CN117384323B - Starch-based precursor material and preparation method and application thereof - Google Patents
Starch-based precursor material and preparation method and application thereof Download PDFInfo
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- 229920002472 Starch Polymers 0.000 title claims abstract description 158
- 239000008107 starch Substances 0.000 title claims abstract description 158
- 235000019698 starch Nutrition 0.000 title claims abstract description 158
- 239000000463 material Substances 0.000 title claims abstract description 55
- 239000002243 precursor Substances 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 238000003756 stirring Methods 0.000 claims abstract description 56
- 238000010438 heat treatment Methods 0.000 claims abstract description 47
- 229910001415 sodium ion Inorganic materials 0.000 claims abstract description 37
- 238000001816 cooling Methods 0.000 claims abstract description 34
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000000178 monomer Substances 0.000 claims abstract description 29
- 238000006243 chemical reaction Methods 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 19
- 239000003999 initiator Substances 0.000 claims abstract description 18
- 238000001035 drying Methods 0.000 claims abstract description 13
- 238000005406 washing Methods 0.000 claims abstract description 13
- 239000012535 impurity Substances 0.000 claims abstract description 7
- 238000012986 modification Methods 0.000 claims abstract description 7
- 230000004048 modification Effects 0.000 claims abstract description 7
- 230000001804 emulsifying effect Effects 0.000 claims abstract description 3
- 238000004321 preservation Methods 0.000 claims abstract description 3
- 229910021385 hard carbon Inorganic materials 0.000 claims description 65
- 239000010405 anode material Substances 0.000 claims description 40
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 27
- 239000000725 suspension Substances 0.000 claims description 24
- 239000008367 deionised water Substances 0.000 claims description 22
- 229910021641 deionized water Inorganic materials 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- 239000011261 inert gas Substances 0.000 claims description 20
- 239000007773 negative electrode material Substances 0.000 claims description 19
- 238000003763 carbonization Methods 0.000 claims description 15
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 12
- 238000004945 emulsification Methods 0.000 claims description 12
- 239000003995 emulsifying agent Substances 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 12
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 12
- 230000001376 precipitating effect Effects 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 5
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 3
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 3
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 3
- 239000011230 binding agent Substances 0.000 claims description 3
- 239000006258 conductive agent Substances 0.000 claims description 3
- LDCRTTXIJACKKU-ONEGZZNKSA-N dimethyl fumarate Chemical compound COC(=O)\C=C\C(=O)OC LDCRTTXIJACKKU-ONEGZZNKSA-N 0.000 claims description 3
- 229960004419 dimethyl fumarate Drugs 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 239000011248 coating agent Substances 0.000 claims description 2
- 238000000576 coating method Methods 0.000 claims description 2
- 238000009656 pre-carbonization Methods 0.000 claims description 2
- 239000003575 carbonaceous material Substances 0.000 abstract description 12
- 238000000197 pyrolysis Methods 0.000 abstract description 6
- 239000013078 crystal Substances 0.000 abstract description 5
- 238000002425 crystallisation Methods 0.000 abstract description 5
- 230000008025 crystallization Effects 0.000 abstract description 5
- 238000002844 melting Methods 0.000 abstract description 3
- 230000008018 melting Effects 0.000 abstract description 3
- 150000001336 alkenes Chemical class 0.000 abstract 1
- 239000000047 product Substances 0.000 description 120
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 17
- 229910052799 carbon Inorganic materials 0.000 description 12
- XMPZTFVPEKAKFH-UHFFFAOYSA-P ceric ammonium nitrate Chemical compound [NH4+].[NH4+].[Ce+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O XMPZTFVPEKAKFH-UHFFFAOYSA-P 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- 238000007670 refining Methods 0.000 description 9
- 238000000967 suction filtration Methods 0.000 description 9
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 8
- 239000002245 particle Substances 0.000 description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 230000018109 developmental process Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000013067 intermediate product Substances 0.000 description 4
- 229910052744 lithium Inorganic materials 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 230000002427 irreversible effect Effects 0.000 description 3
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- 125000003535 D-glucopyranosyl group Chemical group [H]OC([H])([H])[C@@]1([H])OC([H])(*)[C@]([H])(O[H])[C@@]([H])(O[H])[C@]1([H])O[H] 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000010000 carbonizing Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000007790 solid phase Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- HKVFISRIUUGTIB-UHFFFAOYSA-O azanium;cerium;nitrate Chemical compound [NH4+].[Ce].[O-][N+]([O-])=O HKVFISRIUUGTIB-UHFFFAOYSA-O 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 238000005087 graphitization Methods 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 150000002696 manganese Chemical class 0.000 description 1
- 239000013081 microcrystal Substances 0.000 description 1
- 239000005543 nano-size silicon particle Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F251/00—Macromolecular compounds obtained by polymerising monomers on to polysaccharides or derivatives thereof
-
- 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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/058—Construction or manufacture
-
- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/621—Binders
- H01M4/622—Binders being polymers
-
- 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
The invention relates to the technical field of sodium ion batteries, and discloses a starch-based precursor material, a preparation method and application thereof, and a method for preparing the starch-based precursor material, comprising the following steps: s1, taking starch, heating to perform pregelatinization to obtain a product I; s2, emulsifying the product I to obtain a product II; s3, taking a product II, dropwise adding an initiator, and stirring; adding an ethylenically unsaturated monomer, continuously stirring, carrying out heat preservation reaction, and cooling to obtain a product III; s4, removing impurities, washing and drying the product III in sequence to obtain the starch-based precursor material. The method adopts the alkene unsaturated monomer to carry out grafting modification on the starch, introduces a large number of long-chain branches, enhances the entanglement among molecular chains, and the introduced long-chain branch structure can damage the crystallization among the molecular chains of the starch, inhibit the melting and expansion of a crystal area in the pyrolysis process, reduce the conversion of carbon materials into tar, reduce the specific surface area of the materials and improve the overall electrochemical performance of the materials.
Description
Technical Field
The invention relates to the technical field of sodium ion batteries, in particular to a starch-based precursor material and a preparation method and application thereof.
Background
As the continuous exploitation of fossil energy and the environmental problems caused by the same become serious, researchers in the field begin to develop a lot of researches and adopt related measures, and new energy and renewable energy become important ways for realizing the prospect. Lithium batteries are one of new energy storage modes, and after decades of development, the lithium batteries are widely applied to various scenes such as industrial science and technology, daily life and the like. However, with the exploitation and use of lithium, problems such as small reserves of lithium resources and uneven distribution are increasingly remarkable, so that more and more researchers shift the development direction to sodium ion batteries with abundant reserves and similar electrochemical properties.
In sodium ion batteries, development and optimization of the negative electrode material are one of key technologies for realizing the practicability and commercialization of sodium ion batteries. At present, the hard carbon anode material is one of the most development potential of various sodium ion battery anode materials, and has the advantages of low cost, wide sources and the like, and particularly, the biomass precursor of starch has the advantages of rich yield, environmental protection, regeneration and degradability. For example, patent publication No. CN114988391A discloses a preparation method and application of a hard carbon negative electrode material, wherein starch is used as a hard carbon negative electrode material substrate, and the hard carbon negative electrode material substrate is mixed with nano silicon dioxide and then directly subjected to heat treatment at 150-240 ℃ to be pyrolyzed to form the hard carbon material.
However, due to the existence of the inter-molecular chain crystal region structure of the starch, the method for preparing the hard carbon material by directly pyrolyzing and carbonizing the starch in the prior art is adopted, the obtained carbon material is fluffy and porous, and the problems that the carbon yield of the starch is low, the broken carbon structure is unfavorable for sodium ion storage, the irreversible capacity is high and the like exist, so that the application effect of the starch-based negative electrode material in a sodium ion battery is directly affected.
Disclosure of Invention
The invention aims to solve the technical problems that:
at present, when starch is used as a hard carbon negative electrode material base material of a sodium ion battery, the starch is usually directly subjected to high-temperature heat treatment, so that the starch is pyrolyzed and carbonized to form a hard carbon material. In the preparation process, the carbon yield of the starch converted into hard carbon is low, and in the obtained starch-based hard carbon material, a carbon structure is broken, so that the sodium ion storage effect is limited, and the problem of high irreversible capacity also exists, namely, the problem of poor electrochemical comprehensive performance exists in the actual application of the existing starch-based hard carbon anode material in a sodium ion battery.
The invention adopts the technical scheme that:
the invention provides a preparation method of a starch-based precursor material, which comprises the following steps:
s1, starch pregelatinization:
heating starch to perform pregelatinization to obtain a product I;
s2, emulsification:
emulsifying the product I to obtain a product II;
s3, grafting modification:
dripping an initiator into the product II, and stirring; adding an ethylenically unsaturated monomer, continuously stirring, carrying out heat preservation reaction, and cooling to obtain a product III;
s4, removing impurities and forming:
and (3) removing impurities, washing and drying the product III in sequence to obtain the starch-based precursor material.
Preferably, in step S1, starch is mixed with deionized water and stirred to prepare a suspension; the suspension is placed at 60-90 ℃ and stirred for 1.5-3h to obtain the product I.
Preferably, in step S2, polyvinyl alcohol and an emulsifier are added to the product I, and the product II is obtained by heating and preserving heat.
Preferably, in step S4, the impurity removal process includes: and (3) placing the product III in absolute ethyl alcohol, precipitating, filtering and repeating for a plurality of times.
Preferably, in step S3, the ethylenically unsaturated monomer is selected from any one or more of styrene, acrylonitrile, acrylamide, acrylic acid, methacrylic acid, vinyl acetate, dimethyl fumarate.
Preferably, the product II is cooled to 40-45 ℃, kept warm, and the initiator is added in a stirring state, and after the addition of the initiator is finished, the mixture is stirred at a high speed for 1-10min to obtain the modified premix.
Preferably, adding an ethylenically unsaturated monomer into the prepared modified premix, and continuously stirring for 1-3 hours for reaction; after the reaction is finished, heating to 60-85 ℃, preserving heat for 1.5-3h, and cooling to room temperature to obtain a product III.
The starch-based precursor material can be applied to sodium ion batteries, and the application method comprises the following steps:
heating the starch-based precursor material under the protection of inert gas, sequentially carrying out pre-carbonization and carbonization treatment, and cooling to obtain a starch-based hard carbon anode material;
uniformly mixing a starch-based hard carbon anode material with a conductive agent, a binder and a solvent, and coating the mixture on the surface of a current collector of a sodium ion battery to obtain an anode piece; and placing the negative electrode plate in a sodium ion battery environment to obtain the sodium ion battery.
The beneficial effects of the invention are as follows:
according to the research of the invention, starch is used as a base material of a hard carbon negative electrode material of a sodium ion battery, and as the starch is polysaccharide composed of D-glucopyranose units, on one hand, most of glycosidic bonds among the D-glucopyranose units of starch molecular chains are heated and broken, depolymerized to generate an oxygen-containing compound, and finally converted into tar; on the other hand, only a small part of the starch molecular chains are rearranged after dehydration, and converted into carbonyl groups, CO and CO 2 Etc., eventually forming carbon residue. Pyrolysis of the aboveIn the process, the competition of the former pyrolysis way leads to low carbon yield of direct carbonization of starch and low production income; in addition, the starch crystal area in the pyrolysis process is melted to form a viscous intermediate product, and the volume of the intermediate product is expanded due to the overflow of small molecular gas, so that the final carbon material has the defects of overlarge specific surface area, large graphitization trend of a carbon layer, overlarge carbon layer interval and the like, and has lower coulomb effect, overlarge irreversible capacity and poor cycle stability when being used as a hard carbon negative electrode material of a sodium ion battery.
The invention improves the preparation method of hard carbon anode material precursor for starch-based sodium ion battery, firstly, the starch is gelatinized to break hydrogen bond among starch molecular chains, thereby breaking crystallization; further, by graft copolymerizing starch to increase its molecular weight, the carbon yield and the product yield are improved.
Specifically, the gelatinization treatment and a large number of long-chain branched structures formed after grafting can enable the crystal structure to disappear, the phenomenon of melting of a crystal area under a high temperature state is inhibited, a carbonized intermediate product keeps a solid phase, and when micromolecules generated by starch pyrolysis overflow, the volume of a carbon material cannot be expanded, so that the specific surface area of the obtained material is effectively reduced. The highly branched structure can enhance entanglement among molecular chains, and the high-density carbon net is beneficial to carbon plane growth, so that sodium ions are stored when the carbon net is used as a hard carbon anode material. By adopting the starch-based precursor material, in the subsequent high-temperature carbonization process, solid-phase intermediate products are not easy to rearrange, carbon layers are difficult to arrange orderly, and finally, the hard carbon material with graphite microcrystals randomly stacked is obtained; the growth of the carbon layer can enable holes left by gas micromolecule overflow to be converted into a nano closed-cell structure from open cells in the high-temperature carbonization process, so that sodium ions are stored in the holes.
Drawings
Fig. 1 is a graph showing the first-cycle charge and discharge performance test of a sodium ion battery using a starch-based hard carbon negative electrode material in example 2;
fig. 2 is an X-ray diffraction pattern of the starch-based hard carbon negative electrode material in example 2.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention more clear, the technical solutions of the embodiments of the present invention will be clearly and completely described below. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
The invention provides a preparation method of a starch-based precursor material, which comprises the following steps:
(1) Mixing starch and deionized water according to a mass ratio of 1:5-15, stirring at a speed of 250r/min for 30min to prepare a suspension, and continuously stirring the suspension at 60-90 ℃ for 3h to pregelatinize the starch to obtain a product A; this process can disrupt the hydrogen bonding between the starch molecular chains, disrupting crystallization.
(2) Adding 2wt% of polyvinyl alcohol and 2wt% of emulsifier OP-10 into the product A, and preserving the temperature for 320min, and obtaining the product B after the emulsification is sufficient.
(3) Cooling the product B to 40-45 ℃, and continuously stirring at 40-45 ℃, dropwise adding 0.5wt% of an initiator during the period, and stirring at a speed of 400r/min for 5min; adding an ethylenically unsaturated monomer (the dosage of the ethylenically unsaturated monomer is 5-15% of the mass of the starch), and continuously stirring for 2 hours to react; after the reaction is finished, the temperature is increased to 80 ℃, the heat is preserved for 2 hours, the excessive monomer is subjected to homopolymerization, and then the temperature is reduced to room temperature, so that a product C is obtained;
wherein the ethylenically unsaturated monomers include, but are not limited to, any one or more of styrene, acrylonitrile, acrylamide, acrylic acid, methacrylic acid, vinyl acetate, dimethyl fumarate, etc., or any one or more of the above monomers as a dibasic monomer;
initiators include, but are not limited to, ceric ammonium nitrate, persulfates, manganese salts, potassium permanganate, H 2 O 2 Any one or more of a redox system or azobisisobutyronitrile, and the like.
(4) Placing the product C in absolute ethyl alcohol, precipitating, filtering, repeating for many times to obtain a product D; and washing the product D by deionized water, and drying to obtain the starch-based precursor material.
In the invention, the starch crystallization is destroyed by pregelatinization and grafting of a large number of long-chain branches, and the melting phenomenon in the pyrolysis process is inhibited, so that the starch-based precursor material with low specific surface area and high carbon yield is obtained. The person skilled in the art can select other ethylenically unsaturated monomers with the same structural characteristics according to the actual production requirement, so that the ethylenically unsaturated monomers and starch undergo a grafting reaction, and the entanglement among molecular chains is enhanced by introducing a long-chain branched chain structure into starch molecules, so that the crystallization among the molecular chains is destroyed, and the effect beneficial to the sodium ion battery is exerted. Wherein, in the reaction process of introducing the ethylenically unsaturated monomer, the initiator used is also specifically selected according to the monomer selected, and the selection standard and the selection type can be selected by a person skilled in the art according to common technical means.
In the invention, the starch-based precursor material modified by the ethylenically unsaturated monomer can be applied to sodium ion batteries after carbonization and used as a hard carbon anode material.
< example >
Example 1
(1) Preparing a starch-based precursor material:
mixing starch and deionized water according to a mass ratio of 1:10, stirring at a speed of 250r/min for 30min to prepare a suspension, continuously stirring the suspension at 70 ℃ for 3h, and pregelatinizing to obtain a product A;
adding polyvinyl alcohol accounting for 2% of the total mass of the starch and the styrene into the product A, adding an emulsifier OP-10 accounting for 2% of the total mass of the starch and the styrene, and preserving the temperature for 30min, and obtaining a product B after the emulsification is sufficient;
cooling the product B to 40 ℃, continuously stirring at 40 ℃, dropwise adding cerium ammonium nitrate serving as an initiator accounting for 0.5% of the total mass of starch and styrene, stirring at a rate of 400r/min for 5min, adding 10% of the mass of the starch, and continuously stirring for 2h; after the reaction is finished, the temperature is increased to 80 ℃, the heat is preserved for 2 hours, the excessive monomer is subjected to homopolymerization, and then the temperature is reduced, so that a product C is obtained;
precipitating the product C with absolute ethyl alcohol, and carrying out suction filtration to obtain a product D; and washing the product D by deionized water, and drying to obtain the starch-based precursor material.
(2) Preparing a starch-based hard carbon anode material:
heating a precursor material to 600 ℃ at a heating rate of 1 ℃/min under the protection of inert gas to pre-carbonize for 6 hours, cooling to room temperature, and refining product grains to D90 < 10 mu m to obtain a product E;
wherein, the diameter D90 refers to the particle diameter of 90% of the cumulative distribution of the particles, that is, the volume content of the particles smaller than the particle diameter accounts for 90% of the total particles;
under the protection of inert gas, heating the product E to 1300 ℃ at a heating rate of 1 ℃/min for carbonization for 3 hours, and cooling to room temperature to obtain the starch-based hard carbon anode material.
Example 2
(1) Preparing a starch-based precursor material:
mixing starch and deionized water according to a mass ratio of 1:10, stirring at a speed of 250r/min for 30min to prepare a suspension, continuously stirring the suspension at 70 ℃ for 3h, and pregelatinizing to obtain a product A;
adding polyvinyl alcohol accounting for 2% of the total mass of the starch and the acrylamide into the product A, adding an emulsifier OP-10 accounting for 2% of the total mass of the starch and the acrylamide, and preserving the temperature for 30min, and obtaining a product B after the emulsification is sufficient;
cooling the product B to 40 ℃, continuously stirring at 40 ℃, dropwise adding cerium ammonium nitrate serving as an initiator accounting for 0.5% of the total mass of starch and acrylamide, stirring at a rate of 400r/min for 5min, adding acrylamide accounting for 10% of the mass of starch, and continuously stirring for 2h; after the reaction is finished, the temperature is increased to 80 ℃, the heat is preserved for 2 hours, the excessive monomer is subjected to homopolymerization, and then the temperature is reduced, so that a product C is obtained;
precipitating the product C with absolute ethyl alcohol, and carrying out suction filtration to obtain a product D; and washing the product D by deionized water, and drying to obtain the starch-based precursor material.
(2) Preparing a starch-based hard carbon anode material:
heating a precursor material to 600 ℃ at a heating rate of 1 ℃/min under the protection of inert gas to pre-carbonize for 6 hours, cooling to room temperature, and refining product grains to D90 < 10 mu m to obtain a product E;
under the protection of inert gas, heating the product E to 1300 ℃ at a heating rate of 1 ℃/min for carbonization for 3 hours, and cooling to room temperature to obtain the starch-based hard carbon anode material.
Example 3
(1) Preparing a starch-based precursor material:
mixing starch and deionized water according to a mass ratio of 1:10, stirring at a speed of 250r/min for 30min to prepare a suspension, continuously stirring the suspension at 70 ℃ for 3h, and pregelatinizing to obtain a product A;
adding polyvinyl alcohol accounting for 2% of the total mass of the starch and the acrylamide into the product A, adding an emulsifier OP-10 accounting for 2% of the total mass of the starch and the acrylamide, and preserving the temperature for 30min, and obtaining a product B after the emulsification is sufficient;
cooling the product B to 40 ℃, continuously stirring at 40 ℃, dropwise adding cerium ammonium nitrate serving as an initiator accounting for 0.5% of the total mass of starch and acrylamide, stirring at a rate of 400r/min for 5min, adding acrylamide accounting for 5% of the mass of starch, and continuously stirring for 2h; after the reaction is finished, the temperature is increased to 80 ℃, the heat is preserved for 2 hours, the excessive monomer is subjected to homopolymerization, and then the temperature is reduced, so that a product C is obtained;
precipitating the product C with absolute ethyl alcohol, and carrying out suction filtration to obtain a product D; and washing the product D by deionized water, and drying to obtain the starch-based precursor material.
(2) Preparing a starch-based hard carbon anode material:
heating a precursor material to 600 ℃ at a heating rate of 1 ℃/min under the protection of inert gas to pre-carbonize for 6 hours, cooling to room temperature, and refining product grains to D90 < 10 mu m to obtain a product E;
under the protection of inert gas, heating the product E to 1300 ℃ at a heating rate of 1 ℃/min for carbonization for 3 hours, and cooling to room temperature to obtain the starch-based hard carbon anode material.
Example 4
(1) Preparing a starch-based precursor material:
mixing starch and deionized water according to a mass ratio of 1:10, stirring at a speed of 250r/min for 30min to prepare a suspension, continuously stirring the suspension at 70 ℃ for 3h, and pregelatinizing to obtain a product A;
adding polyvinyl alcohol accounting for 2% of the total mass of the starch and the acrylamide into the product A, adding an emulsifier OP-10 accounting for 2% of the total mass of the starch and the acrylamide, and preserving the temperature for 30min, and obtaining a product B after the emulsification is sufficient;
cooling the product B to 40 ℃, continuously stirring at 40 ℃, dropwise adding cerium ammonium nitrate serving as an initiator accounting for 0.5% of the total mass of starch and acrylamide, stirring at a rate of 400r/min for 5min, adding acrylamide accounting for 15% of the mass of starch, and continuously stirring for 2h; after the reaction is finished, the temperature is increased to 80 ℃, the heat is preserved for 2 hours, the excessive monomer is subjected to homopolymerization, and then the temperature is reduced, so that a product C is obtained;
precipitating the product C with absolute ethyl alcohol, and carrying out suction filtration to obtain a product D; and washing the product D by deionized water, and drying to obtain the starch-based precursor material.
(2) Preparing a starch-based hard carbon anode material:
heating a precursor material to 600 ℃ at a heating rate of 1 ℃/min under the protection of inert gas to pre-carbonize for 6 hours, cooling to room temperature, and refining product grains to D90 < 10 mu m to obtain a product E;
under the protection of inert gas, heating the product E to 1300 ℃ at a heating rate of 1 ℃/min for carbonization for 3 hours, and cooling to room temperature to obtain the starch-based hard carbon anode material.
Example 5
(1) Preparing a starch-based precursor material:
mixing starch and deionized water according to a mass ratio of 1:10, stirring at a speed of 250r/min for 30min to prepare a suspension, continuously stirring the suspension at 70 ℃ for 3h, and pregelatinizing to obtain a product A;
adding polyvinyl alcohol accounting for 2% of the total mass of the starch and the acrylamide into the product A, adding an emulsifier OP-10 accounting for 2% of the total mass of the starch and the acrylamide, and preserving the temperature for 30min, and obtaining a product B after the emulsification is sufficient;
cooling the product B to 40 ℃, continuously stirring at 40 ℃, dropwise adding cerium ammonium nitrate serving as an initiator accounting for 0.5% of the total mass of starch and acrylamide, stirring at a rate of 100r/min for 5min, adding acrylamide accounting for 10% of the mass of starch, and continuously stirring for 2h; after the reaction is finished, the temperature is increased to 80 ℃, the heat is preserved for 2 hours, the excessive monomer is subjected to homopolymerization, and then the temperature is reduced, so that a product C is obtained;
precipitating the product C with absolute ethyl alcohol, and carrying out suction filtration to obtain a product D; and washing the product D by deionized water, and drying to obtain the starch-based precursor material.
(2) Preparing a starch-based hard carbon anode material:
heating a precursor material to 600 ℃ at a heating rate of 1 ℃/min under the protection of inert gas to pre-carbonize for 6 hours, cooling to room temperature, and refining product grains to D90 < 10 mu m to obtain a product E;
under the protection of inert gas, heating the product E to 1300 ℃ at a heating rate of 1 ℃/min for carbonization for 3 hours, and cooling to room temperature to obtain the starch-based hard carbon anode material.
Example 6
(1) Preparing a starch-based precursor material:
mixing starch and deionized water according to a mass ratio of 1:10, stirring at a speed of 250r/min for 30min to prepare a suspension, continuously stirring the suspension at 70 ℃ for 3h, and pregelatinizing to obtain a product A;
adding polyvinyl alcohol accounting for 2% of the total mass of the starch and the acrylamide into the product A, adding an emulsifier OP-10 accounting for 2% of the total mass of the starch and the acrylamide, and preserving the temperature for 30min, and obtaining a product B after the emulsification is sufficient;
cooling the product B to 40 ℃, continuously stirring at 40 ℃, dropwise adding cerium ammonium nitrate serving as an initiator accounting for 0.5% of the total mass of starch and acrylamide, stirring at a rate of 700r/min for 5min, adding acrylamide accounting for 10% of the mass of starch, and continuously stirring for 2h; after the reaction is finished, the temperature is increased to 80 ℃, the heat is preserved for 2 hours, the excessive monomer is subjected to homopolymerization, and then the temperature is reduced, so that a product C is obtained;
precipitating the product C with absolute ethyl alcohol, and carrying out suction filtration to obtain a product D; and washing the product D by deionized water, and drying to obtain the starch-based precursor material.
(2) Preparing a starch-based hard carbon anode material:
heating a precursor material to 600 ℃ at a heating rate of 1 ℃/min under the protection of inert gas to pre-carbonize for 6 hours, cooling to room temperature, and refining product grains to D90 < 10 mu m to obtain a product E;
under the protection of inert gas, heating the product E to 1300 ℃ at a heating rate of 1 ℃/min for carbonization for 3 hours, and cooling to room temperature to obtain the starch-based hard carbon anode material.
Example 7
(1) Preparing a starch-based precursor material:
mixing starch and deionized water according to a mass ratio of 1:10, stirring at a speed of 250r/min for 30min to prepare a suspension, continuously stirring the suspension at 70 ℃ for 3h, and pregelatinizing to obtain a product A;
adding polyvinyl alcohol accounting for 2% of the total mass of the starch and the acrylamide into the product A, adding an emulsifier OP-10 accounting for 2% of the total mass of the starch and the acrylamide, and preserving the temperature for 30min, and obtaining a product B after the emulsification is sufficient;
cooling the product B to 40 ℃, continuously stirring at 40 ℃, dropwise adding cerium ammonium nitrate serving as an initiator accounting for 0.5% of the total mass of starch and acrylamide, stirring at a rate of 400r/min for 5min, adding acrylamide accounting for 10% of the mass of starch, and continuously stirring for 30min; after the reaction is finished, the temperature is increased to 80 ℃, the heat is preserved for 2 hours, the excessive monomer is subjected to homopolymerization, and then the temperature is reduced, so that a product C is obtained;
precipitating the product C with absolute ethyl alcohol, and carrying out suction filtration to obtain a product D; and washing the product D by deionized water, and drying to obtain the starch-based precursor material.
(2) Preparing a starch-based hard carbon anode material:
heating a precursor material to 600 ℃ at a heating rate of 1 ℃/min under the protection of inert gas to pre-carbonize for 6 hours, cooling to room temperature, and refining product grains to D90 < 10 mu m to obtain a product E;
under the protection of inert gas, heating the product E to 1300 ℃ at a heating rate of 1 ℃/min for carbonization for 3 hours, and cooling to room temperature to obtain the starch-based hard carbon anode material.
Comparative example
Comparative example 1
The difference between this comparative example and example 1 is that no ethylenically unsaturated monomer such as styrene was added for graft modification treatment in the preparation of the starch-based precursor material.
(1) Preparing a starch-based precursor material:
mixing starch and deionized water according to a mass ratio of 1:10, stirring at a speed of 250r/min for 30min to prepare a suspension, continuously stirring the suspension at 70 ℃ for 3h, and pregelatinizing to obtain a product A;
adding polyvinyl alcohol with the mass of 2% of starch into the product A, adding an emulsifier OP-10 with the mass of 2% of starch, and preserving the temperature for 30min, and obtaining a product B after the emulsification is complete;
precipitating the product B with absolute ethyl alcohol, and carrying out suction filtration to obtain a product C; and washing the product C by deionized water, and drying to obtain the starch-based precursor material.
(2) Preparing a starch-based hard carbon anode material:
heating a precursor material to 600 ℃ at a heating rate of 1 ℃/min under the protection of inert gas to pre-carbonize for 6 hours, cooling to room temperature, and refining product grains to D90 < 10 mu m to obtain a product D;
and under the protection of inert gas, heating the product D to 1300 ℃ at a heating rate of 1 ℃/min for carbonization, carbonizing for 3 hours, and cooling to room temperature to obtain the hard carbon anode material.
Comparative example 2
The difference between this comparative example and example 1 is that 10wt% ethylbenzene was added as a reaction monomer to react with product B when preparing the starch-based precursor material.
(1) Preparing a starch-based precursor material:
mixing starch and deionized water according to a mass ratio of 1:10, stirring at a speed of 250r/min for 30min to prepare a suspension, continuously stirring the suspension at 70 ℃ for 3h, and pregelatinizing to obtain a product A;
adding polyvinyl alcohol accounting for 2% of the total mass of the starch and the ethylbenzene into the product A, adding an emulsifier OP-10 accounting for 2% of the total mass of the starch and the ethylbenzene, and preserving the temperature for 30min, and obtaining a product B after the emulsification is sufficient;
cooling the product B to 40 ℃, continuously stirring at 40 ℃, dropwise adding ammonium cerium nitrate serving as an initiator accounting for 0.5% of the total mass of the starch and the ethylbenzene, stirring at a speed of 400r/min for 5min, adding 10% of the mass of the starch, and continuously stirring for 2h; after the reaction is finished, the temperature is increased to 80 ℃, the heat is preserved for 2 hours, the excessive monomer is subjected to homopolymerization, and then the temperature is reduced, so that a product C is obtained;
precipitating the product C with absolute ethyl alcohol, and carrying out suction filtration to obtain a product D; and washing the product D by deionized water, and drying to obtain the starch-based precursor material.
(2) Preparing a starch-based hard carbon anode material:
heating a precursor material to 600 ℃ at a heating rate of 1 ℃/min under the protection of inert gas to pre-carbonize for 6 hours, cooling to room temperature, and refining product grains to D90 < 10 mu m to obtain a product E;
under the protection of inert gas, heating the product E to 1300 ℃ at a heating rate of 1 ℃/min for carbonization for 3 hours, and cooling to room temperature to obtain the starch-based hard carbon anode material.
< test example >
Sample: examples 1 to 7, comparative examples 1 to 2
The hard carbon negative electrode materials prepared in the examples 1-7 and the comparative examples 1-2 are respectively taken as samples, uniformly mixed with a conductive agent, a binder and a solvent, and then coated on the surface of a current collector of a sodium ion battery to obtain a negative electrode plate of the sodium ion battery, and the sodium ion battery is prepared.
（1）
The material properties of the samples and the electrochemical properties of the prepared sodium ion batteries were tested respectively, and the measurement results are shown in the following table 1:
table 1 different samples and sodium ion battery performance made therefrom
The measurement results in table 1 above revealed that:
compared with the hard carbon anode material prepared in comparative examples 1-2, the starch-based hard carbon anode material prepared by adopting the method of examples 1-7 has the characteristics of obviously more advantageous overall in terms of material properties such as specific surface area, first week charging specific capacity and the like, namely: the modification preparation method for the starch-based hard carbon anode material provided by the invention can obviously and effectively improve the material performance and the electrochemical performance of the material applied to sodium ion batteries.
（2）
From the above test results, example 2 was a group of samples with more outstanding comprehensive properties among the above samples, and the starch-based hard carbon negative electrode material prepared in example 2 was taken and its first-turn charge-discharge properties and X-ray diffraction pattern were measured, respectively.
As shown in fig. 1, a graph of the first-cycle charge and discharge performance of the sodium ion battery using the starch-based hard carbon negative electrode material in example 2 is shown, the abscissa is the specific capacity during charge/discharge, the curve represents the charge and discharge behavior of the negative electrode material, and the sample exhibits a first-cycle charge specific capacity of 406 mAh/g. Compared with the hard carbon anode material obtained in the comparative examples 1-2, the first-cycle charge specific capacity of the hard carbon anode material is remarkably improved, and the first-cycle coulomb efficiency of the hard carbon anode material is higher.
As shown in fig. 2, an X-ray diffraction pattern of the starch-based hard carbon anode material in example 2, where two broad peaks at 23.3 ° and 43.3 ° are characteristic peaks of an amorphous structure, indicates that the hard carbon material has a structure of graphite crystallites with disordered stacking, and this structural feature is beneficial to intercalation or deintercalation of sodium ions in hard carbon, that is, illustrates that sodium ion batteries prepared by using the starch-based hard carbon material can better store sodium ions in the hard carbon material during use.
The above description is only of the preferred embodiments of the present invention and is not intended to limit the present invention, but various modifications and variations can be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. The preparation method of the starch-based hard carbon anode material is characterized by comprising the following steps of:
s1, starch pregelatinization:
heating starch to perform pregelatinization to obtain a product I;
s2, emulsification:
emulsifying the product I to obtain a product II;
s3, grafting modification:
dripping an initiator into the product II, and stirring; adding an ethylenically unsaturated monomer, continuously stirring, carrying out heat preservation reaction, and cooling to obtain a product III;
s4, removing impurities and forming:
removing impurities, washing and drying the product III in sequence to obtain a starch-based precursor material;
s5, preparing a starch-based hard carbon anode material:
and heating the starch-based precursor material under the protection of inert gas, sequentially carrying out pre-carbonization and carbonization treatment, and cooling to obtain the starch-based hard carbon anode material.
2. The method for preparing a starch-based hard carbon negative electrode material according to claim 1, wherein in step S1, starch is mixed with deionized water and stirred to prepare a suspension;
the suspension is placed at 60-90 ℃ and stirred for 1.5-3h to obtain the product I.
3. The method for preparing a starch-based hard carbon negative electrode material according to claim 1, wherein in step S2, polyvinyl alcohol and an emulsifier are added to the product i, and the product ii is obtained by heating and maintaining the temperature.
4. The method for preparing a starch-based hard carbon negative electrode material according to claim 1, wherein in step S4, the impurity removal process comprises:
and (3) placing the product III in absolute ethyl alcohol, precipitating, filtering and repeating for a plurality of times.
5. The method for producing a starch-based hard carbon negative electrode material according to any one of claims 1 to 4, wherein in step S3, the ethylenically unsaturated monomer is selected from any one or more of styrene, acrylonitrile, acrylamide, acrylic acid, methacrylic acid, vinyl acetate, and dimethyl fumarate.
6. The method for preparing a starch-based hard carbon negative electrode material according to claim 5, wherein in the step S3, the product II is cooled to 40-45 ℃, the temperature is kept, an initiator is added in a stirring state, and after the initiator is added, the mixture is stirred at a high speed for 1-10min to obtain a modified premix.
7. The method for preparing a starch-based hard carbon anode material according to claim 6, wherein an ethylenically unsaturated monomer is added to the prepared modified premix, and the mixture is continuously stirred for 1-3 hours for reaction; after the reaction is finished, heating to 60-85 ℃, preserving heat for 1.5-3h, and cooling to room temperature to obtain a product III.
8. A starch-based hard carbon anode material prepared by the preparation method of any one of claims 1 to 7.
9. The use of the starch-based hard carbon anode material according to claim 8 in sodium ion batteries.
10. The use according to claim 9, characterized by the steps of:
uniformly mixing a starch-based hard carbon anode material with a conductive agent, a binder and a solvent, and coating the mixture on the surface of a current collector of a sodium ion battery to obtain an anode piece; and placing the negative electrode plate in a sodium ion battery environment to obtain the sodium ion battery.
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