CN117476858A - Modified sodium ferric sulfate positive electrode material and preparation method and application thereof - Google Patents
Modified sodium ferric sulfate positive electrode material and preparation method and application thereof Download PDFInfo
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- CN117476858A CN117476858A CN202311420109.6A CN202311420109A CN117476858A CN 117476858 A CN117476858 A CN 117476858A CN 202311420109 A CN202311420109 A CN 202311420109A CN 117476858 A CN117476858 A CN 117476858A
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- sulfate
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- cerium oxide
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- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 23
- -1 Modified sodium ferric sulfate Chemical class 0.000 title claims description 4
- 229910000360 iron(III) sulfate Inorganic materials 0.000 title description 2
- 238000010438 heat treatment Methods 0.000 claims abstract description 74
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims abstract description 72
- 229910052938 sodium sulfate Inorganic materials 0.000 claims abstract description 72
- 235000011152 sodium sulphate Nutrition 0.000 claims abstract description 72
- 235000003891 ferrous sulphate Nutrition 0.000 claims abstract description 68
- 239000011790 ferrous sulphate Substances 0.000 claims abstract description 68
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims abstract description 68
- 229910000420 cerium oxide Inorganic materials 0.000 claims abstract description 66
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims abstract description 66
- 239000002096 quantum dot Substances 0.000 claims abstract description 66
- 238000003756 stirring Methods 0.000 claims abstract description 66
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 52
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 42
- 239000000463 material Substances 0.000 claims abstract description 42
- 238000002156 mixing Methods 0.000 claims abstract description 41
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims abstract description 40
- 229910001887 tin oxide Inorganic materials 0.000 claims abstract description 40
- 150000001721 carbon Chemical class 0.000 claims abstract description 38
- 238000009210 therapy by ultrasound Methods 0.000 claims abstract description 34
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 32
- YPPMLCHGJUMYPZ-UHFFFAOYSA-L sodium;iron(2+);sulfate Chemical class [Na+].[Fe+2].[O-]S([O-])(=O)=O YPPMLCHGJUMYPZ-UHFFFAOYSA-L 0.000 claims abstract description 32
- 238000001354 calcination Methods 0.000 claims abstract description 27
- 239000000843 powder Substances 0.000 claims abstract description 27
- 239000000126 substance Substances 0.000 claims abstract description 27
- 239000002086 nanomaterial Substances 0.000 claims abstract description 24
- 238000000227 grinding Methods 0.000 claims abstract description 22
- 229910001415 sodium ion Inorganic materials 0.000 claims abstract description 22
- 238000000137 annealing Methods 0.000 claims abstract description 21
- 239000010405 anode material Substances 0.000 claims abstract description 21
- 238000001035 drying Methods 0.000 claims abstract description 17
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 15
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000011737 fluorine Substances 0.000 claims abstract description 14
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 14
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 12
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 12
- 239000008139 complexing agent Substances 0.000 claims abstract description 12
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims abstract description 8
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims abstract 10
- 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 46
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 28
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 24
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 23
- 239000003109 Disodium ethylene diamine tetraacetate Substances 0.000 claims description 23
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 23
- 229960005070 ascorbic acid Drugs 0.000 claims description 23
- 235000010323 ascorbic acid Nutrition 0.000 claims description 23
- 239000011668 ascorbic acid Substances 0.000 claims description 23
- 235000019301 disodium ethylene diamine tetraacetate Nutrition 0.000 claims description 23
- 238000004108 freeze drying Methods 0.000 claims description 16
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 14
- 229910052750 molybdenum Inorganic materials 0.000 claims description 14
- 239000011733 molybdenum Substances 0.000 claims description 14
- 239000007864 aqueous solution Substances 0.000 claims description 13
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 12
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 12
- 239000002041 carbon nanotube Substances 0.000 claims description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims description 12
- 235000006708 antioxidants Nutrition 0.000 claims description 11
- 229910001448 ferrous ion Inorganic materials 0.000 claims description 11
- 238000007873 sieving Methods 0.000 claims description 11
- CIWBSHSKHKDKBQ-DUZGATOHSA-N D-isoascorbic acid Chemical compound OC[C@@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-DUZGATOHSA-N 0.000 claims description 10
- VGBWDOLBWVJTRZ-UHFFFAOYSA-K cerium(3+);triacetate Chemical compound [Ce+3].CC([O-])=O.CC([O-])=O.CC([O-])=O VGBWDOLBWVJTRZ-UHFFFAOYSA-K 0.000 claims description 10
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 8
- 239000012298 atmosphere Substances 0.000 claims description 8
- 229910052684 Cerium Inorganic materials 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 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
- 239000001257 hydrogen Substances 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 239000000243 solution Substances 0.000 claims description 6
- 229920002125 Sokalan® Polymers 0.000 claims description 5
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 5
- 229910052787 antimony Inorganic materials 0.000 claims description 5
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 5
- 239000004584 polyacrylic acid Substances 0.000 claims description 5
- 229910052715 tantalum Inorganic materials 0.000 claims description 5
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 5
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 5
- 229910052721 tungsten Inorganic materials 0.000 claims description 5
- 239000010937 tungsten Substances 0.000 claims description 5
- RGHNJXZEOKUKBD-SQOUGZDYSA-N D-gluconic acid Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 claims description 4
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 4
- WTDHULULXKLSOZ-UHFFFAOYSA-N Hydroxylamine hydrochloride Chemical compound Cl.ON WTDHULULXKLSOZ-UHFFFAOYSA-N 0.000 claims description 4
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 4
- 230000001681 protective effect Effects 0.000 claims description 4
- 239000006230 acetylene black Substances 0.000 claims description 3
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 2
- RGHNJXZEOKUKBD-UHFFFAOYSA-N D-gluconic acid Natural products OCC(O)C(O)C(O)C(O)C(O)=O RGHNJXZEOKUKBD-UHFFFAOYSA-N 0.000 claims description 2
- DBVJJBKOTRCVKF-UHFFFAOYSA-N Etidronic acid Chemical compound OP(=O)(O)C(O)(C)P(O)(O)=O DBVJJBKOTRCVKF-UHFFFAOYSA-N 0.000 claims description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 2
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 2
- 239000004917 carbon fiber Substances 0.000 claims description 2
- DLNAGPYXDXKSDK-UHFFFAOYSA-K cerium(3+);2-hydroxypropane-1,2,3-tricarboxylate Chemical compound [Ce+3].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O DLNAGPYXDXKSDK-UHFFFAOYSA-K 0.000 claims description 2
- JITPFBSJZPOLGT-UHFFFAOYSA-N cerium(3+);propan-2-olate Chemical compound [Ce+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] JITPFBSJZPOLGT-UHFFFAOYSA-N 0.000 claims description 2
- UADULFIZHZKEOP-UHFFFAOYSA-K cerium(3+);triformate Chemical compound [Ce+3].[O-]C=O.[O-]C=O.[O-]C=O UADULFIZHZKEOP-UHFFFAOYSA-K 0.000 claims description 2
- 235000015165 citric acid Nutrition 0.000 claims description 2
- 239000002019 doping agent Substances 0.000 claims description 2
- 235000019000 fluorine Nutrition 0.000 claims description 2
- 239000000174 gluconic acid Substances 0.000 claims description 2
- 235000012208 gluconic acid Nutrition 0.000 claims description 2
- 239000008103 glucose Substances 0.000 claims description 2
- 229910021389 graphene Inorganic materials 0.000 claims description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 2
- 239000002245 particle Substances 0.000 abstract description 7
- 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 76
- 239000007788 liquid Substances 0.000 description 24
- 239000002243 precursor Substances 0.000 description 17
- 239000012300 argon atmosphere Substances 0.000 description 13
- 239000011734 sodium Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 238000001816 cooling Methods 0.000 description 9
- XZUAPPXGIFNDRA-UHFFFAOYSA-N ethane-1,2-diamine;hydrate Chemical compound O.NCCN XZUAPPXGIFNDRA-UHFFFAOYSA-N 0.000 description 8
- 238000001704 evaporation Methods 0.000 description 8
- 229910052708 sodium Inorganic materials 0.000 description 8
- 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 7
- 239000003792 electrolyte Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 229960001484 edetic acid Drugs 0.000 description 4
- 238000009792 diffusion process Methods 0.000 description 3
- 235000019441 ethanol Nutrition 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 2
- DRVWBEJJZZTIGJ-UHFFFAOYSA-N cerium(3+);oxygen(2-) Chemical class [O-2].[O-2].[O-2].[Ce+3].[Ce+3] DRVWBEJJZZTIGJ-UHFFFAOYSA-N 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
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- 239000002033 PVDF binder Substances 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
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- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000009790 rate-determining step (RDS) Methods 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000009777 vacuum freeze-drying Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/04—Processes of manufacture in general
- H01M4/0402—Methods of deposition of the material
- H01M4/0416—Methods of deposition of the material involving impregnation with a solution, dispersion, paste or dry powder
-
- 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
- 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
- H01M4/1397—Processes of manufacture of electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
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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
- H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
-
- 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
- H01M4/581—Chalcogenides or intercalation compounds thereof
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Composite Materials (AREA)
- Dispersion Chemistry (AREA)
- Materials Engineering (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention belongs to the technical field of sodium ion batteries, and particularly relates to a modified sodium iron sulfate positive electrode material, a preparation method and application thereof. The preparation method provided by the invention comprises the following steps: 1) Mixing cerium oxide quantum dot powder, a carbon source and a solution, performing ultrasonic treatment, drying, calcining and grinding to obtain a cerium oxide quantum dot modified carbon material; 2) Mixing sodium sulfate, ferrous sulfate, a fluorine source, an antioxidant, a complexing agent, the cerium oxide quantum dot modified carbon material obtained in the step 1), the doped tin oxide nano material and water, stirring, and performing heat treatment to obtain a gel substance; 3) And (3) annealing the gel substance obtained in the step (2) to obtain the modified sodium iron sulfate anode material. The material prepared by the invention has the advantages of good particle consistency, stable structure, strong conductivity, excellent electrochemical performance and the like.
Description
Technical Field
The invention belongs to the technical field of sodium ion batteries, and particularly relates to a modified sodium iron sulfate positive electrode material, a preparation method and application thereof.
Background
Sodium Ion Batteries (SiBs) are one of the most promising next generation energy storage technologies, with new opportunities due to their abundant Na reserves and their distribution throughout the world. The positive electrode material of the sodium ion battery overcomes the limitation of raw materials and cost, and has the advantages of abundant resources, long service life and the like due to high voltage (> 3.6V vs Na+/Na, namely the potential difference of sodium ions to metal sodium > 3.6V). In this regard, alluviation rock-type iron-based sulfates (e.g., sodium iron sulfate materials) are considered promising candidates for positive electrode active materials due to their abundant resources, high voltage (3.8V vs na+/Na, i.e., a sodium ion to sodium metal potential difference of 3.8V), and robust polyanionic frameworks.
However, the large band gap of the sodium iron sulfate material prevents rapid transfer of carriers (na+ and electrons) and reaction kinetics, resulting in poor cycle reversibility and rate capability of the battery. In addition, the electrolyte in the electrolyte solution undergoes severe oxidative decomposition at high voltages, resulting in the formation of a solid mesophase, the catholyte mesophase (CEI), which affects the insertion of na+ from the solvated phase to the solid phase, thus constituting an additional rate limiting step for most cathodes.
In the prior art, a micro-nano technology is generally adopted, material particles are controlled to be in a micro-nano size to reduce the migration distance of ions so as to enhance the rate capability of the material, but the measure is solvated with electrolyte in the high-voltage charge-discharge process, so that metal ions are dissolved out, and the electrochemical performance of the material is affected. Aiming at the problem of poor conductivity of the ferrous sodium sulfate anode material, carbon coating or nitrogen-doped carbon coating is mostly adopted in the prior art to improve the electronic conductivity of the material, and the electrochemical properties of the carbon-coated anode material have larger difference due to various preparation processes, so that the stability is poor, and the overall electrochemical performance improvement is limited.
Disclosure of Invention
Therefore, the technical problem to be solved by the invention is to overcome the defect that the carbon-coated sodium iron sulfate positive electrode material prepared by the prior art is poor in multiplying power performance and cycle stability, so as to provide a modified sodium iron sulfate positive electrode material, and a preparation method and application thereof.
The invention provides a preparation method of a modified sodium iron sulfate positive electrode material, which comprises the following steps:
1) Mixing cerium oxide quantum dot powder, a carbon source and a solution, performing ultrasonic treatment, drying, calcining and grinding to obtain a cerium oxide quantum dot modified carbon material;
2) Mixing sodium sulfate, ferrous sulfate, a fluorine source, an antioxidant, a complexing agent, the cerium oxide quantum dot modified carbon material obtained in the step 1), the doped tin oxide nano material and water, stirring, and performing heat treatment to obtain a gel substance;
3) And (3) annealing the gel substance obtained in the step (2) to obtain the modified sodium iron sulfate anode material.
Preferably, the preparation step of the cerium oxide quantum dot powder in step 1) includes: carrying out ultrasonic treatment, freeze drying and heat treatment on the cerium source aqueous solution to obtain cerium oxide quantum dot powder;
preferably, the aqueous solution of cerium source is at least one selected from cerium acetate, cerium isopropoxide, cerium citrate and cerium formate;
preferably, the molar concentration of the cerium source aqueous solution is 0.01-0.2mol/L;
preferably, the ultrasonic power is 0.3-1.0W/cm 2 The ultrasonic time is 0.5-5h;
preferably, the freeze-drying temperature is-115+/-35 ℃ and the freeze-drying time is 5-20 hours;
preferably, the heat treatment temperature is 300-450 ℃, and the heat treatment time is 1-10h;
optionally, the freeze drying step is preceded by a standing step, wherein the standing time is 1-10h.
Alternatively, the invention uses vacuum freeze drying.
Preferably, the solution in step 1) comprises water and ethanol;
mixing cerium oxide quantum dot powder, ethanol and water to perform first ultrasonic treatment, and then adding a carbon source to perform second ultrasonic treatment;
the mass ratio of the cerium oxide quantum dot powder to water to the carbon source is (0.1-10): 100: (1-20);
the volume ratio of the ethanol to the water is (1-5): 1, a step of;
the first ultrasonic power is 0.5-1.0W/cm 2 The first ultrasonic time is 0.5-5h;
the second ultrasonic power is 0.3-0.8W/cm 2 The second ultrasonic time is 0.5-5h;
preferably, the carbon source in the step 1) is at least one selected from carbon fiber, carbon nanotube, graphene oxide, acetylene black and glucose;
the drying temperature in the step 1) is 70-110 ℃, and the drying time is 5-15h;
the dry atmosphere in the step 1) is at least one selected from nitrogen, argon and hydrogen;
the calcination temperature is 350-450 ℃, and the calcination time is 1-5h;
optionally, the calcination heating rate is 1-5 ℃/min;
the drying step in the step 1) is preceded by a stirring step; the stirring speed is 500-5000 rpm, and the stirring time is 1-5h;
the calcination step in step 1) is preceded by a grinding step.
Preferably, in the step 2), sodium sulfate, ferrous sulfate, a fluorine source, an antioxidant, a complexing agent and water are mixed, and then the cerium oxide quantum dot modified carbon material obtained in the step 1) and the doped tin oxide nano material are added for mixing;
the molar ratio of sodium sulfate, ferrous sulfate and fluoride ions in the fluoride source in step 2) is (2.0-3.0): (1.5-2.0): (0.01-0.2);
the molar ratio of the total mole of sodium ions in the sodium sulfate and ferrous ions in the ferrous sulfate to the complexing agent is 1: (1.1-1.5);
the mole ratio of the antioxidant to the ferrous sulfate is (0.1-1.5): 1, a step of;
the addition amount of the cerium oxide quantum dot modified carbon material is 1-15% of the total mass of sodium sulfate and ferrous sulfate;
the addition amount of the doped tin oxide material is 0.1-10% of the total mass of sodium sulfate and ferrous sulfate;
preferably, the addition amount of the doped tin oxide material is 1-5% of the total mass of sodium sulfate and ferrous sulfate.
Preferably, the water in the step 2) is added in an amount which is 1.5 to 4.5 times of the total mass of sodium sulfate, ferrous sulfate, fluorine source, antioxidant and complexing agent;
the doped tin oxide material in the step 2) is at least one selected from antimony doped tin oxide, tantalum doped tin oxide, tungsten doped tin oxide and molybdenum doped tin oxide;
the doped tin oxide material is a nano material;
the content of the dopant in the doped tin oxide material is 0.05-0.20mol%;
the complexing agent in the step 2) is at least one selected from ethylenediamine tetraacetic acid, disodium ethylenediamine tetraacetate, citric acid, gluconic acid, hydroxyethylidene-1, 1-diphosphonic acid, polyacrylic acid and tetrathiodioxyformic acid;
the antioxidant is at least one selected from ascorbic acid, D-isoascorbic acid, thiourea, hydroxylamine hydrochloride, pyrrole and hydroquinone;
the fluorine source in step 2) is selected from ammonium fluoride.
The specific choices of the sodium sulfate and the ferrous sulfate are not particularly limited, and may be anhydrous or hydrate.
Preferably, in the step 2), the stirring is 300-3000 rpm, and the stirring time is 1-5h;
optionally, stirring at 10-40deg.C;
the heating treatment includes a first heating treatment and a second heating treatment;
the temperature of the first heating treatment is 75-90 ℃, the stirring speed of the first heating treatment is 1000-2500 rpm, and the time of the first heating treatment is 1-3h;
the temperature of the second heating treatment is 95-110 ℃, the stirring speed of the second heating treatment is 500-1000 rpm, and the time of the second heating treatment is 0.5-5h.
The present invention is subjected to a second heat treatment to slowly evaporate the water until a viscous gel mass is formed.
Preferably, the annealing temperature in the step 3) is 320-380 ℃, and the annealing time is 6-12h;
the annealing is carried out under a protective atmosphere;
the protective atmosphere is at least one selected from nitrogen, argon and hydrogen;
and step 3), the annealing is finished, and the method further comprises a crushing and sieving treatment step.
The invention provides a modified sodium iron sulfate positive electrode material, which is prepared by the preparation method.
The invention also provides application of the modified sodium iron sulfate anode material prepared by the preparation method in the anode material of the sodium ion battery.
The technical scheme of the invention has the following advantages:
the preparation method of the modified sodium iron sulfate positive electrode material provided by the invention comprises the following steps: 1) Mixing cerium oxide quantum dot powder, a carbon source and a solution, performing ultrasonic treatment, drying, calcining and grinding to obtain a cerium oxide quantum dot modified carbon material; 2) Mixing sodium sulfate, ferrous sulfate, a fluorine source, an antioxidant, a complexing agent, the cerium oxide quantum dot modified carbon material obtained in the step 1), the doped tin oxide nano material and water, stirring, and performing heat treatment to obtain a gel substance; 3) And (3) annealing the gel substance obtained in the step (2) to obtain the modified sodium iron sulfate anode material. On one hand, the fluorine element is adopted for anion doping, and the electronegativity of the fluorine element is higher, so that the binding energy of the fluorine element to metal ions is stronger, the structural stability of the material is enhanced, the reversibility of phase change of the material under high voltage is improved, the dissolution of the metal ions is inhibited, the attenuation of a voltage platform is relieved, and the cycling stability of the material is enhanced; and the fluorine doping can reduce the diffusion barrier of sodium ions, improve the diffusion coefficient and be beneficial to the deintercalation diffusion kinetics of sodium ions and the multiplying power performance of the material. On the other hand, the carbon material is modified by adopting cerium oxide quantum dots, and the cerium oxide quantum dots can be uniformly embedded in the carbon material and on the surface of the carbon material after the simple treatment due to the tiny size, so that a faster charge conduction network is formed, and the conductivity of the carbon material is further improved; coating the anode material by using a doped tin oxide nano material and a cerium oxide quantum dot modified carbon material, wherein the doped tin oxide nano material and the cerium oxide quantum dot modified carbon material are cooperatively embedded into sodium ferrous sulfate anode material particles and form a coating layer on the surface, and the formed composite material forms a composite three-dimensional conductive network inside sodium ferrous sulfate particles, on the surfaces of the particles and among the particles, so that the conductivity of the sodium ferrous sulfate material is cooperatively enhanced, the air stability of the material is improved, the corrosion of electrolyte to the anode material is avoided, the stability of the electrolyte under high voltage is improved, the oxidative decomposition of the electrolyte on the surfaces of the sodium ferrous sulfate material is prevented, and the prepared sodium ferrous sulfate material has excellent multiplying power performance and cycle stability; in addition, the invention adopts a sol-gel method to disperse the raw materials into components with uniform size so as to achieve better mixing uniformity, so that the element doping and in-situ carbon coating are more uniform, the material structure is well embedded, and the electrochemical performance of the material is further improved. The material prepared by the invention has the advantages of good particle consistency, stable structure, strong conductivity, excellent multiplying power performance and cycle stability, and the like, and has good chemical properties.
The invention has the advantages of simple synthesis method, short operation flow and low processing cost, and can directly use the hydrate (such as FeSO) 4 ·7H 2 O), unnecessary dehydration steps are reduced, and production cost is reduced.
Detailed Description
The following examples are provided for a better understanding of the present invention and are not limited to the preferred embodiments described herein, but are not intended to limit the scope of the invention, any product which is the same or similar to the present invention, whether in light of the present teachings or in combination with other prior art features, falls within the scope of the present invention.
The specific experimental procedures or conditions are not noted in the examples and may be followed by the operations or conditions of conventional experimental procedures described in the literature in this field. The reagents or apparatus used were conventional reagent products commercially available without the manufacturer's knowledge.
Example 1
The embodiment provides a preparation method of a modified sodium iron sulfate positive electrode material, which comprises the following steps:
1) 0.03mol/L aqueous solution of cerium acetate 0.8W/cm 2 Ultrasonic treating at-120deg.C for 1 hr, standing for 5 hr to obtain uniformly dispersed liquid, rapidly cooling the liquid in liquid nitrogen, freeze drying at-120deg.C under vacuum for 10 hr, heat treating to obtain cerium oxide quantum dot powder, heat treating at 350deg.C for 3 hr, mixing 5g cerium oxide quantum dot powder, 1500ml anhydrous alcohol and 500ml water, and mixing 0.8W/cm 2 Ultrasonic treatment under power for 30min to disperse uniformly, adding 100g carbon nanotube, and continuing 0.5W/cm 2 Ultrasonic for 30min under power, placing into stirrer after ultrasonic treatment, and stirring for 3 hr with magnetic stirrer at stirring speedDrying for 10 hours at 80 ℃ under argon atmosphere after stirring is finished at 3000 rpm, grinding to obtain a precursor, placing the precursor in a crucible with a cover, feeding the crucible into a muffle furnace, calcining for 2 hours at 400 ℃, calcining at a heating rate of 3 ℃/min, taking out the precursor after cooling to room temperature, and grinding to obtain the cerium oxide quantum dot modified carbon material;
2) Mixing sodium sulfate, ferrous sulfate heptahydrate, ammonium fluoride, ascorbic acid, disodium ethylenediamine tetraacetate and water, wherein the molar ratio of the sodium sulfate to the ferrous sulfate heptahydrate to the ammonium fluoride is 2.5:1.75:0.02, the molar ratio of the total mole of sodium ions in sodium sulfate and ferrous ions in the ferrous sulfate to disodium ethylenediamine tetraacetate being 1:1.2, molar ratio of ascorbic acid to ferrous sulfate of 1.1:1, adding water with the addition amount of 2.5 times of the total mass of sodium sulfate, ferrous sulfate, ammonium fluoride, ascorbic acid and disodium ethylenediamine tetraacetate, adding the cerium oxide quantum dot modified carbon material obtained in the step 1) and the molybdenum doped tin oxide nano material (the molybdenum doped content is 0.1 mol%) for mixing, wherein the addition amount of the cerium oxide quantum dot modified carbon material is 10% of the total mass of sodium sulfate and ferrous sulfate, the addition amount of the molybdenum doped tin oxide nano material is 3% of the total mass of sodium sulfate and ferrous sulfate, stirring and dissolving for 1h at room temperature at 1000 r/min, performing first heating treatment at 85 ℃ for 2h, the stirring rotation speed of the first heating treatment is 1200 r/min, then performing second heating treatment at 100 ℃ at 800 r/min, the second heating treatment time is 1h, and slowly evaporating water to obtain a viscous gel substance;
3) And (3) placing the gel substance obtained in the step (2) in a crucible, annealing for 8 hours in an argon atmosphere at 350 ℃, crushing, and sieving to obtain the modified sodium iron sulfate anode material.
Example 2
The embodiment provides a preparation method of a modified sodium iron sulfate positive electrode material, which comprises the following steps:
1) 0.03mol/L aqueous solution of cerium acetate 0.8W/cm 2 Ultrasonic treatment under power for 1 hr, standing for 5 hr to obtain uniformly dispersed liquid, rapidly cooling the liquid in liquid nitrogen, freeze drying at-120deg.C under vacuum for 10 hr, and heat treating to obtain cerium oxide quantum dot powderThe heat treatment temperature is 350 ℃, the heat treatment time is 3 hours, 5g cerium oxide quantum dot powder, 1500ml absolute ethyl alcohol and 500ml water are mixed, and the concentration is 0.8W/cm 2 Ultrasonic treatment under power for 30min to disperse uniformly, adding 100g carbon nanotube, and continuing 0.5W/cm 2 Ultrasonic treatment is carried out for 30min under power, a stirrer is placed on a magnetic stirrer for stirring for 3h after the ultrasonic treatment is finished, the stirring rotating speed is 3000 r/min, the stirring is finished, the drying is carried out for 10h under the argon atmosphere at 80 ℃, the precursor is obtained after grinding, the precursor is placed in a crucible with a cover, the crucible is sent into a muffle furnace, the calcination is carried out for 2h at 400 ℃, the calcination heating rate is 3 ℃ per min, the material is taken out after the material is cooled to room temperature, and the cerium oxide quantum dot modified carbon material is obtained after grinding;
2) Mixing sodium sulfate, ferrous sulfate heptahydrate, ammonium fluoride, ascorbic acid, disodium ethylenediamine tetraacetate and water, wherein the molar ratio of the sodium sulfate to the ferrous sulfate heptahydrate to the ammonium fluoride is 2.5:1.75:0.08, the molar ratio of the total mole of sodium ions in sodium sulfate and ferrous ions in the ferrous sulfate to disodium ethylenediamine tetraacetate is 1:1.2, molar ratio of ascorbic acid to ferrous sulfate of 1.1:1, adding water with the addition amount of 2.5 times of the total mass of sodium sulfate, ferrous sulfate, ammonium fluoride, ascorbic acid and disodium ethylenediamine tetraacetate, adding the cerium oxide quantum dot modified carbon material obtained in the step 1) and the tungsten doped tin oxide nano material (the content of doped tungsten is 0.1 mol%) for mixing, wherein the addition amount of the cerium oxide quantum dot modified carbon material is 10% of the total mass of sodium sulfate and ferrous sulfate, the addition amount of the tungsten doped tin oxide nano material is 3% of the total mass of sodium sulfate and ferrous sulfate, stirring and dissolving for 1h at room temperature at 1000 r/min, carrying out first heating treatment at 85 ℃ for 2h, the stirring rotation speed of the first heating treatment is 1200 r/min, then carrying out second heating treatment at 100 ℃ at 800 r/min, the second heating treatment time is 2h, and slowly evaporating water to obtain a viscous gel substance;
3) And (3) placing the gel substance obtained in the step (2) in a crucible, annealing for 8 hours in an argon atmosphere at 350 ℃, crushing, and sieving to obtain the modified sodium iron sulfate anode material.
Example 3
1) 0.03mol/L aqueous solution of cerium acetate 0.8W/cm 2 Ultrasonic treating at-120deg.C for 1 hr, standing for 5 hr to obtain uniformly dispersed liquid, rapidly cooling the liquid in liquid nitrogen, freeze drying at-120deg.C under vacuum for 10 hr, heat treating to obtain cerium oxide quantum dot powder, heat treating at 350deg.C for 3 hr, mixing 15g cerium oxide quantum dot powder, 1500ml anhydrous alcohol and 500ml water, and mixing at 0.8W/cm 2 Ultrasonic treatment under power for 30min to disperse uniformly, adding 100g carbon nanotube, and continuing 0.5W/cm 2 Ultrasonic treatment is carried out for 30min under power, a stirrer is placed on a magnetic stirrer for stirring for 3h after the ultrasonic treatment is finished, the stirring rotating speed is 3000 r/min, the stirring is finished, the drying is carried out for 10h under the argon atmosphere at 80 ℃, the precursor is obtained after grinding, the precursor is placed in a crucible with a cover, the crucible is sent into a muffle furnace, the calcination is carried out for 2h at 400 ℃, the calcination heating rate is 3 ℃ per min, the material is taken out after the material is cooled to room temperature, and the cerium oxide quantum dot modified carbon material is obtained after grinding;
2) Mixing sodium sulfate, ferrous sulfate heptahydrate, ammonium fluoride, ascorbic acid, disodium ethylenediamine tetraacetate and water, wherein the molar ratio of the sodium sulfate to the ferrous sulfate heptahydrate to the ammonium fluoride is 2.5:1.75:0.02, the molar ratio of the total mole of sodium ions in sodium sulfate and ferrous ions in the ferrous sulfate to disodium ethylenediamine tetraacetate being 1:1.2, molar ratio of ascorbic acid to ferrous sulfate of 1.1:1, adding water with the addition amount of 2.5 times of the total mass of sodium sulfate, ferrous sulfate, ammonium fluoride, ascorbic acid and disodium ethylenediamine tetraacetate, adding the cerium oxide quantum dot modified carbon material obtained in the step 1) and the molybdenum doped tin oxide nano material (the molybdenum doped content is 0.1 mol%) for mixing, wherein the addition amount of the cerium oxide quantum dot modified carbon material is 10% of the total mass of sodium sulfate and ferrous sulfate, the addition amount of the molybdenum doped tin oxide nano material is 3% of the total mass of sodium sulfate and ferrous sulfate, stirring and dissolving for 1h at room temperature at 3000 r/min, carrying out first heating treatment at 85 ℃ for 2h, the stirring rotation speed of the first heating treatment is 1200 r/min, then carrying out second heating treatment at 100 ℃ and the stirring rotation speed of 1200 r/min, the second heating treatment time is 0.5h, and slowly evaporating water to obtain a sticky gel substance;
3) And (3) placing the gel substance obtained in the step (2) in a crucible, annealing for 8 hours in an argon atmosphere at 350 ℃, crushing, and sieving to obtain the modified sodium iron sulfate anode material.
Example 4
1) 0.01mol/L aqueous solution of cerium acetate 0.3W/cm 2 Ultrasonic treating at-120deg.C for 0.5 hr, standing for 1 hr to obtain uniformly dispersed liquid, rapidly cooling the above liquid in liquid nitrogen, freeze drying at-120deg.C under vacuum for 5 hr, heat treating to obtain cerium oxide quantum dot powder, heat treating at 300deg.C for 1 hr, mixing 1g cerium oxide quantum dot powder, 1500ml anhydrous ethanol and 500ml water, and mixing 0.3W/cm 2 Ultrasonic treatment is carried out for 30min under power to lead the mixture to be evenly dispersed, and then 100g of acetylene black is added to continue 0.3W/cm 2 Ultrasonic treatment is carried out for 30min under power, a stirrer is placed on a magnetic stirrer for stirring for 1h after the ultrasonic treatment is finished, the stirring rotating speed is 500 r/min, the stirring is finished, the drying is carried out for 5h under the nitrogen atmosphere at 70 ℃, the precursor is obtained after grinding, the precursor is placed in a crucible with a cover, the crucible with the cover is sent into a muffle furnace, the calcination is carried out for 1h at 350 ℃, the calcination heating rate is 1 ℃/min, the material is taken out after the material is cooled to room temperature, and the cerium oxide quantum dot modified carbon material is obtained after grinding;
2) Mixing sodium sulfate, ferrous sulfate heptahydrate, ammonium fluoride, thiourea, ethylene diamine tetraacetic acid and water, wherein the molar ratio of the sodium sulfate to the ferrous sulfate heptahydrate to the ammonium fluoride is 2.0:2.0:0.01, the molar ratio of the total mole of sodium ions in sodium sulfate and ferrous ions in ferrous sulfate to ethylenediamine tetraacetic acid is 1:1.1, the molar ratio of thiourea to ferrous sulfate is 0.1:1, adding water in an amount which is 1.5 times of the total mass of sodium sulfate, ferrous sulfate, ammonium fluoride, thiourea and ethylenediamine tetraacetic acid, adding the cerium oxide quantum dot modified carbon material obtained in the step 1) and the tantalum doped tin oxide nano material (the content of doped tantalum is 0.05 mol%) for mixing, wherein the addition amount of the cerium oxide quantum dot modified carbon material is 1% of the total mass of sodium sulfate and ferrous sulfate, the addition amount of the tantalum doped tin oxide nano material is 0.1% of the total mass of sodium sulfate and ferrous sulfate, stirring and dissolving for 1h at room temperature at 2500 r/min, performing first heating treatment at 75 ℃ for 1h at a stirring speed of 1000 r/min, performing second heating treatment at 95 ℃ at a stirring speed of 500 r/min, and slowly evaporating water to obtain a viscous gel substance;
3) And (3) placing the gel substance obtained in the step (2) in a crucible, annealing for 6 hours in a nitrogen atmosphere at 320 ℃, crushing, and sieving to obtain the modified sodium iron sulfate anode material.
Example 5
The embodiment provides a preparation method of a modified sodium iron sulfate positive electrode material, which comprises the following steps:
1) 1.0W/cm of aqueous cerium acetate solution with the concentration of 0.2mol/L 2 Ultrasonic treating at-120deg.C for 5 hr, standing for 10 hr to obtain uniformly dispersed liquid, rapidly cooling the liquid in liquid nitrogen, freeze drying at-120deg.C under vacuum for 20 hr, heat treating to obtain cerium oxide quantum dot powder, heat treating at 450deg.C for 10 hr, mixing 50g cerium oxide quantum dot powder, 1500ml anhydrous alcohol and 500ml water, and stirring at 1.0W/cm 2 Ultrasonic treatment is carried out for 5 hours under power to lead the carbon nano tube to be evenly dispersed, then 100g of carbon nano tube is added for continuing 0.8W/cm 2 Ultrasonic treatment is carried out for 5 hours under power, a stirrer is placed on a magnetic stirrer for stirring for 5 hours after the ultrasonic treatment is finished, the stirring rotating speed is 5000 r/min, the stirring is finished, the drying is carried out for 15 hours under the hydrogen atmosphere at 110 ℃, the precursor is obtained after grinding, the precursor is placed in a crucible with a cover, the crucible with the cover is sent into a muffle furnace, the calcination is carried out for 5 hours at 450 ℃, the calcination heating rate is 5 ℃/min, the material is taken out after the material is cooled to room temperature, and the cerium oxide quantum dot modified carbon material is obtained after grinding;
2) Mixing sodium sulfate, ferrous sulfate heptahydrate, ammonium fluoride, D-isoascorbic acid, polyacrylic acid and water, wherein the molar ratio of the sodium sulfate to the ferrous sulfate heptahydrate to the ammonium fluoride is 3.0:1.5:0.2, the molar ratio of the total mole of sodium ions in sodium sulfate and ferrous ions in ferrous sulfate to polyacrylic acid is 1:1.5, the molar ratio of D-isoascorbic acid to ferrous sulfate is 1.5:1, adding water with the addition amount of 4.5 times of the total mass of sodium sulfate, ferrous sulfate, ammonium fluoride, D-isoascorbic acid and polyacrylic acid, adding the cerium oxide quantum dot modified carbon material obtained in the step 1) and the antimony doped tin oxide nano material (the content of the doped antimony is 0.20 mol%) for mixing, wherein the addition amount of the cerium oxide quantum dot modified carbon material is 15% of the total mass of sodium sulfate and ferrous sulfate, the addition amount of the antimony doped tin oxide nano material is 10% of the total mass of sodium sulfate and ferrous sulfate, stirring and dissolving for 5h at room temperature at 300 r/min, carrying out first heating treatment at 90 ℃ for 3h, the stirring rotation speed of the first heating treatment is 2500 r/min, then carrying out second heating treatment at 110 ℃ and the stirring rotation speed of 1000 r/min, the second heating treatment time is 1.5h, and water slowly evaporates to obtain a sticky gel substance;
3) And (3) placing the gel substance obtained in the step (2) in a crucible, annealing for 12 hours in a hydrogen atmosphere at 380 ℃, crushing and sieving to obtain the modified sodium iron sulfate anode material.
Comparative example 1
The comparative example provides a preparation method of a sodium iron sulfate positive electrode material, which comprises the following steps:
1) Mixing sodium sulfate, ferrous sulfate heptahydrate, ammonium fluoride, ascorbic acid, disodium ethylenediamine tetraacetate and water, wherein the molar ratio of the sodium sulfate to the ferrous sulfate heptahydrate to the ammonium fluoride is 2.5:1.75:0.02, the molar ratio of the total mole of sodium ions in sodium sulfate and ferrous ions in the ferrous sulfate to disodium ethylenediamine tetraacetate being 1:1.2, molar ratio of ascorbic acid to ferrous sulfate of 1.1:1, adding water with the addition amount of 2.5 times of the total mass of sodium sulfate, ferrous sulfate, ammonium fluoride, ascorbic acid and disodium ethylenediamine tetraacetate, adding carbon nano tubes and molybdenum doped tin oxide nano materials (the content of doped molybdenum is 0.1 mol%) and mixing, wherein the addition amount of the carbon nano tubes is 10% of the total mass of sodium sulfate and ferrous sulfate, the addition amount of the molybdenum doped tin oxide nano materials is 3% of the total mass of sodium sulfate and ferrous sulfate, stirring and dissolving for 1h at room temperature at 1000 r/min, performing first heating treatment for 2h at 85 ℃, wherein the stirring speed of the first heating treatment is 1200 r/min, then performing second heating treatment at 100 ℃ and 800 r/min, wherein the second heating treatment time is 1h, and slowly evaporating water to obtain viscous gel substances;
2) And (3) placing the gel substance obtained in the step (1) in a crucible, annealing for 8 hours at the temperature of 350 ℃ in an argon atmosphere, crushing and sieving to obtain the modified sodium iron sulfate anode material.
Comparative example 2
The comparative example provides a preparation method of a modified sodium iron sulfate positive electrode material, which comprises the following steps:
1) 0.03mol/L aqueous solution of cerium acetate 0.8W/cm 2 Ultrasonic treating at-120deg.C for 1 hr, standing for 5 hr to obtain uniformly dispersed liquid, rapidly cooling the liquid in liquid nitrogen, freeze drying at-120deg.C under vacuum for 10 hr, heat treating to obtain cerium oxide quantum dot powder, heat treating at 350deg.C for 3 hr, mixing 5g cerium oxide quantum dot powder, 1500ml anhydrous alcohol and 500ml water, and mixing 0.8W/cm 2 Ultrasonic treatment under power for 30min to disperse uniformly, adding 100g carbon nanotube, and continuing 0.5W/cm 2 Ultrasonic treatment is carried out for 30min under power, a stirrer is placed on a magnetic stirrer for stirring for 3h after the ultrasonic treatment is finished, the stirring rotating speed is 3000 r/min, the stirring is finished, the drying is carried out for 10h under the argon atmosphere at 80 ℃, the precursor is obtained after grinding, the precursor is placed in a crucible with a cover, the crucible is sent into a muffle furnace, the calcination is carried out for 2h at 400 ℃, the calcination heating rate is 3 ℃ per min, the material is taken out after the material is cooled to room temperature, and the cerium oxide quantum dot modified carbon material is obtained after grinding;
2) Mixing sodium sulfate, ferrous sulfate heptahydrate, ammonium fluoride, ascorbic acid, disodium ethylenediamine tetraacetate and water, wherein the molar ratio of the sodium sulfate to the ferrous sulfate heptahydrate to the ammonium fluoride is 2.5:1.75:0.02, the molar ratio of the total mole of sodium ions in sodium sulfate and ferrous ions in the ferrous sulfate to disodium ethylenediamine tetraacetate being 1:1.2, molar ratio of ascorbic acid to ferrous sulfate of 1.1:1, adding water with the addition amount of 2.5 times of the total mass of sodium sulfate, ferrous sulfate, ammonium fluoride, ascorbic acid and disodium ethylenediamine tetraacetate, adding the cerium oxide quantum dot modified carbon material obtained in the step 1) to mix, stirring and dissolving the cerium oxide quantum dot modified carbon material for 1h at 1000 revolutions per minute under the condition of room temperature, performing first heating treatment for 2h at 85 ℃, wherein the stirring speed of the first heating treatment is 1200 revolutions per minute, then performing second heating treatment at 100 ℃ and 800 revolutions per minute, wherein the second heating treatment time is 1h, and slowly evaporating water to obtain a viscous gel substance;
3) And (3) placing the gel substance obtained in the step (2) in a crucible, annealing for 8 hours in an argon atmosphere at 350 ℃, crushing, and sieving to obtain the modified sodium iron sulfate anode material.
Comparative example 3
The comparative example provides a preparation method of a modified sodium iron sulfate positive electrode material, which comprises the following steps:
1) 0.03mol/L aqueous solution of cerium acetate 0.8W/cm 2 Ultrasonic treating at-120deg.C for 1 hr, standing for 5 hr to obtain uniformly dispersed liquid, rapidly cooling the liquid in liquid nitrogen, freeze drying at-120deg.C under vacuum for 10 hr, heat treating to obtain cerium oxide quantum dot powder, heat treating at 350deg.C for 3 hr, mixing 5g cerium oxide quantum dot powder, 1500ml anhydrous alcohol and 500ml water, and mixing 0.8W/cm 2 Ultrasonic treatment under power for 30min to disperse uniformly, adding 100g carbon nanotube, and continuing 0.5W/cm 2 Ultrasonic treatment is carried out for 30min under power, a stirrer is placed on a magnetic stirrer for stirring for 3h after the ultrasonic treatment is finished, the stirring rotating speed is 3000 r/min, the stirring is finished, the drying is carried out for 10h under the argon atmosphere at 80 ℃, the precursor is obtained after grinding, the precursor is placed in a crucible with a cover, the crucible is sent into a muffle furnace, the calcination is carried out for 2h at 400 ℃, the calcination heating rate is 3 ℃ per min, the material is taken out after the material is cooled to room temperature, and the cerium oxide quantum dot modified carbon material is obtained after grinding;
2) Mixing sodium sulfate, ferrous sulfate heptahydrate, ascorbic acid, disodium ethylenediamine tetraacetate and water, wherein the molar ratio of the sodium sulfate to the ferrous sulfate heptahydrate is 2.5:1.75, the molar ratio of the total moles of sodium ions in sodium sulfate and ferrous ions in said ferrous sulfate to disodium ethylenediamine tetraacetate being 1:1.2, molar ratio of ascorbic acid to ferrous sulfate of 1.1:1, adding water with the addition amount of 2.5 times of the total mass of sodium sulfate, ferrous sulfate, ascorbic acid and disodium ethylenediamine tetraacetate, adding the cerium oxide quantum dot modified carbon material obtained in the step 1) and the molybdenum doped tin oxide nano material (the molybdenum doped content is 0.1 mol%) for mixing, wherein the addition amount of the cerium oxide quantum dot modified carbon material is 10% of the total mass of sodium sulfate and ferrous sulfate, the addition amount of the molybdenum doped tin oxide nano material is 3% of the total mass of sodium sulfate and ferrous sulfate, stirring and dissolving for 1h at room temperature at 1000 r/min, performing first heating treatment for 2h at 85 ℃, the stirring rotation speed of the first heating treatment is 1200 r/min, then performing second heating treatment at the stirring rotation speed of 100 ℃ at 800 r/min, the second heating treatment time is 1h, and slowly evaporating water to obtain a viscous gel substance;
3) And (3) placing the gel substance obtained in the step (2) in a crucible, annealing for 8 hours in an argon atmosphere at 350 ℃, crushing, and sieving to obtain the modified sodium iron sulfate anode material.
Comparative example 4
The comparative example provides a preparation method of a modified sodium iron sulfate positive electrode material, which comprises the following steps:
1) 0.03mol/L aqueous solution of cerium acetate 0.8W/cm 2 Ultrasonic treating at-120deg.C for 1 hr, standing for 5 hr to obtain uniformly dispersed liquid, rapidly cooling the liquid in liquid nitrogen, freeze drying at-120deg.C under vacuum for 10 hr, heat treating to obtain cerium oxide quantum dot powder, heat treating at 350deg.C for 3 hr, mixing 5g cerium oxide quantum dot powder, 1500ml anhydrous alcohol and 500ml water, and mixing 0.8W/cm 2 Ultrasonic treatment under power for 30min to disperse uniformly, adding 100g carbon nanotube, and continuing 0.5W/cm 2 Ultrasonic treatment is carried out for 30min under power, a stirrer is placed on a magnetic stirrer for stirring for 3h after the ultrasonic treatment is finished, the stirring rotating speed is 3000 r/min, the stirring is finished, the drying is carried out for 10h under the argon atmosphere at 80 ℃, the precursor is obtained after grinding, the precursor is placed in a crucible with a cover, the crucible is sent into a muffle furnace, the calcination is carried out for 2h at 400 ℃, the calcination heating rate is 3 ℃ per min, the material is taken out after the material is cooled to room temperature, and the cerium oxide quantum dot modified carbon material is obtained after grinding;
2) Mixing sodium sulfate, ferrous sulfate heptahydrate, ascorbic acid, disodium ethylenediamine tetraacetate and water, wherein the molar ratio of the sodium sulfate to the ferrous sulfate heptahydrate is 2.5:1.75, the molar ratio of the total moles of sodium ions in sodium sulfate and ferrous ions in said ferrous sulfate to disodium ethylenediamine tetraacetate being 1:1.2, molar ratio of ascorbic acid to ferrous sulfate of 1.1:1, adding water with the addition amount of 2.5 times of the total mass of sodium sulfate, ferrous sulfate, ascorbic acid and disodium ethylenediamine tetraacetate, adding the cerium oxide quantum dot modified carbon material obtained in the step 1), wherein the addition amount of the cerium oxide quantum dot modified carbon material is 10% of the total mass of sodium sulfate and ferrous sulfate, stirring and dissolving for 1h at room temperature at 1000 r/min, performing first heating treatment for 2h at 85 ℃, wherein the stirring rotation speed of the first heating treatment is 1200 r/min, then performing second heating treatment at the stirring rotation speed of 100 ℃ at 800 r/min, wherein the second heating treatment time is 1h, and slowly evaporating water to obtain a viscous gel substance;
3) And (3) placing the gel substance obtained in the step (2) in a crucible, annealing for 8 hours in an argon atmosphere at 350 ℃, crushing, and sieving to obtain the modified sodium iron sulfate anode material.
Test case
The positive electrode materials of examples 1 to 5 and comparative examples 1 to 4 were each prepared as 80 (the positive electrode materials): 12 (PVDF): 8 (SP) is prepared into a pole piece by homogenate coating according to the mass ratio, sodium metal is used as a counter electrode, glass fiber is used as a diaphragm, and 1mol/L NaPF is used 6 The CR2032 button cell is assembled by placing a positive electrode plate, a sodium plate, a diaphragm, a gasket and an elastic sheet in a button cell as electrolyte (volume ratio of EC to DMC is 1:1). And finally, placing the button cell into a blue electric testing system for electric performance testing. The electrical performance test parameters were set as: the voltage range is 2.0V-4.5V, the first circle is charged and discharged with 0.1C/0.1C to carry out discharge specific capacity test, then the first circle is continuously charged and discharged with 0.2C/0.2C, 0.5C/0.5C and 1C/1C to test the discharge specific capacities under different multiplying power, and the discharge multiplying power performance is evaluated by the ratio of the discharge specific capacity under 1C multiplying power to the discharge specific capacity under 0.1C multiplying power; finally, the cycle performance was evaluated by a specific discharge capacity retention rate of the charge/discharge cycle of 1C/1C for 50 times. The test results are shown in Table 1.
TABLE 1
It is apparent that the above examples are given by way of illustration only and are not limiting of the embodiments. Other variations or modifications of the above teachings will be apparent to those of ordinary skill in the art. It is not necessary here nor is it exhaustive of all embodiments. While still being apparent from variations or modifications that may be made by those skilled in the art are within the scope of the invention.
Claims (10)
1. The preparation method of the modified sodium iron sulfate anode material is characterized by comprising the following steps of:
1) Mixing cerium oxide quantum dot powder, a carbon source and a solution, performing ultrasonic treatment, drying, calcining and grinding to obtain a cerium oxide quantum dot modified carbon material;
2) Mixing sodium sulfate, ferrous sulfate, a fluorine source, an antioxidant, a complexing agent, the cerium oxide quantum dot modified carbon material obtained in the step 1), the doped tin oxide nano material and water, stirring, and performing heat treatment to obtain a gel substance;
3) And (3) annealing the gel substance obtained in the step (2) to obtain the modified sodium iron sulfate anode material.
2. The method of preparing according to claim 1, wherein the preparing step of the cerium oxide quantum dot powder in step 1) comprises: carrying out ultrasonic treatment, freeze drying and heat treatment on the cerium source aqueous solution to obtain cerium oxide quantum dot powder;
preferably, the aqueous solution of cerium source is at least one selected from cerium acetate, cerium isopropoxide, cerium citrate and cerium formate;
preferably, the molar concentration of the cerium source aqueous solution is 0.01-0.2mol/L;
preferably, the ultrasonic power is 0.3-1.0W/cm 2 The ultrasonic time is 0.5-5h;
preferably, the freeze-drying temperature is-115+/-35 ℃ and the freeze-drying time is 5-20 hours;
preferably, the heat treatment temperature is 300-450 ℃, and the heat treatment time is 1-10h;
optionally, the freeze drying step is preceded by a standing step, wherein the standing time is 1-10h.
3. The method of preparation according to claim 1 or 2, wherein the solution in step 1) comprises water and ethanol;
mixing cerium oxide quantum dot powder, ethanol and water to perform first ultrasonic treatment, and then adding a carbon source to perform second ultrasonic treatment;
the mass ratio of the cerium oxide quantum dot powder to water to the carbon source is (0.1-10): 100: (1-20);
the volume ratio of the ethanol to the water is (1-5): 1, a step of;
the first ultrasonic power is 0.5-1.0W/cm 2 The first ultrasonic time is 0.5-5h;
the second ultrasonic power is 0.3-0.8W/cm 2 The second ultrasonic time is 0.5-5h.
4. A method according to any one of claims 1 to 3, wherein the carbon source in step 1) is selected from at least one of carbon fiber, carbon nanotube, graphene oxide, acetylene black, glucose;
the drying temperature in the step 1) is 70-110 ℃, and the drying time is 5-15h;
the dry atmosphere in the step 1) is at least one selected from nitrogen, argon and hydrogen;
the calcination temperature is 350-450 ℃, and the calcination time is 1-5h;
the drying step in the step 1) is preceded by a stirring step; the stirring speed is 500-5000 rpm, and the stirring time is 1-5h;
the calcination step in step 1) is preceded by a grinding step.
5. The preparation method according to any one of claims 1 to 4, wherein in step 2), sodium sulfate, ferrous sulfate, a fluorine source, an antioxidant, a complexing agent and water are mixed, and then the cerium oxide quantum dot modified carbon material obtained in step 1) and the doped tin oxide nanomaterial are added and mixed;
the molar ratio of sodium sulfate, ferrous sulfate and fluoride ions in the fluoride source in step 2) is (2.0-3.0): (1.5-2.0): (0.01-0.2);
the molar ratio of the total mole of sodium ions in the sodium sulfate and ferrous ions in the ferrous sulfate to the complexing agent is 1: (1.1-1.5);
the mole ratio of the antioxidant to the ferrous sulfate is (0.1-1.5): 1, a step of;
the addition amount of the cerium oxide quantum dot modified carbon material is 1-15% of the total mass of sodium sulfate and ferrous sulfate;
the addition amount of the doped tin oxide material is 0.1-10% of the total mass of sodium sulfate and ferrous sulfate;
preferably, the addition amount of the doped tin oxide material is 1-5% of the total mass of sodium sulfate and ferrous sulfate.
6. The method according to any one of claims 1 to 5, wherein the water is added in the amount of 1.5 to 4.5 times the total mass of sodium sulfate, ferrous sulfate, fluorine source, antioxidant, complexing agent in step 2);
the doped tin oxide material in the step 2) is at least one selected from antimony doped tin oxide, tantalum doped tin oxide, tungsten doped tin oxide and molybdenum doped tin oxide;
the doped tin oxide material is a nano material;
the content of the dopant in the doped tin oxide material is 0.05-0.20mol%;
the complexing agent in the step 2) is at least one selected from ethylenediamine tetraacetic acid, disodium ethylenediamine tetraacetate, citric acid, gluconic acid, hydroxyethylidene-1, 1-diphosphonic acid, polyacrylic acid and tetrathiodioxyformic acid;
the antioxidant is at least one selected from ascorbic acid, D-isoascorbic acid, thiourea, hydroxylamine hydrochloride, pyrrole and hydroquinone;
the fluorine source in step 2) is selected from ammonium fluoride.
7. The method according to any one of claims 1 to 6, wherein the stirring in step 2) is 300 to 3000 rpm for 1 to 5 hours;
the heating treatment includes a first heating treatment and a second heating treatment;
the temperature of the first heating treatment is 75-90 ℃, the stirring speed of the first heating treatment is 1000-2500 rpm, and the time of the first heating treatment is 1-3h;
the temperature of the second heating treatment is 95-110 ℃, the stirring speed of the second heating treatment is 500-1000 rpm, and the time of the second heating treatment is 0.5-5h.
8. The method according to any one of claims 1 to 7, wherein the annealing temperature in step 3) is 320 to 380 ℃ and the annealing time is 6 to 12 hours;
the annealing is carried out under a protective atmosphere;
the protective atmosphere is at least one selected from nitrogen, argon and hydrogen;
and step 3), the annealing is finished, and the method further comprises a crushing and sieving treatment step.
9. A modified sodium iron sulfate positive electrode material, characterized in that it is prepared by the preparation method of any one of claims 1 to 8.
10. The use of the modified ferric sodium sulfate positive electrode material prepared by the preparation method of any one of claims 1-8 in a positive electrode material of a sodium ion battery.
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