CN116354405A - In-situ carbon-coated sodium ferrous sulfate composite positive electrode material, preparation and sodium ion battery - Google Patents
In-situ carbon-coated sodium ferrous sulfate composite positive electrode material, preparation and sodium ion battery Download PDFInfo
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- CN116354405A CN116354405A CN202310358536.XA CN202310358536A CN116354405A CN 116354405 A CN116354405 A CN 116354405A CN 202310358536 A CN202310358536 A CN 202310358536A CN 116354405 A CN116354405 A CN 116354405A
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- 239000011734 sodium Substances 0.000 title claims abstract description 58
- 239000002131 composite material Substances 0.000 title claims abstract description 45
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 40
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 36
- 229910001415 sodium ion Inorganic materials 0.000 title claims abstract description 30
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 238000011065 in-situ storage Methods 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 229910052708 sodium Inorganic materials 0.000 title claims description 38
- 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 title claims description 37
- 235000003891 ferrous sulphate Nutrition 0.000 title claims description 32
- 239000011790 ferrous sulphate Substances 0.000 title claims description 32
- 229910000359 iron(II) sulfate Inorganic materials 0.000 title claims description 32
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 title claims 6
- 239000002243 precursor Substances 0.000 claims abstract description 38
- 238000000034 method Methods 0.000 claims abstract description 29
- 238000001354 calcination Methods 0.000 claims abstract description 20
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims abstract description 18
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000003792 electrolyte Substances 0.000 claims abstract description 15
- 230000008569 process Effects 0.000 claims abstract description 15
- 239000002245 particle Substances 0.000 claims abstract description 14
- 229910052938 sodium sulfate Inorganic materials 0.000 claims abstract description 14
- 235000011152 sodium sulphate Nutrition 0.000 claims abstract description 14
- 229910003481 amorphous carbon Inorganic materials 0.000 claims abstract description 12
- 239000010405 anode material Substances 0.000 claims abstract description 12
- 238000001704 evaporation Methods 0.000 claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000011248 coating agent Substances 0.000 claims abstract description 7
- 238000000576 coating method Methods 0.000 claims abstract description 7
- 239000000843 powder Substances 0.000 claims description 19
- 238000010438 heat treatment Methods 0.000 claims description 13
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 12
- 229910052782 aluminium Inorganic materials 0.000 claims description 11
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical group [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 11
- 239000007789 gas Substances 0.000 claims description 11
- 239000011888 foil Substances 0.000 claims description 7
- 229960005070 ascorbic acid Drugs 0.000 claims description 6
- 235000010323 ascorbic acid Nutrition 0.000 claims description 6
- 239000011668 ascorbic acid Substances 0.000 claims description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 239000012528 membrane Substances 0.000 claims description 6
- 239000011164 primary particle Substances 0.000 claims description 6
- 239000002002 slurry Substances 0.000 claims description 6
- 239000002270 dispersing agent Substances 0.000 claims description 5
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 claims description 4
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical group CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 4
- 239000011230 binding agent Substances 0.000 claims description 4
- 239000006258 conductive agent Substances 0.000 claims description 4
- 238000000227 grinding Methods 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 4
- 239000011163 secondary particle Substances 0.000 claims description 4
- 159000000000 sodium salts Chemical class 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 229920001328 Polyvinylidene chloride Polymers 0.000 claims description 3
- 239000006230 acetylene black Substances 0.000 claims description 3
- 239000012298 atmosphere Substances 0.000 claims description 3
- 239000003365 glass fiber Substances 0.000 claims description 3
- 239000005033 polyvinylidene chloride Substances 0.000 claims description 3
- 239000010935 stainless steel Substances 0.000 claims description 3
- 229910001220 stainless steel Inorganic materials 0.000 claims description 3
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 claims description 2
- 229920000858 Cyclodextrin Polymers 0.000 claims description 2
- 229960004106 citric acid Drugs 0.000 claims description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 2
- 229920003063 hydroxymethyl cellulose Polymers 0.000 claims description 2
- 229940031574 hydroxymethyl cellulose Drugs 0.000 claims description 2
- 239000003273 ketjen black Substances 0.000 claims description 2
- 238000003475 lamination Methods 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 claims description 2
- 239000004033 plastic Substances 0.000 claims description 2
- 229920003023 plastic Polymers 0.000 claims description 2
- 239000002985 plastic film Substances 0.000 claims description 2
- 229920006255 plastic film Polymers 0.000 claims description 2
- 230000001681 protective effect Effects 0.000 claims description 2
- 230000000630 rising effect Effects 0.000 claims description 2
- HFHDHCJBZVLPGP-UHFFFAOYSA-N schardinger α-dextrin Chemical compound O1C(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(O)C2O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC2C(O)C(O)C1OC2CO HFHDHCJBZVLPGP-UHFFFAOYSA-N 0.000 claims description 2
- -1 sodium hexafluorophosphate Chemical group 0.000 claims description 2
- BAZAXWOYCMUHIX-UHFFFAOYSA-M sodium perchlorate Chemical compound [Na+].[O-]Cl(=O)(=O)=O BAZAXWOYCMUHIX-UHFFFAOYSA-M 0.000 claims description 2
- 229910001488 sodium perchlorate Inorganic materials 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims 2
- 239000000463 material Substances 0.000 abstract description 21
- 238000005516 engineering process Methods 0.000 abstract description 11
- 230000008020 evaporation Effects 0.000 abstract description 7
- 238000002425 crystallisation Methods 0.000 abstract description 6
- 230000008025 crystallization Effects 0.000 abstract description 6
- 238000005245 sintering Methods 0.000 abstract description 6
- 239000010410 layer Substances 0.000 abstract description 4
- 230000009467 reduction Effects 0.000 abstract description 4
- 239000011149 active material Substances 0.000 abstract description 3
- 230000002349 favourable effect Effects 0.000 abstract description 3
- 125000004122 cyclic group Chemical group 0.000 abstract description 2
- 238000007599 discharging Methods 0.000 abstract description 2
- 230000003628 erosive effect Effects 0.000 abstract description 2
- 239000000376 reactant Substances 0.000 abstract description 2
- 239000002344 surface layer Substances 0.000 abstract description 2
- SURQXAFEQWPFPV-UHFFFAOYSA-L iron(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O SURQXAFEQWPFPV-UHFFFAOYSA-L 0.000 description 30
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 23
- 238000002441 X-ray diffraction Methods 0.000 description 19
- 239000000243 solution Substances 0.000 description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- 238000000498 ball milling Methods 0.000 description 6
- 239000011247 coating layer Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000007790 solid phase Substances 0.000 description 6
- 238000004146 energy storage Methods 0.000 description 5
- 230000007613 environmental effect Effects 0.000 description 5
- 235000019441 ethanol Nutrition 0.000 description 5
- 238000001556 precipitation Methods 0.000 description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000000975 co-precipitation Methods 0.000 description 4
- 238000002484 cyclic voltammetry Methods 0.000 description 4
- 230000002209 hydrophobic effect Effects 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 239000010453 quartz Substances 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 238000001778 solid-state sintering Methods 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 239000010406 cathode material Substances 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 230000018044 dehydration Effects 0.000 description 3
- 238000006297 dehydration reaction Methods 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 241001274216 Naso Species 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 239000012300 argon atmosphere Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000001453 impedance spectrum Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 230000002427 irreversible effect Effects 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 238000005087 graphitization Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- DCYOBGZUOMKFPA-UHFFFAOYSA-N iron(2+);iron(3+);octadecacyanide Chemical class [Fe+2].[Fe+2].[Fe+2].[Fe+3].[Fe+3].[Fe+3].[Fe+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] DCYOBGZUOMKFPA-UHFFFAOYSA-N 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000036961 partial effect Effects 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 229920000447 polyanionic polymer Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000007738 vacuum evaporation 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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
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- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
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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
- 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
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- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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Abstract
The invention relates to an in-situ carbon-coated ferrous sodium sulfate composite positive electrode material, a preparation method and a sodium ion battery, and belongs to the technical field of sodium ion batteries. Adopts the combination technology of evaporation crystallization and in-situ carbon coating, directly uses Na 2 SO 4 、FeSO 4 ·7H 2 O and water-soluble carbon source are reactants, water is quickly evaporated in vacuum at 60-100 ℃ to naturally crystallize, and then a high-purity precursor is obtained in one step, and the precursor is firstly prepared at 200-250 DEG CPre-calcining at the temperature of between 410 and 430 ℃ for 1 to 2 hours, and calcining at the temperature of between 8 and 12 hours, and performing carbothermic reduction to obtain the porous ferrous sodium sulfate composite anode material with the surface layer provided with a uniform amorphous carbon layer. The amorphous carbon layer can inhibit excessive growth of particles in the sintering process, and can prevent further erosion of the electrolyte on the active material in the cyclic charging and discharging process. The porous structure is favorable for the permeation of electrolyte and the increase of sodium ion reactive active sites, and greatly improves the electronic and ionic conductivity of the material, thereby showing excellent rate performance and cycle performance.
Description
Technical Field
The invention relates to an in-situ carbon-coated ferrous sodium sulfate composite positive electrode material, a preparation method and a sodium ion battery, and belongs to the technical field of sodium ion batteries.
Background
The development of large scale energy storage systems (Energy Storage Systems) is critical to the use of intermittent renewable energy sources such as solar, wind, tidal, and the like.With LiFePO 4 The lithium ion battery with the (LFP) positive electrode has been explored in a wind energy and solar energy integrated energy storage system due to the advantages of long cycle life, high safety, low cost and the like. Considering the scarcity and regional distribution of lithium reserves, the existing lithium ion batteries cannot meet the explosive application of large-scale energy storage of electric automobiles and smart grids in the future. Sodium ion batteries with abundant crust elements, environmental protection and safety seem to be better substitutes for upcoming power grid scale energy storage, but the existing sodium ion battery technology cannot meet the practical application requirements yet. It is therefore an urgent need to develop sodium ion batteries with low cost, safety, environmental friendliness and long cycle life.
In sodium ion battery systems, the positive electrode material determines to a large extent the energy density and cycle life of the battery. Compared with the transition metal oxide and Prussian blue analog positive electrode material, the polyanion oxide positive electrode has high thermal stability, ultra-long cycle life and adjustable voltage, and especially the Alluaudiote sodium ferrous sulfate positive electrode material has the highest Fe 2+ /Fe 3+ Redox potential (-3.8V). Compared with other polyanionic cathode materials, the higher working voltage of the material can compensate the defect of lower specific capacity caused by larger mass of the polyanionic group, and can also provide satisfactory energy density. However, the conductivity of the sodium ferrous sulfate anode material is low, so that the dynamics of the material is slow, and the rate capability is poor; at the same time, it is sensitive to moisture and can be decomposed easily to produce SO at 450 DEG C x Gases, which limit the success of sodium ferrous sulfate positive electrode materials, are currently not fully reproducible with lithium iron phosphate (LFP).
The existing preparation method comprises the steps of preparing the sodium ferrous sulfate material by combining a high-energy mechanical ball milling technology with a low-temperature solid state sintering technology, co-precipitation and low-temperature solid state sintering technology and the like.
The FeSO must be first processed by the combination of high-energy mechanical ball milling technique and low-temperature solid state sintering 4 ·7H 2 O is dried in vacuum for 2 to 4 hours to prepare anhydrous FeSO 4 Subsequently, na is added under an inert atmosphere (mostly argon or nitrogen) 2 SO 4 And anhydrous FeSO 4 Proceeding withThe preparation method has the advantages that the steps of preparing the precursor are complicated and the energy consumption is high, the requirements on production environment and equipment are severe, meanwhile, the combination of active material particles obtained by ball milling and carbon sources is mostly in point-to-point contact, and the construction of a high-conductivity network is difficult to realize.
Coprecipitation technology and low temperature solid phase sintering technology utilize precursor Na 2 Fe(SO 4 )·4H 2 O is insoluble in hydrophobic alcohol, a large amount of hydrophobic alcohol such as absolute ethyl alcohol is used as a precipitation solution, 500-2000 mL of ethanol is needed for complete precipitation per 50-100 mL of reaction solution, the reaction solution is required to be added into the hydrophobic alcohol dropwise in the experimental process, the precipitation reaction time is long, and the mixed suspension is subjected to slow vacuum suction filtration for 1-2 hours, then dried in vacuum for more than 6 hours to obtain a precursor, and calcined at 300-400 ℃ for 8-48 hours to obtain the product. The recycling and purification of a large amount of high-purity absolute ethyl alcohol in the experimental process make the method difficult to apply on a large scale.
Disclosure of Invention
In view of the above, the invention aims to provide an in-situ carbon-coated sodium ferrous sulfate composite positive electrode material, a preparation method and a sodium ion battery. The technology of combining evaporative crystallization and in-situ carbon coating is adopted, the operation steps are simple, the experimental condition requirement is low, and Na is directly used 2 SO 4 、FeSO 4 ·7H 2 O and a water-soluble carbon source are reactants, water is quickly evaporated in vacuum at 60-100 ℃ for natural crystallization, and then a high-purity precursor can be obtained in one step, the precursor is firstly pre-calcined at 200-250 ℃ for 1-2 h, then calcined at 410-430 ℃ for 8-12 h, and the porous ferrous sodium sulfate composite anode material with a uniform amorphous carbon layer on the surface layer is obtained through carbothermal reduction. The amorphous carbon layer can inhibit excessive growth of particles in the sintering process, and can prevent further erosion of the electrolyte on the active material in the cyclic charging and discharging process. The porous structure is favorable for the permeation of electrolyte and the increase of sodium ion reactive active sites, and greatly improves the electronic and ionic conductivity of the material, thereby showing excellent rate performance and cycle performance.
In order to achieve the above purpose, the technical scheme of the invention is as follows:
the in-situ carbon coated sodium ferrous sulfate composite positive electrode material is of a porous structure, the particle size of secondary particles is 5-10 mu m, and the composite positive electrode material is formed by tightly stacking 50-80 nm primary particles; the amorphous carbon is coated on the surface of the primary particles, and the total mass of the amorphous carbon is 5-15 wt% of the total mass of the sodium ferrous sulfate composite anode material.
The invention relates to a preparation method of an in-situ carbon-coated sodium ferrous sulfate composite positive electrode material, which comprises the following steps:
(1) Preparing precursor powder by vacuum evaporation and crystallization: na is mixed with 2 SO 4 、FeSO 4 ·7H 2 Adding O and a water-soluble carbon source into deionized water, fully stirring to obtain a uniform light green solution, and then rapidly evaporating the solution at 60-100 ℃ under vacuum to obtain precursor powder;
(2) Preparing a composite positive electrode material by a two-stage solid phase calcination method: and (3) uniformly grinding the precursor powder, placing the precursor powder in a tube furnace in a protective gas atmosphere, firstly heating to 200-250 ℃ for pre-calcining for 1-2 h, then heating to 410-430 ℃ for calcining for 8-12 h, and obtaining the in-situ carbon-coated ferrous sodium sulfate composite anode material after the calcining is finished.
Preferably, in step (1), na 2 SO 4 And FeSO 4 ·7H 2 The mol ratio of O is 1:1-2.
Preferably, in the step (1), the water-soluble carbon source is one or more of ascorbic acid, citric acid, hydroxymethyl cellulose and cyclodextrin.
Preferably, in step (1), the water-soluble carbon source is mixed with FeSO 4 ·7H 2 The mol ratio of O is 1:10-100.
Preferably, in the step (2), the shielding gas is an inert gas (elemental gas corresponding to the element of group 0 in the periodic table of elements) or a mixed gas of the inert gas and hydrogen, and the volume fraction of the hydrogen in the mixed gas is 5% -10%.
Preferably, in the step (2), the temperature rising rate in the pre-calcination and the calcination process is 1-5 ℃/min respectively.
A sodium ion battery comprises a current collector, a positive plate, a negative plate, electrolyte, a diaphragm and a battery shell, and is characterized in that: the current collector is aluminum foil, the in-situ carbon-coated ferrous sodium sulfate composite positive electrode material is positive electrode, the metal sodium is negative electrode, the glass fiber filter membrane is a membrane, and the electrolyte is a soluble sodium salt organic solution.
Preferably, the sodium ion battery positive plate is obtained by uniformly mixing a positive electrode, a conductive agent, a binder and a dispersing agent to obtain slurry, and coating the slurry on an aluminum foil current collector; the sodium ion battery negative plate is obtained by mechanical lamination of metal sodium and aluminum foil; the battery shell adopts a CR2032 battery shell.
Preferably, the conductive agent is more than one of acetylene black, ketjen black and Super P; the binder is polyvinylidene chloride (PVDF); the dispersant is 1-methyl-2-pyrrolidone (NMP); the soluble sodium salt in the electrolyte is sodium hexafluorophosphate (NaPF) 6 ) Or sodium perchlorate (NaClO) 4 ) The method comprises the steps of carrying out a first treatment on the surface of the The organic solvent in the electrolyte is more than one of Ethylene Carbonate (EC), vinylene carbonate (DEC), propylene Carbonate (PC), dimethyl carbonate (DMC) and fluoroethylene carbonate (FEC); the battery shell is made of organic plastics, aluminum shells, aluminum plastic films, stainless steel or composite materials thereof.
Advantageous effects
The invention provides an in-situ carbon coated sodium ferrous sulfate composite positive electrode material, which comprises an in-situ carbon coating layer and sodium ferrous sulfate active ingredients, wherein amorphous carbon coating layer and sodium ferrous sulfate particles in the composite positive electrode material are tightly combined to form uniform porous micron particles, a sufficient conductive network is provided for electron transfer, and the multiplying power performance of the material is greatly improved; in addition, the uniform coating of the carbon coating layer improves the resistance of the material to moisture and oxygen and improves the environmental tolerance of the material. The composite material has a special porous structure, is favorable for the permeation of electrolyte and the increase of sodium ion reaction active sites, so that the physical and chemical properties of the ferrous sodium sulfate composite anode material, such as conductivity, circulation stability, environmental stability and the like, are stably improved.
The invention provides a preparation method of an in-situ carbon coated sodium ferrous sulfate composite positive electrode material, wherein secondary particles of the positive electrode material prepared by an evaporation crystallization and solid phase calcination method have a particle size of about 5-10 mu m and are formed by tightly stacking primary particles with a size of 50-80 nm; the added organic carbon sources are all water-soluble and are uniformly distributed in the precursor particles in the evaporation and crystallization process, and a continuous amorphous carbon coating layer is formed by carbothermal reduction in the subsequent solid-phase sintering process, so that further abnormal growth of the sodium ferrous sulfate crystal particles is effectively inhibited; meanwhile, the volatilization of gas and moisture generated by pyrolysis of the organic carbon source is helpful to construct a porous structure on the surface of the micron particles, which is helpful to the impregnation of electrolyte and provides rich sodium ion reactive sites for the charge and discharge process.
The invention provides a preparation method of an in-situ carbon-coated sodium ferrous sulfate composite positive electrode material, wherein vacuum rapid evaporation dehydration is carried out at 60-100 ℃ in the precursor preparation process, so that a high-purity precursor is ensured to be obtained in a short time, the evaporation temperature is strictly controlled in the process, and precursor Na is required to be strictly controlled when the evaporation temperature is 110-130 ℃ 2 Fe(SO 4 ) 2 ·4H 2 O will be converted into Na 2 Fe(SO 4 ) 2 ·2H 2 O impurity, precursor Na when evaporating temperature is above 130 DEG C 2 Fe(SO 4 ) 2 ·4H 2 O is decomposed into Na 2 Fe(SO 4 ) 2 ·H 2 O、Fe(SO 4 )·H 2 O and NaSO 4 And the like. In the solid phase calcination process, the pre-calcination at 200-250 ℃ can reduce Fe 2 O 3 、Fe 3 O 4 And the generation of the equal impurities, and then sintering at a higher temperature of 410-430 ℃ at a slow heating rate of 1-5 ℃/min, so that the pore diameter and volume of the particle surface are increased, the graphitization degree of the amorphous carbon coating layer is improved, and finally, the ferrous sodium sulfate composite material with porous surface and high conductive carbon coating is obtained, the carbon coating layers are connected with each other to form a conductive network, the conductivity of the material is effectively improved, the sensitivity of the material to moisture and oxygen is effectively reduced, and the environmental stability of the material is improved.
Unlike the combination of high energy mechanical ball milling and low temperature solid state sintering, the present invention omits the mechanical ball milling process to eliminate FeSO 4 ·7H 2 Preparation of FeSO by O vacuum dehydration 4 Can directly use FeSO 4 ·7H 2 The O aqueous solution is used as a raw material, the operation steps are simple, the bonding area of the uniform amorphous carbon coating and the active particles obtained by the method is larger, and compared with the point-to-point contact among particles obtained by a ball milling method, the method is more beneficial to constructing a high-conductivity conductive network.
Different from the coprecipitation technology and the low-temperature solid phase sintering technology, the invention omits the use of a large amount of absolute ethyl alcohol and other hydrophobic alcohols as a precipitation solution, replaces slow drop-by-drop precipitation reaction and slow suction filtration in the coprecipitation technology by utilizing vacuum rapid evaporation and dehydration, and simultaneously avoids the difficult problems of recycling and reutilizing a large amount of absolute ethyl alcohol.
Drawings
Fig. 1 is an X-ray diffraction pattern (XRD) of the precursor material prepared in example 1.
Fig. 2 is an X-ray diffraction pattern (XRD) of the sodium ferrous sulfate composite positive electrode material prepared in example 1.
Fig. 3 is a Scanning Electron Microscope (SEM) of the sodium ferrous sulfate composite cathode material prepared in example 1.
Fig. 4 is an energy spectrum (EDS) of the sodium ferrous sulfate composite cathode material prepared in example 1.
Fig. 5 is a constant current charge and discharge graph of the sodium ion battery of example 1.
Fig. 6 is a Cyclic Voltammogram (CV) of the sodium ion battery of example 1.
FIG. 7 is an Electrochemical Impedance Spectrum (EIS) of the sodium ion cell of example 1.
Fig. 8 is a charge-discharge cycle chart of the sodium ion battery of example 1 for the first 20 cycles.
Fig. 9 is an X-ray diffraction pattern (XRD) of the precursor material prepared in example 2.
Fig. 10 is a constant current charge and discharge graph of the sodium ion battery of example 2.
Fig. 11 is an X-ray diffraction pattern (XRD) of the precursor material prepared in comparative example 1.
Fig. 12 is an X-ray diffraction pattern (XRD) of the precursor material prepared in comparative example 2.
Detailed Description
The present invention will be described in further detail with reference to specific examples.
Example 1
The synthesis steps of the sodium ferrous sulfate material used in the invention are as follows: 0.8875g of anhydrous sodium sulfate (Na) 2 SO 4 ) 1.7375g of ferrous sulfate heptahydrate (FeSO) 4 ·7H 2 O), 0.11g of ascorbic acid, dissolving in 10mL of deionized water, and magnetically stirring for 30min to form a light green solution; the pale green solution was rapidly evaporated in vacuo at 80 ℃ to give a precursor powder.
And (3) after uniformly grinding the precursor powder, rapidly transferring the precursor powder into an alumina quartz boat, placing the alumina quartz boat in a tube furnace in an argon atmosphere, heating to 200 ℃ at a heating rate of 5 ℃/min, presintering for 2 hours, adjusting the heating rate to 1 ℃/min, heating to 425 ℃ and calcining for 8 hours, and obtaining the in-situ carbon-coated ferrous sodium sulfate anode material after the calcining is finished.
FIG. 1 shows the X-ray diffraction pattern (XRD) of the precursor powder described in this example, together with Na 2 Fe(SO 4 ) 2 ·4H 2 The standard card of O has high matching degree and good crystallinity. The diffraction peak (2 theta= 27.028 °) shows the highest intensity, indicating that the (120) crystal plane is the dominant crystal plane.
FIG. 2 is an X-ray diffraction (XRD) pattern of the sodium ferrous sulfate composite positive electrode material described in this example, together with an Alluaudite type Na 2.5 Fe 1.75 (SO 4 ) 3 Is matched with standard card of (2), has good crystallinity, and does not observe impurity Fe 2 O 3 And Fe (Fe) 3 O 4 Meanwhile, due to the fact that a Cu target detects a sample containing Fe, a fluorescence signal is generated, and therefore the XRD diffraction pattern is high in back.
Fig. 3 is a Scanning Electron Microscope (SEM) of a sodium ferrous sulfate positive electrode material, and it can be clearly seen that the secondary particles have a size of 5 to 10 μm and are formed by aggregation of primary particles having a size of 50 to 80nm, and the enlarged view can be seen that the surface of the material has an obvious porous structure.
Fig. 4 is an energy spectrum (EDS) of a sodium ferrous sulfate positive electrode material, which shows a uniform distribution of the main element (Na, fe, S, O) contained.
The composite positive electrode material, acetylene black (Super P) and polyvinylidene chloride (PVDF) are mixed according to the mass ratio of 80:10:10, 1-methyl-2-pyrrolidone is adopted as a dispersing agent, the materials are uniformly mixed to form slurry, and then the slurry is coated on an aluminum foil by a scraper. Vacuum drying at 120deg.C for 12 hr, cutting to obtain positive plate with diameter of 11mm, using sodium metal plate as negative electrode, using glass fiber filter membrane (Whatman GF/D) as membrane, using 1M NaClO 4 Dissolved in EC: PC (volume ratio 1:1) and 5vol% of FEC was added as electrolyte. The stainless steel shell is taken as a shell, and the CR2032 type button battery is assembled.
The sodium ion battery assembled by the above process is at room temperature (25 ℃) and 2.0-4.5V (vs. Na/Na) + ) The charge and discharge test was performed in the voltage range of (a), and the charge and discharge curves, cyclic voltammogram, electrochemical impedance spectrum and the charge and discharge curves of the first 20 cycles are shown in fig. 5, 6, 7 and 8. The median discharge voltage at 0.05C was about 3.6V, the reversible specific discharge capacity reached 60mAh/g, and the battery discharge energy density was 216Wh/kg (based on the mass of the positive electrode active material). The cyclic voltammogram shows that the first charge and discharge of the alloy has irreversible phenomenon, which is caused by irreversible migration of Fe1 site iron to Na1 site vacancy during the first charge, and the alloy has two oxidation potentials near 3.25V and 3.75V and three reduction potentials near 3.25V, 3.75V and 4.05V. At a rate of 0.1C, the specific discharge capacity reaches 55mAh/g, the specific discharge capacity of 50mAh/g is still maintained after 20 weeks of circulation (1 C=120 mA/g), and the capacity retention rate reaches 90.9%.
Example 2
The synthesis steps of the sodium ferrous sulfate composite anode material used in the invention are as follows: 0.8875g of anhydrous sodium sulfate (Na) 2 SO 4 ) 3.475g of ferrous sulfate heptahydrate (FeSO) 4 ·7H 2 O), 0.11g of ascorbic acid, dissolving in 10mL of deionized water, and magnetically stirring for 30min to form a light green transparent solution; the pale green solution was rapidly evaporated in vacuo at 100 ℃ to give a precursor powder.
And (3) after uniformly grinding the precursor powder, rapidly transferring the precursor powder into an alumina quartz boat, placing the alumina quartz boat in a tube furnace in an argon atmosphere, heating to 200 ℃ at a heating rate of 5 ℃/min, presintering for 2 hours, adjusting the heating rate to 1 ℃/min, heating to 425 ℃ and calcining for 8 hours, and obtaining the in-situ carbon-coated ferrous sodium sulfate anode material after the calcining is finished.
FIG. 9 shows an X-ray diffraction pattern (XRD) of the precursor powder of the present example, and Na 2 Fe(SO 4 ) 2 ·4H 2 Standard cards of O (PDF # 97-019-4363) match exactly.
The sodium ion battery as in example 1 was assembled using the sodium ferrous sulfate composite positive electrode material of this example, and charge and discharge tests were performed at room temperature in a voltage range of 2.0 to 4.5V, with the charge and discharge curves shown in fig. 10. The discharge median voltage at 0.05C is about 3.6V, and the specific capacity of the first-turn discharge reaches 40mAh/g (1C=120 mA/g).
Comparative example 1
The synthesis steps of the sodium ferrous sulfate composite anode precursor material used in the invention are as follows: 0.8875g of anhydrous sodium sulfate (Na) 2 SO 4 ) 3.475g of ferrous sulfate heptahydrate (FeSO 4 ·7H 2 O), 0.11g of ascorbic acid, was dissolved in 10mL of deionized water and magnetically stirred for half an hour to form a pale green transparent solution. The pale green solution was rapidly evaporated in vacuo at 110 ℃ to give a precursor powder.
FIG. 11 is an X-ray diffraction pattern (XRD) of the precursor powder of this comparative example, with Na 2 Fe(SO 4 ) 2 ·2H 2 Standard cards of O (PDF # 97-019-4362) match exactly.
Comparative example 2
The synthesis steps of the sodium ferrous sulfate composite anode precursor material used in the invention are as follows: 0.8875g of anhydrous sodium sulfate (Na) 2 SO 4 ) 1.7375g of ferrous sulfate heptahydrate (FeSO 4 ·7H 2 O), 0.11g of ascorbic acid, was dissolved in 10mL of deionized water and magnetically stirred for half an hour to form a pale green solution. The pale green solution was rapidly evaporated in vacuo at 150 ℃ to give a precursor powder.
FIG. 12 is an X-ray of the precursor powder of this comparative exampleLine diffraction pattern (XRD), from the matching result, precursor material Na 2 Fe(SO 4 ) 2 ·4H 2 O has been decomposed into Na 2 Fe(SO 4 ) 2 ·H 2 O、NaSO 4 And Fe (SO) 4 )·H 2 O, and other impurities.
In view of the foregoing, it will be appreciated that the invention includes but is not limited to the foregoing embodiments, any equivalent or partial modification made within the spirit and principles of the invention.
Claims (10)
1. A preparation method of an in-situ carbon-coated ferrous sodium sulfate composite positive electrode material is characterized by comprising the following steps of: the method comprises the following steps:
(1) Na is mixed with 2 SO 4 、FeSO 4 ·7H 2 Adding O and a water-soluble carbon source into deionized water, fully stirring to obtain a uniform light green solution, and then rapidly evaporating the solution at 60-100 ℃ under vacuum to obtain precursor powder;
(2) And (3) uniformly grinding the precursor powder, placing the precursor powder in a tube furnace in a protective gas atmosphere, firstly heating to 200-250 ℃ for pre-calcining for 1-2 h, then heating to 410-430 ℃ for calcining for 8-12 h, and obtaining the in-situ carbon-coated ferrous sodium sulfate composite anode material after the calcining is finished.
2. The method for preparing the in-situ carbon-coated sodium ferrous sulfate composite positive electrode material according to claim 1, which is characterized by comprising the following steps: in step (1), na 2 SO 4 And FeSO 4 ·7H 2 The mol ratio of O is 1:1-2.
3. The method for preparing the in-situ carbon-coated sodium ferrous sulfate composite positive electrode material according to claim 1, which is characterized by comprising the following steps: in the step (1), the water-soluble carbon source is one or more of ascorbic acid, citric acid, hydroxymethyl cellulose and cyclodextrin.
4. An in situ carbon coated sulfuric acid as defined in claim 1The preparation method of the ferrous sodium composite anode material is characterized by comprising the following steps of: the water-soluble carbon source and FeSO 4 ·7H 2 The mol ratio of O is 1:10-100.
5. The method for preparing the in-situ carbon-coated sodium ferrous sulfate composite positive electrode material according to claim 1, which is characterized by comprising the following steps: in the step (2), the shielding gas is inert gas or mixed gas of inert gas and hydrogen; in the mixed gas, the volume fraction of the hydrogen is 5-10%.
6. The method for preparing the in-situ carbon-coated sodium ferrous sulfate composite positive electrode material according to claim 1, which is characterized by comprising the following steps: in the step (2), the temperature rising rate in the pre-calcination and the calcination process is respectively 1-5 ℃/min.
7. An in-situ carbon coated ferrous sodium sulfate composite positive electrode material is characterized in that: the composite positive electrode material is prepared by the method of any one of claims 1 to 6; the composite positive electrode material is of a porous structure, the particle size of the secondary particles is 5-10 mu m, and the composite positive electrode material is formed by tightly stacking primary particles of 50-80 nm; the amorphous carbon is coated on the surface of the primary particles, and the total mass of the amorphous carbon is 5-15 wt% of the total mass of the sodium ferrous sulfate composite anode material.
8. A sodium ion battery comprises a current collector, a positive plate, a negative plate, electrolyte, a diaphragm and a battery shell, and is characterized in that: the current collector is aluminum foil, the in-situ carbon-coated ferrous sodium sulfate composite positive electrode material is positive electrode, the metal sodium is negative electrode, the glass fiber filter membrane is a membrane, and the electrolyte is a soluble sodium salt organic solution.
9. A sodium ion battery as defined in claim 8, wherein: the sodium ion battery positive plate is obtained by uniformly mixing a positive electrode, a conductive agent, a binder and a dispersing agent to obtain slurry, and coating the slurry on an aluminum foil current collector; the sodium ion battery negative plate is obtained by mechanical lamination of metal sodium and aluminum foil; the battery shell adopts a CR2032 battery shell.
10. A sodium ion battery as defined in claim 9, wherein: the conductive agent is more than one of acetylene black, ketjen black and Super P; the binder is polyvinylidene chloride; the dispersing agent is 1-methyl-2-pyrrolidone; the soluble sodium salt in the electrolyte is sodium hexafluorophosphate or sodium perchlorate; the organic solvent in the electrolyte is more than one of ethylene carbonate, vinylene carbonate, propylene carbonate, dimethyl carbonate and fluoroethylene carbonate; the battery shell is made of organic plastics, aluminum shells, aluminum plastic films, stainless steel or composite materials thereof.
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