CN115676804B - Porous hard carbon anode material based on asphalt, and preparation method and application thereof - Google Patents
Porous hard carbon anode material based on asphalt, and preparation method and application thereof Download PDFInfo
- Publication number
- CN115676804B CN115676804B CN202211662760.XA CN202211662760A CN115676804B CN 115676804 B CN115676804 B CN 115676804B CN 202211662760 A CN202211662760 A CN 202211662760A CN 115676804 B CN115676804 B CN 115676804B
- Authority
- CN
- China
- Prior art keywords
- hard carbon
- asphalt
- anode material
- carbon anode
- porous
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 229910021385 hard carbon Inorganic materials 0.000 title claims abstract description 169
- 239000010426 asphalt Substances 0.000 title claims abstract description 115
- 239000010405 anode material Substances 0.000 title claims abstract description 55
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000000843 powder Substances 0.000 claims abstract description 48
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 32
- 229910001415 sodium ion Inorganic materials 0.000 claims abstract description 27
- 238000000034 method Methods 0.000 claims abstract description 25
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 15
- 230000003647 oxidation Effects 0.000 claims abstract description 15
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 15
- 238000001694 spray drying Methods 0.000 claims abstract description 15
- 238000005406 washing Methods 0.000 claims abstract description 14
- 239000002253 acid Substances 0.000 claims abstract description 12
- 238000003763 carbonization Methods 0.000 claims abstract description 10
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 10
- 239000002245 particle Substances 0.000 claims abstract description 8
- 238000010000 carbonizing Methods 0.000 claims abstract description 3
- 238000003756 stirring Methods 0.000 claims description 49
- 239000008367 deionised water Substances 0.000 claims description 44
- 229910021641 deionized water Inorganic materials 0.000 claims description 44
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 44
- 239000002002 slurry Substances 0.000 claims description 38
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 26
- 239000007833 carbon precursor Substances 0.000 claims description 25
- 238000001035 drying Methods 0.000 claims description 23
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 22
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 22
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 15
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 15
- 239000011324 bead Substances 0.000 claims description 15
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 15
- 239000003607 modifier Substances 0.000 claims description 15
- 239000001301 oxygen Substances 0.000 claims description 15
- 229910052760 oxygen Inorganic materials 0.000 claims description 15
- 239000007921 spray Substances 0.000 claims description 14
- 239000012298 atmosphere Substances 0.000 claims description 13
- 238000000967 suction filtration Methods 0.000 claims description 13
- 238000001816 cooling Methods 0.000 claims description 11
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 8
- 239000003245 coal Substances 0.000 claims description 8
- 238000010790 dilution Methods 0.000 claims description 8
- 239000012895 dilution Substances 0.000 claims description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 7
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 6
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 6
- 229910017604 nitric acid Inorganic materials 0.000 claims description 6
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 claims description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 6
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 5
- 229920000178 Acrylic resin Polymers 0.000 claims description 5
- 239000004925 Acrylic resin Substances 0.000 claims description 5
- IMQLKJBTEOYOSI-GPIVLXJGSA-N Inositol-hexakisphosphate Chemical compound OP(O)(=O)O[C@H]1[C@H](OP(O)(O)=O)[C@@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@@H]1OP(O)(O)=O IMQLKJBTEOYOSI-GPIVLXJGSA-N 0.000 claims description 5
- IMQLKJBTEOYOSI-UHFFFAOYSA-N Phytic acid Natural products OP(O)(=O)OC1C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C1OP(O)(O)=O IMQLKJBTEOYOSI-UHFFFAOYSA-N 0.000 claims description 5
- 239000003208 petroleum Substances 0.000 claims description 5
- 229940068041 phytic acid Drugs 0.000 claims description 5
- 235000002949 phytic acid Nutrition 0.000 claims description 5
- 239000000467 phytic acid Substances 0.000 claims description 5
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 4
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 4
- 239000002202 Polyethylene glycol Substances 0.000 claims description 4
- 239000001110 calcium chloride Substances 0.000 claims description 4
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 4
- 239000005011 phenolic resin Substances 0.000 claims description 4
- 229920001568 phenolic resin Polymers 0.000 claims description 4
- 229920001223 polyethylene glycol Polymers 0.000 claims description 4
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 4
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 4
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 4
- 238000004321 preservation Methods 0.000 claims description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 4
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 3
- CTENFNNZBMHDDG-UHFFFAOYSA-N Dopamine hydrochloride Chemical compound Cl.NCCC1=CC=C(O)C(O)=C1 CTENFNNZBMHDDG-UHFFFAOYSA-N 0.000 claims description 3
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 3
- 229960001149 dopamine hydrochloride Drugs 0.000 claims description 3
- ZWLUXSQADUDCSB-UHFFFAOYSA-N phthalaldehyde Chemical compound O=CC1=CC=CC=C1C=O ZWLUXSQADUDCSB-UHFFFAOYSA-N 0.000 claims description 3
- 235000011056 potassium acetate Nutrition 0.000 claims description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 3
- 239000001103 potassium chloride Substances 0.000 claims description 3
- 235000011164 potassium chloride Nutrition 0.000 claims description 3
- 230000000630 rising effect Effects 0.000 claims description 3
- 239000001632 sodium acetate Substances 0.000 claims description 3
- 235000017281 sodium acetate Nutrition 0.000 claims description 3
- 239000011780 sodium chloride Substances 0.000 claims description 3
- 235000011148 calcium chloride Nutrition 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 2
- 235000011181 potassium carbonates Nutrition 0.000 claims description 2
- 235000017550 sodium carbonate Nutrition 0.000 claims description 2
- 235000002639 sodium chloride Nutrition 0.000 claims description 2
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 2
- 230000008569 process Effects 0.000 abstract description 16
- 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 15
- 229910052708 sodium Inorganic materials 0.000 abstract description 15
- 239000011734 sodium Substances 0.000 abstract description 15
- 238000005245 sintering Methods 0.000 abstract description 14
- 239000011148 porous material Substances 0.000 abstract description 6
- 238000003860 storage Methods 0.000 abstract description 6
- 239000013081 microcrystal Substances 0.000 abstract description 5
- 230000009286 beneficial effect Effects 0.000 abstract description 3
- 239000011229 interlayer Substances 0.000 abstract description 3
- 230000001737 promoting effect Effects 0.000 abstract description 3
- 230000005518 electrochemistry Effects 0.000 abstract description 2
- 230000001590 oxidative effect Effects 0.000 abstract description 2
- 238000009818 secondary granulation Methods 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 abstract 1
- 230000020477 pH reduction Effects 0.000 abstract 1
- 238000010438 heat treatment Methods 0.000 description 38
- 239000007773 negative electrode material Substances 0.000 description 17
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 14
- 239000000463 material Substances 0.000 description 13
- 229910052799 carbon Inorganic materials 0.000 description 10
- 238000001914 filtration Methods 0.000 description 9
- 239000010410 layer Substances 0.000 description 9
- 238000012986 modification Methods 0.000 description 9
- 230000004048 modification Effects 0.000 description 9
- 239000004576 sand Substances 0.000 description 9
- 238000007873 sieving Methods 0.000 description 9
- 238000005303 weighing Methods 0.000 description 9
- 230000000977 initiatory effect Effects 0.000 description 8
- 238000000227 grinding Methods 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 239000010406 cathode material Substances 0.000 description 5
- 239000002105 nanoparticle Substances 0.000 description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 4
- 238000004132 cross linking Methods 0.000 description 4
- 238000005469 granulation Methods 0.000 description 4
- 230000003179 granulation Effects 0.000 description 4
- 229910002804 graphite Inorganic materials 0.000 description 4
- 239000010439 graphite Substances 0.000 description 4
- 238000009830 intercalation Methods 0.000 description 4
- 230000002687 intercalation Effects 0.000 description 4
- 229910052744 lithium Inorganic materials 0.000 description 4
- 229910001416 lithium ion Inorganic materials 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000007865 diluting Methods 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 230000002349 favourable effect Effects 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 125000005842 heteroatom Chemical group 0.000 description 3
- 230000001976 improved effect Effects 0.000 description 3
- 238000013508 migration Methods 0.000 description 3
- 230000005012 migration Effects 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 239000002194 amorphous carbon material Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000009831 deintercalation Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000012798 spherical particle Substances 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 229910003481 amorphous carbon Inorganic materials 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 239000007770 graphite material Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 238000007709 nanocrystallization Methods 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 229910021384 soft carbon Inorganic materials 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
Classifications
-
- 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 belongs to the field of electrochemistry, and in particular relates to a porous hard carbon anode material based on asphalt, a preparation method and application thereof. Firstly, modifying asphalt powder by using a cross-linking agent or a modifying agent to improve the disorder degree in the carbonization process, then uniformly distributing nano asphalt particles and the modifying agent by spray drying and secondary granulation to improve the disorder state of asphalt in the sintering process, and simultaneously forming a multistage pore canal structure by using a uniform pore-forming agent in the ball forming process in the acidification and washing process; finally, carbonizing the mixture after high-temperature pre-oxidation and oxidizing a microcrystalline interface by matching with strong acid to strengthen the repulsive force among the microcrystals, thereby realizing the purpose of increasing the interlayer spacing of the hard carbon microcrystals. The porous hard carbon anode material has a large microcrystalline interlayer spacing and a multistage pore structure, contains mesopores and macropores, effectively improves the sodium storage performance of the hard carbon material, has a stable structure and low price, has a good application prospect, and is beneficial to promoting the industrialization process of sodium ion batteries.
Description
Technical Field
The invention belongs to the field of electrochemistry, and relates to a negative electrode material, in particular to a porous hard carbon negative electrode material based on asphalt, and a preparation method and application thereof.
Background
The large-scale application of Lithium Ion Batteries (LIBs) plays a vital role in the sustainable development of society, but the serious shortage of global lithium resources results in a great increase in the production cost of LIBs. The lithium resource in China is lower, and under the unstable international situation, the new generation battery technology is forced to be laid out. Sodium in the same main group as lithium has abundant and widely distributed sodium reserves, and has a similar rocking chair type working principle as a corresponding lithium ion battery, so that Sodium Ion Batteries (SIBs) are expected to become energy storage power supplies widely applied after the lithium ion batteries.
In SIBs, sodium has a larger ionic radius than lithium, so that the reaction diffusion process is more difficult than that of lithium ions, and the volume expansion of the negative electrode after sodium storage is larger, so that the reaction diffusion difficulty is further increased. Among various studied anode materials, the carbon material has the advantages of low cost, good conductivity, high sodium storage capacity (200-500 mAh/g) and low sodium embedding potential, and has commercial application prospect. The interlayer spacing of the common graphite material is smaller, so that the sodium storage capacity is difficult to develop; the arrangement regularity of the carbon layer of the soft carbon material is lower than that of graphite, and the short-range ordered carbon layer structure is favorable for sodium ion migration, but still needs to be subjected to structural optimization; hard carbon materials are considered to be the most promising negative electrode materials for sodium ion batteries because of their unique structure that is not graphitized, with multiple types of reversible sodium storage sites. The hard carbon precursor sources mainly comprise resins, asphalts and biomasses, wherein the asphalts are expected to become hard carbon materials for large-scale application due to stable raw material supply and low price, and the technological attack of asphalt raw material structure modification, carbonization and the like is the key point of current research.
Patent publication No. CN 109148883A discloses a sodium ion battery cathode material based on asphalt and a preparation method thereof, wherein an asphalt precursor is placed in a muffle furnace for pre-oxidation, and then high-temperature carbonization is carried out under the protection of inert gas to obtain an amorphous carbon material, wherein the pre-oxidation breaks the ordered structure of the asphalt, so that the amorphous carbon material with a disordered structure is formed in the subsequent carbonization process. The processing of this patent is relatively simple, but the amorphous carbon formed contains a large number of long-range, ordered carbon layer structures and lower layer spacing, which is detrimental to rapid deintercalation of sodium ions.
Patent publication No. CN 109148838A discloses a sodium ion battery anode material based on carbon material and asphalt, wherein the carbon material and asphalt are mechanically mixed and then are subjected to heat treatment in the air, so that the asphalt is coated on the surface of the carbon material, and then the irregularly-shaped composite carbon material with the surface coated with the asphalt ordered carbon material is obtained through high-temperature treatment. The material is of an externally ordered and internally disordered composite structure, and can form certain interfacial resistance to the embedding process of sodium ions, so that the material is not beneficial to rapid embedding of the sodium ions.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a porous hard carbon anode material based on asphalt, and a preparation method and application thereof. The porous hard carbon material based on asphalt has a highly disordered multi-stage pore structure, has large carbon layer spacing and excellent sodium storage performance, and is favorable for rapid intercalation and deintercalation of sodium ions.
In order to achieve the above purpose, the technical scheme of the invention is realized as follows:
the porous hard carbon anode material based on asphalt comprises the following steps:
(1) Dissolving the modifier in ethanol, sequentially adding asphalt powder and a pore-forming agent, sanding, adding a cross-linking agent, and uniformly mixing to obtain the nano asphalt slurry A. Firstly, carrying out sanding treatment on asphalt powder to obtain slurry of nano particles, then carrying out surface crosslinking modification on the slurry by using a soluble crosslinking agent (i.e. a modifier), realizing effective modification of the interior and the edge of the asphalt nano particles, and simultaneously adding a small amount of pore-forming agent to promote uniform dispersion of asphalt components and the modifier in the material; the pore-forming agent is removed during a subsequent washing process, causing the material to form a macroporous structure.
(2) And carrying out spray drying treatment on the nano asphalt slurry A under the protection of nitrogen atmosphere to obtain hard carbon precursor powder B. The secondary balling and granulating process of spray drying treatment also ensures the uniform dispersion of the asphalt component and the modifier in the material; in addition, the porous structure of the material formed into the ball by the secondary process can relieve the volume change in the sodium intercalation process while improving the migration efficiency of sodium ions, and also realize the effective doping of hetero atoms in the modifier and improve the electrochemical activity of the material.
(3) And pre-oxidizing the hard carbon precursor powder B in an oxygen atmosphere, carbonizing at a high temperature in a nitrogen atmosphere, naturally cooling and crushing to obtain the hard carbon material C. The spherical particles subjected to spray granulation are carbonized after air oxidation, so that the disorder degree of the material is improved, and a porous structure is formed.
(4) And (3) placing the hard carbon material C in strong acid for oxidation treatment, and carrying out suction filtration, washing and drying to obtain a modified hard carbon product D. And (3) carrying out strong acid oxidation on the carbonized sample, regulating and controlling the carbon layer spacing of the graphite microcrystals, and promoting sodium ion intercalation.
(5) Dispersing the modified hard carbon product D in deionized water, dropwise adding hydrazine hydrate, stirring, carrying out suction filtration and drying to obtain the porous hard carbon anode material.
Preferably, the modifier in the step (1) is any one of phenolic resin, polyvinylpyrrolidone, acrylic resin and polyethylene glycol; the pore-forming agent is any one of sodium chloride, sodium carbonate, sodium acetate, potassium chloride, potassium carbonate, potassium acetate and calcium chloride; the cross-linking agent is any one of gamma-aminopropyl triethoxysilane, phytic acid, dopamine hydrochloride, cetyl trimethyl ammonium bromide and phthalic dicarboxaldehyde.
Preferably, the asphalt in the step (1) is coal-based asphalt or petroleum asphalt with a softening point of 200-300 ℃; the particle size D50 of the asphalt powder is 100-500 mu m; the asphalt powder has a particle size D50 of 200-500 nm after sanding.
Preferably, the mass volume ratio of the modifier to the ethanol in the step (1) is (2-10) g, 100: 100 mL; the mass ratio of the modifier to the asphalt powder is (0.2-1): 1; the mass ratio of the pore-forming agent to the asphalt powder is (0.1-0.3): 1; the mass ratio of the cross-linking agent to the asphalt powder is (0.05-0.2): 1; the sanding treatment time is 0.5-3 h, the rotating speed is 1500-3000 r/min, and the used sanding beads are zirconium oxide beads; the zirconia beads have a particle size of 0.1 to 0.5. 0.5 mm.
Preferably, the spray pressure of the spray drying treatment in the step (2) is 0.2 Mpa and the temperature is 180 ℃; the granularity D50 of the hard carbon precursor powder B is 8-15 mu m.
Preferably, the temperature of the pre-oxidation treatment in the step (3) is 300-400 ℃, the heating rate is 2-5 ℃/min, and the heat preservation time is 1-3 h; the high-temperature carbonization treatment temperature is 1200-1400 ℃, the temperature rising rate is 2-10 ℃/min, and the heat preservation time is 2-4 h.
Preferably, the strong acid in the step (4) is concentrated sulfuric acid or concentrated nitric acid; the oxidation treatment is specifically that strong acid is added into the hard carbon material C according to the mass volume ratio of 1g (5-15) mL, then stirring is carried out for 0.5-4 h, and deionized water is added for dilution; the volume ratio of the strong acid to the deionized water is 1 (10-20).
Preferably, the mass of the modified hard carbon product D in the step (5) is 10-50% of the mass of deionized water; the mass ratio of the hydrazine hydrate to the modified hard carbon product D is (0.1-0.5): 1; the hydrazine hydrate treatment time is 10-30 min.
The invention also comprises the porous hard carbon anode material based on asphalt prepared by the method.
The invention also comprises application of the porous hard carbon anode material based on asphalt in preparing sodium ion batteries.
The invention has the beneficial effects that:
1. the invention provides a preparation method of a porous hard carbon anode material based on asphalt, which comprises the steps of firstly, carrying out sanding treatment on asphalt powder to obtain slurry of nano particles, carrying out surface crosslinking modification on the slurry by using a soluble crosslinking agent to realize effective modification of the interior and the edge of the asphalt nano particles, and carrying out uniform dispersion of an interior asphalt component and a modifying agent by using a pore-forming agent and a secondary balling granulation process to promote the disordered state of a carbonization process of the interior asphalt component and the modifying agent, wherein the pore-forming agent is removed in a subsequent washing process, so that the material forms a macroporous structure; then, the spherical particles subjected to spray granulation are subjected to one-step sectional sintering, the structure of an organic carbon chain in asphalt is changed by air oxidation, then a disordered state is further enhanced in a sintering process of high-temperature carbonization to form a porous structure, and a sample after carbonization is subjected to strong acid oxidation to enable groups such as carboxyl, hydroxyl and the like to be generated on the surface of a carbon layer to regulate and control the carbon layer spacing of graphite microcrystals, so that the aim of expanding the carbon layer spacing is fulfilled, and sodium ion embedding is facilitated. The porous structure formed by spray granulation and secondary balling can realize uniform distribution of nanoscale asphalt particles and modifier in the material, so that the volume change of the sodium embedding process can be relieved while the migration efficiency of sodium ions is improved; when the modifier containing hetero atoms is used for modification, the doping of the hetero atoms in the material can be realized, and the electrochemical activity of the material is effectively improved.
2. In order to improve the disordered state of the hard carbon material, the disordered effect is mainly enhanced and the sodium embedding site is increased in the following four ways: (1) After asphalt nanocrystallization, high-efficiency crosslinking modification is performed by using a soluble crosslinking agent in a liquid phase environment; (2) The nano asphalt nano particles and the modifier are uniformly distributed in the secondary granulation process; (3) The method comprises the steps of a one-step sectional method sintering process, firstly, increasing the content of oxygen-containing functional groups through pre-oxidation treatment under the oxygen atmosphere at low temperature, and then, improving the crosslinking degree through high-temperature sintering under the inert atmosphere; (4) And (3) performing acid oxidation treatment and reduction after carbonization, performing oxygen-containing functional group modification on the surface of the graphite microcrystal, increasing interfacial repulsive force to increase the distance, and performing reduction to remove the oxygen-containing functional group to improve the conductivity.
3. The porous hard carbon cathode material based on asphalt prepared by the invention has a highly disordered and spherical porous structure, the pore level of the porous hard carbon cathode material comprises macropores and mesopores, hard carbon formed by a plurality of carbon sources is contained in the porous hard carbon cathode material, the long-short chain structure of the porous hard carbon cathode material is crosslinked with each other by the multi-carbon sources, the formation of the highly disordered structure is promoted, the first charge specific capacity of the sodium-ion half battery prepared by the material can reach 336.5 mAh/g under the current density of 30 mA/g, and the first effect can reach 86.5%. The porous hard carbon negative electrode material based on asphalt has the advantages of novel structure, high first effect of sodium intercalation, good multiplying power performance and excellent stability, and the preparation process is simple and novel, has adjustable and controllable structure, has industrialization prospect, is favorable for promoting the industrialization process of sodium ion batteries, and provides reference for the design of novel hard carbon negative electrode materials.
Drawings
In order to more clearly illustrate the embodiments of the invention or the technical solutions in the prior art, the drawings that are required in the embodiments or the description of the prior art will be briefly described, it being obvious that the drawings in the following description are only some embodiments of the invention, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a scanning electron microscope image of the pitch-based porous hard carbon anode material of example 1 at a magnification of 2.0 KX.
Fig. 2 is a pore size distribution diagram of the pitch-based porous hard carbon anode material in example 1.
Fig. 3 is a first charge-discharge curve of the pitch-based porous hard carbon anode material of example 1.
Fig. 4 is a cycle stability curve of the pitch-based porous hard carbon anode material in example 1.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without any inventive effort, are intended to be within the scope of the invention.
In the following examples, the microcosmic morphology of the prepared porous hard carbon anode material based on asphalt was measured by using a Hitachi S-3400N scanning electron microscope; the battery performance test was carried out using a battery test system model LANHE CT2001A, available from Wuhan, blue electric electronics Inc.
The battery performance test is specifically as follows: preparing slurry from the prepared porous hard carbon anode material based on asphalt, conductive carbon black and a binder PVDF according to the mass ratio of 8:1:1, uniformly coating the slurry on an aluminum foil, and drying the slurry to prepare an electrode; the electrolyte is 1.0 mol L -1 NaClO of (C) 4 The organic solution is prepared by processing EC: DEC with a volume ratio of 1:1, 5% FEC as an additive, glass fiber as a diaphragm and sodium flake as an anode into a CR2025 button cell; first-round discharge test was discharged to 0.01V with 30 mA/g and recharged to 2.0V; the cycle performance test is carried out by using 50 mA/g for constant-current charge and discharge test, the charge and discharge voltage range is 0.01-2V, and the test is carried out under the constant temperature condition of 25 ℃.
Example 1
The preparation method of the porous hard carbon anode material based on asphalt in the embodiment is as follows:
(1) Dissolving 6 g phenolic resin in 100 mL ethanol, sequentially adding coal-based asphalt powder with the softening point of 10 g and the D50 of 200 ℃ and 1g sodium chloride, stirring uniformly, transferring into a 0.1 mm zirconia bead sand mill, grinding into 0.5 h, grinding at the speed of 2000 r/min, wherein the asphalt granularity D50 after grinding is 200 nm, adding 2 g gamma-aminopropyl triethoxysilane, and stirring uniformly to obtain nano asphalt slurry A;
(2) Spray drying the nano asphalt slurry A under the protection of nitrogen atmosphere, wherein the spray pressure is 0.2 MPa, the temperature is 180 ℃, and the hard carbon precursor powder B with the granularity D50 of 10 mu m is obtained;
(3) Placing the hard carbon precursor powder B in a sintering furnace, heating to 300 ℃ at a heating rate of 2 ℃/min under an oxygen atmosphere, preserving heat for 1 h, then changing into a nitrogen atmosphere, heating to 1350 ℃ at a heating rate of 2 ℃/min, preserving heat for 2 h, naturally cooling, crushing, and sieving with a 200-mesh sieve to obtain a hard carbon material C;
(4) Weighing 1g hard carbon material C, treating 1 h in 10 mL concentrated sulfuric acid, adding 100 mL deionized water for dilution, stirring and suction filtering, washing 3 times (20 mL each time) with deionized water, and drying in a blast oven at 100 ℃ to obtain a modified hard carbon product D;
(5) Dispersing 1g of modified hard carbon product D in deionized water, uniformly stirring, wherein the mass of the modified hard carbon product D is 10% of that of the deionized water, dropwise adding 0.5. 0.5 g hydrazine hydrate, stirring for 10 min, and then carrying out suction filtration and drying to obtain the porous hard carbon negative electrode material based on asphalt.
The porous hard carbon anode material based on asphalt of the embodiment is prepared into slurry, then smeared and assembled into a sodium ion half battery, and tested under the current density of 30 mA/g, the initial charge specific capacity is measured to reach 325.6 mAh/g, the initial effect is 86.5%, and the porous hard carbon anode material has good circulation and multiplying power performance.
Fig. 1 is a scanning electron microscope image of the porous hard carbon anode material based on asphalt of the present embodiment under a magnification of 2.0KX, and it can be seen from the figure that the overall structure of the porous hard carbon material is uniform and spherical.
Fig. 2 is a pore size distribution diagram of the porous hard carbon negative electrode material, and it can be seen that the porous hard carbon material contains abundant mesopores and macropores.
Fig. 3 is a first charge-discharge curve of the porous hard carbon negative electrode material, and it can be seen that the porous hard carbon material has high specific capacity and first coulombic efficiency.
Fig. 4 is a graph showing the cycle stability of the porous hard carbon negative electrode material, and it can be seen that the porous hard carbon material has excellent cycle stability.
Example 2
The preparation method of the porous hard carbon anode material based on asphalt in the embodiment is as follows:
(1) Dissolving 5 g polyvinylpyrrolidone in 100 mL ethanol, sequentially adding 10 g petroleum asphalt powder with a softening point of 250 ℃ and a D50 of 500 mu m, 2 g sodium carbonate, stirring uniformly, transferring into a 0.2 mm zirconia bead sand mill, sanding for 3 hours at a sanding rotating speed of 1500 r/min, wherein the asphalt granularity D50 after sanding is 500 nm, adding 2 g phytic acid, and stirring uniformly to obtain nano asphalt slurry A;
(2) Carrying out spray drying treatment on the slurry A under the protection of nitrogen atmosphere, wherein the spray pressure is 0.2 MPa, the temperature is 180 ℃, and the hard carbon precursor powder B with the granularity D50 of 15 mu m is obtained;
(3) Placing the hard carbon precursor powder B in a sintering furnace, heating to 350 ℃ at a heating rate of 2 ℃/min under an oxygen atmosphere, preserving heat for 2 h, then heating to 1300 ℃ at a heating rate of 5 ℃/min under a nitrogen atmosphere, preserving heat for 2 h, naturally cooling, crushing, and sieving with a 200-mesh sieve to obtain a hard carbon material C;
(4) Weighing 1g hard carbon product C, treating 0.5 h in 5mL concentrated sulfuric acid, diluting with 100 mL deionized water, stirring, filtering, washing with deionized water for 3 times (20 mL each time), and drying in a blast oven at 100deg.C to obtain modified hard carbon product D;
(5) Dispersing 1g of modified hard carbon product D in deionized water, uniformly stirring, wherein the mass of the modified hard carbon product D is 50% of that of the deionized water, dropwise adding 0.1. 0.1 g hydrazine hydrate, stirring for 20 min, and carrying out suction filtration and drying to obtain the porous hard carbon negative electrode material based on asphalt.
The porous hard carbon anode material based on asphalt of the embodiment is prepared into slurry, then smeared and assembled into a sodium ion half battery, and the initial charge specific capacity reaches 315.3 mAh/g and the initial effect reaches 82.4% under the current density of 30 mA/g, so that the porous hard carbon anode material has good circulation and multiplying power performance.
Example 3
The preparation method of the porous hard carbon anode material based on asphalt in the embodiment is as follows:
(1) Dissolving 2 g acrylic resin in 100 mL ethanol, sequentially adding coal-based asphalt powder with the softening point of 10 g and the softening point of 300 ℃ and the D50 of 250 mu m, 1g sodium acetate, stirring uniformly, transferring into a 0.5 mm zirconia bead sand mill, sanding for 2 h, wherein the sanding speed is 2500 r/min, the asphalt granularity D50 after sanding is 200 nm, adding 2 g dopamine hydrochloride, and stirring uniformly to obtain nano asphalt slurry A;
(2) Carrying out spray drying treatment on the slurry A under the protection of nitrogen atmosphere, wherein the spray pressure is 0.2 MPa, the temperature is 180 ℃, and the hard carbon precursor powder B with the granularity D50 of 10 mu m is obtained;
(3) Placing the hard carbon precursor powder B in a sintering furnace, heating to 300 ℃ at a heating rate of 5 ℃/min under an oxygen atmosphere, preserving heat for 1 h, changing into a nitrogen atmosphere, heating to 1400 ℃ at a heating rate of 10 ℃/min, preserving heat for 2 h, naturally cooling, crushing, and sieving with a 200-mesh sieve to obtain a hard carbon material C;
(4) Weighing 1g hard carbon product C, treating 2 h in 15mL of concentrated sulfuric acid, adding 150 mL deionized water for dilution, stirring, filtering, washing with deionized water for 3 times (20 mL each time), and drying in a blast oven at 100 ℃ to obtain a modified hard carbon product D;
(5) Dispersing 1g of modified hard carbon product D in deionized water, uniformly stirring, wherein the mass of the modified hard carbon product D is 20% of that of the deionized water, dropwise adding 0.1. 0.1 g hydrazine hydrate, stirring for 30 min, and then carrying out suction filtration and drying to obtain the porous hard carbon negative electrode material based on asphalt.
The porous hard carbon anode material based on asphalt of the embodiment is prepared into slurry, then smeared and assembled into a sodium ion half battery, and the initial charge specific capacity reaches 285.4 mAh/g and the initial effect reaches 81.5% under the current density of 30 mA/g, so that the porous hard carbon anode material has good circulation and multiplying power performance.
Example 4
The preparation method of the porous hard carbon anode material based on asphalt in the embodiment is as follows:
(1) Dissolving 3 g polyethylene glycol in 100 mL ethanol, sequentially adding 10 g petroleum asphalt powder with a softening point of 230 ℃ and a D50 of 200 mu m and 1.5 g potassium chloride, stirring uniformly, transferring into a 0.3 mm zirconia bead sand mill, grinding 1.5 h, grinding at a grinding speed of 2500 r/min, grinding to obtain asphalt with a granularity D50 of 300 nm, adding 0.5 g gamma-aminopropyl triethoxysilane, and stirring uniformly to obtain nano asphalt slurry A;
(2) Carrying out spray drying treatment on the slurry A under the protection of nitrogen atmosphere, wherein the spray pressure is 0.2 MPa, the temperature is 180 ℃, and the hard carbon precursor powder B with the granularity D50 of 12 mu m is obtained;
(3) Placing the hard carbon precursor powder B in a sintering furnace, heating to 300 ℃ at a heating rate of 5 ℃/min under an oxygen atmosphere, preserving heat for 2 h, then heating to 1300 ℃ at a heating rate of 5 ℃/min under a nitrogen atmosphere, preserving heat for 4 h, naturally cooling, crushing, and sieving with a 200-mesh sieve to obtain a hard carbon material C;
(4) Weighing 1g hard carbon product C, treating the hard carbon product C in 15mL concentrated sulfuric acid for 4 h, adding 300 mL deionized water for dilution, stirring and filtering, washing with deionized water for 3 times (20 mL each time), and drying in a blast oven at 100 ℃ to obtain a modified hard carbon product D;
(5) Dispersing 1g of modified hard carbon product D in deionized water, uniformly stirring, wherein the mass of the modified hard carbon product D is 10% of that of the deionized water, dropwise adding 0.2. 0.2 g hydrazine hydrate, stirring for 20 min, and carrying out suction filtration and drying to obtain the porous hard carbon negative electrode material based on asphalt.
The porous hard carbon anode material based on asphalt of the embodiment is prepared into slurry, then smeared and assembled into a sodium ion half battery, and the initial charge specific capacity reaches 291.4 mAh/g and the initial effect is 83.2% when tested under the current density of 30 mA/g, so that the porous hard carbon anode material has good circulation and multiplying power performance.
Example 5
The preparation method of the porous hard carbon anode material based on asphalt in the embodiment is as follows:
(1) Dissolving 5 g acrylic resin in 100 mL ethanol, sequentially adding coal-based asphalt powder with a softening point of 10 g of 270 ℃ and a D50 of 300 mu m and 2 g potassium carbonate, stirring uniformly, sanding in a 0.4 mm zirconia bead sand mill for 2 h, wherein the sanding speed is 3000 r/min, the asphalt granularity D50 after sanding is 200 nm, adding 1g hexadecyl trimethyl ammonium bromide, and stirring uniformly to obtain nano asphalt slurry A;
(2) Carrying out spray drying treatment on the slurry A under the protection of nitrogen atmosphere, wherein the spray pressure is 0.2 MPa, the temperature is 180 ℃, and the hard carbon precursor powder B with the granularity D50 of 10 mu m is obtained;
(3) Placing the hard carbon precursor powder B in a sintering furnace, heating to 350 ℃ at a heating rate of 3 ℃/min under an oxygen atmosphere, preserving heat for 3h, changing into a nitrogen atmosphere, heating to 1200 ℃ at a heating rate of 3 ℃/min, preserving heat for 4 h, naturally cooling, crushing, and sieving with a 200-mesh sieve to obtain a hard carbon material C;
(4) Weighing 1g hard carbon product C, treating 2 h in 5mL concentrated nitric acid, adding 75 mL deionized water for dilution, stirring, filtering, washing with deionized water for 3 times (20 mL each time), and drying in a blast oven at 100 ℃ to obtain a modified hard carbon product D;
(5) Dispersing 1g of modified hard carbon product D in deionized water, uniformly stirring, wherein the mass of the modified hard carbon product D is 25% of that of the deionized water, dropwise adding 0.1. 0.1 g hydrazine hydrate, stirring for 30 min, and then carrying out suction filtration and drying to obtain the porous hard carbon negative electrode material based on asphalt.
The porous hard carbon anode material based on asphalt of the embodiment is prepared into slurry, then smeared and assembled into a sodium ion half battery, and tested under the current density of 30 mA/g, the first charge specific capacity reaches 298.3 mAh/g, and the first effect reaches 81.7%, so that the porous hard carbon anode material has good circulation and multiplying power performance.
Example 6
The preparation method of the porous hard carbon anode material based on asphalt in the embodiment is as follows:
(1) Dissolving 10 g phenolic resin in 100 mL ethanol, sequentially adding 10 g petroleum asphalt powder with a softening point of 300 ℃ and a D50 of 150 mu m and 2 g potassium acetate, stirring uniformly, transferring into a 0.5 mm zirconia bead sand mill, sanding at a sanding speed of 2000 r/min, wherein the asphalt granularity D50 after sanding is 250 nm, adding 2 g phthalic dicarboxaldehyde, and stirring uniformly to obtain nano asphalt slurry A;
(2) Carrying out spray drying treatment on the slurry A under the protection of nitrogen atmosphere, wherein the spray pressure is 0.2 MPa, the temperature is 180 ℃, and the hard carbon precursor powder B with the granularity D50 of 14 mu m is obtained;
(3) Placing the hard carbon precursor powder B in a sintering furnace, heating to 350 ℃ at a heating rate of 3 ℃/min under an oxygen atmosphere, preserving heat for 3h, then heating to 1400 ℃ at a heating rate of 5 ℃/min under a nitrogen atmosphere, preserving heat for 2 h, naturally cooling, crushing, and sieving with a 200-mesh sieve to obtain a hard carbon material C;
(4) Weighing 1g hard carbon product C, treating 0.5 h in 10 mL concentrated nitric acid, diluting with 200 mL deionized water, stirring, filtering, washing with deionized water for 3 times (20 mL each time), and drying in a blast oven at 100deg.C to obtain modified hard carbon product D;
(5) Dispersing 1g of modified hard carbon product D in deionized water, uniformly stirring, wherein the mass of the modified hard carbon product D is 30% of that of the deionized water, dropwise adding 0.2. 0.2 g hydrazine hydrate, stirring for 20 min, and carrying out suction filtration and drying to obtain the porous hard carbon negative electrode material based on asphalt.
The porous hard carbon anode material based on asphalt of the embodiment is prepared into slurry, then smeared and assembled into a sodium ion half battery, and the initial charge specific capacity reaches 336.5 mAh/g and the initial effect is 86.2% under the current density of 30 mA/g, so that the porous hard carbon anode material has good circulation and multiplying power performance.
Example 7
The preparation method of the porous hard carbon anode material based on asphalt in the embodiment is as follows:
(1) Dissolving 3 g polyethylene glycol in 100 mL ethanol, sequentially adding 10 g coal-based asphalt powder with a softening point of 250 ℃ and a D50 of 200 mu m and 1g calcium chloride, stirring uniformly, transferring into a 0.2 mm zirconia bead sand mill, sanding at a sanding speed of 1500 r/min, adding 2 g phytic acid, and stirring uniformly to obtain nano asphalt slurry A;
(2) Carrying out spray drying treatment on the slurry A under the protection of nitrogen atmosphere, wherein the spray pressure is 0.2 MPa, the temperature is 180 ℃, and the hard carbon precursor powder B with the granularity D50 of 8 mu m is obtained;
(3) Placing the hard carbon precursor powder B in a sintering furnace, heating to 400 ℃ at a heating rate of 5 ℃/min under an oxygen atmosphere, preserving heat for 1 h, changing into a nitrogen atmosphere, heating to 1400 ℃ at a heating rate of 10 ℃/min, preserving heat for 2 h, naturally cooling, crushing, and sieving with a 200-mesh sieve to obtain a hard carbon material C;
(4) Weighing 1g hard carbon product C, treating 0.5 h in 5mL concentrated nitric acid, diluting with 50 mL deionized water, stirring, filtering, washing with deionized water for 3 times (20 mL each time), and drying in a blast oven at 100deg.C to obtain modified hard carbon product D;
(5) Dispersing 1g of modified hard carbon product D in deionized water, uniformly stirring, wherein the mass of the modified hard carbon product D is 20% of that of the deionized water, dropwise adding 0.25. 0.25 g hydrazine hydrate, stirring for 15 min, and then carrying out suction filtration and drying to obtain the porous hard carbon negative electrode material based on asphalt.
The porous hard carbon anode material based on asphalt of the embodiment is prepared into slurry, then smeared and assembled into a sodium ion half battery, and the initial charge specific capacity reaches 283.7 mAh/g and the initial effect is 85.2% under the current density of 30 mA/g, so that the porous hard carbon anode material has good circulation and multiplying power performance.
Example 8
The preparation method of the porous hard carbon anode material based on asphalt in the embodiment is as follows:
(1) Dissolving 3 g acrylic resin in 100 mL ethanol, sequentially adding coal-based asphalt powder with a softening point of 10 g and a D50 of 400 mu m, 1.5 g calcium chloride and stirring uniformly, transferring into a 0.1 mm zirconia bead sand mill, sanding for 3h, wherein the sanding speed is 3000 r/min, the asphalt granularity D50 after sanding is 100 nm, adding 2 g gamma-aminopropyl triethoxysilane and stirring uniformly to obtain nano asphalt slurry A;
(2) Carrying out spray drying treatment on the slurry A under the protection of nitrogen atmosphere, wherein the spray pressure is 0.2 MPa, the temperature is 180 ℃, and the hard carbon precursor powder B with the granularity D50 of 8 mu m is obtained;
(3) Placing the hard carbon precursor powder B in a sintering furnace, heating to 400 ℃ at a heating rate of 5 ℃/min under an oxygen atmosphere, preserving heat for 1 h, then changing into a nitrogen atmosphere, heating to 1400 ℃ at a heating rate of 5 ℃/min, preserving heat for 2 h, naturally cooling, crushing, and sieving with a 200-mesh sieve to obtain a hard carbon material C;
(4) Weighing 1g hard carbon product C, treating the hard carbon product C in 15mL concentrated nitric acid for 4 h, adding 225 mL deionized water for dilution, stirring and filtering, washing with deionized water for 3 times (20 mL each time), and drying in a blast oven at 100 ℃ to obtain a modified hard carbon product D;
(5) Dispersing 1g of modified hard carbon product D in deionized water, uniformly stirring, wherein the mass of the modified hard carbon product D is 30% of that of the deionized water, dropwise adding 0.5. 0.5 g hydrazine hydrate, stirring for 10 min, and then carrying out suction filtration and drying to obtain the porous hard carbon negative electrode material based on asphalt.
The porous hard carbon anode material based on asphalt of the embodiment is prepared into slurry, then smeared and assembled into a sodium ion half battery, and the initial charge specific capacity reaches 305.4 mAh/g and the initial effect reaches 81.5% under the current density of 30 mA/g, so that the porous hard carbon anode material has good circulation and multiplying power performance.
Example 9
The preparation method of the porous hard carbon anode material based on asphalt in the embodiment is as follows:
(1) Dissolving 5 g polyvinylpyrrolidone in 100 mL ethanol, sequentially adding coal-based asphalt powder with the softening point of 10 g being 300 ℃ and the D50 being 300 mu m, 3 g sodium carbonate, stirring uniformly, transferring into a 0.2 mm zirconia bead sand mill, sanding for 3 hours, wherein the sanding speed is 1500 r/min, the granularity D50 of the asphalt after sanding is 150 nm, adding 2 g phytic acid, and stirring uniformly to obtain nano asphalt slurry A;
(2) Carrying out spray drying treatment on the slurry A under the protection of nitrogen atmosphere, wherein the spray pressure is 0.2 MPa, the temperature is 180 ℃, and the hard carbon precursor powder B with the granularity D50 of 10 mu m is obtained;
(3) Placing the hard carbon precursor powder B in a sintering furnace, heating to 350 ℃ at a heating rate of 2 ℃/min under an oxygen atmosphere, preserving heat for 2 h, then heating to 1300 ℃ at a heating rate of 2 ℃/min under a nitrogen atmosphere, preserving heat for 2.5 h, naturally cooling, crushing, and sieving with a 200-mesh sieve to obtain a hard carbon material C;
(4) Weighing 1g hard carbon product C, treating 0.5 h in 10 mL concentrated sulfuric acid, adding 100 mL deionized water for dilution, stirring, filtering, washing with deionized water for 3 times (20 mL each time), and drying in a blast oven at 100 ℃ to obtain a modified hard carbon product D;
(5) Dispersing 1g of modified hard carbon product D in deionized water, uniformly stirring, wherein the mass of the modified hard carbon product D is 50% of that of the deionized water, dropwise adding 0.1. 0.1 g hydrazine hydrate, stirring for 20 min, and carrying out suction filtration and drying to obtain the porous hard carbon negative electrode material based on asphalt.
The porous hard carbon anode material based on asphalt of the embodiment is prepared into slurry, then smeared and assembled into a sodium ion half battery, and the initial charge specific capacity reaches 285.6 mAh/g and the initial effect reaches 82.0% when tested under the current density of 30 mA/g, so that the porous hard carbon anode material has good circulation and multiplying power performance.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, alternatives, and improvements that fall within the spirit and scope of the invention.
Claims (8)
1. The preparation method of the porous hard carbon anode material based on asphalt is characterized by comprising the following steps:
(1) Dissolving a modifier in ethanol, sequentially adding asphalt powder and a pore-forming agent, sanding, adding a cross-linking agent, and uniformly mixing to obtain nano asphalt slurry A;
(2) Spray drying the nano asphalt slurry A under the protection of nitrogen atmosphere to obtain hard carbon precursor powder B;
(3) Pre-oxidizing the hard carbon precursor powder B in an oxygen atmosphere, carbonizing at a high temperature in a nitrogen atmosphere, naturally cooling and crushing to obtain a hard carbon material C;
(4) Placing the hard carbon material C in strong acid for oxidation treatment, and carrying out suction filtration, washing and drying to obtain a modified hard carbon product D;
(5) Dispersing the modified hard carbon product D in deionized water, dropwise adding hydrazine hydrate, stirring, carrying out suction filtration and drying to obtain a porous hard carbon anode material;
the modifier in the step (1) is any one of phenolic resin, polyvinylpyrrolidone, acrylic resin and polyethylene glycol; the pore-forming agent is any one of sodium chloride, sodium carbonate, sodium acetate, potassium chloride, potassium carbonate, potassium acetate and calcium chloride; the cross-linking agent is any one of gamma-aminopropyl triethoxysilane, phytic acid, dopamine hydrochloride, cetyl trimethyl ammonium bromide and phthalic dicarboxaldehyde;
the mass volume ratio of the modifier to the ethanol in the step (1) is (2-10) g, 100: 100 mL; the mass ratio of the modifier to the asphalt powder is (0.2-1): 1; the mass ratio of the pore-forming agent to the asphalt powder is (0.1-0.3): 1; the mass ratio of the cross-linking agent to the asphalt powder is (0.05-0.2): 1; the sanding treatment time is 0.5-3 h, the rotating speed is 1500-3000 r/min, and the used sanding beads are zirconium oxide beads; the zirconia beads have a particle size of 0.1 to 0.5. 0.5 mm.
2. The method for preparing the pitch-based porous hard carbon anode material according to claim 1, wherein: the asphalt in the step (1) is coal-based asphalt or petroleum asphalt with a softening point of 200-300 ℃; the particle size D50 of the asphalt powder is 100-500 mu m; the asphalt powder has a particle size D50 of 200-500 nm after sanding.
3. The method for preparing the pitch-based porous hard carbon anode material according to claim 1, wherein: the spray pressure of the spray drying treatment in the step (2) is 0.2 Mpa and the temperature is 180 ℃; the granularity D50 of the hard carbon precursor powder B is 8-15 mu m.
4. The method for preparing the pitch-based porous hard carbon anode material according to claim 1, wherein: the temperature of the pre-oxidation treatment in the step (3) is 300-400 ℃, the temperature rising rate is 2-5 ℃/min, and the heat preservation time is 1-3 h; the high-temperature carbonization treatment temperature is 1200-1400 ℃, the temperature rising rate is 2-10 ℃/min, and the heat preservation time is 2-4 h.
5. The method for preparing the pitch-based porous hard carbon anode material according to claim 1, wherein: the strong acid in the step (4) is concentrated sulfuric acid or concentrated nitric acid; the oxidation treatment is specifically that strong acid is added into the hard carbon material C according to the mass volume ratio of 1g (5-15) mL, then stirring is carried out for 0.5-4 h, and deionized water is added for dilution; the volume ratio of the strong acid to the deionized water is 1 (10-20).
6. The method for preparing the pitch-based porous hard carbon anode material according to claim 1, wherein: the mass of the modified hard carbon product D in the step (5) is 10-50% of the mass of deionized water; the mass ratio of the hydrazine hydrate to the modified hard carbon product D is (0.1-0.5): 1; the hydrazine hydrate treatment time is 10-30 min.
7. A porous, pitch-based hard carbon anode material prepared by the method of any one of claims 1-6.
8. Use of the pitch-based porous hard carbon anode material of claim 7 in the preparation of sodium ion batteries.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211662760.XA CN115676804B (en) | 2022-12-23 | 2022-12-23 | Porous hard carbon anode material based on asphalt, and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211662760.XA CN115676804B (en) | 2022-12-23 | 2022-12-23 | Porous hard carbon anode material based on asphalt, and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115676804A CN115676804A (en) | 2023-02-03 |
| CN115676804B true CN115676804B (en) | 2024-01-30 |
Family
ID=85056112
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211662760.XA Active CN115676804B (en) | 2022-12-23 | 2022-12-23 | Porous hard carbon anode material based on asphalt, and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115676804B (en) |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101186292A (en) * | 2006-11-22 | 2008-05-28 | 辽宁工程技术大学 | Method for preparing carbon cathode material and lithium iron battery using the material |
| CN107732240A (en) * | 2017-09-05 | 2018-02-23 | 合肥工业大学 | The preparation method of anode material of lithium-ion battery, and negative material prepared therefrom |
| CN108807892A (en) * | 2018-06-06 | 2018-11-13 | 郑州中科新兴产业技术研究院 | A kind of preparation method of asphaltic base silicon-carbon nanometer sheet lithium cell negative pole material |
| CN110504413A (en) * | 2018-05-16 | 2019-11-26 | 宝山钢铁股份有限公司 | A kind of nitrogen doped silicon carbosphere and its manufacturing method |
| CN113800496A (en) * | 2021-08-06 | 2021-12-17 | 深圳市德方纳米科技股份有限公司 | Hard carbon material and preparation method and application thereof |
| CN114715936A (en) * | 2022-04-18 | 2022-07-08 | 鸡西市唯大新材料科技有限公司 | Negative electrode NaSbS of lithium or sodium ion battery2Preparation method of @ C composite material |
| CN115036473A (en) * | 2022-05-19 | 2022-09-09 | 福州大学 | Hard carbon precursor and doped phase-based sodium ion battery negative electrode material and preparation method thereof |
| CN115911320A (en) * | 2022-11-22 | 2023-04-04 | 中国科学院深圳先进技术研究院 | Composite hard carbon material and preparation method and application thereof |
-
2022
- 2022-12-23 CN CN202211662760.XA patent/CN115676804B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101186292A (en) * | 2006-11-22 | 2008-05-28 | 辽宁工程技术大学 | Method for preparing carbon cathode material and lithium iron battery using the material |
| CN107732240A (en) * | 2017-09-05 | 2018-02-23 | 合肥工业大学 | The preparation method of anode material of lithium-ion battery, and negative material prepared therefrom |
| CN110504413A (en) * | 2018-05-16 | 2019-11-26 | 宝山钢铁股份有限公司 | A kind of nitrogen doped silicon carbosphere and its manufacturing method |
| CN108807892A (en) * | 2018-06-06 | 2018-11-13 | 郑州中科新兴产业技术研究院 | A kind of preparation method of asphaltic base silicon-carbon nanometer sheet lithium cell negative pole material |
| CN113800496A (en) * | 2021-08-06 | 2021-12-17 | 深圳市德方纳米科技股份有限公司 | Hard carbon material and preparation method and application thereof |
| CN114715936A (en) * | 2022-04-18 | 2022-07-08 | 鸡西市唯大新材料科技有限公司 | Negative electrode NaSbS of lithium or sodium ion battery2Preparation method of @ C composite material |
| CN115036473A (en) * | 2022-05-19 | 2022-09-09 | 福州大学 | Hard carbon precursor and doped phase-based sodium ion battery negative electrode material and preparation method thereof |
| CN115911320A (en) * | 2022-11-22 | 2023-04-04 | 中国科学院深圳先进技术研究院 | Composite hard carbon material and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115676804A (en) | 2023-02-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108598414B (en) | Amorphous zinc oxide/carbon composite lithium ion battery cathode material and preparation method thereof | |
| CN106711461A (en) | Spherical porous silicon/carbon composite material as well as preparation method and application thereof | |
| CN104617281A (en) | Method for preparing sodium-ion battery antimony/nitrogen-doped carbon nanosheet negative electrode composite material | |
| CN108063233A (en) | A kind of silicon-carbon cathode material and preparation method thereof | |
| CN108448080A (en) | A kind of graphene coated silicon/metal composite negative pole material and preparation method thereof | |
| CN108899530B (en) | Silicon-carbon composite material and preparation method and application thereof | |
| CN108878826B (en) | Sodium manganate/graphene composite electrode material and preparation method and application thereof | |
| CN110668418B (en) | Preparation method of hard carbon microspheres with high specific capacitance | |
| CN108682813A (en) | A kind of preparation method and application of Si-C composite material | |
| CN110395728B (en) | Preparation method of porous carbon sphere negative electrode material for lithium battery | |
| CN114044508B (en) | Hard carbon microsphere and preparation method and application thereof | |
| CN111320161A (en) | Preparation method and application of asphalt-based carbon nanosheet | |
| CN114702022A (en) | Preparation method and application of hard carbon negative electrode material | |
| CN112086642B (en) | Graphitized carbon-coated high-specific-surface-area porous carbon sphere and preparation method and application thereof | |
| CN113436905A (en) | Preparation method of carbon/nickel oxide composite electrode material | |
| CN111933908A (en) | Gamma irradiation regulated and controlled popcorn hard carbon/SnP3Method for preparing sodium ion battery cathode by composite material | |
| CN115676804B (en) | Porous hard carbon anode material based on asphalt, and preparation method and application thereof | |
| CN114944480B (en) | Preparation method of honeycomb porous tin-carbon composite material | |
| CN115440982A (en) | High-performance silicon-carbon negative electrode material for lithium battery and preparation method thereof | |
| CN106784759A (en) | A kind of silicon/activated carbon composite negative pole material and preparation method thereof | |
| CN112952070A (en) | Graphite lithium battery negative electrode material and preparation method thereof | |
| CN115332507B (en) | Carbon-coated sodium iron phosphate composite electrode material and preparation and application thereof | |
| CN114068923A (en) | Modification method of graphite and application of graphite in lithium ion battery | |
| CN111987298B (en) | Method for compounding lithium battery silicon carbon by using homogenizer and lithium battery silicon carbon cathode | |
| CN116344779B (en) | Lithium battery composite negative electrode material and lithium battery |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |