CN116692830A - Hard carbon material, preparation method thereof, negative electrode material and alkali metal ion battery - Google Patents
Hard carbon material, preparation method thereof, negative electrode material and alkali metal ion battery Download PDFInfo
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- CN116692830A CN116692830A CN202310876384.2A CN202310876384A CN116692830A CN 116692830 A CN116692830 A CN 116692830A CN 202310876384 A CN202310876384 A CN 202310876384A CN 116692830 A CN116692830 A CN 116692830A
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- ion battery
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- 239000003575 carbonaceous material Substances 0.000 title claims abstract description 199
- 229910021385 hard carbon Inorganic materials 0.000 title claims abstract description 186
- 229910001413 alkali metal ion Inorganic materials 0.000 title claims abstract description 19
- 239000007773 negative electrode material Substances 0.000 title claims abstract description 15
- 238000002360 preparation method Methods 0.000 title abstract description 40
- 238000011282 treatment Methods 0.000 claims abstract description 130
- 241001494508 Arundo donax Species 0.000 claims abstract description 44
- 230000004913 activation Effects 0.000 claims abstract description 44
- 239000002243 precursor Substances 0.000 claims abstract description 33
- 239000002994 raw material Substances 0.000 claims abstract description 30
- 238000003763 carbonization Methods 0.000 claims abstract description 29
- 238000010000 carbonizing Methods 0.000 claims abstract description 10
- 238000004519 manufacturing process Methods 0.000 claims abstract 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 48
- 238000001035 drying Methods 0.000 claims description 43
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 38
- 238000010438 heat treatment Methods 0.000 claims description 38
- 238000009656 pre-carbonization Methods 0.000 claims description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 29
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 28
- 239000002245 particle Substances 0.000 claims description 26
- 238000005406 washing Methods 0.000 claims description 24
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims description 23
- 229910001415 sodium ion Inorganic materials 0.000 claims description 23
- 239000012298 atmosphere Substances 0.000 claims description 22
- 239000007789 gas Substances 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 21
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 19
- 229910052757 nitrogen Inorganic materials 0.000 claims description 19
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 15
- 229910052739 hydrogen Inorganic materials 0.000 claims description 15
- 239000001257 hydrogen Substances 0.000 claims description 15
- 238000002156 mixing Methods 0.000 claims description 15
- 239000002904 solvent Substances 0.000 claims description 15
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 14
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 14
- 229910052786 argon Inorganic materials 0.000 claims description 14
- 230000001681 protective effect Effects 0.000 claims description 14
- 239000000126 substance Substances 0.000 claims description 14
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 12
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 12
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 11
- 229910052799 carbon Inorganic materials 0.000 claims description 11
- 229910001416 lithium ion Inorganic materials 0.000 claims description 11
- 238000007873 sieving Methods 0.000 claims description 10
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 9
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 8
- 239000011229 interlayer Substances 0.000 claims description 8
- 229910052760 oxygen Inorganic materials 0.000 claims description 8
- 239000001301 oxygen Substances 0.000 claims description 8
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 8
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 claims description 7
- 229910001414 potassium ion Inorganic materials 0.000 claims description 7
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 6
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 6
- 229910021529 ammonia Inorganic materials 0.000 claims description 4
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 4
- 235000011181 potassium carbonates Nutrition 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 239000005456 alcohol based solvent Substances 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- 239000013078 crystal Substances 0.000 claims description 3
- 238000007598 dipping method Methods 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 3
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 239000011736 potassium bicarbonate Substances 0.000 claims description 3
- 229910000028 potassium bicarbonate Inorganic materials 0.000 claims description 3
- 235000015497 potassium bicarbonate Nutrition 0.000 claims description 3
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims description 3
- 235000017550 sodium carbonate Nutrition 0.000 claims description 3
- 238000002791 soaking Methods 0.000 claims description 2
- 235000017166 Bambusa arundinacea Nutrition 0.000 claims 1
- 235000017491 Bambusa tulda Nutrition 0.000 claims 1
- 241001330002 Bambuseae Species 0.000 claims 1
- 235000014676 Phragmites communis Nutrition 0.000 claims 1
- 235000015334 Phyllostachys viridis Nutrition 0.000 claims 1
- 241000287219 Serinus canaria Species 0.000 claims 1
- 239000011425 bamboo Substances 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 4
- 239000010405 anode material Substances 0.000 abstract description 3
- 238000009776 industrial production Methods 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 20
- 239000011148 porous material Substances 0.000 description 15
- 239000000243 solution Substances 0.000 description 14
- 238000003860 storage Methods 0.000 description 14
- 238000012360 testing method Methods 0.000 description 14
- 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 description 12
- 229910052708 sodium Inorganic materials 0.000 description 12
- 239000011734 sodium Substances 0.000 description 12
- 239000008367 deionised water Substances 0.000 description 10
- 229910021641 deionized water Inorganic materials 0.000 description 10
- 239000000047 product Substances 0.000 description 10
- 230000005347 demagnetization Effects 0.000 description 9
- 238000011056 performance test Methods 0.000 description 9
- 238000001816 cooling Methods 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 239000012299 nitrogen atmosphere Substances 0.000 description 6
- 239000002028 Biomass Substances 0.000 description 5
- 238000004140 cleaning Methods 0.000 description 5
- 238000000227 grinding Methods 0.000 description 5
- 239000012535 impurity Substances 0.000 description 5
- 239000013067 intermediate product Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 239000012300 argon atmosphere Substances 0.000 description 4
- 239000011889 copper foil Substances 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 238000005245 sintering Methods 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- 239000004743 Polypropylene Substances 0.000 description 3
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- -1 polypropylene Polymers 0.000 description 3
- 229920001155 polypropylene Polymers 0.000 description 3
- 238000004537 pulping Methods 0.000 description 3
- 238000010298 pulverizing process Methods 0.000 description 3
- 238000004080 punching Methods 0.000 description 3
- 238000005096 rolling process Methods 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 235000012239 silicon dioxide Nutrition 0.000 description 3
- 239000012798 spherical particle Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- 239000003929 acidic solution Substances 0.000 description 2
- 230000003113 alkalizing effect Effects 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 238000009831 deintercalation Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000009830 intercalation Methods 0.000 description 2
- 230000002687 intercalation Effects 0.000 description 2
- 229920005610 lignin Polymers 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 230000008707 rearrangement Effects 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- 241000894007 species Species 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 description 1
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- 235000017060 Arachis glabrata Nutrition 0.000 description 1
- 244000105624 Arachis hypogaea Species 0.000 description 1
- 235000010777 Arachis hypogaea Nutrition 0.000 description 1
- 235000018262 Arachis monticola Nutrition 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- 235000001759 Citrus maxima Nutrition 0.000 description 1
- 244000276331 Citrus maxima Species 0.000 description 1
- 241000383566 Donax <angiosperm> Species 0.000 description 1
- 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 description 1
- 229920002488 Hemicellulose Polymers 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- 240000002853 Nelumbo nucifera Species 0.000 description 1
- 235000006508 Nelumbo nucifera Nutrition 0.000 description 1
- 235000006510 Nelumbo pentapetala Nutrition 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 1
- 229930006000 Sucrose Natural products 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 239000010426 asphalt Substances 0.000 description 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011847 coal-based material Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000012983 electrochemical energy storage Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 239000007770 graphite material Substances 0.000 description 1
- 238000005087 graphitization Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000013081 microcrystal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 235000020232 peanut Nutrition 0.000 description 1
- 239000002006 petroleum coke Substances 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 239000010908 plant waste Substances 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920000767 polyaniline Polymers 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000661 sodium alginate Substances 0.000 description 1
- 235000010413 sodium alginate Nutrition 0.000 description 1
- 229940005550 sodium alginate Drugs 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- 239000003232 water-soluble binding agent Substances 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- 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)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The application provides a hard carbon material and a preparation method thereof, a negative electrode material and an alkali metal ion battery, and relates to the technical field of battery materials. The hard carbon material internally comprises a closed cell structure, and the closed cell volume is 0.113cm 3 /g‑0.272cm 3 /g; the raw materials for preparing the hard carbon material comprise arundo donax. A method of making a hard carbon material comprising: pre-carbonizing arundo donax to obtain a precursor carbon material; sequentially carrying out alkalization treatment and activation treatment on the precursor carbon material to obtain an intermediate carbon material; and performing hard carbonization treatment on the intermediate carbon material to obtain the hard carbon material. The application uses the arundo donax which is cheap and easy to obtain as the raw material, effectively reduces the preparation cost of the hard carbon material,the preparation method is suitable for industrial production, has good application prospect, and the prepared hard carbon material has the characteristics of high capacity, high initial efficiency, excellent multiplying power performance and cycle performance, and is suitable for being used as an alkali metal ion battery anode material.
Description
Technical Field
The application relates to the technical field of battery materials, in particular to a hard carbon material and a preparation method thereof, a negative electrode material and an alkali metal ion battery.
Background
The development of new energy technology has been attracting attention, in which electrochemical energy storage is a hot spot of research, so that alkali metal ion batteries have been widely studied. The lithium ion battery is commercialized successfully, and the technology is mature, but the lithium ion battery is limited by the problems of low lithium resource content, uneven distribution and the like, so that the cost of the lithium ion battery is increased; the sodium ion battery and the potassium ion battery are considered as complementers of the lithium ion battery, and have excellent application prospects in the energy storage field. Currently, the negative electrode material of the alkali metal ion battery is mainly a carbon-based material, such as a graphite material, but the structural stability of graphite is poor, the compatibility with electrolyte is poor, the rate performance is poor, and the negative electrode material also shows low sodium storage capacity in the sodium ion battery. Therefore, it is expected to prepare a novel anode material having high specific capacity, excellent rate performance and long cycle life. The hard carbon material belongs to non-graphitized carbon, graphite microcrystals in the hard carbon material are arranged randomly and disordered, the interlayer spacing is larger than that of graphite, and a cavity structure is formed, so that the intercalation and deintercalation of alkaline ions are facilitated. Therefore, the hard carbon material is used as a negative electrode of an alkali metal ion battery, and has high specific capacity, excellent rate performance and cycle stability.
At present, the sources of precursors of hard carbon materials are mainly classified into biomass, high molecular species, resins, petrochemical byproducts and coal-based carbon materials. The high molecular precursor is mainly extracted from biomass to obtain chemical products including glucose, sucrose, starch, cellulose, lignin and the like, and has the defects of poor conductive performance and the like, is not beneficial to the transmission of electrons, and is not suitable for preparing hard carbon materials; the resin precursor mainly comprises phenolic resin, polyaniline, polyacrylonitrile and the like, has higher carbon yield, and the prepared hard carbon material has stable structure, but organic solvents are needed in the preparation process of the hard carbon, so that the difficulty of the crosslinking reaction is effectively controlled; the petrochemical byproducts and coal-based materials are mainly coal, asphalt, petroleum coke and the like, and have the advantages of low cost, high carbon yield and the like, but graphitization is easy to occur in the high-temperature carbonization process, so that a highly ordered carbon layer structure is formed, and sodium ion storage is not facilitated; the biomass precursors are mainly agricultural and forestry plant wastes such as lotus leaves, peanut shells, shaddock peels and the like, and the hard carbon materials prepared by taking the biomass precursors as raw materials can greatly reduce the cost. Therefore, it is urgently required to develop a biomass raw material with low cost to prepare a hard carbon material, and use the hard carbon material as a negative electrode material of an alkali metal ion battery to improve the specific capacity and cycle performance of the battery.
Disclosure of Invention
The application aims to provide a hard carbon material, a preparation method thereof, a negative electrode material and an alkali metal ion battery.
In order to achieve the above object, the technical scheme of the present application is as follows:
in a first aspect, the present application provides a hard carbon material comprising a closed cell structure within the hard carbon material, the closed cell volume being 0.113cm 3 /g-0.272cm 3 /g; the raw materials for preparing the hard carbon material comprise arundo donax.
With reference to the first aspect, in a preferred embodiment of the present application, the hard carbon material meets at least one of the following conditions:
a. the carbon content in the hard carbon material is more than or equal to 89wt%, the oxygen content is less than or equal to 5.5wt%, the nitrogen content is less than or equal to 0.5wt%, and the hydrogen content is less than or equal to 0.7wt%;
b. the hard carbon material has a particle size d50=4.5 μm to 30 μm;
c. the interlayer distance d002 of the (002) crystal face of the hard carbon material is 0.355nm-0.405nm;
d. the specific surface area of the hard carbon material is 1.2m 2 /g-30m 2 /g。
In a second aspect, the present application also provides a method for preparing the hard carbon material according to the first aspect, including:
pre-carbonizing arundo donax to obtain a precursor carbon material;
sequentially carrying out alkalization treatment and activation treatment on the precursor carbon material to obtain an intermediate carbon material;
and carrying out hard carbonization treatment on the intermediate carbon material to obtain the hard carbon material.
With reference to the second aspect, in a preferred embodiment of the present application, the preparation method satisfies at least one of the following conditions:
A. before the pre-carbonization treatment, the method comprises the following steps: washing and drying the arundo donax with water, and then crushing to obtain arundo donax particles;
B. the atmosphere conditions of the pre-carbonization treatment are as follows: in a vacuum or protective gas atmosphere;
C. the temperature of the pre-carbonization treatment is 350-550 ℃ and the time is 0.5-12 h;
D. the heating rate of the pre-carbonization treatment is 1 ℃/min-10 ℃/min.
In a preferred embodiment of the application, the preparation method further fulfils at least one of the following conditions:
E. the alkalization treatment comprises: mixing the precursor carbon material, alkaline substances and a solvent, then dipping, filtering and then carrying out first drying treatment;
F. the activation treatment includes: placing the product obtained by the alkalization treatment in vacuum or protective gas atmosphere for activation;
G. the temperature of the activation treatment is 550-900 ℃ and the time is 0.5-8 h;
H. the heating rate of the activation treatment is 1 ℃/min-20 ℃/min;
I. after the activation treatment, the method further comprises: and (3) repeatedly carrying out acid washing and water washing on the product obtained by the activation treatment, and then carrying out second drying treatment.
Further preferably, the preparation method further satisfies at least one of the following conditions:
J. the alkaline substance comprises at least one of lithium hydroxide, sodium hydroxide, potassium hydroxide, lithium carbonate, sodium carbonate, potassium carbonate, sodium bicarbonate and potassium bicarbonate;
K. the solvent comprises at least one of water and alcohol solvents;
and L, the mass ratio of the precursor carbon material to the alkaline substance to the solvent is 1: (0.01-0.2): (0.25-2);
m. the soaking time is 0.5h-10h;
n. the shielding gas comprises at least one of nitrogen, argon, ammonia, mixed gas of nitrogen and hydrogen and mixed gas of argon and hydrogen;
the acid solution used for acid washing comprises at least one of hydrochloric acid, sulfuric acid, nitric acid and phosphoric acid solution, and the concentration of the acid solution is 0.1mol/L-10mol/L;
and P, the temperature of the first drying treatment and the second drying treatment is 80-120 ℃ and the time is 8-16 h.
In a preferred embodiment of the application, the preparation method further fulfils at least one of the following conditions:
the atmosphere conditions of the hard carbonization treatment are as follows: in a vacuum or protective gas atmosphere;
R, the temperature of the hard carbonization treatment is 900-2200 ℃ and the time is 0.5-10 h;
s, the heating rate of the hard carbonization treatment is 1 ℃/min-15 ℃/min.
With reference to the second aspect, in a preferred embodiment of the present application, after the hard carbonization treatment, the method further includes: and crushing, sieving and demagnetizing the hard carbon treatment product to obtain the hard carbon material.
In a third aspect, the present application provides a negative electrode material comprising the hard carbon material of the first aspect.
In a fourth aspect, the present application provides an alkali metal ion battery comprising the negative electrode material of the third aspect, the alkali metal ion battery comprising a lithium ion battery, a sodium ion battery or a potassium ion battery.
The application has the beneficial effects that:
the hard carbon material provided by the application adopts arundo donax with the characteristics of simplicity, easiness in obtaining, low cost and the like as the raw material, and has a closed pore structure inside, so that the hard carbon material can be applied to an alkali metal ion battery, and the electrochemical performance of the battery is improved.
The preparation method of the hard carbon material has simple process, and the low-cost and easily-obtained arundo donax is used as the raw material, so that the preparation cost of the hard carbon material is effectively reduced, and the preparation method is suitable for industrial production. Specifically, through low-temperature pre-carbonization treatment, a precursor carbon material with preliminary pores can be formed, residual silicon dioxide impurities in the carbon material are removed through alkalization treatment and medium-temperature activation treatment, a porous structure of the carbon material is realized, and then through high-temperature hard carbonization treatment, rearrangement of a carbon layer is realized, the pore structure of the hard carbon material is regulated and controlled, and a rich closed-pore structure is obtained.
The hard carbon material is used in the negative electrode material of the alkali metal ion battery, and has the advantages that the surface pores and defects of the hard carbon material are few, the inside of the hard carbon material is provided with a rich closed cell structure, and the first coulomb efficiency and the cyclic stability are improved.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings that are needed in the embodiments will be briefly described below, it being understood that the following drawings only illustrate some embodiments of the present application and therefore should not be considered as limiting the scope of the present application.
FIG. 1 is an XRD pattern of a hard carbon material prepared in example 1;
FIG. 2 is an XRD pattern of the hard carbon material prepared in comparative example 1;
FIG. 3 is an XRD pattern of the hard carbon material prepared in comparative example 4;
FIG. 4 is an SEM image of a hard carbon material prepared according to example 1;
FIG. 5 is an SEM image of a hard carbon material prepared according to comparative example 4;
FIG. 6 is a charge-discharge curve of the hard carbon material prepared in example 1 in a lithium ion battery;
FIG. 7 is a graph showing the charge and discharge of the hard carbon material prepared in example 2 in a sodium ion battery;
FIG. 8 is a graph showing the charge and discharge of the hard carbon material prepared in example 3 in a potassium ion battery;
FIG. 9 is a graph showing the cycle performance of the hard carbon material prepared according to the third embodiment of example 8 in a sodium ion battery;
FIG. 10 is a graph showing the desorption of nitrogen from the hard carbon material of example 10;
fig. 11 is a graph showing the rate performance of the hard carbon material prepared in the iv-th example 10 in a sodium ion battery.
Detailed Description
The term as used herein:
"prepared from … …" is synonymous with "comprising". The terms "comprising," "including," "having," "containing," or any other variation thereof, as used herein, are intended to cover a non-exclusive inclusion. For example, a composition, step, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, step, method, article, or apparatus. The conjunction "consisting of … …" excludes any unspecified element, step or component.
When an equivalent, concentration, or other value or parameter is expressed as a range, preferred range, or a range bounded by a list of upper preferable values and lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. For example, when ranges of "1 to 5" are disclosed, the described ranges should be construed to include ranges of "1 to 4", "1 to 3", "1 to 2 and 4 to 5", "1 to 3 and 5", and the like. When a numerical range is described herein, unless otherwise indicated, the range is intended to include its endpoints and all integers and fractions within the range.
In these examples, the parts and percentages are by mass unless otherwise indicated.
"parts by mass" means a basic unit of measurement showing the mass ratio of a plurality of components, and 1 part may be any unit mass, for example, 1g may be expressed, 2.689g may be expressed, and the like. If we say that the mass part of the a component is a part and the mass part of the B component is B part, the ratio a of the mass of the a component to the mass of the B component is represented as: b. alternatively, the mass of the A component is aK, and the mass of the B component is bK (K is an arbitrary number and represents a multiple factor). It is not misunderstood that the sum of the parts by mass of all the components is not limited to 100 parts, unlike the parts by mass.
"and/or" is used to indicate that one or both of the illustrated cases may occur, e.g., a and/or B include (a and B) and (a or B).
The first object of the present application is to provide a hard carbon material comprising a closed cell structure inside, the closed cell volume being 0.113cm 3 /g-0.272cm 3 Per g, for example, may be 0.113cm 3 /g、0.129cm 3 /g、0.156cm 3 /g、0.175cm 3 /g、0.203cm 3 /g、0.224cm 3 /g、0.255cm 3 /g、0.272cm 3 Per g is alternatively 0.113cm 3 /g-0.272cm 3 Any value between/g. In particular, the hard carbon material is prepared from arundo donax as a raw material.
In a preferred embodiment of the application, the carbon content in the hard carbon material is more than or equal to 89wt%, for example 89wt%, 90wt%, 93wt%, 95wt%, 97wt% or 99wt%; the oxygen content is less than or equal to 5.5wt%, and can be 0.1wt%, 1wt%, 2wt%, 3wt%, 5wt% or 5.5wt%, for example; the nitrogen content is less than or equal to 0.5wt%, and can be, for example, 0.01wt%, 0.02wt%, 0.05wt%, 0.1wt%, 0.3wt% or 0.5wt%; the hydrogen content is less than or equal to 0.7wt%, for example, 0.01wt%, 0.1wt%, 0.3wt%, 0.5wt% or 0.7wt%.
In a preferred embodiment of the application, the particle size d50=4.5 μm-30 μm of the hard carbon material may be, for example, 4.5 μm, 5 μm, 1 μm, 15 μm, 20 μm, 25 μm, 30 μm or any value between 4.5 μm-30 μm.
In a preferred embodiment of the present application, the interlayer distance d002 of the (002) crystal face of the hard carbon material is 0.355nm to 0.405nm.
In a preferred embodiment of the application, the hard carbon material has a specific surface area of 1.2m 2 /g-30m 2 Per g, for example, may be 1.2m 2 /g、2m 2 /g、3m 2 /g、5m 2 /g、10m 2 /g、20m 2 /g、30m 2 /g is alternatively 1.2m 2 /g-30m 2 Any value between/g.
The second object of the present application is to provide a method for preparing the hard carbon material, comprising:
s1, carrying out pre-carbonization treatment on arundo donax to obtain a precursor carbon material;
s2, sequentially carrying out alkalization treatment and activation treatment on the precursor carbon material to obtain an intermediate carbon material;
s3, performing hard carbonization treatment on the intermediate carbon material to obtain the hard carbon material.
The raw materials of the arundo donax used in the application can be wild arundo donax, planted arundo donax or planted super arundo donax, and the raw materials are wide in source, simple and easy to obtain, low in cost, contain a large amount of cellulose, hemicellulose and lignin, and are suitable for preparing high-performance hard carbon materials.
In a preferred embodiment of the present application, before the pre-carbonization treatment in S1, the method comprises: and (3) cleaning and drying the arundo donax with water, and then crushing to obtain arundo donax particles.
Specifically, the temperature required for drying is 80-150 ℃ and the time is 4-24 hours, and the crushing treatment performed after the drying is coarse crushing treatment. More preferably, the drying is performed at a temperature of 80℃to 100 ℃.
In a preferred embodiment of the present application, the pre-carbonization treatment in S1 is performed in a vacuum or in an atmosphere of a protective gas. The shielding gas may be any one of nitrogen, argon, ammonia, a mixture of nitrogen and hydrogen, and a mixture of argon and hydrogen, and is more preferably nitrogen or argon.
In a preferred embodiment of the present application, the temperature of the pre-carbonization treatment in S1 is 350 ℃ to 550 ℃, for example, it may be 350 ℃, 400 ℃, 450 ℃, 500 ℃, 550 ℃ or any value between 350 ℃ and 550 ℃, more preferably 400 ℃ to 500 ℃.
The pre-carbonization treatment time is 0.5h to 12h, and may be, for example, 0.5h, 1h, 3h, 5h, 8h, 10h, 12h, or any value between 0.5h to 12h, and more preferably 2h to 6h.
The temperature rising rate of the pre-carbonization treatment is 1 ℃/min-10 ℃/min, for example, 1 ℃/min, 3 ℃/min, 5 ℃/min, 8 ℃/min, 10 ℃/min or any value between 1 ℃/min-10 ℃/min, more preferably 2 ℃/min-5 ℃/min.
The aim of the pre-carbonization is to remove volatile matters and water in the arundo donax raw material, improve the strength of the carbon material and form primary pores in the carbon material particles.
In a preferred embodiment of the present application, the alkalizing treatment in S2 comprises: and mixing the precursor carbon material, an alkaline substance and a solvent, then dipping, filtering and then performing first drying treatment.
Specifically, the alkaline substance includes at least one of lithium hydroxide, sodium hydroxide, potassium hydroxide, lithium carbonate, sodium carbonate, potassium carbonate, sodium bicarbonate, and potassium bicarbonate, and more preferably sodium hydroxide, sodium carbonate, or sodium bicarbonate.
The solvent comprises at least one of water and alcohol solvents, and more preferably deionized water.
The mass ratio of the precursor carbon material, the alkaline substance and the solvent in the alkalizing treatment process is 1: (0.01-0.2): (0.25-2), which may be, for example, 1:0.01:0.25, 1:0.05:0.5, 1:0.1: 1. 1:0.15:1.5, 1:0.2:2 is either 1: (0.01-0.2): any value between (0.25-2), more preferably 1: (0.06-0.1): (0.5-1).
The time required for the impregnation is 0.5h to 10h, and may be, for example, 0.5h, 1h, 3h, 5h, 8h, 10h or any value between 0.5h and 10h, more preferably 5h to 10h.
The temperature of the first drying treatment is 80-120 ℃ and the time is 8-16 h.
In a preferred embodiment of the present application, the activation treatment in S2 includes: and (3) placing the product obtained by the alkalization treatment in a vacuum or protective gas atmosphere for activation. Wherein the shielding gas comprises at least one of nitrogen, argon, ammonia, mixed gas of nitrogen and hydrogen and mixed gas of argon and hydrogen.
In a preferred embodiment of the present application, the temperature of the activation treatment in S2 is 550 ℃ to 900 ℃, for example, may be 550 ℃, 600 ℃, 700 ℃, 800 ℃, 900 ℃ or any value between 550 ℃ and 900 ℃, more preferably 600 ℃ to 800 ℃.
The temperature of the activation treatment is 0.5h to 8h, and may be, for example, 0.5h, 1h, 2h, 5h, 6h, 8h, or any value between 0.5h and 8h, and more preferably 2h to 4h.
The heating rate of the activation treatment is 1℃to 20℃per minute, and may be, for example, 1℃per minute, 3℃per minute, 5℃per minute, 10℃per minute, 15℃per minute, 20℃per minute, or any value between 1℃per minute and 20℃per minute, more preferably 1℃per minute to 5℃per minute.
The application aims to remove the residual silicon dioxide impurity in the precursor carbon material and realize the porous structure of the carbon material.
In a preferred embodiment of the present application, after the activation treatment in S2, further comprising: and (3) repeatedly carrying out acid washing and water washing on the product obtained by the activation treatment, and then carrying out second drying treatment. Wherein the temperature of the second drying treatment is 80-120 ℃ and the time is 8-16 h.
It will be appreciated that the washing solution is neutral and then subjected to a second drying treatment, and the repeated pickling and washing is carried out to remove the residual alkaline solutes and metallic impurities in the product.
Further preferably, the acidic solution used for the acid washing includes at least one of hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid solution, and the concentration of the acidic solution is 0.1mol/L to 10mol/L, more preferably 0.5mol/L to 6mol/L.
In a preferred embodiment of the present application, the hard carbonization treatment in S3 is also required to be performed in a vacuum or an atmosphere of a protective gas.
In a preferred embodiment of the present application, the temperature of the hard-carbonizing treatment in S3 is 900 to 2200 ℃, for example, may be 900 ℃, 1000 ℃, 1200 ℃, 1400 ℃, 1600 ℃, 1800, 2000, 2200, or any value between 900 to 2200 ℃, more preferably 1200 to 1800 ℃.
The time for the hard carbonization treatment is 0.5h to 10h, and may be, for example, 0.5h, 1h, 2h, 5h, 6h, 8h, or any value between 0.5h to 10h, and more preferably 1h to 3h.
The heating rate of the hard carbonization treatment is 1 ℃/min to 15 ℃/min, and may be, for example, 1 ℃/min, 3 ℃/min, 5 ℃/min, 10 ℃/min, 15 ℃/min or any value between 1 ℃/min and 15 ℃/min, and more preferably 2 ℃/min to 5 ℃/min.
The application adopts high-temperature hard carbonization treatment to convert the carbon material into a hard carbon material, regulate and control the pore structure of the hard carbon material and obtain a structure with abundant closed pores.
In a preferred embodiment of the present application, after the hard carbonization treatment in S3, the method further comprises: and crushing, sieving and demagnetizing the hard carbon treatment product to obtain the hard carbon material.
Specifically, in the case of pulverizing, an air flow pulverizer is used for pulverizing; when sieving, the mesh number is 200-1500 mesh, more preferably 300-500 mesh; the demagnetizing is carried out by a demagnetizing machine.
A third object of the present application is to provide a negative electrode material comprising the hard carbon material described above.
A fourth object of the present application is to provide an alkali metal ion battery comprising the above-described anode material, wherein the alkali metal ion battery comprises a lithium ion battery, a sodium ion battery or a potassium ion battery.
Embodiments of the present application will be described in detail below with reference to specific examples, but it will be understood by those skilled in the art that the following examples are only for illustrating the present application and should not be construed as limiting the scope of the present application. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
Example 1
The embodiment provides a hard carbon material, and the preparation method thereof comprises the following steps:
(1): washing the planted super arundo donax with pure water, placing in a drying oven, drying at 80 ℃ for 15 hours, and mechanically coarsely crushing to obtain arundo donax particles.
(2): and (3) placing the arundo donax particles prepared in the step (1) into an atmosphere furnace, heating to 450 ℃ at a heating rate of 2 ℃/min under the nitrogen atmosphere, preserving heat for 4 hours, and performing pre-carbonization treatment to obtain the precursor carbon material.
(3): and (3) mixing the precursor carbon material prepared in the step (2), sodium hydroxide and deionized water according to the mass ratio of 1:0.15: and (3) after 0.75 of the raw materials are uniformly mixed, placing the raw materials in a vacuum box type furnace for drying treatment for 10 hours at 100 ℃, transferring the raw materials into an activation furnace, heating the raw materials to 650 ℃ at a heating rate of 5 ℃/min under a nitrogen atmosphere, preserving heat for 3 hours, performing activation treatment, cooling, repeatedly cleaning the raw materials for 3 times by using a hydrochloric acid solution with the concentration of 0.5mol/L and deionized water in sequence, washing the raw materials to be neutral, and placing the raw materials in a drying box for drying treatment for 10 hours at 80 ℃ to obtain the intermediate product carbon material.
(4): and (3) placing the intermediate product carbon material prepared in the step (3) in a high-temperature sintering furnace, heating to 1200 ℃ at a heating rate of 2 ℃/min under argon atmosphere, preserving heat for 4 hours, performing hard carbonization treatment, cooling, grinding by a jet mill, sieving by a 400-mesh screen, performing demagnetization treatment by a demagnetization machine, and mixing by a high-speed mixer to obtain the hard carbon material.
The hard carbon material prepared in this example was subjected to XRD test and scanning electron microscope test, respectively. The XRD test result is shown in figure 1, which shows that the prepared hard carbon material is amorphous hard carbon material and has higher disorder degree; according to the Bragg formula, the inter-plane distance d002 of the hard carbon material (002) is calculated to be 0.39nm, which is favorable for the intercalation and deintercalation of alkaline metal ions.
The morphology of the hard carbon material is shown in the SEM photograph of FIG. 4, and the hard carbon material is seen to be random particles, the particle size is about 0.4 μm to 21.2 μm, and the particles are smaller.
The embodiment also provides a negative electrode plate, and the hard carbon material prepared by the embodiment is used as a negative electrode active material. The preparation method of the negative electrode plate comprises the following steps:
according to the mass ratio of 90:4: weighing the hard carbon material prepared in the embodiment, conductive carbon black and polyvinylidene fluoride (PVDF), adding a proper amount of N-methyl pyrrolidone (NMP), mixing uniformly, continuously stirring in a high-speed pulping machine to obtain slurry, uniformly coating the slurry on copper foil, placing the copper foil in a vacuum drying oven at 120 ℃, drying for 12 hours, and finally rolling and punching to prepare the hard carbon negative plate. The surface density of the negative plate is 6.5mg/cm 2 -7.0mg/cm 2 。
The embodiment also provides a lithium ion battery, specifically, the hard carbon negative plate prepared in the embodiment is used as a working electrode, the metal lithium plate is used as a counter electrode, the Celgard 2325 polypropylene-based three-layer film is used as a battery diaphragm, and 1.0M LiPF 6 The solution of/EC+DEC+EMC (volume ratio of 1:1:1) is used as electrolyte, and the lithium ion battery is assembled in a glove box which is filled with argon and strictly controls the water oxygen index.
And standing the assembled lithium ion battery for 24 hours, and performing performance test by using a LAND battery tester, wherein the charge and discharge test voltage is 0-1.5V, and the current density is 50mA/g. The charge-discharge curve of the hard carbon negative electrode is shown in fig. 6, the first lithium storage specific capacity is 207.2mAh/g, and the first coulombic efficiency is 63.1%.
Example 2
The hard carbon material of this example and the preparation method thereof remain the same as in example 1.
The preparation method of the negative electrode plate provided by the embodiment comprises the following steps: according to the mass ratio of 92:3:5 weighing the hard carbon material prepared in example 1, conductive carbon black and sodium alginate, adding a proper amount of deionized water, mixing uniformly, continuously stirring in a high-speed pulping machine to obtain slurry, uniformly coating on copper foil, drying at 80 ℃ in a vacuum drying oven for 12 hours, and finally rolling and punching to obtain a hard carbon negative plate with the surface density of 6mg/cm 2 -6.5mg/cm 2 。
The embodiment provides a sodium ion battery, the hard carbon negative film prepared by the embodiment is used as a working electrode, the metal sodium sheet is used as a counter electrode, celgard2400 polypropylene film is used as a diaphragm,0.8MNaPF 6 the solution of/EC+DEC+PC (volume ratio of 3:2:5) was used as electrolyte, and the sodium ion battery was assembled in a glove box filled with argon and strictly controlled in water oxygen index.
After the battery is kept stand for 24 hours, a LAND battery tester is used for performance test, the charge and discharge test voltage is 0-1.5V, and the current density is 50mA/g. The charge-discharge curve of the hard carbon negative electrode is shown in fig. 7, the first sodium storage specific capacity is 270.4mAh/g, and the first coulombic efficiency is 92.4%.
Example 3
The hard carbon material of this example and the preparation method thereof remain the same as in example 1.
The preparation method of the negative electrode plate provided by the embodiment comprises the following steps: according to the mass ratio of 90:5:5 weighing the hard carbon material prepared in example 1, conductive carbon black and water-soluble binder, adding proper amount of deionized water, mixing uniformly, continuously stirring in a high-speed pulping machine to obtain slurry, uniformly coating on copper foil, drying at 100deg.C in a vacuum drying oven for 12 hours, and finally rolling and punching to obtain hard carbon negative plate with surface density of 5.5mg/cm 2 -6.2mg/cm 2 。
This example provides a potassium ion battery, in which the hard carbon negative electrode sheet prepared in this example is used as a working electrode, the metal potassium sheet is used as a counter electrode, celgard2500 polypropylene film is used as a diaphragm, and 0.8MKClO is used as a separator 4 The solution of/EC+DEC (volume ratio 1:1) was used as electrolyte, and the potassium ion battery was assembled in a glove box filled with argon and strictly controlled in water oxygen index.
After the battery is kept stand for 24 hours, a LAND battery tester is used for performance test, the charge and discharge test voltage is 0-1.5V, and the current density is 50mA/g. The charge-discharge curve of the hard carbon negative electrode is shown in fig. 8, the first potassium storage specific capacity is 191.8mAh/g, and the first coulombic efficiency is 66.8%.
Example 4
This example provides two hard carbon materials, the preparation of which is the same as example 1, except that: in the step (1) of the first species, the planted super arundo donax is replaced by wild arundo donax;
and II, replacing the planted superarundo donax with the planted arundo donax in the step (1).
The two hard carbon materials are prepared into a hard carbon negative plate and assembled into a sodium ion battery, and the specific preparation process is consistent with that of the embodiment 2.
The sodium storage specific capacity of the hard carbon anode prepared in the first type is 205.9mAh/g, and the coulomb efficiency is 77.9%; the sodium storage specific capacity of the hard carbon cathode prepared in the second step is 243.5mAh/g, and the coulombic efficiency is 88.3%.
Example 5
This example provides three hard carbon materials, the preparation of which is the same as example 1, except that: the pre-carbonization temperature in the step (2) of the first type is 350 ℃, the pre-carbonization time is 12 hours, and the heating rate is 10 ℃/min;
the pre-carbonization temperature in the step (2) of the II is 500 ℃, the pre-carbonization time is 6 hours, and the heating rate is 5 ℃/min;
the pre-carbonization temperature in the step (2) of the III type is 550 ℃, the pre-carbonization time is 1 hour, and the heating rate is 1 ℃/min.
The three hard carbon materials are prepared into a hard carbon negative plate and assembled into a sodium ion battery, and the specific preparation process is consistent with that of the embodiment 2.
The sodium storage specific capacity of the hard carbon anode prepared in the first type is 249.9mAh/g, and the coulomb efficiency is 87.6%; the sodium storage specific capacity of the hard carbon cathode manufactured in the II is 242.6mAh/g, the coulombic efficiency is 88.2%, and the sodium storage specific capacity of the hard carbon cathode manufactured in the III is 249.5mAh/g, and the coulombic efficiency is 87.3%.
Example 6
This example provides six hard carbon materials, the preparation of which is the same as example 1, except that: in the step (3) of the first type, sodium hydroxide is replaced by potassium hydroxide, and the mass ratio of the precursor carbon material to the alkaline solute to the solvent is 1:0.2:2;
In the step (3) of the II, sodium hydroxide is replaced by sodium carbonate, and the mass ratio of the precursor carbon material to the alkaline solute to the solvent is 1:0.01:2;
in the step (3) of the third kind, sodium hydroxide is replaced by sodium bicarbonate, and the mass ratio of the precursor carbon material to the alkaline solute to the solvent is 1:0.05:1, a step of;
in the step (3) of the fourth type, sodium hydroxide is replaced by a mixture of sodium hydroxide and sodium bicarbonate (the mass ratio is 1:1), and the mass ratio of the precursor carbon material, the alkaline substance and the solvent is 1:0.01:0.25;
in the step (3) of the fifth seed, sodium hydroxide is replaced by a mixture of sodium carbonate and sodium bicarbonate, and the mass ratio of the precursor carbon material, the alkaline substance and the solvent is 1:0.2:1, a step of;
in the step (3) of the VI, sodium hydroxide is replaced by a mixture of potassium hydroxide and potassium carbonate, and the mass ratio of the precursor carbon material, the alkaline substance and the solvent is 1:0.2:0.25.
the 6 hard carbon materials provided in this example were compared with the hard carbon material prepared in example 1, and found that: the substitution of the alkaline substance has an influence on the specific surface area of the hard carbon material. The specific surface area of the hard carbon material prepared after the activation of sodium carbonate is the smallest, the specific surface area of the hard carbon material prepared after the activation of sodium hydroxide, sodium bicarbonate and the mixture of the sodium hydroxide and the sodium bicarbonate is a little larger, the specific surface area of the activated potassium hydroxide is the largest, and the pore-forming effect of the potassium hydroxide is better than that of other activators, but most of the pore-forming agents are of open pore structures.
Example 7
This example provides three hard carbon materials, the preparation of which is the same as example 1, except that: the activation temperature in the step (3) of the first type is 550 ℃, the activation time is 8 hours, and the heating rate is 20 ℃/min;
the activation temperature in the step (3) of the II is 900 ℃, the activation time is 0.5 hour, and the heating rate is 1 ℃/min;
the activation temperature in step (3) of the third kind is 700 ℃, the activation time is 4 hours, and the temperature rising rate is 3 ℃/min.
The three hard carbon materials are prepared into a hard carbon negative plate and assembled into a sodium ion battery, and the specific preparation process is consistent with that of the embodiment 2.
The sodium storage specific capacity of the hard carbon negative electrode prepared from the first hard carbon material is 234.4mAh/g; the sodium storage specific capacity of the hard carbon negative electrode prepared from the II hard carbon material is 249.3mAh/g, and the sodium storage specific capacity of the hard carbon negative electrode prepared from the III hard carbon material is 252.7mAh/g.
Example 8
This example provides three hard carbon materials, the preparation of which is the same as example 1, except that: the hard-carbonizing treatment temperature in the step (4) of the first type is 900 ℃, the hard-carbonizing treatment time is 10 hours, and the heating rate is 15 ℃/min;
step II ((4) the hard-carbonizing treatment temperature is 2200 ℃, the hard-carbonizing treatment time is 1 hour, and the heating rate is 5 ℃/min);
The hard-carbonizing treatment temperature in step (4) of the third kind was 1300 ℃, the hard-carbonizing treatment time was 3 hours, and the heating rate was 2 ℃/min.
The content of four elements of carbon, hydrogen, oxygen and nitrogen in the hard carbon material prepared in the third step was analyzed by an organic Element Analyzer (EA), and the result showed that the carbon content was 90.1wt%, the hydrogen content was 0.70wt%, the oxygen content was 5.1wt% and the nitrogen content was 0.46wt%.
The three hard carbon materials are tested by a true density instrument to have the true densities of 1.75g/cm respectively 3 ，1.62g/cm 3 ，1.55g/cm 3 According to formula V close Pore ＝1/(ρ ture ) 1/2.26, calculated to be 0.129cm closed cell volume of the hard carbon material 3 /g，0.175cm 3 /g，0.203cm 3 /g。
The three hard carbon materials are prepared into a hard carbon negative plate and assembled into a sodium ion battery, and the specific preparation process is consistent with that of the embodiment 2.
The first sodium storage specific capacity of the hard carbon negative electrode prepared from the III hard carbon material is 277.3mAh/g, and after 50 times of circulation, the capacity retention rate is 97.4%, as shown in figure 9.
Example 9
This example provides five hard carbon materials, the preparation method of which is the same as example 1, except that: the protective atmosphere in the step (4) of the first kind is changed into vacuum;
the protective atmosphere in the step (4) of the II is replaced by argon;
the protective atmosphere in the step (4) of the III type is changed into ammonia gas;
The protective atmosphere in the step (4) of the IV is changed into nitrogen/hydrogen mixed gas;
the protective atmosphere in the step (4) of the fifth seed is changed into argon/hydrogen mixed gas.
The five hard carbon materials are prepared into a hard carbon negative plate and assembled into a sodium ion battery, and the specific preparation process is consistent with that of the embodiment 2.
The specific capacity of the hard carbon negative electrode prepared from the I-type hard carbon material is 253.9mAh/g under the test condition of 50mA/g of current density.
Example 10
This example provides four hard carbon materials, the preparation method of which is the same as example 1, except that: the screen mesh number in the step (4) of the first type is changed to 200 meshes;
the mesh number in step (4) of the II is changed to 500 mesh;
the mesh number in step (4) of the third kind is changed to 1000 mesh;
the mesh number in step (4) of the fourth type is changed to 1500 mesh.
The particle size and specific surface area of the four hard carbon materials were measured by a laser particle size analyzer and a full-automatic specific surface and pore size analyzer (nitrogen adsorption BET method), and the results were:
the hard carbon material obtained in the first step had a median particle diameter (D50) of 22.1. Mu.m, and a specific surface area of 3.3m as seen from an analysis of a nitrogen adsorption/desorption curve (shown in FIG. 10) 2 /g。
The hard carbon material produced in the second step has a median particle diameter (D50) of 11.4 μm and a specific surface area of 5.7m 2 /g。
The hard carbon material produced in the third step has a median particle diameter (D50) of 8.6 μm and a specific surface area of 13.9m 2 /g。
The hard carbon material obtained in the fourth step has a median particle diameter (D50) of 5.5 μm and a specific surface area of 28.2m 2 /g。
The preparation of the hard carbon negative electrode and the assembly of the sodium ion battery are basically consistent with the embodiment 2, and the voltage interval of the electrochemical performance test is 0-1.5V.
The rate capability of the hard carbon anode prepared in the fourth step is shown in figure 11, and the specific capacities of the hard carbon anode are 301.69, 289.67, 278.1, 266.3, 246.53 and 187.29mAh/g under the test conditions of current densities of 25, 50, 100, 200, 500 and 1000mA/g respectively.
Comparative example 1
This comparative example provides a hard carbon material prepared in the same manner as in example 1, except that: the treatment of the step (2) and the step (3) is not carried out;
the method comprises the following steps: washing Arundo donax with pure water, drying at 80deg.C for 15 hr, and mechanically coarse pulverizing to obtain Arundo donax granule; and (3) placing arundo donax particles in a high-temperature sintering furnace, heating to 1200 ℃ at a heating rate of 2 ℃/min under argon atmosphere, preserving heat for 3 hours, performing hard carbonization treatment, cooling, grinding by an air flow mill, sieving by a 400-mesh screen, performing demagnetization treatment by a demagnetization machine, and mixing by a high-speed mixer to obtain the hard carbon material.
The preparation of the hard carbon negative electrode sheet, the assembly of the sodium ion battery and the electrochemical performance test were substantially identical to example 2.
Under the test condition of 50mA/g, the highest specific capacity of the hard carbon anode is 207.6mAh/g, the initial coulombic efficiency is 79.4%, after 3 circles of circulation, under the test condition of 200mA/g, the specific capacity is 197.0mAh/g, and after 20 circles of circulation, the capacity retention rate is 99.3%.
Comparative example 2
This comparative example provides a hard carbon material prepared in the same manner as in example 1, except that: the treatment of step (2) is not performed;
specifically, (1): and (3) washing the arundo donax with pure water, putting the arundo donax in a drying oven, drying at 80 ℃ for 15 hours, and mechanically coarsely crushing to obtain arundo donax particles.
(2): and (3) mixing the pre-arundo donax particles prepared in the step (1), sodium hydroxide and deionized water according to the mass ratio of 1:0.15:0.75 is evenly mixed, then is placed in a vacuum box type furnace for drying treatment for 10 hours at 100 ℃, then is moved into an activation furnace, is heated to 650 ℃ at a heating rate of 5 ℃/min under the atmosphere of nitrogen, is insulated for 3 hours, is subjected to activation treatment, is repeatedly washed for 3 times by a hydrochloric acid solution with the concentration of 0.5mol/L and deionized water in sequence after being cooled, is placed in a drying box for drying treatment for 10 hours at 80 ℃ after being washed to be neutral, and is an intermediate product carbon material;
(3): and (3) placing the intermediate product carbon material prepared in the step (2) in a high-temperature sintering furnace, heating to 1200 ℃ at a heating rate of 2 ℃/min under argon atmosphere, preserving heat for 2 hours, performing hard carbonization treatment, cooling, grinding by a jet mill, sieving by a 320-mesh screen, performing demagnetization treatment by a demagnetization machine, and mixing by a high-speed mixer to obtain the hard carbon material.
The preparation of the hard carbon negative electrode sheet, the assembly of the sodium ion battery and the electrochemical performance test were substantially identical to example 2.
The highest specific capacity of the hard carbon negative electrode under the test condition of 50mA/g is 209.73mAh/g, and the initial coulombic efficiency is 68.12%.
Comparative example 3
This comparative example provides a hard carbon material prepared in the same manner as in example 1, except that: the activation treatment in step (3) is not performed;
specifically, (1): and (3) washing the arundo donax with pure water, putting the arundo donax in a drying oven, drying at 80 ℃ for 15 hours, and mechanically coarsely crushing to obtain arundo donax particles.
(2): and (3) placing the arundo donax particles prepared in the step (1) into an atmosphere furnace, heating to 450 ℃ at a heating rate of 2 ℃/min under the nitrogen atmosphere, preserving heat for 4 hours, and performing pre-carbonization treatment to obtain the precursor carbon material.
(3): and (3) placing the precursor carbon material prepared in the step (2) in a vacuum box furnace, drying at 100 ℃ for 10 hours, transferring to an activation furnace, heating to 650 ℃ at a heating rate of 5 ℃/min under nitrogen atmosphere, preserving heat for 3 hours, cooling, repeatedly cleaning for 3 times sequentially with 0.5mol/L hydrochloric acid solution and deionized water, washing to neutrality, and placing in a drying box for drying at 80 ℃ for 10 hours to obtain the intermediate carbon material.
(4): and (3) placing the intermediate product carbon material prepared in the step (3) in a high-temperature sintering furnace, heating to 1200 ℃ at a heating rate of 2 ℃/min under argon atmosphere, preserving heat for 2 hours, performing hard carbonization treatment, cooling, grinding by a jet mill, sieving by a 320-mesh screen, performing demagnetization treatment by a demagnetization machine, and mixing by a high-speed mixer to obtain the hard carbon material.
The preparation of the hard carbon negative electrode sheet, the assembly of the sodium ion battery and the electrochemical performance test were substantially identical to example 2.
The highest specific capacity of the hard carbon negative electrode under the test condition of 50mA/g is 207.90mAh/g, and the initial coulombic efficiency is 72.76%.
Comparative example 4
This comparative example provides a hard carbon material prepared in the same manner as in example 1, except that: the high Wen Yingtan treatment in the step (4) is not performed;
specifically, (1): and (3) washing the arundo donax with pure water, putting the arundo donax in a drying oven, drying at 80 ℃ for 15 hours, and mechanically coarsely crushing to obtain arundo donax particles.
(2): and (3) placing the arundo donax particles prepared in the step (1) into an atmosphere furnace, heating to 450 ℃ at a heating rate of 2 ℃/min under the nitrogen atmosphere, preserving heat for 4 hours, and performing pre-carbonization treatment to obtain the precursor carbon material.
(3): and (3) mixing the precursor carbon material prepared in the step (2), sodium hydroxide and deionized water according to the mass ratio of 1:0.15: and (3) after 0.75 of the raw materials are uniformly mixed, placing the raw materials in a vacuum box furnace for drying treatment for 10 hours at 100 ℃, then transferring the raw materials into an activation furnace, heating the raw materials to 650 ℃ at a heating rate of 5 ℃/min under a nitrogen atmosphere, preserving heat for 3 hours, performing activation treatment, cooling, repeatedly cleaning the raw materials for 3 times by using a hydrochloric acid solution with the concentration of 0.5mol/L and deionized water, placing the raw materials in a drying box for drying treatment for 10 hours at 80 ℃ after washing to neutrality, cooling, grinding the raw materials by a jet mill, sieving the raw materials by a 320-mesh sieve, performing demagnetization treatment by a demagnetizing machine, and mixing the raw materials by a high-speed mixer to obtain the hard carbon material.
The preparation of the hard carbon negative electrode sheet, the assembly of the sodium ion battery and the electrochemical performance test were substantially identical to example 2.
The highest specific capacity of the hard carbon negative electrode under the test condition of 50mA/g is 177.27mAh/g, and the initial coulombic efficiency is 67.05%.
Characterization testing of XRD was performed on the hard carbon materials prepared in example 1 and comparative examples 1 to 4, and it was found that the XRD patterns showed distinct hard carbon peaks, so that the products prepared in example 1 and comparative examples 1 to 4 were both hard carbon materials. Fig. 2 shows the XRD spectrum of the hard carbon material prepared in comparative example 1, and fig. 3 shows the XRD spectrum of the hard carbon material prepared in comparative example 4. Although the high-temperature hard carbonization treatment was not performed in comparative example 4, and only the low-temperature pre-carbonization treatment and the medium-temperature activation treatment were performed, the peaks of hard carbon were still approximately seen from the XRD image of fig. 3. Further, the interlayer spacing of the hard carbon material prepared in comparative example 1 was 0.362nm, which is 0.39nm, as compared with the interlayer spacing of the hard carbon material of example 1, indicating that the interlayer spacing of the material was also affected by the activation treatment and the acid washing treatment, and the interlayer spacing could be increased.
Fig. 5 is an SEM image of the hard carbon material prepared in comparative example 4. Comparing the micro-morphology of the hard carbon material of example 1 of fig. 5 with that of fig. 4, it is evident that the two hard carbon materials are not the same size. In particular, the hard carbon material prepared in example 1 had spherical particles therein, whereas comparative example 4 was not subjected to the high-temperature hard-carbonization treatment, wherein the spherical particles were significantly reduced as compared with the spherical particles in example 1, probably because the temperature of the hard-carbonization treatment was higher, so that a part of the material was converted into spherical shapes.
Comparing the results of the electrochemical performance tests of the sodium ion batteries of example 2 and comparative examples 1 to 4 above, it can be presumed that: the pre-carbonization treatment can remove volatile matters and moisture in the arundo donax raw material, so that the strength of the carbon material is improved, and preliminary pores are formed in the carbon material particles; the alkalization treatment can remove the residual silicon dioxide impurities in the carbon material, so as to realize the porous structure of the carbon material; the purpose of acid washing or water washing is to remove residual alkaline solute and magnetic metal impurities in the carbon material; the high-temperature hard carbonization treatment aims to convert the carbon material into a hard carbon material, regulate and control the pore structure of the hard carbon material and obtain a structure with abundant closed pores. The higher the carbonization temperature is, the slower the heating rate is, the enough energy and time are ensured, the rearrangement of the carbon layer of the hard carbon material is realized, the ordering of the hard carbon structure is increased, the pores and defects are reduced, and the first coulomb efficiency and the cycling stability of the hard carbon cathode are improved. Therefore, the technical scheme in the embodiment of the application has the advantages that after the pre-carbonization treatment, the alkalization and medium-temperature activation treatment and the high-temperature hard carbonization treatment, the prepared hard carbon material has higher specific capacity and first coulombic efficiency in the sodium ion battery.
As can be seen from the analysis, the application prepares the arundo donax-based hard carbon material by the processes of cleaning, coarse crushing, low-temperature pre-carbonization, medium-temperature activation, high Wen Yingtan treatment, fine crushing, sieving, demagnetizing, mixing and the like, and can be used as the cathode material of an alkali metal ion battery; the application has the advantages of wide sources of raw materials, simplicity, easy acquisition, low cost and simple preparation method and process, and is suitable for industrial production.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present application, and not for limiting the same; although the application has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the application.
Furthermore, those skilled in the art will appreciate that while some embodiments herein include some features but not others included in other embodiments, combinations of features of different embodiments are meant to be within the scope of the application and form different embodiments. For example, any of the above-described claimed embodiments may be used in any combination. The information disclosed in this background section is only for enhancement of understanding of the general background of the application and should not be taken as an acknowledgement or any form of suggestion that this information forms the prior art already known to a person skilled in the art.
Claims (10)
1. A hard carbon material, characterized in that the hard carbon material internally comprises a closed cell structure, and the closed cell volume is 0.113cm 3 /g-0.272cm 3 /g; the raw materials for preparing the hard carbon material comprise reed canary grassAnd (5) bamboo.
2. The hard carbon material of claim 1, wherein at least one of the following conditions is satisfied:
a. the carbon content in the hard carbon material is more than or equal to 89wt%, the oxygen content is less than or equal to 5.5wt%, the nitrogen content is less than or equal to 0.5wt%, and the hydrogen content is less than or equal to 0.7wt%;
b. the hard carbon material has a particle size d50=4.5 μm to 30 μm;
c. the interlayer distance d002 of the (002) crystal face of the hard carbon material is 0.355nm-0.405nm;
d. the specific surface area of the hard carbon material is 1.2m 2 /g-30m 2 /g。
3. A method for producing the hard carbon material according to claim 1 or 2, comprising:
pre-carbonizing arundo donax to obtain a precursor carbon material;
sequentially carrying out alkalization treatment and activation treatment on the precursor carbon material to obtain an intermediate carbon material;
and carrying out hard carbonization treatment on the intermediate carbon material to obtain the hard carbon material.
4. A method of preparing as claimed in claim 3, wherein at least one of the following conditions is met:
A. before the pre-carbonization treatment, the method comprises the following steps: washing and drying the arundo donax with water, and then crushing to obtain arundo donax particles;
B. The atmosphere conditions of the pre-carbonization treatment are as follows: in a vacuum or protective gas atmosphere;
C. the temperature of the pre-carbonization treatment is 350-550 ℃ and the time is 0.5-12 h;
D. the heating rate of the pre-carbonization treatment is 1 ℃/min-10 ℃/min.
5. A method of preparing as claimed in claim 3, wherein at least one of the following conditions is met:
E. the alkalization treatment comprises: mixing the precursor carbon material, alkaline substances and a solvent, then dipping, filtering and then carrying out first drying treatment;
F. the activation treatment includes: placing the product obtained by the alkalization treatment in vacuum or protective gas atmosphere for activation;
G. the temperature of the activation treatment is 550-900 ℃ and the time is 0.5-8 h;
H. the heating rate of the activation treatment is 1 ℃/min-20 ℃/min;
I. after the activation treatment, the method further comprises: and (3) repeatedly carrying out acid washing and water washing on the product obtained by the activation treatment, and then carrying out second drying treatment.
6. The method of preparing as claimed in claim 5, wherein at least one of the following conditions is also satisfied:
J. the alkaline substance comprises at least one of lithium hydroxide, sodium hydroxide, potassium hydroxide, lithium carbonate, sodium carbonate, potassium carbonate, sodium bicarbonate and potassium bicarbonate;
K. The solvent comprises at least one of water and alcohol solvents;
and L, the mass ratio of the precursor carbon material to the alkaline substance to the solvent is 1: (0.01-0.2): (0.25-2);
m. the soaking time is 0.5h-10h;
n. the shielding gas comprises at least one of nitrogen, argon, ammonia, mixed gas of nitrogen and hydrogen and mixed gas of argon and hydrogen;
the acid solution used for acid washing comprises at least one of hydrochloric acid, sulfuric acid, nitric acid and phosphoric acid solution, and the concentration of the acid solution is 0.1mol/L-10mol/L;
and P, the temperature of the first drying treatment and the second drying treatment is 80-120 ℃ and the time is 8-16 h.
7. The method of claim 3, further satisfying at least one of the following conditions:
the atmosphere conditions of the hard carbonization treatment are as follows: in a vacuum or protective gas atmosphere;
r, the temperature of the hard carbonization treatment is 900-2200 ℃ and the time is 0.5-10 h;
s, the heating rate of the hard carbonization treatment is 1 ℃/min-15 ℃/min.
8. The method of any one of claims 3-7, further comprising, after the hard carbonization treatment: and crushing, sieving and demagnetizing the hard carbon treatment product to obtain the hard carbon material.
9. A negative electrode material comprising the hard carbon material according to claim 1 or 2.
10. An alkali metal ion battery comprising the negative electrode material of claim 9, the alkali metal ion battery comprising a lithium ion battery, a sodium ion battery, or a potassium ion battery.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117352727A (en) * | 2023-10-31 | 2024-01-05 | 深圳贝特瑞钠电新材料科技有限公司 | Negative electrode material, preparation method thereof and sodium ion battery |
| CN118039884A (en) * | 2024-04-11 | 2024-05-14 | 鑫享电港科技有限公司 | Sodium ion battery bamboo charcoal composite negative electrode and preparation method thereof |
| CN118515260A (en) * | 2024-07-23 | 2024-08-20 | 国科炭美新材料(湖州)有限公司 | Bamboo-based hard carbon negative electrode material, preparation method thereof and alkali metal battery |
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2023
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117352727A (en) * | 2023-10-31 | 2024-01-05 | 深圳贝特瑞钠电新材料科技有限公司 | Negative electrode material, preparation method thereof and sodium ion battery |
| CN118039884A (en) * | 2024-04-11 | 2024-05-14 | 鑫享电港科技有限公司 | Sodium ion battery bamboo charcoal composite negative electrode and preparation method thereof |
| CN118515260A (en) * | 2024-07-23 | 2024-08-20 | 国科炭美新材料(湖州)有限公司 | Bamboo-based hard carbon negative electrode material, preparation method thereof and alkali metal battery |
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