CN116621158B - Asphalt/starch derived hard carbon, preparation method thereof and anode material containing asphalt/starch derived hard carbon - Google Patents
Asphalt/starch derived hard carbon, preparation method thereof and anode material containing asphalt/starch derived hard carbon Download PDFInfo
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- CN116621158B CN116621158B CN202310892039.8A CN202310892039A CN116621158B CN 116621158 B CN116621158 B CN 116621158B CN 202310892039 A CN202310892039 A CN 202310892039A CN 116621158 B CN116621158 B CN 116621158B
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- 229920002472 Starch Polymers 0.000 title claims abstract description 67
- 239000008107 starch Substances 0.000 title claims abstract description 67
- 235000019698 starch Nutrition 0.000 title claims abstract description 67
- 239000010426 asphalt Substances 0.000 title claims abstract description 47
- 229910021385 hard carbon Inorganic materials 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000010405 anode material Substances 0.000 title description 3
- 238000000034 method Methods 0.000 claims abstract description 18
- 239000003054 catalyst Substances 0.000 claims abstract description 17
- 238000010438 heat treatment Methods 0.000 claims abstract description 15
- 150000003863 ammonium salts Chemical class 0.000 claims abstract description 14
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910001415 sodium ion Inorganic materials 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 9
- 230000001681 protective effect Effects 0.000 claims abstract description 7
- 239000007773 negative electrode material Substances 0.000 claims abstract description 6
- 239000000126 substance Substances 0.000 claims abstract description 6
- 238000010000 carbonizing Methods 0.000 claims abstract description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 15
- 238000003763 carbonization Methods 0.000 claims description 11
- 230000008569 process Effects 0.000 claims description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 9
- 239000007789 gas Substances 0.000 claims description 9
- 239000001301 oxygen Substances 0.000 claims description 9
- 229910052760 oxygen Inorganic materials 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 8
- 238000004140 cleaning Methods 0.000 claims description 6
- 238000004321 preservation Methods 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 4
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 4
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 4
- 239000006258 conductive agent Substances 0.000 claims description 4
- 238000000227 grinding Methods 0.000 claims description 4
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 4
- 230000000630 rising effect Effects 0.000 claims description 4
- 238000007873 sieving Methods 0.000 claims description 4
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 4
- 239000003245 coal Substances 0.000 claims description 3
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 claims description 2
- 235000019270 ammonium chloride Nutrition 0.000 claims description 2
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 2
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 2
- 238000000498 ball milling Methods 0.000 claims description 2
- 239000011230 binding agent Substances 0.000 claims description 2
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 2
- 235000011147 magnesium chloride Nutrition 0.000 claims description 2
- 239000001103 potassium chloride Substances 0.000 claims description 2
- 235000011164 potassium chloride Nutrition 0.000 claims description 2
- 235000010333 potassium nitrate Nutrition 0.000 claims description 2
- 239000004323 potassium nitrate Substances 0.000 claims description 2
- 235000010344 sodium nitrate Nutrition 0.000 claims description 2
- 239000004317 sodium nitrate Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 238000003801 milling Methods 0.000 claims 1
- 238000000643 oven drying Methods 0.000 claims 1
- 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 abstract description 6
- 239000003575 carbonaceous material Substances 0.000 abstract description 6
- 239000011734 sodium Substances 0.000 abstract description 6
- 229910052708 sodium Inorganic materials 0.000 abstract description 6
- 238000003860 storage Methods 0.000 abstract description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 11
- 239000011295 pitch Substances 0.000 description 10
- 239000002243 precursor Substances 0.000 description 9
- 229910052799 carbon Inorganic materials 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 230000003647 oxidation Effects 0.000 description 8
- 238000007254 oxidation reaction Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 5
- 238000004132 cross linking Methods 0.000 description 5
- AYLGSTDCFRCVPA-UHFFFAOYSA-O [N+](=O)([O-])[O-].[NH4+].[N+](=O)([O-])[O-].[Mg+] Chemical compound [N+](=O)([O-])[O-].[NH4+].[N+](=O)([O-])[O-].[Mg+] AYLGSTDCFRCVPA-UHFFFAOYSA-O 0.000 description 4
- 230000002378 acidificating effect Effects 0.000 description 4
- 125000000524 functional group Chemical group 0.000 description 4
- 238000000197 pyrolysis Methods 0.000 description 4
- 230000008707 rearrangement Effects 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 3
- 238000006297 dehydration reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 230000037361 pathway Effects 0.000 description 3
- 239000002253 acid Substances 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 238000005899 aromatization reaction Methods 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 238000006356 dehydrogenation reaction Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000005187 foaming Methods 0.000 description 2
- 238000005087 graphitization Methods 0.000 description 2
- TWNIBLMWSKIRAT-VFUOTHLCSA-N levoglucosan Chemical compound O[C@@H]1[C@@H](O)[C@H](O)[C@H]2CO[C@@H]1O2 TWNIBLMWSKIRAT-VFUOTHLCSA-N 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- 239000013081 microcrystal Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- WQZGKKKJIJFFOK-ZZWDRFIYSA-N L-glucose Chemical compound OC[C@@H]1OC(O)[C@@H](O)[C@H](O)[C@H]1O WQZGKKKJIJFFOK-ZZWDRFIYSA-N 0.000 description 1
- XDAKIXYKMWJOGI-UHFFFAOYSA-N [Cl-].[Mg+].[N+](=O)([O-])[O-].[NH4+] Chemical compound [Cl-].[Mg+].[N+](=O)([O-])[O-].[NH4+] XDAKIXYKMWJOGI-UHFFFAOYSA-N 0.000 description 1
- GZCGUPFRVQAUEE-VANKVMQKSA-N aldehydo-L-glucose Chemical compound OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)C=O GZCGUPFRVQAUEE-VANKVMQKSA-N 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000007833 carbon precursor Substances 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000011294 coal tar pitch Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- YNKVVRHAQCDJQM-UHFFFAOYSA-P diazanium dinitrate Chemical compound [NH4+].[NH4+].[O-][N+]([O-])=O.[O-][N+]([O-])=O YNKVVRHAQCDJQM-UHFFFAOYSA-P 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000006462 rearrangement reaction Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 230000003335 steric effect Effects 0.000 description 1
- 239000011269 tar Substances 0.000 description 1
- 238000005406 washing 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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention relates to the technical field of sodium ion batteries, and discloses asphalt/starch derived hard carbon, a preparation method thereof and a negative electrode material containing the asphalt/starch derived hard carbon, wherein the preparation method comprises the following steps: s1, blending asphalt, starch, ammonium salt and a catalyst to obtain a pretreatment substance; s2, placing the pretreated matter in atmosphere, and heating to react to obtain an intermediate; and S3, introducing protective gas into the intermediate, and carbonizing to obtain the asphalt/starch derived hard carbon. The hard carbon material prepared by the method provides more sodium storage sites and more sodium storage capacity.
Description
Technical Field
The invention relates to the technical field of sodium ion batteries, in particular to asphalt/starch derived hard carbon, a preparation method thereof and a negative electrode material containing the asphalt/starch derived hard carbon.
Background
In recent years, sodium ion batteries have wide application prospects in the field of new energy sources due to the advantages of abundant sources, low cost, high safety performance and the like. In the technical field of battery materials, hard carbon materials are difficult to graphitize at high temperature, and have stronger sodium storage capacity, and lower working potential is more the most potential negative electrode material of the sodium ion battery.
One of the precursors of the hard carbon material of the sodium ion battery is asphalt. For the pitch-based precursor, the generation of viscous carbonaceous residues caused by excessive hydrogen content in the precursor is solved, the crosslinking degree of the precursor or intermediate product is enhanced to destroy the order of a carbon layer, the method is an original solution means for solving the problem that the pitch-based precursor is easy to graphitize at high temperature, and the conventional process is to introduce air with a certain flow rate to perform pre-oxidation or crosslinking treatment at low temperature.
Similarly, starch has been extensively studied for its abundant yield and unique original spherical structure, but due to the problem of poor thermal stability, a large amount of volatile materials mainly containing l-glucose are generated at the early stage of carbonization to have lower carbon yield, and the subsequent aromatization and carbon rearrangement phenomena are unfavorable due to structure melting and foaming, and the precursor crosslinking or air stabilization treatment is generally adopted to improve the carbon yield.
Patent publication No. CN 109148883A discloses a sodium ion battery anode material based on asphalt, a preparation method and application thereof, and an asphalt-based precursor prepared by the material is oxidized in an oxidizing gas atmosphere, so that insufficient oxidation can be caused by material stacking, and the inorganic hard carbon structure is uneven, and the performance and the structure are relatively poor. And the modified asphalt derived hard carbon is difficult to reach the rich pore structure of biomass-based or resin-based hard carbon, and the lower sodium storage capacity is difficult to reach the brand-new angle in the future industry.
Disclosure of Invention
The invention solves the technical problems that:
the method is used for solving the problem of poor performance caused by uneven structure of the asphalt-based hard carbon obtained in the prior art.
The invention adopts the technical scheme that:
the present invention aims to provide asphalt/starch derived hard carbon, a preparation method thereof, and a negative electrode material containing the same.
The specific contents are as follows:
first, the invention provides a preparation method of asphalt/starch derived hard carbon, which comprises the following steps:
s1, blending asphalt, starch, ammonium salt and a catalyst to obtain a pretreatment substance;
s2, placing the pretreated matter in atmosphere, and heating to react to obtain an intermediate;
and S3, introducing protective gas into the intermediate, and carbonizing to obtain the asphalt/starch derived hard carbon.
Second, the present invention provides a pitch/starch derived hard carbon obtained by the aforementioned preparation method.
Third, the invention provides a negative electrode material of a sodium ion battery, which comprises asphalt/starch derived hard carbon, a conductive agent and an adhesive.
The invention has the beneficial effects that:
(1) Through carrying out the blending treatment with pitch and starch for pitch adsorbs on starch surface, and then makes starch have monodispersity, can make starch can evenly be heated before the pyrolysis, prevents that whole process from having piled up because of the powder has caused heat and has made starch granule take place to fuse before stable abundant (that is the structure melts and foaming merges).
(2) The pretreatment is subjected to a heating reaction (namely a pre-oxidation process), so that the asphalt is subjected to a sufficient dehydrogenation reaction, and more oxygen-containing functional groups can be introduced; simultaneously, the starch structure is fully stabilized through the pre-oxidation process.
(3) Through the preoxidation process, acidic substances provided in raw materials are utilized, meanwhile, dehydration reaction among starch molecules is promoted, neutral acidic conditions provided by acidic atmosphere are favorable for crosslinking carboxylic acid, amide and other functional groups of coal tar pitch with starch branched hydroxyl groups, so that the two functional groups are further macromolecular, a starch molecular chain crosslinked with the pitch supports an aromatic ring structure of the pitch in the carbonization process, the decomposition energy barrier of the pitch is raised, carbon rearrangement of the pitch in the carbonization process is hindered by means of steric effect of the aromatic ring, excessive graphitization generated by the pitch is reduced or prevented, more sodium storage sites can be provided by hard carbon, and more sodium storage capacity is provided.
(4) By introducing the catalyst into the pretreatment, compared with the technology of oxidizing asphalt in an oxidizing gas atmosphere, the precursor introduces more oxygen-containing functional groups, has better dehydrogenation effect, and has more uniform integral pre-oxidation degree, so that the precursor has better electrochemical stability. The solid product remaining after pyrolysis of the catalyst can effectively disperse the carbonaceous particles, thereby allowing the reactants to be heated uniformly during the carbon rearrangement process.
Drawings
FIG. 1 is an SEM image of an intermediate of example 1;
fig. 2 is a charge-discharge diagram of a battery obtained with the hard carbon material of example 1.
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.
Technical proposal
The invention provides a preparation method of asphalt/starch derived hard carbon, which comprises the following steps:
s1, blending asphalt, starch, ammonium salt and a catalyst to obtain a pretreatment substance;
s2, placing the pretreated matter in atmosphere, and heating to react to obtain an intermediate;
and S3, introducing protective gas into the intermediate, and carbonizing to obtain the asphalt/starch derived hard carbon.
During carbonization of starch, there are two competing reaction pathways:
the first way mainly comprises the steps of breaking glycosidic bonds among all constituent units in starch to generate the levoglucosan, and further generating macromolecular oxygen-containing compounds such as the levoglucosan, namely tar substances;
in the second way, the basic constituent unit in the starch is subjected to chemical dehydration reaction before the glycosidic bond is broken, so that the hydroxyl group at the C6 position is removed in the form of water molecules, the glycosidic bond is broken, a high molecular carbon intermediate is generated, and the rearrangement reaction of the carbon residue structure is further generated to generate the carbon structure.
Therefore, to promote the formation of carbonaceous structures during carbonization of starch, it is necessary to make the pathway into the main reaction pathway in the carbonization reaction in a certain way.
Through S1 and S2, the starch structure is fully stabilized, namely the dehydration reaction of starch molecules is promoted, microcrystals formed by hydrogen bonds between/in starch molecule chains are damaged in advance, when glycosidic bonds are broken, microcrystals formed by hydrogen bonds between/in starch chains are not fused, reactions mainly comprising volatilized L-glucose are hindered, and the pyrolysis reaction path of starch is inclined to the path II.
In some embodiments of the present invention, in some embodiments,
the asphalt is medium/high temperature coal-based asphalt, and the softening point is 120-280 ℃;
the mesh number of the asphalt is more than or equal to 800 meshes;
the starch is oven dry starch, and the kind of starch is not limited herein.
The ammonium salt comprises at least one of ammonium sulfate, ammonium nitrate and ammonium chloride; the ammonium salt is added for continuously pyrolyzing at 100-500 ℃ to generate acid gas, and the ammonium salt can provide acid for reactants during the pre-oxidation period, so that the system is convenient to dehydrate, and the crosslinking activity of starch and asphalt is improved, and the ammonium salt is mainly used for providing a pH slightly acidic condition.
The catalyst comprises at least one of magnesium chloride, potassium chloride, sodium nitrate, potassium nitrate and magnesium nitrate, and the purpose of the catalyst is to decompose to generate oxygen under the heat treatment, so that the hard carbon precursor is conveniently subjected to the pre-oxidation treatment from all parts of the reaction materials.
Through the treatment of S1, the monodispersity of the starch is maintained by utilizing the adsorption of asphalt on the surface of the starch, so that the subsequent fusion of a starch structure caused by uneven heating caused by stacking is prevented.
In some embodiments, the mass ratio of asphalt, starch, ammonium salt and catalyst is 1:0.2-1:0.01-0.03:0.05-0.2.
In some embodiments, in S1, the blending is ball milling, ultrasonic or grinding.
In some embodiments, S2 comprises: the atmosphere is oxygen; the temperature rising rate is 0.5-3 ℃/min; heating to 250-350 ℃; the heat preservation time is 1-3 h; the flow rate of the atmosphere was 80ml/min.
By heating at a lower heating rate, the hydroxyl on the starch branched chain can be effectively consumed by introducing oxygen before the glycosidic bond of the starch is broken, and the glycosidic bond is prevented from generating a large amount of volatile matters in the levorotation mode during the pyrolysis of the starch; asphalt is oxidized at a certain temperature, so that after aromatic rings are subjected to thermal condensation at a low temperature, aliphatic side chains are obviously reduced, the aromatization degree is increased, and excessive graphitization caused by carbon rearrangement can be blocked to a certain extent due to the steric hindrance effect.
In some embodiments, S3 comprises: the protective gas is nitrogen; the temperature rising rate is 3-5 ℃/min; the carbonization temperature is 1100-1500 ℃; the heat preservation time is 2-5 h.
In some embodiments, in S3, after carbonization, the mixture is post-treated; the post-treatment comprises grinding, sieving and cleaning.
Specifically, the cleaning operation is that the particles obtained by sieving are blended with hydrochloric acid, and the hard carbon particles are obtained by drying after repeated cleaning by water; mol (hydrochloric acid) =2.2 to 3:1; the hydrochloric acid was 50 vol% hydrochloric acid.
The invention provides a sodium ion battery cathode material, asphalt/starch derived hard carbon, a conductive agent and an adhesive; the hard carbon material, the conductive agent (SP) and the binder (CMC, SBR) are uniformly mixed with a certain amount of deionized water according to the mass ratio of x to y to n (x is more than or equal to 80 and less than or equal to 95; y is more than or equal to 2 and less than or equal to 10; m is more than or equal to 1 and less than or equal to 3.5; n is more than or equal to 2 and less than or equal to 6.5) and then coated on a current collector, so as to prepare the sodium ion battery negative electrode plate.
Examples 1 to 5
The preparation method of the hard carbon material specifically comprises the following steps:
crushing medium/high temperature coal-based asphalt (with a softening point of 120-280 ℃), sieving (more than or equal to 800 meshes), and mixing the sieved asphalt with absolute dry starch, ammonium salt and a catalyst in a ball mill to obtain a mixture.
Placing the mixture in a carbonization reaction cavity, introducing oxygen (atmosphere), heating to 300 ℃ at a heating rate of 2 ℃/min, and preserving heat for 2 hours, wherein the flow rate of the introduced oxygen is 80 ml/min; after the heat preservation is finished, introducing nitrogen (protective gas) is changed, then heating to 1400 ℃ at a heating rate of 3-5 ℃/min, and preserving the heat for 5 hours.
The treated material was ground and sieved (mesh number 400) to obtain treated material particles, and the treated material particles were mixed with 50 vol% hydrochloric acid and stirred, mol HCl: mol catalyst=2.5:1. And repeatedly washing the obtained product with deionized water to neutrality, and drying to obtain hard carbon particles.
Table 1 proportions of examples 1 to 5
| Examples | Ammonium salts | Catalyst | Starch: asphalt: ammonium salt: mass ratio of catalyst |
| Example 1 | Ammonium nitrate | Magnesium nitrate | 1:0.5:0.02:0.1 |
| Example 2 | Ammonium nitrate | Magnesium nitrate | 1:0.2:0.02:0.1 |
| Example 3 | Ammonium nitrate | Magnesium nitrate | 1:0.5:0.01:0.1 |
| Example 4 | Ammonium nitrate | Magnesium nitrate | 1:0.5:0.02:0.05 |
| Example 5 | Ammonium nitrate | Magnesium chloride | 1:0.5:0.02:0.1 |
Comparative examples 1 to 3
Comparative example 1: the catalyst in example 1 was replaced with oxide-magnesia.
Comparative example 2: the ammonium salt-ammonium nitrate in example 1 was replaced with oxide-magnesium oxide.
Comparative example 3: the atmosphere in example 1 was changed to nitrogen.
The electrochemical performance of the assembled batteries of examples 1 to 5 and comparative examples 1 and 2 was measured under the conditions of a current density of 25 mA/g and a voltage range of 0 to 3V, and the test results are shown in Table 2.
TABLE 2 electrochemical Performance test results
In example 1, SEM photograph of an intermediate obtained by the pre-oxidation treatment is shown in FIG. 1.
The charge-discharge diagram of example 1 is shown in fig. 2.
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 asphalt/starch derived hard carbon is characterized by comprising the following steps of:
s1, blending asphalt, starch, ammonium salt and a catalyst to obtain a pretreatment substance; the ammonium salt comprises at least one of ammonium sulfate, ammonium nitrate and ammonium chloride; the catalyst comprises at least one of magnesium chloride, potassium chloride, sodium nitrate, potassium nitrate and magnesium nitrate;
s2, placing the pretreated matter in atmosphere, and heating to react to obtain an intermediate; the atmosphere is oxygen;
and S3, introducing protective gas into the intermediate, and carbonizing to obtain the asphalt/starch derived hard carbon.
2. The method for preparing asphalt/starch derived hard carbon according to claim 1, wherein in S1, the blending mode is ball milling, ultrasonic milling or grinding.
3. The method of preparing pitch/starch derived hard carbon according to claim 1 wherein S2 comprises at least one of features (1) to (4):
(1) The temperature rising rate is 0.5-3 ℃/min;
(2) Heating to 250-350 ℃;
(3) The heat preservation time is 1-3 h;
(4) The flow rate of the atmosphere was 80ml/min.
4. The method for preparing pitch/starch derived hard carbon according to claim 1 wherein S3 comprises at least one of features (1) to (4):
(1) The protective gas is nitrogen;
(2) The temperature rising rate is 3-5 ℃/min;
(3) The carbonization temperature is 1100-1500 ℃;
(4) The heat preservation time is 2-5 h.
5. The method for preparing asphalt/starch derived hard carbon according to claim 1, wherein in S3, after carbonization, the mixture is subjected to post-treatment; the post-treatment comprises grinding, sieving and cleaning.
6. The method for preparing asphalt/starch derived hard carbon according to claim 5, wherein the cleaning is carried out by blending the sieved particles with hydrochloric acid, cleaning with water, and oven drying to obtain hard carbon particles; mol (hydrochloric acid): mol (catalyst) =2.2 to 3:1.
7. A process for the preparation of a pitch/starch derived hard carbon according to any one of claims 1 to 6 wherein, in S1,
the mass ratio of asphalt, starch, ammonium salt and catalyst is 1:0.2-1:0.01-0.03:0.05-0.2.
8. The method for producing a pitch/starch derived hard carbon according to any one of claims 1 to 6 wherein S1 comprises at least one of features (1) to (3):
(1) The asphalt is medium/high temperature coal-based asphalt, and the softening point is 120-280 ℃;
(2) The mesh number of the asphalt is more than or equal to 800 meshes;
(3) The starch is oven-dried starch.
9. A pitch/starch derived hard carbon obtainable by the process of any one of claims 1 to 8.
10. A negative electrode material for sodium ion batteries, comprising the asphalt/starch derived hard carbon according to claim 9, a conductive agent and a binder.
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