CN116154138A - Sodium ion battery positive electrode material, preparation method and application thereof, and sodium ion battery - Google Patents
Sodium ion battery positive electrode material, preparation method and application thereof, and sodium ion battery Download PDFInfo
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- CN116154138A CN116154138A CN202310215164.5A CN202310215164A CN116154138A CN 116154138 A CN116154138 A CN 116154138A CN 202310215164 A CN202310215164 A CN 202310215164A CN 116154138 A CN116154138 A CN 116154138A
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- positive electrode
- electrode material
- ion battery
- sodium ion
- sodium
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- 239000007774 positive electrode material Substances 0.000 title claims abstract description 285
- 229910001415 sodium ion Inorganic materials 0.000 title claims abstract description 109
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title claims abstract description 103
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000013078 crystal Substances 0.000 claims abstract description 75
- 239000002245 particle Substances 0.000 claims abstract description 49
- 239000010405 anode material Substances 0.000 claims abstract description 22
- 239000002243 precursor Substances 0.000 claims description 55
- 239000011734 sodium Substances 0.000 claims description 50
- 238000005245 sintering Methods 0.000 claims description 36
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 34
- 238000000034 method Methods 0.000 claims description 34
- 238000002156 mixing Methods 0.000 claims description 32
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 32
- 238000006243 chemical reaction Methods 0.000 claims description 24
- 238000010438 heat treatment Methods 0.000 claims description 24
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 22
- 239000002019 doping agent Substances 0.000 claims description 22
- 239000011572 manganese Substances 0.000 claims description 22
- 229910052708 sodium Inorganic materials 0.000 claims description 22
- 239000012298 atmosphere Substances 0.000 claims description 20
- 238000000975 co-precipitation Methods 0.000 claims description 19
- 239000008139 complexing agent Substances 0.000 claims description 16
- 229910052759 nickel Inorganic materials 0.000 claims description 15
- 229910052748 manganese Inorganic materials 0.000 claims description 14
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 13
- 229910052742 iron Inorganic materials 0.000 claims description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 239000012716 precipitator Substances 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 7
- 238000002441 X-ray diffraction Methods 0.000 claims description 6
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 5
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 4
- 229910017119 AlPO Inorganic materials 0.000 claims description 4
- 229910019142 PO4 Inorganic materials 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- 229910003514 Sr(OH) Inorganic materials 0.000 claims description 4
- 229910006249 ZrSi Inorganic materials 0.000 claims description 4
- 229910021332 silicide Inorganic materials 0.000 claims description 4
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 229910052721 tungsten Inorganic materials 0.000 claims description 4
- 229910052744 lithium Inorganic materials 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 229910021193 La 2 O 3 Inorganic materials 0.000 claims description 2
- 229910017639 MgSi Inorganic materials 0.000 claims description 2
- 101100496858 Mus musculus Colec12 gene Proteins 0.000 claims description 2
- 229910004122 SrSi Inorganic materials 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 230000001590 oxidative effect Effects 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 239000004317 sodium nitrate Substances 0.000 claims description 2
- 235000010344 sodium nitrate Nutrition 0.000 claims description 2
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims description 2
- 229910001948 sodium oxide Inorganic materials 0.000 claims description 2
- 229910052720 vanadium Inorganic materials 0.000 claims description 2
- 229910052727 yttrium Inorganic materials 0.000 claims description 2
- 150000001805 chlorine compounds Chemical class 0.000 claims 2
- 150000002222 fluorine compounds Chemical class 0.000 claims 2
- 235000021317 phosphate Nutrition 0.000 claims 2
- 150000003013 phosphoric acid derivatives Chemical class 0.000 claims 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 claims 1
- 150000004679 hydroxides Chemical class 0.000 claims 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 23
- 239000001301 oxygen Substances 0.000 description 23
- 229910052760 oxygen Inorganic materials 0.000 description 23
- 230000000630 rising effect Effects 0.000 description 19
- 238000012360 testing method Methods 0.000 description 19
- 230000000052 comparative effect Effects 0.000 description 15
- 239000000463 material Substances 0.000 description 14
- 238000005056 compaction Methods 0.000 description 13
- 239000002131 composite material Substances 0.000 description 11
- 238000009826 distribution Methods 0.000 description 9
- 239000000243 solution Substances 0.000 description 8
- 239000003792 electrolyte Substances 0.000 description 7
- 238000004321 preservation Methods 0.000 description 6
- 230000002195 synergetic effect Effects 0.000 description 6
- 230000009286 beneficial effect Effects 0.000 description 5
- 238000011056 performance test Methods 0.000 description 5
- 230000005540 biological transmission Effects 0.000 description 4
- 239000010406 cathode material Substances 0.000 description 4
- 230000002950 deficient Effects 0.000 description 4
- 238000011534 incubation Methods 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 230000001276 controlling effect Effects 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000011888 foil Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000012266 salt solution Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 2
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 239000001099 ammonium carbonate Substances 0.000 description 2
- 239000012300 argon atmosphere Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 2
- 239000012065 filter cake Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000012216 screening Methods 0.000 description 2
- 238000007873 sieving Methods 0.000 description 2
- FVBUAEGBCNSCDD-UHFFFAOYSA-N silicide(4-) Chemical compound [Si-4] FVBUAEGBCNSCDD-UHFFFAOYSA-N 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- LLBZPESJRQGYMB-UHFFFAOYSA-N 4-one Natural products O1C(C(=O)CC)CC(C)C11C2(C)CCC(C3(C)C(C(C)(CO)C(OC4C(C(O)C(O)C(COC5C(C(O)C(O)CO5)OC5C(C(OC6C(C(O)C(O)C(CO)O6)O)C(O)C(CO)O5)OC5C(C(O)C(O)C(C)O5)O)O4)O)CC3)CC3)=C3C2(C)CC1 LLBZPESJRQGYMB-UHFFFAOYSA-N 0.000 description 1
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical compound [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000005260 alpha ray Effects 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 1
- 235000012501 ammonium carbonate Nutrition 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 150000003841 chloride salts Chemical class 0.000 description 1
- 235000015165 citric acid Nutrition 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- DCYOBGZUOMKFPA-UHFFFAOYSA-N iron(2+);iron(3+);octadecacyanide Chemical compound [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
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 229940099596 manganese sulfate Drugs 0.000 description 1
- 239000011702 manganese sulphate Substances 0.000 description 1
- 235000007079 manganese sulphate Nutrition 0.000 description 1
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000447 polyanionic polymer Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 229960003351 prussian blue Drugs 0.000 description 1
- 239000013225 prussian blue Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- H01M4/362—Composites
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
-
- 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
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
-
- 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
-
- 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)
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- General Chemical & Material Sciences (AREA)
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- Composite Materials (AREA)
- Crystallography & Structural Chemistry (AREA)
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Abstract
The invention relates to the field of sodium ion battery anode materials, and discloses a sodium ion battery anode material, a preparation method and application thereof, and a sodium ion battery. The positive electrode material comprises a positive electrode material A and a positive electrode material B; the positive electrode material A is monocrystalline particles, and the positive electrode material B is an aggregate; and, the positive electrode material a and the positive electrode material B each independently have a characteristic diffraction peak of (002) crystal face and/or (003) crystal face at a 2θ of 14 ° -18 °, and the 2θ angle of the (002) crystal face characteristic diffraction peak is smaller than the 2θ angle of the (003) crystal face characteristic diffraction peak; the positive electrode material A has at least a characteristic diffraction peak of a (002) crystal plane, and the positive electrode material B has at least a characteristic diffraction peak of a (003) crystal plane. The positive electrode material has stable structure under high voltage and good cycle performance.
Description
Technical Field
The invention relates to the technical field of sodium ion battery anode materials, in particular to a sodium ion battery anode material, a preparation method and application thereof, and a sodium ion battery.
Background
In recent years, sodium ion batteries are widely paid attention to as complementary technologies of lithium ion batteries, and because sodium resources are abundant in reserve and low in price, the manufacturing cost of the batteries can be greatly reduced under the background of rapid increase of the current lithium and cobalt resource prices, and the sodium ion batteries are expected to be applied to low-speed electric vehicles and energy storage fields on a large scale.
In sodium ion battery systems, one of the most critical materials at present is the positive electrode material. The positive electrode material comprises a layered oxide positive electrode material, a Prussian blue positive electrode material and a polyanion positive electrode material. Wherein, layered oxide type NaMeO 2 The positive electrode material (me=ni, fe, mn, etc.) is recognized as the most promising positive electrode material for sodium-ion batteries due to the advantages of simple structure, adjustable content of each element, easy mass production, excellent electrochemical properties, etc.
The layered oxide is mainly divided into a P2 type structure and an O3 type structure according to the different stacking sequences of the sodium occupation mode and the oxygen layer, wherein the P2 type layered oxide shows better multiplying power capability; whereas the O3 type layered oxide exhibits a higher theoretical capacity.
However, both the P2 type layered oxide and the O3 type layered oxide are exposed to high voltages (> 4.2V, vs Na) + Na) undergo complex phase changes, resulting in structural failure and rapid capacity decay, thereby greatly limiting the further development of layered oxide materials.
Disclosure of Invention
The invention aims to overcome the problems of the prior layered oxide sodium ion battery positive electrode material, and provides a sodium ion battery positive electrode material, a preparation method and application thereof, and a sodium ion battery. The sodium ion battery anode material is a multiphase composite oxide anode material, and the cycle performance of the anode material can be greatly improved through the synergistic effect between the composite phases.
In order to achieve the above object, a first aspect of the present invention provides a positive electrode material for a sodium ion battery, which contains a positive electrode material a and a positive electrode material B; wherein the positive electrode material A is monocrystalline particles, and the positive electrode material B is an agglomerate; and, in addition, the method comprises the steps of,
in the XRD patterns of the positive electrode material A and the positive electrode material B, each independently has a characteristic diffraction peak of a (002) crystal face and/or a (003) crystal face at a 2 theta of 14-18 degrees, and the 2 theta angle of the characteristic diffraction peak of the (002) crystal face is smaller than the 2 theta angle of the characteristic diffraction peak of the (003) crystal face;
wherein the positive electrode material A has at least a characteristic diffraction peak of the (002) crystal plane, and the positive electrode material B has at least a characteristic diffraction peak of the (003) crystal plane.
A second aspect of the present invention provides a method for preparing the positive electrode material of a sodium ion battery according to the first aspect, the method comprising: mixing the positive electrode material A and the positive electrode material B;
preferably, the method for preparing the positive electrode material a includes:
(1) Mixing a nickel source, an iron source, a manganese source, a precipitator and a complexing agent in the presence of a solvent to perform a first coprecipitation reaction to obtain a precursor I;
(2) Mixing the precursor I with a sodium source, a doping agent containing M and/or a doping agent containing M' for first sintering to obtain the positive electrode material A;
Preferably, the method for preparing the positive electrode material B includes:
(a) Mixing a nickel source, an iron source, a manganese source, a precipitator and a complexing agent in the presence of a solvent to perform a second coprecipitation reaction to obtain a precursor II;
(b) And mixing the precursor II with a sodium source, a dopant containing M and/or a dopant containing M' for secondary sintering to obtain the positive electrode material B.
The third aspect of the invention provides the positive electrode material of the sodium ion battery described in the first aspect or the application of the preparation method described in the second aspect in the sodium ion battery.
According to a fourth aspect of the invention, there is provided a sodium ion battery comprising the positive electrode material of the sodium ion battery of the first aspect.
Through the technical scheme, the sodium ion battery anode material provided by the invention is a multiphase composite oxide anode material with synergistic addition, wherein the anode material A is single crystal particles, has good multiplying power performance and cycle performance, and simultaneously has a characteristic diffraction peak of (002) crystal face at the position of 14-18 degrees 2 theta, so that the anode material A has wider Na + The transmission channel and abundant sodium vacancies have larger Na interlayer spacing and Na + The Na ion transmission rate can be improved and the integrity of the layered structure can be maintained by direct diffusion between two adjacent triangular prism sites, so that the device has better multiplying power performance and cycle performance; the positive electrode material B is an aggregate, namely has higher capacity, and simultaneously has a characteristic diffraction peak of a (003) crystal face at a position of 14-18 degrees of 2 theta, so that the positive electrode material B has higher capacity, the positive electrode material of the sodium ion battery obtained by mixing the positive electrode material A and the positive electrode material B can minimize the phase change of the whole wide potential area, the structural damage of layered oxides under high voltage is further relieved, and the cycle performance of the positive electrode material of the sodium ion battery is greatly improved through the synergistic effect between composite phases.
Preferably, the particle sizes of the positive electrode material A and the positive electrode material B are respectively limited, so that the positive electrode material of the sodium ion battery forms a hierarchical structure, and the single crystal positive electrode material A and the agglomerated positive electrode material B are mixed according to the weight ratio in a specified range, so that higher compaction density can be obtained, and the positive electrode material of the sodium ion battery has higher structural stability and better cycling stability while ensuring high-rate and high-capacity performance output.
In addition, the preparation method provided by the invention is characterized in that on one hand, D of the precursor I and the precursor II is controlled 50 The positive electrode material A and the positive electrode material B with narrower particle size distribution range are obtained, so that the materials for blending are uniform and the electrical property is stable; on the other hand by controlling n (Na) in the positive electrode material A and the positive electrode material B, respectivelyn (Me) to obtain a positive electrode material A having at least a characteristic diffraction peak of a (002) crystal face, having a P2 or P2/O3 type crystal structure, and a positive electrode material B having at least a characteristic diffraction peak of a (003) crystal face, having an O3 or O3/P2 type (P2/O3 type) crystal structure, and then, respectively controlling sintering temperatures, heating rates, oxygen contents and doping elements of the positive electrode material A and the positive electrode material B during sintering, so that the positive electrode material A forms a small-particle single crystal structure to further promote Na ion transmission rate of the positive electrode material A; the positive electrode material B is enabled to form large-particle aggregates, so that the positive electrode material B can be further enabled to release more sodium ions, the phase change of the whole wide potential area is enabled to be minimized, and the structural damage of the layered oxide under high voltage is relieved. Finally, by controlling the weight ratio of the positive electrode material A to the positive electrode material B, higher compaction density is obtained.
In a word, the positive electrode material A obtained by the preparation method provided by the invention has excellent multiplying power performance and cycle performance; the obtained positive electrode material B can release more sodium ions. The positive electrode material A and the positive electrode material B are mixed, and the obtained positive electrode material of the sodium ion battery has higher compaction density, high structural stability and good cycle stability while ensuring high-rate and high-capacity performance output.
Drawings
FIG. 1 is an SEM image of precursor I prepared according to example 1 of the invention;
FIG. 2 is an SEM image of precursor II prepared according to example 1 of the present invention;
fig. 3 is an SEM picture of the positive electrode material a prepared in example 1 of the present invention;
fig. 4 is an SEM picture of the positive electrode material B prepared in example 1 of the present invention;
fig. 5 is an SEM picture of the positive electrode material of the sodium ion battery prepared in example 1 of the present invention;
FIG. 6 is an XRD pattern of P2 type single crystal positive electrode material A prepared in example 1 of the present invention;
FIG. 7 is an XRD pattern of O3-type agglomerated cathode material B prepared in example 1 of the present invention;
FIG. 8 is an XRD pattern of the P2/O3 type agglomerated positive electrode material B prepared in example 2 of the present invention.
Detailed Description
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
In the present invention, unless explicitly stated, neither the "first", "second", "third" nor "fourth" represent a sequence, nor are they limiting as to the respective materials or operations, only for distinguishing between the respective materials or operations, for example, the "first" and "second" in the "first incubation period" and the "second incubation period" are only for distinguishing to mean that this is not the same incubation period.
The room temperature according to the invention means 25.+ -. 2 ℃ unless otherwise specified.
In the case where the contrary description is not made in the present invention, the term "P2 type single crystal material" is a single crystal positive electrode material whose crystal form is P2 type; the term P2/O3 type single crystal material is a composite phase single crystal positive electrode material with a crystal form of P2/O3 transition type; the term P2/O3 type agglomerated material is a composite phase agglomerated positive electrode material with a crystal form of P2/O3 transition type; the term "O3 type agglomerated material" refers to an agglomerated positive electrode material having a crystalline form of O3 type.
In the case where the contrary description is not made in the present invention, "Me" means the sum of Ni, fe, mn, M and M' elements; "n (Na)/n (Me)" means n (Na)/n (Ni+Fe+Mn+M+M '), i.e., the ratio of the total molar amount of Na element to Ni+Fe+Mn+M+M' element.
The first aspect of the invention provides a positive electrode material of a sodium ion battery, which comprises a positive electrode material A and a positive electrode material B;
wherein the positive electrode material A is monocrystalline particles, and the positive electrode material B is an agglomerate; and, in addition, the method comprises the steps of,
in the XRD patterns of the positive electrode material A and the positive electrode material B, each independently has a characteristic diffraction peak of a (002) crystal face and/or a (003) crystal face at a 2 theta of 14-18 degrees, and the 2 theta angle of the characteristic diffraction peak of the (002) crystal face is smaller than the 2 theta angle of the characteristic diffraction peak of the (003) crystal face;
wherein the positive electrode material A has at least a characteristic diffraction peak of the (002) crystal plane, and the positive electrode material B has at least a characteristic diffraction peak of the (003) crystal plane.
The inventor of the invention finds that when XRD test results of the positive electrode material A and the positive electrode material B contained in the positive electrode material of the sodium ion battery meet the conditions, the phase change of the whole wide potential area can be minimized, so that the structural damage of the layered oxide under high voltage is relieved, the synergistic effect is generated on the electrochemical performance, and the electrochemical performance of the positive electrode material of the sodium ion battery can be greatly improved.
According to some embodiments of the invention, preferably, the median particle diameter D of the positive electrode material a 50 1 to 5. Mu.m, preferably 2 to 4. Mu.m, more preferably 3.6 to 4. Mu.m;
according to some embodiments of the invention, preferably, the median particle diameter D of the positive electrode material B 50 Preferably from 6 to 16. Mu.m, more preferably from 8 to 14. Mu.m, and still more preferably from 12.3 to 13.9. Mu.m.
The adoption of the preferred embodiment is beneficial to further improving the multiplying power performance of the positive electrode material of the sodium ion battery and further increasing the capacity of the positive electrode material of the sodium ion battery.
According to some embodiments of the invention, preferably, the sodium ion battery positive electrode material has a median particle diameter D 50 Is 1-20 μm, preferably 5-15 μm.
According to some embodiments of the present invention, preferably, the weight ratio of the positive electrode material a to the positive electrode material B is 1:0.1 to 9, preferably 1:0.4-2.5. The adoption of the preferred embodiment is beneficial to promoting the synergistic performance of the positive electrode material A and the positive electrode material B, so that the cycle performance and the capacity of the positive electrode material of the sodium ion battery are maximally compatible.
According to the invention, the size distribution of the positive electrode material A and the positive electrode material B contained in the positive electrode material of the sodium ion battery and the content ratio of the positive electrode material A to the positive electrode material B are regulated in a grading manner, so that the compaction density of the positive electrode material of the sodium ion battery and the volume energy density of an electrode containing the positive electrode material of the sodium ion battery are improved.
According to some embodiments of the invention, preferably, the positive electrode material a has a composition represented by formula I:
Na a1 (Ni x1 Fe y1 Mn z1 M m1 M′ n1 )O 2 a formula I;
wherein a is more than or equal to 0.50 1 ≤1.10，0≤x 1 ≤0.5，0≤y 1 ≤0.5，0≤z 1 ≤0.5，0≤m 1 ≤0.5，0≤n 1 ≤0.1，0.05≤m 1 +n 1 ≤0.1，m 1 、n 1 Not at the same time 0, x 1 +y 1 +z 1 +m 1 +n 1 ＝1。
According to some embodiments of the invention, preferably, the positive electrode material B has a composition represented by formula II:
Na a2 (Ni x2 Fe y2 Mn z2 M m2 M′ n2 )O 2 a formula II;
wherein a is more than or equal to 0.50 2 ≤1.10，0≤x 2 ≤0.5，0≤y 2 ≤0.5，0≤z 2 ≤0.5，0≤m 2 ≤0.1，0≤n 2 ≤0.1，0.05≤m 2 +n 2 ≤0.1，m 2 、n 2 Not at the same time 0, x 2 +y 2 +z 2 +m 2 +n 2 ＝1。
According to some embodiments of the invention, preferably, in formula I and formula II, M is selected from at least one element of Cu, co, V, cr, ti, mg, sn, zn, al, zr, nb, Y, W, la and M' is selected from at least one element of Li, al, mg, ti, zr, sr, la, nb, B, W.
According to some embodiments of the invention, preferably, a 1 ：(x 1 +y 1 +z 1 +m 1 +n 1 ) =0.5-0.8: 1, preferably 0.6-0.80:1, more preferably 0.67-0.8:1.
according to some embodiments of the invention, preferably, a 2 ：(x 2 +y 2 +z 2 +m 2 +n 2 ) =0.7-1.1: 1, preferably 0.8-1.05:1, more preferably 0.8-1:1.
according to some embodiments of the invention, preferably, a 2 And a 1 The difference between (2) and (0) is 0-0.5, preferably 0.2-0.35. By adopting the preferred embodiment, the optimal combination of the positive electrode material A of the P2 type monocrystalline particles or the P2/O3 type monocrystalline particles and the positive electrode material B of the P2/O3 type agglomerates or the O3 type agglomerates is facilitated, and the capacity, the multiplying power and the cycle performance of the positive electrode material of the sodium ion battery are further improved.
According to some embodiments of the present invention, it is preferable that the range of values of 2θ angles of the characteristic diffraction peaks of the (002) crystal planes of the positive electrode material a and the positive electrode material B are each 15.7 ° or more, and the range of values of 2θ angles of the characteristic diffraction peaks of the (003) crystal planes of the positive electrode material a and the positive electrode material B are each 16.7 ° or less. With the above preferred embodiments, n (Na)/n (Me) in the positive electrode material a and the positive electrode material B is between 0.5 and 1.1, so that the positive electrode material a and the positive electrode material B have better rate performance and capacity.
According to some embodiments of the invention, the positive electrode material a has a broader Na + Transport channels and abundant sodium vacancies, na + The anode material of the sodium ion battery has better multiplying power performance by directly diffusing between two adjacent triangular prism sites; the positive electrode material B has higher n (Na)/n (Me), so that the positive electrode material of the sodium ion battery has higher capacity.
According to some embodiments of the present invention, it is preferable that a ratio of a characteristic diffraction peak intensity to a strongest diffraction peak intensity of the (002) crystal plane is defined as I A The ratio of the characteristic diffraction peak intensity to the strongest diffraction peak intensity of the (003) crystal face is I B The positive electrode material a satisfies: i is more than or equal to 0.4 A /(I A +I B ) Less than or equal to 1.0; the positive electrode material B satisfies 0.ltoreq.I A /(I A +I B ) Less than or equal to 0.4. By adopting the preferred embodiment, the positive electrode material A with the single crystal structure can greatly improve the Na ion transmission rate and maintain the integrity of the layered structure, and the positive electrode material B with the agglomerated structure can remove more sodium ions, so that the electrochemical performance of the positive electrode material of the sodium ion battery has better synergy.
A second aspect of the present invention provides a method for preparing the positive electrode material of a sodium ion battery according to the first aspect, the method comprising: the positive electrode material a and the positive electrode material B were mixed.
According to some embodiments of the present invention, preferably, the method of preparing the positive electrode material a includes:
(1) Mixing a nickel source, an iron source, a manganese source, a precipitator and a complexing agent in the presence of a solvent to perform a first coprecipitation reaction to obtain a precursor I;
(2) And mixing the precursor I with a sodium source, a dopant containing M and/or a dopant containing M' for first sintering to obtain the positive electrode material A.
According to some embodiments of the present invention, preferably, the method of preparing the positive electrode material B includes:
(a) Mixing a nickel source, an iron source, a manganese source, a precipitator and a complexing agent in the presence of a solvent to perform a second coprecipitation reaction to obtain a precursor II;
(b) And mixing the precursor II with a sodium source, a dopant containing M and/or a dopant containing M' for secondary sintering to obtain the positive electrode material B.
According to some embodiments of the invention, preferably, the morphology of the precursor I in step (1) and/or the precursor II in step (a) is spherical or spheroid. More preferably, the precursor I in step (1) and the precursor II in step (a) are both spherical.
According to some embodiments of the invention, preferably, D of the precursor I and the precursor II 50 The range of the value of (2) is 1-20 mu m.
According to some embodiments of the invention, it is preferred to define that the precursor corresponds to 10% of the volume distribution resulting from the particle size testParticle size of D 10 50% of the volume distribution corresponds to a particle size D 50 The volume distribution 90% corresponds to a particle size D 90 And defining the uniformity of the precursor as K 90 And K is 90 ＝(D 90 -D 10 )/D 50 K of the precursor I and/or the precursor II 90 And less than 1.0, and narrow particle size distribution.
By adopting the preferred embodiment, the preparation of the anode material A and the anode material B with uniform particle size is facilitated, the grading effect in the subsequent blending process is better, and the compaction density is higher.
According to a preferred embodiment of the present invention, the precursor I in step (1) and the precursor II in step (a) are both spherical and K is the same as K 90 ＜1.0，D 50 The range of the value of (2) is 1-20 mu m.
According to some embodiments of the present invention, preferably, in step (2), the median particle diameter D of the positive electrode material a 50 1 to 5. Mu.m, preferably 2 to 4. Mu.m, more preferably 3.6 to 4. Mu.m.
According to some embodiments of the invention, preferably, in step (2), the sodium source is used in an amount such that, in terms of stoichiometry: n (Na)/n (Me) is 0.5 to 0.85, preferably 0.6 to 0.85.
According to some embodiments of the invention, preferably, in step (B), the median particle diameter D of the positive electrode material B 50 Preferably from 6 to 16. Mu.m, more preferably from 8 to 14. Mu.m, and still more preferably from 12.3 to 13.9. Mu.m.
According to some embodiments of the invention, preferably, in step (b), the sodium source is used in an amount such that, in terms of stoichiometry: n (Na)/n (Me) is 0.7 to 1.1, preferably 0.8 to 1.05.
According to some embodiments of the present invention, the nickel source, the iron source, and the manganese source may be a soluble nickel source, a soluble iron source, and a soluble manganese source conventionally used in the art, but are not particularly limited thereto, and preferably, the nickel source, the iron source, and the manganese source are selected from at least one of sulfate, nitrate, and chloride salts containing Ni, fe, and Mn.
According to some embodiments of the present invention, the precipitant may be a precipitant conventionally used in the art, without particular limitation, and preferably, the precipitant is at least one of NaOH, KOH and LiOH. The concentration of the precipitant may be 3-10mol/L.
According to some embodiments of the present invention, the complexing agent may be a complexing agent conventionally used in the art, without particular limitation, and preferably, the complexing agent is at least one of ammonia, ammonium bicarbonate, ammonium carbonate, citric acid, and disodium edetate. The concentration of the complexing agent may be 2-11mol/L.
According to some embodiments of the present invention, the sodium source may be a soluble sodium salt conventionally used in the art, without particular limitation, and preferably, the sodium source is selected from at least one of sodium carbonate, sodium hydroxide, sodium nitrate, and sodium oxide.
According to some embodiments of the invention, preferably, the dopant containing M is selected from at least one of an oxide, a phosphate, a fluoride, a chloride, a hydroxide, and a silicide containing M, preferably from CuO, co (OH) 2 、V 2 O 5 、Cr 2 O 3 、TiO 2 、MgCO 3 、Sr(OH) 2 、SrCO 3 、Al 2 O 3 、AlPO 4 、AlCl 3 、ZrO、Zr(HPO 4 ) 2 、ZrSi 2 、Nb 2 O 5 、Y 2 O 3 、WO 3 、NaF 3 And La (La) 2 O 3 At least one of them.
According to some embodiments of the invention, preferably, the dopant containing M 'is selected from at least one of an oxide, a phosphate, a carbonate, a fluoride, a chloride, a hydroxide and a silicide containing M', preferably from Li 2 CO 3 、Al 2 O 3 、AlPO 4 、AlCl 3 、MgO、Mg 3 (PO 4 ) 2 、MgCO 3 、MgSi 2 、MgF 2 、MgCl 2 、TiO 2 、ZrO、Zr(HPO 4 ) 2 、ZrSi 2 、Sr(OH) 2 、SrCO 3 、SrSi 2 、SrF 2 、SrCl 2 、La 2 O 3 、Nb 2 O 5 、B 2 O 3 And WO 3 At least one of them.
According to some embodiments of the invention, preferably, the co-precipitation method used in the first co-precipitation reaction and/or the second co-precipitation reaction is a batch method, specifically comprising: and (3) inputting the nickel source, the iron source, the manganese source, the precipitant and the complexing agent into a reaction kettle by using a metering pump within a certain time, and discharging after the precipitate is fully crystallized and grown in the reaction kettle. The batch method is adopted to carry out coprecipitation reaction, which is favorable for obtaining precursors with narrower particle size distribution.
According to some embodiments of the invention, preferably, the conditions of the first and/or second coprecipitation reaction comprise: the pH value is 10.0-12.5, the temperature is 40-80 ℃, the time is 48-120h, and the stirring speed is 100-800rpm.
According to some embodiments of the invention, preferably, the first sintering and/or the second sintering is performed in an oxidizing atmosphere, and the conditions of the first sintering and/or the second sintering include: the temperature is 600-1200 ℃, the time is 10-20h, and the temperature rising rate is 0.5-10 ℃/min.
According to some embodiments of the invention, preferably, the temperature of the second sintering is lower than the temperature of the first sintering.
According to some embodiments of the invention, preferably, in step (2), the first sintering comprises a first temperature increasing stage, a second temperature increasing stage and a first heat preserving stage; the oxygen concentration in the atmosphere of the first temperature rising stage is smaller than that in the atmosphere of the second temperature rising stage, and the temperature rising rate of the first temperature rising stage is larger than that of the second temperature rising stage;
more preferably, the difference between the oxygen concentration in the atmosphere of the second temperature raising stage and the oxygen concentration in the atmosphere of the first temperature raising stage is 10 to 100vol%;
More preferably, the difference between the temperature rising rate of the first temperature rising stage and the temperature rising rate of the second temperature rising stage is 2-15 ℃/min.
The adoption of the preferred embodiment is beneficial to remarkably improving the compaction density and the structural stability of the blended sodium ion battery anode material.
According to a preferred embodiment of the present invention, in step (2), the first sintering includes:
(2-1) a first temperature increase stage: in an oxygen-deficient atmosphere with the oxygen concentration less than or equal to 10vol%, heating to T1 ℃ at a first heating rate more than or equal to 3 ℃/min;
(2-2) a second temperature increase stage: in the atmosphere with the oxygen concentration of more than or equal to 20vol%, heating to T2 ℃ at a second heating rate of less than or equal to 2 ℃/min;
(2-3) a first heat preservation stage: preserving heat for T1 hour in the temperature range of T2-10 ℃ to T2+10 ℃;
wherein, the range of T1 is 600 ℃ to 800 ℃ and T1 is more than or equal to 600 ℃; t2 is the temperature of the first sintering, and T2 is more than or equal to 900 ℃ and less than or equal to 1100 ℃; t1 is the heat preservation time, and t1 is more than or equal to 5 hours and less than or equal to 15 hours.
According to some embodiments of the invention, in the step (2), the difference between the heating rate of the first heating stage and the heating rate of the second heating stage is 2-15 ℃/min,600 ℃ is less than or equal to T1 and less than or equal to 800 ℃,900 ℃ is less than or equal to T2 and less than or equal to 1100 ℃,5h is less than or equal to T1 and less than or equal to 15h, which is beneficial to forming the small-particle monocrystalline material from the positive electrode material A, the structure can be added with the positive electrode material A with a P2 or P2/O3 type crystal structure, the phase change of the whole wide potential area is minimized, the structural damage of the layered oxide under high voltage is relieved, the structural stability is high while the high-rate and high-capacity performance output is ensured, and the circulation stability is good.
According to some embodiments of the invention, preferably, in step (b), the second sintering comprises a third temperature ramp up stage, a fourth temperature ramp up stage and a second temperature hold stage; the oxygen concentration in the atmosphere of the third temperature rising stage is smaller than that in the atmosphere of the fourth temperature rising stage, and the temperature rising rate of the third temperature rising stage is larger than that of the fourth temperature rising stage;
more preferably, the difference between the oxygen concentration in the atmosphere of the fourth temperature raising stage and the oxygen concentration in the atmosphere of the third temperature raising stage is 10 to 100vol%;
more preferably, the difference between the temperature rise rate of the third temperature rise stage and the temperature rise rate of the fourth temperature rise stage is 2 to 10 ℃/min.
The adoption of the preferred embodiment is beneficial to remarkably improving the compaction density and the structural stability of the blended sodium ion battery anode material.
According to a preferred embodiment of the present invention, in step (b), the second sintering includes:
(b-1) a third temperature increase stage: in an oxygen-deficient atmosphere with the oxygen concentration less than or equal to 10vol%, heating to T3 ℃ at a third heating rate more than or equal to 3 ℃/min;
(b-2) a fourth warming stage: in the atmosphere with the oxygen concentration of more than or equal to 20vol%, heating to T4 ℃ at a fourth heating rate of less than or equal to 2 ℃/min;
(b-3) a second incubation stage: preserving heat for T2 hours in the temperature range of T4-10 ℃ to T4+10 ℃;
wherein, the range of T3 is 600 ℃ to 800 ℃ and T3 is more than or equal to 600 ℃; t4 is the temperature of the second sintering, and T4 is more than or equal to 800 ℃ and less than or equal to 900 ℃; t2 is the heat preservation time, and t2 is more than or equal to 5h and less than or equal to 15h.
According to some embodiments of the invention, in step (b), the difference between the rate of rise of the third temperature rise stage and the rate of rise of the fourth temperature rise stage is 2-10 ℃/min,600 ℃ to 800 ℃ and 800 ℃ to 4 ℃ to 900 ℃; the structure can be added with the positive electrode material B with an O3 or O3/P2 type crystal structure, so that the phase change of the whole wide potential area is minimized, the structural damage of the layered oxide under high voltage is relieved, the high-rate and high-capacity performance output is ensured, and meanwhile, the structure stability is high and the circulation stability is good.
According to a particularly preferred embodiment of the present invention, the method for preparing a positive electrode material of a sodium ion battery comprises:
s1, mixing a nickel source, an iron source, a manganese source, a precipitator and a complexing agent in the presence of a solvent to perform a first coprecipitation reaction to obtain a precursor I;
s2, mixing the precursor I with a sodium source, a doping agent containing M and/or a doping agent containing M' for first sintering to obtain a positive electrode material A;
S3, mixing a nickel source, an iron source, a manganese source, a precipitator and a complexing agent in the presence of a solvent to perform a second coprecipitation reaction to obtain a precursor II;
s4, mixing the precursor II with a sodium source, a doping agent containing M and/or a doping agent containing M' for second sintering to obtain a positive electrode material B;
and S5, mixing the positive electrode material A and the positive electrode material B.
The third aspect of the invention provides the positive electrode material of the sodium ion battery described in the first aspect or the application of the preparation method described in the second aspect in the sodium ion battery.
According to a fourth aspect of the invention, there is provided a sodium ion battery comprising the positive electrode material of the sodium ion battery of the first aspect.
According to some embodiments of the invention, the sodium ion battery further comprises a negative electrode and an electrolyte. The types of the negative electrode and the electrolyte are not particularly limited, and a negative electrode and an electrolyte of a conventional type in the art may be used, and for example, the electrolyte may be a general commercial electrolyte.
The present invention will be described in detail by examples.
In the following examples and comparative examples, all the raw materials used are commercially available products unless otherwise specified.
In the following examples and comparative examples, the relevant parameters were tested by the following methods:
(1) The composition of the positive electrode material is measured by an ICP method; the instrument used was PE Optima 7000DV under test conditions of 0.1g sample completely dissolved in 3mL HNO 3 Diluting to 250mL in a mixed acid solution of +9mL of HCl for testing;
(2) Observing the morphology of the material by a Scanning Electron Microscope (SEM), wherein the used instrument is a scanning electron microscope of the model S-4800 of Hitachi CHI company, japan;
(3) The particle size of the positive electrode material was measured using a malvern particle sizer;
(4) The crystal structure of the positive electrode material was tested by XRD; the instrument used was an X-ray diffractometer (Smart Lab 9 KW), the test conditions were: the X-ray source is a K alpha ray of Cu, the scanning range is 10 degrees to 80 degrees, the scanning speed is 1 degree/min, and the scanning step length is 0.02 degree;
(5) The powder compaction density of the positive electrode material is measured by adopting a powder compaction method; the instrument used was a powder compaction instrument (MCP-PD 51) with a test condition of 20KN.
(6) Electrochemical performance test: in the following examples and comparative examples, the electrochemical performance of the cathode materials was tested using a button sodium ion battery of the R2025 type.
The preparation process of the sodium ion battery specifically comprises the following steps:
preparing a pole piece: the positive electrode material of the sodium ion battery, the conductive agent SuperP and polyvinylidene fluoride (PVDF) are prepared according to the following proportion of 90:5: and (5) fully mixing the mixture with a proper amount of N-methyl pyrrolidone (NMP) to form uniform slurry, coating the slurry on aluminum foil, drying the aluminum foil at 120 ℃ for 12 hours, and then stamping and forming the aluminum foil by using 100MPa pressure to prepare the positive electrode plate with the diameter of 12mm and the thickness of 120 mu m.
And (3) battery assembly: in an argon-filled glove box with water content and oxygen content less than 5ppm, assembling a positive electrode plate, a diaphragm, a negative electrode plate and electrolyte into an R2025 button type sodium ion battery, and standing for 6h. Wherein, the negative electrode plate uses a metal sodium plate with the diameter of 14mm and the thickness of 1 mm; the membrane uses a rubberized membrane with a thickness of 25 μm; the electrolyte uses 1mol/L NaPF 6 A mixed solution of methyl ethyl carbonate (EMC) and Propylene Carbonate (PC) in a ratio of 4:6.
Electrochemical performance test:
in the following examples and comparative examples, electrochemical performance test was performed on R2025 type button sodium ion battery using a Shenzhen New Will cell test system (CT 3008), under the first charge and discharge capacity test conditions of [email protected], at 25deg.C, and constant voltage cutoff current of 0.02C; the cycle performance test conditions were [email protected] at 25deg.C. And respectively carrying out constant-current charge and discharge tests on the button sodium ion battery at 0.1C and 1C, and evaluating the charge and discharge specific capacity, the cycle performance and the volume energy density of the positive electrode material of the sodium ion battery, wherein the higher the capacity retention rate in the cycle process is, the higher the material stability is, and the better the cycle performance of a battery system is.
Example 1
S1: nickel sulfate, ferric sulfate and manganese sulfate are mixed according to the mole ratio of nickel, iron and manganese elements of 20:40:40 to obtain a mixed salt solution with the concentration of 2 mol/L; dissolving sodium hydroxide into a precipitant solution with the concentration of 8 mol/L; dissolving ammonia water into complexing agent solution with the concentration of 10.4 mol/L;
Introducing 100L of mixed salt solution, precipitator solution and complexing agent solution into a reaction kettle in a parallel flow mode for mixing to carry out a first coprecipitation reaction, then continuously carrying out a crystal growth reaction under the protection of argon atmosphere, carrying out suction filtration on the obtained precursor slurry, washing, drying a filter cake at 120 ℃, and screening to obtain a precursor I;
wherein, the conditions of the first coprecipitation reaction are as follows: the pH value is 12.38, the temperature is 60 ℃, the time is 80 hours, and the stirring rotating speed is 700rpm; d of precursor I 50 And K 90 See table 1;
s2: mixing the precursor I with Na 2 CO 3 CuO and Sr (OH) 2 Mixing, sintering, cooling, crushing and sieving to obtain positive electrode material A with median particle diameter D 50 See table 4;
wherein, the dosage of the sodium source (namely n (Na)/n (Ni+Fe+Mn+M+M')) and the crystal form of the positive electrode material A are shown in the table 1 according to the stoichiometric ratio;
the first sintering is carried out in an oxygen atmosphere, and specifically, the steps of the first sintering are as follows:
a first temperature rising stage: in an oxygen-deficient atmosphere with an oxygen concentration of 5vol%, heating to 700 ℃ at a first heating rate of 3 ℃/min;
a second temperature rising stage: in an atmosphere with the oxygen concentration of 20vol%, heating to 900 ℃ at a second heating rate of 1 ℃/min;
A first heat preservation stage: preserving heat for 15 hours at the temperature ranging from 890 ℃ to 910 ℃;
s3: according to the step S1, introducing 100L of mixed salt solution, precipitant solution and complexing agent solution into a reaction kettle in a parallel flow mode for mixing to carry out a second coprecipitation reaction, then continuously carrying out a crystallization growth reaction under the protection of argon atmosphere, carrying out suction filtration on the obtained precursor slurry, washing, drying a filter cake at 120 ℃, and screening to obtain a precursor II;
wherein, the conditions of the second coprecipitation reaction are as follows: the pH value is 12.10, the temperature is 60 ℃, the time is 80 hours, and the stirring rotating speed is 400rpm; d of precursor II 50 And K 90 See table 1;
s4: mixing the precursor II with Na 2 CO 3 CuO and Sr (OH) 2 Mixing, sintering, cooling, crushing and sieving to obtain positive electrode material B with median particle diameter D 50 See table 4;
wherein, the dosage of the sodium source (namely n (Na)/n (Ni+Fe+Mn+M+M')) and the crystal form of the positive electrode material B are shown in the table 1 according to the stoichiometric ratio;
the second sintering is carried out in an oxygen atmosphere, and specifically the step of the second sintering is as follows:
and a third temperature rising stage: in an oxygen-deficient atmosphere with the oxygen concentration of 5vol%, heating to 700 ℃ at a third heating rate of 3.5 ℃/min;
Fourth temperature rising stage: in an atmosphere with the oxygen concentration of 20vol%, heating to 850 ℃ at a fourth heating rate of 1.5 ℃/min;
and a second heat preservation stage: preserving heat for 10 hours at a temperature ranging from 840 ℃ to 860 ℃;
s5: and mixing the positive electrode material A prepared by the S2 with the positive electrode material B prepared by the S4 (the weight ratio of the positive electrode material A to the positive electrode material B is shown in the table 1) to obtain the positive electrode material of the sodium ion battery.
Example 2
The procedure of example 1 was followed except that in step S4, the n (Na)/n (Me) ratio was varied to obtain a P2/O3 type agglomerated positive electrode material B (see Table 1 in detail), and the remainder was the same to obtain a sodium ion battery positive electrode material.
Example 3
The procedure of example 1 was followed except that the n (Na)/n (Me) ratio in step S2 was varied to obtain P2/O3 type single crystal positive electrode material A (see Table 1 in detail), and the rest was the same to obtain a sodium ion battery positive electrode material.
Example 4
The procedure of example 3 was followed except that in step S5, the weight ratio of the positive electrode material a to the positive electrode material B (see table 1 in detail) was the same, and the positive electrode material for a sodium ion battery was obtained.
Example 5
According to the method of example 3, except that in step S2 and step S4, the dopant containing M is TiO 2 The dopant containing M' is B 2 O 3 The rest are the same, and the sodium ion battery anode material is obtained.
Example 6
The procedure of example 3 is followed, except that the median particle diameter D of precursor I in step S1 and precursor II in step S3 is 50 (see Table 1 in detail) the remainder are the same, and the sodium ion battery anode material is obtained.
Example 7
The procedure of example 3 was followed except that in step S5, the weight ratio of the positive electrode material a to the positive electrode material B (see table 1 in detail) was the same, and the positive electrode material for a sodium ion battery was obtained.
Example 8
The procedure of example 3 is followed, except that the median particle diameter D of precursor I in step S1 and precursor II in step S3 is 50 (see Table 1 in detail) and median particle diameters D of the resulting cathode materials A and B 50 (see Table 4 in detail) the remainder are the same, and the sodium ion battery anode material is obtained.
Comparative example 1
According to the method of example 1, except that in step S2, the n (Na)/n (Me) dosage ratio is different, O3 type single crystal positive electrode material a is obtained; in the step S4, the dosage ratio of n (Na)/n (Me) is different, and the P2 type agglomerated positive electrode material B is obtained; the specific results are shown in Table 1, and the rest are the same, so that the positive electrode material of the sodium ion battery is obtained.
Comparative example 2
The method of example 3 was followed except that in step S4, the third temperature raising stage was raised to 700 ℃ at a third temperature raising rate of 3 ℃/min; the fourth heating stage heats to 900 ℃ at a fourth heating rate of 1 ℃/min; the second heat preservation stage is used for preserving heat for 15 hours in the temperature range of 890-910 ℃; thus, O3 type single crystal positive electrode material B (see Table 1 in detail) is obtained, and the rest materials are the same, so that the sodium ion battery positive electrode material is obtained.
TABLE 1
Note that: a, a 2 -a 1 * Namely, a in the chemical formula of the positive electrode material 2 And a 1 Is a difference in (c).
The compositions of the positive electrode materials prepared in the above examples and comparative examples are shown in table 2.
TABLE 2
Test case
(1) Topography testing
The invention tests the scanning electron microscope images of the precursor I, the precursor II, the positive electrode material A, the positive electrode material B and the positive electrode material of the sodium ion battery prepared in the above examples and comparative examples, and provides SEM pictures of the precursor I, the precursor II, the positive electrode material A, the positive electrode material B and the positive electrode material of the sodium ion battery prepared in the example 1, and the results are shown in figures 1-5, and as can be seen from figures 1 and 2, the particle structure of the precursor I is small and round, and the particle surface is loose; the surface of the precursor II is compact; as can be seen from fig. 3, the single crystallization degree of the positive electrode material a is good, and the surface of the positive electrode material a is smooth and round; as can be seen from fig. 4, the surface of the agglomerated cathode material B is round and dense. As can be seen from fig. 5, in the positive electrode material for sodium ion battery of the present invention, the single crystal positive electrode material a is mixed with the agglomerated positive electrode material B, and small particles are filled between large particles, so that the positive electrode material has good grading property.
(2) Physical property test
The present invention tested XRD of the P2 type single crystal positive electrode material A, P/O3 type single crystal positive electrode material A, P/O3 type agglomerated positive electrode material B and O3 type agglomerated positive electrode material B in the above examples and comparative examples, and exemplarily provided XRD images of the P2 type single crystal positive electrode material A, O type agglomerated positive electrode material B prepared in example 1 and the P2/O3 type agglomerated positive electrode material B prepared in example 2, the results of which are shown in fig. 6 to 8, respectively.
XRD characteristic diffraction peak parameters of the positive electrode materials prepared in the above examples and comparative examples are shown in Table 3.
TABLE 3 Table 3
The invention tests the median particle diameter D of the positive electrode material A, the positive electrode material B and the positive electrode material of the sodium ion battery prepared in the above examples and comparative examples 50 And compacted density, as specifically shown in table 4.
TABLE 4 Table 4
From the above results, it can be seen that the K90 of the precursor I and the precursor II obtained by the method described in the present application are smaller than 1, the particle size distribution is narrower, and it can be seen from FIGS. 1 to 4One step shows that the obtained positive electrode material A and positive electrode material B have uniform particle size, wherein, when the median particle diameter D of the positive electrode material A and the positive electrode material B is 50 When the value range of the composite oxide and the mixing proportion of the anode material A and the anode material B are in the preferred range, namely, when the particle size distribution of the size particles of the multiphase composite oxide and the content ratio of each composite phase are regulated and controlled in a grading manner, the compaction density of the material and the volume energy density of the prepared electrode can be improved (corresponding to Table 5).
(3) Electrochemical performance test
The electrochemical properties of the positive electrode materials of the sodium ion batteries prepared in the examples and the comparative examples are tested, wherein the electrochemical properties comprise a specific capacity of 0.1C for first discharge, a specific capacity of 1C for discharge, rate capability, cycle performance and volume energy density, and specific test results are shown in Table 5.
TABLE 5
According to the results, in the positive electrode material of the sodium ion battery, after the P2, P2/O3 or O3 crystal forms are combined with single crystals or agglomerates according to the specific forms disclosed by the application, the positive electrode material has better multiplying power performance and cycle performance, can generate synergistic effect on electrochemical performance, greatly improves the electrochemical performance of the positive electrode material of the sodium ion battery, and can further improve the compaction density of the positive electrode material of the sodium ion by further limiting the mixing proportion of the positive electrode material A and the positive electrode material B and the median particle size of the positive electrode material A and the positive electrode material B, so that the structural damage of layered oxides under high voltage is relieved; in addition, the multiplying power performance and the cycle performance of the positive electrode material of the sodium ion battery can be further improved through doping elements. Wherein:
as is clear from comparison of example 1 and comparative example 1, comparative example 3 and comparative example 2, when the positive electrode material a is single crystal particles and the positive electrode material a has a characteristic diffraction peak of the (002) crystal plane at 14 ° -18 ° 2θ, while the positive electrode material B is an agglomerate and the positive electrode material B has a characteristic diffraction peak of the (003) crystal plane at 14 ° -18 ° 2θ, in other words, the sodium ion positive electrode material provided by the present invention contains the positive electrode material a and the positive electrode material B, the positive electrode material a exhibits at least P2 type crystal characteristics and has the properties of single crystal particles, the positive electrode material B exhibits at least O3 type crystal characteristics and exhibits the properties of agglomerated particles, and the positive electrode material a and the positive electrode material B of the characteristics are mixed to form a sodium ion positive electrode material having a high capacity and a long cycle combined performance and a higher volume energy density than the positive electrode material of a sodium ion battery containing the O3 type single crystal positive electrode material a and the P2 type agglomerated positive electrode material B.
As can be seen from comparing the test results of the examples 1 and 2, the structural stability of the positive electrode material of the sodium ion battery can be further enhanced and the rate performance and the cycle performance of the positive electrode material of the sodium ion battery can be further improved after the P2/O3 type composite phase agglomerated positive electrode material B is mixed with the P2 type single crystal positive electrode material a.
As can be seen from comparing the test results of example 1 and example 3, the capacity and the volume energy density of the positive electrode material of the sodium ion battery can be further enhanced on the basis of the stable rate performance and the cycle performance after the P2/O3 type composite phase single crystal positive electrode material a is mixed with the O3 type agglomerated positive electrode material B.
As can be seen from comparing the test results of example 3 and example 5, the combination of doping elements of different types in the positive electrode material of the sodium ion battery can further enhance the stability of the single crystal structure and further improve the cycle performance and the rate performance of the positive electrode material of the sodium ion battery.
As can be seen from comparing the test results of examples 3 to 4 and example 7, the content of the positive electrode material a and the positive electrode material B in the positive electrode material for sodium ion battery is within the preferred range defined in the present invention, and the compacted density of the positive electrode material for sodium ion battery is further improved.
As can be seen from comparing the test results of example 3, example 6 and example 8, the median particle diameter D of the positive electrode material A and the positive electrode material B 50 In the preferred range defined by the invention, the compaction density and the volumetric energy density of the positive electrode material of the sodium ion battery can be further improved on the basis of stable multiplying power performance and cycle performance.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.
Claims (10)
1. The positive electrode material of the sodium ion battery is characterized by comprising a positive electrode material A and a positive electrode material B; wherein the positive electrode material A is monocrystalline particles, and the positive electrode material B is an agglomerate; and, in addition, the method comprises the steps of,
in the XRD patterns of the positive electrode material A and the positive electrode material B, each independently has a characteristic diffraction peak of a (002) crystal face and/or a (003) crystal face at a 2 theta of 14-18 degrees, and the 2 theta angle of the characteristic diffraction peak of the (002) crystal face is smaller than the 2 theta angle of the characteristic diffraction peak of the (003) crystal face;
Wherein the positive electrode material A has at least a characteristic diffraction peak of the (002) crystal plane, and the positive electrode material B has at least a characteristic diffraction peak of the (003) crystal plane.
2. The sodium ion battery positive electrode material of claim 1, wherein the positive electrode material a has a median particle diameter D 50 1 to 5. Mu.m, preferably 2 to 4. Mu.m, more preferably 3.6 to 4. Mu.m;
and/or, the median diameter D of the positive electrode material B 50 6 to 16. Mu.m, preferably 8 to 14. Mu.m, more preferably 12.3 to 13.9. Mu.m;
and/or, the median particle diameter D of the sodium ion battery anode material 50 1-20 μm, preferably 5-15 μm;
preferably, the weight ratio of the positive electrode material a to the positive electrode material B is 1:0.1 to 9, preferably 1:0.4-2.5.
3. The sodium ion battery positive electrode material of claim 1, wherein the positive electrode material a has a composition represented by formula I:
Na a1 (Ni x1 Fe y1 Mn z1 M m1 M′ n1 )O 2 a formula I;
wherein a is more than or equal to 0.50 1 ≤1.10，0≤x 1 ≤0.5，0≤y 1 ≤0.5，0≤z 1 ≤0.5，0≤m 1 ≤0.5，0≤n 1 ≤0.1，0.05≤m 1 +n 1 ≤0.1，m 1 、n 1 Not at the same time 0, x 1 +y 1 +z 1 +m 1 +n 1 ＝1；
The positive electrode material B has a composition shown in a formula II:
Na a2 (Ni x2 Fe y2 Mn z2 M m2 M′ n2 )O 2 a formula II;
wherein a is more than or equal to 0.50 2 ≤1.10，0≤x 2 ≤0.5，0≤y 2 ≤0.5，0≤z 2 ≤0.5，0≤m 2 ≤0.1，0≤n 2 ≤0.1，0.05≤m 2 +n 2 ≤0.1，m 2 、n 2 Not at the same time 0, x 2 +y 2 +z 2 +m 2 +n 2 ＝1；
M is at least one element selected from Cu, co, V, cr, ti, mg, sn, zn, al, zr, nb, Y, W, la, and M' is at least one element selected from Li, al, mg, ti, zr, sr, la, nb, B, W;
Preferably, a 1 ：(x 1 +y 1 +z 1 +m 1 +n 1 ) =0.5-0.8: 1, preferably 0.6-0.80:1, more preferably 0.67-0.8:1, a step of;
preferably, a 2 ：(x 2 +y 2 +z 2 +m 2 +n 2 ) =0.7-1.1: 1, preferably 0.8-1.05:1, more preferably 0.8-1:1, a step of;
preferably, a 2 And a 1 The difference between (2) and (0) is 0-0.5, preferably 0.2-0.35.
4. The sodium-ion battery positive electrode material according to any one of claims 1 to 3, wherein the range of 2 theta angles of the characteristic diffraction peaks of the (002) crystal planes of the positive electrode material a and the positive electrode material B is 15.7 ° or more, and the range of 2 theta angles of the characteristic diffraction peaks of the (003) crystal planes of the positive electrode material a and the positive electrode material B is 16.7 ° or less.
5. The positive electrode material for sodium-ion battery according to claim 4, wherein a ratio of a characteristic diffraction peak intensity to a strongest diffraction peak intensity of the (002) crystal face is defined as I A The ratio of the characteristic diffraction peak intensity to the strongest diffraction peak intensity of the (003) crystal face is I B The positive electrode material a satisfies: i is more than or equal to 0.4 A /(I A +I B ) Less than or equal to 1.0; the positive electrode material B satisfies 0.ltoreq.I A /(I A +I B )≤0.4。
6. A method for preparing the positive electrode material of the sodium ion battery according to any one of claims 1 to 5, comprising:
mixing the positive electrode material A and the positive electrode material B;
Preferably, the method for preparing the positive electrode material a includes:
(1) Mixing a nickel source, an iron source, a manganese source, a precipitator and a complexing agent in the presence of a solvent to perform a first coprecipitation reaction to obtain a precursor I;
(2) Mixing the precursor I with a sodium source, a doping agent containing M and/or a doping agent containing M' for first sintering to obtain the positive electrode material A;
preferably, the method for preparing the positive electrode material B includes:
(a) Mixing a nickel source, an iron source, a manganese source, a precipitator and a complexing agent in the presence of a solvent to perform a second coprecipitation reaction to obtain a precursor II;
(b) And mixing the precursor II with a sodium source, a dopant containing M and/or a dopant containing M' for secondary sintering to obtain the positive electrode material B.
7. The process according to claim 6, wherein the precursor I in step (1) and the precursor II in step (a) are both spherical and K is the same as K 90 ＜1.0；D 50 The value range of (2) is 1-20 mu m;
preferably, in step (2), the median particle diameter D of the positive electrode material a 50 1 to 5. Mu.m, preferably 2 to 4. Mu.m, more preferably 3.6 to 4. Mu.m;
preferably, in step (2), the sodium source is used in an amount such that, in terms of stoichiometry: n (Na)/n (Me) is 0.5 to 0.85, preferably 0.6 to 0.85;
Preferably, in step (B), the median particle diameter D of the positive electrode material B 50 6 to 16. Mu.m, preferably 8 to 14. Mu.m, more preferably 12.3 to 13.9. Mu.m;
preferably, in step (b), the sodium source is used in an amount such that, in stoichiometric proportions: n (Na)/n (Me) is 0.7 to 1.1, preferably 0.8 to 1.05;
preferably, in step (2) and step (b), the sodium sources are each independently selected from at least one of sodium carbonate, sodium hydroxide, sodium nitrate and sodium oxide;
the M-containing dopants are each independently selected from at least one of M-containing oxides, phosphates, fluorides, chlorides, hydroxides, and silicides, preferably from CuO, co (OH) 2 、V 2 O 5 、Cr 2 O 3 、TiO 2 、MgCO 3 、Sr(OH) 2 、SrCO 3 、Al 2 O 3 、AlPO 4 、AlCl 3 、ZrO、Zr(HPO 4 ) 2 、ZrSi 2 、Nb 2 O 5 、Y 2 O 3 、WO 3 、NaF 3 And La (La) 2 O 3 At least one of (a) and (b);
the M 'containing dopants are each independently selected from the group consisting of M' containing oxides, phosphates, carbonates, fluorides, chlorides, hydrogenAt least one of the oxides and silicides, preferably selected from Li 2 CO 3 、Al 2 O 3 、AlPO 4 、AlCl 3 、MgO、Mg 3 (PO 4 ) 2 、MgCO 3 、MgSi 2 、MgF 2 、MgCl 2 、TiO 2 、ZrO、Zr(HPO 4 ) 2 、ZrSi 2 、Sr(OH) 2 、SrCO 3 、SrSi 2 、SrF 2 、SrCl 2 、La 2 O 3 、Nb 2 O 5 、B 2 O 3 And WO 3 At least one of them.
8. The production method according to any one of claims 6 to 7, wherein the conditions of the first coprecipitation reaction and/or the second coprecipitation reaction include: the pH value is 10.0-12.5, the temperature is 40-80 ℃, the time is 48-120h, and the stirring rotating speed is 100-800rpm;
Preferably, the first sintering and/or the second sintering is performed in an oxidizing atmosphere, and the conditions of the first sintering and/or the second sintering include: the temperature is 600-1200 ℃, the time is 10-20h, and the heating rate is 0.5-10 ℃/min;
preferably, the temperature of the second sintering is lower than the temperature of the first sintering;
more preferably, the conditions of the first sintering include: the temperature is 900-1100 ℃ and the time is 5-15h; the conditions for the second sintering include: the temperature is 800-900 ℃ and the time is 5-15h.
9. Use of the positive electrode material of a sodium ion battery according to any one of claims 1 to 5 or the preparation method according to any one of claims 6 to 8 in a sodium ion battery.
10. A sodium ion battery, characterized in that the sodium ion battery comprises a sodium ion battery positive electrode material according to any one of claims 1-5.
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| CN117497728A (en) * | 2023-12-04 | 2024-02-02 | 湖南美特新材料科技有限公司 | Sodium ion battery positive electrode material and preparation method thereof |
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| CN116525814A (en) * | 2023-06-29 | 2023-08-01 | 宁波容百新能源科技股份有限公司 | Positive electrode material, preparation method thereof, positive electrode plate and sodium ion battery |
| CN116525814B (en) * | 2023-06-29 | 2023-11-28 | 宁波容百新能源科技股份有限公司 | Positive electrode material, preparation method thereof, positive electrode plate and sodium ion battery |
| CN117497728A (en) * | 2023-12-04 | 2024-02-02 | 湖南美特新材料科技有限公司 | Sodium ion battery positive electrode material and preparation method thereof |
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