CN118248874A - Hard carbon composite material and preparation method and application thereof - Google Patents
Hard carbon composite material and preparation method and application thereof Download PDFInfo
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- CN118248874A CN118248874A CN202410070187.6A CN202410070187A CN118248874A CN 118248874 A CN118248874 A CN 118248874A CN 202410070187 A CN202410070187 A CN 202410070187A CN 118248874 A CN118248874 A CN 118248874A
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- Prior art keywords
- alginate
- transition metal
- hard carbon
- composite material
- sodium
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- 229910021385 hard carbon Inorganic materials 0.000 title claims abstract description 76
- 239000002131 composite material Substances 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title abstract description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 116
- 229920000615 alginic acid Polymers 0.000 claims abstract description 106
- 229940072056 alginate Drugs 0.000 claims abstract description 104
- 239000002243 precursor Substances 0.000 claims abstract description 61
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 58
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 42
- 230000007704 transition Effects 0.000 claims abstract description 38
- 150000003624 transition metals Chemical class 0.000 claims abstract description 32
- 235000010443 alginic acid Nutrition 0.000 claims abstract description 30
- 238000002156 mixing Methods 0.000 claims abstract description 30
- FHVDTGUDJYJELY-UHFFFAOYSA-N 6-{[2-carboxy-4,5-dihydroxy-6-(phosphanyloxy)oxan-3-yl]oxy}-4,5-dihydroxy-3-phosphanyloxane-2-carboxylic acid Chemical compound O1C(C(O)=O)C(P)C(O)C(O)C1OC1C(C(O)=O)OC(OP)C(O)C1O FHVDTGUDJYJELY-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000012266 salt solution Substances 0.000 claims abstract description 25
- 238000010000 carbonizing Methods 0.000 claims abstract description 21
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims abstract description 21
- 238000001035 drying Methods 0.000 claims abstract description 17
- 238000000498 ball milling Methods 0.000 claims abstract description 16
- 239000001488 sodium phosphate Substances 0.000 claims abstract description 14
- 238000003763 carbonization Methods 0.000 claims abstract description 11
- 229910000162 sodium phosphate Inorganic materials 0.000 claims abstract description 10
- 239000011734 sodium Substances 0.000 claims description 45
- 239000007864 aqueous solution Substances 0.000 claims description 44
- 229910001415 sodium ion Inorganic materials 0.000 claims description 32
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical group CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims description 25
- 239000000661 sodium alginate Substances 0.000 claims description 25
- 235000010413 sodium alginate Nutrition 0.000 claims description 25
- 229940005550 sodium alginate Drugs 0.000 claims description 25
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims description 23
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 22
- 229910052708 sodium Inorganic materials 0.000 claims description 22
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 19
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 12
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 9
- 239000004202 carbamide Substances 0.000 claims description 9
- 239000007773 negative electrode material Substances 0.000 claims description 9
- 235000011008 sodium phosphates Nutrition 0.000 claims description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical group N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 8
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 claims description 8
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 7
- 229910052698 phosphorus Inorganic materials 0.000 claims description 7
- 239000011574 phosphorus Substances 0.000 claims description 7
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 6
- 239000000648 calcium alginate Substances 0.000 claims description 6
- 235000010410 calcium alginate Nutrition 0.000 claims description 6
- 229960002681 calcium alginate Drugs 0.000 claims description 6
- OKHHGHGGPDJQHR-YMOPUZKJSA-L calcium;(2s,3s,4s,5s,6r)-6-[(2r,3s,4r,5s,6r)-2-carboxy-6-[(2r,3s,4r,5s,6r)-2-carboxylato-4,5,6-trihydroxyoxan-3-yl]oxy-4,5-dihydroxyoxan-3-yl]oxy-3,4,5-trihydroxyoxane-2-carboxylate Chemical compound [Ca+2].O[C@@H]1[C@H](O)[C@H](O)O[C@@H](C([O-])=O)[C@H]1O[C@H]1[C@@H](O)[C@@H](O)[C@H](O[C@H]2[C@H]([C@@H](O)[C@H](O)[C@H](O2)C([O-])=O)O)[C@H](C(O)=O)O1 OKHHGHGGPDJQHR-YMOPUZKJSA-L 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 6
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 6
- 229920000877 Melamine resin Polymers 0.000 claims description 4
- 238000004108 freeze drying Methods 0.000 claims description 4
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 claims description 4
- 229940048086 sodium pyrophosphate Drugs 0.000 claims description 4
- 235000019818 tetrasodium diphosphate Nutrition 0.000 claims description 4
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 claims description 4
- 229910000406 trisodium phosphate Inorganic materials 0.000 claims description 4
- 235000019801 trisodium phosphate Nutrition 0.000 claims description 4
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 3
- 239000001099 ammonium carbonate Substances 0.000 claims description 3
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 3
- 150000001868 cobalt Chemical class 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- 229910000403 monosodium phosphate Inorganic materials 0.000 claims description 3
- 235000019799 monosodium phosphate Nutrition 0.000 claims description 3
- 150000002815 nickel Chemical class 0.000 claims description 3
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 2
- 239000002994 raw material Substances 0.000 abstract description 7
- 239000003575 carbonaceous material Substances 0.000 description 22
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 16
- 238000007710 freezing Methods 0.000 description 16
- 230000008014 freezing Effects 0.000 description 16
- 239000000243 solution Substances 0.000 description 12
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 10
- 239000000463 material Substances 0.000 description 10
- 238000001816 cooling Methods 0.000 description 9
- 239000007788 liquid Substances 0.000 description 9
- 229910001416 lithium ion Inorganic materials 0.000 description 9
- 238000004140 cleaning Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 239000011261 inert gas Substances 0.000 description 8
- 239000011229 interlayer Substances 0.000 description 8
- 239000011148 porous material Substances 0.000 description 7
- 230000002441 reversible effect Effects 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 239000010439 graphite Substances 0.000 description 6
- 229910002804 graphite Inorganic materials 0.000 description 6
- 239000000499 gel Substances 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- 238000001878 scanning electron micrograph Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 238000011161 development Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- 229910014572 C—O—P Inorganic materials 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 239000011888 foil Substances 0.000 description 3
- 229910001428 transition metal ion Inorganic materials 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000013543 active substance Substances 0.000 description 2
- 230000006978 adaptation Effects 0.000 description 2
- 229960001126 alginic acid Drugs 0.000 description 2
- 239000000783 alginic acid Substances 0.000 description 2
- 150000004781 alginic acids Chemical class 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000000017 hydrogel Substances 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
- 229910021384 soft carbon Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- -1 transition metal salt Chemical class 0.000 description 2
- 229910017351 Fe2 P Inorganic materials 0.000 description 1
- 229910019398 NaPF6 Inorganic materials 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 238000005087 graphitization Methods 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000011534 incubation Methods 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 150000002505 iron Chemical class 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 229910052752 metalloid Inorganic materials 0.000 description 1
- 150000002738 metalloids Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000013081 microcrystal Substances 0.000 description 1
- 239000011268 mixed slurry Substances 0.000 description 1
- 229910052754 neon Inorganic materials 0.000 description 1
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 238000009656 pre-carbonization Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 229910052704 radon Inorganic materials 0.000 description 1
- SYUHGPGVQRZVTB-UHFFFAOYSA-N radon atom Chemical compound [Rn] SYUHGPGVQRZVTB-UHFFFAOYSA-N 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000011076 safety test Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
-
- 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
-
- 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)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Composite Materials (AREA)
- Inorganic Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The application discloses a hard carbon composite material, a preparation method and application thereof, comprising the following steps: mixing alginate with a transition metal salt solution to form a transition metal-alginate gel, drying, and a transition metal-alginate precursor; nitrogen doping and pre-carbonizing the transition metal-alginate precursor to obtain a nitrogen doped transition metal-alginate precursor; mixing the nitrogen-doped transition metal-alginate precursor with sodium phosphate, and performing ball milling and carbonization to obtain the hard carbon composite material; the hard carbon composite material has the advantages of simple preparation method, wide sources and lower preparation cost by taking alginate as a raw material.
Description
Technical Field
The application relates to the technical field of sodium ion batteries, in particular to a hard carbon composite material and a preparation method and application thereof.
Background
With the development of new energy industry, lithium ion batteries are widely applied to industries such as electric automobiles, but the further development is limited by a series of key problems such as lithium resource reserves, lithium ion battery cost and the like. Sodium is the fourth most abundant metal element on earth, the relative abundance of the sodium-ion battery in the crust is about 2.74%, and compared with the lithium element (about 0.0017%), the sodium-ion battery is focused on due to the natural advantages of abundant resources, low cost and the like, and can be widely applied to the scenes of power batteries, energy storage and the like.
The cost of the key materials of the sodium ion battery has great advantages compared with that of the lithium ion battery, sodium and lithium have similar physical and chemical properties, and the research and development of the sodium ion battery and the design of a production line can be used as references for the lithium ion battery. And the safety performance of the sodium ion battery is obviously superior to that of a lithium ion battery, and the risk of fire or explosion can be obviously reduced in safety tests such as needling, extrusion, overcharging, overdischarging and the like.
Although sodium ion batteries have the significant advantages described above over lithium ion batteries, the sodium ion batteries are not theoretically as dense in mass and volume energy as lithium ion batteries due to the much larger radius and volume of sodium ions than lithium ions. When the sodium ions with larger volume are embedded and separated in the electrode material, the requirements on the comprehensive performance and structural stability of the material are higher. These reasons put higher demands on the research of key materials such as positive electrode, negative electrode and electrolyte of sodium ion batteries.
The sodium ion radius is large, and the interlayer spacing (0.335 nm) of a commercial graphite anode for lithium ion batteries is small, so that the graphite is difficult to accommodate sodium ions intercalated between the layers. The hard carbon material has more defects, rich pore structure, low price, higher storage capacity (theoretical capacity is 300 mAh/g), lower working potential, better safety and cycling stability and the like, and is considered to be the most promising commercial sodium ion battery anode material at present.
The disordered amorphous structure provides the hard carbon material with more defects and micropores, which can provide more active sodium storage sites. Meanwhile, the larger interlayer spacing in the hard carbon material is not only beneficial to the diffusion of sodium ions, but also can keep the structure stable in the sodium modification/sodium removal process of the hard carbon material. However, its inherent disordered microstructure makes it less conductive and less rate-able. Therefore, a new hard carbon negative electrode material is needed to solve the problems of low specific capacity and initial coulombic efficiency of the hard carbon material.
Disclosure of Invention
In order to solve the above-mentioned shortcomings in the art, the present application aims to provide a hard carbon composite material, and a preparation method and application thereof. The hard carbon composite material provided by the application is used as a negative electrode material of a sodium ion battery, and has the advantages of high specific capacity, high first coulombic efficiency, high rate capability and the like.
According to some embodiments of the present application, there is provided a method of preparing a hard carbon composite material, comprising:
Mixing an alginate aqueous solution with a transition metal salt solution to form a mixed solution, and stirring and reacting to prepare a transition metal-alginate gel;
drying the transition metal-alginate gel to produce a transition metal-alginate precursor;
nitrogen doping is carried out on the transition metal-alginate precursor to prepare a nitrogen doped transition metal-alginate precursor;
and mixing the nitrogen-doped transition metal-alginate precursor with sodium phosphate, and performing ball milling and carbonization to obtain the hard carbon composite material.
According to some embodiments of the application, the drying is freeze-drying or ambient temperature drying.
According to some embodiments of the application, the alginate is selected from sodium alginate and/or calcium alginate;
optionally, the mass concentration of the alginate aqueous solution is 1-2wt%.
According to some embodiments of the application, the transition metal salt solution is selected from one or more of an iron salt solution, a cobalt salt solution, a nickel salt solution; preferably one or more of cobalt nitrate aqueous solution, nickel nitrate aqueous solution and ferric chloride aqueous solution;
optionally, the transition metal salt solution has a mass concentration of 3-10wt%.
According to some embodiments of the application, the sodium phosphate salt is selected from one or more of disodium hydrogen phosphate, sodium dihydrogen phosphate, sodium pyrophosphate, and trisodium phosphate.
According to some embodiments of the application, the mixing volume ratio of the aqueous alginate solution to the transition metal salt solution is 1 (1-1.25).
According to some embodiments of the application, the nitrogen doping comprises: the transition metal-alginate precursor is mixed with a nitrogen source and then pre-carbonized at 500-700 ℃.
According to some embodiments of the application, the nitrogen source is selected from one or more of urea, melamine, ammonia, ammonium carbonate.
According to some embodiments of the application, the transition metal-alginate precursor to nitrogen source mass ratio is 1 (2-2.5).
According to some embodiments of the application, the nitrogen source is selected from ammonia gas, and the flow rate of the ammonia gas is 1-20L/min.
According to some embodiments of the application, the nitrogen doped transition metal-alginate precursor to sodium phosphate salt mass ratio is 1 (1-1.5).
According to some embodiments of the application, the carbonization temperature is 700-1000 ℃ and the incubation time is 2-4h.
According to another aspect of the present application, there is provided a hard carbon composite material comprising: carbon element, transition metal element M, phosphorus element, nitrogen element and sodium element;
the transition metal element M is crosslinked in the hard carbon composite material to form a C-M-P structure;
The nitrogen element forms a C-N structure inside the hard carbon composite material;
the sodium element is deposited on the surface of the hard carbon composite material and/or forms a C-O-Na structure.
According to some embodiments of the application, the hard carbon composite material has a carbon content of > 50wt%, a sodium content of 8-10wt%, a transition metal content of 22-25wt%, a phosphorus content of 8-10wt%, a nitrogen content of 2-3wt%, and a balance of < 2wt%.
According to some embodiments of the application, the hard carbon composite has a median particle diameter D 50 of 5-7 μm and a specific surface area of 370-390m 2/g.
According to an aspect of the present application, there is provided a negative electrode tab including a negative electrode current collector and a negative electrode active material layer including the hard carbon composite material manufactured by the above-described manufacturing method, or the hard carbon composite material described above.
According to an aspect of the present application, there is provided a sodium ion battery comprising the negative electrode tab described above.
Compared with the prior art, the application at least has the following beneficial effects:
the application provides a hard carbon composite material, which is prepared by taking alginate as a raw material, and the surface layer interval of the hard carbon material is increased by nitrogen doping, so that the content of deposited sodium on the surface of the hard carbon material is increased; utilizing the function of cross-linking metal ions of alginate to cross-link with transition metal ions to form a transition metal-alginate gel structure; and C-O-P, metal phosphide and C-O-Na are formed by high-temperature carbonization, so that the first coulomb efficiency, reversible specific capacity and rate capability are enhanced, and the conductivity of the material is improved.
The hard carbon composite material has the advantages of simple preparation method, wide sources and lower preparation cost by taking alginate as a raw material.
Drawings
FIG. 1 is an SEM image at 2000 Xmagnification of Na 2 O-CoP@NHC in example 1 of the present application.
FIG. 2 is an SEM image at 30000 times magnification of Na 2 O-CoP@NHC in example 1 of the present application.
FIG. 3 is a SEM image of the Na 2 O-CoP@NHC of example 1 of the application at 650000 x magnification.
FIG. 4 is a SEM image of the Na 2 O-CoP@NHC of example 1 of the application at 1200000 magnification.
FIG. 5 is an XPS plot of Na 2 O-CoP@NHC of example 1 of the present application.
FIG. 6 is an XRD pattern for Na 2 O-CoP@NHC of example 1 of the present application.
Detailed Description
The technical solutions of the present application will be clearly and completely described in conjunction with the embodiments of the present application, and it is apparent that the described embodiments are some embodiments of the present application, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the application without making any inventive effort, are intended to be within the scope of the application.
It is particularly pointed out that similar substitutions and modifications to the application will be apparent to those skilled in the art, which are all deemed to be included in the application. It will be apparent to those skilled in the relevant art that variations and modifications can be made in the methods and applications described herein, or in the appropriate variations and combinations, without departing from the spirit and scope of the application. It will be apparent that the described embodiments are only some, but not all, embodiments of the application.
The application is carried out according to the conventional conditions or the conditions suggested by manufacturers if the specific conditions are not noted, and the raw materials or auxiliary materials and the reagents or instruments are conventional products which can be obtained commercially if the manufacturers are not noted.
The present application will be described in detail below.
Currently, the lack of suitable negative electrode materials is a challenge that hinders the development of sodium ion batteries. Existing anode materials include intercalation-type, alloy-type and conversion-type materials. Among them, metals/alloys and metal compounds have a high capacity, but have a large volume expansion during charge and discharge cycles and poor cycle performance. In contrast, the carbon-based material has rich resources, stable physical and chemical properties, high conductivity and no toxicity, and is a cathode material with great development prospect.
The carbon material may be divided into soft carbon and hard carbon according to whether the carbon material can be sufficiently graphitized by high temperature heat treatment at 2800 ℃. When the temperature is raised, the inter-layer distance of soft carbon and the change speed of microcrystals are much greater than those of hard carbon, and graphitization of hard carbon is difficult to be performed by high temperature heat treatment. Because of the small interlayer spacing of graphite and the large radius of sodium ions, the graphite cannot be directly used as the negative electrode of a sodium ion power supply. Hard carbon tends to have larger interlayer spacing, more nano holes and more defect sites, so that more sodium ions can be stored, and the hard carbon has higher specific capacity, and is one of the most promising sodium ion negative electrode materials at present.
The mechanism of sodium storage in hard carbon materials has been controversial for many years, but it is widely believed that sodium ions fill nanopores on low potential platforms to form metalloid clusters. The pores in the hard carbon material are mainly formed by randomly stacking graphite sheets, and the diameters of the pores are not uniform, but the diameters of the pores become smaller and smaller along with the increase of carbonization temperature, so that the conductive performance, the rate capability and the like of the hard carbon material are poor.
Based on the above problems, the present application provides a method for preparing a hard carbon composite material, comprising:
Step one: mixing an alginate aqueous solution with a transition metal salt solution to form a mixed solution, and stirring and reacting to prepare a transition metal-alginate gel;
Step two: drying the transition metal-alginate gel to produce a transition metal-alginate precursor;
step three: nitrogen doping is carried out on the transition metal-alginate precursor to prepare a nitrogen doped transition metal-alginate precursor;
Step four: and mixing the nitrogen-doped transition metal-alginate precursor with sodium phosphate, and performing ball milling and carbonization to obtain the hard carbon composite material.
In the first step, alginic acid is mixed with a transition metal salt solution, and then alginic acid is crosslinked with transition metal ions to form a transition metal-alginate hydrogel structure.
Wherein the alginate material is selected from alginate such as sodium alginate and calcium alginate; the mass concentration of the alginate aqueous solution is 1-2wt%.
The transition metal salt solution is at least one selected from ferric salt solution, cobalt salt solution and nickel salt solution; optionally cobalt nitrate aqueous solution, nickel nitrate aqueous solution, ferric chloride and other transition metal aqueous solutions; the mass concentration of the transition metal salt solution is 3-10wt%.
The volume ratio of the alginate aqueous solution to the transition metal salt solution is 1 (1-1.25).
In the second step, the transition metal-alginate hydrogel is dried at normal temperature or freeze-dried to avoid subsequent uneven carbonization. Wherein, the freeze drying is to freeze in liquid nitrogen and then freeze in a low temperature freeze drying box for 5-24h at the temperature of minus 40 to minus 10 ℃.
In the third step, the step of nitrogen doping the transition metal-alginate precursor comprises the following steps: immersing transition metal-alginate precursor in aqueous solution of nitrogen source such as urea, melamine and ammonia water at normal temperature, immersing in liquid phase for 5-24h, and pre-carbonizing at 500-700 deg.C for 1-2h.
And/or directly mixing transition metal-alginate precursor with solid-phase nitrogen source such as ammonium carbonate, and pre-carbonizing at 500-700 deg.C for 1-2 hr.
Wherein the mass ratio of the transition metal-alginate precursor to the nitrogen source is 1 (2-2.5).
And/or introducing ammonia gas or mixed gas of ammonia gas and protective gas into the transition metal-alginate precursor at the introducing amount of 1-20L/min, and pre-carbonizing for 1-2h at 500-700 ℃.
Wherein the shielding gas is selected from one or more of argon, helium, neon, xenon and radon.
According to the application, the nitrogen doping step is carried out simultaneously, so that a part of alginate is cracked, gas generated by the cracking and the like can form pores, and meanwhile, the alginate is cracked to generate active sites, thereby being beneficial to doping and bonding of subsequent atoms.
In the fourth step, the ball milling is as follows: ball milling for 6-8h at a rotating speed of 400 r/min; the carbonization is carried out for 2-4 hours at 700-1000 ℃.
The sodium phosphate salt is disodium hydrogen phosphate, sodium dihydrogen phosphate, sodium pyrophosphate, trisodium phosphate and other sodium phosphate salts.
The mass ratio of the nitrogen doped transition metal-alginate precursor to the sodium phosphate salt is 1 (1-1.5); preferably 1:1.
In the preparation method, the proportion of each element in the finally prepared hard carbon composite material is regulated and controlled by controlling the adding proportion of each raw material. Wherein, in the mixing proportion of the alginate and the transition metal salt, if the transition metal salt is reduced, the cross-linking of the alginate and the transition metal is reduced, thereby reducing the metal content of the subsequent material; if the carbonization temperature is too high, the loss of metal sodium can be caused, so that the first coulomb efficiency, reversible specific capacity, multiplying power performance, conductivity and the like of the hard carbon composite material are affected.
The hard carbon composite material of the present application comprises: carbon element, transition metal element M, phosphorus element, nitrogen element and sodium element; the transition metal element M is crosslinked in the hard carbon composite material to form a C-M-P structure;
The nitrogen element forms a C-N structure inside the hard carbon composite material;
the sodium element is deposited on the surface of the hard carbon composite material and/or forms a C-O-Na structure.
Wherein, the carbon element accounts for more than 50 percent, the transition metal element accounts for 25 percent to 35 percent, the phosphorus element accounts for 8 percent to 10 percent, and the nitrogen element accounts for 2 percent to 3 percent; the other elements account for less than 2 percent; the median particle diameter D 50 of the hard carbon composite material is 5-7 mu m, and the specific surface area is 370-390m 2/g. Optionally, the median particle diameter D 50 is 5-5.5 μm, 5.5-6 μm, 6-6.5 μm, 6.5-7 μm; the specific surface area is 370-375m 2/g、375-380m2/g、380-385m2/g、385-390m2/g.
The application prepares the hard carbon material by taking the alginate as the raw material, wherein the natural alginate has wide sources and relatively low cost.
According to the application, the alginate has the function of crosslinking metal ions, natural alginate and transition metal salt solution are adopted to crosslink to form metal-alginate, and nitrogen-doped metal-alginate precursor is formed by dipping or high-temperature pyrolysis of nitrogen-containing precursor and pre-carbonization.
Mixing a nitrogen-doped metal-alginate precursor with sodium phosphate, performing ball milling, pyrolyzing sodium phosphate at high temperature to generate a covalent bond stable structure of C-O-P in situ, forming a transition metal phosphide with cross-linked transition metal ions therein to form a C-M-P structure, and depositing a part of sodium to form a C-O-Na structure and a part of sodium to form a transition metal nitrogen-doped hard carbon material on the surface along with the pyrolysis. The electrochemical performance of the obtained hard carbon material is obviously improved. The reversible specific capacity can reach 320 mAh.g -1, and the rate capability can be effectively increased. The sodium deposited on the surface and the formed C-O-Na structure can effectively reduce irreversible loss of sodium ions in electrolyte caused by charge and discharge after the battery is assembled, the initial coulomb efficiency is more than 90%, the conductivity of the material is improved, and the performance of a finished battery is improved in all directions.
The technical scheme of the application is further described below by combining specific embodiments.
Example 1
Preparing sodium alginate into sodium alginate aqueous solution with the mass fraction of 1.5%, and preparing cobalt nitrate aqueous solution with the mass fraction of 5% from cobalt nitrate;
Mixing the prepared sodium alginate aqueous solution and cobalt nitrate aqueous solution according to a ratio of 1:1 to form Co-alginate hydrosol, freezing in liquid nitrogen, and placing in a freezing low-temperature drying oven for 24 hours to form Co-alginate precursor;
Immersing the prepared Co-alginate precursor in urea solution for 12 hours according to the mass ratio of 1:2, pre-carbonizing at a high temperature of 600 ℃, and preserving heat for 2 hours to form a nitrogen-doped Co-alginate precursor;
Mixing a nitrogen-doped Co-alginate precursor and disodium hydrogen phosphate according to a mass ratio of 1:1, ball-milling for 8 hours at 400r/min, carbonizing at 1000 ℃ under the condition of inert gas, and preserving heat for 4 hours; after cooling, ethanol is used for cleaning, and the transition metal nitrogen doped hard carbon composite material, namely Na 2 O-CoP@NHC.
Example 2
Preparing sodium alginate into sodium alginate aqueous solution with the mass fraction of 2%, and preparing nickel nitrate aqueous solution with the mass fraction of 10% from nickel nitrate;
Mixing the prepared sodium alginate aqueous solution and nickel nitrate aqueous solution according to a ratio of 1:1 to form Ni-alginate hydrosol, freezing in liquid nitrogen, and placing in a freezing low-temperature drying oven for 24 hours to form a Ni-alginate precursor;
Immersing a Ni-alginate precursor in a urea solution for 12 hours according to the mass ratio of 1:2, carbonizing at a high temperature of 600 ℃, and preserving heat for 2 hours to form a nitrogen-doped Ni-alginate precursor;
mixing a nitrogen-doped Ni-alginate precursor and disodium hydrogen phosphate according to a mass ratio of 1:1, ball-milling for 8 hours at 400r/min, carbonizing at 1000 ℃ under the condition of inert gas, and preserving heat for 4 hours; after cooling, ethanol is used for cleaning, and the transition metal nitrogen doped hard carbon composite material, namely Na 2O-Ni2 P@NHC.
Example 3
Preparing sodium alginate into sodium alginate water solution with the mass fraction of 1%, and preparing ferric chloride water solution with the mass fraction of 3% from ferric chloride;
Mixing the prepared sodium alginate aqueous solution and ferric chloride aqueous solution according to a ratio of 1:1 to form Fe-alginate hydrosol, freezing in liquid nitrogen, and placing in a freezing low-temperature drying oven for 24 hours to form Fe-alginate precursor;
Immersing Fe-alginate precursor in urea solution for 12h according to the mass ratio of 1:2, carbonizing at 600 ℃ at high temperature, and preserving heat for 2h to form nitrogen-doped Fe-alginate precursor;
Mixing a nitrogen-doped Fe-alginate precursor and disodium hydrogen phosphate according to a mass ratio of 1:1, ball-milling for 8 hours at 400r/min, carbonizing at 1000 ℃ under the condition of inert gas, and preserving heat for 4 hours; after cooling, ethanol is used for cleaning, and the transition metal nitrogen doped hard carbon composite material, namely Na 2O-Fe2 P@NHC.
Example 4
Preparing calcium alginate into calcium alginate aqueous solution with the mass fraction of 1.5%, and preparing cobalt nitrate aqueous solution with the mass fraction of 5% from cobalt nitrate;
Mixing the prepared calcium alginate aqueous solution and cobalt nitrate aqueous solution according to a ratio of 1:1 to form Co-alginate hydrosol, freezing in liquid nitrogen, and placing in a freezing low-temperature drying oven for 24 hours to form Co-alginate precursor;
immersing the Co-alginate precursor in urea solution for 12 hours according to the mass ratio of 1:2, carbonizing at a high temperature of 600 ℃, and preserving heat for 2 hours to form a nitrogen-doped Co-alginate precursor;
Mixing a nitrogen-doped Co-alginate precursor and disodium hydrogen phosphate according to a mass ratio of 1:1, ball-milling for 8 hours at 400r/min, carbonizing at 1000 ℃ under the condition of inert gas, and preserving heat for 4 hours; after cooling, ethanol is used for cleaning, and the transition metal nitrogen doped hard carbon composite material, namely Na 2 O-CoP@NHC.
Example 5
Preparing sodium alginate into sodium alginate aqueous solution with the mass fraction of 1.5%, and preparing cobalt nitrate aqueous solution with the mass fraction of 5% from cobalt nitrate;
Mixing the prepared sodium alginate aqueous solution and cobalt nitrate aqueous solution according to a ratio of 1:1 to form Co-alginate hydrosol, freezing in liquid nitrogen, and placing in a freezing low-temperature drying oven for 24 hours to form Co-alginate precursor;
Mixing the Co-alginate precursor with melamine, carbonizing at 600 ℃ at high temperature, and preserving heat for 2 hours to form a nitrogen-doped Co-alginate precursor;
Mixing a nitrogen-doped Co-alginate precursor and disodium hydrogen phosphate according to a mass ratio of 1:1, ball-milling for 8 hours at 400r/min, carbonizing at 1000 ℃ under the condition of inert gas, and preserving heat for 4 hours; after cooling, ethanol is used for cleaning, and the transition metal nitrogen doped hard carbon material, namely Na 2 O-CoP@NHC is used.
Example 6
Preparing sodium alginate into sodium alginate aqueous solution with the mass fraction of 1.5%, and preparing cobalt nitrate aqueous solution with the mass fraction of 5% from cobalt nitrate;
Mixing the prepared sodium alginate aqueous solution and cobalt nitrate aqueous solution according to a ratio of 1:1 to form Co-alginate hydrosol, freezing in liquid nitrogen, and placing in a freezing low-temperature drying oven for 24 hours to form Co-alginate precursor;
immersing the Co-alginate precursor in urea solution for 12 hours according to the mass ratio of 1:2, carbonizing at a high temperature of 600 ℃, and preserving heat for 2 hours to form a nitrogen-doped Co-alginate precursor;
Mixing a nitrogen-doped Co-alginate precursor and sodium pyrophosphate according to a mass ratio of 1:1, ball-milling for 8 hours at 400r/min, carbonizing at 1000 ℃ under the condition of inert gas, and preserving heat for 4 hours; after cooling, ethanol is used for cleaning, and the transition metal nitrogen doped hard carbon material, namely Na 2 O-CoP@NHC is used.
Example 7
Preparing sodium alginate into sodium alginate aqueous solution with the mass fraction of 1.5%, and preparing cobalt nitrate aqueous solution with the mass fraction of 5% from cobalt nitrate;
Mixing the prepared sodium alginate aqueous solution and cobalt nitrate aqueous solution according to a ratio of 1:1 to form Co-alginate hydrosol, freezing in liquid nitrogen, and placing in a freezing low-temperature drying oven for 24 hours to form Co-alginate precursor;
immersing the Co-alginate precursor in urea solution for 12 hours according to the mass ratio of 1:2, carbonizing at a high temperature of 600 ℃, and preserving heat for 2 hours to form a nitrogen-doped Co-alginate precursor;
Mixing a nitrogen-doped Co-alginate precursor and trisodium phosphate according to a mass ratio of 1:1, ball-milling for 8 hours at 400r/min, carbonizing at 1000 ℃ under the condition of inert gas, and preserving heat for 4 hours; after cooling, ethanol is used for cleaning, and the transition metal nitrogen doped hard carbon composite material, namely Na 2 O-CoP@NHC.
Comparative example 1
Sodium alginate is used as a raw material to prepare a hard carbon material:
preparing sodium alginate into sodium alginate water solution with the mass fraction of 1.5%, freezing in liquid nitrogen, and placing in a freezing low-temperature drying oven for 24 hours to form an alginate precursor;
pre-carbonizing the prepared alginate precursor at 600 ℃, preserving heat for 2 hours, ball-milling for 8 hours at 400r/min, carbonizing at 1000 ℃ under the condition of inert gas, and preserving heat for 4 hours; and (5) cleaning by using ethanol after cooling to obtain the hard carbon material.
Comparative example 2
The preparation procedure differs from example 1 in that: the other preparation steps were identical to example 1 without addition of a transition metal salt solution, i.e. without addition of a 5% by mass aqueous cobalt nitrate solution.
Comparative example 3
The preparation procedure differs from example 1 in that: the other preparation steps were identical to example 1 without nitrogen doping, i.e. without adding a nitrogen source.
Comparative example 4
The preparation procedure differs from example 1 in that: the ball milling was carried out without adding sodium phosphate, and the other preparation steps were the same as in example 1.
Experimental example
1. Taking example 1 as an example, the hard carbon composite material of the present application was tested, and the results are shown in fig. 1 to 6.
FIGS. 1-4 are SEM images of 2000, 30000, 650000, 1200000 of the Na 2 O-CoP@NHC of example 1, respectively.
As shown in fig. 1 to 4, it can be observed that the hard carbon composite material has a rich pore structure, and the pores are uniformly distributed, which is favorable for intercalation and deintercalation of sodium ions.
FIG. 5 is an XPS pattern of Na 2 O-CoP@NHC of example 1, and FIG. 6 is an XRD pattern of Na 2 O-CoP@NHC of example 1.
As shown in FIG. 5, metallic sodium, na 2 O, na-O-C structure is present in the hard carbon composite.
As shown in fig. 6, characteristic peaks at 44.2 °, 51.5 ° and 75.8 ° correspond to diffraction of metallic Co in the N-Co/C sample, and a peak of 25 ° is a diffraction peak of an interlayer structure of a (002) crystal face of the graphite interlayer structure, corresponding to a characteristic broad peak of hard carbon.
2. The negative electrode materials obtained in examples and comparative examples were subjected to specific surface area detection, and sodium ion batteries were each prepared according to the following method.
The preparation method of the button type sodium ion battery comprises the following steps:
The preparation method comprises the following steps of: active substances SP and CMC, wherein SBR=92:2:2:4, respectively weighing a negative electrode material and SP, CMC, SBR, and uniformly mixing in deionized water to prepare slurry; and (3) coating the uniformly mixed slurry on an aluminum foil current collector, drying in an oven at 80 ℃ for 1h, taking out, and cooling to room temperature.
And (5) adjusting the rolling interval to roll the pole pieces. The rolled pole piece is cut to form a small disc with the diameter of 14mm and weighed to be m 1, and the aluminum foil current collector is also cut to form an aluminum foil disc with the diameter of 14mm and weighed to be m 2. Wherein (m 1-m2) 0.94 is the mass of active substance, denoted m 3. And placing the weighed small wafer into an oven at 80 ℃ for vacuum drying for 12 hours.
Transferring the vacuum-dried small wafer into a glove box, taking a sodium wafer as a counter electrode and an auxiliary electrode, taking an electrolyte 1M NaPF6/EC as DMC (digital control system) and a glass fiber diaphragm as diaphragms, and assembling the sodium ion button cell in the glove box with oxygen and water content of less than 0.01 ppm;
The assembled button type sodium ion battery is stationary for 12h. And (3) testing electrochemical performance of the stationary button type sodium ion battery on a Wuhan blue electric battery testing system at constant current. The test results are shown in table 1:
TABLE 1
From the data in table 1, it can be seen from comparative example 1 that the reversible charge-discharge and initial efficiency of untreated sodium alginate are poor; according to comparative examples 2 to 4, the hard carbon material ratio table, the reversible specific capacity and the first coulombic efficiency are all improved by adding the transition metal; the result shows that the specific surface area and the reversible specific capacity of the carbon material doped with nitrogen are increased by nitrogen doping, but the technical effect of the embodiment of the application is not achieved.
Therefore, the hard carbon composite material enlarges the interlayer spacing by utilizing nitrogen doping, and can provide more sodium storage sites; the performance of the material is greatly improved by adding sodium phosphate, on one hand, the added sodium phosphate can provide a phosphorus source and transition metal to form transition metal phosphide, on the other hand, the reversible specific capacity of a C-O-P bond generated on the surface in situ can be effectively increased, and on the other hand, the added sodium phosphate can be pre-sodized on the surface, so that the structure of C-O-Na is formed, and the improvement of the first effect is facilitated.
The assembled button-type sodium ion battery was subjected to 0.1C, 0.2C, 0.5C, 1.0C rate tests for electrochemical performance on a martial arts electric battery test system. The test results are shown in table 2:
TABLE 2
According to the electrochemical performance data of the 0.1C, 0.2C, 0.5C and 1.0C rate tests of Table 2, it can be seen that the rate performance of the hard carbon composite materials prepared by the nitrogen doping and the treatment of the transition metal and the phosphate in the examples 1 to 7 of the application is obviously improved compared with that of the comparative examples.
The above description of the embodiments is only for aiding in the understanding of the method of the present application and its core ideas. It should be noted that it will be apparent to those skilled in the art that various modifications and adaptations of the application can be made without departing from the principles of the application and these modifications and adaptations are intended to be within the scope of the application as defined in the following claims.
Claims (10)
1. A method for preparing a hard carbon composite material, comprising:
Mixing an alginate aqueous solution with a transition metal salt solution to form a mixed solution, and stirring and reacting to prepare a transition metal-alginate gel;
drying the transition metal-alginate gel to produce a transition metal-alginate precursor;
nitrogen doping is carried out on the transition metal-alginate precursor to prepare a nitrogen doped transition metal-alginate precursor;
and mixing the nitrogen-doped transition metal-alginate precursor with sodium phosphate, and performing ball milling and carbonization to obtain the hard carbon composite material.
2. The method according to claim 1, wherein the alginate is selected from sodium alginate and/or calcium alginate;
Preferably, the mass concentration of the alginate aqueous solution is 1-2wt%;
Preferably, the transition metal salt solution is selected from one or more of ferric salt solution, cobalt salt solution and nickel salt solution; preferably one or more of cobalt nitrate aqueous solution, nickel nitrate aqueous solution and ferric chloride aqueous solution;
more preferably, the transition metal salt solution has a mass concentration of 3 to 10wt%;
Further preferably, the mixing volume ratio of the alginate aqueous solution to the transition metal salt solution is 1 (1-1.25);
The drying is freeze drying or normal temperature drying.
3. The method of preparing according to claim 1, wherein the nitrogen doping comprises: mixing the transition metal-alginate precursor with a nitrogen source, and pre-carbonizing at 500-700 ℃;
preferably, the nitrogen source is selected from one or more of urea, melamine, ammonia water and ammonium carbonate;
More preferably, the mass ratio of the transition metal-alginate precursor to the nitrogen source is 1 (2-2.5);
and/or the nitrogen source is selected from ammonia gas, and the flow rate of the ammonia gas is 1-20L/min.
4. The method according to claim 1, wherein the sodium phosphate salt is one or more selected from the group consisting of disodium hydrogen phosphate, sodium dihydrogen phosphate, sodium pyrophosphate and trisodium phosphate;
preferably, the mass ratio of the nitrogen doped transition metal-alginate precursor to the sodium phosphate salt is 1 (1-1.5).
5. The method according to claim 1, wherein the carbonization temperature is 700-1000 ℃ and the holding time is 2-4 hours.
6. A hard carbon composite material, comprising: carbon element, transition metal element M, phosphorus element, nitrogen element and sodium element;
the transition metal element M is crosslinked in the hard carbon composite material to form a C-M-P structure;
The nitrogen element forms a C-N structure inside the hard carbon composite material;
the sodium element is deposited on the surface of the hard carbon composite material and/or forms a C-O-Na structure.
7. The hard carbon composite material according to claim 6, wherein the content of carbon element in the hard carbon composite material is more than 50wt%, the content of sodium element is 8-10wt%, the content of transition metal element is 22-25wt%, the content of phosphorus element is 8-10wt%, the content of nitrogen element is 2-3wt%, and the content of other elements is less than 2wt%.
8. The hard carbon composite material according to claim 6, wherein the hard carbon composite material has a median particle diameter D 50 to 7 μm and a specific surface area of 370 to 390m 2/g.
9. A negative electrode sheet comprising a negative electrode current collector and a negative electrode active material layer, the negative electrode active material layer comprising the hard carbon composite material produced by the production method according to any one of claims 1 to 5, or the hard carbon composite material according to any one of claims 6 to 8.
10. A sodium ion battery comprising the negative electrode tab of claim 9.
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| CN115347178A (en) * | 2022-09-26 | 2022-11-15 | 惠州亿纬锂能股份有限公司 | Nitrogen-boron co-doped pre-sodium negative electrode material and preparation method and application thereof |
| CN117133900A (en) * | 2023-09-13 | 2023-11-28 | 四川星耀新能源科技有限公司 | High-rate coal-based hard carbon composite negative electrode material, preparation method thereof and sodium ion battery |
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