CN113629219A - Sodium-ion battery positive electrode material, sodium-ion battery and preparation method and application thereof - Google Patents
Sodium-ion battery positive electrode material, sodium-ion battery and preparation method and application thereof Download PDFInfo
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- CN113629219A CN113629219A CN202110815671.3A CN202110815671A CN113629219A CN 113629219 A CN113629219 A CN 113629219A CN 202110815671 A CN202110815671 A CN 202110815671A CN 113629219 A CN113629219 A CN 113629219A
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- positive electrode
- ion battery
- sodium
- negative electrode
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- 238000002360 preparation method Methods 0.000 title claims abstract description 106
- 229910001415 sodium ion Inorganic materials 0.000 title claims abstract description 98
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title claims abstract description 95
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 95
- 239000000843 powder Substances 0.000 claims abstract description 97
- 238000001035 drying Methods 0.000 claims abstract description 91
- 238000000498 ball milling Methods 0.000 claims abstract description 72
- 239000002243 precursor Substances 0.000 claims abstract description 67
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 36
- 238000001354 calcination Methods 0.000 claims abstract description 36
- 238000001238 wet grinding Methods 0.000 claims abstract description 34
- 238000001816 cooling Methods 0.000 claims abstract description 33
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 9
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 9
- 238000003825 pressing Methods 0.000 claims abstract description 4
- 239000011734 sodium Substances 0.000 claims description 131
- 239000002904 solvent Substances 0.000 claims description 129
- 229910021385 hard carbon Inorganic materials 0.000 claims description 90
- -1 polypropylene Polymers 0.000 claims description 68
- 239000002033 PVDF binder Substances 0.000 claims description 63
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 63
- 239000011248 coating agent Substances 0.000 claims description 62
- 238000000576 coating method Methods 0.000 claims description 62
- 238000004080 punching Methods 0.000 claims description 60
- 239000003792 electrolyte Substances 0.000 claims description 45
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Inorganic materials O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 34
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 33
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 33
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 32
- 238000004321 preservation Methods 0.000 claims description 29
- 238000000034 method Methods 0.000 claims description 13
- 239000011230 binding agent Substances 0.000 claims description 9
- 239000002482 conductive additive Substances 0.000 claims description 9
- 239000007773 negative electrode material Substances 0.000 claims description 8
- 239000004743 Polypropylene Substances 0.000 claims description 7
- 229920001155 polypropylene Polymers 0.000 claims description 7
- 159000000000 sodium salts Chemical class 0.000 claims description 7
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- 239000011267 electrode slurry Substances 0.000 claims description 6
- 229910052749 magnesium Inorganic materials 0.000 claims description 6
- 239000004033 plastic Substances 0.000 claims description 6
- 229920003023 plastic Polymers 0.000 claims description 6
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 5
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 5
- 229910052791 calcium Inorganic materials 0.000 claims description 5
- 229910052802 copper Inorganic materials 0.000 claims description 5
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 5
- 229910001488 sodium perchlorate Inorganic materials 0.000 claims description 5
- 229910052719 titanium Inorganic materials 0.000 claims description 5
- 229910052725 zinc Inorganic materials 0.000 claims description 5
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims description 4
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 4
- 229910052681 coesite Inorganic materials 0.000 claims description 4
- 229910052906 cristobalite Inorganic materials 0.000 claims description 4
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 239000000661 sodium alginate Substances 0.000 claims description 4
- 235000010413 sodium alginate Nutrition 0.000 claims description 4
- 229940005550 sodium alginate Drugs 0.000 claims description 4
- BAZAXWOYCMUHIX-UHFFFAOYSA-M sodium perchlorate Chemical compound [Na+].[O-]Cl(=O)(=O)=O BAZAXWOYCMUHIX-UHFFFAOYSA-M 0.000 claims description 4
- 229910021384 soft carbon Inorganic materials 0.000 claims description 4
- 229910052682 stishovite Inorganic materials 0.000 claims description 4
- 229910052905 tridymite Inorganic materials 0.000 claims description 4
- 108010010803 Gelatin Proteins 0.000 claims description 3
- 229920002125 Sokalan® Polymers 0.000 claims description 3
- QXZNUMVOKMLCEX-UHFFFAOYSA-N [Na].FC(F)(F)S(=O)(=O)NS(=O)(=O)C(F)(F)F Chemical compound [Na].FC(F)(F)S(=O)(=O)NS(=O)(=O)C(F)(F)F QXZNUMVOKMLCEX-UHFFFAOYSA-N 0.000 claims description 3
- 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 3
- 239000006229 carbon black Substances 0.000 claims description 3
- 239000008273 gelatin Substances 0.000 claims description 3
- 229920000159 gelatin Polymers 0.000 claims description 3
- 235000019322 gelatine Nutrition 0.000 claims description 3
- 235000011852 gelatine desserts Nutrition 0.000 claims description 3
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 3
- 239000003273 ketjen black Substances 0.000 claims description 3
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 3
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims description 3
- 239000004584 polyacrylic acid Substances 0.000 claims description 2
- 238000007790 scraping Methods 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 11
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 11
- 239000010405 anode material Substances 0.000 abstract description 10
- 239000002253 acid Substances 0.000 abstract description 9
- 239000002994 raw material Substances 0.000 abstract description 6
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 abstract description 5
- 238000003860 storage Methods 0.000 abstract description 4
- 230000001351 cycling effect Effects 0.000 abstract description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 62
- 229910052782 aluminium Inorganic materials 0.000 description 60
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 60
- 239000011888 foil Substances 0.000 description 60
- 238000002156 mixing Methods 0.000 description 59
- 238000011056 performance test Methods 0.000 description 58
- 238000003756 stirring Methods 0.000 description 58
- 239000000203 mixture Substances 0.000 description 49
- 238000010438 heat treatment Methods 0.000 description 32
- 238000012360 testing method Methods 0.000 description 32
- GNRSAWUEBMWBQH-UHFFFAOYSA-N nickel(II) oxide Inorganic materials [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 31
- 239000004677 Nylon Substances 0.000 description 30
- 239000003365 glass fiber Substances 0.000 description 30
- 239000012528 membrane Substances 0.000 description 30
- 229920001778 nylon Polymers 0.000 description 30
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 30
- 239000010406 cathode material Substances 0.000 description 29
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 28
- 230000000630 rising effect Effects 0.000 description 25
- 239000000463 material Substances 0.000 description 7
- 238000004364 calculation method Methods 0.000 description 6
- 230000008901 benefit Effects 0.000 description 5
- 229910052744 lithium Inorganic materials 0.000 description 4
- 229910004838 Na2/3Ni1/3Mn2/3O2 Inorganic materials 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- QPLDLSVMHZLSFG-UHFFFAOYSA-N CuO Inorganic materials [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- 235000012431 wafers Nutrition 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N zinc oxide Inorganic materials [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 229910019398 NaPF6 Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000012983 electrochemical energy storage Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 229910003455 mixed metal oxide Inorganic materials 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 230000008707 rearrangement Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- YLKTWKVVQDCJFL-UHFFFAOYSA-N sodium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Na+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F YLKTWKVVQDCJFL-UHFFFAOYSA-N 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
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- 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
- H01M4/0471—Processes of manufacture in general involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis
-
- 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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/058—Construction or manufacture
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- 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
- H01M4/139—Processes of manufacture
- H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
-
- 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
- H01M4/364—Composites as mixtures
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- 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
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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Abstract
The invention discloses a sodium ion battery anode material, a sodium ion battery and a preparation method and application thereof, wherein anhydrous ethanol is dripped into a metal oxide to be used as a wet grinding medium for ball milling treatment, and then precursor powder which is uniformly mixed is obtained by drying; pressing the precursor powder into a round flaky structure, then calcining at high temperature in air atmosphere and preserving heatNaturally cooling to obtain Na2/3Ni1/3‑xAxMn2/3‑yByO2And (3) a positive electrode material. The invention obtains the sodium ion battery anode material with high specific energy and high cycling stability by simple preparation means and cheap raw materials, and assembles the sodium ion battery by simple and easy operation, and the prepared sodium ion battery has the characteristics of 25 DEG C>The high energy density of 230Wh/kg and the average working voltage of 3.6V can be comparable to the existing commercial lithium iron phosphate-based lithium ion battery, the energy density far exceeds that of a lead-acid storage battery, and the lithium iron phosphate-based lithium ion battery has wide application prospects in a plurality of fields such as electric bicycles and the like.
Description
Technical Field
The invention belongs to the technical field of sodium ion batteries, and particularly relates to a sodium ion battery positive electrode material, a sodium ion battery and a preparation method and application thereof.
Background
At present, most of power supplies used by electric bicycles are lead-acid batteries. Lead is the main raw material of lead-acid batteries and accounts for more than 60 percent of the mass of the batteries. As is well known, lead is a toxic heavy metal, pollutes the environment and harms human health. Furthermore, lead acid batteries have a low energy density, typically not exceeding 50Wh/kg, which is 1/5 for lithium ion batteries only, and do not have a high cycle life, with deep cycles not exceeding 300 times, which is 1/2 for lithium ion batteries only. However, compared with lead-acid batteries, lithium ion batteries have disadvantages in terms of cost and safety, and the application of the lithium ion batteries in the field of electric bicycles is greatly restricted.
Sodium ion batteries are electrochemical energy storage devices that have a similar operating principle as lithium ion batteries. The sodium ion battery has obvious cost advantage because the sodium element is abundant in natural resources and low in price, and the sodium ion battery can use cheaper aluminum foils as current collectors of a positive electrode and a negative electrode. Although the energy density of the current sodium ion battery is difficult to be equal to that of the lithium ion battery, the energy density of the current sodium ion battery is far higher than that of the lead-acid battery. In addition, the sodium ion battery has high safety and excellent high and low temperature performance. Therefore, the sodium ion battery has wide application prospect in the field of electric bicycles.
In order to further improve the energy density of sodium ions and improve the market competitiveness of the sodium ions, the development of a high-voltage and high-specific-capacity positive electrode material is very important. P2 type layered transition metal oxide Na2/3Ni1/3Mn2/3O2Due to the high operating voltage (>3.6V), large theoretical specific capacity (173mAh/g), easy preparation, good air stability and high specific energyA potential positive electrode material of a sodium ion battery. However, this material undergoes sodium/vacancy ordered rearrangement and phase transition from P2 to O2 during the process of sodium ion deintercalation, resulting in poor cycle stability and rate capability of the battery, which severely hinders its commercial application.
Disclosure of Invention
The invention aims to solve the technical problem of providing a sodium ion battery anode material, a sodium ion battery, a preparation method and application thereof, which aim at overcoming the defects in the prior art and have high specific capacity, high working voltage and high cycling stability.
The invention adopts the following technical scheme:
a preparation method of a positive electrode material of a sodium-ion battery comprises the following steps:
dropwise adding absolute ethyl alcohol into the metal oxide to be used as a wet grinding medium for ball milling treatment, and then drying to obtain precursor powder which is uniformly mixed; pressing the precursor powder into a round flaky structure, then calcining at high temperature in air atmosphere and preserving heat, and naturally cooling to obtain Na2/3Ni1/3-xAxMn2/3-yByO2And (3) a positive electrode material.
Specifically, the metal oxide contains Na2CO3、NiO、MnO2And Li2CO3、MgO、ZnO、CuO、CaO、TiO2、Fe2O3And SiO2One or more of; the molar ratio of the element Na to the element Ni is 2-4, and the molar ratio of the element Na to the element Mn is 1-2.
Specifically, the addition amount of the absolute ethyl alcohol is 1% -5% of the total mass of the metal oxide, the rotation speed of ball milling treatment is 200-600 r/min, and the time is 1-12 h.
Specifically, the heating rate is 1-20 ℃/min-1The calcining temperature is 800-1200 ℃, and the heat preservation time is 5-20 h.
Specifically, the element a includes at least one of Mg, Zn, Cu, and Ca; the element B comprises at least one of Ti, Fe and Si, and the doping contents of the elements A and B are as follows: x is more than or equal to 0 and less than or equal to 1/6, and y is more than or equal to 0 and less than or equal to 1/3.
The invention also provides a preparation method of the sodium-ion battery, which comprises the following steps:
according to the formula (8-9): (0.5-1): (0.5-1) putting the positive/negative electrode material, the conductive additive and the binder into a polypropylene plastic box, and adding NMP, wherein the positive electrode material in the positive/negative electrode material is the positive electrode material prepared by the method of claim 1 or the positive electrode material of the sodium-ion battery of claim 5, and the negative electrode material is commercial hard carbon or soft carbon; performing ball milling treatment on a polypropylene plastic box to obtain uniformly mixed positive/negative electrode slurry; coating the positive/negative electrode slurry in a scraping way and carrying out vacuum drying treatment to obtain positive and negative electrode sheets with uniform thickness; punching the positive and negative plates into round plates with the same size, and determining the corresponding positive and negative electrodes based on the positive and negative electrode capacity ratio of 0.9-1.2 for battery assembly; the positive electrode and the negative electrode were prepared into a sodium ion battery using an electrolyte and a separator.
Specifically, the conductive additive is one or more of carbon black, Super P and Ketjen black, and the binder is one or more of polyvinylidene fluoride or polyacrylic acid, sodium carboxymethylcellulose, sodium alginate and gelatin.
Specifically, the electrolyte has a concentration of 0.1-1.5M, and comprises a solvent and sodium salt, wherein the solvent comprises at least one of dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, ethylene carbonate and propylene carbonate; the sodium salt comprises one or more of sodium hexafluorophosphate, sodium perchlorate and sodium bis (trifluoromethylsulfonyl) imide.
Another aspect of the invention is a sodium ion battery having a high energy density of >230Wh/kg and an average operating voltage of 3.6V at 25 ℃.
The invention also provides the application of the sodium ion battery in the electric bicycle.
Compared with the prior art, the invention has at least the following beneficial effects:
the invention relates to a preparation method of a sodium-ion battery anode material, which utilizes the synergistic effect of multiple elements without sacrificing the original material Na2/3Ni1/3Mn2/3O2High operating voltage and high specific capacityIn this case, the phase transition of P2-O2, which impairs the cycle stability and the rate-doubling property, is successfully suppressed, thereby achieving a stable high specific energy output.
Further, the metal oxide at least comprises Na2CO3, NiO, MnO2 and one or more of Li2CO3, MgO, ZnO, CuO, CaO, TiO2, Fe2O3 and SiO2, wherein the molar ratio of the element Na to the element Ni is 2-4, and the molar ratio of the element Na to the element Mn is 1-2. Na, Ni and Mn are main elements of the anode material, and the anode material is low in price and environment-friendly.
Furthermore, absolute ethyl alcohol is used as a wet grinding solvent, and the effect of fully grinding the mixed metal oxide is achieved by adjusting the ball milling rotating speed and time, so that precursor powder which is uniformly mixed and has fine particle size is obtained.
Further, the pure P2 phase cathode material is obtained with the lowest energy consumption by adjusting the temperature rising rate, the calcining temperature and the holding time.
The positive electrode material of the sodium-ion battery is characterized in that an element A is a +1 or +2 valent element and comprises at least one of Li, Mg, Zn, Cu and Ca, an element B is a +3 or +4 valent element and comprises at least one of Ti, Fe and Si, and the doping contents of the elements A and B are as follows: x is more than or equal to 0 and less than or equal to 1/6, y is more than or equal to 0 and less than or equal to 1/3, and due to the limited effect of a single element, multiple functional advantages cannot be simultaneously realized, so that the comprehensive performance of the cathode material is furthest improved by utilizing the synergistic effect among multiple elements, and the content of doped elements cannot be excessive, otherwise the advantages of high voltage and high capacity of the original material are greatly sacrificed.
A preparation method of a sodium ion battery comprises the steps of utilizing a simple ball milling mixing technology to fully and uniformly mix positive/negative electrode materials, conductive additives and binders, then obtaining positive/negative electrodes with uniform thickness through subsequent coating and drying processes, and finally selecting positive and negative electrodes with proper capacity ratios to assemble the sodium ion battery.
Further, the conductive additive and the binder are added to improve the electron conductivity of the positive/negative electrode and maintain the electrode sheet structure, respectively, but since both are inactive materials and cannot provide additional capacity, the content of both should be reduced as much as possible on the premise of obtaining stable and excellent performance.
Furthermore, the electrolyte with high cost performance is obtained by selecting the solvent and sodium salt and optimizing the concentration of the electrolyte.
A sodium ion battery has high energy density of 230Wh/kg and average working voltage of 3.6V at 25 ℃, can be comparable with the existing commercial lithium iron phosphate-based lithium ion battery, has energy density far exceeding that of a lead-acid storage battery, and has wide application prospect.
In conclusion, the positive electrode material of the sodium-ion battery with high specific energy and high cycle stability is obtained by simple preparation means and cheap raw materials, and the sodium-ion battery is assembled by simple and easy operation, the prepared sodium-ion battery has high energy density of more than 230Wh/kg and average working voltage of 3.6V at 25 ℃, can be comparable with the existing commercial lithium iron phosphate-based lithium ion battery, has energy density far exceeding that of a lead-acid storage battery, and has wide application prospect in a plurality of fields such as electric bicycles and the like.
The technical solution of the present invention is further described in detail by the accompanying drawings and embodiments.
Drawings
FIG. 1 shows a high-voltage positive electrode material Na in example 10.67Li0.06Mg0.06Ni0.21Mn0.6Ti0.07O2XRD results of (1);
FIG. 2 shows a high-voltage positive electrode material Na in example 10.67Li0.06Mg0.06Ni0.21Mn0.6Ti0.07O2SEM image of (a);
FIG. 3 is the first charge-discharge curve of the sodium-ion battery of example 1;
fig. 4 is a cycle performance curve of the sodium ion battery of example 1.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are some, not all, embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
It will be understood that the terms "comprises" and/or "comprising," when used in this specification and the appended claims, specify the presence of stated features, integers, steps, operations, elements, and/or components, but do not preclude the presence or addition of one or more other features, integers, steps, operations, elements, components, and/or groups thereof.
It is also to be understood that the terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used in the specification of the present invention and the appended claims, the singular forms "a," "an," and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise.
It should be further understood that the term "and/or" as used in this specification and the appended claims refers to and includes any and all possible combinations of one or more of the associated listed items.
The invention provides a sodium ion battery and a preparation method thereof, and relates to a high-voltage positive electrode material Na2/3Ni1/3- xAxMn2/3-yByO2Preparing a positive electrode and a negative electrode, and assembling and testing a sodium ion battery; the sodium ion battery comprises a positive electrode, a negative electrode, electrolyte and a diaphragm, wherein the positive electrode is made of high-voltage positive electrode material Na2/3Ni1/3-xAxMn2/3-yByO2The negative electrode is composed of hard carbon, a conductive additive and a binder, the electrolyte is a carbonate electrolyte, and the diaphragm is a glass fiber membrane. The sodium ion battery provided by the invention has the following advantages: high operating voltage (>3.6V) and high energy density (>230Wh/kg), excellent safety and cycle stability, and moreover, the battery is easy to prepare, low in production cost, readily available in raw materials, and suitable for large-scale commercial production.
The invention relates to a positive electrode material of a sodium-ion battery, which is prepared from Na2/3Ni1/3Mn2/3O2As an original material, a high-temperature calcination technology is adopted to introduce various functional elements (such as Li, Mg, Ca, Ti, Zn and Cu) into the raw material, and Na with high specific capacity, high working voltage and high cycling stability is obtained by element combination and optimized doping capacity2/3Ni1/3-xAxMn2/3-yByO2(x is more than or equal to 0 and less than or equal to 1/6, and y is more than or equal to 0 and less than or equal to 1/3) the positive electrode material of the sodium-ion battery. Wherein A is selected from at least one of Mg, Zn, Cu, Ca and Li, and is preferably Mg and Li; b is at least one selected from Ti, Fe and Si, preferably Ti.
A preparation method of a positive electrode material of a sodium-ion battery comprises the following steps:
s101, weighing metal oxide (Na) with corresponding stoichiometric ratio according to components of Na2/3Ni1/3-xAxMn2/3-yByO2, x is more than or equal to 0 and less than or equal to 1/6, and y is more than or equal to 0 and less than or equal to 1/32CO3、NiO、MnO2Element A oxide and element B oxide) are put into a nylon ball milling tank, 1-5% of absolute ethyl alcohol in mass fraction is dripped as a wet milling solvent, a planetary ball mill is used for ball milling for 1-12 hours at the rotating speed of 200-600 r/min, and then the solvent is dried in an oven to obtain precursor powder which is uniformly mixed;
the rotation speed of the ball mill is preferably 450r/min, and the ball milling time is preferably 4 h.
S102, pressing the precursor powder obtained in the step S101 into small wafers by using a powder tablet press, and then putting the small wafers into a muffle furnace at a speed of 1-20 ℃/min-1The temperature is increased to 800-1200 ℃ at the temperature rising rate, then the heat is preserved and calcined for 5-20 h, and Na is obtained after natural cooling2/3Ni1/3-xAxMn2/3-yByO2X is more than or equal to 0 and less than or equal to 1/6, and y is more than or equal to 0 and less than or equal to 1/3.
Wherein the heating rate is preferably 10 ℃/min-1The calcination temperature is preferably 950 ℃, and the holding time is preferably 15 h.
A preparation method of a sodium-ion battery comprises the following steps:
s1, using (8-9): (0.5-1): (0.5-1) weighing the positive/negative electrode material, the conductive additive and the binder according to the mass ratio, putting the materials into a polypropylene (PP) plastic box, and adding 10 wt% of NMP;
wherein the anode material is the anode material Na of the sodium-ion battery prepared by the invention2/3Ni1/3-xAxMn2/3-yByO2(x is more than or equal to 0 and less than or equal to 1/6, and y is more than or equal to 0 and less than or equal to 1/3), and the cathode material is commercial hard carbon.
Preferably, the conductive additive is one or more of carbon black, Super P, ketjen black, preferably Super P.
Preferably, the binder and the solvent are one or more of polyvinylidene fluoride (PVDF) using N-methylpyrrolidone (NMP) as a solvent, polyacrylic acid (PAA), sodium carboxymethyl cellulose (CMC), Sodium Alginate (SA), and gelatin (each using water as a solvent), and PVDF is preferred.
S2, putting the PP plastic box obtained in the step S1 into a nylon ball milling tank, and performing ball milling for 0.5-3 hours to obtain uniformly mixed positive/negative electrode slurry;
s3, pouring the positive/negative electrode slurry obtained in the step S2 onto a commercial aluminum foil which is wiped clean, and carrying out blade coating by using a scraper;
s4, putting the uniformly spread slurry into a vacuum oven for drying treatment to obtain a positive electrode and a negative electrode;
s5, preparing the sodium-ion battery by using the positive electrode and the negative electrode prepared in the step S4, the electrolyte and the diaphragm.
The sodium ion battery comprises four parts, namely a positive electrode, a negative electrode, electrolyte and a diaphragm, wherein the electrolyte comprises a solvent and sodium salt, and the diaphragm is a glass fiber membrane of the company of whatman.
The electrolyte is an ester electrolyte, and the concentration of the ester electrolyte is 0.1-1.5M, preferably 1M.
The solvent is at least one selected from dimethyl carbonate (DMC), diethyl carbonate (DEC), Ethyl Methyl Carbonate (EMC), Ethylene Carbonate (EC) and Propylene Carbonate (PC), and is preferably a mixed solvent of PC and DMC in a volume ratio of 1: 1;
the sodium salt is selected from sodium hexafluorophosphate (NaPF)6) Sodium perchlorate (NaClO)4) Sodium bis (trifluoromethylsulfonyl) imide (NaTFSI), preferably sodium perchlorate (NaClO)4)。
The selection and matching of the positive and negative plates are based on the following principles: the positive electrode capacity/negative electrode capacity is 0.9 to 1.2, preferably 1.05.
The sodium ion battery prepared by the method works at 25 ℃, has high energy density of more than 230Wh/kg, average working voltage of 3.6V and excellent cycle performance, and is suitable for electric bicycles.
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are some, but not all, embodiments of the present invention. The components of the embodiments of the present invention generally described and illustrated in the figures herein may be arranged and designed in a wide variety of different configurations. Thus, the following detailed description of the embodiments of the present invention, presented in the figures, is not intended to limit the scope of the invention, as claimed, but is merely representative of selected embodiments of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
1. Preparation of Na0.67Li0.06Mg0.06Ni0.21Mn0.6Ti0.07O2Positive electrode material
First, 10.05mmol of Na was weighed2CO3、0.9mmol Li2CO3、1.8mmol MgO、6.3mmol NiO、18mmol MnO2And 2.1mmol TiO2Putting the mixture into a nylon ball milling tank, dropwise adding 1 wt% of absolute ethyl alcohol as a wet milling solvent, ball milling the mixture for 4 hours at the rotating speed of 450r/min by using a planetary ball mill, and drying the solvent in an oven at the temperature of 80 ℃ to obtain precursor powder which is uniformly mixed. Then, the precursor powder was pressed into a small disk having a diameter of 12mm under a pressure of 16MPa using a powder tablet press, and placed in a muffle furnace at a temperature rising rate of 10 ℃/min-1Heating to 950 ℃, carrying out heat preservation and calcination for 15h, and naturally cooling to obtain the cathode material.
The phase of the obtained positive electrode material is determined by X-ray powder diffraction test, the test result is shown in figure 1, and except the characteristic diffraction peak of the P2 phase, other miscellaneous peaks do not exist in the diffraction pattern, which indicates that the product has high purity.
The positive electrode material obtained above was subjected to a topography observation using a scanning electron microscope, as shown in fig. 2. As can be seen, the positive electrode material is sheet-shaped and has a particle size of about 3 μm.
2. Preparation of Na0.67Li0.06Mg0.06Ni0.21Mn0.6Ti0.07O2Positive electrode
Mixing the prepared positive electrode material with Super P and PVDF according to the mass ratio of 8:1:1, adding NMP as a solvent, uniformly stirring, coating on an aluminum foil, drying in a blast oven at 80 ℃, and punching into a pole piece by using a punch with the diameter of 10 mm.
3. Preparation of hard carbon cathode
Mixing hard carbon, Super P and PVDF according to the mass ratio of 8:1:1, adding NMP as a solvent, uniformly stirring, coating on an aluminum foil, drying in a blast oven at 80 ℃, and punching into a pole piece by using a punch with the diameter of 10 mm.
4. Assembled sodium ion battery and performance test
Selecting Na with a ratio of positive electrode capacity to negative electrode capacity of 1.050.67Li0.06Mg0.06Ni0.21Mn0.6Ti0.07O2Positive electrode and hard carbon negative electrode, 1M NaClO using a glass fiber membrane of Whatman having a diameter of 16mm as a separator4The solution of PC/DMC (volume ratio is 1:1) is used as electrolyte to assemble the CR2025 button cell.
The assembled button cell is subjected to constant-current charge and discharge performance test on a LAND cell test system (provided by Wuhan blue electronics, Inc.), the charge and discharge cutoff voltage is 1-4.4V, a figure 3 shows a charge and discharge curve of the sodium ion cell under the multiplying power of 0.2C, the discharge specific capacity of the cell is close to 290mAh/g, the working voltage exceeds 3.5V, and the energy density calculated based on the mass of positive and negative electrodes is up to 230 Wh/kg. Fig. 4 shows the long cycle performance of the sodium ion battery at 0.2C rate, and the capacity retention rate of the battery is as high as 89% after 40 cycles.
Example 2
1. Preparation of Na0.67Li0.06Mg0.06Ni0.21Mn0.6Ti0.07O2Positive electrode material
First, 10.05mmol of Na was weighed2CO3、0.9mmol Li2CO3、1.8mmol MgO、6.3mmol NiO、18mmol MnO2And 2.1mmol TiO2Putting the mixture into a nylon ball milling tank, dropwise adding 3 wt% of absolute ethyl alcohol as a wet milling solvent, ball milling the mixture for 4 hours at the rotating speed of 450r/min by using a planetary ball mill, and drying the solvent in an oven at the temperature of 80 ℃ to obtain precursor powder which is uniformly mixed. Then, the precursor powder was pressed into a small disk having a diameter of 12mm under a pressure of 16MPa using a powder tablet press, and placed in a muffle furnace at a temperature rising rate of 10 ℃/min-1Heating to 950 ℃, carrying out heat preservation and calcination for 15h, and naturally cooling to obtain the cathode material.
2. Preparation of Na0.67Li0.06Mg0.06Ni0.21Mn0.6Ti0.07O2Positive electrode
Mixing the prepared positive electrode material with Super P and PVDF according to the mass ratio of 9:0.5:0.5, adding NMP as a solvent, uniformly stirring, coating on an aluminum foil, drying in a blast oven at 80 ℃, and punching into a pole piece by using a punch with the diameter of 10 mm.
3. Preparation of hard carbon cathode
Mixing hard carbon, Super P and PVDF according to the mass ratio of 9:0.5:0.5, adding NMP as a solvent, uniformly stirring, coating on an aluminum foil, drying in a blast oven at 80 ℃, and punching into a pole piece by using a punch with the diameter of 10 mm.
4. Assembled sodium ion battery and performance test
Selecting Na with a ratio of positive electrode capacity to negative electrode capacity of 1.050.67Li0.06Mg0.06Ni0.21Mn0.6Ti0.07O2Positive electrode and hard carbon negative electrode, 1M NaClO using a glass fiber membrane of Whatman having a diameter of 16mm as a separator4The solution of PC/DMC (volume ratio is 1:1) is used as electrolyte to assemble the CR2025 button cell.
And (3) carrying out constant-current charge and discharge performance test on the assembled button cell on a LAND cell test system (provided by Wuhan blue electronics Co., Ltd.), wherein the charge and discharge cutoff voltage is 1-4.4V, the discharge specific capacity of the cell at 0.2C multiplying power is 285mAh/g, the working voltage is 3.52V, and the energy density calculated based on the mass of the positive electrode and the negative electrode is up to 234 Wh/kg.
Example 3
1. Preparation of Na0.67Li0.06Mg0.06Ni0.21Mn0.6Ti0.07O2Positive electrode material
First, 10.05mmol of Na was weighed2CO3、0.9mmol Li2CO3、1.8mmol MgO、6.3mmol NiO、18mmol MnO2And 2.1mmol TiO2Putting the mixture into a nylon ball milling tank, dropwise adding 5 wt% of absolute ethyl alcohol as a wet milling solvent, ball milling the mixture for 4 hours at the rotating speed of 450r/min by using a planetary ball mill, and drying the solvent in an oven at the temperature of 80 ℃ to obtain precursor powder which is uniformly mixed. Then, the precursor powder was pressed into a small disk having a diameter of 12mm under a pressure of 16MPa using a powder tablet press, and placed in a muffle furnace at a temperature rising rate of 10 ℃/min-1Heating to 950 ℃, carrying out heat preservation and calcination for 15h, and naturally cooling to obtain the cathode material.
2. Preparation of Na0.67Li0.06Mg0.06Ni0.21Mn0.6Ti0.07O2Positive electrode
Mixing the prepared positive electrode material with Super P and PVDF according to the mass ratio of 9:0.5:0.5, adding NMP as a solvent, uniformly stirring, coating on an aluminum foil, drying in a blast oven at 80 ℃, and punching into a pole piece by using a punch with the diameter of 10 mm.
3. Preparation of hard carbon cathode
Mixing hard carbon, Super P and PVDF according to the mass ratio of 9:0.5:0.5, adding NMP as a solvent, uniformly stirring, coating on an aluminum foil, drying in a blast oven at 80 ℃, and punching into a pole piece by using a punch with the diameter of 10 mm.
4. Assembled sodium ion battery and performance test
Selecting Na with a ratio of positive electrode capacity to negative electrode capacity of 1.050.67Li0.06Mg0.06Ni0.21Mn0.6Ti0.07O2Positive electrode and hard carbon negative electrode, 1M NaClO using a glass fiber membrane of Whatman having a diameter of 16mm as a separator4The solution of PC/DMC (volume ratio is 1:1) is used as electrolyte to assemble the CR2025 button cell.
And (3) carrying out constant-current charge and discharge performance test on the assembled button cell on a LAND cell test system (provided by Wuhan blue electronics Co., Ltd.), wherein the charge and discharge cutoff voltage is 1-4.4V, the discharge specific capacity of the cell at 0.2C multiplying power is 292mAh/g, the working voltage is 3.54V, and the energy density obtained by calculation based on the mass of the positive electrode and the negative electrode is up to 244 Wh/kg.
Example 4
1. Preparation of Na0.67Li0.06Mg0.06Ni0.21Mn0.6Ti0.07O2Positive electrode material
First, 10.05mmol of Na was weighed2CO3、0.9mmol Li2CO3、1.8mmol MgO、6.3mmol NiO、18mmol MnO2And 2.1mmol TiO2Putting the mixture into a nylon ball milling tank, dropwise adding 3 wt% of absolute ethyl alcohol as a wet milling solvent, ball milling for 4 hours at the rotating speed of 200r/min by using a planetary ball mill, and drying the solvent in an oven at the temperature of 80 ℃ to obtain precursor powder which is uniformly mixed. Then, the precursor powder was pressed into a small disk having a diameter of 12mm under a pressure of 16MPa using a powder tablet press, and placed in a muffle furnace at a temperature rising rate of 10 ℃/min-1Heating to 950 ℃, carrying out heat preservation and calcination for 15h, and naturally cooling to obtain the cathode material.
2. Preparation of Na0.67Li0.06Mg0.06Ni0.21Mn0.6Ti0.07O2Positive electrode
Mixing the prepared positive electrode material with Super P and PVDF according to the mass ratio of 9:0.5:0.5, adding NMP as a solvent, uniformly stirring, coating on an aluminum foil, drying in a blast oven at 80 ℃, and punching into a pole piece by using a punch with the diameter of 10 mm.
3. Preparation of hard carbon cathode
Mixing hard carbon, Super P and PVDF according to the mass ratio of 9:0.5:0.5, adding NMP as a solvent, uniformly stirring, coating on an aluminum foil, drying in a blast oven at 80 ℃, and punching into a pole piece by using a punch with the diameter of 10 mm.
4. Assembled sodium ion battery and performance test
Selecting Na with a ratio of positive electrode capacity to negative electrode capacity of 1.050.67Li0.06Mg0.06Ni0.21Mn0.6Ti0.07O2Positive electrode and hard carbon negative electrode, 1M NaClO using a glass fiber membrane of Whatman having a diameter of 16mm as a separator4The solution of PC/DMC (volume ratio is 1:1) is used as electrolyte to assemble the CR2025 button cell.
And (3) carrying out constant-current charge and discharge performance test on the assembled button cell on a LAND cell test system (provided by Wuhan blue electronics Co., Ltd.), wherein the charge and discharge cutoff voltage is 1-4.4V, the discharge specific capacity of the cell at 0.2C multiplying power is 276mAh/g, the working voltage is 3.43V, and the energy density obtained by calculation based on the mass of the positive electrode and the negative electrode is up to 220 Wh/kg.
Example 5
1. Preparation of Na0.67Li0.06Mg0.06Ni0.21Mn0.6Ti0.07O2Positive electrode material
First, 10.05mmol of Na was weighed2CO3、0.9mmol Li2CO3、1.8mmol MgO、6.3mmol NiO、18mmol MnO2And 2.1mmol TiO2Putting the mixture into a nylon ball milling tank, dropwise adding 3 wt% of absolute ethyl alcohol as a wet milling solvent, ball milling the mixture for 4 hours at the rotating speed of 600r/min by using a planetary ball mill, and drying the solvent in an oven at the temperature of 80 ℃ to obtain precursor powder which is uniformly mixed. Then, the precursor powder was pressed into a small disk having a diameter of 12mm under a pressure of 16MPa using a powder tablet press, and placed in a muffle furnace at a temperature rising rate of 10 ℃/min-1Heating to 950 ℃, carrying out heat preservation and calcination for 15h, and naturally cooling to obtain the cathode material.
2. Preparation of Na0.67Li0.06Mg0.06Ni0.21Mn0.6Ti0.07O2Positive electrode
Mixing the prepared positive electrode material with Super P and PVDF according to the mass ratio of 9:0.5:0.5, adding NMP as a solvent, uniformly stirring, coating on an aluminum foil, drying in a blast oven at 80 ℃, and punching into a pole piece by using a punch with the diameter of 10 mm.
3. Preparation of hard carbon cathode
Mixing hard carbon, Super P and PVDF according to the mass ratio of 9:0.5:0.5, adding NMP as a solvent, uniformly stirring, coating on an aluminum foil, drying in a blast oven at 80 ℃, and punching into a pole piece by using a punch with the diameter of 10 mm.
4. Assembled sodium ion battery and performance test
Selecting Na with a ratio of positive electrode capacity to negative electrode capacity of 1.050.67Li0.06Mg0.06Ni0.21Mn0.6Ti0.07O2Positive electrode and hard carbon negative electrode, 1M NaClO using a glass fiber membrane of Whatman having a diameter of 16mm as a separator4The solution of PC/DMC (volume ratio is 1:1) is used as electrolyte to assemble the CR2025 button cell.
And (3) carrying out constant-current charge and discharge performance test on the assembled button cell on a LAND cell test system (provided by Wuhan blue electronics Co., Ltd.), wherein the charge and discharge cutoff voltage is 1-4.4V, the discharge specific capacity of the cell at 0.2C multiplying power is 294mAh/g, the working voltage is 3.51V, and the energy density obtained by calculation based on the mass of the positive electrode and the negative electrode is up to 239 Wh/kg.
Example 6
1. Preparation of Na0.67Li0.06Mg0.06Ni0.21Mn0.6Ti0.07O2Positive electrode material
First, 10.05mmol of Na was weighed2CO3、0.9mmol Li2CO3、1.8mmol MgO、6.3mmol NiO、18mmol MnO2And 2.1mmol TiO2Putting the mixture into a nylon ball milling tank, dropwise adding 3 wt% of absolute ethyl alcohol as a wet milling solvent, ball milling the mixture for 1 hour at the rotating speed of 450r/min by using a planetary ball mill, and drying the solvent in an oven at the temperature of 80 ℃ to obtain precursor powder which is uniformly mixed. Then, the precursor powder was pressed into a small disk having a diameter of 12mm under a pressure of 16MPa using a powder tablet press, and placed in a muffle furnace at a temperature rising rate of 10 ℃/min-1Heating to 950 ℃, carrying out heat preservation and calcination for 15h, and naturally cooling to obtain the cathode material.
2. Preparation of Na0.67Li0.06Mg0.06Ni0.21Mn0.6Ti0.07O2Positive electrode
Mixing the prepared positive electrode material with Super P and PVDF according to the mass ratio of 8:1:1, adding NMP as a solvent, uniformly stirring, coating on an aluminum foil, drying in a blast oven at 80 ℃, and punching into a pole piece by using a punch with the diameter of 10 mm.
3. Preparation of hard carbon cathode
Mixing hard carbon, Super P and PVDF according to the mass ratio of 8:1:1, adding NMP as a solvent, uniformly stirring, coating on an aluminum foil, drying in a blast oven at 80 ℃, and punching into a pole piece by using a punch with the diameter of 10 mm.
4. Assembled sodium ion battery and performance test
Selecting Na with a ratio of positive electrode capacity to negative electrode capacity of 1.050.67Li0.06Mg0.06Ni0.21Mn0.6Ti0.07O2Positive electrode and hard carbon negative electrode, 1M NaClO using a glass fiber membrane of Whatman having a diameter of 16mm as a separator4The solution of PC/DMC (volume ratio is 1:1) is used as electrolyte to assemble the CR2025 button cell.
And (3) carrying out constant-current charge and discharge performance test on the assembled button cell on a LAND cell test system (provided by Wuhan blue electronics Co., Ltd.), wherein the charge and discharge cutoff voltage is 1-4.4V, the discharge specific capacity of the cell at 0.2C multiplying power is 289mAh/g, the working voltage is 3.5V, and the energy density obtained by calculation based on the mass of the positive electrode and the negative electrode is up to 235 Wh/kg.
Example 7
1. Preparation of Na0.67Li0.06Mg0.06Ni0.21Mn0.6Ti0.07O2Positive electrode material
First, 10.05mmol of Na was weighed2CO3、0.9mmol Li2CO3、1.8mmol MgO、6.3mmol NiO、18mmol MnO2And 2.1mmol TiO2Putting into a nylon ball milling tank, dripping 1 wt% of absolute ethyl alcohol as a wet milling solvent, ball milling for 8h at the rotating speed of 450r/min by using a planetary ball mill, and then putting into an oven at 80 DEG CAnd drying the solvent to obtain precursor powder which is uniformly mixed. Then, the precursor powder was pressed into a small disk having a diameter of 12mm under a pressure of 16MPa using a powder tablet press, and placed in a muffle furnace at a temperature rising rate of 10 ℃/min-1Heating to 950 ℃, carrying out heat preservation and calcination for 15h, and naturally cooling to obtain the cathode material.
2. Preparation of Na0.67Li0.06Mg0.06Ni0.21Mn0.6Ti0.07O2Positive electrode
Mixing the prepared positive electrode material with Super P and PVDF according to the mass ratio of 8:1:1, adding NMP as a solvent, uniformly stirring, coating on an aluminum foil, drying in a blast oven at 80 ℃, and punching into a pole piece by using a punch with the diameter of 10 mm.
3. Preparation of hard carbon cathode
Mixing hard carbon, Super P and PVDF according to the mass ratio of 8:1:1, adding NMP as a solvent, uniformly stirring, coating on an aluminum foil, drying in a blast oven at 80 ℃, and punching into a pole piece by using a punch with the diameter of 10 mm.
4. Assembled sodium ion battery and performance test
Selecting Na with a ratio of positive electrode capacity to negative electrode capacity of 1.050.67Li0.06Mg0.06Ni0.21Mn0.6Ti0.07O2Positive electrode and hard carbon negative electrode, 1M NaClO using a glass fiber membrane of Whatman having a diameter of 16mm as a separator4The solution of PC/DMC (volume ratio is 1:1) is used as electrolyte to assemble the CR2025 button cell.
And (3) carrying out constant-current charge and discharge performance test on the assembled button cell on an LAND cell test system (provided by Wuhan blue electronics Co., Ltd.), wherein the charge and discharge cutoff voltage is 1-4.4V, the discharge specific capacity of the cell at 0.2C multiplying power is 295mAh/g, the working voltage is 3.52V, and the energy density obtained by calculation based on the mass of the positive electrode and the negative electrode is up to 243 Wh/kg.
Example 8
1. Preparation of Na0.67Li0.06Mg0.06Ni0.21Mn0.6Ti0.07O2Positive electrode material
First, 10 is weighed.05mmol Na2CO3、0.9mmol Li2CO3、1.8mmol MgO、6.3mmol NiO、18mmol MnO2And 2.1mmol TiO2Putting the mixture into a nylon ball milling tank, dropwise adding 1 wt% of absolute ethyl alcohol as a wet milling solvent, ball milling the mixture for 12 hours at the rotating speed of 450r/min by using a planetary ball mill, and drying the solvent in an oven at the temperature of 80 ℃ to obtain precursor powder which is uniformly mixed. Then, the precursor powder was pressed into a small disk having a diameter of 12mm under a pressure of 16MPa using a powder tablet press, and placed in a muffle furnace at a temperature rising rate of 10 ℃/min-1Heating to 950 ℃, carrying out heat preservation and calcination for 15h, and naturally cooling to obtain the cathode material.
2. Preparation of Na0.67Li0.06Mg0.06Ni0.21Mn0.6Ti0.07O2Positive electrode
Mixing the prepared positive electrode material with Super P and PVDF according to the mass ratio of 8:1:1, adding NMP as a solvent, uniformly stirring, coating on an aluminum foil, drying in a blast oven at 80 ℃, and punching into a pole piece by using a punch with the diameter of 10 mm.
3. Preparation of hard carbon cathode
Mixing hard carbon, Super P and PVDF according to the mass ratio of 8:1:1, adding NMP as a solvent, uniformly stirring, coating on an aluminum foil, drying in a blast oven at 80 ℃, and punching into a pole piece by using a punch with the diameter of 10 mm.
4. Assembled sodium ion battery and performance test
Selecting Na with a ratio of positive electrode capacity to negative electrode capacity of 1.050.67Li0.06Mg0.06Ni0.21Mn0.6Ti0.07O2Positive electrode and hard carbon negative electrode, 1M NaClO using a glass fiber membrane of Whatman having a diameter of 16mm as a separator4The solution of PC/DMC (volume ratio is 1:1) is used as electrolyte to assemble the CR2025 button cell.
And (3) carrying out constant-current charge and discharge performance test on the assembled button cell on a LAND cell test system (provided by Wuhan blue electronics Co., Ltd.), wherein the charge and discharge cutoff voltage is 1-4.4V, the discharge specific capacity of the cell at 0.2C multiplying power is 296mAh/g, the working voltage is 3.52V, and the energy density obtained by calculation based on the mass of the positive electrode and the negative electrode is up to 247 Wh/kg.
Example 9
1. Preparation of Na0.67Li0.06Mg0.06Ni0.21Mn0.6Ti0.07O2Positive electrode material
First, 10.05mmol of Na was weighed2CO3、0.9mmol Li2CO3、1.8mmol MgO、6.3mmol NiO、18mmol MnO2And 2.1mmol TiO2Putting the mixture into a nylon ball milling tank, dropwise adding 2 wt% of absolute ethyl alcohol as a wet milling solvent, ball milling the mixture for 4 hours at the rotating speed of 450r/min by using a planetary ball mill, and drying the solvent in an oven at the temperature of 80 ℃ to obtain precursor powder which is uniformly mixed. Then, the precursor powder was pressed into a small disk having a diameter of 12mm under a pressure of 16MPa using a powder tablet press, and placed in a muffle furnace at a temperature rise rate of 1 ℃/min-1Heating to 950 ℃, carrying out heat preservation and calcination for 15h, and naturally cooling to obtain the cathode material.
2. Preparation of Na0.67Li0.06Mg0.06Ni0.21Mn0.6Ti0.07O2Positive electrode
Mixing the prepared positive electrode material with Super P and PVDF according to the mass ratio of 8:1:1, adding NMP as a solvent, uniformly stirring, coating on an aluminum foil, drying in a blast oven at 80 ℃, and punching into a pole piece by using a punch with the diameter of 10 mm.
3. Preparation of hard carbon cathode
Mixing hard carbon, Super P and PVDF according to the mass ratio of 8:1:1, adding NMP as a solvent, uniformly stirring, coating on an aluminum foil, drying in a blast oven at 80 ℃, and punching into a pole piece by using a punch with the diameter of 10 mm.
4. Assembled sodium ion battery and performance test
Selecting Na with a ratio of positive electrode capacity to negative electrode capacity of 1.050.67Li0.06Mg0.06Ni0.21Mn0.6Ti0.07O2Positive electrode and hard carbon negative electrode, 1M NaClO using a glass fiber membrane of Whatman having a diameter of 16mm as a separator4The solution of PC/DMC (volume ratio is 1:1) is used as electrolyte to assemble the CR2025 button cell.
And (3) carrying out constant-current charge and discharge performance test on the assembled button cell on a LAND cell test system (provided by Wuhan blue electronics Co., Ltd.), wherein the charge and discharge cutoff voltage is 1-4.4V, the discharge specific capacity of the cell at 0.2C multiplying power is 285mAh/g, the working voltage is 3.52V, and the energy density calculated based on the mass of the positive electrode and the negative electrode is up to 234 Wh/kg.
Example 10
1. Preparation of Na0.67Li0.06Mg0.06Ni0.21Mn0.6Ti0.07O2Positive electrode material
First, 10.05mmol of Na was weighed2CO3、0.9mmol Li2CO3、1.8mmol MgO、6.3mmol NiO、18mmol MnO2And 2.1mmol TiO2Putting the mixture into a nylon ball milling tank, dropwise adding 2 wt% of absolute ethyl alcohol as a wet milling solvent, ball milling the mixture for 4 hours at the rotating speed of 450r/min by using a planetary ball mill, and drying the solvent in an oven at the temperature of 80 ℃ to obtain precursor powder which is uniformly mixed. Then, the precursor powder was pressed into a small disk having a diameter of 12mm under a pressure of 16MPa using a powder tablet press, and placed in a muffle furnace at a temperature rise rate of 5 ℃/min-1Heating to 950 ℃, carrying out heat preservation and calcination for 15h, and naturally cooling to obtain the cathode material.
2. Preparation of Na0.67Li0.06Mg0.06Ni0.21Mn0.6Ti0.07O2Positive electrode
Mixing the prepared positive electrode material with Super P and PVDF according to the mass ratio of 8:1:1, adding NMP as a solvent, uniformly stirring, coating on an aluminum foil, drying in a blast oven at 80 ℃, and punching into a pole piece by using a punch with the diameter of 10 mm.
3. Preparation of hard carbon cathode
Mixing hard carbon, Super P and PVDF according to the mass ratio of 8:1:1, adding NMP as a solvent, uniformly stirring, coating on an aluminum foil, drying in a blast oven at 80 ℃, and punching into a pole piece by using a punch with the diameter of 10 mm.
4. Assembled sodium ion battery and performance test
Selecting Na with a ratio of positive electrode capacity to negative electrode capacity of 1.050.67Li0.06Mg0.06Ni0.21Mn0.6Ti0.07O2Positive electrode and hard carbon negative electrode, 1M NaClO using a glass fiber membrane of Whatman having a diameter of 16mm as a separator4The solution of PC/DMC (volume ratio is 1:1) is used as electrolyte to assemble the CR2025 button cell.
And (3) carrying out constant-current charge and discharge performance test on the assembled button cell on a LAND cell test system (provided by Wuhan blue electronics Co., Ltd.), wherein the charge and discharge cutoff voltage is 1-4.4V, the discharge specific capacity of the cell at 0.2C multiplying power is 285mAh/g, the working voltage is 3.52V, and the energy density calculated based on the mass of the positive electrode and the negative electrode is up to 234 Wh/kg.
Example 11
1. Preparation of Na0.67Li0.06Mg0.06Ni0.21Mn0.6Ti0.07O2Positive electrode material
First, 10.05mmol of Na was weighed2CO3、0.9mmol Li2CO3、1.8mmol MgO、6.3mmol NiO、18mmol MnO2And 2.1mmol TiO2Putting the mixture into a nylon ball milling tank, dropwise adding 4 wt% of absolute ethyl alcohol as a wet milling solvent, ball milling for 4 hours at the rotating speed of 450r/min by using a planetary ball mill, and drying the solvent in an oven at the temperature of 80 ℃ to obtain precursor powder which is uniformly mixed. Then, the precursor powder was pressed into a small disk having a diameter of 12mm under a pressure of 16MPa using a powder tablet press, and placed in a muffle furnace at a temperature rise rate of 15 ℃/min-1Heating to 950 ℃, carrying out heat preservation and calcination for 15h, and naturally cooling to obtain the cathode material.
2. Preparation of Na0.67Li0.06Mg0.06Ni0.21Mn0.6Ti0.07O2Positive electrode
Mixing the prepared positive electrode material with Super P and PVDF according to the mass ratio of 8:1:1, adding NMP as a solvent, uniformly stirring, coating on an aluminum foil, drying in a blast oven at 80 ℃, and punching into a pole piece by using a punch with the diameter of 10 mm.
3. Preparation of hard carbon cathode
Mixing hard carbon, Super P and PVDF according to the mass ratio of 8:1:1, adding NMP as a solvent, uniformly stirring, coating on an aluminum foil, drying in a blast oven at 80 ℃, and punching into a pole piece by using a punch with the diameter of 10 mm.
4. Assembled sodium ion battery and performance test
Selecting Na with a ratio of positive electrode capacity to negative electrode capacity of 1.050.67Li0.06Mg0.06Ni0.21Mn0.6Ti0.07O2Positive electrode and hard carbon negative electrode, 1M NaClO using a glass fiber membrane of Whatman having a diameter of 16mm as a separator4The solution of PC/DMC (volume ratio is 1:1) is used as electrolyte to assemble the CR2025 button cell.
And (3) carrying out constant-current charge and discharge performance test on the assembled button cell on a LAND cell test system (provided by Wuhan blue electronics Co., Ltd.), wherein the charge and discharge cutoff voltage is 1-4.4V, the discharge specific capacity of the cell at 0.2C multiplying power is 285mAh/g, the working voltage is 3.52V, and the energy density calculated based on the mass of the positive electrode and the negative electrode is up to 234 Wh/kg.
Example 12
1. Preparation of Na0.67Li0.06Mg0.06Ni0.21Mn0.6Ti0.07O2Positive electrode material
First, 10.05mmol of Na was weighed2CO3、0.9mmol Li2CO3、1.8mmol MgO、6.3mmol NiO、18mmol MnO2And 2.1mmol TiO2Putting the mixture into a nylon ball milling tank, dropwise adding 4 wt% of absolute ethyl alcohol as a wet milling solvent, ball milling for 4 hours at the rotating speed of 450r/min by using a planetary ball mill, and drying the solvent in an oven at the temperature of 80 ℃ to obtain precursor powder which is uniformly mixed. Then, the precursor powder was pressed into small disks of 12mm diameter under a pressure of 16MPa using a powder tablet press, and placed in a muffle furnace at a temperature rise rate of 20 ℃/min-1Heating to 950 ℃, carrying out heat preservation and calcination for 15h, and naturally cooling to obtain the cathode material.
2. Preparation of Na0.67Li0.06Mg0.06Ni0.21Mn0.6Ti0.07O2Positive electrode
Mixing the prepared positive electrode material with Super P and PVDF according to the mass ratio of 8:1:1, adding NMP as a solvent, uniformly stirring, coating on an aluminum foil, drying in a blast oven at 80 ℃, and punching into a pole piece by using a punch with the diameter of 10 mm.
3. Preparation of hard carbon cathode
Mixing hard carbon, Super P and PVDF according to the mass ratio of 8:1:1, adding NMP as a solvent, uniformly stirring, coating on an aluminum foil, drying in a blast oven at 80 ℃, and punching into a pole piece by using a punch with the diameter of 10 mm.
4. Assembled sodium ion battery and performance test
Selecting Na with a ratio of positive electrode capacity to negative electrode capacity of 1.050.67Li0.06Mg0.06Ni0.21Mn0.6Ti0.07O2Positive electrode and hard carbon negative electrode, 1M NaClO using a glass fiber membrane of Whatman having a diameter of 16mm as a separator4The solution of PC/DMC (volume ratio is 1:1) is used as electrolyte to assemble the CR2025 button cell.
And (3) carrying out constant-current charge and discharge performance test on the assembled button cell on a LAND cell test system (provided by Wuhan blue electronics Co., Ltd.), wherein the charge and discharge cutoff voltage is 1-4.4V, the discharge specific capacity of the cell at 0.2C multiplying power is 285mAh/g, the working voltage is 3.52V, and the energy density calculated based on the mass of the positive electrode and the negative electrode is up to 234 Wh/kg.
Example 13
1. Preparation of Na0.67Li0.06Mg0.06Ni0.21Mn0.6Ti0.07O2Positive electrode material
First, 10.05mmol of Na was weighed2CO3、0.9mmol Li2CO3、1.8mmol MgO、6.3mmol NiO、18mmol MnO2And 2.1mmol TiO2Putting the mixture into a nylon ball milling tank, dropwise adding 4 wt% of absolute ethyl alcohol as a wet milling solvent, ball milling for 4 hours at the rotating speed of 450r/min by using a planetary ball mill, and drying the solvent in an oven at the temperature of 80 ℃ to obtain precursor powder which is uniformly mixed. Then, the precursor powder was pressed into a small disk having a diameter of 12mm under a pressure of 16MPa using a powder tablet press, and placed in a muffle furnace at a temperature rising rate of 10 ℃/min-1Heating to 800 ℃, keeping the temperature and calcining for 15h,and naturally cooling to obtain the cathode material.
2. Preparation of Na0.67Li0.06Mg0.06Ni0.21Mn0.6Ti0.07O2Positive electrode
Mixing the prepared positive electrode material with Super P and PVDF according to the mass ratio of 8:1:1, adding NMP as a solvent, uniformly stirring, coating on an aluminum foil, drying in a blast oven at 80 ℃, and punching into a pole piece by using a punch with the diameter of 10 mm.
3. Preparation of hard carbon cathode
Mixing hard carbon, Super P and PVDF according to the mass ratio of 8:1:1, adding NMP as a solvent, uniformly stirring, coating on an aluminum foil, drying in a blast oven at 80 ℃, and punching into a pole piece by using a punch with the diameter of 10 mm.
4. Assembled sodium ion battery and performance test
Selecting Na with a ratio of positive electrode capacity to negative electrode capacity of 1.050.67Li0.06Mg0.06Ni0.21Mn0.6Ti0.07O2Positive electrode and hard carbon negative electrode, 1M NaClO using a glass fiber membrane of Whatman having a diameter of 16mm as a separator4The solution of PC/DMC (volume ratio is 1:1) is used as electrolyte to assemble the CR2025 button cell.
And (3) carrying out constant-current charge and discharge performance test on the assembled button cell on a LAND cell test system (provided by Wuhan blue electronics Co., Ltd.), wherein the charge and discharge cutoff voltage is 1-4.4V, the discharge specific capacity of the cell at 0.2C multiplying power is 285mAh/g, the working voltage is 3.52V, and the energy density calculated based on the mass of the positive electrode and the negative electrode is up to 234 Wh/kg.
Example 14
1. Preparation of Na0.67Li0.06Mg0.06Ni0.21Mn0.6Ti0.07O2Positive electrode material
First, 10.05mmol of Na was weighed2CO3、0.9mmol Li2CO3、1.8mmol MgO、6.3mmol NiO、18mmol MnO2And 2.1mmol TiO2Putting into a nylon ball milling tank, dripping 3 wt% of absolute ethyl alcohol as a wet milling solvent, and using a planetThe ball mill is used for ball milling for 4h at the rotating speed of 450r/min, and then the solvent is dried in an oven at the temperature of 80 ℃ to obtain precursor powder which is uniformly mixed. Then, the precursor powder was pressed into a small disk having a diameter of 12mm under a pressure of 16MPa using a powder tablet press, and placed in a muffle furnace at a temperature rising rate of 10 ℃/min-1And heating to 1200 ℃, carrying out heat preservation and calcination for 15h, and naturally cooling to obtain the anode material.
2. Preparation of Na0.67Li0.06Mg0.06Ni0.21Mn0.6Ti0.07O2Positive electrode
Mixing the prepared positive electrode material with Super P and PVDF according to the mass ratio of 8:1:1, adding NMP as a solvent, uniformly stirring, coating on an aluminum foil, drying in a blast oven at 80 ℃, and punching into a pole piece by using a punch with the diameter of 10 mm.
3. Preparation of hard carbon cathode
Mixing hard carbon, Super P and PVDF according to the mass ratio of 8:1:1, adding NMP as a solvent, uniformly stirring, coating on an aluminum foil, drying in a blast oven at 80 ℃, and punching into a pole piece by using a punch with the diameter of 10 mm.
4. Assembled sodium ion battery and performance test
Selecting Na with a ratio of positive electrode capacity to negative electrode capacity of 1.050.67Li0.06Mg0.06Ni0.21Mn0.6Ti0.07O2Positive electrode and hard carbon negative electrode, 1M NaClO using a glass fiber membrane of Whatman having a diameter of 16mm as a separator4The solution of PC/DMC (volume ratio is 1:1) is used as electrolyte to assemble the CR2025 button cell.
And (3) carrying out constant-current charge and discharge performance test on the assembled button cell on a LAND cell test system (provided by Wuhan blue electronics Co., Ltd.), wherein the charge and discharge cutoff voltage is 1-4.4V, the discharge specific capacity of the cell at 0.2C multiplying power is 285mAh/g, the working voltage is 3.52V, and the energy density calculated based on the mass of the positive electrode and the negative electrode is up to 234 Wh/kg.
Example 15
1. Preparation of Na0.67Li0.06Mg0.06Ni0.21Mn0.6Ti0.07O2Positive electrodeMaterial
First, 10.05mmol of Na was weighed2CO3、0.9mmol Li2CO3、1.8mmol MgO、6.3mmol NiO、18mmol MnO2And 2.1mmol TiO2Putting the mixture into a nylon ball milling tank, dropwise adding 2 wt% of absolute ethyl alcohol as a wet milling solvent, ball milling the mixture for 4 hours at the rotating speed of 450r/min by using a planetary ball mill, and drying the solvent in an oven at the temperature of 80 ℃ to obtain precursor powder which is uniformly mixed. Then, the precursor powder was pressed into a small disk having a diameter of 12mm under a pressure of 16MPa using a powder tablet press, and placed in a muffle furnace at a temperature rising rate of 10 ℃/min-1Heating to 950 ℃, carrying out heat preservation and calcination for 5h, and naturally cooling to obtain the cathode material.
2. Preparation of Na0.67Li0.06Mg0.06Ni0.21Mn0.6Ti0.07O2Positive electrode
Mixing the prepared positive electrode material with Super P and PVDF according to the mass ratio of 8:1:1, adding NMP as a solvent, uniformly stirring, coating on an aluminum foil, drying in a blast oven at 80 ℃, and punching into a pole piece by using a punch with the diameter of 10 mm.
3. Preparation of hard carbon cathode
Mixing hard carbon, Super P and PVDF according to the mass ratio of 8:1:1, adding NMP as a solvent, uniformly stirring, coating on an aluminum foil, drying in a blast oven at 80 ℃, and punching into a pole piece by using a punch with the diameter of 10 mm.
4. Assembled sodium ion battery and performance test
Selecting Na with a ratio of positive electrode capacity to negative electrode capacity of 1.050.67Li0.06Mg0.06Ni0.21Mn0.6Ti0.07O2Positive electrode and hard carbon negative electrode, 1M NaClO using a glass fiber membrane of Whatman having a diameter of 16mm as a separator4The solution of PC/DMC (volume ratio is 1:1) is used as electrolyte to assemble the CR2025 button cell.
And (3) carrying out constant-current charge and discharge performance test on the assembled button cell on a LAND cell test system (provided by Wuhan blue electronics Co., Ltd.), wherein the charge and discharge cutoff voltage is 1-4.4V, the discharge specific capacity of the cell at 0.2C multiplying power is 285mAh/g, the working voltage is 3.52V, and the energy density calculated based on the mass of the positive electrode and the negative electrode is up to 234 Wh/kg.
Example 16
1. Preparation of Na0.67Li0.06Mg0.06Ni0.21Mn0.6Ti0.07O2Positive electrode material
First, 10.05mmol of Na was weighed2CO3、0.9mmol Li2CO3、1.8mmol MgO、6.3mmol NiO、18mmol MnO2And 2.1mmol TiO2Putting the mixture into a nylon ball milling tank, dropwise adding 2 wt% of absolute ethyl alcohol as a wet milling solvent, ball milling the mixture for 4 hours at the rotating speed of 450r/min by using a planetary ball mill, and drying the solvent in an oven at the temperature of 80 ℃ to obtain precursor powder which is uniformly mixed. Then, the precursor powder was pressed into a small disk having a diameter of 12mm under a pressure of 16MPa using a powder tablet press, and placed in a muffle furnace at a temperature rising rate of 10 ℃/min-1Heating to 950 ℃, carrying out heat preservation and calcination for 10h, and naturally cooling to obtain the cathode material.
2. Preparation of Na0.67Li0.06Mg0.06Ni0.21Mn0.6Ti0.07O2Positive electrode
Mixing the prepared positive electrode material with Super P and PVDF according to the mass ratio of 8:1:1, adding NMP as a solvent, uniformly stirring, coating on an aluminum foil, drying in a blast oven at 80 ℃, and punching into a pole piece by using a punch with the diameter of 10 mm.
3. Preparation of hard carbon cathode
Mixing hard carbon, Super P and PVDF according to the mass ratio of 8:1:1, adding NMP as a solvent, uniformly stirring, coating on an aluminum foil, drying in a blast oven at 80 ℃, and punching into a pole piece by using a punch with the diameter of 10 mm.
4. Assembled sodium ion battery and performance test
Selecting Na with a ratio of positive electrode capacity to negative electrode capacity of 1.050.67Li0.06Mg0.06Ni0.21Mn0.6Ti0.07O2Positive electrode and hard carbon negative electrode, 1M NaClO using a glass fiber membrane of Whatman having a diameter of 16mm as a separator4PC/DMC (volume ratio 1:1)The solution was used as an electrolyte to assemble a CR2025 button cell.
And (3) carrying out constant-current charge and discharge performance test on the assembled button cell on a LAND cell test system (provided by Wuhan blue electronics Co., Ltd.), wherein the charge and discharge cutoff voltage is 1-4.4V, the discharge specific capacity of the cell at 0.2C multiplying power is 285mAh/g, the working voltage is 3.52V, and the energy density calculated based on the mass of the positive electrode and the negative electrode is up to 234 Wh/kg.
Example 17
1. Preparation of Na0.67Li0.06Mg0.06Ni0.21Mn0.6Ti0.07O2Positive electrode material
First, 10.05mmol of Na was weighed2CO3、0.9mmol Li2CO3、1.8mmol MgO、6.3mmol NiO、18mmol MnO2And 2.1mmol TiO2Putting the mixture into a nylon ball milling tank, dropwise adding 3 wt% of absolute ethyl alcohol as a wet milling solvent, ball milling the mixture for 4 hours at the rotating speed of 450r/min by using a planetary ball mill, and drying the solvent in an oven at the temperature of 80 ℃ to obtain precursor powder which is uniformly mixed. Then, the precursor powder was pressed into a small disk having a diameter of 12mm under a pressure of 16MPa using a powder tablet press, and placed in a muffle furnace at a temperature rising rate of 10 ℃/min-1Heating to 950 ℃, carrying out heat preservation and calcination for 20h, and naturally cooling to obtain the cathode material.
2. Preparation of Na0.67Li0.06Mg0.06Ni0.21Mn0.6Ti0.07O2Positive electrode
Mixing the prepared positive electrode material with Super P and PVDF according to the mass ratio of 8:1:1, adding NMP as a solvent, uniformly stirring, coating on an aluminum foil, drying in a blast oven at 80 ℃, and punching into a pole piece by using a punch with the diameter of 10 mm.
3. Preparation of hard carbon cathode
Mixing hard carbon, Super P and PVDF according to the mass ratio of 8:1:1, adding NMP as a solvent, uniformly stirring, coating on an aluminum foil, drying in a blast oven at 80 ℃, and punching into a pole piece by using a punch with the diameter of 10 mm.
4. Assembled sodium ion battery and performance test
Selecting Na with a ratio of positive electrode capacity to negative electrode capacity of 1.050.67Li0.06Mg0.06Ni0.21Mn0.6Ti0.07O2Positive electrode and hard carbon negative electrode, 1M NaClO using a glass fiber membrane of Whatman having a diameter of 16mm as a separator4The solution of PC/DMC (volume ratio is 1:1) is used as electrolyte to assemble the CR2025 button cell.
And (3) carrying out constant-current charge and discharge performance test on the assembled button cell on a LAND cell test system (provided by Wuhan blue electronics Co., Ltd.), wherein the charge and discharge cutoff voltage is 1-4.4V, the discharge specific capacity of the cell at 0.2C multiplying power is 285mAh/g, the working voltage is 3.52V, and the energy density calculated based on the mass of the positive electrode and the negative electrode is up to 234 Wh/kg.
Example 18
1. Preparation of Na0.67Li0.06Mg0.06Ni0.21Mn0.6Ti0.07O2Positive electrode material
First, 10.05mmol of Na was weighed2CO3、0.9mmol Li2CO3、1.8mmol MgO、6.3mmol NiO、18mmol MnO2And 2.1mmol TiO2Putting the mixture into a nylon ball milling tank, dropwise adding 3 wt% of absolute ethyl alcohol as a wet milling solvent, ball milling the mixture for 4 hours at the rotating speed of 450r/min by using a planetary ball mill, and drying the solvent in an oven at the temperature of 80 ℃ to obtain precursor powder which is uniformly mixed. Then, the precursor powder was pressed into a small disk having a diameter of 12mm under a pressure of 16MPa using a powder tablet press, and placed in a muffle furnace at a temperature rising rate of 10 ℃/min-1Heating to 950 ℃, carrying out heat preservation and calcination for 15h, and naturally cooling to obtain the cathode material.
2. Preparation of Na0.67Li0.06Mg0.06Ni0.21Mn0.6Ti0.07O2Positive electrode
Mixing the prepared positive electrode material with Super P and PVDF according to the mass ratio of 8.5:0.75:0.75, adding NMP as a solvent, uniformly stirring, coating on an aluminum foil, drying in a blast oven at 80 ℃, and punching into a pole piece by using a punch with the diameter of 10 mm.
3. Preparation of hard carbon cathode
Mixing hard carbon, Super P and PVDF according to the mass ratio of 8:1:1, adding NMP as a solvent, uniformly stirring, coating on an aluminum foil, drying in a blast oven at 80 ℃, and punching into a pole piece by using a punch with the diameter of 10 mm.
4. Assembled sodium ion battery and performance test
Selecting Na with a ratio of positive electrode capacity to negative electrode capacity of 1.050.67Li0.06Mg0.06Ni0.21Mn0.6Ti0.07O2Positive electrode and hard carbon negative electrode, 1M NaClO using a glass fiber membrane of Whatman having a diameter of 16mm as a separator4The solution of PC/DMC (volume ratio is 1:1) is used as electrolyte to assemble the CR2025 button cell.
And (3) carrying out constant-current charge and discharge performance test on the assembled button cell on a LAND cell test system (provided by Wuhan blue electronics Co., Ltd.), wherein the charge and discharge cutoff voltage is 1-4.4V, the discharge specific capacity of the cell at 0.2C multiplying power is 285mAh/g, the working voltage is 3.52V, and the energy density calculated based on the mass of the positive electrode and the negative electrode is up to 234 Wh/kg. .
Example 19
1. Preparation of Na0.67Li0.06Mg0.06Ni0.21Mn0.6Ti0.07O2Positive electrode material
First, 10.05mmol of Na was weighed2CO3、0.9mmol Li2CO3、1.8mmol MgO、6.3mmol NiO、18mmol MnO2And 2.1mmol TiO2Putting the mixture into a nylon ball milling tank, dropwise adding 3 wt% of absolute ethyl alcohol as a wet milling solvent, ball milling the mixture for 4 hours at the rotating speed of 450r/min by using a planetary ball mill, and drying the solvent in an oven at the temperature of 80 ℃ to obtain precursor powder which is uniformly mixed. Then, the precursor powder was pressed into a small disk having a diameter of 12mm under a pressure of 16MPa using a powder tablet press, and placed in a muffle furnace at a temperature rising rate of 10 ℃/min-1Heating to 950 ℃, carrying out heat preservation and calcination for 15h, and naturally cooling to obtain the cathode material.
2. Preparation of Na0.67Li0.06Mg0.06Ni0.21Mn0.6Ti0.07O2Positive electrode
Mixing the prepared positive electrode material with Super P and PVDF according to the mass ratio of 9:0.5:0.5, adding NMP as a solvent, uniformly stirring, coating on an aluminum foil, drying in a blast oven at 80 ℃, and punching into a pole piece by using a punch with the diameter of 10 mm.
3. Preparation of hard carbon cathode
Mixing hard carbon, Super P and PVDF according to the mass ratio of 8:1:1, adding NMP as a solvent, uniformly stirring, coating on an aluminum foil, drying in a blast oven at 80 ℃, and punching into a pole piece by using a punch with the diameter of 10 mm.
4. Assembled sodium ion battery and performance test
Selecting Na with a ratio of positive electrode capacity to negative electrode capacity of 1.050.67Li0.06Mg0.06Ni0.21Mn0.6Ti0.07O2Positive electrode and hard carbon negative electrode, 1M NaClO using a glass fiber membrane of Whatman having a diameter of 16mm as a separator4The solution of PC/DMC (volume ratio is 1:1) is used as electrolyte to assemble the CR2025 button cell.
And (3) carrying out constant-current charge and discharge performance test on the assembled button cell on a LAND cell test system (provided by Wuhan blue electronics Co., Ltd.), wherein the charge and discharge cutoff voltage is 1-4.4V, the discharge specific capacity of the cell at 0.2C multiplying power is 285mAh/g, the working voltage is 3.52V, and the energy density calculated based on the mass of the positive electrode and the negative electrode is up to 234 Wh/kg.
Example 20
1. Preparation of Na0.67Li0.06Mg0.06Ni0.21Mn0.6Ti0.07O2Positive electrode material
First, 10.05mmol of Na was weighed2CO3、0.9mmol Li2CO3、1.8mmol MgO、6.3mmol NiO、18mmol MnO2And 2.1mmol TiO2Putting the mixture into a nylon ball milling tank, dropwise adding 3 wt% of absolute ethyl alcohol as a wet milling solvent, ball milling the mixture for 4 hours at the rotating speed of 450r/min by using a planetary ball mill, and drying the solvent in an oven at the temperature of 80 ℃ to obtain precursor powder which is uniformly mixed. The precursor powder was then pressed into small disks of 12mm diameter using a powder tablet press under a pressure of 16MPa and placed in a muffleIn the furnace, the temperature is raised at a rate of 10 ℃/min-1Heating to 950 ℃, carrying out heat preservation and calcination for 15h, and naturally cooling to obtain the cathode material.
2. Preparation of Na0.67Li0.06Mg0.06Ni0.21Mn0.6Ti0.07O2Positive electrode
Mixing the prepared positive electrode material with Super P and PVDF according to the mass ratio of 8:1:1, adding NMP as a solvent, uniformly stirring, coating on an aluminum foil, drying in a blast oven at 80 ℃, and punching into a pole piece by using a punch with the diameter of 10 mm.
3. Preparation of hard carbon cathode
Mixing hard carbon, Super P and PVDF according to the mass ratio of 8:1:1, adding NMP as a solvent, uniformly stirring, coating on an aluminum foil, drying in a blast oven at 80 ℃, and punching into a pole piece by using a punch with the diameter of 10 mm.
4. Assembled sodium ion battery and performance test
Selecting Na with a ratio of positive electrode capacity to negative electrode capacity of 0.90.67Li0.06Mg0.06Ni0.21Mn0.6Ti0.07O2Positive electrode and hard carbon negative electrode, 1M NaClO using a glass fiber membrane of Whatman having a diameter of 16mm as a separator4The solution of PC/DMC (volume ratio is 1:1) is used as electrolyte to assemble the CR2025 button cell.
And (3) carrying out constant-current charge and discharge performance test on the assembled button cell on a LAND cell test system (provided by Wuhan blue electronics Co., Ltd.), wherein the charge and discharge cutoff voltage is 1-4.4V, the discharge specific capacity of the cell at 0.2C multiplying power is 285mAh/g, the working voltage is 3.52V, and the energy density calculated based on the mass of the positive electrode and the negative electrode is up to 234 Wh/kg.
Example 21
1. Preparation of Na0.67Li0.06Mg0.06Ni0.21Mn0.6Ti0.07O2Positive electrode material
First, 10.05mmol of Na was weighed2CO3、0.9mmol Li2CO3、1.8mmol MgO、6.3mmol NiO、18mmol MnO2And 2.1mmol TiO2Putting into nylonAnd (3) dropwise adding 3 wt% of absolute ethyl alcohol into the ball milling tank to serve as a wet milling solvent, ball milling for 4 hours at the rotating speed of 450r/min by using a planetary ball mill, and drying the solvent in an oven at 80 ℃ to obtain precursor powder which is uniformly mixed. Then, the precursor powder was pressed into a small disk having a diameter of 12mm under a pressure of 16MPa using a powder tablet press, and placed in a muffle furnace at a temperature rising rate of 10 ℃/min-1Heating to 950 ℃, carrying out heat preservation and calcination for 15h, and naturally cooling to obtain the cathode material.
2. Preparation of Na0.67Li0.06Mg0.06Ni0.21Mn0.6Ti0.07O2Positive electrode
Mixing the prepared positive electrode material with Super P and PVDF according to the mass ratio of 8:1:1, adding NMP as a solvent, uniformly stirring, coating on an aluminum foil, drying in a blast oven at 80 ℃, and punching into a pole piece by using a punch with the diameter of 10 mm.
3. Preparation of hard carbon cathode
Mixing hard carbon, Super P and PVDF according to the mass ratio of 8:1:1, adding NMP as a solvent, uniformly stirring, coating on an aluminum foil, drying in a blast oven at 80 ℃, and punching into a pole piece by using a punch with the diameter of 10 mm.
4. Assembled sodium ion battery and performance test
Selecting Na with a ratio of positive electrode capacity to negative electrode capacity of 1.20.67Li0.06Mg0.06Ni0.21Mn0.6Ti0.07O2Positive electrode and hard carbon negative electrode, 1M NaClO using a glass fiber membrane of Whatman having a diameter of 16mm as a separator4The solution of PC/DMC (volume ratio is 1:1) is used as electrolyte to assemble the CR2025 button cell.
And (3) carrying out constant-current charge and discharge performance test on the assembled button cell on a LAND cell test system (provided by Wuhan blue electronics Co., Ltd.), wherein the charge and discharge cutoff voltage is 1-4.4V, the discharge specific capacity of the cell at 0.2C multiplying power is 285mAh/g, the working voltage is 3.52V, and the energy density calculated based on the mass of the positive electrode and the negative electrode is up to 234 Wh/kg.
Example 22
1. Preparation of Na0.67Li0.06Mg0.06Ni0.21Mn0.6Ti0.07O2Positive electrode material
First, 10.05mmol of Na was weighed2CO3、0.9mmol Li2CO3、1.8mmol MgO、6.3mmol NiO、18mmol MnO2And 2.1mmol TiO2Putting the mixture into a nylon ball milling tank, dropwise adding 3 wt% of absolute ethyl alcohol as a wet milling solvent, ball milling the mixture for 4 hours at the rotating speed of 450r/min by using a planetary ball mill, and drying the solvent in an oven at the temperature of 80 ℃ to obtain precursor powder which is uniformly mixed. Then, the precursor powder was pressed into a small disk having a diameter of 12mm under a pressure of 16MPa using a powder tablet press, and placed in a muffle furnace at a temperature rising rate of 10 ℃/min-1Heating to 950 ℃, carrying out heat preservation and calcination for 15h, and naturally cooling to obtain the cathode material.
2. Preparation of Na0.67Li0.06Mg0.06Ni0.21Mn0.6Ti0.07O2Positive electrode
Mixing the prepared positive electrode material with Super P and PVDF according to the mass ratio of 8:1:1, adding NMP as a solvent, uniformly stirring, coating on an aluminum foil, drying in a blast oven at 80 ℃, and punching into a pole piece by using a punch with the diameter of 10 mm.
3. Preparation of hard carbon cathode
Mixing hard carbon, Super P and PVDF according to the mass ratio of 8:1:1, adding NMP as a solvent, uniformly stirring, coating on an aluminum foil, drying in a blast oven at 80 ℃, and punching into a pole piece by using a punch with the diameter of 10 mm.
4. Assembled sodium ion battery and performance test
Selecting Na with a ratio of positive electrode capacity to negative electrode capacity of 0.90.67Li0.06Mg0.06Ni0.21Mn0.6Ti0.07O2Positive electrode and hard carbon negative electrode, 1M NaClO using a glass fiber membrane of Whatman having a diameter of 16mm as a separator4The solution of PC/DMC (volume ratio is 1:1) is used as electrolyte to assemble the CR2025 button cell.
And (3) carrying out constant-current charge and discharge performance test on the assembled button cell on a LAND cell test system (provided by Wuhan blue electronics Co., Ltd.), wherein the charge and discharge cutoff voltage is 1-4.4V, the discharge specific capacity of the cell at 0.2C multiplying power is 285mAh/g, the working voltage is 3.52V, and the energy density calculated based on the mass of the positive electrode and the negative electrode is up to 234 Wh/kg.
Example 23
1. Preparation of Na0.67Li0.06Mg0.06Ni0.21Mn0.6Ti0.07O2Positive electrode material
First, 10.05mmol of Na was weighed2CO3、0.9mmol Li2CO3、1.8mmol MgO、6.3mmol NiO、18mmol MnO2And 2.1mmol TiO2Putting the mixture into a nylon ball milling tank, dropwise adding 3 wt% of absolute ethyl alcohol as a wet milling solvent, ball milling the mixture for 4 hours at the rotating speed of 450r/min by using a planetary ball mill, and drying the solvent in an oven at the temperature of 80 ℃ to obtain precursor powder which is uniformly mixed. Then, the precursor powder was pressed into a small disk having a diameter of 12mm under a pressure of 16MPa using a powder tablet press, and placed in a muffle furnace at a temperature rising rate of 10 ℃/min-1Heating to 950 ℃, carrying out heat preservation and calcination for 15h, and naturally cooling to obtain the cathode material.
2. Preparation of Na0.67Li0.06Mg0.06Ni0.21Mn0.6Ti0.07O2Positive electrode
Mixing the prepared positive electrode material with Super P and PVDF according to the mass ratio of 8:1:1, adding NMP as a solvent, uniformly stirring, coating on an aluminum foil, drying in a blast oven at 80 ℃, and punching into a pole piece by using a punch with the diameter of 10 mm.
3. Preparation of Soft carbon cathode
Mixing hard carbon, Super P and PVDF according to the mass ratio of 8:1:1, adding NMP as a solvent, uniformly stirring, coating on an aluminum foil, drying in a blast oven at 80 ℃, and punching into a pole piece by using a punch with the diameter of 10 mm.
4. Assembled sodium ion battery and performance test
Selecting Na with a ratio of positive electrode capacity to negative electrode capacity of 1.050.67Li0.06Mg0.06Ni0.21Mn0.6Ti0.07O2Positive electrode and soft carbon negative electrode, glass of Whatman corporation with a diameter of 16mmGlass fiber film as separator, 1M NaClO4The solution of PC/DMC (volume ratio is 1:1) is used as electrolyte to assemble the CR2025 button cell.
And (3) carrying out constant-current charge and discharge performance test on the assembled button cell on a LAND cell test system (provided by Wuhan blue electronics Co., Ltd.), wherein the charge and discharge cutoff voltage is 1-4.4V, the discharge specific capacity of the cell at 0.2C multiplying power is 285mAh/g, the working voltage is 3.52V, and the energy density calculated based on the mass of the positive electrode and the negative electrode is up to 234 Wh/kg.
Example 24
1. Preparation of Na0.67Li0.06Ni0.27Mn0.6Ti0.07O2Positive electrode material
First, 10.05mmol of Na was weighed2CO3、0.9mmol Li2CO3、8.1mmol NiO、18mmol MnO2And 2.1mmol TiO2Putting the mixture into a nylon ball milling tank, dropwise adding 3 wt% of absolute ethyl alcohol as a wet milling solvent, ball milling the mixture for 4 hours at the rotating speed of 450r/min by using a planetary ball mill, and drying the solvent in an oven at the temperature of 80 ℃ to obtain precursor powder which is uniformly mixed. Then, the precursor powder was pressed into a small disk having a diameter of 12mm under a pressure of 16MPa using a powder tablet press, and put into a muffle furnace at a temperature rising rate of 10 ℃ for 10 ℃ min-1Heating to 950 ℃, carrying out heat preservation and calcination for 15h, and naturally cooling to obtain the anode material.
2. Preparation of Na0.67Li0.06Ni0.27Mn0.6Ti0.07O2Positive electrode
Mixing the prepared positive electrode material with Super P and PVDF according to the mass ratio of 8:1:1, adding NMP as a solvent, uniformly stirring, coating on an aluminum foil, drying in a blast oven at 80 ℃, and punching into a pole piece by using a punch with the diameter of 10 mm.
3. Preparation of hard carbon cathode
Mixing hard carbon, Super P and PVDF according to the mass ratio of 8:1:1, adding NMP as a solvent, uniformly stirring, coating on an aluminum foil, drying in a blast oven at 80 ℃, and punching into a pole piece by using a punch with the diameter of 10 mm.
4. Assembled sodium ion battery and performance test
Selecting Na with a ratio of positive electrode capacity to negative electrode capacity of 1.050.67Li0.06Ni0.27Mn0.6Ti0.07O2Positive electrode and hard carbon negative electrode, 1M NaClO using a glass fiber membrane of Whatman having a diameter of 16mm as a separator4The solution of PC/DMC (volume ratio is 1:1) is used as electrolyte to assemble the CR2025 button cell.
And (3) carrying out constant-current charge and discharge performance test on the assembled button cell on a LAND cell test system (provided by Wuhan blue electronics Co., Ltd.), wherein the charge and discharge cutoff voltage is 1-4.4V, the discharge specific capacity of the cell at 0.2C multiplying power is 285mAh/g, the working voltage is 3.52V, and the energy density calculated based on the mass of the positive electrode and the negative electrode is up to 234 Wh/kg.
Example 25
1. Preparation of Na0.67Mg0.06Ni0.27Mn0.6Ti0.07O2Positive electrode material
First, 10.05mmol of Na was weighed2CO3、1.8mmol MgO、8.1mmol NiO、18mmol MnO2And 2.1mmol TiO2Putting the mixture into a nylon ball milling tank, dropwise adding 3 wt% of absolute ethyl alcohol as a wet milling solvent, ball milling the mixture for 4 hours at the rotating speed of 450r/min by using a planetary ball mill, and drying the solvent in an oven at the temperature of 80 ℃ to obtain precursor powder which is uniformly mixed. Then, the precursor powder was pressed into a small disk having a diameter of 12mm under a pressure of 16MPa using a powder tablet press, and placed in a muffle furnace at a temperature rising rate of 10 ℃/min-1Heating to 950 ℃, carrying out heat preservation and calcination for 15h, and naturally cooling to obtain the cathode material.
2. Preparation of Na0.67Mg0.06Ni0.27Mn0.6Ti0.07O2Positive electrode
Mixing the prepared positive electrode material with Super P and PVDF according to the mass ratio of 8:1:1, adding NMP as a solvent, uniformly stirring, coating on an aluminum foil, drying in a blast oven at 80 ℃, and punching into a pole piece by using a punch with the diameter of 10 mm.
3. Preparation of hard carbon cathode
Mixing hard carbon, Super P and PVDF according to the mass ratio of 8:1:1, adding NMP as a solvent, uniformly stirring, coating on an aluminum foil, drying in a blast oven at 80 ℃, and punching into a pole piece by using a punch with the diameter of 10 mm.
4. Assembled sodium ion battery and performance test
Selecting Na with a ratio of positive electrode capacity to negative electrode capacity of 1.050.67Mg0.06Ni0.27Mn0.6Ti0.07O2Positive electrode and hard carbon negative electrode, 1M NaClO using a glass fiber membrane of Whatman having a diameter of 16mm as a separator4The solution of PC/DMC (volume ratio is 1:1) is used as electrolyte to assemble the CR2025 button cell.
And (3) carrying out constant-current charge and discharge performance test on the assembled button cell on a LAND cell test system (provided by Wuhan blue electronics Co., Ltd.), wherein the charge and discharge cutoff voltage is 1-4.4V, the discharge specific capacity of the cell at 0.2C multiplying power is 285mAh/g, the working voltage is 3.52V, and the energy density calculated based on the mass of the positive electrode and the negative electrode is up to 234 Wh/kg.
Example 26
1. Preparation of Na0.67Li0.06Mg0.06Ni0.21Mn0.67O2Positive electrode material
First, 10.05mmol of Na was weighed2CO3、0.9mmol Li2CO31.8mmol MgO, 6.3mmol NiO and 20.1mmol MnO2Putting the mixture into a nylon ball milling tank, dropwise adding 3 wt% of absolute ethyl alcohol as a wet milling solvent, ball milling the mixture for 4 hours at the rotating speed of 450r/min by using a planetary ball mill, and drying the solvent in an oven at the temperature of 80 ℃ to obtain precursor powder which is uniformly mixed. Then, the precursor powder was pressed into a small disk having a diameter of 12mm under a pressure of 16MPa using a powder tablet press, and put into a muffle furnace at a temperature rising rate of 10 ℃ for 10 ℃ min-1Heating to 950 ℃, carrying out heat preservation and calcination for 15h, and naturally cooling to obtain the cathode material.
2. Preparation of Na0.67Li0.06Mg0.06Ni0.21Mn0.67O2Positive electrode
Mixing the prepared positive electrode material with Super P and PVDF according to the mass ratio of 8:1:1, adding NMP as a solvent, uniformly stirring, coating on an aluminum foil, drying in a blast oven at 80 ℃, and punching into a pole piece by using a punch with the diameter of 10 mm.
3. Preparation of hard carbon cathode
Mixing hard carbon, Super P and PVDF according to the mass ratio of 8:1:1, adding NMP as a solvent, uniformly stirring, coating on an aluminum foil, drying in a blast oven at 80 ℃, and punching into a pole piece by using a punch with the diameter of 10 mm.
4. Assembled sodium ion battery and performance test
Selecting Na with a ratio of positive electrode capacity to negative electrode capacity of 1.050.7Li0.03Mg0.03Ni0.27Mn0.67O2Positive electrode and hard carbon negative electrode, 1M NaClO using a glass fiber membrane of Whatman having a diameter of 16mm as a separator4The solution of PC/DMC (volume ratio is 1:1) is used as electrolyte to assemble the CR2025 button cell.
And (3) carrying out constant-current charge and discharge performance test on the assembled button cell on a LAND cell test system (provided by Wuhan blue electronics Co., Ltd.), wherein the charge and discharge cutoff voltage is 1-4.4V, the discharge specific capacity of the cell at 0.2C multiplying power is 285mAh/g, the working voltage is 3.52V, and the energy density calculated based on the mass of the positive electrode and the negative electrode is up to 234 Wh/kg.
Example 27
1. Preparation of Na0.67Li0.06Ni0.27Mn0.67O2Positive electrode material
First, 10.05mmol of Na was weighed2CO3、0.9mmol Li2CO38.1mmol NiO and 20.1mmol MnO2Putting the mixture into a nylon ball milling tank, dropwise adding 3 wt% of absolute ethyl alcohol as a wet milling solvent, ball milling the mixture for 4 hours at the rotating speed of 450r/min by using a planetary ball mill, and drying the solvent in an oven at the temperature of 80 ℃ to obtain precursor powder which is uniformly mixed. Then, the precursor powder was pressed into a small disk having a diameter of 12mm under a pressure of 16MPa using a powder tablet press, and put into a muffle furnace at a temperature rising rate of 10 ℃ for 10 ℃ min-1Heating to 950 ℃, carrying out heat preservation and calcination for 15h, and naturally cooling to obtain the cathode material.
2. Preparation of Na0.67Li0.06Ni0.27Mn0.67O2Positive electrode
Mixing the prepared positive electrode material with Super P and PVDF according to the mass ratio of 8:1:1, adding NMP as a solvent, uniformly stirring, coating on an aluminum foil, drying in a blast oven at 80 ℃, and punching into a pole piece by using a punch with the diameter of 10 mm.
3. Preparation of hard carbon cathode
Mixing hard carbon, Super P and PVDF according to the mass ratio of 8:1:1, adding NMP as a solvent, uniformly stirring, coating on an aluminum foil, drying in a blast oven at 80 ℃, and punching into a pole piece by using a punch with the diameter of 10 mm.
4. Assembled sodium ion battery and performance test
Selecting Na with a ratio of positive electrode capacity to negative electrode capacity of 1.050.67Li0.06Ni0.27Mn0.67O2Positive electrode and hard carbon negative electrode, 1M NaClO using a glass fiber membrane of Whatman having a diameter of 16mm as a separator4The solution of PC/DMC (volume ratio is 1:1) is used as electrolyte to assemble the CR2025 button cell.
And (3) carrying out constant-current charge and discharge performance test on the assembled button cell on a LAND cell test system (provided by Wuhan blue electronics Co., Ltd.), wherein the charge and discharge cutoff voltage is 1-4.4V, the discharge specific capacity of the cell at 0.2C multiplying power is 285mAh/g, the working voltage is 3.52V, and the energy density calculated based on the mass of the positive electrode and the negative electrode is up to 234 Wh/kg.
Example 28
1. Preparation of Na0.67Mg0.06Ni0.27Mn0.67O2Positive electrode material
First, 10.05mmol of Na was weighed2CO31.8mmol MgO, 8.1mmol NiO and 20.1mmol MnO2Putting the mixture into a nylon ball milling tank, dropwise adding 3 wt% of absolute ethyl alcohol as a wet milling solvent, ball milling the mixture for 4 hours at the rotating speed of 450r/min by using a planetary ball mill, and drying the solvent in an oven at the temperature of 80 ℃ to obtain precursor powder which is uniformly mixed. Then, the precursor powder was pressed into a small disk having a diameter of 12mm under a pressure of 16MPa using a powder tablet press, and put into a muffle furnace at a temperature rising rate of 10 ℃ for 10 ℃ min-1Heating to 950 ℃, keeping the temperature, calcining for 15 hours, and naturally cooling to obtain the positive electrodeA pole material.
2. Preparation of Na0.67Mg0.06Ni0.27Mn0.67O2Positive electrode
Mixing the prepared positive electrode material with Super P and PVDF according to the mass ratio of 8:1:1, adding NMP as a solvent, uniformly stirring, coating on an aluminum foil, drying in a blast oven at 80 ℃, and punching into a pole piece by using a punch with the diameter of 10 mm.
3. Preparation of hard carbon cathode
Mixing hard carbon, Super P and PVDF according to the mass ratio of 8:1:1, adding NMP as a solvent, uniformly stirring, coating on an aluminum foil, drying in a blast oven at 80 ℃, and punching into a pole piece by using a punch with the diameter of 10 mm.
4. Assembled sodium ion battery and performance test
Selecting Na with a ratio of positive electrode capacity to negative electrode capacity of 1.050.67Mg0.06Ni0.27Mn0.67O2Positive electrode and hard carbon negative electrode, 1M NaClO using a glass fiber membrane of Whatman having a diameter of 16mm as a separator4The solution of PC/DMC (volume ratio is 1:1) is used as electrolyte to assemble the CR2025 button cell.
And (3) carrying out constant-current charge and discharge performance test on the assembled button cell on a LAND cell test system (provided by Wuhan blue electronics Co., Ltd.), wherein the charge and discharge cutoff voltage is 1-4.4V, the discharge specific capacity of the cell at 0.2C multiplying power is 285mAh/g, the working voltage is 3.52V, and the energy density calculated based on the mass of the positive electrode and the negative electrode is up to 234 Wh/kg.
Example 29
1. Preparation of Na0.67Mn0.6Ti0.07O2Positive electrode material
First, 10.05mmol of Na was weighed2CO3、18mmol MnO2And 2.1mmol TiO2Putting the mixture into a nylon ball milling tank, dropwise adding 3 wt% of absolute ethyl alcohol as a wet milling solvent, ball milling the mixture for 4 hours at the rotating speed of 450r/min by using a planetary ball mill, and drying the solvent in an oven at the temperature of 80 ℃ to obtain precursor powder which is uniformly mixed. Then, the precursor powder was pressed into a small disk having a diameter of 12mm under a pressure of 16MPa using a powder tablet press, and put intoIn a muffle furnace, heating at a rate of 10 deg.C for 10 min-1Heating to 950 ℃, carrying out heat preservation and calcination for 15h, and naturally cooling to obtain the cathode material.
2. Preparation of Na0.67Mn0.6Ti0.07O2Positive electrode
Mixing the prepared positive electrode material with Super P and PVDF according to the mass ratio of 8:1:1, adding NMP as a solvent, uniformly stirring, coating on an aluminum foil, drying in a blast oven at 80 ℃, and punching into a pole piece by using a punch with the diameter of 10 mm.
3. Preparation of hard carbon cathode
Mixing hard carbon, Super P and PVDF according to the mass ratio of 8:1:1, adding NMP as a solvent, uniformly stirring, coating on an aluminum foil, drying in a blast oven at 80 ℃, and punching into a pole piece by using a punch with the diameter of 10 mm.
4. Assembled sodium ion battery and performance test
Selecting Na with a ratio of positive electrode capacity to negative electrode capacity of 1.050.67Mn0.6Ti0.07O2Positive electrode and hard carbon negative electrode, 1M NaClO using a glass fiber membrane of Whatman having a diameter of 16mm as a separator4The solution of PC/DMC (volume ratio is 1:1) is used as electrolyte to assemble the CR2025 button cell.
5. Assembled sodium ion battery module
Selecting Na with a ratio of positive electrode capacity to negative electrode capacity of 1.050.67Mn0.6Ti0.07O2Positive and hard carbon negative electrodes, 1M NaPF6The EC/DEC (volume ratio of 1:1) solution is used as an electrolyte, a 48V/10Ah 22650 cylindrical battery is assembled by adopting a winding process, and the battery module is used for an electric bicycle.
And (3) carrying out constant-current charge and discharge performance test on the assembled button cell on a LAND cell test system (provided by Wuhan blue electronics Co., Ltd.), wherein the charge and discharge cutoff voltage is 1-4.4V, the discharge specific capacity of the cell at 0.2C multiplying power is 285mAh/g, the working voltage is 3.52V, and the energy density calculated based on the mass of the positive electrode and the negative electrode is up to 234 Wh/kg.
In conclusion, the positive electrode material of the sodium-ion battery, the sodium-ion battery and the preparation method and application thereof are provided, the positive electrode material of the sodium-ion battery with high specific energy and high cycle stability is obtained through a simple preparation method and cheap raw materials, the sodium-ion battery is assembled through simple and easy operation, the prepared sodium-ion battery has high energy density of 230Wh/kg and average working voltage of 3.6V at 25 ℃, can be comparable with the existing commercial lithium iron phosphate-based lithium ion battery, has energy density far exceeding that of a lead-acid storage battery, and has wide application prospects in various fields such as electric bicycles and the like.
The above-mentioned contents are only for illustrating the technical idea of the present invention, and the protection scope of the present invention is not limited thereby, and any modification made on the basis of the technical idea of the present invention falls within the protection scope of the claims of the present invention.
Claims (10)
1. A preparation method of a positive electrode material of a sodium-ion battery is characterized by comprising the following steps:
dropwise adding absolute ethyl alcohol into the metal oxide to be used as a wet grinding medium for ball milling treatment, and then drying to obtain precursor powder which is uniformly mixed;
pressing the precursor powder into a round flaky structure, then calcining at high temperature in air atmosphere and preserving heat, and naturally cooling to obtain Na2/3Ni1/3-xAxMn2/3-yByO2And (3) a positive electrode material.
2. The method of claim 1, wherein the metal oxide comprises Na2CO3、NiO、MnO2And Li2CO3、MgO、ZnO、CuO、CaO、TiO2、Fe2O3And SiO2One or more of; the molar ratio of the element Na to the element Ni is 2-4, and the molar ratio of the element Na to the element Mn is 1-2.
3. The method according to claim 1, wherein the addition amount of the absolute ethyl alcohol is 1-5% of the total mass of the metal oxides, the rotation speed of the ball milling treatment is 200-600 r/min, and the time is 1-12 h.
4. The method according to claim 1, wherein the temperature rise rate is 1-20 ℃/min-1The calcining temperature is 800-1200 ℃, and the heat preservation time is 5-20 h.
5. The positive electrode material for sodium-ion batteries prepared by the method of claim 1, wherein the element a comprises at least one of Mg, Zn, Cu and Ca; the element B comprises at least one of Ti, Fe and Si, and the doping contents of the elements A and B are as follows: x is more than or equal to 0 and less than or equal to 1/6, and y is more than or equal to 0 and less than or equal to 1/3.
6. A preparation method of a sodium ion battery is characterized by comprising the following steps:
according to the formula (8-9): (0.5-1): (0.5-1) putting the positive/negative electrode material, the conductive additive and the binder into a polypropylene plastic box, and adding NMP, wherein the positive electrode material in the positive/negative electrode material is the positive electrode material prepared by the method of claim 1 or the positive electrode material of the sodium-ion battery of claim 5, and the negative electrode material is commercial hard carbon or soft carbon; performing ball milling treatment on a polypropylene plastic box to obtain uniformly mixed positive/negative electrode slurry; coating the positive/negative electrode slurry in a scraping way and carrying out vacuum drying treatment to obtain positive and negative electrode sheets with uniform thickness; punching the positive and negative plates into round plates with the same size, and determining the corresponding positive and negative electrodes based on the positive and negative electrode capacity ratio of 0.9-1.2 for battery assembly; the positive electrode and the negative electrode were prepared into a sodium ion battery using an electrolyte and a separator.
7. The method of claim 6, wherein the conductive additive is one or more of carbon black, Super P, Ketjen black, and the binder is one or more of polyvinylidene fluoride or polyacrylic acid, sodium carboxymethylcellulose, sodium alginate, and gelatin.
8. The method of claim 6, wherein the electrolyte has a concentration of 0.1 to 1.5M, and comprises a solvent and a sodium salt, wherein the solvent comprises at least one of dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, ethylene carbonate and propylene carbonate; the sodium salt comprises one or more of sodium hexafluorophosphate, sodium perchlorate and sodium bis (trifluoromethylsulfonyl) imide.
9. A sodium ion battery prepared according to the method of claim 6, having a high energy density of >230Wh/kg at 25 ℃ and an average operating voltage of 3.6V.
10. Use of a sodium-ion battery prepared according to the method of claim 6 or a sodium-ion battery according to claim 9 in an electric bicycle.
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| CN114122382A (en) * | 2021-11-24 | 2022-03-01 | 西安交通大学 | Layered positive electrode material of P3 type sodium-ion battery and preparation method and application thereof |
| CN114132971A (en) * | 2021-11-26 | 2022-03-04 | 西安交通大学 | Sodium ion battery positive electrode material with composite symbiotic structure, preparation method and sodium ion battery |
| CN114853079A (en) * | 2022-06-02 | 2022-08-05 | 大连中比动力电池有限公司 | Layered sodium ion positive electrode material and preparation method thereof |
| CN114927681A (en) * | 2022-05-16 | 2022-08-19 | 华侨大学 | P2 type five-element high-entropy sodium laminar positive electrode material and preparation method and application thereof |
| CN114927663A (en) * | 2022-05-26 | 2022-08-19 | 中国科学技术大学 | Five-membered layered oxide sodium ion battery positive electrode material and preparation method and application thereof |
| CN115188959A (en) * | 2022-07-26 | 2022-10-14 | 南开大学 | Fluoride ion-doped manganese-based layered oxide positive electrode material with air stability, and preparation method and application thereof |
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| CN114122382A (en) * | 2021-11-24 | 2022-03-01 | 西安交通大学 | Layered positive electrode material of P3 type sodium-ion battery and preparation method and application thereof |
| CN114122382B (en) * | 2021-11-24 | 2024-04-02 | 西安交通大学 | Layered positive electrode material of P3 type sodium ion battery, and preparation method and application thereof |
| CN114132971A (en) * | 2021-11-26 | 2022-03-04 | 西安交通大学 | Sodium ion battery positive electrode material with composite symbiotic structure, preparation method and sodium ion battery |
| CN114132971B (en) * | 2021-11-26 | 2023-03-14 | 西安交通大学 | Sodium ion battery positive electrode material with composite symbiotic structure, preparation method and sodium ion battery |
| CN114927681A (en) * | 2022-05-16 | 2022-08-19 | 华侨大学 | P2 type five-element high-entropy sodium laminar positive electrode material and preparation method and application thereof |
| CN114927681B (en) * | 2022-05-16 | 2024-03-12 | 华侨大学 | P2 type five-membered high-entropy sodium layered positive electrode material and preparation method and application thereof |
| CN114927663A (en) * | 2022-05-26 | 2022-08-19 | 中国科学技术大学 | Five-membered layered oxide sodium ion battery positive electrode material and preparation method and application thereof |
| CN114853079A (en) * | 2022-06-02 | 2022-08-05 | 大连中比动力电池有限公司 | Layered sodium ion positive electrode material and preparation method thereof |
| CN115188959A (en) * | 2022-07-26 | 2022-10-14 | 南开大学 | Fluoride ion-doped manganese-based layered oxide positive electrode material with air stability, and preparation method and application thereof |
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