for preparing the above-mentioned hard carbon anode material included the following steps: [0061] (1) 50g of PEG-4000 was dissolved in 1000m1 of deionized water to prepare a 5% PEG-4000 as an organic polymer pore-forming solution; [0062] (2) Under the protection of nitrogen gas, corn starch was placed in a sintering furnace, heated to 220°C at a heating rate of I °C/min to undergo cross-linking treatment for 30 hours, and then after cooling to 50°C, a first sintered product was obtained; [0063] (3) 100m1 of the 5% PEG-4000 polymer solution from step (1) and 100g of the first sintered product from step (2) were well mixed to obtain a precursor; [0064] (4) The precursor obtained in step (3) was placed in a sintering furnace, and heated to 300°C at a heating rate of 3°C/min under a nitrogen atmosphere to undergo aromatic cyclization treatment for 3 hours to produce a raw material with pores; [0065] (5) The raw material with pores by aromatic cyclization in step (4) was placed in a -8 -sintering furnace, and heated from 400°C to 1100°C at a heating rate of 5°C/min under a nitrogen atmosphere to undergo high temperature carbonization treatment for 2 hours, and then the above-mentioned hard carbon anode material was obtained.
Example 3
[0066] A method for preparing the above-mentioned hard carbon anode material included the following steps: the following steps: [0067] (1) 50g of PEG-4000 was dissolved in 1000m1 of deionized water, to prepare a 5% PEG-4000 as an organic polymer pore-forming solution; [0068] (2) Under the protection of nitrogen gas, corn starch was placed in a sintering furnace, heated to 220°C at a heating rate of 1°C/min to undergo cross-linking treatment for 30 hours, and then after cooling to 50°C, a first sintered product was obtained; 1-0069-1 (3) 100ml of the 5% PEG-4000 as an organic polymer pore-forming solution from step (1) and 100g of the first sintered product from step (2) were well mixed to obtain a precursor; [0070] (4) The precursor obtained in step (3) was placed in a sintering furnace, and heated to 500°C at a heating rate of 3°C/min under a nitrogen atmosphere to undergo aromatic cyclization treatment for 3 hours to produce a raw material with pores; [0071] (5) The raw material with pores by aromatic cyclization in step (4) was placed in a sintering furnace, and heated from 400°C to 1 100°C at a heating rate of 5°C/min under a nitrogen atmosphere to undergo high temperature carbonization treatment for 2 hours, and then the above-mentioned hard carbon anode material was obtained.
Example 4
[0072] The preparing steps were the same as Example 1, except that step (2) in Example 4 was as following. Under the protection of nitrogen gas, corn starch was placed in a sintering furnace, heated to 215°C at a heating rate of 1°C/min to perform cross-linking treatment for 6 hours, and then heated to 225°C at a heating rate of 1°C/min and maintained at the temperature for 12h.
After cooling to 50°C, a first sintered product was obtained.
Example 5
[0073] The preparing steps were the same as Example I, except that step (2) in Example 5 was as following. Under the protection of nitrogen gas, corn starch was placed in a sintering furnace, heated to 230°C at a heating rate of I °C/min to perform cross-linking treatment for 8 hours. After cooling to 50°C, a first sintered product was obtained.
Example 6
[0074] The preparing steps were the same as Example I, except that the starch used in Example 6 was potato starch.
Example 7
[0075] The preparing steps were the same as Example 1, except that the starch used in Example 7 was wheat starch.
Example 8
[0076] The preparing steps were the same as Example 1, except that the polymer used in Example 8 was polyvinyl alcohol.
Example 9
[0077] The preparing steps were the same as Example 1, except that the polymer used in Example 9 was carboxy methyl cellulose sodium.
Example 10
[0078] The preparing steps were the same as Example 1, except that the polymer concentration in Example 10 was changed.
[0079] A method for preparing the above-mentioned hard carbon anode material included the following steps: [0080] (1) 100g of PEG-4000 (polyethylene glycol 4000) was dissolved in 1000m1 of deionized water to prepare a 10% PEG-4000 as an organic polymer pore-forming solution; [0081] (2) Under the protection of nitrogen gas, corn starch was placed in a sintering furnace, and heated to 220°C at a heating rate of 1°C/min to undergo cross-linking treatment for 30 hours, and after cooling to 50°C, a first sintered product was obtained; [0082] (3) 100m1 of 10% PEG-4000 polymer solution from step (1) and 100g of the first sintered product from step (2) were well mixed to obtain a precursor; [0083] (4) The precursor obtained in step (3) was placed in a sintering furnace, under a nitrogen atmosphere, and heated to 400°C at a heating rate of 3°C/min to undergo aromatic cyclization treatment for 3 hours to produce a raw material with pores; and [0084] (5) The raw material with pores by aromatic cyclization in step (4) was placed in a sintering furnace, under a nitrogen atmosphere, and heated from 400°C to 1100°C at a heating rate of 5°C/min to undergo high temperature carbonization treatment for 2 hours, and then the above-mentioned hard carbon anode material was obtained.
Example 11
[0085] The preparing steps were the same as Example 1, except that the polymer concentration in Example 11 was changed.
[0086] A method for preparing the above-mentioned hard carbon anode material included the following steps: [0087] (1) 150g of PEG-4000 (polyethylene glycol 4000) was dissolved in 1000m1 of deionized water, to prepare a 15% PEG-4000 as an organic polymer pore-forming solution; [0088] (2) Under the protection of nitrogen gas, corn starch was placed in a sintering furnace, and heated to 220°C at a heating rate of PC/min to undergo cross-linking treatment for 30 hours, and then after cooling to 50°C, a first sintered product was obtained; [0089] (3) 100m1 of the 15% PEG-4000 polymer solution from step (1) and 100g of the first sintered product from step (2) were well mixed to obtain a precursor; [0090] (4) The precursor obtained in step (3) was placed in a sintering furnace, under a nitrogen atmosphere, and heated to 400°C at a heating rate of 3°C/min, to undergo aromatic cyclization treatment for 3 hours to produce a raw material with pores; and [0091] (5) The raw material with pores by aromatic cyclization in step (4) was placed in a sintering furnace, and heated from 400°C to 1100°C at a heating rate of 5°C/min under a nitrogen atmosphere to undergo high temperature carbonization treatment for 2 hours, and then the above-mentioned hard carbon anode material was obtained.
Example 12
[0092] The preparing steps were the same as Example 1, except that the polymer concentration 15 in Example 12 was changed.
[0093] A method for preparing the above-mentioned hard carbon anode material included the following steps: the following steps: [0094] ( ) 200g of PEG-4000 (polyethylene glycol 4000) was dissolved in 1000m1 of deionized water, to prepare a 20% PEG-4000 as an organic polymer pore-forming solution; [0095] (2) Under the protection of nitrogen gas, corn starch was placed in a sintering furnace, and heated to 220°C at a heating rate of I °C/min to undergo cross-linking treatment for 30 hours, and then after cooling to 50°C, a first sintered product was obtained; [0096] (3) 100m1 of the 20% PEG-4000 as an organic polymer pore-forming solution from step (1) and 100g of the first sintered product from step (2) were well mixed to obtain a precursor; [0097] (4) The precursor obtained in step (3) was placed in a sintering furnace, and heated to 400°C at a heating rate of 3°C/min under a nitrogen atmosphere, to undergo aromatic cyclization treatment for 3 hours to produce a raw material with pores; and -12 - [0098] (5) The raw material with pores by aromatic cyclization in step (4) was placed in a sintering furnace, and heated from 400°C to 1100°C at a heating rate of 5°C/min under a nitrogen atmosphere to undergo high temperature carbonization treatment for 2 hours, and then the above-mentioned hard carbon anode material was obtained.
Comparative Example 1 [0099] I OOg of corn starch was maintained at 230°C and subjected to cross-linking treatment for 8 hours, and then a starch precursor was obtained. The starch precursor was maintained at 400°C to undergo aromatic cyclization treatment for 2 hours, and maintained at a temperature of 1100°C to undergo high temperature carbonization treatment for 3 hours. After cooling to the room temperature, a hard carbon material was obtained.
[0100] In Comparative Example I, due to the preparation raw materials did not included the polymer, there was almost no pores formed in the final product of hard carbon material.
Comparative Example 2 [0101] The preparing steps were the same as Example 1, except that the polymer of Comparative Example 2 was phenolic resin 2123.
[0102] In Comparative Example 2, due to the use of the more thermally stable polymer, there was almost no pore formed in the final product of hard carbon material.
Performance Testing: [0103] The schematic diagram of the internal structure of the above-mentioned hard carbon anode material is shown in FIG. 1, which shows that the material has a disordered interlayer structure inside and a microporous structure distributed outside.
[0104] The SEM (scanning electron microscope) image of the hard carbon anode material prepared in Example 1 is shown in FIG. 2, which shows that the hard carbon anode material is spherical particle with a diameter of I5-20µm.
[0105] Table 1 shows the specific surface areas of the hard carbon products prepared in examples 1, 2, 3 and Comparative Example 1. These data were measured by using a specific surface area tester made by BSD instrument.
[0106] Table 1 Specific surface areas of the hard carbon products Example 1 Example 2 Example 3 Example 10 Example 11 Example 12 Comparative
Example 1
Specific 0.436 1.02 1.09 1.09 1.29 1.33 43.4 surface area (11.12/0 [0107] It can be seen from Table 1 that, the hard carbon products prepared in examples 1-3 have a smaller specific surface area than that of Comparative Example 1, especially in Example 1, it is only 0.436 m2/g.
[0108] When starch is not subjected to treatment for pore-forming, there are some natural defects on its surface, resulting in a larger specific surface area. When starch has been subjected to treatment for pore-forming by the addition of the polymer, the starch undergoes a certain structure change, and it shows pores inside while defects at its surface repair themselves, resulting in a reduction in specific surface area.
[0109] In the preparation process of Comparative Example 1, no polymer was added, so there 15 was no reaction between starch and the polymer, furthermore there was no step of decomposing polymer in the system during the heating, thus no step of forming a pore structure.
[0110] In examples 1-3, although the starch biomass-based hard carbon materials were prepared by step-by-step sintering using the three-step pyrolysis, they are different in their product structures and in their sizes of internal and external pores, these are due to the different sintering temperatures and difference reactions in the systems.
[0111] Table 2 shows the electrochemical performance of the hard carbon anodes for sodium ion batteries prepared in Example 1, 2, 3 and Comparative Example 1. The data was measured by a blue electric test cabinet.
[0112] Table 2 Comparison among the electrochemical performance of the hard carbon -14 -anodes for sodium ion batteries Electrochemical performance Example 1 Example 2 Example 3 Comparative Example 1 First specific discharge capacity (naAh/g) 334.7 330.4 329.8 275.6 First charge and discharge efficiency (%) 88.83 86.88 86.64 79.5 cycles at a rate of 0.1C, capacity retention rate (%) 83 825 82.6 66.8 Example 10 Example 11 Example 12 First specific discharge capacity (mAh/g) 333.9 332.7 332.4 First charge and discharge efficiency (%) 87.5 86.9 86.6 cycles at a rate of 0.1C, capacity retention rate (%) 82.8 81.9 80.8 [0113] It can he seen from Table 2 that the hard carbon products prepared in the examples have better electrochemical performance than that of Comparative Example 1, especially Example 1.
The hard carbon product of Comparative Example 1 has lower first charge and discharge efficiency and first specific discharge capacity, which is due to that its specific surface area is overlarge, and thus part of its sodium ions are consumed to form a solid electrolyte film [0114] The above are only the examples of the present disclosure, and not intended to limit the scope of the present invention. All equivalent transformations based on the contents of the description, or direct or indirect application in the relevant technical fields should he included in the protection scope of the present invention.
-15 -
Claims (10)
- CLAIMS1. A hard carbon anode material, wherein the substrate of the hard carbon anode material is prepared by using starch as a raw material; and inner pores of the hard carbon anode material have a diameter larger than the diameter of surface pores thereof.
- 2. The hard carbon anode material according to claim I, wherein the starch is amylose and/or amylopectin, and preferably selected from the group consisting of potato starch, corn starch, wheat starch, sweet potato starch, tapioca starch and a mixture thereof.
- 3. The hard carbon anode material according to claim 1, wherein the hard carbon anode material is a spherical particle with a diameter of 15-20jtm.
- 4. The hard carbon anode material according to claim 1, wherein the inner pores have a diameter of X, where 0< X < 5nm.
- 5. A method for preparing the hard carbon anode material according to claims I to 4, comprising the following steps: mixing a cross-linked starch with a thermally unstable polymer to obtain a precursor; and subjecting the precursor to aromatic cyclization treatment and carbonization treatment to obtain the hard carbon anode material.
- 6. The method according to claim 5, wherein the polymer is selected from the group consisting of polyethylene glycol, polyvinyl alcohol, carboxy methyl cellulose sodium, N-methylpyrrolidone and a mixture thereof -16 -
- 7. The method according to claim 5, wherein the mass ratio of the polymer and the cross-linked starch is 0.05: 1 -0.5: 1.
- 8. The method according to claim 5, wherein the aromatic cyclization treatment is carried out at a temperature of 300-500°C for a duration of 2-6h.
- 9. The method according to claim 5, wherein the carbonization treatment is carried out at a temperature of 1000-1400°C for a duration of 0.5-3h.
- 10. A sodium ion battery, comprising a sodium sheet cathode and a hard carbon anode, wherein the hard carbon anode comprises the hard carbon anode material according to any one of claims 1-4.-17 -
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