CN111564630B - A kind of hard carbon material and preparation method thereof - Google Patents
A kind of hard carbon material and preparation method thereof Download PDFInfo
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- 229910021385 hard carbon Inorganic materials 0.000 title claims abstract description 60
- 239000003575 carbonaceous material Substances 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000007833 carbon precursor Substances 0.000 claims abstract description 33
- 238000005406 washing Methods 0.000 claims abstract description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 21
- 239000002245 particle Substances 0.000 claims abstract description 18
- 229910001415 sodium ion Inorganic materials 0.000 claims abstract description 17
- 238000010438 heat treatment Methods 0.000 claims abstract description 15
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 14
- 230000001681 protective effect Effects 0.000 claims abstract description 12
- 238000004108 freeze drying Methods 0.000 claims abstract description 11
- 239000007773 negative electrode material Substances 0.000 claims abstract description 10
- 238000009656 pre-carbonization Methods 0.000 claims abstract description 10
- 239000012298 atmosphere Substances 0.000 claims abstract description 8
- 238000000197 pyrolysis Methods 0.000 claims abstract description 8
- 239000002253 acid Substances 0.000 claims abstract description 7
- 230000007935 neutral effect Effects 0.000 claims abstract description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 15
- 239000000243 solution Substances 0.000 claims description 13
- 238000003860 storage Methods 0.000 claims description 13
- 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 11
- 229910052708 sodium Inorganic materials 0.000 claims description 11
- 239000011734 sodium Substances 0.000 claims description 11
- 229910002804 graphite Inorganic materials 0.000 claims description 10
- 239000010439 graphite Substances 0.000 claims description 10
- 240000002319 Citrus sinensis Species 0.000 claims description 9
- 235000005976 Citrus sinensis Nutrition 0.000 claims description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 239000011149 active material Substances 0.000 claims description 6
- 239000011229 interlayer Substances 0.000 claims description 5
- 239000001100 (2S)-5,7-dihydroxy-2-(3-hydroxy-4-methoxyphenyl)chroman-4-one Substances 0.000 claims description 4
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 4
- QUQPHWDTPGMPEX-UHFFFAOYSA-N Hesperidine Natural products C1=C(O)C(OC)=CC=C1C1OC2=CC(OC3C(C(O)C(O)C(COC4C(C(O)C(O)C(C)O4)O)O3)O)=CC(O)=C2C(=O)C1 QUQPHWDTPGMPEX-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 239000010405 anode material Substances 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 4
- QUQPHWDTPGMPEX-UTWYECKDSA-N aurantiamarin Natural products COc1ccc(cc1O)[C@H]1CC(=O)c2c(O)cc(O[C@@H]3O[C@H](CO[C@@H]4O[C@@H](C)[C@H](O)[C@@H](O)[C@H]4O)[C@@H](O)[C@H](O)[C@H]3O)cc2O1 QUQPHWDTPGMPEX-UTWYECKDSA-N 0.000 claims description 4
- APSNPMVGBGZYAJ-GLOOOPAXSA-N clematine Natural products COc1cc(ccc1O)[C@@H]2CC(=O)c3c(O)cc(O[C@@H]4O[C@H](CO[C@H]5O[C@@H](C)[C@H](O)[C@@H](O)[C@H]5O)[C@@H](O)[C@H](O)[C@H]4O)cc3O2 APSNPMVGBGZYAJ-GLOOOPAXSA-N 0.000 claims description 4
- 238000007710 freezing Methods 0.000 claims description 4
- 230000008014 freezing Effects 0.000 claims description 4
- 229940025878 hesperidin Drugs 0.000 claims description 4
- VUYDGVRIQRPHFX-UHFFFAOYSA-N hesperidin Natural products COc1cc(ccc1O)C2CC(=O)c3c(O)cc(OC4OC(COC5OC(O)C(O)C(O)C5O)C(O)C(O)C4O)cc3O2 VUYDGVRIQRPHFX-UHFFFAOYSA-N 0.000 claims description 4
- QUQPHWDTPGMPEX-QJBIFVCTSA-N hesperidin Chemical compound C1=C(O)C(OC)=CC=C1[C@H]1OC2=CC(O[C@H]3[C@@H]([C@@H](O)[C@H](O)[C@@H](CO[C@H]4[C@@H]([C@H](O)[C@@H](O)[C@H](C)O4)O)O3)O)=CC(O)=C2C(=O)C1 QUQPHWDTPGMPEX-QJBIFVCTSA-N 0.000 claims description 4
- ARGKVCXINMKCAZ-UHFFFAOYSA-N neohesperidine Natural products C1=C(O)C(OC)=CC=C1C1OC2=CC(OC3C(C(O)C(O)C(CO)O3)OC3C(C(O)C(O)C(C)O3)O)=CC(O)=C2C(=O)C1 ARGKVCXINMKCAZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 4
- 229910003481 amorphous carbon Inorganic materials 0.000 claims description 3
- 239000011230 binding agent Substances 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 239000006258 conductive agent Substances 0.000 claims description 2
- 239000000835 fiber Substances 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 230000008520 organization Effects 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 241000207199 Citrus Species 0.000 claims 1
- 235000020971 citrus fruits Nutrition 0.000 claims 1
- 235000013399 edible fruits Nutrition 0.000 claims 1
- 238000001816 cooling Methods 0.000 abstract description 11
- 238000005520 cutting process Methods 0.000 abstract description 7
- 238000001914 filtration Methods 0.000 abstract description 6
- 238000005360 mashing Methods 0.000 abstract description 6
- 239000002699 waste material Substances 0.000 abstract 1
- 239000000047 product Substances 0.000 description 12
- 238000001035 drying Methods 0.000 description 11
- 239000000463 material Substances 0.000 description 11
- 239000011248 coating agent Substances 0.000 description 10
- 238000000576 coating method Methods 0.000 description 10
- 238000010000 carbonizing Methods 0.000 description 7
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 6
- 229910001416 lithium ion Inorganic materials 0.000 description 6
- 239000002028 Biomass Substances 0.000 description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 5
- 238000004140 cleaning Methods 0.000 description 5
- 229910052744 lithium Inorganic materials 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 238000010335 hydrothermal treatment Methods 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 239000012299 nitrogen atmosphere Substances 0.000 description 4
- 238000000498 ball milling Methods 0.000 description 3
- 239000000084 colloidal system Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 238000012983 electrochemical energy storage Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000003763 carbonization Methods 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 238000009830 intercalation Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000001814 pectin Substances 0.000 description 2
- 235000010987 pectin Nutrition 0.000 description 2
- 229920001277 pectin Polymers 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000000341 volatile oil Substances 0.000 description 2
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 description 1
- 235000017166 Bambusa arundinacea Nutrition 0.000 description 1
- 235000017491 Bambusa tulda Nutrition 0.000 description 1
- 241001330002 Bambuseae Species 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- ZZZCUOFIHGPKAK-UHFFFAOYSA-N D-erythro-ascorbic acid Natural products OCC1OC(=O)C(O)=C1O ZZZCUOFIHGPKAK-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 235000015334 Phyllostachys viridis Nutrition 0.000 description 1
- 229930003268 Vitamin C Natural products 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000011425 bamboo Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 239000002872 contrast media Substances 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000000661 sodium alginate Substances 0.000 description 1
- 235000010413 sodium alginate Nutrition 0.000 description 1
- 229940005550 sodium alginate Drugs 0.000 description 1
- 229910001488 sodium perchlorate Inorganic materials 0.000 description 1
- 235000019154 vitamin C Nutrition 0.000 description 1
- 239000011718 vitamin C Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
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- 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
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/20—Graphite
- C01B32/205—Preparation
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- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/20—Graphite
- C01B32/21—After-treatment
- C01B32/215—Purification; Recovery or purification of graphite formed in iron making, e.g. kish graphite
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
- C07H1/00—Processes for the preparation of sugar derivatives
- C07H1/06—Separation; Purification
- C07H1/08—Separation; Purification from natural products
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- C07—ORGANIC CHEMISTRY
- C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
- C07H17/00—Compounds containing heterocyclic radicals directly attached to hetero atoms of saccharide radicals
- C07H17/04—Heterocyclic radicals containing only oxygen as ring hetero atoms
- C07H17/06—Benzopyran radicals
- C07H17/065—Benzo[b]pyrans
- C07H17/07—Benzo[b]pyran-4-ones
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- H01M10/00—Secondary cells; Manufacture thereof
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- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
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- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
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Abstract
本发明涉及一种硬碳材料及其制备方法，所述硬碳材料通过以下步骤制备得到：将橙皮水洗、切碎，置于水热反应釜中反应一定时间，然后冷却、捣碎、过滤、清洗、冷冻干燥得到碳前体；加热得到的碳前体，进行预炭化处理；将预炭化后的碳前体在保护性气氛下进行高温热解处理；将所得产物用酸溶液洗涤，再用清水冲洗至中性，然后干燥，得到所述硬碳材料。本发明实现了废物利用，而且操作工艺简单易行，所得硬碳材料大小均匀，粒度在0.5～5μm，作为钠离子电池的负极材料具有较高的比容量密度(>290mAh/g)，循环性能良好。采用本发明方法获得的硬碳材料是一种优异的钠离子电池负极材料。
The invention relates to a hard carbon material and a preparation method thereof. The hard carbon material is prepared by the following steps: washing orange peels, cutting them into pieces, placing them in a hydrothermal reaction kettle to react for a certain period of time, then cooling, mashing and filtering , washing, freeze-drying to obtain a carbon precursor; heating the obtained carbon precursor, carrying out pre-carbonization treatment; subjecting the pre-carbonized carbon precursor to high-temperature pyrolysis treatment under a protective atmosphere; washing the obtained product with an acid solution, and then Rinse with clean water until neutral, and then dry to obtain the hard carbon material. The invention realizes the utilization of waste, and the operation process is simple and feasible, the obtained hard carbon material has a uniform size, and the particle size is 0.5-5 μm. good. The hard carbon material obtained by the method of the present invention is an excellent negative electrode material for sodium ion batteries.
Description
Technical Field
The invention relates to the field of novel secondary battery electrode materials, in particular to a hard carbon material and a preparation method thereof.
Background
Lithium ion batteries are the most common electrochemical energy storage device in the current society, and with the development of large-scale energy storage technologies for portable electronic equipment, electric automobiles and new energy power generation, the demand increases day by day and the demand of lithium also increases. Because the reserve of lithium is limited and the distribution is uneven, the price of the lithium-related material is greatly increased, and the cost of the lithium ion battery is improved. The limited lithium resources also make sustainable use of lithium ion batteries challenging. To solve this problem, the development of inexpensive non-lithium-based electrochemical energy storage devices with excellent performance has become a new research focus in recent years. Among them, similar to the working principle of lithium ion batteries, sodium ion batteries that are not limited by resources are receiving much attention.
Graphite is the most mature and widely applied negative electrode material of the lithium ion battery, but sodium ions are difficult to be embedded into a graphite layer because the ion radius of the sodium ions is larger than that of the lithium ions, and the graphite cannot be used as the negative electrode material of the sodium ion battery. The hard carbon is microscopically in an irregular amorphous structure and is formed by stacking single-layer graphene sheets with small sizes in a disordered mode, so that a structure similar to a card house is constructed, more storage active points can be provided for ions, the diffusion of the ions in the structure is facilitated, the storage and the de-intercalation of sodium ions are facilitated, and the high stability can be kept in the sodium ion de-intercalation process, so that the hard carbon is a preferred cathode material of a sodium ion battery at present.
The preparation of hard carbon cathode materials by using biomass materials is a research hotspot in the field of electrochemical energy storage. The preparation of hard carbon and other carbonaceous materials from biomass is usually carried out by cleaning, drying and crushing the raw materials, and then pyrolyzing at high temperature. Because plant fibers or biological macromolecules have strong toughness and are difficult to break after drying, the size of the pyrolyzed hard carbon particles is large and uneven, the subsequent processes such as electrode coating and the like are not facilitated, and a thin coating or a coating with uniform thickness is difficult to obtain.
Disclosure of Invention
The invention aims to overcome the defects that the existing hard carbon negative electrode material is uneven in size and difficult to perform electrode coating, and provides a hard carbon material prepared from orange peels as a raw material, wherein black powder with uniform size is obtained by means of a unique net-shaped internal organization structure of the orange peels and a specific process, the particle size is 0.5-5 mu m, and the hard carbon material is very favorable for electrode coating.
In the traditional technology, the preparation of the biomass hard carbon material can also adopt a mode of firstly carbonizing and then ball milling to reduce the size of hard carbon particles, so that the effect of uniform size is obtained. However, the ball milling process is not only time consuming and energy consuming, but also introduces additional impurities, requiring additional electromagnetic or acid washing impurity removal steps. In addition, the hard carbon powder obtained by ball milling needs to be sieved to remove the excessively fine carbon powder particles, so that the bulk density of the hard carbon is improved, and therefore, the advantage of directly obtaining a refined material is not provided.
The orange peel contains a large amount of colloid, vitamin C and essential oil, and microscopically presents network tissues. Unlike biomass of high cellulose content such as wood and bamboo, orange peel is easily degraded by a suitable hydrothermal treatment, so that an organic carbonaceous feedstock with uniform particles can be obtained.
The orange peel also contains pectin such as pectin and essential oil, and plays a role of a binder in the natural drying process of the orange peel, so that the dried orange peel is hard and is not easy to mechanically break. The impurities are easy to decompose and volatilize in the high-temperature carbonization process, block the air outlet of heat treatment equipment, are adsorbed on the surface of the carbon material and generate chemical vapor deposition of carbon, and influence the hard carbon to obtain an ideal interlayer spacing and microstructure.
In order to overcome the above difficulties, the present invention is carried out by: 1) the method comprises the following steps of carrying out hydrothermal treatment on the orange peels, wherein the orange peels contain substances such as hesperidin, the substances are directly heated to volatilize strong smell, the texture structure of the orange peels is protected, in addition, the decomposition and volatilization of colloid in the orange peels can cause the blockage of an air outlet of heat treatment equipment, and the influence on the microstructure structure of a hard carbon material is not good, so that the method firstly carries out hydrothermal treatment on the orange peels, decomposes and removes the colloid from the orange peels by utilizing the hydrothermal treatment, firstly obtains raw materials with uniform size, and solves the problems that the dried biomass is not easy to crush, the hard carbon material has large particles and uneven size; meanwhile, useful substances such as hesperidin in the orange peels are collected into a liquid phase for other purposes through hydrothermal degradation; the hydrothermal residue filter cake is freeze-dried, the fluffy state of the raw materials is kept, and the key is that the powdery raw materials are obtained by later heating. 2) According to the invention, the freeze-dried fluffy carbon precursor is pre-carbonized and then pyrolyzed at high temperature, so that the carbon particles are prevented from being seriously agglomerated in the pyrolysis process, and the particle size uniformity of the material is kept. As the organic matters which are easy to cause adhesion are removed in the pre-carbonization process, the material is ensured to keep uniformly dispersed during high-temperature pyrolysis. 3) The method comprises the steps of carrying out high-temperature pyrolysis on the material, heating the material to 1000-1500 ℃ under the protection of flowing nitrogen or argon to carry out carbonization, and when the temperature is lower than 1000 ℃, carbonizing a carbon precursor insufficiently and mainly taking an amorphous state; above 1600 ℃ the short-range ordered graphite interlayer spacing of the hard carbon is reduced, which is not beneficial to sodium ion storage. 4) Finally, the material is washed by acid solution to remove impurities, so that the material can exert electrochemical activity and is safe to use.
The specific scheme is as follows:
a method of preparing a hard carbon material, comprising the steps of:
step 1): washing and cutting orange peels with water, placing the orange peels into a hydrothermal reaction kettle, adding a proper amount of water, carrying out hydrothermal reaction for a certain time under a sealing condition to recover hesperidin in the orange peels, then cooling, mashing, filtering, washing, freeze-drying, and carrying out freeze-drying to obtain fluffy carbon precursor;
step 2): heating the carbon precursor obtained in the step 1), and carrying out pre-carbonization treatment at the temperature of 200-;
step 3): carrying out high-temperature pyrolysis treatment on the pre-carbonized carbon precursor in a protective atmosphere;
step 4): washing the product obtained in the step 3) with an acid solution, washing the product with clear water to be neutral, and drying the product to obtain the hard carbon material.
Further, the orange peel in the step 1) is one or more of navel orange, ice orange, sweet orange and orange, and is preferably fresh orange peel.
Further, the hydrothermal reaction in the step 1) is carried out at the temperature of 150-180 ℃, and the reaction time is 4-8 hours.
Further, the step 1) of freeze drying is carried out in a freeze dryer, the freezing temperature is below minus 55 ℃, the freezing time is 24-36 hours, and the shape of the mesh tissue in the orange peel is kept through freeze drying, so that the fluffy carbon precursor is obtained.
Further, the pre-carbonization in the step 2) is carried out in a muffle furnace under an air atmosphere, the pre-carbonization temperature is 210-290 ℃, and the pre-carbonization time is 2-12 hours.
Further, the high-temperature pyrolysis temperature in the step 3) is 1000-1500 ℃, the heat preservation time is 1-5 hours, and the heating rate is 3-5 ℃/min;
optionally, the protective atmosphere is high purity nitrogen or argon or a mixture of both.
Further, the acid solution in the step 4) may be any one of aqueous solutions of hydrochloric acid, nitric acid, sulfuric acid and hydrofluoric acid, and the concentration is 0.1-1 mol/L.
The invention also protects the hard carbon material prepared by the preparation method of the hard carbon material, wherein the hard carbon material is black powder with uniform particle size, the particle size range is 0.5-5 mu m, the graphitized amorphous carbon content is lower than 5wt%, the short-range ordered graphite content is higher than 95wt%, and the short-range ordered graphite interlayer spacing is 0.3-0.5nm, preferably 0.3-0.4 nm.
The invention also discloses a sodium ion battery negative electrode material which comprises an active material, a conductive agent and a binder, wherein the active material is the hard carbon material, and the sodium ion battery negative electrode material can be directly coated on a current collecting sheet to form an electrode.
Further, the specific sodium storage capacity of the negative electrode material of the sodium ion battery at 0.05A/g is not lower than 290mAh/g, the maximum specific sodium storage capacity at 2A/g reaches 90mAh/g, and the specific sodium storage capacity after the negative electrode material is circulated for 500 times at a multiplying power of 0.5A/g is still kept above 200 mAh/g.
Has the advantages that:
the hard carbon material prepared by the method has uniform granularity and excellent sodium storage performance, the specific capacity of sodium storage at 0.05A/g is not less than 290mAh/g, the specific capacity of sodium storage at 2A/g reaches 90mAh/g, the specific capacity of sodium storage after circulation for 500 times at 0.5A/g multiplying power is still kept above 200mAh/g, and the hard carbon material has better market development prospect.
Drawings
In order to illustrate the technical solution of the present invention more clearly, the drawings will be briefly described below, and it is apparent that the drawings in the following description relate only to some embodiments of the present invention and are not intended to limit the present invention.
Fig. 1 is a scanning electron microscope image of a hard carbon material provided in an embodiment 1 of the present invention;
fig. 2 is a rate performance graph of a hard carbon anode material provided in one embodiment 5 of the present invention;
fig. 3 is a graph of cycle performance of a hard carbon anode material provided in one embodiment 5 of the present invention;
FIG. 4 is a scanning electron micrograph of comparative example 1 according to the present invention.
Detailed Description
Preferred embodiments of the present invention will be described in more detail below. While the following describes preferred embodiments of the present invention, it should be understood that the present invention may be embodied in various forms and should not be limited by the embodiments set forth herein. The examples do not specify particular techniques or conditions, and are performed according to the techniques or conditions described in the literature in the art or according to the product specifications. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products commercially available. In the following examples, "%" means weight percent, unless otherwise specified.
Example 1
Washing fresh navel orange peel with water, cutting, placing in a hydrothermal reaction kettle, adding appropriate amount of water (to submerge the orange peel), performing hydrothermal reaction at 180 deg.C for 4 hr under sealed condition, cooling, mashing, filtering, cleaning, and lyophilizing at-55 deg.C for 36 hr to obtain carbon precursor; putting the obtained carbon precursor into an alumina crucible, and pre-carbonizing the carbon precursor for 12 hours at 210 ℃ in a muffle furnace; heating the pre-carbonized carbon precursor to 1300 ℃ at the speed of 3 ℃/min under the protective high-purity nitrogen atmosphere, preserving the heat for 3h, and cooling along with the furnace; washing the obtained product with 0.1mol/L diluted hydrochloric acid solution, washing with clear water to neutrality, and drying at 60 ℃ to obtain the hard carbon material.
Fig. 1 is a scanning electron micrograph of the hard carbon material obtained in this example, which shows that the hard carbon particles have a uniform size of 0.5 to 5 μm. This granularity scope is favorable to electrode coating very much, because need mix thick dress with active material and auxiliary reagent during the coating, coats on the electrode surface, forms the thick coating of 100 ~ 200um, consequently, active material's granularity is little, and the size is all the key that obtains high quality electrode.
Example 2
Washing fresh navel orange peel with water, cutting, placing in a hydrothermal reaction kettle, adding appropriate amount of water (to submerge the orange peel), performing hydrothermal reaction at 150 deg.C for 8 hr under sealed condition, cooling, mashing, filtering, cleaning, and lyophilizing at-55 deg.C for 24 hr to obtain carbon precursor; putting the obtained carbon precursor into an alumina crucible, and pre-carbonizing the carbon precursor for 12 hours at 200 ℃ in a muffle furnace; heating the pre-carbonized carbon precursor to 1000 ℃ at the speed of 3 ℃/min under the protective high-purity nitrogen atmosphere, preserving the heat for 5h, and cooling along with the furnace; washing the obtained product with 0.1mol/L diluted hydrochloric acid solution, washing with clear water to neutrality, and drying at 60 ℃ to obtain the hard carbon material.
Example 3
Washing fresh navel orange peel with water, cutting, placing in a hydrothermal reaction kettle, adding appropriate amount of water (to submerge the orange peel), performing hydrothermal reaction at 160 deg.C for 7 hr under sealed condition, cooling, mashing, filtering, cleaning, and freeze drying at-55 deg.C for 30 hr to obtain carbon precursor; putting the obtained carbon precursor into an alumina crucible, and pre-carbonizing the carbon precursor for 12 hours at 300 ℃ in a muffle furnace; heating the pre-carbonized carbon precursor to 1400 ℃ at the speed of 3 ℃/min under the protective high-purity nitrogen atmosphere, preserving the heat for 2h, and cooling along with the furnace; washing the obtained product with 0.1mol/L diluted hydrochloric acid solution, washing with clear water to neutrality, and drying at 60 ℃ to obtain the hard carbon material.
Example 4
Washing fresh navel orange peel with water, cutting, placing in a hydrothermal reaction kettle, adding appropriate amount of water (to submerge the orange peel), performing hydrothermal reaction at 170 deg.C for 5 hr under sealed condition, cooling, mashing, filtering, cleaning, and lyophilizing at-55 deg.C for 36 hr to obtain carbon precursor; putting the obtained carbon precursor into an alumina crucible, and pre-carbonizing the carbon precursor for 12 hours at 290 ℃ in a muffle furnace; heating the pre-carbonized carbon precursor to 1500 ℃ at the speed of 3 ℃/min in the protective high-purity nitrogen atmosphere, preserving the heat for 1h, and cooling along with the furnace; washing the obtained product with 0.1mol/L diluted hydrochloric acid solution, washing with clear water to neutrality, and drying at 60 ℃ to obtain the hard carbon material.
Example 5
Mixing the hard carbon material prepared in the example 1, conductive carbon black and sodium alginate in a mass ratio of 80: 10: 10 mixing in deionized water, grinding into paste, coating on copper foil current collector, drying at 80 deg.C for 12 hr, cutting into several pole pieces with diameter of 12mm, weighing, calculating the mass of hard carbon material (active substance), placing in argon protective glove box, using metal sodium sheet as counter electrode, using glass fiber as diaphragm, and using 1mol/L NaClO4And the/PC solution is used as an electrolyte, a 2032 button type mobile battery is assembled, and a sodium ion half-battery is subjected to charge-discharge test in a constant current charge-discharge mode, wherein the current density range is 0.05-3A/g, and the voltage range is 0-2.5V.
The test results are shown in fig. 2 and fig. 3, and fig. 2 is a curve of the specific mass capacity of the hard carbon material in relation to the current density. The charge and discharge tests show that the specific mass capacity of the material exceeds 290mAh/g at 0.05A/g and is 90/g at 2A/g. FIG. 3 is a cycle curve of the hard carbon material, and it can be seen that the specific sodium storage capacity after 500 cycles at a rate of 0.5A/g is still maintained above 200 mAh/g. The hard carbon material prepared by the invention has the advantages of high specific capacity and good cycle performance.
Comparative example 1
Washing fresh navel orange peel with water, chopping, and directly drying in a heating furnace at 80 deg.C to obtain carbon precursor; putting the obtained carbon precursor into an alumina crucible, and pre-carbonizing the carbon precursor for 12 hours at 210 ℃ in a muffle furnace; heating the pre-carbonized carbon precursor to 1300 ℃ at the speed of 3 ℃/min under the protective atmosphere, preserving the heat for 3h, and cooling along with the furnace; and washing the obtained product with 0.1mol/L diluted hydrochloric acid solution, washing the product with clear water to be neutral, and drying the product at 60 ℃ to obtain the contrast material.
FIG. 4 is a scanning electron micrograph of a comparative material. It can be seen that the hard carbon particles are not uniform in size, vary in particle size from 0.5 to 30 μm, and present difficulties in electrode coating.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various features described in the above embodiments may be combined in any suitable manner without departing from the scope of the invention. The invention is not described in detail in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.
Claims (10)
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| CN114388736B (en) * | 2021-12-15 | 2024-01-30 | 海南大学 | Method for preparing hard carbon negative electrode of lithium/sodium ion battery by biomass charcoal |
| CN116102012B (en) * | 2023-01-03 | 2024-09-06 | 广东邦普循环科技有限公司 | Method for preparing hard carbon anode material by using waste thermosetting plastic |
| CN118811800B (en) * | 2024-09-14 | 2025-01-24 | 大秦数字能源技术股份有限公司 | A cheap, high-performance hard carbon anode material for sodium-ion secondary batteries |
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