CN112758911A - Hard carbon material, preparation method and application thereof, and lithium ion battery - Google Patents
Hard carbon material, preparation method and application thereof, and lithium ion battery Download PDFInfo
- Publication number
- CN112758911A CN112758911A CN202011643725.4A CN202011643725A CN112758911A CN 112758911 A CN112758911 A CN 112758911A CN 202011643725 A CN202011643725 A CN 202011643725A CN 112758911 A CN112758911 A CN 112758911A
- Authority
- CN
- China
- Prior art keywords
- precursor
- temperature
- hard carbon
- carbon material
- solvent
- 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.)
- Granted
Links
- 229910021385 hard carbon Inorganic materials 0.000 title claims abstract description 58
- 239000003575 carbonaceous material Substances 0.000 title claims abstract description 57
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 238000010438 heat treatment Methods 0.000 claims abstract description 44
- 239000002243 precursor Substances 0.000 claims abstract description 32
- 238000000034 method Methods 0.000 claims abstract description 22
- 239000007788 liquid Substances 0.000 claims abstract description 21
- 239000002002 slurry Substances 0.000 claims abstract description 21
- 238000001694 spray drying Methods 0.000 claims abstract description 17
- 239000002994 raw material Substances 0.000 claims abstract description 13
- 238000002156 mixing Methods 0.000 claims abstract description 5
- 238000010000 carbonizing Methods 0.000 claims abstract description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 50
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 26
- 239000002904 solvent Substances 0.000 claims description 20
- 229910052799 carbon Inorganic materials 0.000 claims description 18
- 238000003763 carbonization Methods 0.000 claims description 18
- 239000007789 gas Substances 0.000 claims description 18
- 239000010426 asphalt Substances 0.000 claims description 16
- 239000003960 organic solvent Substances 0.000 claims description 15
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical group CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 14
- 229910002804 graphite Inorganic materials 0.000 claims description 14
- 239000010439 graphite Substances 0.000 claims description 14
- 239000002245 particle Substances 0.000 claims description 14
- 238000004321 preservation Methods 0.000 claims description 13
- 239000004215 Carbon black (E152) Substances 0.000 claims description 10
- 239000006258 conductive agent Substances 0.000 claims description 10
- 229930195733 hydrocarbon Natural products 0.000 claims description 10
- 150000002430 hydrocarbons Chemical class 0.000 claims description 10
- 239000003999 initiator Substances 0.000 claims description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 9
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 claims description 8
- 239000003849 aromatic solvent Substances 0.000 claims description 8
- 239000003431 cross linking reagent Substances 0.000 claims description 8
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 7
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium peroxydisulfate Substances [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 7
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 claims description 7
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 7
- 239000005011 phenolic resin Substances 0.000 claims description 7
- 229920001568 phenolic resin Polymers 0.000 claims description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 6
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 6
- 150000002978 peroxides Chemical class 0.000 claims description 6
- 230000001681 protective effect Effects 0.000 claims description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 5
- 239000002041 carbon nanotube Substances 0.000 claims description 5
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 5
- 239000002270 dispersing agent Substances 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 claims description 4
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims description 4
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical group N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 4
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 4
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims description 4
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 claims description 4
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 claims description 4
- 239000006185 dispersion Substances 0.000 claims description 4
- 125000000623 heterocyclic group Chemical group 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 239000000178 monomer Substances 0.000 claims description 4
- 239000012934 organic peroxide initiator Substances 0.000 claims description 4
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 claims description 4
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 4
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 4
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 4
- 229920000428 triblock copolymer Polymers 0.000 claims description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 4
- 229920002554 vinyl polymer Polymers 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 3
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 3
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 3
- 239000006230 acetylene black Substances 0.000 claims description 3
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 239000012530 fluid Substances 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 239000011269 tar Substances 0.000 claims description 3
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 claims description 3
- WVAFEFUPWRPQSY-UHFFFAOYSA-N 1,2,3-tris(ethenyl)benzene Chemical compound C=CC1=CC=CC(C=C)=C1C=C WVAFEFUPWRPQSY-UHFFFAOYSA-N 0.000 claims description 2
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims description 2
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 claims description 2
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 claims description 2
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 claims description 2
- 239000004641 Diallyl-phthalate Substances 0.000 claims description 2
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 claims description 2
- 239000011837 N,N-methylenebisacrylamide Substances 0.000 claims description 2
- 239000003570 air Substances 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- QUDWYFHPNIMBFC-UHFFFAOYSA-N bis(prop-2-enyl) benzene-1,2-dicarboxylate Chemical compound C=CCOC(=O)C1=CC=CC=C1C(=O)OCC=C QUDWYFHPNIMBFC-UHFFFAOYSA-N 0.000 claims description 2
- 239000001273 butane Substances 0.000 claims description 2
- 239000013256 coordination polymer Substances 0.000 claims description 2
- 239000003822 epoxy resin Substances 0.000 claims description 2
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 claims description 2
- 229910021389 graphene Inorganic materials 0.000 claims description 2
- 239000003350 kerosene Substances 0.000 claims description 2
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 claims description 2
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 239000003208 petroleum Substances 0.000 claims description 2
- 229920000647 polyepoxide Polymers 0.000 claims description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 2
- 229920005989 resin Polymers 0.000 claims description 2
- 239000011347 resin Substances 0.000 claims description 2
- 238000012216 screening Methods 0.000 claims description 2
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 2
- 125000003944 tolyl group Chemical group 0.000 claims description 2
- 229910001873 dinitrogen Inorganic materials 0.000 claims 1
- 238000009472 formulation Methods 0.000 claims 1
- 239000007773 negative electrode material Substances 0.000 abstract description 7
- 239000011148 porous material Substances 0.000 abstract description 6
- 238000009776 industrial production Methods 0.000 abstract description 5
- 230000001427 coherent effect Effects 0.000 abstract description 4
- 230000002441 reversible effect Effects 0.000 abstract description 3
- 238000000605 extraction Methods 0.000 abstract description 2
- 238000003780 insertion Methods 0.000 abstract description 2
- 230000037431 insertion Effects 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 11
- 239000000463 material Substances 0.000 description 10
- 238000012360 testing method Methods 0.000 description 6
- 230000014759 maintenance of location Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- 239000003990 capacitor Substances 0.000 description 3
- 238000007796 conventional method Methods 0.000 description 3
- 239000011889 copper foil Substances 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000002950 deficient Effects 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000009830 intercalation Methods 0.000 description 2
- 230000002687 intercalation Effects 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 239000013081 microcrystal Substances 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229920006316 polyvinylpyrrolidine Polymers 0.000 description 2
- 238000007493 shaping process Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 238000004438 BET method Methods 0.000 description 1
- 239000004971 Cross linker Substances 0.000 description 1
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- -1 polypropylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 238000009656 pre-carbonization Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000007348 radical reaction Methods 0.000 description 1
- 239000002109 single walled nanotube Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Inorganic Chemistry (AREA)
- Power Engineering (AREA)
- Organic Chemistry (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Manufacturing & Machinery (AREA)
- Carbon And Carbon Compounds (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a hard carbon material, a preparation method and application thereof, and a lithium ion battery. The preparation method comprises the following steps: (1) mixing and heating the raw materials of the precursor A to obtain liquid slurry; spray drying the liquid slurry to obtain a precursor A; (2) curing the precursor A to obtain a precursor B; wherein the curing treatment sequentially comprises; performing primary heat treatment at the temperature of 150-350 ℃; performing secondary heat treatment at the temperature of 360-420 ℃; performing third-stage heat treatment at the temperature of 450-650 ℃; (3) and carbonizing the precursor B. The hard carbon material has stable quality, reasonable pore channel structure and lower resistivity, is convenient for the insertion and the extraction of lithium ions, and has high reversible capacity, better heavy current performance, excellent cycle performance and high first discharge efficiency when being used as a negative electrode material of a lithium ion battery; the preparation method is simple, the process flow is coherent, and the method can be used for industrial production.
Description
Technical Field
The invention relates to a hard carbon material, a preparation method and application thereof, and a lithium ion battery.
Background
With the development of electronic power technology, secondary batteries cannot meet increasingly stringent requirements because of the difficulty in overcoming their disadvantages. Therefore, lithium ion batteries with high energy density, strong environmental adaptability and long cycle life gradually become widely used electrochemical power sources, and are continuously developed in the fields of microelectronics, wearable equipment, mobile terminals, power storage, transportation and the like.
The conventional lithium ion battery adopts a graphite negative electrode material, but the rapid lithium ion intercalation capability is weaker due to the lattice structure of graphite, so that the rapid charging capability of the lithium ion battery taking the graphite as the negative electrode material is poorer. The hard carbon material has a tiny domain similar to a graphite crystal, and has disordered stacking and pore channel structures of a defective graphite layer, so that solvated lithium ions can be rapidly diffused to the surface of graphite microcrystals in the hard carbon material, the diffusion resistance and the migration distance of the lithium ions are greatly reduced, and the lithium ions can be rapidly embedded into the graphite microcrystals and adsorbed in the disordered stacking pore channels of the tiny defective graphite layer. Therefore, compared with graphite, the hard carbon material is more suitable for serving as a lithium ion battery cathode material, the rapid charging capability is improved, the hard carbon material can be used under a low-temperature condition, and meanwhile, the composite ion adsorption of a lithium ion capacitor can be met.
In patent CN1947286A, porous asphalt is prepared by a crosslinking reaction method, and then a hard carbon material which is difficult to graphitize is prepared by air oxidation; however, the preparation method has complex steps, long process route and high cost, and is not suitable for industrial production. The patent CN10301127A discloses that asphalt with a softening point of 200-280 ℃ is used as a raw material, the raw material is crushed and then is added into a tube furnace to be heated and solidified in the air atmosphere, the solidified asphalt powder is added into a carbonization furnace to be heated to 700-1300 ℃ for carbonization treatment, and an asphalt hard carbon material is obtained; although the preparation method has simple process, the batch preparation samples are fewer, and meanwhile, the preparation process needs more factors to be controlled, which is not favorable for stable production.
Therefore, it is desirable to provide a hard carbon material with better electrochemical performance, simple process and stable production, and a preparation method thereof.
Disclosure of Invention
The invention aims to overcome the defects of poor electrochemical performance, long process flow, complex technical route and unstable batch of the hard carbon material in the prior art, and provides the hard carbon material, a preparation method and application thereof and a lithium ion battery. The hard carbon material has stable quality, reasonable pore channel structure and lower resistivity, is convenient for the insertion and the extraction of lithium ions, and has high reversible capacity, better heavy current performance, excellent cycle performance and high first discharge efficiency when being used as a negative electrode material of a lithium ion battery; the preparation method is simple, the process flow is coherent, and the method can be used for industrial production.
In order to achieve the purpose, the invention provides the following technical scheme:
one of the technical schemes provided by the invention is as follows: a preparation method of a hard carbon material comprises the following steps:
(1) mixing and heating the raw materials of the precursor A to obtain liquid slurry; then carrying out spray drying on the liquid slurry to obtain a precursor A;
wherein the raw materials of the precursor A comprise a carbon source, an organic solvent and a cross-linking agent; the temperature of the spray drying is 80-150 ℃;
(2) curing the precursor A to obtain a precursor B;
wherein the curing treatment sequentially comprises: performing primary heat treatment at the temperature of 150-350 ℃; performing secondary heat treatment at the temperature of 360-420 ℃; performing third-stage heat treatment at the temperature of 450-650 ℃;
(3) and carbonizing the precursor B.
In the step (1), the carbon residue value of the carbon source is more than 30%.
The carbon source can be one or more of asphalt, tar, petroleum resin, phenolic resin and epoxy resin; preferably bitumen.
The softening point of the asphalt can be 200-300 ℃.
The phenolic resin may have a carbon residue value of 50% or more.
In the step (1), the organic solvent may be one or more of an aromatic solvent, an aliphatic hydrocarbon or a homologue thereof, an aliphatic alcohol solvent, and a heterocyclic substance or a homologue thereof; preferably, the solvent is a mixture of an aromatic solvent and an aliphatic hydrocarbon solvent.
The aromatic solvent may be one or more of benzene, naphthalene, anthracene, phenanthrene, and homologs thereof. The aliphatic hydrocarbon or its homologue solvent may be one or more of butane, pentane, hexane, heptane, naphtha, light hydrocarbon gas, wash oil and kerosene. Wherein, the light hydrocarbon gas is also called condensate as known to those skilled in the art. The light hydrocarbon gas can be petrochemical light hydrocarbon gas and/or coal chemical light hydrocarbon gas.
The aliphatic alcohol solvent may be one or more of methanol, ethanol, propanol and butanol. The heterocyclic substance or homologue thereof solvent may be one or more of furan, pyrrole and quinoline.
The organic solvent can be a compound of aromatic solvent and aliphatic hydrocarbon solvent.
The organic solvent is preferably the compound of naphthalene, wash oil and petrochemical light hydrocarbon gas; the content of naphthalene is preferably 10-30%, the content of wash oil is preferably 30-50%, and the content of petrochemical light hydrocarbon gas is preferably 30-50%; the percentage is the mass percentage of each component in the organic solvent.
The organic solvent is preferably the compound of naphthalene and wash oil; wherein the content of naphthalene is preferably 70-90%, and the content of wash oil is preferably 10-30%; the percentage is the mass percentage of each component in the organic solvent.
In step (1), the amount of the cross-linking agent may be conventional in the art; for example, the crosslinking agent accounts for 10 to 100 mass% of the carbon source in terms of the carbon residue value of the carbon source.
The cross-linking agent can be one or more of multifunctional vinyl monomer, azo initiator, organic peroxide initiator and inorganic peroxide initiator; preferably an inorganic peroxide initiator.
The polyfunctional vinyl monomer may undergo a crosslinking reaction by a radical reaction, and may be generally one or more of divinylbenzene, trivinylbenzene, diallyl phthalate, ethylene glycol dimethacrylate and N, N-methylenebisacrylamide.
The azo initiator may be azobisisobutyronitrile.
The organic peroxide initiator may be one or more of Benzoyl Peroxide (BPO), lauroyl peroxide, cumene hydroperoxide, dicumyl peroxide and t-butyl hydroperoxide.
The inorganic peroxide initiator can be one or more of ammonium persulfate, potassium persulfate, sodium persulfate, hydrogen peroxide, air and oxygen; ammonium persulfate and air are preferred.
In the step (1), the raw material of the precursor a may further include a pore-forming agent.
Wherein the pore former can generally be a material that is incompatible with the carbon source; preferably a phenolic resin.
The pore-forming agent may also be a material that has a significant difference in carbon residue from the carbon source, such as polyvinylpyrrolidone or a polyoxyethylene-polyoxypropylene-polyoxyethylene triblock copolymer. Preferably, the carbon source is asphalt, and the pore-forming agent is polyvinylpyrrolidone; or the carbon source is tar, and the pore-forming agent is a polyoxyethylene-polyoxypropylene-polyoxyethylene triblock copolymer (F127).
In the step (1), the raw material of the precursor a may further include a conductive agent for enhancing the conductive capability of the hard carbon material.
The conductive agent can be one or more of conductive graphite, graphite micropowder, carbon nanotubes, graphene and acetylene black; carbon nanotubes are preferred.
The conductive agent is generally dispersible in the dispersant to provide a conductive agent dispersion. The dispersant is preferably N, N dimethylformamide. Such as a carbon nanotube-N, N Dimethylformamide (DMF) dispersion.
In the step (1), the viscosity of the liquid slurry can be 10000-100000 CP.
Wherein the viscosity of the liquid slurry is generally adjusted by adding a solvent before the spray-drying. The solvent is preferably toluene or wash oil. The viscosity of the liquid slurry is typically less than 80% of the maximum allowable viscosity of the spray drying apparatus.
In the step (1), the adding sequence of the components in the raw materials of the precursor A can be any sequence during the mixing.
In the step (1), the heating temperature can be lower than the decomposition temperature of any one component in the raw materials of the precursor A; generally, the temperature is 40 to 120 ℃, preferably 50 to 90 ℃, and more preferably 80 ℃.
The heated device may be a pressure vessel. The pressure of the pressure vessel may be 8Mpa or less.
The holding time for heating can be conventional in the art, for example, 3 to 8 hours, preferably 6 hours.
In the step (1), the pressure of the spray drying can be 0.1-1 MPa.
The apparatus for spray drying may be conventional in the art, and is preferably an apparatus comprising a three-fluid atomising nozzle and a drying tower.
In the step (1), the temperature of the spray drying is preferably 120-140 ℃.
The heat preservation time of the spray drying can be 1-8 hours, and preferably 2 hours.
In the step (1), the shape of the precursor a is preferably spherical. The particle size D50 of the precursor A is preferably 5-15 μm. The particle size D90/D10 of the precursor A is preferably less than 15.
In the step (2), the temperature of the first-stage heat treatment is preferably 170 ℃. The temperature of the second stage heat treatment is preferably 360 ℃. The temperature of the third stage heat treatment is preferably 600 ℃.
The time of the first-stage heat treatment can be 1-8 hours, and preferably 4 hours. The time of the second-stage heat treatment can be 1-8 hours, and preferably 3 hours. The time of the third-stage heat treatment can be 1-8 hours, and preferably 2 hours.
The first stage heat treatment enables the materials to be crosslinked and solidified. And the second-stage heat treatment is used for oxidizing and shaping the material. And the third-stage heat treatment pre-carbonizes the material and removes volatile matters and impurity atoms in the organic matters.
In step (3), the carbonization treatment may be conventional in the art.
The temperature of the carbonization treatment can be 900-1500 ℃, and is preferably 900-1200 ℃. The temperature rise mode can be temperature program rise, and the temperature program rise speed can be 1-5 ℃/min.
The carbonization treatment time can be 1-6 hours.
The carbonization treatment may be carried out under a protective gas. Wherein, the protective gas can be inert gas, nitrogen or reducing gas. The inert gas is preferably argon. The flow rate of the protective gas is preferably 0.001-0.05L/(Kg & min).
The carbonization treatment may be vacuum carbonization. Wherein the negative pressure of the vacuum carbonization is less than or equal to 100 Pa.
The equipment for the carbonization treatment may be conventional in the art, and is preferably kiln equipment, such as a rotary kiln, a tube furnace, a box furnace, a pusher kiln, a tunnel kiln or a roller kiln.
In the step (3), it is preferable to further include a step of classifying or screening the carbonized product.
The second technical scheme provided by the invention is as follows: a hard carbon material is prepared by the preparation method of the hard carbon material.
Wherein the particle size D50 of the hard carbon material can be 5-30 μm; preferably 6-20 μm; more preferably 8 to 16 μm; for example 8.2. mu.m, 8.3. mu.m, 8.6. mu.m, 11.1. mu.m or 15.3. mu.m.
The specific surface area of the hard carbon material can be 3-10 m2(ii)/g; preferably 3 to 8m2(ii)/g; more preferably 3 to 7m2(ii)/g; for example 3.3m2/g、5.8m2/g、6.2m2G or 6.5m2/g。
The third technical scheme provided by the invention is as follows: an application of the hard carbon material in a lithium ion battery or a super capacitor.
Wherein the supercapacitor may be an asymmetric supercapacitor.
The fourth technical scheme provided by the invention is as follows: an electrode comprising a hard carbon material as hereinbefore described.
The preparation method of the electrode can be a conventional method in the field. The electrode is preferably a negative electrode.
The fifth technical scheme provided by the invention is as follows: a lithium ion battery comprising an electrode as hereinbefore described.
The preparation method of the lithium ion battery can be a conventional method in the field.
On the basis of the common knowledge in the field, the above preferred conditions can be combined randomly to obtain the preferred embodiments of the invention.
The reagents and starting materials used in the present invention are commercially available.
The positive progress effects of the invention are as follows:
(1) the hard carbon material has a sphere-like structure, reasonable particle size distribution, smooth and mellow surface, good fluidity and small specific surface area (6.5 m)2Below/g); the pore size structure is reasonable, and mesopores in the particles facilitate the infiltration of electrolyte and the rapid arrival of lithium ions at the negative electrode material, so that the rapid lithium ion intercalation and deintercalation are carried out; the microporous structure in the particles is beneficial to improving the adsorption of lithium ions, so that the specific capacity of the negative electrode material is improved;
when the hard carbon material is used as a lithium ion battery cathode material, the reversible capacity is high (the first charge capacity is as high as more than 402 mAh/g), the heavy current performance is good (the 3C rapid discharge constant current ratio is as high as more than 52%), the cycle performance is excellent (the capacity retention rate is as high as more than 98.8% after 100 cycles), and the first discharge efficiency is high (more than 81.6%).
(2) The hard carbon material can be compatible with the existing lithium ion battery industrial system and super capacitor industrial system, and can be directly used instead.
(3) The preparation method of the hard carbon material is simple, the process flow is coherent, and the hard carbon material can be used for industrial production.
Drawings
Fig. 1 is an SEM image of the hard carbon material prepared in example 1.
Fig. 2 is an XRD pattern of the hard carbon material prepared in example 1.
Detailed Description
The invention is further illustrated by the following examples, which are not intended to limit the scope of the invention. The experimental methods without specifying specific conditions in the following examples were selected according to the conventional methods and conditions, or according to the commercial instructions. All materials were commercially available without further processing.
In the following examples and comparative examples:
the asphalt adopts 220 ℃ high-softening-point asphalt, the organic solvent adopts 30% of naphthalene and 70% of tetrahydrofuran, the cross-linking agent adopts ammonium persulfate, the pore-forming agent adopts polyvinylpyrrolidone K30, the conductive agent is a single-walled carbon nanotube, the dispersing agent is N, N dimethylformamide, wherein the mass percentage of the carbon nanotube in the carbon nanotube-N, N dimethylformamide dispersion liquid is 0.2%
Example 1
Step (1): preparing liquid slurry according to the following weight ratio, wherein the asphalt comprises the following components in parts by weight: naphthalene: oil washing: ammonium persulfate: polyvinylpyrrolidone K30: single-walled carbon nanotubes (swnts) 100:100:20:50:10: 0.1.
And transferring the liquid slurry into a pressure container to heat at 80 ℃, continuously stirring for 6 hours, then reducing the temperature to room temperature, and adjusting the viscosity of the liquid slurry to 50000CP by using toluene after the temperature of the liquid slurry is reduced to room temperature to obtain the liquid slurry with the adjusted viscosity.
Spraying the liquid slurry with the viscosity adjusted by a three-fluid atomizing nozzle to enable the particle size of sprayed droplets to be about 9 microns;
putting the sprayed fog drops into a hot air tower at the temperature of 120 ℃ for drying, and keeping the temperature for 2 hours; obtaining a precursor A.
Step (2): curing the precursor A obtained in the step (1) to obtain a precursor B;
wherein, a rotary furnace is adopted for curing treatment. Wherein the temperature of the first-stage heat treatment is 170 ℃, and the heat preservation time is 4 hours; the temperature of the second-stage heat treatment is 360 ℃, and the heat preservation time is 3 hours; the temperature of the third-stage heat treatment is 600 ℃, and the heat preservation time is 2 hours.
The revolution speed was 10 revolutions per minute and the air flow rate was 0.3L/(Kg min).
And (3): and carbonizing in an atmosphere furnace. Wherein the flow rate of the nitrogen atmosphere is 0.05L/(Kg min), the temperature is raised to 1000 ℃ at 4 ℃/min, the heat preservation is finished for 3 hours, and the hard carbon material is obtained after the temperature is naturally reduced to the room temperature.
Example 2
Step (1): the particle size of the sprayed fog drops is about 12 mu m; the rest of the procedure was the same as in example 1.
Step (2): the heat preservation time of the first-stage heat treatment is 2 hours; the heat preservation time of the second-stage heat treatment is 2 hours; the heat preservation time of the third-stage heat treatment is 1 hour; the rest of the procedure was the same as in example 1.
And (3): the same as in example 1.
Example 3
Step (1): preparing liquid slurry according to the following weight ratio, wherein the asphalt comprises the following components in parts by weight: naphthalene: oil washing: ammonium persulfate is 100:100:20: 50; the rest of the procedure was the same as in example 2.
Step (2): the same as in example 2.
And (3): the same as in example 1.
Comparative example 1
The phenolic resin is crushed into powder with the grain diameter D50 of 9 mu m, and then the powder is directly carbonized by an atmosphere furnace, the flow rate of nitrogen atmosphere is 0.05L/(Kg min), the temperature is raised to 1000 ℃ at 4 ℃/min, and the heat preservation is finished for 3 hours. Naturally cooling to room temperature, and discharging to obtain the hard carbon material.
Comparative example 2
Step (1): the same as in example 1.
Step (2): secondary heat treatment is carried out by adopting a rotary furnace. Wherein the temperature of the first-stage heat treatment is 360 ℃, and the heat preservation time is 3 hours; the temperature of the second-stage heat treatment is 600 ℃, and the heat preservation time is 2 hours; the rest of the procedure was the same as in example 1.
And (3): the same as in example 1.
Comparative example 3
Step (1): the same as in example 1.
Step (2): the temperature of the second-stage heat treatment is 500 ℃; the rest of the procedure was the same as in example 1.
And (3): the same as in example 1.
Effect example 1
The hard carbon materials prepared in the above examples and comparative examples were subjected to the following performance tests using a method conventional in the art.
(1) The particle size D50 of the hard char material was measured using Mastersize 2000 (Malvern 2000) and the results are given in Table 1.
(2) The specific surface area of the hard carbon material was measured by the BET method which is conventional in the art, and the results are shown in table 1.
(3) And measuring an SEM image of the hard carbon material by adopting a ZEISS 500 field emission scanning electron microscope. The SEM image of the hard carbon material obtained in example 1 is shown in fig. 1. As can be seen from FIG. 1, the hard carbon material obtained in example 1 has a high sphericity, a smooth surface, and no particle blocking or surface roughness, protrusions, pits, cracks, etc.
(4) The XRD pattern of the hard carbon material prepared in example 1 was measured using a Brookfield D8X-ray diffractometer (scanning pattern. theta. -2. theta., step 2 °/s), and the result is shown in FIG. 2. As can be seen from fig. 2, the diffraction pattern of the hard carbon material obtained in example 1 was consistent with that of typical hard carbon, and no impurity and dry diffraction peaks were observed.
Effect example 2
(1) Preparation of the electrodes
Respectively mixing the hard carbon materials prepared in the above examples or comparative examples with an acetylene black conductive agent and a PVDF binder according to a mass ratio of 8:1:1 at room temperature, and taking NMP as a solvent to prepare uniform slurry, uniformly coating the slurry on a copper foil, wherein the coating surface density is about 6mg/cm2Then the copper foil is put into a vacuum drying oven to be dried for 12 hours at the temperature of 80 ℃. Cutting the dried copper foil into 2cm in area2The wafer of (a) is made into a working electrode.
(2) Button type assembly
Under the condition of room temperature, taking a metal lithium sheet as a negative electrode and a counter electrode, taking the product obtained in the step (1) as a working electrode, taking a Celgard2400 polypropylene porous membrane as a diaphragm, and taking 1mol/L LiPF6The electrolyte solution of EC and DEC (volume ratio of 1: 1) is assembled into a CR-2032 type button cell in a vacuum glove box, and is sealed mechanically.
(3) Specific capacity and capacity retention rate test
Electrochemical testing was started after the assembled cell was allowed to stand at room temperature for 24 h. On an Arbin battery test system, according to the design capacity of 400mAh/g, the current of 0.1C is adopted in the first test cycle, and the charging and discharging voltage interval is 0 mV-2V. The mixture was left for 5 minutes after the completion of the charge or discharge. The button cell 3C rapid discharge constant current ratio test adopts the button cell after 3 weeks of 0.1C circulation, firstly carries out 0.1C charge to 2V, then uses 3C to discharge to 5mV to obtain the capacity a, and then uses 0.1C to discharge to 5mV to obtain the capacity b. The 3C fast discharge constant current ratio is a/(a + b) × 100%. After 100 cycles, the capacity retention rate adopts a constant current of 0.5C to carry out charge-discharge cycle. Capacity retention after 100 cycles was 103 th charge capacity/third charge capacity 100%.
Through tests, the capacity of the quick-charging graphite prepared in the above examples or comparative examples for a lithium ion battery, the 3C quick-discharge constant current ratio and the effect of capacity retention rate after 1000 cycles are shown in table 1.
TABLE 1
Note: in Table 1, "/" indicates that the resulting material was agglomerated, and the particle diameter D50 could not be measured.
As can be seen from Table 1, the components of the hard carbon materials prepared in the embodiments 1 to 3 are cooperated, so that the hard carbon materials have obvious advantages in specific capacity, first efficiency and 3C rapid discharge constant current ratio. Comparative example 1 no crosslinker was added; the carbonization treatment does not comprise curing treatment, and crosslinking curing, oxidation shaping and pre-carbonization do not occur; from the experimental results, the prepared material has low first charge capacity and first efficiency, and is difficult to apply to the negative electrode material of the commercial lithium battery. Comparative example 2 includes only the first-stage heat treatment and the second-stage heat treatment, and comparative example 3 has a higher temperature for the second-stage heat treatment; from the above experimental results, it can be seen that the materials prepared in comparative examples 2 and 3 were not only lumpy, but also had low initial charge capacity and initial efficiency, and also had poor quick charge performance.
The preparation method of the hard carbon material in the embodiment is simple, the process flow is coherent, the hard carbon material can be used for industrial production, and the problems of complex preparation method, long process route, more control points and the like in the prior art are solved; and the prepared hard carbon material has high capacity, high first efficiency, long cycle life and good quick charging performance.
Claims (10)
1. A preparation method of a hard carbon material comprises the following steps:
(1) mixing and heating the raw materials of the precursor A to obtain liquid slurry; then carrying out spray drying on the liquid slurry to obtain a precursor A;
wherein the raw materials of the precursor A comprise a carbon source, an organic solvent and a cross-linking agent; the temperature of the spray drying is 80-150 ℃;
(2) curing the precursor A to obtain a precursor B;
wherein the curing treatment sequentially comprises; performing primary heat treatment at the temperature of 150-350 ℃; performing secondary heat treatment at the temperature of 360-420 ℃; performing third-stage heat treatment at the temperature of 450-650 ℃;
(3) and carbonizing the precursor B.
2. The method for producing a hard carbon material according to claim 1, wherein in the step (1), the carbon source has a carbon residue value of 30% or more;
and/or the carbon source is one or more of asphalt, tar, petroleum resin, phenolic resin and epoxy resin; preferably bitumen;
wherein the softening point of the asphalt is preferably 200-300 ℃; the carbon residue value of the phenolic resin is preferably more than 50%;
and/or the organic solvent is one or more of aromatic solvent, aliphatic hydrocarbon or homologous compound solvent thereof, aliphatic alcohol solvent and heterocyclic substance or homologous compound solvent thereof; preferably, the aromatic solvent and the aliphatic hydrocarbon solvent are compounded;
wherein, the aromatic solvent is preferably one or more of benzene, naphthalene, anthracene, phenanthrene and homologues thereof; the aliphatic hydrocarbon or the homologous compound solvent thereof is preferably one or more of butane, pentane, hexane, heptane, naphtha, light hydrocarbon gas, wash oil and kerosene;
the aliphatic alcohol solvent is preferably one or more of methanol, ethanol, propanol and butanol; the heterocyclic substances or homologous compound solvents thereof are preferably one or more of furan, pyrrole and quinoline;
preferably, the organic solvent is a compound of an aromatic solvent and an aliphatic hydrocarbon solvent;
more preferably, the organic solvent is the compound of naphthalene, wash oil and petrochemical light hydrocarbon gas; the content of naphthalene is preferably 10-30%, the content of wash oil is preferably 30-50%, and the content of petrochemical light hydrocarbon gas is preferably 30-50%; the percentage is the mass percentage of each component in the organic solvent;
more preferably, the organic solvent is a complex formulation of naphthalene and wash oil; wherein the content of naphthalene is preferably 70-90%, and the content of wash oil is preferably 10-30%; the percentage is the mass percentage of each component in the organic solvent;
and/or the cross-linking agent accounts for 10-100% of the carbon source by mass according to the carbon residue value of the carbon source;
and/or the cross-linking agent is one or more of a multifunctional vinyl monomer, an azo initiator, an organic peroxide initiator and an inorganic peroxide initiator; preferably an inorganic peroxide initiator;
wherein the multifunctional vinyl monomer is preferably one or more of divinylbenzene, trivinylbenzene, diallyl phthalate, ethylene glycol dimethacrylate and N, N-methylenebisacrylamide;
the azo initiator is preferably azobisisobutyronitrile;
the organic peroxide initiator is preferably one or more of benzoyl peroxide, lauroyl peroxide, cumene hydroperoxide, dicumyl peroxide and tert-butyl hydroperoxide;
the inorganic peroxide initiator is preferably one or more of ammonium persulfate, potassium persulfate, sodium persulfate, hydrogen peroxide, air and oxygen; more preferably ammonium persulfate and air.
3. The method for preparing a hard carbon material according to claim 1, wherein in the step (1), the raw material of the precursor a further comprises a pore-forming agent;
the pore-forming agent is preferably one or more of phenolic resin, polyvinylpyrrolidone and polyoxyethylene-polyoxypropylene-polyoxyethylene triblock copolymer;
more preferably, the carbon source is asphalt, and the pore-forming agent is polyvinylpyrrolidone;
or, more preferably, the carbon source is tar, and the pore-forming agent is a polyoxyethylene-polyoxypropylene-polyoxyethylene triblock copolymer;
and/or, in the step (1), the raw material of the precursor A further comprises a conductive agent;
preferably, the conductive agent is one or more of conductive graphite, graphite micropowder, carbon nanotubes, graphene and acetylene black; preferably carbon nanotubes;
preferably, the conductive agent is dispersed in a dispersant to obtain a conductive agent dispersion liquid; the dispersant is preferably N, N-dimethylformamide;
and/or in the step (1), the viscosity of the liquid slurry is 10000-100000 CP;
wherein, before the spray drying, the viscosity of the liquid slurry is preferably adjusted by adding a solvent; the solvent is preferably toluene or wash oil; the viscosity of the liquid slurry is preferably less than 80% of the maximum allowable viscosity of the spray drying apparatus.
4. The method for preparing a hard carbon material according to claim 1, wherein in the step (1), the heating temperature is 40 to 120 ℃, preferably 50 to 90 ℃, and more preferably 80 ℃;
and/or the heated device is a pressure vessel; the pressure of the pressure vessel is preferably below 8 Mpa;
and/or the heating heat preservation time is 3-8 hours, preferably 6 hours;
and/or the pressure of the spray drying is 0.1-1 Mpa;
and/or the spray drying equipment is equipment comprising a three-fluid atomizing nozzle and a drying tower;
and/or the temperature of the spray drying is 120-140 ℃;
and/or the heat preservation time of the spray drying is 1-8 hours, preferably 2 hours;
and/or the shape of the precursor A is spherical;
and/or the particle size D50 of the precursor A is 5-15 μm;
and/or the particle size D90/D10 of the precursor A is less than 15.
5. The method for preparing a hard carbon material according to claim 1, wherein, in the step (2), the temperature of the first-stage heat treatment is 170 ℃;
and/or the temperature of the second stage heat treatment is 360 ℃;
and/or the temperature of the third-stage heat treatment is 600 ℃;
and/or the time of the first-stage heat treatment is 1-8 hours, preferably 4 hours;
and/or the time of the second-stage heat treatment is 1-8 hours, preferably 3 hours;
and/or the time of the third-stage heat treatment is 1-8 hours, preferably 2 hours.
6. The method for preparing a hard carbon material according to claim 1, wherein in the step (3), the temperature of the carbonization treatment is 900 to 1500 ℃, preferably 900 to 1200 ℃;
the temperature rise mode is preferably temperature programming, and the speed of the temperature programming is preferably 1-5 ℃/min;
and/or the carbonization treatment time is 1-6 hours;
and/or the carbonization treatment is carried out under protective gas;
wherein the protective gas is preferably inert gas, nitrogen gas or reducing gas; the inert gas is preferably argon; the flow rate of the protective gas is preferably 0.001-0.05L/(Kg & min);
and/or, the carbonization treatment is vacuum carbonization; the negative pressure of the vacuum carbonization is preferably less than or equal to 100 Pa;
and/or the carbonization treatment equipment is kiln equipment, preferably a rotary furnace, a tubular furnace, a box furnace, a pushed slab kiln, a tunnel kiln or a roller kiln;
and/or, the step (3) also comprises the step of grading or screening the carbonized product.
7. A hard carbon material produced by the method for producing a hard carbon material according to any one of claims 1 to 6;
wherein the particle size D50 of the hard carbon material is preferably 5-30 μm; more preferably 6 to 20 μm; further preferably 8 to 16 μm;
the specific surface area of the hard carbon material is preferably 3-10 m2(ii)/g; more preferably 3 to 8m2(ii)/g; more preferably 3 to 7m2/g。
8. Use of the hard carbon material of claim 7 in a lithium ion battery or supercapacitor; the supercapacitor is preferably an asymmetric supercapacitor.
9. An electrode comprising the hard carbon material of claim 7, preferably a negative electrode.
10. A lithium ion battery comprising an electrode according to claim 9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011643725.4A CN112758911B (en) | 2020-12-31 | 2020-12-31 | Hard carbon material, preparation method and application thereof, and lithium ion battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011643725.4A CN112758911B (en) | 2020-12-31 | 2020-12-31 | Hard carbon material, preparation method and application thereof, and lithium ion battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112758911A true CN112758911A (en) | 2021-05-07 |
| CN112758911B CN112758911B (en) | 2023-02-10 |
Family
ID=75698654
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011643725.4A Active CN112758911B (en) | 2020-12-31 | 2020-12-31 | Hard carbon material, preparation method and application thereof, and lithium ion battery |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112758911B (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114368739A (en) * | 2021-12-28 | 2022-04-19 | 上海杉杉科技有限公司 | Hard carbon material, preparation method thereof, electrode, battery and application |
| CN114702022A (en) * | 2022-03-15 | 2022-07-05 | 广东邦普循环科技有限公司 | Preparation method and application of hard carbon negative electrode material |
| CN115215321A (en) * | 2022-07-26 | 2022-10-21 | 华南理工大学 | Preparation method and application of hard carbon microsphere material |
| CN115838165A (en) * | 2022-12-29 | 2023-03-24 | 赣州立探新能源科技有限公司 | Hard carbon negative electrode material, preparation method thereof and secondary battery |
| WO2023087129A1 (en) * | 2021-11-16 | 2023-05-25 | 宁波杉杉新材料科技有限公司 | Preparation method for carbon electrode material and carbon electrode material |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102479942A (en) * | 2010-11-30 | 2012-05-30 | 上海杉杉科技有限公司 | Hard carbon negative electrode material, its preparation method and application |
| CN106099109A (en) * | 2016-06-22 | 2016-11-09 | 大连理工大学 | A kind of preparation method and applications of asphaltic base hard charcoal nanometer sheet |
| CN106532009A (en) * | 2016-12-21 | 2017-03-22 | 上海杉杉科技有限公司 | Preparation method of high capacity lithium ion battery hard carbon composite negative electrode material |
| WO2020200812A1 (en) * | 2019-04-02 | 2020-10-08 | Heraeus Battery Technology Gmbh | Process for the preparation of a porous carbonaceous material, porous carbonaceous material, and a catalyst made of the material |
-
2020
- 2020-12-31 CN CN202011643725.4A patent/CN112758911B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102479942A (en) * | 2010-11-30 | 2012-05-30 | 上海杉杉科技有限公司 | Hard carbon negative electrode material, its preparation method and application |
| CN106099109A (en) * | 2016-06-22 | 2016-11-09 | 大连理工大学 | A kind of preparation method and applications of asphaltic base hard charcoal nanometer sheet |
| CN106532009A (en) * | 2016-12-21 | 2017-03-22 | 上海杉杉科技有限公司 | Preparation method of high capacity lithium ion battery hard carbon composite negative electrode material |
| WO2020200812A1 (en) * | 2019-04-02 | 2020-10-08 | Heraeus Battery Technology Gmbh | Process for the preparation of a porous carbonaceous material, porous carbonaceous material, and a catalyst made of the material |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2023087129A1 (en) * | 2021-11-16 | 2023-05-25 | 宁波杉杉新材料科技有限公司 | Preparation method for carbon electrode material and carbon electrode material |
| CN114368739A (en) * | 2021-12-28 | 2022-04-19 | 上海杉杉科技有限公司 | Hard carbon material, preparation method thereof, electrode, battery and application |
| CN114702022A (en) * | 2022-03-15 | 2022-07-05 | 广东邦普循环科技有限公司 | Preparation method and application of hard carbon negative electrode material |
| CN114702022B (en) * | 2022-03-15 | 2023-09-12 | 广东邦普循环科技有限公司 | Preparation method and application of hard carbon anode material |
| CN115215321A (en) * | 2022-07-26 | 2022-10-21 | 华南理工大学 | Preparation method and application of hard carbon microsphere material |
| CN115838165A (en) * | 2022-12-29 | 2023-03-24 | 赣州立探新能源科技有限公司 | Hard carbon negative electrode material, preparation method thereof and secondary battery |
| CN115838165B (en) * | 2022-12-29 | 2024-05-17 | 赣州立探新能源科技有限公司 | Hard carbon negative electrode material, preparation method thereof and secondary battery |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112758911B (en) | 2023-02-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN112758911B (en) | Hard carbon material, preparation method and application thereof, and lithium ion battery | |
| CN112573923A (en) | High-rate lithium ion battery artificial graphite negative electrode material and preparation method thereof | |
| CN105789594B (en) | A kind of silicon/oxidative silicon/carbon composite and its preparation method and application | |
| JP5509458B2 (en) | Negative electrode material and manufacturing method thereof | |
| CN112768691B (en) | Coating agent, coating modified graphite negative electrode material, preparation method and application thereof, and lithium ion battery | |
| CN113800496A (en) | Hard carbon material and preparation method and application thereof | |
| CN105958070A (en) | Preparation method for artificial graphite negative electrode material for lithium ion battery | |
| CN108448080A (en) | A kind of graphene coated silicon/metal composite negative pole material and preparation method thereof | |
| WO2022121400A1 (en) | Coating agent, fast-charging graphite, preparation method therefor and application thereof, and battery | |
| CN112713274B (en) | Nano silicon-carbon composite material, preparation method, application and lithium ion battery | |
| CN113113572B (en) | High-rate natural graphite-based composite material for lithium ion battery and preparation method and application thereof | |
| CN105810946A (en) | Preparation method of natural graphite cathode material for lithium ion batteries | |
| CN109037603B (en) | Novel method for preparing asphalt-based spherical porous doping modified hard carbon negative electrode material | |
| CN114335522A (en) | Coal-based carbon negative electrode material, preparation method and application thereof, and battery containing coal-based carbon negative electrode material | |
| CN108682830B (en) | Silicon-carbon composite negative electrode material of lithium ion battery and preparation method thereof | |
| WO2024067447A1 (en) | Graphite negative electrode material, preparation method therefor and application thereof | |
| CN111799098A (en) | Porous carbon/metal oxide composite material and preparation method and application thereof | |
| CN110085823B (en) | Nano composite negative electrode material and preparation method and application thereof | |
| CN114988391A (en) | Preparation method and application of hard carbon negative electrode material | |
| CN108807903B (en) | Preparation method of composite modified lithium battery negative electrode material for lithium battery | |
| CN114314556A (en) | Resin-based carbon negative electrode material, preparation method and application thereof, and battery containing resin-based carbon negative electrode material | |
| CN114538431A (en) | Quick-charging graphite negative electrode material for lithium battery and preparation method thereof | |
| CN113991077B (en) | Graphite composite material for lithium battery and preparation method thereof | |
| CN109935793B (en) | Preparation method of lithium ion battery composite graphene negative electrode material | |
| CN112713277B (en) | Hard carbon material, preparation method and application thereof, and lithium ion 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 |