CN117878324A - Oxide positive electrode material for gradient doped sodium ion battery and preparation method thereof - Google Patents
Oxide positive electrode material for gradient doped sodium ion battery and preparation method thereof Download PDFInfo
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- CN117878324A CN117878324A CN202311763683.1A CN202311763683A CN117878324A CN 117878324 A CN117878324 A CN 117878324A CN 202311763683 A CN202311763683 A CN 202311763683A CN 117878324 A CN117878324 A CN 117878324A
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- 239000007774 positive electrode material Substances 0.000 title claims abstract description 50
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 229910001415 sodium ion Inorganic materials 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000000126 substance Substances 0.000 claims abstract description 13
- 239000000243 solution Substances 0.000 claims description 165
- 238000006243 chemical reaction Methods 0.000 claims description 78
- 239000002243 precursor Substances 0.000 claims description 47
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 42
- 239000011734 sodium Substances 0.000 claims description 33
- 239000011572 manganese Substances 0.000 claims description 32
- 238000000034 method Methods 0.000 claims description 32
- 239000010405 anode material Substances 0.000 claims description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- 239000011777 magnesium Substances 0.000 claims description 17
- 239000002245 particle Substances 0.000 claims description 14
- 239000012266 salt solution Substances 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 11
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 10
- 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 10
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 10
- 239000008139 complexing agent Substances 0.000 claims description 10
- 238000005245 sintering Methods 0.000 claims description 10
- 229910052708 sodium Inorganic materials 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- URQWOSCGQKPJCM-UHFFFAOYSA-N [Mn].[Fe].[Ni] Chemical compound [Mn].[Fe].[Ni] URQWOSCGQKPJCM-UHFFFAOYSA-N 0.000 claims description 8
- 239000002019 doping agent Substances 0.000 claims description 8
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 7
- 230000008569 process Effects 0.000 claims description 7
- 239000010406 cathode material Substances 0.000 claims description 6
- 229910052749 magnesium Inorganic materials 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- 239000011701 zinc Substances 0.000 claims description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 4
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 4
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 4
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims description 4
- 230000000630 rising effect Effects 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
- UBXAKNTVXQMEAG-UHFFFAOYSA-L strontium sulfate Chemical compound [Sr+2].[O-]S([O-])(=O)=O UBXAKNTVXQMEAG-UHFFFAOYSA-L 0.000 claims description 4
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 4
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 4
- 229960001763 zinc sulfate Drugs 0.000 claims description 4
- ZXAUZSQITFJWPS-UHFFFAOYSA-J zirconium(4+);disulfate Chemical compound [Zr+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ZXAUZSQITFJWPS-UHFFFAOYSA-J 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- 229910021555 Chromium Chloride Inorganic materials 0.000 claims description 2
- 230000032683 aging Effects 0.000 claims description 2
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 2
- 239000011609 ammonium molybdate Substances 0.000 claims description 2
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 2
- 229940010552 ammonium molybdate Drugs 0.000 claims description 2
- SZOADBKOANDULT-UHFFFAOYSA-K antimonous acid Chemical compound O[Sb](O)O SZOADBKOANDULT-UHFFFAOYSA-K 0.000 claims description 2
- 229910052787 antimony Inorganic materials 0.000 claims description 2
- 229910000379 antimony sulfate Inorganic materials 0.000 claims description 2
- MVMLTMBYNXHXFI-UHFFFAOYSA-H antimony(3+);trisulfate Chemical compound [Sb+3].[Sb+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O MVMLTMBYNXHXFI-UHFFFAOYSA-H 0.000 claims description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 2
- 239000004327 boric acid Substances 0.000 claims description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 2
- QSWDMMVNRMROPK-UHFFFAOYSA-K chromium(3+) trichloride Chemical compound [Cl-].[Cl-].[Cl-].[Cr+3] QSWDMMVNRMROPK-UHFFFAOYSA-K 0.000 claims description 2
- GRWVQDDAKZFPFI-UHFFFAOYSA-H chromium(III) sulfate Chemical compound [Cr+3].[Cr+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O GRWVQDDAKZFPFI-UHFFFAOYSA-H 0.000 claims description 2
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims description 2
- 229940044175 cobalt sulfate Drugs 0.000 claims description 2
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 2
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 claims description 2
- 239000001095 magnesium carbonate Substances 0.000 claims description 2
- 229910000021 magnesium carbonate Inorganic materials 0.000 claims description 2
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims description 2
- 235000019341 magnesium sulphate Nutrition 0.000 claims description 2
- IIDYTZRUUWUVQF-UHFFFAOYSA-D niobium(5+) pentasulfate Chemical compound [Nb+5].[Nb+5].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O IIDYTZRUUWUVQF-UHFFFAOYSA-D 0.000 claims description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 2
- DKNJHLHLMWHWOI-UHFFFAOYSA-L ruthenium(2+);sulfate Chemical compound [Ru+2].[O-]S([O-])(=O)=O DKNJHLHLMWHWOI-UHFFFAOYSA-L 0.000 claims description 2
- 239000004317 sodium nitrate Substances 0.000 claims description 2
- 235000010344 sodium nitrate Nutrition 0.000 claims description 2
- ZNCPFRVNHGOPAG-UHFFFAOYSA-L sodium oxalate Chemical compound [Na+].[Na+].[O-]C(=O)C([O-])=O ZNCPFRVNHGOPAG-UHFFFAOYSA-L 0.000 claims description 2
- 229940039790 sodium oxalate Drugs 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
- 230000000087 stabilizing effect Effects 0.000 claims description 2
- FAKFSJNVVCGEEI-UHFFFAOYSA-J tin(4+);disulfate Chemical compound [Sn+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O FAKFSJNVVCGEEI-UHFFFAOYSA-J 0.000 claims description 2
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 claims description 2
- 229910052723 transition metal Inorganic materials 0.000 claims description 2
- 229910052720 vanadium Inorganic materials 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 2
- 239000012535 impurity Substances 0.000 claims 1
- 159000000000 sodium salts Chemical class 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 18
- 230000002829 reductive effect Effects 0.000 abstract description 7
- 230000002427 irreversible effect Effects 0.000 abstract description 3
- 239000007788 liquid Substances 0.000 description 28
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 20
- 238000003756 stirring Methods 0.000 description 19
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 18
- 238000000975 co-precipitation Methods 0.000 description 16
- 230000001105 regulatory effect Effects 0.000 description 16
- 229910000863 Ferronickel Inorganic materials 0.000 description 15
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 11
- 229910052757 nitrogen Inorganic materials 0.000 description 10
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 9
- 241000080590 Niso Species 0.000 description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 9
- 229910052786 argon Inorganic materials 0.000 description 9
- 238000007664 blowing Methods 0.000 description 9
- 229910052748 manganese Inorganic materials 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 238000001816 cooling Methods 0.000 description 8
- 239000012071 phase Substances 0.000 description 8
- 238000009826 distribution Methods 0.000 description 7
- 150000002696 manganese Chemical class 0.000 description 7
- 238000009792 diffusion process Methods 0.000 description 6
- 230000002572 peristaltic effect Effects 0.000 description 6
- 238000000967 suction filtration Methods 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 230000001276 controlling effect Effects 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 229910021645 metal ion Inorganic materials 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 3
- 238000004146 energy storage Methods 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 241001296405 Tiso Species 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 230000009977 dual effect Effects 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000036961 partial effect Effects 0.000 description 2
- 239000007790 solid phase Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 1
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- NTUKYEWPMLPVHZ-UHFFFAOYSA-N [Mn].[Ni].[Fe].[Mg] Chemical compound [Mn].[Ni].[Fe].[Mg] NTUKYEWPMLPVHZ-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 229940062993 ferrous oxalate Drugs 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 238000010406 interfacial reaction Methods 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- DALUDRGQOYMVLD-UHFFFAOYSA-N iron manganese Chemical class [Mn].[Fe] DALUDRGQOYMVLD-UHFFFAOYSA-N 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- OWZIYWAUNZMLRT-UHFFFAOYSA-L iron(2+);oxalate Chemical compound [Fe+2].[O-]C(=O)C([O-])=O OWZIYWAUNZMLRT-UHFFFAOYSA-L 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
- 239000003273 ketjen black Substances 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- 239000011565 manganese chloride Substances 0.000 description 1
- 235000002867 manganese chloride Nutrition 0.000 description 1
- 229940099607 manganese chloride Drugs 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
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 1
- RGVLTEMOWXGQOS-UHFFFAOYSA-L manganese(2+);oxalate Chemical compound [Mn+2].[O-]C(=O)C([O-])=O RGVLTEMOWXGQOS-UHFFFAOYSA-L 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
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 150000002815 nickel Chemical class 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 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
- DOLZKNFSRCEOFV-UHFFFAOYSA-L nickel(2+);oxalate Chemical compound [Ni+2].[O-]C(=O)C([O-])=O DOLZKNFSRCEOFV-UHFFFAOYSA-L 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 229920002981 polyvinylidene fluoride 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
- 238000011160 research Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
Classifications
-
- 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
Landscapes
- Battery Electrode And Active Subsutance (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention provides a high-performance oxide positive electrode material for a gradient doped sodium ion battery and a preparation method thereof, wherein the positive electrode material is O3 type layered oxide for the sodium ion battery, and the content of doping elements is increased from the core of the material to the surface in a gradient manner. The chemical formula of the positive electrode material is NaNi x Fe y Mn z M a O 2 Wherein a is more than 0 and less than or equal to 0.1, x is more than 0 and less than 1, y is more than 0 and less than 1, z is more than 0 and less than 1, x+y+z+a=1, and M is a doping element. The inventionThe clear positive electrode material has a better spherical shape, the concentration of doping elements is gradually increased from the core of the material, the irreversible capacity loss of the positive electrode material of the sodium ion battery is reduced, the circulation stability and the safety performance are improved, and the problems of poor circulation stability and unstable surface structure of the positive electrode material of the sodium ion battery are solved.
Description
Technical Field
The invention belongs to the field of sodium battery materials, and particularly relates to a high-performance gradient doped oxide positive electrode material for a sodium ion battery and a preparation method thereof.
Background
Lithium ion batteries have been widely used in the fields of portable electronic devices, electric vehicles, large-scale energy storage, and the like. However, lithium resource shortage and lithium carbonate cost problems are increasingly prominent, and development of a novel energy storage system is urgent. In recent years, low-cost sodium ion batteries have attracted extensive attention in academia and commercial industries, and are expected to replace lithium ion batteries in the field of large-scale energy storage.
The positive electrode material is used as a key component of a sodium ion battery system, has high development capacity, good cycle stability, safety and low cost, and has great significance for promoting the large-scale commercial application of sodium ion batteries. The layered oxide anode material has the characteristics of higher energy density and easiness in preparation, so that the layered oxide anode material is widely researched by people and enters an industrialization stage at an increased speed. However, there are still some basic scientific issues to be solved by layered oxide cathode materials. For example, the ginger-taylor distortion can affect the stability of the structure or promote the dissolution of metal ions, and the complex structure evolution process can lead to larger deformation, cause the crushing of particles and Na in the sintering process + Depositing residual alkali (NaOH/Na) on the surface of the positive electrode material 2 CO 3 /NaHCO 3 ) Leading to serious interfacial reactions and gassing problems, and poor air stability leading to reduced or failed cell performance, etc.
Ion doping is one of the effective means for inhibiting structural phase change and improving the stability of lattice structure, and the main doping ions comprise Cu 2+ 、Zn 2+ 、Mg 2+ 、Ti 2+ And the plasma metal ions improve ion diffusion kinetics and improve the electrochemical performance of the electrode material by regulating and controlling a sodium interlayer structure. When the solid-phase sintering method is used for preparing the sodium ion battery anode material, the doping diffusion speed and uniformity of doping elements have important influence on the quality of products, and the phenomena of uneven doping element distribution and partial enrichment are easy to occur. More importantly, the solid phase sintering has the defects of high energy consumption and long period.
Disclosure of Invention
The invention aims to solve the technical problems and overcome the defects and shortcomings in the background art, and provides an oxide positive electrode material for a gradient doped sodium ion battery with high performance and good structural stability and a preparation method thereof.
In order to solve the technical problems, the technical scheme provided by the invention is as follows:
the positive electrode material is a layered oxide, doped elements are added into the positive electrode material, the content of the doped elements gradually increases from the inside to the surface of the positive electrode material, the gradient increases, the maximum concentration is reached on the surface of the positive electrode material, and the doped elements account for 1-7% of the mole ratio of the transition metal elements.
In the invention, the doping elements in the sodium ion positive electrode material of the layered oxide form continuous gradient distribution, the doping element content of the material changes from inside to outside in a gradient manner, and the concentration on the surface of the particles is higher, so that the interface between the material and the electrolyte is more stable, side reactions are reduced, the concentration of the doping elements in the material is reduced, the capacity of the material is improved, and the cycle life and safety of the battery are improved.
Compared with the traditional doping mode of dispersing doped ions by means of diffusion and adopting coprecipitation to realize uniform doping, gradient doping can combine the advantages of bulk phase and surface doping on one hand, the dual functions of surface element-rich doping and bulk phase element-less doping are exerted, the structural stability of the surface and bulk phase is improved, a stable doped layer is constructed at a position close to the surface on the other hand, the surface structure is stabilized, and the generation of microcracks is inhibited. On the other hand, the gradient distribution of the doping elements can reduce the dosage of non-chemical active doping elements, thereby effectively improving the electrochemical performance of the doped anode material. According to the invention, the feeding mode of the doping element is regulated and controlled by a coprecipitation method, so that the gradient distribution of the doping element is realized.
Preferably, the layered oxide for the sodium ion battery is an O3 type layered positive electrode material, and the chemical formula is NaNi x Fe y Mn z M a O 2 Wherein 0 < x < 1,0 < y <, 0 < z < 1, x+y+z+a=1.
Preferably, the molecular formula of the positive electrode material is NaNi 0.333 Fe 0.333 Mn 0.333-a M a O 2 Wherein a is more than 0 and less than or equal to 0.1, and the doping element M is one or a combination of more than one of Mg, cu, zn, co, ca, ba, sr, al, B, cr, zr, ti, sn, V, mo, ru, nb and Sb.
Preferably, the doping element is Mg, ti or Zn.
The researchers in the invention carry out a lot of effective work on the doping modification strategy of the layered oxide, and the researches show that the doping of electrochemical inert elements such as Mg, ti, zn, zr in the layered oxide is an effective strategy for improving the structural stability of the layered oxide and inhibiting irreversible phase change. Therefore, in the invention, inert elements are introduced in the coprecipitation process, so that the uniform distribution of doping elements is realized, and the cycling stability of the positive electrode material is enhanced.
Based on the general inventive concept, the invention also provides a preparation method of the gradient doped oxide anode material, which comprises the following steps:
(1) Preparing a nickel-iron-manganese mixed salt solution A, pH regulator B1 and a complexing agent B2, and preparing a low-concentration dopant solution C1 and a high-concentration dopant solution C2;
(2) Adding deionized water into a reaction kettle, controlling the pH value of the solution to be 10.5-11.5 by utilizing a pH regulator B1, simultaneously adding the solution A, pH regulator B1, a complexing agent B2 and a solution C with gradually increased concentration, which is formed by continuously adding a C2 solution into the C1 solution, into the reaction kettle in the presence of nitrogen or argon, stabilizing the pH value in the reaction kettle to be 10.5-11.5 in the reaction process, controlling the temperature to be 45-65 ℃, controlling all the solutions to be added at the same time, and then aging, filtering and drying to obtain precursor particles;
(3) And (3) uniformly mixing the precursor particles obtained in the step (2) with a sodium source, and then sintering at a high temperature to obtain the gradient doped oxide anode material.
In order to realize gradient distribution of metal atoms, the invention considers that the solubility of hydroxides of different metal ions is accumulated in a larger difference, so complexing agents are added in the coprecipitation process, metal ions are firstly complexed with the complexing agents to form coordination complexes, then the coordination complexes react with hydroxide radicals slowly to form hydroxide precipitates, meanwhile, ferronickel manganese mixed salt solution and solution C with gradually increased concentration, which is formed by continuously adding C2 solution into continuously stirred C1 solution, are synchronously added in the reaction process, and the solubility of the solution of doping elements is gradually increased, so that gradient distribution of metal element atoms is realized.
Preferably, the concentration of the nickel-iron-manganese mixed salt solution A in the step (1) is 1-4 mol.L -1 The pH regulator B1 is 1-4mol.L -1 Sodium hydroxide solution and complexing agent B2 of 0.1-1 mol.L -1 Ammonia water solution; the concentration of the high-concentration dopant solution C2 is 0.1-1 mol.L -1 The initial concentration of the low-concentration dopant solution C1 is 0 mol.L -1 。
Preferably, the nickel salt in the nickel-iron-manganese mixed salt in the step (1) comprises one or a combination of more of nickel sulfate, nickel nitrate, nickel chloride and nickel oxalate; the ferric salt in the ferronickel manganese mixed salt comprises one or a combination of more of ferric sulfate, ferric nitrate, ferric chloride and ferrous oxalate; the manganese salt in the ferronickel manganese mixed salt comprises one or a combination of a plurality of manganese sulfate, manganese nitrate, manganese chloride and manganese oxalate.
Preferably, the high-concentration doping solution C2 and the low-concentration doping solution C1 are one or more of zirconium sulfate, magnesium sulfate, zinc sulfate, copper sulfate, zinc sulfate, cobalt sulfate, aluminum hydroxide, magnesium carbonate, calcium carbonate, barium sulfate, strontium sulfate, aluminum hydroxide, boric acid, chromium sulfate, chromium chloride, zirconium sulfate, tin sulfate, titanium hydroxide, zirconium oxide, ammonium molybdate, ruthenium sulfate, niobium sulfate, antimony sulfate, and antimony hydroxide.
Preferably, the precursor particles have a particle size in the range of 3 μm to 15 μm.
Preferably, the stirring speed of the reaction kettle is 300-800r/min.
Preferably, the feeding flow rate of the solution A in the step (2) into the reaction kettle is 1-5 L.h -1 The method comprises the steps of carrying out a first treatment on the surface of the The feeding flow of the pH regulator B1 into the reaction kettle is 1-5 L.h -1 The method comprises the steps of carrying out a first treatment on the surface of the The feeding flow of the complexing agent B2 added into the reaction kettle is 0.1-1 L.h -1 The method comprises the steps of carrying out a first treatment on the surface of the The feeding flow of the solution C with gradually increased concentration into the reaction kettle is 0.1-1 L.h -1 。
Further, the feeding flow rate of the solution A in the step (2) into the reaction kettle is 2-4 L.h -1 The method comprises the steps of carrying out a first treatment on the surface of the The feeding flow of the pH regulator B1 into the reaction kettle is 2-4 L.h -1 。
Preferably, the sodium source in the mixed raw material D in the step (3) is selected from one or more of sodium hydroxide, sodium carbonate, sodium oxide, sodium oxalate and sodium nitrate, and the molar ratio of the metal element in the precursor particles to the sodium element in the sodium source (ni+fe+mn+m): na is 1: (0.8-1.1).
Preferably, in the step (3), the high-temperature sintering equipment is a box furnace or a tube furnace, and the parameters of the high-temperature sintering are as follows: the temperature rising rate is 3-10 ℃ min -1 Heat-treating at 750-950 deg.C for 10-20 hr.
In the invention, for material synthesis, the temperature rising speed is too high, which is unfavorable for the reaction of sodium carbonate and a precursor, and partial sodium carbonate residue increases the residual alkali.
Compared with the prior art, the invention has the beneficial effects that:
(1) The gradient doped oxide positive electrode material has a good spherical morphology, the concentration of doping elements is gradually increased from the surface of the internal value of the material, the irreversible capacity loss of the positive electrode material of the sodium ion battery is reduced, the circulation stability and the safety performance are improved, and the problems of poor circulation stability and unstable surface structure of the positive electrode material of the sodium ion battery are solved.
(2) According to the invention, the coprecipitation method is adopted for gradient doping, the feeding condition of the doped metal salt solution is controlled to accurately realize gradient distribution of doping elements from particle cores to particle surfaces, so that the conductivity and structural stability of the sodium ion battery anode material can be effectively improved, the discharge capacity and the circulation performance of the material are further improved, and the prepared high-performance gradient doped sodium ion battery anode material can meet the requirements more; compared with diffusion doping and uniform doping, gradient doping can play the dual roles of surface element-rich doping and bulk phase element-less doping, on one hand, a stable doping layer is constructed at a position close to the surface to stabilize the surface structure and inhibit the generation of microcracks, on the other hand, the dosage of non-chemical active dopants can be reduced, the surface and bulk phase stability of the oxide positive electrode material is improved, and the stress in the charge and discharge process is relieved. The sodium ion battery anode material prepared by the method has wide application prospect in the field of novel battery materials in the future.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are required in the embodiments or the description of the prior art will be briefly described, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is an XRD pattern of the positive electrode material prepared in example 1;
FIG. 2 is an electron microscopic view of the positive electrode material prepared in example 1;
fig. 3 is a graph showing 100 cycle performance comparisons of the positive electrode materials prepared in comparative examples 1, 2,1 and 3.
Detailed Description
The present invention will be described more fully hereinafter with reference to the accompanying drawings, in which preferred embodiments are shown, for the purpose of illustrating the invention, but the scope of the invention is not limited to the specific embodiments shown.
Unless defined otherwise, all technical and scientific terms used hereinafter have the same meaning as commonly understood by one of ordinary skill in the art. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the scope of the present invention.
Unless otherwise specifically indicated, the various raw materials, reagents, instruments, equipment and the like used in the present invention are commercially available or may be prepared by existing methods.
Example 1:
preparation of gradient doped oxide positive electrode material, wherein a=0.05 is set as chemical formula
NaNi 0.333 Fe 0.333 Mn 0.283 Mg 0.05 O 2 . The method comprises the following steps:
(1) 2 mol.L of configuration -1 A ferronickel manganese mixed salt solution A, wherein the ferronickel manganese salt is NiSO 4 、FeSO 4 、MnSO 4 Is a mixture of (1), ni: fe: mn molar ratio of 0.333:0.333:0.283. in addition, 4 mol.L -1 NaOH solution B1 of 0.2 mol.L -1 0.5 mol.L of aqueous ammonia solution B2 of (A) -1 Is MgSO of (2) 4 Solution C1 having an initial concentration of 0 mol.L -1 Is MgSO of (2) 4 Solution C2.
(2) The temperature of the reaction kettle is controlled at 55 ℃ by using circulating water, the stirring speed of a stirring paddle in the reaction kettle is set at 600rpm, deionized water is added into the reaction kettle, and the pH value is regulated to 11 by using a solution B1. After the pH of the system is stable, continuously adding the solution A, the solution B1, the solution B2 and the solution C2 into the continuously stirred solution C1 by using a peristaltic pump under the atmosphere of nitrogen or argon to form a solution C with gradually increased concentration, and adding the solution C into a coprecipitation reaction kettle in parallel flow, wherein the concentration is between 1 and 5 L.h -1 Regulating solution B1 in the range of 0.1-1 L.h -1 The liquid inlet speed of B2 in the range stabilizes the pH at 11, the liquid inlet speeds of the solution A, the solution B1 and the solution B2 entering the reaction kettle are respectively 2L/h,0.5L/h and the liquid inlet speed of the C2 solution added into the C1 solution is 0.4L/h, and the concentration of the solution C entering the reaction kettle is gradually increasedThe liquid speed is 2L/h, so that all materials are added at the same time. After the addition, part of the precursor is taken out from the reaction kettle for washing and suction filtration for multiple times, and then the precursor is dried for 24 hours by blowing at 80 ℃ to obtain the precursor (Ni) 0.333 Fe 0.333 Mn 0.283 Mg 0.05 )OH 2 。
(3) Taking fully dried precursor and Na 2 CO 3 Thoroughly mixing, wherein the molar ratio of the two is Na:
(ni+fe+mn+mg) =1.05: 1 in an air atmosphere at 5 ℃ min -1 And (3) raising the temperature to 850 ℃ and preserving heat for 15h, and then naturally cooling to room temperature to obtain the gradient doped oxide anode material.
Fig. 1 is an XRD pattern of the positive electrode material prepared in example 1, and as can be seen from the figure, the gradient doped oxide positive electrode material obtained in example 1 has an O3 phase structure.
Fig. 2 is an electron microscope image of the positive electrode material prepared in example 1, and as can be seen from the image, the gradient doped oxide positive electrode material obtained in example 1 has a better spherical morphology.
Example 2:
preparation of gradient doped oxide positive electrode material, wherein a=0.07 is set as chemical formula
NaNi 0.333 Fe 0.333 Mn 0.263 Mg 0.07 O 2 . The method comprises the following steps:
(1) 2 mol.L of configuration -1 A ferronickel manganese mixed salt solution A, wherein the ferronickel manganese salt is NiSO 4 、FeSO 4 、MnSO 4 Is a mixture of (1), ni: fe: mn molar ratio of 0.333:0.333:0.263. in addition, 4 mol.L -1 NaOH solution B1 of 0.2 mol.L -1 0.5 mol.L of aqueous ammonia solution B2 of (A) -1 Is MgSO of (2) 4 Solution C1 having an initial concentration of 0 mol.L -1 Is MgSO of (2) 4 Solution C2.
(2) The temperature of the reaction kettle is controlled at 55 ℃ by using circulating water, the stirring speed of a stirring paddle in the reaction kettle is set at 600rpm, deionized water is added into the reaction kettle, and the pH value is regulated to 11 by using a solution B1. After the pH of the system is stable, a peristaltic pump is used under the atmosphere of nitrogen or argonControlling the continuous addition of solution A and solution B1, solution B2 and C2 to the continuously stirred solution C1 to form a solution C with gradually increased concentration, and feeding the solution C into the coprecipitation reaction kettle in parallel flow mode, wherein the concentration is controlled to be higher than that of the solution C by 1-5 L.h -1 Regulating solution B1 in the range of 0.1-1 L.h -1 The liquid feeding speed of B2 in the range stabilizes the pH at 11, the liquid feeding speeds of the solution A, the solution B1 and the solution B2 entering the reaction kettle are respectively 2L/h,0.5L/h, the liquid feeding speed of the C2 solution added into the C1 solution is 0.56L/h, and the liquid feeding speed of the solution C with gradually increased concentration entering the reaction kettle is 2L/h, so that all materials are added simultaneously. After the addition, part of the precursor is taken out from the reaction kettle for washing and suction filtration for multiple times, and then the precursor is dried for 24 hours by blowing at 80 ℃ to obtain the precursor (Ni) 0.333 Fe 0.333 Mn 0.263 Mg 0.07 )OH 2 。
(3) Taking fully dried precursor and Na 2 CO 3 Thoroughly mixing, wherein the molar ratio of the two is Na:
(ni+fe+mn+mg) =1.05: 1 in an air atmosphere at 5 ℃ min -1 And (3) raising the temperature to 850 ℃ and preserving heat for 15h, and then naturally cooling to room temperature to obtain the gradient doped oxide anode material.
Example 3:
preparation of gradient doped oxide positive electrode material, wherein a=0.03 is set as chemical formula
NaNi 0.333 Fe 0.333 Mn 0.303 Mg 0.03 O 2 . The method comprises the following steps:
(1) 2 mol.L of configuration -1 A ferronickel manganese mixed salt solution A, wherein the ferronickel manganese salt is NiSO 4 、FeSO 4 、MnSO 4 Is a mixture of (1), ni: fe: mn molar ratio of 0.333:0.333:0.303. in addition, 4 mol.L -1 NaOH solution B1 of 0.2 mol.L -1 0.25 mol.L of aqueous ammonia solution B2 of (A) -1 Is MgSO of (2) 4 Solution C1 having an initial concentration of 0 mol.L -1 Is MgSO of (2) 4 Solution C2.
(2) The temperature of the reaction kettle is controlled to be 55 ℃ by using circulating water, the stirring speed of a stirring paddle in the reaction kettle is set to be 600rpm, and the reaction kettle is characterized in thatDeionized water was added to the reaction vessel and the pH was adjusted to 11 with solution B1. After the pH of the system is stable, continuously adding the solution A, the solution B1, the solution B2 and the solution C2 into the continuously stirred solution C1 by using a peristaltic pump under the atmosphere of nitrogen or argon to form a solution C with gradually increased concentration, and adding the solution C into a coprecipitation reaction kettle in parallel flow, wherein the concentration is between 1 and 5 L.h -1 Regulating solution B1 in the range of 0.1-1 L.h -1 The liquid feeding speed of B2 in the range stabilizes the pH at 11, the liquid feeding speeds of the solution A, the solution B1 and the solution B2 entering the reaction kettle are respectively 2L/h,0.5L/h, the liquid feeding speed of the C2 solution added into the C1 solution is 0.48L/h, and the liquid feeding speed of the solution C with gradually increased concentration entering the reaction kettle is 2L/h, so that all materials are added simultaneously. After the addition, part of the precursor is taken out from the reaction kettle for washing and suction filtration for multiple times, and then the precursor is dried for 24 hours by blowing at 80 ℃ to obtain the precursor (Ni) 0.333 Fe 0.333 Mn 0.303 Mg 0.03 )OH 2 。
(3) Taking fully dried precursor and Na 2 CO 3 Thoroughly mixing, wherein the molar ratio of the two is Na:
(ni+fe+mn+mg) =1.05: 1 in an air atmosphere at 5 ℃ min -1 And (3) raising the temperature to 850 ℃ and preserving heat for 15h, and then naturally cooling to room temperature to obtain the gradient doped oxide anode material.
Example 4:
preparation of gradient doped oxide positive electrode material, wherein a=0.01 is set as chemical formula
NaNi 0.333 Fe 0.333 Mn 0.323 Mg 0.01 O 2 . The method comprises the following steps:
(1) 2 mol.L of configuration -1 A ferronickel manganese mixed salt solution A, wherein the ferronickel manganese salt is NiSO 4 、FeSO 4 、MnSO 4 Is a mixture of (1), ni: fe: mn molar ratio of 0.333:0.333:0.323. in addition, 4 mol.L -1 NaOH solution B1 of 0.2 mol.L -1 0.25 mol.L of aqueous ammonia solution B2 of (A) -1 Is MgSO of (2) 4 Solution C1 having an initial concentration of 0 mol.L -1 Is MgSO of (2) 4 Solution C2.
(2) The temperature of the reaction kettle is controlled at 55 ℃ by using circulating water, the stirring speed of a stirring paddle in the reaction kettle is set at 600rpm, deionized water is added into the reaction kettle, and the pH value is regulated to 11 by using a solution B1. After the pH of the system is stable, continuously adding the solution A, the solution B1, the solution B2 and the solution C2 into the continuously stirred solution C1 by using a peristaltic pump under the atmosphere of nitrogen or argon to form a solution C with gradually increased concentration, and adding the solution C into a coprecipitation reaction kettle in parallel flow, wherein the concentration is between 1 and 5 L.h -1 Regulating solution B1 in the range of 0.1-1 L.h -1 The liquid feeding speed of the solution B2 in the range stabilizes the pH at 11, the liquid feeding speeds of the solution B1 and the solution B2 are regulated during the period to stabilize the pH at 11, the liquid feeding speeds of the solution A, the solution B1 and the solution B2 entering the reaction kettle are respectively 2L/h,0.5L/h and the liquid feeding speed of the C2 solution added into the C1 solution are 0.16L/h, and the liquid feeding speed of the solution C with gradually increased concentration entering the reaction kettle is 2L/h, so that all materials are added simultaneously. After the addition, part of the precursor is taken out from the reaction kettle for washing and suction filtration for multiple times, and then the precursor is dried for 24 hours by blowing at 80 ℃ to obtain the precursor (Ni) 0.333 Fe 0.333 Mn 0.3239 Mg 0.01 )OH 2 。
(3) Taking fully dried precursor and Na 2 CO 3 Thoroughly mixing, wherein the molar ratio of the two is Na:
(ni+fe+mn+mg) =1.05: 1 in an air atmosphere at 5 ℃ min -1 And (3) raising the temperature to 850 ℃ and preserving heat for 15h, and then naturally cooling to room temperature to obtain the gradient doped oxide anode material.
Example 5:
preparation of gradient doped oxide positive electrode material, wherein a=0.03 is set as chemical formula
NaNi 0.333 Fe 0.333 Mn 0.303 Ti 0.03 O 2 . The method comprises the following steps:
(1) 2 mol.L of configuration -1 A ferronickel manganese mixed salt solution A, wherein the ferronickel manganese salt is NiSO 4 ，FeSO 4 ，MnSO 4 Is a mixture of (1), ni: fe: mn molar ratio of 0.333:0.333:0.303. in addition, 4 mol.L -1 NaOH solution B1 of 0.2 mol.L -1 0.5 mol.L of aqueous ammonia solution B2 of (A) -1 TiSO of (C) 4 Solution C1 having an initial concentration of 0 mol.L -1 TiSO of (C) 4 Concentration solution C2.
(2) The temperature of the reaction kettle is controlled at 55 ℃ by using circulating water, the stirring speed of a stirring paddle in the reaction kettle is set at 600rpm, deionized water is added into the reaction kettle, and the pH value is regulated to 11.5 by using solution B1. After the pH of the system is stable, continuously adding the solution A, the solution B1, the solution B2 and the solution C2 into the continuously stirred solution C1 by using a peristaltic pump under the atmosphere of nitrogen or argon to form a solution C with gradually increased concentration, and adding the solution C into a coprecipitation reaction kettle in parallel flow, wherein the concentration is between 1 and 5 L.h -1 Regulating solution B1 in the range of 0.1-1 L.h -1 The liquid feeding speed of B2 in the range stabilizes the pH at 11, the liquid feeding speeds of the solution A, the solution B1 and the solution B2 entering the reaction kettle are 2L/h,0.5L/h and the liquid feeding speed of the C2 solution added into the C1 solution are 0.48L/h, and the liquid feeding speed of the solution C with gradually increased concentration entering the reaction kettle is 1L/h, so that all materials are added simultaneously. After the addition, part of the precursor is taken out from the reaction kettle for washing and suction filtration for multiple times, and then the precursor is dried for 24 hours by blowing at 80 ℃ to obtain the precursor (Ni) 0.333 Fe 0.333 Mn 0.303 Ti 0.03 )OH 2 。
(3) Taking fully dried precursor and Na 2 CO 3 Thoroughly mixing, wherein the molar ratio of the two is Na:
(ni+fe+mn+ti) =1.05: 1 in an air atmosphere at 5 ℃ min -1 And (3) raising the temperature to 850 ℃ and preserving heat for 15h, and then naturally cooling to room temperature to obtain the gradient doped oxide anode material.
Example 6:
preparation of gradient doped oxide positive electrode material, wherein a=0.03 is set as chemical formula
NaNi 0.333 Fe 0.333 Mn 0.303 Zn 0.03 O 2 . The method comprises the following steps:
(1) 2 mol.L of configuration -1 Nickel-iron-manganese mixed salt solution A, wherein nickelThe ferro-manganese salt is NiSO 4 ，FeSO 4 ，MnSO 4 Is a mixture of (1), ni: fe: mn molar ratio of 0.333:0.333:0.303. in addition, 4 mol.L -1 NaOH mixed solution B1 of (2), 0.2 mol.L -1 1.2 mol.L of aqueous ammonia solution B2 of (A) -1 ZnSO of (2) 4 Solution C1 having an initial concentration of 0 mol.L -1 ZnSO of (2) 4 Solution C2.
(2) The temperature of the reaction kettle is controlled at 55 ℃ by using circulating water, the stirring speed of a stirring paddle in the reaction kettle is set at 600rpm, deionized water is added into the reaction kettle, and the pH value is regulated to 10.5 by using solution B1. After the pH of the system is stable, continuously adding the solution A, the solution B1, the solution B2 and the solution C2 into the continuously stirred solution C1 by using a peristaltic pump under the atmosphere of nitrogen or argon to form a solution C with gradually increased concentration, and adding the solution C into a coprecipitation reaction kettle in parallel flow, wherein the concentration is between 1 and 5 L.h -1 Regulating solution B1 in the range of 0.1-1 L.h -1 The liquid feeding speed of B2 in the range stabilizes the pH at 11, the liquid feeding speeds of the solution A, the solution B1 and the solution B2 entering the reaction kettle are 2L/h,0.5L/h and the liquid feeding speed of the C2 solution added into the C1 solution are 0.48L/h respectively, and the liquid feeding speed of the solution C with gradually increased concentration entering the reaction kettle is 1L/h, so that all materials are added simultaneously. After the addition, part of the precursor is taken out from the reaction kettle for washing and suction filtration for multiple times, and then the precursor is dried for 24 hours by blowing at 80 ℃ to obtain the precursor (Ni) 0.333 Fe 0.333 Mn 0.303 Zn 0.03 )OH 2 。
(3) Taking fully dried precursor and Na 2 CO 3 Thoroughly mixing, wherein the molar ratio of the two is Na:
(ni+fe+mn+zn) =1.05: 1 in an air atmosphere at 5 ℃ min -1 And (3) raising the temperature to 850 ℃ and preserving heat for 15h, and then naturally cooling to room temperature to obtain the gradient doped oxide anode material.
Comparative example 1:
preparation of sodium ion battery oxide positive electrode material with chemical formula of Na (Ni 0.333 Fe 0.333 Mn 0.333 )O 2 . The method comprises the following steps:
(1) The concentration is 2 mol.L -1 A ferronickel manganese mixed salt solution A, wherein the ferronickel manganese salt is NiSO 4 ，FeSO 4 ，MnSO 4 Is a mixture of (1), ni: fe: mn molar ratio of 0.333:0.333:0.333. in addition, 4 mol.L -1 NaOH solution B1 of 0.2 mol.L -1 Ammonia solution B2 of (a).
(2) The temperature of the reaction kettle is controlled at 55 ℃ by using circulating water, the stirring speed of a stirring paddle in the reaction kettle is set at 600rpm, deionized water is added into the reaction kettle, and the pH value is regulated to 11 by using a solution B2. After the pH of the system is stable, the solution A and the solutions B1 and B2 are added into a coprecipitation reaction kettle in parallel flow under the atmosphere of nitrogen or argon, and the pH is stabilized at 11 by adjusting the liquid inlet speed of the solution B1.
(3) After the charging is finished, part of the precursor is taken out from the reaction kettle to be washed and suction filtered for multiple times, and then the precursor is dried for 24 hours by blowing at 80 ℃ to obtain the precursor Ni 0.333 Fe 0.333 Mn 0.333 (OH) 2 。
(4) Taking fully dried precursor and Na 2 CO 3 Thoroughly mixing, wherein the molar ratio of the two is Na:
(ni+fe+mn) =1.05: 1 in an air atmosphere at 5 ℃ min -1 And (3) heating to 900 ℃ and preserving heat for 15 hours, and then naturally cooling to room temperature to obtain the sodium ion battery oxide anode material.
The difference from example 1 is that no MgSO was added during the coprecipitation 4 And synthesizing a precursor by using the solution.
Comparative example 2:
preparation of diffusion doped modified oxide cathode material, setting a=0.05, namely chemical formula as Na (Ni 0.333 Fe 0.333 Mn 0.333 ) 0.95 Mg 0.05 O 2 . The method comprises the following steps:
(1) 2 mol.L of configuration -1 A nickel-iron-manganese mixed salt solution A, wherein the nickel-iron-manganese salt is NiSO 4 ，FeSO 4 ，MnSO 4 Is a mixture of (1), ni: fe: mn molar ratio of 0.333:0.333:0.333. in addition, 4 mol.L -1 NaOH solution B1 of 0.2 mol.L -1 Aqueous ammonia solution of (2)B2。
(2) The temperature of the reaction kettle is controlled at 55 ℃ by using circulating water, the stirring speed of a stirring paddle in the reaction kettle is set at 600rpm, deionized water is added into the reaction kettle, and the pH value is regulated to 11 by using a solution B2. After the pH of the system is stable, the solution A and the solutions B1 and B2 are added into a coprecipitation reaction kettle in parallel flow under the atmosphere of nitrogen or argon, and the pH is stabilized at 11 by adjusting the liquid inlet speed of the solution B1.
(3) After the charging is finished, part of the precursor is taken out from the reaction kettle to be washed and suction filtered for multiple times, and then the precursor is dried for 24 hours by blowing at 80 ℃ to obtain the precursor Ni 0.333 Fe 0.333 Mn 0.333 (OH) 2 。
(4) Taking fully dried precursor and Na 2 CO 3 Mixing MgO and Na in the molar ratio: mg:
(ni+fe+mn) =1.05: 0.05:1 in an air atmosphere at 5 ℃ min -1 After the temperature rising speed is increased to 880 ℃, the temperature is kept for 15 hours, and the doped modified oxide anode material is obtained after the natural temperature is reduced to the room temperature.
The difference from example 1 is that MgO was added in one sintering to synthesize a doped oxide cathode material.
Comparative example 3:
preparation of uniformly doped modified oxide positive electrode material, wherein a=0.05 is set as NaNi 0.333 Fe 0.333 Mn 0.283 Mg 0.05 O 2 . The method comprises the following steps:
(1) 2 mol.L of configuration -1 Wherein the nickel-iron-manganese-magnesium salt is NiSO 4 ，FeSO 4 ，MnSO 4 ，MgSO 4 Is a mixture of (1), ni: fe: mn: mg molar ratio of 0.333:0.333:0.283:0.005. in addition, 4 mol.L -1 NaOH solution B1 of 0.2 mol.L -1 Solution B2 having an ammonia concentration of (B).
(2) The temperature of the reaction kettle is controlled at 55 ℃ by using circulating water, the stirring speed of a stirring paddle in the reaction kettle is set at 600rpm, and the pH value is adjusted to 11 by using the solution B2. After the pH of the system is stable, the solution A and the solutions B1 and B2 are added into a coprecipitation reaction kettle in parallel flow under the atmosphere of nitrogen or argon, and the pH is stabilized at 11 by adjusting the liquid inlet speed of the solution B1.
(3) After the charging is finished, part of the precursor is taken out from the reaction kettle to be washed and suction filtered for multiple times, and then the precursor is dried for 24 hours by blowing at 80 ℃ to obtain the precursor Ni 0.333 Fe 0.333 Mn 0.283 Mg 0.05 (OH) 2 。
(4) Taking fully dried precursor and Na 2 CO 3 Thoroughly mixing, wherein the molar ratio of the two is Na:
(ni+fe+mn+mg) =1.05: 1 in an air atmosphere at 5 ℃ min -1 And (3) raising the temperature to 850 ℃ and preserving heat for 15h, and then naturally cooling to room temperature to obtain the doped modified oxide cathode material.
The difference from example 1 is that MgSO was added during the coprecipitation process 4 Synthesizing a uniformly doped precursor.
The positive electrode materials prepared in examples 1 to 5 and comparative examples 1 to 3 were prepared into batteries by the following procedure:
1. the preparation method of the positive plate and the battery comprises the following steps: taking layered oxide anode material, ketjen black and PVDF according to the proportion of 8:1:1 and a proper amount of NMP solvent. And then, uniformly coating the slurry on the surface of an aluminum foil, and carrying out hollow drying at 120 ℃ for 12 hours to obtain the positive electrode plate. And assembling the positive electrode plate, the negative electrode plate (sodium plate) and the electrolyte into a battery to be tested. Wherein the formula of the electrolyte is 1mol/L of mixed solution of ethylene carbonate and dimethyl carbonate of NaPF 6.
2. And (3) cyclic charge and discharge test: at 25 ℃, the battery is charged and discharged at a rate of 0.3C in a voltage range of 2-4V, and is cycled for 3 circles, and then is charged and discharged at a rate of 1C, and is cycled for 100 circles.
The test results are shown in table 1 below:
table 1: electrochemical performance comparison of half-cells assembled for examples and comparative examples
As can be seen from table 1, the graded doped layered metal oxide has higher charge-discharge capacity and coulombic efficiency, and better cycle performance than the normal diffusion doped and uniform doped samples. Since it is an inert element, the charge capacity is somewhat lowered with an increase in the doping amount, wherein 100-cycle performance of example 1, example 3, comparative example 1 and comparative example 2 is shown in fig. 3; the gradient doping material has high specific capacity and good cycle stability. The layered oxide cathode material of the sodium ion battery has excellent electrochemical performance.
The foregoing is merely a preferred example of the present invention and is not intended to limit the embodiments of the present invention, and those skilled in the art can easily make corresponding variations or modifications according to the main concept and spirit of the present invention, so that the protection scope of the present invention shall be subject to the protection scope of the claims.
Claims (10)
1. The oxide positive electrode material for the gradient doped sodium ion battery is characterized in that the positive electrode material is a layered oxide, doping elements are added into the positive electrode material, the doping element content is gradually distributed from the inside to the surface of the positive electrode material in a gradient manner, the maximum concentration is reached on the surface of the positive electrode material after the gradient is increased, and the doping elements account for 1-7% of the mole ratio of transition metal elements.
2. The gradient doped oxide positive electrode material for sodium ion battery according to claim 1, wherein the layered oxide for sodium ion battery is an O3 type layered positive electrode material, and has a chemical formula of NaNi x Fe y Mn z M a O 2 Wherein 0 < a is less than or equal to 0.1,0 < x is less than 1,0 < y is less than 1,0 < z is less than 1, and x+y+z+a=1.
3. The gradient doped oxide positive electrode material for sodium ion battery according to claim 2, wherein the molecular formula of the positive electrode material is NaNi 0.333 Fe 0.333 Mn 0.333-a M a O 2 The doping element M is one or a combination of more of Mg, cu, zn, co, ca, ba, sr, al, B, cr, zr, ti, sn, V, mo, ru, nb and Sb.
4. The gradient doped oxide cathode material for sodium ion batteries according to claim 2, wherein the doping element is Mg, ti or Zn.
5. The method for preparing a gradient doped oxide positive electrode material according to claim 1, comprising the steps of:
(1) Preparing a nickel-iron-manganese mixed salt solution A, pH regulator B1 and a complexing agent B2, and preparing a low-concentration dopant solution C1 and a high-concentration dopant solution C2;
(2) Adding deionized water into a reaction kettle, controlling the pH value of the solution to be 10.5-11.5 by utilizing a pH regulator B1, simultaneously adding the solution A, pH regulator B1 and a complexing agent B2 into the reaction kettle and continuously adding a C2 solution into the continuously stirred C1 solution to form a solution C with gradually increased concentration, stabilizing the pH value in the reaction kettle to be 10.5-11.5 in the reaction process, controlling the temperature to be 45-65 ℃, controlling all the solutions to be added simultaneously, and aging, filtering and drying to obtain precursor particles;
(3) And (3) uniformly mixing the precursor particles obtained in the step (2) with sodium salt, and then sintering at a high temperature to obtain the gradient doped oxide anode material.
6. The preparation method according to claim 5, wherein the concentration of the nickel-iron-manganese mixed salt solution A in the step (1) is 1-4 mol.L -1 The pH regulator B1 is 1-4mol.L -1 Sodium hydroxide solution and complexing agent B2 of 0.1-1 mol.L -1 Ammonia water solution; the concentration of the high-concentration dopant solution C2 is 0.1-1 mol.L -1 The low concentration is doped withThe initial concentration of the impurity solution C1 is 0 mol.L -1 。
7. The process according to claim 5, wherein the flow rate of the solution A fed into the reaction vessel in the step (2) is 1-5 L.h -1 The method comprises the steps of carrying out a first treatment on the surface of the The feeding flow of the pH regulator B1 into the reaction kettle is 1-5 L.h -1 The method comprises the steps of carrying out a first treatment on the surface of the The feeding flow of the complexing agent B2 added into the reaction kettle is 0.1-1 L.h -1 The method comprises the steps of carrying out a first treatment on the surface of the The feeding flow of the solution C with gradually increased concentration into the reaction kettle is 0.1-1 L.h -1 。
8. The method according to claim 5, wherein the high concentration doping solution C2 and the low concentration doping solution C1 are one or more of zirconium sulfate, magnesium sulfate, zinc sulfate, copper sulfate, zinc sulfate, cobalt sulfate, aluminum hydroxide, magnesium carbonate, calcium carbonate, barium sulfate, strontium sulfate, aluminum hydroxide, boric acid, chromium sulfate, chromium chloride, zirconium sulfate, tin sulfate, titanium hydroxide, zirconium oxide, ammonium molybdate, ruthenium sulfate, niobium sulfate, antimony sulfate, and antimony hydroxide; the particle size of the precursor particles ranges from 3 μm to 15 μm.
9. The preparation method according to claim 5, wherein the sodium source in the mixed raw material D in the step (3) is selected from one or more of sodium hydroxide, sodium carbonate, sodium oxide, sodium oxalate and sodium nitrate, and the molar ratio of the metal element in the precursor particles to the sodium element in the sodium source (Ni+Fe+Mn+M) to Na is 1: (0.8-1.1).
10. The method according to claim 5, wherein the high-temperature sintering equipment in the step (3) is a box furnace or a tube furnace, and the parameters of the high-temperature sintering are as follows: the temperature rising rate is 3-10 ℃ min -1 Heat-treating at 750-950 deg.C for 10-20 hr.
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