CN116514098A - Hard carbon material, preparation method and application thereof, and battery - Google Patents
Hard carbon material, preparation method and application thereof, and battery Download PDFInfo
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- CN116514098A CN116514098A CN202310501574.6A CN202310501574A CN116514098A CN 116514098 A CN116514098 A CN 116514098A CN 202310501574 A CN202310501574 A CN 202310501574A CN 116514098 A CN116514098 A CN 116514098A
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- hard carbon
- carbon material
- magnesium salt
- magnesium
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- 229910021385 hard carbon Inorganic materials 0.000 title claims abstract description 58
- 239000003575 carbonaceous material Substances 0.000 title claims abstract description 55
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 159000000003 magnesium salts Chemical class 0.000 claims abstract description 62
- 229920000428 triblock copolymer Polymers 0.000 claims abstract description 37
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 36
- 238000002156 mixing Methods 0.000 claims abstract description 32
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 30
- 239000011148 porous material Substances 0.000 claims abstract description 29
- 238000005406 washing Methods 0.000 claims abstract description 28
- 238000000034 method Methods 0.000 claims abstract description 25
- 239000011734 sodium Substances 0.000 claims abstract description 25
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims abstract description 23
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 23
- 239000002253 acid Substances 0.000 claims abstract description 22
- 238000009656 pre-carbonization Methods 0.000 claims abstract description 19
- 238000003763 carbonization Methods 0.000 claims abstract description 13
- 238000010438 heat treatment Methods 0.000 claims description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- 239000000654 additive Substances 0.000 claims description 18
- 230000000996 additive effect Effects 0.000 claims description 18
- 239000002245 particle Substances 0.000 claims description 16
- 238000010298 pulverizing process Methods 0.000 claims description 14
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 11
- 238000009826 distribution Methods 0.000 claims description 11
- 239000008103 glucose Substances 0.000 claims description 11
- 229910001416 lithium ion Inorganic materials 0.000 claims description 10
- -1 polyethylene Polymers 0.000 claims description 10
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 9
- 229910001415 sodium ion Inorganic materials 0.000 claims description 9
- 239000004698 Polyethylene Substances 0.000 claims description 8
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims description 8
- 229920000573 polyethylene Polymers 0.000 claims description 8
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 6
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 6
- 239000004743 Polypropylene Substances 0.000 claims description 6
- 230000000694 effects Effects 0.000 claims description 6
- 229920001155 polypropylene Polymers 0.000 claims description 6
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 4
- RVDLHGSZWAELAU-UHFFFAOYSA-N 5-tert-butylthiophene-2-carbonyl chloride Chemical compound CC(C)(C)C1=CC=C(C(Cl)=O)S1 RVDLHGSZWAELAU-UHFFFAOYSA-N 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 239000001755 magnesium gluconate Substances 0.000 claims description 4
- 229960003035 magnesium gluconate Drugs 0.000 claims description 4
- 235000015778 magnesium gluconate Nutrition 0.000 claims description 4
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical group [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 claims description 4
- IAKLPCRFBAZVRW-XRDLMGPZSA-L magnesium;(2r,3s,4r,5r)-2,3,4,5,6-pentahydroxyhexanoate;hydrate Chemical compound O.[Mg+2].OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O.OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O IAKLPCRFBAZVRW-XRDLMGPZSA-L 0.000 claims description 4
- IUYHWZFSGMZEOG-UHFFFAOYSA-M magnesium;propane;chloride Chemical compound [Mg+2].[Cl-].C[CH-]C IUYHWZFSGMZEOG-UHFFFAOYSA-M 0.000 claims description 4
- 229920001568 phenolic resin Polymers 0.000 claims description 4
- 239000005011 phenolic resin Substances 0.000 claims description 4
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 claims description 3
- 229940069446 magnesium acetate Drugs 0.000 claims description 3
- 239000011654 magnesium acetate Substances 0.000 claims description 3
- 235000011285 magnesium acetate Nutrition 0.000 claims description 3
- 229960005336 magnesium citrate Drugs 0.000 claims description 3
- 239000004337 magnesium citrate Substances 0.000 claims description 3
- 235000002538 magnesium citrate Nutrition 0.000 claims description 3
- PLSARIKBYIPYPF-UHFFFAOYSA-H trimagnesium dicitrate Chemical compound [Mg+2].[Mg+2].[Mg+2].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O PLSARIKBYIPYPF-UHFFFAOYSA-H 0.000 claims description 3
- QHUNJMXHQHHWQP-UHFFFAOYSA-N trimethylsilyl acetate Chemical compound CC(=O)O[Si](C)(C)C QHUNJMXHQHHWQP-UHFFFAOYSA-N 0.000 claims description 3
- KTVKQTNGWVJHFL-UHFFFAOYSA-N 2-ethylchromen-4-one Chemical compound C1=CC=C2OC(CC)=CC(=O)C2=C1 KTVKQTNGWVJHFL-UHFFFAOYSA-N 0.000 claims description 2
- 244000060011 Cocos nucifera Species 0.000 claims description 2
- 235000013162 Cocos nucifera Nutrition 0.000 claims description 2
- 244000017020 Ipomoea batatas Species 0.000 claims description 2
- 235000002678 Ipomoea batatas Nutrition 0.000 claims description 2
- 240000003183 Manihot esculenta Species 0.000 claims description 2
- 235000016735 Manihot esculenta subsp esculenta Nutrition 0.000 claims description 2
- 240000008790 Musa x paradisiaca Species 0.000 claims description 2
- 235000018290 Musa x paradisiaca Nutrition 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 240000007594 Oryza sativa Species 0.000 claims description 2
- 235000007164 Oryza sativa Nutrition 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- RHZUVFJBSILHOK-UHFFFAOYSA-N anthracen-1-ylmethanolate Chemical compound C1=CC=C2C=C3C(C[O-])=CC=CC3=CC2=C1 RHZUVFJBSILHOK-UHFFFAOYSA-N 0.000 claims description 2
- 239000003830 anthracite Substances 0.000 claims description 2
- 238000005056 compaction Methods 0.000 claims description 2
- OLLFKUHHDPMQFR-UHFFFAOYSA-N dihydroxy(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](O)(O)C1=CC=CC=C1 OLLFKUHHDPMQFR-UHFFFAOYSA-N 0.000 claims description 2
- 239000003822 epoxy resin Substances 0.000 claims description 2
- 235000013312 flour Nutrition 0.000 claims description 2
- 239000010903 husk Substances 0.000 claims description 2
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 2
- DQDWATOXYCARFV-UHFFFAOYSA-M magnesium;2-methanidylpropane;bromide Chemical compound [Mg+2].[Br-].CC(C)[CH2-] DQDWATOXYCARFV-UHFFFAOYSA-M 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 claims description 2
- 238000005554 pickling Methods 0.000 claims description 2
- 229920001748 polybutylene Polymers 0.000 claims description 2
- 229920000647 polyepoxide Polymers 0.000 claims description 2
- 229920001451 polypropylene glycol Polymers 0.000 claims description 2
- 229920001296 polysiloxane Polymers 0.000 claims description 2
- 229920001592 potato starch Polymers 0.000 claims description 2
- 235000009566 rice Nutrition 0.000 claims description 2
- 229960004889 salicylic acid Drugs 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims 1
- 239000010426 asphalt Substances 0.000 claims 1
- 239000011257 shell material Substances 0.000 claims 1
- 229910052710 silicon Inorganic materials 0.000 claims 1
- 239000010703 silicon Substances 0.000 claims 1
- 239000000047 product Substances 0.000 description 56
- 238000001816 cooling Methods 0.000 description 33
- 239000000243 solution Substances 0.000 description 29
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 24
- 238000003756 stirring Methods 0.000 description 22
- 239000012299 nitrogen atmosphere Substances 0.000 description 20
- 239000000463 material Substances 0.000 description 19
- 238000001035 drying Methods 0.000 description 16
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 12
- 238000007605 air drying Methods 0.000 description 12
- 235000011114 ammonium hydroxide Nutrition 0.000 description 12
- 229910052757 nitrogen Inorganic materials 0.000 description 12
- 238000007873 sieving Methods 0.000 description 11
- 238000000967 suction filtration Methods 0.000 description 11
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 9
- 238000010000 carbonizing Methods 0.000 description 9
- 238000004321 preservation Methods 0.000 description 9
- 238000004108 freeze drying Methods 0.000 description 8
- 238000009830 intercalation Methods 0.000 description 7
- 230000002687 intercalation Effects 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 7
- 229920002415 Pluronic P-123 Polymers 0.000 description 6
- 229910002804 graphite Inorganic materials 0.000 description 6
- 239000010439 graphite Substances 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 239000010405 anode material Substances 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 230000001681 protective effect Effects 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000007710 freezing Methods 0.000 description 2
- 230000008014 freezing Effects 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 238000012216 screening Methods 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 229910003481 amorphous carbon Inorganic materials 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000011260 aqueous acid Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 239000003814 drug Substances 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
- 238000002474 experimental method Methods 0.000 description 1
- 238000005087 graphitization Methods 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 238000010335 hydrothermal treatment Methods 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229940091250 magnesium supplement Drugs 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000003361 porogen Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000007790 scraping Methods 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
-
- 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)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention discloses a hard carbon material, a preparation method and application thereof, and a battery. The preparation method of the hard carbon material comprises the following steps: mixing a carbon source, a triblock copolymer and a magnesium salt, and then sequentially carrying out pre-carbonization, acid washing, crushing and carbonization to prepare a hard carbon material; or mixing a carbon source, a triblock copolymer and a magnesium salt, and performing solvothermal treatment to obtain a hard carbon material; wherein, the mass ratio of the magnesium salt to the triblock copolymer is 1: (0.1-10); the mass ratio of the magnesium salt to the carbon source is 1: (6-200). The hard carbon material prepared by the method has controllable pore diameter structure, the pore diameter range is of a micropore grade, the high potential region sodium embedding capacity is higher on the premise that the sum of the high potential region sodium embedding capacity and the low potential region sodium embedding capacity meets the practical application requirement, meanwhile, the three-dimensional structure is stable, the uniformity among different batches of products is high, and the preparation method is simple.
Description
Technical Field
The invention particularly relates to a hard carbon material, a preparation method and application thereof, and a battery.
Background
Graphite is a lithium ion battery cathode material, the theoretical specific capacity of the graphite is 372mAh/g, and the actual use capacity of the graphite can reach 360-365mAh/g at present, so that the graphite approaches the theoretical limit. The current power, energy storage and consumer markets place higher demands on the fast charge performance and safety performance of the anode material. In addition, the problem of lithium resource shortage is increasingly highlighted in the face of the rapid increase of demand due to the fact that the crust abundance of lithium content is not high, along with mining technology and market reasons.
Sodium ion batteries with an energy density of 160Wh/kg were published by the Nide age in 2021, 7. The energy density of the lithium ion battery in the market is 160-300Wh/kg, and the energy density of the sodium ion battery is lower than that of the lithium ion battery, so that the lithium ion battery is an important supplement to the low energy density battery market.
Graphite negative electrode can not be used as negative electrode material of sodium ion battery due to the limitation of the self carbon layer spacing and other factors. The hard carbon material has larger interlayer spacing, larger pore diameter and richer porosity, and can be simultaneously applied to the cathodes of lithium ion batteries and sodium ion batteries. Hard carbon, an amorphous carbon, also cannot be converted to graphite at graphitization temperatures. The root cause is the long-range disordered carbon layer arrangement in the structure. The dissimilarity and the presence of heteroatoms lead to more defects of their own, and the accumulation of different configurations also leads to a great deal of variability in the pore structure. It is the presence of defects and voids that provide more space for the storage of lithium and sodium ions.
In theory, the lithium and sodium storage process of the hard carbon anode material is mainly divided into three stages of adsorption, pore filling and intercalation reaction, and the pore filling stage can provide a larger capacity range. Thus, the pore structure of the hard carbon anode material has an important influence on the electrochemical and kinetic performance of the battery. For hard carbon materials, how to regulate and control a proper pore structure so that the hard carbon materials can have excellent electrochemical performance and dynamic performance is a current problem to be solved urgently.
Disclosure of Invention
The invention solves the technical problem that the pore structure of a hard carbon material is difficult to controllably regulate and control in the prior art, and provides the hard carbon material, and the preparation method, the application and the battery thereof. The hard carbon material prepared by the method has controllable pore diameter structure, the pore diameter range is of a micropore level, and meanwhile, on the premise that the sum of the sodium embedding capacity of the high-low potential area meets the practical application requirement, the sodium embedding capacity of the high-potential area is higher, the three-dimensional structure is stable, the uniformity among different batches of products is high, and the preparation method is simple.
The invention provides a preparation method of a hard carbon material, which comprises the following steps:
mixing a carbon source, a triblock copolymer and a magnesium salt, and then sequentially carrying out pre-carbonization, acid washing, crushing and carbonization to prepare the hard carbon material;
or mixing a carbon source, a triblock copolymer and a magnesium salt, and performing solvothermal treatment to obtain the hard carbon material;
wherein the mass ratio of the magnesium salt to the triblock copolymer is 1: (0.1-10); the mass ratio of the magnesium salt to the carbon source is 1: (5-200).
In the present invention, the carbon source may be conventional in the art, and is preferably one or more of phenolic resin, epoxy resin, sweet potato starch, banana peel, coconut shell, anthracite, pitch, corncob, rice husk, glucose and tapioca flour. The mass ratio of the magnesium salt to the carbon source is preferably 1: (5-100), more preferably 1: (6 to 60), for example, 1:6.7, 1: 15. 1:20 or 1:60.
in the present invention, the triblock copolymer may be a triblock copolymer that is conventionally used in the art as a porogen, such as polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer (PEO-PPO-PEO), polyethylene oxide-polybutylene oxide-polyethylene oxide triblock copolymer (PEO-PBO-PEO), or polypropylene oxide-polyethylene oxide-polypropylene oxide triblock copolymer (PPO-PEO-PPO).
Wherein the number average molecular weight of the polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer may be conventional in the art, for example 10000-12000 or 5000-6000.
In the present invention, the magnesium salt may be an inorganic magnesium salt or an organic magnesium salt, preferably an organic magnesium salt. Wherein the inorganic magnesium salt is preferably magnesium nitrate and/or magnesium chloride. The organic magnesium salt is preferably one or more of magnesium ethoxide, magnesium acetate, magnesium gluconate, magnesium citrate, magnesium tert-butoxide, isopropyl magnesium chloride and isobutyl magnesium bromide.
Wherein the mass of the magnesium salt and the triblock copolymer is preferably 1: (0.1 to 8), for example, 1:0.17, 1:0.5, 1:3 or 1:6.
in the present invention, it is preferable that an additive is further added in the step of mixing. The additive may be any suitable additive in the art for preparing hard carbon materials, preferably a siliceous agent, more preferably one or more of trimethylsilyl acetate, tetraethyl silicate, polysiloxanes and diphenyl silanediol. The amount of the additive may be conventional in the art, and the ratio of the mass of the magnesium salt to the volume of the additive may be 1: (0.5-25) g/mL, preferably 1: (1-20) g/mL, for example 1:1.4g/mL, 1:5.6g/mL or 1:16g/mL.
In the present invention, the mixing may be performed in a conventional manner and under conditions in the art for preparing hard carbon materials.
In the step of mixing, the mixing order of the materials can be arbitrary, and it is preferable to add the triblock copolymer, the magnesium salt, the additive and the carbon source sequentially, or add the triblock copolymer, the additive, the magnesium salt and the carbon source sequentially, or add the triblock copolymer, the carbon source and the magnesium salt sequentially.
The mixing is performed in a solvent as is conventional in the art. The solvent is preferably water or an acid-containing aqueous solution. The acid is preferably HCl. The concentration of the aqueous acid-containing solution may be 1 to 8mol/L, preferably 1 to 3mol/L, such as 2mol/L.
The temperature of the mixing is preferably 30 to 80 ℃, more preferably 60 to 80 ℃, for example 60 ℃ or 80 ℃. The heating means during the mixing is preferably water bath heating. The mixing time is preferably 2 to 24 hours, more preferably 10 to 16 hours, for example 14 hours.
The mixing is carried out under agitation, as is conventional in the art. The rotational speed of the stirring may be 500 to 3000rpm, preferably 1000 to 2500rpm. Preferably, the mixing is to mix part of the materials for 1-4 hours under the stirring of 1000-2500 rpm, and then mix the materials with the rest materials for 10-15 hours under the stirring of 400-600 rpm.
In a preferred embodiment of the invention, the mixing is carried out by mixing a part of the materials for 2 hours under stirring at 1800rpm and then mixing the mixture with the rest of the materials for 12 hours under stirring at 500rpm.
In the present invention, after the mixing is completed, cooling and drying are also performed according to the conventional method in the art, specifically, cooling to room temperature and then freeze drying are performed.
In the present invention, the pre-carbonization may be performed according to conventional conditions for pre-carbonization in the art. The pre-carbonization temperature may be 250 to 700 ℃, preferably 400 to 550 ℃, such as 420 ℃, 450 ℃ or 500 ℃. The pre-carbonization time may be 1 to 10 hours, preferably 1 to 4 hours, for example 2 hours or 3 hours. The pre-carbonization is generally carried out under a protective atmosphere which does not react with the reaction system, such as nitrogen or inert gas.
In the present invention, the acid washing may be performed under conventional conditions for acid washing in the art. The acid is preferably one or more of hydrochloric acid, phosphoric acid, sulfuric acid, hydrofluoric acid, nitric acid, salicylic acid and acetic acid. The concentration of the acid may be 0.1 to 5.0mol/L, preferably 0.5 to 2.0mol/L, such as 1.0mol/L. In a preferred embodiment, the acid is 1.0mol/L hydrofluoric acid. The time for the pickling may be 1 to 10 hours, preferably 2 to 6 hours, for example 4 hours.
After the acid washing, washing to neutrality and drying are also included according to conventional in the art.
Wherein the wash may be neutral by washing with water or lye. The alkali in the alkali liquor can be one or more of sodium hydroxide, ammonia water, potassium hydroxide and lithium hydroxide. The concentration of the alkali in the lye may be from 0.1 to 2.0mol/L, preferably from 0.5 to 1.5mol/L, for example 1.0mol/L.
Wherein the drying temperature may be 50 to 180 ℃, preferably 60 to 100 ℃, for example 80 ℃. The drying time may be 3 to 24 hours, preferably 8 to 12 hours, for example 10 hours. Wherein, the drying mode can be forced air drying.
In the present invention, the pulverization may be carried out according to conventional conditions for pulverization in the art. The particle size of the comminution may be from 3 to 8 μm, for example 5 μm. The comminuting device may be a jet mill.
In the present invention, the carbonization may be performed according to conventional conditions for pulverization in the art. The carbonization temperature may be 800-1600 ℃, preferably 900-1400 ℃, e.g. 1150 ℃. The carbonization time may be 1 to 12 hours, preferably 2 to 6 hours, for example 4 hours. The rate of heating to the carbonization temperature may be 0.5 to 10 c/min, preferably 1 to 5 c/min, for example 3.5 c/min. The carbonization is generally carried out under a protective atmosphere which does not react with the reaction system, such as nitrogen or inert gas. The protective atmosphere may be introduced at a flow rate of 0.5 to 40L/min, preferably 0.5 to 10L/min, for example 1L/min or 5L/min. And after carbonization, the process of cooling and naturally cooling to room temperature is also included.
In the present invention, the kind of solvent used in the solvothermal treatment process may be conventional in the art, such as water or ethanol. The solvothermal treatment may be at a temperature of 80 to 200 ℃, preferably 160 to 200 ℃, for example 170 ℃, 180 ℃ or 190 ℃. The solvothermal treatment time may be from 4 to 18 hours, preferably from 6 to 10 hours, for example 7, 8 or 9 hours. In a preferred embodiment of the present invention, the solvothermal treatment is a hydrothermal treatment at 180 ℃ for 8 hours.
In the present invention, the carbonization is preferably further performed after completion of sieving.
The invention also provides the hard carbon material prepared by the preparation method of the hard carbon material.
The invention also provides a hard carbon material, the pore size distribution range of which is micro-pore grade, preferably 0.4-1nm.
Preferred examples of hard carbon materials of the present invention also have one or more of the following parameters: particle diameter D 50 3-6 μm, and a compaction density of 0.6-1.2g/cm 3 Specific surface area of 4-20m 2 The sum of the sodium embedding capacity of the high and low potential areas is 340-3838 mAh.g -1 The sodium embedding capacity of the high potential area is 58-142mAh.g -1 The sodium embedding capacity of the low potential area is 210-299mAh.g -1 And the first effect is 82% -88%.
The invention also provides application of the hard carbon material in preparing sodium ion batteries or lithium ion batteries.
The invention also provides a battery which comprises the hard carbon material, wherein the battery is a sodium ion battery or a lithium ion battery.
On the basis of conforming to the common knowledge in the field, the above preferred conditions can be arbitrarily combined to obtain the preferred examples of the invention.
The reagents and materials used in the present invention are commercially available.
The invention has the positive progress effects that:
(1) The pore diameter range of the hard carbon material prepared by the invention can be of a micropore grade, and the pore diameter in the range can be continuous or discontinuous;
(2) The hard carbon material prepared by the invention has higher sodium embedding capacity in a high potential area on the premise that the sum of the sodium embedding capacities in the high potential area and the low potential area meets the actual application requirement;
(3) The hard carbon material prepared by the method has controllable pore diameter structure, stable three-dimensional structure and high uniformity among different batches of products;
(4) The preparation method of the hard carbon material is simple and has low requirements on experimental equipment.
Drawings
FIG. 1 is a graph showing pore size distribution of a hard carbon material prepared in example 2.
FIG. 2 is a graph showing pore size distribution of the hard carbon material prepared in example 3.
FIG. 3 is a graph showing pore size distribution of the hard carbon material prepared in example 5.
FIG. 4 is a graph showing pore size distribution of the hard carbon material prepared in example 6.
FIG. 5 is a graph showing pore size distribution of the hard carbon material prepared in example 11.
Detailed Description
The invention is further illustrated by means of the following examples, which are not intended to limit the scope of the invention. The experimental methods, in which specific conditions are not noted in the following examples, were selected according to conventional methods and conditions, or according to the commercial specifications.
In the following examples, pluronic P123 refers to a polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer having a number average molecular weight of 5000-6000, and is commercially available from Guogui reagent under the product model XW90031165; f127 number average molecular weight is 10000-12000, and is purchased from national medicine reagent, and the product model is XW90031161.
Example 1
(1) Mixing: the triblock copolymer Pluronic P123 100g and magnesium salt MgNO 3 200g (mass ratio of magnesium salt to triblock copolymer: 1:0.5) was added to 2.0M aqueous HCl solution, and 280mL of trimethylsilyl acetate as an additive (mass ratio of magnesium salt to volume of additive: 1:1.4 g/mL) was added while maintaining the water bath environment at 60 ℃. The rotation was maintained at 1800 rpm. Adding 3kg of glucose (the mass ratio of magnesium salt to carbon source is 1:15) solution as a carbon source into the solution after 2 hours, then reducing the rotating speed to 500rpm, keeping stirring for 12 hours, removing the heating equipment, naturally cooling to room temperature, and performing freeze-drying treatment.
(2) Pre-carbonization: the obtained product is subjected to heat treatment and heat preservation for 2 hours in a nitrogen atmosphere at 420 ℃ and naturally cooled to room temperature.
(3) Acid washing and washing: the product was immersed in a 1.0M HF solution, stirred for 4 hours, and then washed with a 1mol/L aqueous ammonia solution and suction filtered to neutrality.
(4) Drying and crushing: air drying the product obtained by suction filtration at 80deg.C for 10 hr, and pulverizing the obtained product to particle diameter D with jet mill 50 Is 5 μm.
(5) Carbonizing: the crushed product is transferred to a box-type furnace, and is heated from room temperature to 1150 ℃ at a heating rate of 3.5 ℃/min under nitrogen atmosphere, and is kept for 4 hours. In the process of temperature and natural cooling, the flow rate of nitrogen is kept at 1L/min. And (5) taking materials after cooling to room temperature, and sieving.
Example 2
(1) Mixing: pluronic P123 100g is added into 2.0M HCl aqueous solution, tetraethyl silicate 280mL (the ratio of the mass of magnesium salt to the volume of the additive is 1:1.4 g/mL) is added under the condition of keeping the water bath environment at 60 ℃, and MgNO is added after 12 hours 3 200g (mass ratio of magnesium salt to triblock copolymer 1:0.5).The rotation was maintained at 1800 rpm. After 2 hours, glucose 3kg (mass ratio of magnesium salt to carbon source is 1:15) solution is added into the solution, then the rotating speed is reduced to 500rpm, stirring is kept for 12 hours, then the heating equipment is removed, and the temperature is naturally reduced to room temperature, and then freeze drying treatment is carried out.
(2) Pre-carbonization: the obtained product is subjected to heat treatment and heat preservation for 2 hours in a nitrogen atmosphere at 420 ℃ and naturally cooled to room temperature.
(3) Acid washing and washing: the product was immersed in a 1.0M HF solution, stirred for 4 hours, and then washed with a 1mol/L aqueous ammonia solution and suction filtered to neutrality.
(4) Drying and crushing: air drying the product obtained by suction filtration at 80deg.C for 10 hr, and pulverizing the obtained product to particle diameter D with jet mill 50 Is 5 μm.
(5) Carbonizing: the crushed product is transferred to a box-type furnace, and is heated from room temperature to 1150 ℃ at a heating rate of 3.5 ℃/min under nitrogen atmosphere, and is kept for 4 hours. In the process of temperature and natural cooling, the flow rate of nitrogen is kept at 1L/min. And (5) taking materials after cooling to room temperature, and sieving.
Example 3
(1) Mixing: pluronic P123 300g was added to 2.0M aqueous HCl, tetraethyl silicate 280mL (mass of magnesium salt to volume of additive 1:5.6 g/mL) was added while maintaining the water bath at 60℃and magnesium ethoxide 50g (mass ratio of magnesium salt to triblock copolymer 1:6) was added after 12h. The rotation was maintained at 1800 rpm. After 2 hours, glucose 3kg (mass ratio of magnesium salt to carbon source is 1:60) solution is added into the solution, then the rotating speed is reduced to 500rpm, stirring is kept for 12 hours, then the heating equipment is removed, and the temperature is naturally reduced to room temperature, and then freeze drying treatment is carried out.
(2) Pre-carbonization: the obtained product is subjected to heat treatment and heat preservation for 2 hours in a nitrogen atmosphere at 420 ℃, and naturally cooled to room temperature.
(3) Acid washing and washing: the product was immersed in a 1.0M HF solution, stirred for 4 hours, and then washed with a 1mol/L aqueous ammonia solution and suction filtered to neutrality.
(4) Drying and crushing: air drying the product obtained by suction filtration at 80deg.C for 10 hr, and pulverizing the obtained product to particle diameter D with jet mill 50 Is 5 μm.
(5) Carbonizing: the crushed product is transferred to a box-type furnace, and is heated from room temperature to 1150 ℃ at a heating rate of 3.5 ℃/min under nitrogen atmosphere, and is kept for 4 hours. In the process of temperature and natural cooling, the flow rate of nitrogen is kept at 1L/min. And (5) taking materials after cooling to room temperature, and sieving.
Example 4
(1) Mixing: pluronic P123 300g was added to 2.0M aqueous HCl, tetraethyl silicate 280mL (mass of magnesium salt to volume of additive 1:5.6 g/mL) was added in a water bath at 60℃for 12h, and MgNO was added 3 50g (mass ratio of magnesium salt to triblock copolymer 1:6). The rotation was maintained at 1800 rpm. After 2 hours, glucose 3kg (mass ratio of magnesium salt to carbon source is 1:60) solution is added into the solution, then the rotating speed is reduced to 500rpm, stirring is kept for 12 hours, then the heating equipment is removed, and the temperature is naturally reduced to room temperature, and then freeze drying treatment is carried out.
(2) Pre-carbonization: the obtained product is subjected to heat treatment and heat preservation for 2 hours in a nitrogen atmosphere at 420 ℃ and naturally cooled to room temperature.
(3) Acid washing and washing: the product was immersed in a 1.0M HF solution, stirred for 4 hours, and then washed with a 1mol/L aqueous ammonia solution and suction filtered to neutrality.
(4) Drying and crushing: air drying the product obtained by suction filtration at 80deg.C for 10 hr, and pulverizing the obtained product to particle diameter D with jet mill 50 Is 5 μm.
(5) Carbonizing: the crushed product is transferred to a box-type furnace, and is heated from room temperature to 1150 ℃ at a heating rate of 3.5 ℃/min under nitrogen atmosphere, and is kept for 4 hours. In the process of temperature and natural cooling, the flow rate of nitrogen is kept at 1L/min. And (5) taking materials after cooling to room temperature, and sieving.
Example 5
(1) Mixing: pluronic P123 (30 g) was added to 2.0M aqueous HCl, tetraethyl silicate (80 mL) (the ratio of the mass of magnesium salt to the volume of the additive: 1:16 g/mL) was added at 60℃to the water bath, and MgNO was added after 12 hours 3 5g (mass ratio of magnesium salt to triblock copolymer 1:6). The rotation was maintained at 1800 rpm. After 2 hours, will againGlucose 300g (mass ratio of magnesium salt to carbon source 1:60) solution was added to the above solution, and then the rotation speed was reduced to 500rpm and kept stirring for 12 hours.
(2) And (3) solvothermal treatment: the solution was transferred to a 500mL hydrothermal kettle and treated at 180℃for 8 hours under normal pressure. And naturally cooling to room temperature, opening the kettle body, immersing the product obtained after sedimentation and centrifugation in 1.0M HF solution, stirring for 4 hours, and washing and suction-filtering to neutrality by using 1mol/L ammonia water solution. And (3) carrying out forced air drying on the product obtained by suction filtration at 80 ℃ for 10 hours, cooling to room temperature, taking materials, and screening.
Example 6
(1) Mixing: adding F127.30 g into 2.0M HCl aqueous solution, maintaining water bath environment at 60deg.C, adding tetraethyl silicate 80mL (the ratio of magnesium salt mass to additive volume is 1:16 g/mL), and adding MgNO after 12h 3 5g (mass ratio of magnesium salt to triblock copolymer 1:6). The rotation was maintained at 1800 rpm. After 2 hours, 300g of glucose (mass ratio of magnesium salt to carbon source 1:60) solution was added to the above solution, and then the rotation speed was reduced to 500rpm and kept stirring for 12 hours.
(2) And (3) solvothermal treatment: the solution was transferred to a 500mL hydrothermal kettle and treated at 180℃for 8 hours under normal pressure. And naturally cooling to room temperature, opening the kettle body, immersing the product obtained after sedimentation and centrifugation in 1.0M HF solution, stirring for 4 hours, and washing and suction-filtering to neutrality by using 1mol/L ammonia water solution. And (3) carrying out forced air drying on the product obtained by suction filtration at 80 ℃ for 10 hours, cooling to room temperature, taking materials, and screening.
Example 7
(1) Mixing: f127 300g is added into deionized water, 2kg of glucose is added under the condition of keeping the water bath environment at 60 ℃, 100g of magnesium acetate (the mass ratio of magnesium salt to triblock copolymer is 1:3 and the mass ratio of magnesium salt to carbon source is 1:20) is added after stirring for 2 hours at 1800rpm, then the rotating speed is reduced to 500rpm, stirring is kept for 12 hours, then the heating equipment is removed, and the freezing and drying treatment is carried out after naturally cooling to room temperature.
(2) Pre-carbonization: the obtained product is subjected to heat treatment and heat preservation for 2 hours in a nitrogen atmosphere at 420 ℃ and naturally cooled to room temperature.
(3) Acid washing and washing: the product was immersed in a 1.0M HF solution, stirred for 4 hours, and then washed with a 1mol/L aqueous ammonia solution and suction filtered to neutrality.
(4) Drying and crushing: air drying the product obtained by suction filtration at 80deg.C for 10 hr, and pulverizing the obtained product to particle diameter D with jet mill 50 Is 5 μm.
(5) Carbonizing: the crushed product is transferred to a box-type furnace, and is heated from room temperature to 1150 ℃ at a heating rate of 3.5 ℃/min under nitrogen atmosphere, and is kept for 4 hours. In the process of temperature and natural cooling, the flow rate of nitrogen is kept at 1L/min. And (5) taking materials after cooling to room temperature, and sieving.
Example 8
(1) Mixing: f127 300g is added into deionized water, 2kg of glucose is added under the condition of keeping the water bath environment at 60 ℃, stirring is carried out for 2 hours at 1800rpm, 100g of magnesium gluconate (the mass ratio of magnesium salt to triblock copolymer is 1:3, the mass ratio of magnesium salt to carbon source is 1:20) is added, then the rotating speed is reduced to 500rpm, stirring is kept for 12 hours, then the heating equipment is removed, and the freezing and drying treatment is carried out after the temperature is naturally reduced to room temperature.
(2) Pre-carbonization: the obtained product is subjected to heat treatment and heat preservation for 2 hours in a nitrogen atmosphere at 420 ℃ and naturally cooled to room temperature.
(3) Acid washing and washing: the product was immersed in a 1.0M HF solution, stirred for 4 hours, and then washed with a 1mol/L aqueous ammonia solution and suction filtered to neutrality.
(4) Drying and crushing: air drying the product obtained by suction filtration at 80deg.C for 10 hr, and pulverizing the obtained product to particle diameter D with jet mill 50 Is 5 μm.
(5) Carbonizing: the crushed product is transferred to a box-type furnace, and is heated from room temperature to 1150 ℃ at a heating rate of 3.5 ℃/min under nitrogen atmosphere, and is kept for 4 hours. In the process of temperature and natural cooling, the flow rate of nitrogen is kept at 1L/min. And (5) taking materials after cooling to room temperature, and sieving.
Example 9
(1) Mixing: adding F127 300g into deionized water, maintaining the water bath environment at 60 ℃, adding 2kg of glucose, stirring at 1800rpm for 2 hours, adding 100g of magnesium ethoxide (the mass ratio of magnesium salt to triblock copolymer is 1:3, and the mass ratio of magnesium salt to carbon source is 1:20), reducing the rotation speed to 500rpm, maintaining stirring for 12 hours, removing the heating equipment, naturally cooling to room temperature, and performing freeze drying treatment.
(2) Pre-carbonization: the obtained product is subjected to heat treatment and heat preservation for 2 hours in a nitrogen atmosphere at 420 ℃ and naturally cooled to room temperature.
(3) Acid washing and washing: the product was immersed in a 1.0M HF solution, stirred for 4 hours, and then washed with a 1mol/L aqueous ammonia solution and suction filtered to neutrality.
(4) Drying and crushing: air drying the product obtained by suction filtration at 80deg.C for 10 hr, and pulverizing the obtained product to particle diameter D with jet mill 50 Is 5 μm.
(5) Carbonizing: the crushed product is transferred to a box-type furnace, and is heated from room temperature to 1150 ℃ at a heating rate of 3.5 ℃/min under nitrogen atmosphere, and is kept for 4 hours. In the process of temperature and natural cooling, the flow rate of nitrogen is kept at 1L/min. And (5) taking materials after cooling to room temperature, and sieving.
Example 10
(1) Mixing: adding F127 300g into deionized water, maintaining the water bath environment at 80 ℃, adding 2kg of water-soluble phenolic resin, stirring at 1800rpm for 2h, adding 100g of magnesium gluconate (the mass ratio of magnesium salt to triblock copolymer is 1:3, and the mass ratio of magnesium salt to carbon source is 1:20), then reducing the rotation speed to 500rpm, maintaining stirring for 12h, removing the heating equipment, naturally cooling to room temperature, and performing freeze drying treatment.
(2) Pre-carbonization: the obtained product is subjected to heat treatment and heat preservation for 2 hours in a nitrogen atmosphere at 420 ℃ and naturally cooled to room temperature.
(3) Acid washing and washing: the product was immersed in a 1.0M HF solution, stirred for 4 hours, and then washed with a 1mol/L aqueous ammonia solution and suction filtered to neutrality.
(4) Drying and crushing: air drying the product obtained by suction filtration at 80deg.C for 10 hr, and pulverizing the obtained product to particle diameter D with jet mill 50 Is 5 μm.
(5) Carbonizing: the crushed product is transferred to a box-type furnace, and is heated from room temperature to 1150 ℃ at a heating rate of 3.5 ℃/min under nitrogen atmosphere, and is kept for 4 hours. In the process of temperature and natural cooling, the flow rate of nitrogen is kept at 1L/min. And (5) taking materials after cooling to room temperature, and sieving.
Example 11
(1) Mixing: f127 50g is added into deionized water, 2kg of water-soluble phenolic resin is added under the condition of keeping the water bath environment at 80 ℃, the mixture is stirred for 2 hours at 1800rpm, 300g of magnesium citrate (the mass ratio of magnesium salt to triblock copolymer is 1:0.17, and the mass ratio of magnesium salt to carbon source is 1:6.7) is added, then the rotation speed is reduced to 500rpm, the mixture is kept stirring for 12 hours, then the heating equipment is removed, and the mixture is naturally cooled to room temperature and then subjected to freeze drying treatment.
(2) Pre-carbonization: the obtained product is subjected to heat treatment and heat preservation for 2 hours in a nitrogen atmosphere at 420 ℃ and naturally cooled to room temperature.
(3) Acid washing and washing: the product was immersed in a 1.0M HF solution, stirred for 4 hours, and then washed with a 1mol/L aqueous ammonia solution and suction filtered to neutrality.
(4) Drying and crushing: air drying the product obtained by suction filtration at 80deg.C for 10 hr, and pulverizing the obtained product to particle diameter D with jet mill 50 Is 5 μm.
(5) Carbonizing: the crushed product is transferred to a box-type furnace, and is heated from room temperature to 1150 ℃ at a heating rate of 3.5 ℃/min under nitrogen atmosphere, and is kept for 4 hours. In the process of temperature and natural cooling, the flow rate of nitrogen is kept at 1L/min. And (5) taking materials after cooling to room temperature, and sieving.
Comparative example 1
Placing glucose 3kg into a box furnace, heat-treating at 450deg.C under nitrogen atmosphere for 2 hr, naturally cooling to room temperature, pulverizing the obtained product to particle diameter D with jet mill 50 Is 5 μm. The crushed product is transferred to a box-type furnace, and is heated from room temperature to 1150 ℃ at a heating rate of 3.5 ℃/min under nitrogen atmosphere, and is kept for 4 hours. In the process of temperature and natural cooling, the flow rate of nitrogen is kept at 1L/min. And (5) taking materials after cooling to room temperature, and sieving.
Effect examples
1. Test method
1. Pore size testing:
for the embodiment1-11 and the hard carbon material prepared in the comparative example, when the pore size distribution is tested, the analyzer model adopted is a full-automatic specific surface area and pore analyzer ASAP 2460, the test condition is that carbon dioxide is used as an absorption and desorption medium, the powder degassing temperature is 300 ℃, and the relative air pressure interval P/P is tested 0 0 to 1.
2. Electrochemical performance test
Slurries were prepared from the hard carbon materials prepared in examples 1 to 11 and comparative examples, in which the hard carbon materials: and (2) a binder: the weight ratio of the conductive carbon black is 95:2.5:2.5. then the prepared sizing agent is scraped on copper foil, the scraping thickness is between 250 and 300 mu m, the dried pole piece is used for preparing a CR2430 battery shell, and the counter electrode is Na piece, and the oxygen and water content are increased<Assembled into button cell in a glove box environment of 0.1ppm, the electrolyte used was 1.0M NaPF 6 (EC: dmc=1:1). After the assembly is completed, the test of Na-deintercalation capacity is carried out according to the multiplying power of C/20 after the overnight holding is carried out for 8 hours, wherein the intercalation capacity is the specific capacity of the first intercalation Na. The first effect is the percentage of the pull-out capacity to the total embedded capacity.
2. Test results
1. Pore size distribution
Fig. 1, fig. 2, fig. 3, fig. 4, and fig. 5 are pore size distribution cases of example 2, example 3, example 5, example 6, and example 11, respectively. As can be seen from the figure: the pore size distribution of examples 2, 3, 5, 6 and 11 of the present invention is in the range of 0.4-1nm, and is continuous or discontinuous.
2. Particle size, compacted density, specific surface area, cumulative pore volume, electrochemical properties
Table 1 shows the physicochemical and electrochemical performance parameters of the hard carbon materials prepared in examples 1 to 11 and comparative examples.
TABLE 1 physicochemical and electrochemical Properties parameters of the products of examples 1-11
As can be seen from Table 1, the hard carbon materials prepared in examples 1 to 11 have a particle diameter D 50 3.0-6.0 μm and a compacted density of 0.70-1.1g.cm -3 The specific surface area is 4.5-18.0m 2 .g -1 The sum of the sodium embedding capacity of the high and low potential areas is 340-3838 mAh -1 The sodium embedding capacity of the high potential area is 58-142mAh.g -1 The sodium embedding capacity of the low potential area is 210-299mAh.g -1 The first effect is 82% -88%.
The hard carbon material prepared by the method can ensure that the sum of the sodium embedding capacity of the high-low potential region meets the requirement of actual use in actual application, and can also ensure that the sodium embedding capacity of the high-potential region is higher.
By comparing examples 1-6 with examples 7-11, it was found that the high potential region showed a higher sodium intercalation capacity and the low potential region showed a lower sodium intercalation capacity after the addition of the additive.
By comparing the embodiment 3 with the embodiment 4, it is known that when the magnesium source is an organic magnesium salt, the prepared hard carbon material has higher sum of sodium intercalation capacity in high-low potential region and higher sodium intercalation capacity in high-potential region, and has more excellent electrochemical performance.
Claims (10)
1. The preparation method of the hard carbon material is characterized by comprising the following steps:
mixing a carbon source, a triblock copolymer and a magnesium salt, and then sequentially carrying out pre-carbonization, acid washing, crushing and carbonization to prepare the hard carbon material;
or mixing a carbon source, a triblock copolymer and a magnesium salt, and performing solvothermal treatment to obtain the hard carbon material;
wherein the mass ratio of the magnesium salt to the triblock copolymer is 1: (0.1-10); the mass ratio of the magnesium salt to the carbon source is 1: (5-200).
2. The method of producing a hard carbon material according to claim 1, wherein the method of producing satisfies one or more of the following conditions:
(1) The carbon source is one or more of phenolic resin, epoxy resin, sweet potato starch, banana peel, coconut shell, anthracite, asphalt, corncob, rice husk, glucose and tapioca flour;
(2) The mass ratio of the magnesium salt to the carbon source is 1: (5-100), preferably 1: (6 to 60), for example, 1:6.7, 1: 15. 1:20 or 1:60;
(3) The triblock copolymer is a polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer, a polyethylene oxide-polybutylene oxide-polyethylene oxide triblock copolymer or a polypropylene oxide-polyethylene oxide-polypropylene oxide triblock copolymer;
(4) The magnesium salt is inorganic magnesium salt or organic magnesium salt; the inorganic magnesium salt is preferably magnesium nitrate and/or magnesium chloride; the organic magnesium salt is preferably one or more of magnesium ethoxide, magnesium acetate, magnesium gluconate, magnesium citrate, magnesium tert-butoxide, isopropyl magnesium chloride and isobutyl magnesium bromide; and
(5) The mass ratio of the magnesium salt to the triblock copolymer is 1: (0.1 to 8), for example, 1:0.17, 1:0.5, 1:3 or 1:6.
3. the method for producing a hard carbon material according to claim 1, wherein an additive is further added in the step of mixing;
wherein the additive is preferably a silicon-containing agent, more preferably one or more of trimethylsilyl acetate, tetraethyl silicate, polysiloxane, and diphenylsilanediol;
the ratio of the mass of the magnesium salt to the volume of the additive is preferably 1: (0.5-25) g/mL, more preferably 1: (1-20) g/mL, for example 1:1.4g/mL, 1:5.6g/mL or 1:16g/mL.
4. The method of producing a hard carbon material according to claim 1, wherein the method of producing satisfies one or more of the following conditions:
(1) The pre-carbonization temperature is 250 to 700 ℃, preferably 400 to 550 ℃, such as 420 ℃, 450 ℃ or 500 ℃;
(2) The pre-carbonization time is 1 to 10 hours, preferably 1 to 4 hours, for example 2 hours or 3 hours;
(3) The acid is one or more of hydrochloric acid, phosphoric acid, sulfuric acid, hydrofluoric acid, nitric acid, salicylic acid and acetic acid;
(4) The concentration of the acid is 0.1 to 5.0mol/L, preferably 0.5 to 2.0mol/L, such as 1.0mol/L; and
(5) The pickling time is 1 to 10 hours, preferably 2 to 6 hours, for example 4 hours.
5. The method of producing a hard carbon material according to claim 1, wherein the method of producing satisfies one or more of the following conditions:
(1) The particle size of the pulverization is 3 to 8 μm, for example 5 μm;
(2) The carbonization temperature is 800-1600 ℃, preferably 900-1400 ℃, such as 1150 ℃;
(3) The carbonization time is 1 to 12 hours, preferably 2 to 6 hours, for example 4 hours; and
(4) The rate of heating to the carbonization temperature is 0.5 to 10 c/min, preferably 1 to 5 c/min, for example 3.5 c/min.
6. The method of producing a hard carbon material according to claim 1, wherein the solvothermal treatment satisfies one or more of the following conditions:
(1) The solvent used in the solvothermal treatment process is water or ethanol;
(2) The solvothermal treatment is at a temperature of 80 to 200 ℃, preferably 160 to 200 ℃, such as 170 ℃, 180 ℃ or 190 ℃; and
(3) The solvothermal treatment is for a period of 4 to 18 hours, preferably 6 to 10 hours, for example 7, 8 or 9 hours.
7. A hard carbon material, characterized in that it is produced by the method for producing a hard carbon material according to any one of claims 1 to 6.
8. A hard carbon material characterized by a pore size distribution in the order of micropores, preferably 0.4-1nm;
preferably, the hard carbon material has one or more of the following parameters: particle diameter D 50 3-6 μm, and a compaction density of 0.6-1.2g/cm 3 Specific surface area of 4-20m 2 The sum of the sodium embedding capacity of the high and low potential areas is 340-3838 mAh.g -1 The sodium embedding capacity of the high potential area is 58-142mAh.g -1 The sodium embedding capacity of the low potential area is 210-299mAh.g -1 And the first effect is 82% -88%.
9. Use of a hard carbon material according to claim 7 or 8 for the preparation of a sodium ion battery or a lithium ion battery.
10. A battery comprising the hard carbon material of claim 7 or 8, wherein the battery is a sodium ion battery or a lithium ion battery.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN116731527A (en) * | 2023-06-15 | 2023-09-12 | 浙江华宇钠电新能源科技有限公司 | Asphalt mixture and application thereof in preparing sodium ion battery for vehicle |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN116731527A (en) * | 2023-06-15 | 2023-09-12 | 浙江华宇钠电新能源科技有限公司 | Asphalt mixture and application thereof in preparing sodium ion battery for vehicle |
| CN116731527B (en) * | 2023-06-15 | 2023-10-31 | 浙江华宇钠电新能源科技有限公司 | Asphalt mixture and application thereof in preparing sodium ion battery for vehicle |
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