CN117038975A - Modified hard carbon anode material, preparation method thereof, anode and sodium ion battery - Google Patents
Modified hard carbon anode material, preparation method thereof, anode and sodium ion battery Download PDFInfo
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- CN117038975A CN117038975A CN202311044220.XA CN202311044220A CN117038975A CN 117038975 A CN117038975 A CN 117038975A CN 202311044220 A CN202311044220 A CN 202311044220A CN 117038975 A CN117038975 A CN 117038975A
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- sodium
- hard carbon
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- 229910021385 hard carbon Inorganic materials 0.000 title claims abstract description 113
- 229910001415 sodium ion Inorganic materials 0.000 title claims abstract description 36
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 239000010405 anode material Substances 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 74
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 63
- MJEPCYMIBBLUCJ-UHFFFAOYSA-K sodium titanium(4+) phosphate Chemical compound P(=O)([O-])([O-])[O-].[Ti+4].[Na+] MJEPCYMIBBLUCJ-UHFFFAOYSA-K 0.000 claims abstract description 57
- 239000002245 particle Substances 0.000 claims abstract description 29
- 239000002103 nanocoating Substances 0.000 claims abstract description 27
- 239000007773 negative electrode material Substances 0.000 claims abstract description 26
- 239000010410 layer Substances 0.000 claims abstract description 24
- 239000000203 mixture Substances 0.000 claims abstract description 17
- 239000007788 liquid Substances 0.000 claims abstract description 16
- 239000000843 powder Substances 0.000 claims abstract description 15
- 238000005245 sintering Methods 0.000 claims abstract description 13
- 238000001035 drying Methods 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims description 20
- 239000011734 sodium Substances 0.000 claims description 19
- 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 17
- 229910052708 sodium Inorganic materials 0.000 claims description 17
- 239000002270 dispersing agent Substances 0.000 claims description 16
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 15
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 15
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 claims description 15
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 15
- 229910052698 phosphorus Inorganic materials 0.000 claims description 15
- 239000011574 phosphorus Substances 0.000 claims description 15
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 15
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims description 15
- 239000010936 titanium Substances 0.000 claims description 15
- 229910052719 titanium Inorganic materials 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 12
- 238000004519 manufacturing process Methods 0.000 claims description 11
- 239000002202 Polyethylene glycol Substances 0.000 claims description 10
- 229920002125 Sokalan® Polymers 0.000 claims description 10
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 10
- 229920002401 polyacrylamide Polymers 0.000 claims description 10
- 239000004584 polyacrylic acid Substances 0.000 claims description 10
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 10
- 229920001223 polyethylene glycol Polymers 0.000 claims description 10
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 10
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 10
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 10
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 9
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 claims description 7
- 229910000403 monosodium phosphate Inorganic materials 0.000 claims description 7
- 235000019799 monosodium phosphate Nutrition 0.000 claims description 7
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 claims description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 6
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 6
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 claims description 6
- 229930006000 Sucrose Natural products 0.000 claims description 5
- 239000005720 sucrose Substances 0.000 claims description 5
- 239000004408 titanium dioxide Substances 0.000 claims description 5
- 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 claims description 4
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 4
- 239000001488 sodium phosphate Substances 0.000 claims description 4
- 229910000162 sodium phosphate Inorganic materials 0.000 claims description 4
- 235000011008 sodium phosphates Nutrition 0.000 claims description 4
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 4
- 229920001450 Alpha-Cyclodextrin Polymers 0.000 claims description 3
- 229920000858 Cyclodextrin Polymers 0.000 claims description 3
- 239000001116 FEMA 4028 Substances 0.000 claims description 3
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 3
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 3
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 3
- HFHDHCJBZVLPGP-RWMJIURBSA-N alpha-cyclodextrin Chemical compound OC[C@H]([C@H]([C@@H]([C@H]1O)O)O[C@H]2O[C@@H]([C@@H](O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O3)[C@H](O)[C@H]2O)CO)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@@H]3O[C@@H]1CO HFHDHCJBZVLPGP-RWMJIURBSA-N 0.000 claims description 3
- 229940043377 alpha-cyclodextrin Drugs 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 3
- 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 claims description 3
- WHGYBXFWUBPSRW-FOUAGVGXSA-N beta-cyclodextrin Chemical compound OC[C@H]([C@H]([C@@H]([C@H]1O)O)O[C@H]2O[C@@H]([C@@H](O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O3)[C@H](O)[C@H]2O)CO)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@@H]3O[C@@H]1CO WHGYBXFWUBPSRW-FOUAGVGXSA-N 0.000 claims description 3
- 235000011175 beta-cyclodextrine Nutrition 0.000 claims description 3
- 229960004853 betadex Drugs 0.000 claims description 3
- 229960004106 citric acid Drugs 0.000 claims description 3
- 239000008103 glucose Substances 0.000 claims description 3
- 229960001031 glucose Drugs 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 239000006012 monoammonium phosphate Substances 0.000 claims description 3
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 3
- 235000011007 phosphoric acid Nutrition 0.000 claims description 3
- 239000001632 sodium acetate Substances 0.000 claims description 3
- 235000017281 sodium acetate Nutrition 0.000 claims description 3
- 235000017550 sodium carbonate Nutrition 0.000 claims description 3
- 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 3
- 235000010288 sodium nitrite Nutrition 0.000 claims description 3
- 229940048086 sodium pyrophosphate Drugs 0.000 claims description 3
- 229960004793 sucrose Drugs 0.000 claims description 3
- 235000019818 tetrasodium diphosphate Nutrition 0.000 claims description 3
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 claims description 3
- 229910000349 titanium oxysulfate Inorganic materials 0.000 claims description 3
- 238000001704 evaporation Methods 0.000 claims description 2
- 239000003792 electrolyte Substances 0.000 abstract description 17
- 239000000463 material Substances 0.000 abstract description 11
- 239000002131 composite material Substances 0.000 abstract description 2
- 239000011248 coating agent Substances 0.000 description 15
- 238000000576 coating method Methods 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 15
- 239000007789 gas Substances 0.000 description 14
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- 239000003575 carbonaceous material Substances 0.000 description 9
- 238000009831 deintercalation Methods 0.000 description 7
- 238000007086 side reaction Methods 0.000 description 7
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 238000003860 storage Methods 0.000 description 6
- 229910052786 argon Inorganic materials 0.000 description 5
- 239000011247 coating layer Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 238000000354 decomposition reaction Methods 0.000 description 4
- 239000007784 solid electrolyte Substances 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 239000011888 foil Substances 0.000 description 3
- 239000011261 inert gas Substances 0.000 description 3
- 239000010416 ion conductor Substances 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000003763 carbonization Methods 0.000 description 2
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 125000005842 heteroatom Chemical group 0.000 description 2
- 238000009830 intercalation Methods 0.000 description 2
- 230000002687 intercalation Effects 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical group [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- 229910021384 soft carbon Inorganic materials 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000007770 graphite material Substances 0.000 description 1
- 238000005087 graphitization Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- YPPMLCHGJUMYPZ-UHFFFAOYSA-L sodium;iron(2+);sulfate Chemical compound [Na+].[Fe+2].[O-]S([O-])(=O)=O YPPMLCHGJUMYPZ-UHFFFAOYSA-L 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000000185 sucrose group Chemical group 0.000 description 1
- 238000002411 thermogravimetry Methods 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
- H01M4/04—Processes of manufacture in general
-
- 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
- H01M4/366—Composites as layered products
-
- 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
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
Abstract
The application relates to the technical field of battery materials, and discloses a modified hard carbon negative electrode material, a preparation method thereof, a negative electrode and a sodium ion battery. The modified hard carbon negative electrode material comprises a hard carbon inner core and a nano coating layer which is coated on the surface of the hard carbon inner core and is formed by carbon doped sodium titanium phosphate particles; in the nano coating layer, the mass ratio of carbon to sodium titanium phosphate is 0.1-10:100; the mass ratio of the hard carbon core to the sodium titanium phosphate in the nano coating layer is 100:0.1-10. The preparation method of the modified hard carbon anode material comprises the following steps: drying the solid-liquid mixture to obtain dry powder; sintering the powder at 800-1000 ℃ in an inert atmosphere to obtain a hard carbon anode material with a carbon-doped titanium sodium phosphate nano coating layer coated on the surface; the solid-liquid mixture is composed of a composite solution and hard carbon particles which are mutually and uniformly dispersed. The modified hard carbon anode material and the preparation method thereof can avoid the problems that the SEI film of the sodium ion battery is easy to regenerate, and the electrolyte is continuously consumed and gas is produced.
Description
Technical Field
The application relates to the technical field of battery materials, in particular to a modified hard carbon negative electrode material and a preparation method thereof, a negative electrode and a sodium ion battery.
Background
Currently, the development of new energy is increasingly emphasized as the energy crisis and the environmental crisis are more serious. Among them, sodium Ion Batteries (SIBs) are considered as one of the key technologies in the energy storage field due to the abundant reserves of raw material resources, low cost and superior performance.
The negative electrode material is used as one of key materials of the sodium ion battery, and the sodium storage capacity, the coulombic efficiency and the cycle stability of the negative electrode material can greatly influence the performance of the battery. Therefore, the development of high-performance sodium ion battery anode materials is a key to the development of high-performance sodium ion batteries. The current sodium ion battery cathode material comprises carbon-based materials, alloy materials, titanium-based materials and the like, wherein the carbon-based materials are the main stream choice in the current industry due to the advantages of wide sources of raw materials, low cost, high Chu Narong, high cycle stability and the like. And in the carbon-based materials, the graphite and soft carbon materials have low sodium storage capacity, so that the practical application of the sodium ion battery is difficult to meet. The hard carbon material has excellent sodium storage performance, high capacity (300 mAh/g), low potential (0.1V vs. Na/Na) + ) And good cycle stability, and is considered as the most potential negative electrode material of the sodium ion battery.
Since hard carbon is produced by carbonization of different precursors at lower temperatures, there are more heteroatom functionalities on the surface and gas emissions during carbonization can lead to the creation of a large number of voids. Therefore, the surface of the hard carbon often has more defects and heteroatom functional groups, so that the interface contact with the electrolyte is more, side reactions are more, and the formed solid electrolyte interface film is not uniform and stable enough. The battery has low coulomb efficiency for the first time, and the electrolyte is continuously decomposed and gas is produced in the circulating process.
In the prior art, in order to reduce side reactions at the interface of the cathode, the first coulomb efficiency and the circulation stability of the hard carbon material are improved, and the electrolyte decomposition and the gas production are reduced. Hard carbon materials are usually coated, and a common coating mode is to coat soft carbon or graphite materials with higher graphitization degree on the surface of the hard carbon, so that pores and defects on the surface of the hard carbon are reduced. These methods can improve the stability of Solid Electrolyte Interface (SEI) formed by decomposition of electrolyte, but due to the components of sodium ion solid electrolyte itself (such as NaF, na 2 CO 3 ) The SEI film still has the problems of electrolyte consumption and gas production caused by continuous dissolution and reconstruction of the SEI film due to higher solubility in the electrolyte. There is thus a need to further improve the stability of the sodium ion solid electrolyte interface SEI itself.
In view of this, the present application has been made.
Disclosure of Invention
The application aims to provide a modified hard carbon anode material and a preparation method thereof, an anode and a sodium ion battery, and aims to solve at least one of the problems in the background art.
The application is realized in the following way:
in a first aspect, the application provides a modified hard carbon negative electrode material, which comprises a hard carbon inner core and a nano coating layer coated on the surface of the hard carbon inner core and formed by carbon doped sodium titanium phosphate particles;
in the nano coating layer, the mass ratio of carbon to sodium titanium phosphate is 0.1-10:100;
the mass ratio of the hard carbon core to the sodium titanium phosphate in the nano coating layer is 100:0.1-10.
In an alternative embodiment, the hard carbon core has a particle size of 0.5um to 50um;
optionally, in the nano coating layer, the mass ratio of carbon to sodium titanium phosphate is 0.5-5:100;
optionally, the mass ratio of the hard carbon core to the sodium titanium phosphate in the nano coating layer is 100:0.5-5.
In a second aspect, the application provides a method for preparing a modified hard carbon anode material, comprising the following steps:
drying the solid-liquid mixture to obtain dry powder;
sintering the dry powder at 800-1000 ℃ in an inert atmosphere to obtain a hard carbon anode material with a carbon-coated titanium sodium phosphate nano coating layer on the surface;
the solid-liquid mixture consists of a phosphorus source, a carbon source, a titanium source, a sodium source and hard carbon particles which are mutually and uniformly dispersed; the mass ratio of the carbon element provided by the carbon source to the target sodium titanium phosphate to be generated is 0.1-10:100;
the mass ratio of the hard carbon particles to the target sodium titanium phosphate to be generated is 100:0.1-10.
In alternative embodiments, the phosphorus source is selected from one or more of phosphoric acid, monoammonium phosphate, sodium dihydrogen phosphate, disodium hydrogen phosphate, sodium phosphate;
optionally, the carbon source is at least one selected from the group consisting of citric acid, sucrose, glucose, α -cyclodextrin, β -cyclodextrin, polyacrylamide, sodium carboxymethylcellulose, polyethylene glycol, polyvinylpyrrolidone, polyacrylic acid, and polyacrylonitrile;
optionally, the titanium source is selected from at least one of titanium dioxide, tetrabutyl titanate, and titanyl sulfate;
alternatively, the sodium source is selected from at least one of sodium dihydrogen phosphate, disodium hydrogen phosphate, sodium nitrite, sodium pyrophosphate, sodium bicarbonate, sodium carbonate, and sodium acetate.
In an alternative embodiment, when the carbon source does not include at least one of polyacrylamide, sodium carboxymethyl cellulose, polyethylene glycol, polyvinylpyrrolidone, polyacrylic acid, and polyacrylonitrile, the composite solution further contains a dispersing agent;
optionally, the dispersing agent is at least one selected from polyacrylamide, sodium carboxymethyl cellulose, polyethylene glycol, polyvinylpyrrolidone, polyacrylic acid and polyacrylonitrile;
optionally, the mass ratio of dispersant to hard carbon is 0.1-5:100.
In an alternative embodiment, the method for preparing the uniformly mixed solid-liquid mixture into dry gel powder comprises the following steps: and heating and evaporating water in the solid-liquid mixture to obtain dry gel powder.
In an alternative embodiment, the hard carbon particles have a particle size of 0.5 μm to 50 μm.
In a third aspect, the present application provides a modified hard carbon anode material, prepared by a method according to any one of the preceding embodiments.
In a fourth aspect, the present application provides a negative electrode made from a modified hard carbon negative electrode material as described in the previous embodiments.
In a fifth aspect, the present application provides a sodium ion battery comprising a negative electrode as in the previous embodiments.
The application has the following beneficial effects:
the modified hard carbon negative electrode material provided by the application has the following effects that the surface of the modified hard carbon negative electrode material is coated with the nano coating formed by carbon doped sodium titanium phosphate particles:
the SEI interface film is equivalent to the SEI interface film which is formed in advance and is highly stable, so that the decomposition of electrolyte is reduced, and the continuous generation of side reaction is inhibited; the SEI film has high stability in electrolyte, avoids the problems that the conventional SEI film of the sodium ion battery is easy to regenerate, and further causes continuous consumption of the electrolyte and gas production, and improves the normal temperature and high temperature cycle performance and high temperature storage performance of the battery;
the sodium titanium phosphate is used as a sodium ion conductor, has a crystal structure of a three-dimensional space frame, is favorable for rapid deintercalation of sodium ions, and reduces the damage of the deintercalation of sodium ions to an interface, so that the multiplying power and the cycle performance of the battery are improved;
carbon is doped in the coating layer of the sodium titanium phosphate, so that the ionic conductivity is improved and the electronic conductivity is also improved.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present application more clear, the technical solutions of the embodiments of the present application will be clearly and completely described below. 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.
The modified hard carbon negative electrode material, the preparation method thereof, the negative electrode and the sodium ion battery provided by the application are specifically described below.
The modified hard carbon negative electrode material provided by the embodiment of the application comprises a hard carbon inner core and a nano coating layer coated on the surface of the hard carbon inner core and formed by carbon doped sodium titanium phosphate particles;
in the nano coating layer, the mass ratio of carbon to sodium titanium phosphate is 0.1-10:100 (for example, 0.1:100, 0.5:100, 1:100, 3:100, 5:100, 8:100 or 10:100);
the mass ratio of the hard carbon core to the sodium titanium phosphate in the nano-coating layer is 100:0.1-10 (for example, 100:0.1, 100:0.5, 100:1, 100:2, 100:3, 100:4 or 100:5).
According to the modified hard carbon negative electrode material provided by the embodiment of the application, the carbon-doped titanium sodium phosphate nano coating layer is coated on the surface of the hard carbon in advance, which is equivalent to the formation of a highly stable SEI interface film in advance, so that the decomposition of electrolyte is reduced, and the continuous generation of side reaction is inhibited; the SEI film has high stability in electrolyte, avoids the problems that the conventional SEI film of the sodium ion battery is easy to regenerate, and further causes continuous consumption of the electrolyte and gas production, and improves the normal temperature and high temperature cycle performance and high temperature storage performance of the battery; the sodium titanium phosphate is used as a sodium ion conductor, has a crystal structure of a three-dimensional space frame, is favorable for rapid deintercalation of sodium ions, and reduces the damage of the deintercalation of sodium ions to an interface, so that the multiplying power and the cycle performance of the battery are improved; carbon is doped in the coating layer of the sodium titanium phosphate, so that the ionic conductivity is improved and the electronic conductivity is also improved.
It should be noted that the carbon doping amount is not too much, and excessive doping amount beyond the range of the mixing ratio required by the application may cause side reaction to be aggravated, affect circulation, and cause gas production to be increased. The coating amount of the carbon-doped sodium titanium phosphate nano coating layer is not too much, and the excessive coating amount exceeding the proportioning range required by the application can reduce the available capacity of the hard carbon and influence the multiplying power and the cycle performance of the material.
Preferably, the mass ratio of carbon to sodium titanium phosphate in the nano-coating is 0.5-5:100 (e.g., 0.5:100, 1:100, 3:100, 4:100, or 5:100).
The doping amount of carbon has a better effect in the above range.
Preferably, the mass ratio of the hard carbon core to the sodium titanium phosphate in the nano-coating is 100:0.5-5 (e.g., 100:0.5, 100:1, 100:2, 100:3, 100:4, or 100:5).
The coating amount of the sodium titanium phosphate has a better effect in the above range.
Preferably, the hard carbon core has a particle size of 1 μm to 20. Mu.m.
When the particle size of the hard carbon core is 1-20 mu m, the particle size of the prepared modified hard carbon anode material is about 1-30 mu m, and when the modified hard carbon anode material is applied to anode preparation, the performance of the obtained anode material can be ensured to be better.
The preparation method of the modified hard carbon anode material provided by the embodiment of the application comprises the following steps:
drying the solid-liquid mixture to obtain dry powder;
sintering the dry powder at 800-1000 ℃ in an inert atmosphere to obtain a hard carbon anode material with a carbon-coated titanium sodium phosphate nano coating layer on the surface;
the solid-liquid mixture consists of a phosphorus source, a carbon source, a titanium source, a sodium source and hard carbon particles which are mutually and uniformly dispersed; the mass ratio of the carbon element provided by the carbon source to the target sodium titanium phosphate to be generated is 0.1-10:100;
the mass ratio of the hard carbon particles to the target sodium titanium phosphate to be generated is 100:0.1-10.
The application provides a gel dry method for preparing a modified hard carbon negative electrode material, which can react on the surface of hard carbon particles at a proper temperature in an inert atmosphere to generate nanoscale carbon and nanoscale sodium titanium phosphate, so that the method can realize that carbon-doped sodium titanium phosphate nanoparticles form a nano-sized coating layer on the surface of the hard carbon, and the prepared modified hard carbon negative electrode material has good electrochemical performance.
The preparation method specifically comprises the following steps:
s1, preparing a mixed solution
Dispersing a phosphorus source, a carbon source, a titanium source and sodium salt into deionized water, wherein the phosphorus source, the titanium source and the sodium salt react to generate sodium titanium phosphate (NaTi) 2 (PO4) 3 ) Is added according to the stoichiometric ratio of the raw materials; and the carbon source is fed according to the mass ratio of the carbon element provided by the carbon source to the target sodium titanium phosphate to be generated of 0.1-10:100.
Optionally, the phosphorus source is selected from one or more of phosphoric acid, monoammonium phosphate, sodium dihydrogen phosphate, disodium hydrogen phosphate and sodium phosphate;
optionally, the carbon source is at least one selected from the group consisting of citric acid, sucrose, glucose, α -cyclodextrin, β -cyclodextrin, polyacrylamide, sodium carboxymethylcellulose, polyethylene glycol, polyvinylpyrrolidone, polyacrylic acid, and polyacrylonitrile;
optionally, the titanium source is selected from at least one of titanium dioxide, tetrabutyl titanate, and titanyl sulfate;
optionally, the sodium source is at least one selected from sodium dihydrogen phosphate, disodium hydrogen phosphate, sodium nitrite, sodium pyrophosphate, sodium bicarbonate, sodium carbonate, and sodium acetate.
The phosphorus source and the sodium source may be provided by the same substance, for example, sodium dihydrogen phosphate, disodium hydrogen phosphate, and sodium phosphate.
S2, preparation of solid-liquid mixture
And (3) putting hard carbon particles into the mixed solution obtained in the step (S1), and uniformly stirring to obtain a solid-liquid mixture. The mass ratio of the feeding amount of the hard carbon to the target sodium titanium phosphate to be generated is 100:0.1-10.
Because polyacrylamide, sodium carboxymethyl cellulose, polyethylene glycol, polyvinylpyrrolidone, polyacrylic acid, and polyacrylonitrile can act as a dispersant in addition to being a carbon source. Therefore, when the carbon source added in the step S1 does not include at least one of polyacrylamide, sodium carboxymethyl cellulose, polyethylene glycol, polyvinylpyrrolidone, polyacrylic acid, and polyacrylonitrile, in order to ensure that the hard carbon has better dispersibility when the hard carbon particles are added in the step, a dispersing agent is added to the mixed solution.
Specifically, the dispersing agent is at least one selected from polyacrylamide, sodium carboxymethyl cellulose, polyethylene glycol, polyvinylpyrrolidone, polyacrylic acid and polyacrylonitrile.
Preferably, a good dispersing effect is ensured, the mass ratio of dispersant to hard carbon being 0.1 to 2:100 (e.g. 0.1:100, 0.5:100, 1:100, 1.5:100 or 2:100).
Preferably, the hard carbon particles have a particle diameter of 1 μm to 20 μm in order to give the produced anode material better performance.
S3, preparing dry powder
Heating the solid-liquid mixture to evaporate water to obtain dry powder.
S4, sintering
And sintering the obtained dry powder at 800-1000 ℃ (such as 800 ℃, 900 ℃ or 1000 ℃) in an inert atmosphere to obtain the hard carbon anode material with the surface coated with the carbon-doped sodium titanium phosphate nano coating layer.
The negative electrode provided by the embodiment of the application is prepared from the modified hard carbon negative electrode material provided by the embodiment of the application.
The battery provided by the embodiment of the application comprises the negative electrode provided by the embodiment of the application.
The features and capabilities of the present application are described in further detail below in connection with the examples.
In the following examples, the determination method of the carbon content in the carbon source is: according to the result of the thermogravimetric analysis TGA test, the carbon source is remained in the mass ratio at the temperature of 800-1000 ℃.
Example 1
In this example, modified hard carbon negative electrode materials were prepared according to the steps S1 to S4 described above.
The phosphorus source is ammonia dihydrogen phosphate, the titanium source is titanium dioxide, the sodium source is sodium carbonate, the carbon source is sodium carboxymethyl cellulose, and the sodium carboxymethyl cellulose has the function of a dispersing agent, so that the dispersing agent is not added in the embodiment;
the feeding amount of the phosphorus source is 3.45g, the feeding amount of the titanium source is 1.6g, and the feeding amount of the sodium sourceThe amount of the mixture was 0.53g, so that 0.01mol, i.e., 4.04g of NaTi could be produced 2 (PO4) 3 The method comprises the steps of carrying out a first treatment on the surface of the The carbon source is charged in an amount of 0.32g, and the carbon coating amount is about 0.08g; the mass ratio of the carbon element to the sodium titanium phosphate is 2:100.
The dosage of deionized water is 500mL;
the particle size of the hard carbon ranges from 1 mu m to 20 mu m, and the feeding amount of the hard carbon is 200g, namely the mass ratio of the hard carbon to the generated sodium titanium phosphate is about 100:2;
the sintering temperature is 900 ℃, and the inert gas is argon during sintering.
Example 2
In this example, modified hard carbon negative electrode materials were prepared according to the steps S1 to S4 described above.
The phosphorus source is ammonia dihydrogen phosphate, the titanium source is titanium dioxide, the sodium source is sodium carbonate, and the carbon source is sucrose and sodium carboxymethyl cellulose, wherein the sodium carboxymethyl cellulose has the function of a dispersing agent, so that the dispersing agent is not added in the embodiment;
the feeding amount of the phosphorus source is 3.45g, the feeding amount of the titanium source is 1.6g, and the feeding amount of the sodium source is 0.53g, so that 0.01mol, namely 4.04g of NaTi can be generated 2 (PO4) 3 The method comprises the steps of carrying out a first treatment on the surface of the The total dosage of the carbon source is 0.8g, wherein the dosage of sucrose is 0.1g, and the dosage of sodium carboxymethylcellulose is 0.7g, and the carbon coating amount is about 0.2g; the mass ratio of the carbon element to the sodium titanium phosphate is 5:100.
The dosage of deionized water is 1000mL;
the particle size of the hard carbon ranges from 1 mu m to 20 mu m, the feeding amount of the hard carbon is 404g, namely the mass ratio of the hard carbon to the generated sodium titanium phosphate is about 100:1;
the sintering temperature is 800 ℃, and the inert gas is argon during sintering.
Example 3
In this example, modified hard carbon negative electrode materials were prepared according to the steps S1 to S4 described above.
The phosphorus source is ammonia dihydrogen phosphate, the titanium source is tetrabutyl titanate, the sodium source is sodium carbonate, and the carbon source is sodium polyacrylate, wherein the sodium polyacrylate has the function of a dispersing agent, so that the dispersing agent is not added in the embodiment;
the feeding amount of the phosphorus source is 3.96g, the feeding amount of the titanium source is 6.8g, and the feeding amount of the sodium source is 0.53g, so that 0.01mol, namely 4.04g of NaTi can be generated 2 (PO4) 3 The method comprises the steps of carrying out a first treatment on the surface of the The carbon source feeding amount is 0.16g, and the carbon coating amount is about 0.04g; the mass ratio of the carbon element to the sodium titanium phosphate is 1:100.
The dosage of deionized water is 200mL;
the particle size of the hard carbon ranges from 1 mu m to 20 mu m, the feeding amount of the hard carbon is 120g, namely the mass ratio of the hard carbon to the generated sodium titanium phosphate is about 100:3.37;
the sintering temperature is 1000 ℃, and the inert gas is argon during sintering.
Example 4
This embodiment is substantially the same as embodiment 1, except that: the amount of the carbon source to be charged was 0.08g.
Example 5
This embodiment is substantially the same as embodiment 1, except that: the amount of carbon source charged was 1.6g.
Example 6
This embodiment is substantially the same as embodiment 1, except that: the amount of the hard carbon fed was 4040g, i.e., the mass ratio of the hard carbon to the produced sodium titanium phosphate was about 100:0.1.
Example 7
This embodiment is substantially the same as embodiment 1, except that: the amount of the hard carbon fed was 40.4g, i.e., the mass ratio of the hard carbon to the produced sodium titanium phosphate was about 100:10.
Comparative example 1
This comparative example is substantially the same as example 1, except that: no carbon source was added.
Comparative example 2
This comparative example provides the same hard carbon as in example 1 without any treatment.
Comparative example 3
This comparative example is substantially the same as example 5, except that: the amount of carbon source charged was 5g.
Comparative example 4
This comparative example is substantially the same as example 7, except that: the amount of the hard carbon charged was 20g.
Experimental example
Testing the electrical properties of the hard carbon material:
and (3) taking the hard carbon prepared in the embodiment as a negative electrode material of the sodium ion battery to prepare a negative electrode plate, and forming a CR2032 button battery with the metal sodium plate to evaluate the hard carbon material. The method comprises the steps of homogenizing hard carbon and SP, CMC, SBr in deionized water according to a mass ratio of 90:5:2:3, coating on aluminum foil, and drying to prepare a sodium ion battery negative plate; the diaphragm adopts a PP base film with the thickness of 20 mu m; the electrolyte adopts 1.0mol/L NaPF 6 The solution dissolved in EC: dec=5:5 was assembled into a CR2032 type button cell in a glove box filled with argon for evaluation, and the capacity, rate and cycle performance of the material were tested.
Material capacity and first efficiency test: discharging the assembled CR2032 button battery to 0V according to a constant current of 0.1C, and standing for 1min; and then charging to 2V according to a constant current of 0.1C, and testing the capacity and the first coulombic efficiency.
And (3) testing the multiplying power performance of the material: discharging the assembled CR2032 button battery to 0V according to a constant current of 0.1C, and standing for 1min; and then charging to 2V according to 5C constant current, and testing the capacity.
Material cycle performance test: discharging the assembled CR2032 button battery to 0V according to a constant current of 0.5C, and standing for 1min; and then charging to 2V according to constant current of 0.5C, and circulating for 100 circles to record the capacity retention rate.
Sodium ion full cell gas production test:
the hard carbon prepared in the embodiment is used as a negative electrode material of a sodium ion battery to be manufactured into a negative electrode plate, and the negative electrode plate and a positive electrode plate made of a ferric sodium sulfate positive electrode material are assembled into a single-piece soft-package battery. The method comprises the steps of homogenizing hard carbon and SP, CMC, SBr in deionized water according to a mass ratio of 90:5:2:3, coating on aluminum foil, and drying to prepare a sodium ion battery negative plate; homogenizing sodium iron sulfate, SP and PVDF in NMP according to the mass ratio of 90:5:5, coating on aluminum foil, drying to prepare a sodium ion battery positive plate, and adopting a PP base film with the thickness of 20 mu m as a diaphragm; the electrolyte adopts 1.0mol/L NaPF 6 The solution dissolved in PC: emc=4:6 was assembled into a monolithic soft pack battery in a glove box filled with argon, and after 100 cycles at 45 ℃, the measurements were performedAnd (5) testing gas production.
The gas production is tested by adopting a drainage method: placing the assembled and sealed untested soft package battery into a container filled with water, and testing the volume V1 of the discharged water; after 100 cycles of cycle life test, the battery is soaked in a container filled with water, and the volume V2 of the discharged water is tested. The gas yield is V2-V1.
The results are recorded in table 1.
Table 1 electrochemical properties of the batteries prepared in each of examples and comparative examples
As can be seen from the table, the modified hard carbon negative electrode material prepared by the embodiment of the application has better electrochemical performance, compared with unmodified hard carbon (comparative example 2), the performance is greatly improved, particularly the gas yield is obviously reduced, and the cycle capacity retention rate is greatly improved;
comparing example 1 with comparative example 1, the capacity and multiplying power of example 1 are obviously better, which shows that doping carbon in the sodium titanium phosphate coating layer can improve the conductivity of the coating material, thereby improving the capacity and multiplying power.
Comparing comparative example 3 with example 5, the cycle performance of comparative example 3 is poor, and the assembled full cell shows more gas production, which means that the carbon dosage is not too high, but too high can cause side reaction to be aggravated, affect the cycle, and cause the gas production to be increased.
Comparing comparative example 4 with example 7, the capacity, first effect, rate and cycle performance of comparative example 4 are all less good, which means that the coating amount is not too large, and too large coating amount can reduce the available capacity of hard carbon, and can affect the rate and cycle performance of the material.
Comparing examples 4 and 5 with examples 2 and 3, respectively, the performance of examples 2 and 3 is better, which shows that setting the ratio of carbon to sodium titanium phosphate to be 0.5-5:100 can lead the performance of the prepared modified hard carbon anode material to be better.
Comparing examples 6 and 7 with examples 2 and 3, respectively, the performances of examples 2 and 3 are better, which shows that setting the mass ratio of the hard carbon to the sodium titanium phosphate in the nano coating layer to be 100:0.5-5 can lead the performances of the prepared modified hard carbon anode material to be better.
In summary, the modified hard carbon anode material and the preparation method thereof provided by the embodiment of the application have the following advantages:
1. by coating the titanium sodium phosphate with a three-dimensional sodium ion intercalation and deintercalation channel on the surface of the hard carbon, the SEI film with high stability is pre-manufactured to replace the SEI film which is naturally formed during battery formation, so that the solubility of SEI in electrolyte is reduced, the condition that SEI at an interface is repeatedly dissolved and regenerated is avoided, the side reaction of the electrolyte at the interface is reduced, and the normal temperature and high temperature cycle and storage performance of the battery are improved.
2. The sodium titanium phosphate is used as a Nasicon type sodium ion conductor and coated on the surface of hard carbon, so that the speed of sodium ion intercalation and deintercalation is improved, and the damage of sodium ion deintercalation to an interface is reduced. The multiplying power and the cycle performance of the battery are improved.
3. The sintering process can form carbon doped sodium titanium phosphate, so that the conductivity of the coating layer is improved, and the conductivity reduction caused by coating the sodium titanium phosphate is avoided. The rate capability of the battery is improved.
The above is only a preferred embodiment of the present application, and is not intended to limit the present application, but various modifications and variations can be made to the present application by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present application should be included in the protection scope of the present application.
Claims (10)
1. The modified hard carbon negative electrode material is characterized by comprising a hard carbon inner core and a nano coating layer which is coated on the surface of the hard carbon inner core and is formed by carbon doped sodium titanium phosphate particles;
in the nano coating layer, the mass ratio of carbon to sodium titanium phosphate is 0.1-10:100;
the mass ratio of the hard carbon inner core to the sodium titanium phosphate in the nano coating layer is 100:0.1-10.
2. The modified hard carbon negative electrode material according to claim 1, wherein the hard carbon core has a particle diameter of 0.5 μm to 50 μm;
optionally, in the nano coating layer, the mass ratio of carbon to sodium titanium phosphate is 0.5-5:100;
optionally, the mass ratio of the hard carbon core to the sodium titanium phosphate in the nano coating layer is 100:0.5-5.
3. The preparation method of the modified hard carbon anode material is characterized by comprising the following steps of:
drying the solid-liquid mixture to obtain dry powder;
sintering the dry powder at 800-1000 ℃ in an inert atmosphere to obtain a hard carbon anode material with a carbon-coated titanium sodium phosphate nano coating layer on the surface;
the solid-liquid mixture consists of a phosphorus source, a carbon source, a titanium source, a sodium source and hard carbon particles which are mutually and uniformly dispersed;
the mass ratio of the carbon element provided by the carbon source to the target sodium titanium phosphate to be generated is 0.1-10:100;
the mass ratio of the hard carbon particles to the target sodium titanium phosphate to be generated is 100:0.1-10.
4. The method according to claim 3, wherein the phosphorus source is selected from one or more of phosphoric acid, monoammonium phosphate, sodium dihydrogen phosphate, disodium hydrogen phosphate, and sodium phosphate;
optionally, the carbon source is at least one selected from the group consisting of citric acid, sucrose, glucose, α -cyclodextrin, β -cyclodextrin, polyacrylamide, sodium carboxymethyl cellulose, polyethylene glycol, polyvinylpyrrolidone, polyacrylic acid, and polyacrylonitrile;
optionally, the titanium source is selected from at least one of titanium dioxide, tetrabutyl titanate, and titanyl sulfate;
optionally, the sodium source is selected from at least one of sodium dihydrogen phosphate, disodium hydrogen phosphate, sodium nitrite, sodium pyrophosphate, sodium bicarbonate, sodium carbonate, and sodium acetate.
5. The method according to claim 3, wherein when the carbon source does not include at least one of polyacrylamide, sodium carboxymethyl cellulose, polyethylene glycol, polyvinylpyrrolidone, polyacrylic acid, and polyacrylonitrile, the solid-liquid mixture further contains a dispersant;
optionally, the dispersing agent is at least one selected from polyacrylamide, sodium carboxymethyl cellulose, polyethylene glycol, polyvinylpyrrolidone, polyacrylic acid and polyacrylonitrile;
optionally, the mass ratio of the dispersing agent to the hard carbon is 0.1-5:100.
6. The method of preparing the dry gel powder according to claim 5, wherein the method of preparing the solid-liquid mixture is as follows: and heating and evaporating water in the solid-liquid mixture to obtain the dry gel powder.
7. The method according to claim 3, wherein the hard carbon particles have a particle diameter of 0.5 μm to 50. Mu.m.
8. A modified hard carbon negative electrode material characterized by being produced by the production method according to any one of claims 3 to 7.
9. A negative electrode, characterized by being produced using the modified hard carbon negative electrode material according to claim 1, 2 or 8.
10. A sodium ion battery comprising a negative electrode according to claim 9.
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