CN117133906A - Coated oxygen-site doped modified sodium ion battery positive electrode material and preparation method thereof - Google Patents
Coated oxygen-site doped modified sodium ion battery positive electrode material and preparation method thereof Download PDFInfo
- Publication number
- CN117133906A CN117133906A CN202311327618.4A CN202311327618A CN117133906A CN 117133906 A CN117133906 A CN 117133906A CN 202311327618 A CN202311327618 A CN 202311327618A CN 117133906 A CN117133906 A CN 117133906A
- Authority
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- China
- Prior art keywords
- ion battery
- sodium ion
- oxygen
- doped modified
- sodium
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical class [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title claims abstract description 69
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000007774 positive electrode material Substances 0.000 title claims description 27
- 238000005245 sintering Methods 0.000 claims abstract description 46
- 239000010405 anode material Substances 0.000 claims abstract description 44
- 238000001816 cooling Methods 0.000 claims abstract description 35
- 239000000203 mixture Substances 0.000 claims abstract description 33
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 32
- 239000011734 sodium Substances 0.000 claims abstract description 30
- 239000002243 precursor Substances 0.000 claims abstract description 29
- 238000000034 method Methods 0.000 claims abstract description 27
- 150000003624 transition metals Chemical class 0.000 claims abstract description 24
- 238000000498 ball milling Methods 0.000 claims abstract description 16
- 238000002156 mixing Methods 0.000 claims abstract description 16
- 229910001415 sodium ion Inorganic materials 0.000 claims abstract description 15
- 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 abstract description 13
- 230000008569 process Effects 0.000 claims abstract description 12
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 12
- 238000000975 co-precipitation Methods 0.000 claims abstract description 9
- 239000002019 doping agent Substances 0.000 claims abstract description 9
- 239000000243 solution Substances 0.000 claims description 54
- 238000006243 chemical reaction Methods 0.000 claims description 46
- 238000010438 heat treatment Methods 0.000 claims description 46
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 27
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 15
- 239000000460 chlorine Substances 0.000 claims description 14
- 239000011259 mixed solution Substances 0.000 claims description 14
- 239000000126 substance Substances 0.000 claims description 14
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 12
- 239000008139 complexing agent Substances 0.000 claims description 12
- 239000001301 oxygen Substances 0.000 claims description 12
- 229910052760 oxygen Inorganic materials 0.000 claims description 12
- 229910052593 corundum Inorganic materials 0.000 claims description 10
- 239000010431 corundum Substances 0.000 claims description 10
- 239000010406 cathode material Substances 0.000 claims description 9
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 9
- 235000017550 sodium carbonate Nutrition 0.000 claims description 9
- -1 transition metal salt Chemical class 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 7
- 239000001509 sodium citrate Substances 0.000 claims description 7
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 4
- 229910052731 fluorine Inorganic materials 0.000 claims description 4
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 3
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 3
- 229910052801 chlorine Inorganic materials 0.000 claims description 3
- 239000011737 fluorine Substances 0.000 claims description 3
- 229910052748 manganese Inorganic materials 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 239000004317 sodium nitrate Substances 0.000 claims description 3
- 235000010344 sodium nitrate Nutrition 0.000 claims description 3
- BDOYKFSQFYNPKF-UHFFFAOYSA-N 2-[2-[bis(carboxymethyl)amino]ethyl-(carboxymethyl)amino]acetic acid;sodium Chemical compound [Na].[Na].OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O BDOYKFSQFYNPKF-UHFFFAOYSA-N 0.000 claims description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 2
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052794 bromium Inorganic materials 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- 229940039748 oxalate Drugs 0.000 claims description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- 239000001632 sodium acetate Substances 0.000 claims description 2
- 235000017281 sodium acetate Nutrition 0.000 claims description 2
- 235000011083 sodium citrates 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
- 159000000000 sodium salts Chemical group 0.000 claims description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 2
- 235000011152 sodium sulphate Nutrition 0.000 claims description 2
- 238000000967 suction filtration Methods 0.000 claims description 2
- XFLNVMPCPRLYBE-UHFFFAOYSA-J tetrasodium;2-[2-[bis(carboxylatomethyl)amino]ethyl-(carboxylatomethyl)amino]acetate;tetrahydrate Chemical compound O.O.O.O.[Na+].[Na+].[Na+].[Na+].[O-]C(=O)CN(CC([O-])=O)CCN(CC([O-])=O)CC([O-])=O XFLNVMPCPRLYBE-UHFFFAOYSA-J 0.000 claims description 2
- 229910001428 transition metal ion Inorganic materials 0.000 claims description 2
- 150000001450 anions Chemical class 0.000 abstract description 4
- 230000037427 ion transport Effects 0.000 abstract description 4
- 230000002349 favourable effect Effects 0.000 abstract description 2
- 238000000197 pyrolysis Methods 0.000 abstract description 2
- 238000012546 transfer Methods 0.000 abstract description 2
- 239000000463 material Substances 0.000 description 51
- 230000000052 comparative effect Effects 0.000 description 16
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 16
- 239000011572 manganese Substances 0.000 description 16
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 239000008367 deionised water Substances 0.000 description 10
- 229910021641 deionized water Inorganic materials 0.000 description 10
- 239000003513 alkali Substances 0.000 description 9
- 239000011248 coating agent Substances 0.000 description 7
- 238000000576 coating method Methods 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 230000004048 modification Effects 0.000 description 6
- 238000012986 modification Methods 0.000 description 6
- 239000002585 base Substances 0.000 description 5
- 239000011247 coating layer Substances 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 229910021645 metal ion Inorganic materials 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 230000002572 peristaltic effect Effects 0.000 description 5
- 230000001681 protective effect Effects 0.000 description 5
- 238000005086 pumping Methods 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 4
- 238000001704 evaporation Methods 0.000 description 4
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 4
- 239000008247 solid mixture Substances 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 238000005054 agglomeration Methods 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 238000002484 cyclic voltammetry Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000012983 electrochemical energy storage Methods 0.000 description 3
- 239000011790 ferrous sulphate Substances 0.000 description 3
- 235000003891 ferrous sulphate Nutrition 0.000 description 3
- 230000000977 initiatory effect Effects 0.000 description 3
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 3
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 229940099596 manganese sulfate Drugs 0.000 description 3
- 239000011702 manganese sulphate Substances 0.000 description 3
- 235000007079 manganese sulphate Nutrition 0.000 description 3
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 3
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 230000000630 rising effect Effects 0.000 description 3
- 238000004626 scanning electron microscopy Methods 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 230000006978 adaptation Effects 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 229960002089 ferrous chloride Drugs 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 239000011775 sodium fluoride Substances 0.000 description 2
- 235000013024 sodium fluoride Nutrition 0.000 description 2
- 239000011232 storage material Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 229910015902 Bi 2 O 3 Inorganic materials 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-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
- 229910018970 NaNi0.5Mn0.5O2 Inorganic materials 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- URQWOSCGQKPJCM-UHFFFAOYSA-N [Mn].[Fe].[Ni] Chemical compound [Mn].[Fe].[Ni] URQWOSCGQKPJCM-UHFFFAOYSA-N 0.000 description 1
- MCDLETWIOVSGJT-UHFFFAOYSA-N acetic acid;iron Chemical compound [Fe].CC(O)=O.CC(O)=O MCDLETWIOVSGJT-UHFFFAOYSA-N 0.000 description 1
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000006399 behavior Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 229940011182 cobalt acetate Drugs 0.000 description 1
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- 229960000355 copper sulfate Drugs 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000001066 destructive effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011066 ex-situ storage Methods 0.000 description 1
- 229960001781 ferrous sulfate Drugs 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 238000009766 low-temperature sintering Methods 0.000 description 1
- 229940071125 manganese acetate Drugs 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
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229940078494 nickel acetate Drugs 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- 229940053662 nickel sulfate Drugs 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 238000004537 pulping Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 239000011163 secondary particle Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000032258 transport Effects 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
- 229960001763 zinc sulfate Drugs 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/40—Nickelates
- C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
- C01G53/44—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese
-
- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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Abstract
The invention provides a coated oxygen-site doped modified sodium ion battery anode material and a preparation method thereof, and relates to the technical field of sodium ion batteries. The method comprises the following steps: preparing a transition metal hydroxide precursor by co-precipitation; then mixing and ball milling the transition metal hydroxide precursor, a sodium source and a doping agent to obtain a mixture; carrying out one-step/two-step pyrolysis treatment in an aerobic atmosphere, and cooling to room temperature; and finally adding oxide, and performing blending sintering treatment to obtain the coated oxygen-site doped modified sodium ion battery anode material. The oxygen-doped anions in the coated oxygen-doped modified sodium ion battery anode material can increase the distance between sodium ion transport channels, is favorable for rapid transfer of sodium ions in the charge-discharge process, has excellent air stability, and can be used as a sodium-electricity anode material with high specific volume, high multiplying power and high air stability.
Description
Technical Field
The invention relates to the technical field of sodium ion batteries, in particular to a coated oxygen-site doped modified sodium ion battery anode material and a preparation method thereof.
Background
In the technical field of electrochemical energy storage, a lithium ion battery occupies 92% of the global electrochemical energy storage machine scale, and is the most important electrochemical energy storage technology at the present stage. However, lithium resources on earth are short and unevenly distributed, and with the widespread use of lithium ion batteries, the price of lithium salts is rising. Compared with lithium resources, the sodium resources are abundant, the content of lithium in the crust is only 0.0065 percent, and the content of sodium is 400 times of that of the sodium. Sodium ion batteries are one of the most promising alternatives due to their similar electrochemical reaction mechanisms as lithium ion batteries. At present, the theoretical specific capacity of the positive electrode material of the sodium ion battery is relatively low, and part of routes contain rare metal elements, so that the positive electrode material plays a key role in the overall energy density and manufacturing cost of the battery. The future layered oxide route has the greatest energy density development potential, good multiplying power and low-temperature performance, relatively low cycle life and the like.
NaNi 1/3 Fe 1/3 Mn 1/3 O 2 Is a very promising sodiumThe layered oxide cathode material of the ion battery has the advantages of low preparation cost, simple synthesis method, high specific capacity and the like, so that the layered oxide cathode material of the ion battery is widely paid attention to. However, the problems of slow reaction kinetics, poor rate performance and the like of the materials are caused by the problems of mismatch of larger sodium ion radius and ion transport channels and the like of the materials. To solve the above problems, researchers have explored various modification approaches, such as the group of the Yang-kook Sun professor of the university of Han in Korea designed a P2-Na 2/3 MnO 2 Coating O3-NaNi 0.5 Mn 0.5 O 2 The heterostructure positive electrode material (Energy Storage material, 2022,47,515-525) is formed, and the sodium ion transport channel of the P2 type material is wider than that of the O3 type, so that the material has the characteristics of high capacity of an inner core part, high stability of an outer core and multiplying power; the university of lanzhou university of science Li Shiyou teaches that the subject group designs an ex-situ F and in-situ Mg double doped Na 0.67 Ni 0.15 Fe 0.2 Mn 0.65 F x O 2-x Materials due to F - Radius of radiusAnd O 2- Radius->Similarly, the strong negative power of F can change the binding energy of oxygen element in the crystal lattice so as to improve Na + Is a diffusion rate (Energy storage material, 2022,45,1153-1164). In addition, in order to improve the air stability of the material, a material which has high conductivity and is insensitive to air is coated on the sodium-electric layered oxide positive electrode material, for example, the group of the professor Yang-Kook Sun subjects uses Al 2 O 3 Coating is carried out by directly ball milling with the cathode material, but the residual sodium or residual alkali on the surface of the material cannot be effectively removed (J.Mater.chem.A. 2017,5,23671-23680). In general, the existing preparation conditions of various modification strategies are usually very strict, the conditions such as the dosage of the doping agent, the preparation temperature and the like are required to be strictly controlled, the problems of air stability and surface sodium residue of the material cannot be solved, and the pressure is brought to the cost control and the industrialized large-scale popularization of the material。
Therefore, the invention designs a coated oxygen-site doped modified sodium ion battery anode material with high multiplying power and high air stability and a preparation method thereof.
Disclosure of Invention
The invention provides a coated oxygen-site doped modified sodium ion battery anode material and a preparation method thereof, and aims to solve the problems in the prior art.
In order to achieve the above purpose, the embodiment of the invention provides a coated oxygen-site doped modified sodium ion battery anode material and a preparation method thereof, wherein the method comprises the following steps: preparing a transition metal hydroxide precursor by co-precipitation; then mixing and ball milling the transition metal hydroxide precursor, a sodium source and a doping agent to obtain a mixture; carrying out one-step/two-step pyrolysis treatment in an aerobic atmosphere, and cooling to room temperature; and finally adding oxide, and performing blending sintering treatment to obtain the coated oxygen-site doped modified sodium ion battery anode material. The oxygen-doped anions in the coated oxygen-doped modified sodium ion battery anode material can increase the distance between sodium ion transport channels, is favorable for rapid transfer of sodium ions in the charge-discharge process, has excellent air stability, and can be used as a sodium-electricity anode material with high specific volume, high multiplying power and high air stability. The coated oxygen-doped modified sodium ion battery anode material is O3 type nickel-iron-manganese-based layered oxide and is a polycrystalline material with the granularity D50 of 2-5 mu m formed by secondary particle agglomeration.
The embodiment of the invention provides a coated oxygen-site doped modified sodium ion battery anode material, which has a chemical general formula as follows: na (Ni) x Fe y Mn z M 1-x-y-z )O 2-a X a @Na b Y c O d The method comprises the steps of carrying out a first treatment on the surface of the Wherein M is V 3+ 、Cr 3+ 、Co 3+ 、Cu 2+ 、Zn 2+ 、Zr 4+ 、Al 3+ 、Sb 3+ 、Bi 3+ 、La 3+ 、Ti 4+ 、Mg 2+ 、Nb 5+ 、Ta 5+ 、W 6 + 、Mo 6+ At least one of (a) and (b); x is F - 、Cl - 、Br - At least one of (a) and (b); y is at least one of B, bi, zr, mo; each component in the chemical formula meets the conservation of charge and the conservation of stoichiometry; and 0 is<x+y+z is less than or equal to 1; a is more than or equal to 0 and less than or equal to 0.1. More preferably, 0.9.ltoreq.x+y+z.ltoreq.1; a is more than or equal to 0 and less than or equal to 0.04; and @ stands for cladding.
Based on one general inventive concept, the embodiment of the invention provides a preparation method of the coated oxygen-site doped modified sodium ion battery anode material, which comprises the following steps:
s1: introducing inert gas in advance, adding a transition metal salt mixed solution, a complex and a precipitant into a reaction kettle at the same time according to a certain flow rate, controlling the pH value, the reaction temperature and the stirring rate, performing coprecipitation reaction, and performing suction filtration, washing, drying and separation to obtain a transition metal hydroxide precursor;
s2: placing the transition metal hydroxide precursor, a sodium source and a doping agent in a ball milling container for ball milling treatment to obtain a mixture; placing the mixture into a corundum crucible, transferring the corundum crucible into a muffle furnace, and performing one-step or two-step heat treatment in an oxygen atmosphere to obtain an oxygen-doped modified sodium ion battery anode material;
s3: and mixing and stirring the oxygen-doped modified sodium ion battery anode material, oxide and solvent uniformly, and performing sintering treatment to obtain the cathode material.
Preferably, the transition metal salt is at least one of sulfate, nitrate, chloride, oxalate, acetate and carbonate, and the transition metal is at least three or more transition metals including Ni, fe and Mn simultaneously; the total concentration of transition metal ions in the transition metal salt mixed solution is 0.5-5 mol/L; the complexing agent is at least one of ammonia water, sodium citrate solution, ethylene diamine tetraacetic acid tetrasodium solution and ethylene diamine tetraacetic acid disodium solution, and the concentration is 0.2-3 mol/L; the precipitant is at least one of sodium hydroxide and potassium hydroxide, and the concentration is 0.5-5 mol/L.
PreferablyThe chemical composition formula of the oxygen-site doped modified sodium ion battery anode material is as follows: na (Ni) x Fe y Mn z M 1-x-y-z )O 2-a X a The method comprises the steps of carrying out a first treatment on the surface of the Wherein M is V 3+ 、Cr 3+ 、Co 3+ 、Cu 2+ 、Zn 2+ 、Zr 4+ 、Al 3+ 、Sb 3+ 、Bi 3+ 、La 3+ 、Ti 4+ 、Mg 2+ 、Nb 5+ 、Ta 5+ 、W 6+ 、Mo 6+ At least one of (a) and (b); x is F - 、Cl - 、Br - At least one of (a) and (b); wherein 0 is<x+y+z is less than or equal to 1; a is more than or equal to 0 and less than or equal to 0.1. More preferably, 0.9.ltoreq.x+y+z.ltoreq.1; a is more than or equal to 0 and less than or equal to 0.04.
Preferably, the sodium source is at least one of sodium oxide, sodium carbonate, sodium bicarbonate, sodium acetate, sodium nitrate, sodium citrate, sodium sulfate, and sodium oxalate; more preferably, sodium carbonate, sodium bicarbonate and sodium nitrate; the doping agent is sodium salt or transition metal salt of fluorine, chlorine and bromine; more preferably, sodium fluoride, sodium chloride, fluorinated transition metals and chlorinated transition metals.
Preferably, in the step S1, the pH is 9-13, the reaction temperature is 50 ℃, the stirring speed is 400r/min, and the reaction time is 12-48 h.
Preferably, the ball milling container is made of any one of agate, polytetrafluoroethylene, corundum, zirconia and ceramic; the ball milling time is 1-12 h.
Preferably, the heat treatment in step S2 is one or two steps:
(1) The one-step heat treatment process comprises the following steps: heating to 700-1000 ℃ at a heating rate of 2-10 ℃/min in air or oxygen atmosphere, and sintering at constant temperature for 5-30 hours; cooling to room temperature at a cooling rate of 2-10 ℃/min; more preferably, the sintering temperature is 750-900 ℃ and the time is 8-15 hours; the cooling rate is 3-6 ℃/min;
(2) The two-step heat treatment process comprises the following steps: in air or oxygen atmosphere, heating to 300-600 ℃ at a heating rate of 2-10 ℃/min, and presintering for 2-8 hours at constant temperature; further heating to 700-1000 ℃ at a heating rate of 2-10 ℃/min, and sintering at constant temperature for 5-30 hours; and then cooling to room temperature at a cooling rate of 2-10 ℃/min. More preferably, the pre-sintering temperature is 450-550 ℃ for 4-6 hours; the temperature rising rate is 3-6 ℃/min; sintering temperature is 750-900 ℃ and sintering time is 8-15 h; the cooling rate is 3-6 ℃/min.
Preferably, the oxide is B 2 O 3 、Bi 3 O 3 、MoO 2 、ZrO 2 At least one of (a) and (b); the solvent is any one of methanol, ethanol and propanol. More preferably, the oxide is B 2 O 3 And ZrO(s) 2 。
Preferably, the mass of the oxide is 0.1-2% of the mass of the oxygen-doped modified sodium ion battery anode material. More preferably, 0.2% to 1%.
Preferably, the sintering process in step S3 is specifically: heating to 400-800 ℃ at a heating rate of 2-10 ℃/min in air or oxygen atmosphere, and sintering at constant temperature for 1-12 hours; and then cooling to room temperature at a cooling rate of 2-10 ℃/min. More preferably, the temperature rising rate is 3-6 ℃/min; sintering temperature is 500-750 ℃ and sintering time is 2-6 hours; the cooling rate is 3-6 ℃/min.
The scheme of the invention has the following beneficial effects:
(1) The invention adds oxide to react with surface residual alkali, can fully utilize the reaction of the oxide with the residual alkali such as sodium hydroxide, sodium carbonate and the like on the surface to generate a stable and conductive coating layer, solves the problem of performance reduction caused by the surface residual alkali, and can greatly improve the air stability of the material by being used for isolating air.
(2) The sintering temperature is low, and the sintered material has uniform microscopic morphology; through doping modification, na is effectively improved + Is beneficial to Na under large multiplying power + Diffusion and transport of (a). Adopts cheap fluorine, chlorine and bromine salt as doping agent, realizes uniform oxygen position doping by co-sintering halogen element to reduce Mn 3+ /Mn 4+ Thereby inhibiting John-Teller effect in the charge-discharge process and effectively improving the cycle stability of the material. In addition, the doping agent is directly added for mixing and sintering, so that the modification cost is low, and the original sintering is not changedJunction conditions and the like, and can also improve the electrochemical performance of the material.
(3) The method selects the nickel/iron/manganese-based multi-hydroxide precursor, which is beneficial to large-scale production and application. The polycrystalline structure material is obtained by low-temperature sintering, and the polycrystalline structure material has higher specific capacity, but the part of the surface exposed to air reacts with moisture and carbon dioxide to generate NaOH and Na 2 CO 3 And the like, the active substances are easy to generate jelly-like slurry in the pulping process, and a series of behaviors for reducing the cycle performance of the battery can be induced in the charging and discharging processes. Compared with the conventional method for destroying the surface structure of the material and reducing the performance of the material by adopting water washing, acid washing and the like, the invention obtains a single uniform compact coating layer by adding the proper oxide and carrying out in-situ reaction with residual alkali on the surface of the material at a proper temperature, achieves the double effects of removing the residual sodium on the surface and effectively improving the air stability of the material, and successfully prepares the sodium-electricity layered oxide anode material with high multiplying power, high specific volume and good air stability. The invention also solves the problems of multi-scene application of the layered oxide material and the like.
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 needed in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only 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 X-ray diffraction pattern of samples prepared in example 1 and comparative example 1 of the present invention;
FIG. 2 is a scanning electron microscope image of a sample prepared in example 1 of the present invention;
FIG. 3 is a scanning electron microscope image of a sample prepared in comparative example 1 of the present invention;
FIG. 4 is a charge and discharge curve of a sodium ion button cell assembled from samples of the cathode materials prepared in example 1 and comparative example 1 of the present invention at a 0.1C rate, with an operating voltage of 2.0-4.0V vs. Na + /Na；
FIG. 5 is a graph showing the rate performance of sodium button cell assembled from the positive electrode material samples prepared in example 1 and comparative example 1 according to the present invention, tested at different rates;
FIG. 6 is a Cyclic Voltammetry (CV) curve of a sodium ion button cell assembled from a sample of the positive electrode material prepared in example 1 of the present invention;
fig. 7 is a Cyclic Voltammetry (CV) curve of a sodium ion button cell assembled from a sample of the positive electrode material prepared in comparative example 1 of the present invention.
Fig. 8 is a cycle curve of a sodium ion button cell assembled from the positive electrode material sample prepared in example 1 of the present invention before and after 48 hours of placement in an air environment (25 ℃,50% rh).
Detailed Description
In order to make the technical problems, technical solutions and advantages to be solved more apparent, the following detailed description will be given with reference to the accompanying drawings and specific embodiments.
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.
Aiming at the existing problems, the invention provides a coated oxygen-site doped modified sodium ion battery anode material and a preparation method thereof.
Example 1
The preparation of the coated oxygen-site doped modified sodium ion battery anode material comprises the following steps:
s1, nickel sulfate, ferrous sulfate and manganese sulfate are mixed according to the following ratio of 1:1:1 in the molar ratio of deionized water to prepare a mixed solution with the total metal ion concentration of 2 mol/L; simultaneously preparing 1mol/L ammonia water complexing agent solution and 2mol/L sodium hydroxide precipitant solution. The reaction vessel is prepared by adopting a reaction kettle as a precursor, and nitrogen is introduced in advance as protective gas. Adding a base solution consisting of deionized water, a complexing agent solution and a precipitant solution into a reaction kettle, controlling the pH value to be 11-12, and then pumping a metal salt mixed solution, a complex solution and the precipitant solution into the reaction kettle at the same time through peristaltic pumps according to a certain flow rate, wherein the reaction temperature is controlled to be 50 ℃, and the stirring rate is controlled to be 400r/min. After the addition is completed, the reaction temperature is maintained and the reaction is continued to age for 24 hours for one coprecipitation. Filtering, washing and drying, and separating the precursor from the solution to obtain a transition metal hydroxide precursor product;
s2, mixing the prepared transition metal hydroxide precursor with sodium carbonate and sodium chloride according to the following ratio of 2:0.995: the mixture was placed in a ball mill vessel at a molar ratio of 0.01 for ball milling for 4 hours. After the mixture is uniformly mixed, the mixture is placed in a corundum crucible and transferred into a muffle furnace, and two-step sintering treatment is carried out in an air atmosphere. The temperature is raised to 500 ℃ at a heating rate of 3 ℃/min, the constant temperature sintering is carried out for 5 hours at the temperature, and the temperature is raised to 880 ℃ from 500 ℃ at a heating rate of 3 ℃/min, and the constant temperature sintering is carried out for 10 hours at the temperature. Cooling to room temperature at a cooling rate of 5 ℃/min under an air atmosphere. The material is crushed and sieved to obtain the oxygen-doped modified sodium ion battery anode material.
S3, mixing oxygen-site doped modified sodium ion battery anode material with 1% by mass ratio of B 2 O 3 Dispersing in ethanol solution, stirring the system at normal temperature for 2 hours, heating to 70 ℃ and evaporating the solvent, and heating the obtained solid mixture to 600 ℃ at a heating rate of 3 ℃/min under air atmosphere to perform one-step sintering treatment. And (3) sintering for 4 hours at constant temperature, and cooling to room temperature at a cooling rate of 3 ℃/min to obtain the coated oxygen-doped modified sodium ion battery anode material.
According to B 2 O 3 With surface residual alkali (Na) 2 CO 3 NaOH) to form a single Na 2 B 8 O 13 As the principle of the coating layer, the chemical composition formula of the coating type oxygen-site doped modified sodium ion battery anode material is as follows: na (Ni) 1/3 Fe 1/3 Mn 1/3 )O 1.99 Cl 0.01 @1-Na 2 B 8 O 13 The structure is characterized in fig. 1. As can be seen, in comparison with comparative example 1, we found that the (003) diffraction peak of the material appears to shift to the left, indicating that the (003) interplanar spacing in the material is widened and that anions (chloride ions) are successfully doped into the internal structure of the material. The microstructure of the material is further illustrated in FIG. 2, which shows that the material is a polycrystalline material with a particle size D50 of about 3 μm, which is formed by agglomeration of nano-sized particles, by scanning electron microscopy. By comparison with comparative example 1, the overall structure of the material was substantially preserved, indicating that doping to this extent did not have a destructive effect on the structure of the material, and we have found no Na 2 B 8 O 13 May be caused by too little coating amount. Fig. 4 shows the specific capacity test result of the material, wherein the specific discharge capacity is 132mAh/g and the initial effect is 88.7% at a charge-discharge rate of 0.1C. The performance results were significantly better than those of the unmodified sample of comparative example 1 (the specific discharge capacity was 120mAh/g, and the initial effect was 84.6%). To further verify the air stability of the coated doped modified sodium ion cathode material, the sample of example 1 was placed in an air environment (25 ℃ and 50% rh) for 48 hours, and the cycle performance of the sample before and after the placement was evaluated, and according to the test data of fig. 8, it can be seen that the coated doped modified sodium ion cathode material of example 1 has excellent air stability, and the gram capacity and cycle retention rate of the material during the cycle are substantially consistent with those of the sample before the placement.
Example 2
The preparation of the coated oxygen-site doped modified sodium ion battery anode material comprises the following steps:
s1, nickel chloride, ferrous chloride and manganese chloride are mixed according to the following ratio of 2:5:3, dissolving the mixture in deionized water according to a molar ratio to prepare a mixed solution with the total metal ion concentration of 4 mol/L; simultaneously preparing a sodium citrate complexing agent solution with the concentration of 2mol/L and a potassium hydroxide precipitant solution with the concentration of 4 mol/L. The reaction vessel is prepared by adopting a reaction kettle as a precursor, and nitrogen is introduced in advance as protective gas. Adding a base solution consisting of deionized water, a complexing agent solution and a precipitant solution into a reaction kettle, controlling the pH value to be in a range of 12-13, and then pumping a metal salt mixed solution, a complex solution and the precipitant solution into the reaction kettle at the same time through peristaltic pumps according to a certain flow rate, wherein the reaction temperature is controlled to be 60 ℃, and the stirring rate is controlled to be 450r/min. After the addition is completed, the reaction temperature is maintained and the reaction is continued to age for 24 hours for one coprecipitation. Filtering, washing and drying, and separating the precursor from the solution to obtain a transition metal hydroxide precursor product;
s2, mixing the prepared transition metal hydroxide precursor with sodium carbonate and sodium fluoride according to the following ratio of 2:0.98: the mixture was placed in a ball mill vessel at a molar ratio of 0.04 for ball milling for 4 hours. After the mixture is uniformly mixed, the mixture is placed in a corundum crucible and transferred to a muffle furnace, and two-step sintering treatment is carried out in an air atmosphere. The temperature is raised to 500 ℃ at a heating rate of 3 ℃/min, the constant temperature sintering is carried out for 4 hours at the temperature, the temperature is further raised to 900 ℃ from 500 ℃ at a heating rate of 5 ℃/min, and the constant temperature sintering is carried out for 12 hours at the temperature. Cooling to room temperature at a cooling rate of 5 ℃/min under an air atmosphere. The material is crushed and sieved to obtain the oxygen-doped modified sodium ion battery anode material.
S3, mixing the oxygen-doped modified sodium ion battery anode material with ZrO in a mass ratio of 1% 2 Dispersing in ethanol solution, stirring the system at normal temperature for 2 hours, heating to 70 ℃ and evaporating the solvent, and heating the obtained solid mixture to 600 ℃ at a heating rate of 3 ℃/min under air atmosphere to perform one-step sintering treatment. And (3) sintering for 4 hours at constant temperature, and cooling to room temperature at a cooling rate of 3 ℃/min to obtain the coated oxygen-doped modified sodium ion battery anode material.
According to ZrO 2 With surface residual alkali (Na) 2 CO 3 NaOH) to form a single Na 2 ZrO 3 As the principle of the coating layer, the chemical composition formula of the coating type oxygen-site doped modified sodium ion battery anode material is as follows: na (Ni) 0.2 Fe 0.5 Mn 0.3 )O 1.98 Cl 0.02 @1-Na 2 ZrO 3 The structure is characterized in fig. 1. The microstructure of the material is further illustrated in FIG. 3, which shows by scanning electron microscopy that the material is a polycrystalline material with a particle size D50 of about 3 μm, which is formed by agglomeration of nano-sized particles. By comparison with comparative example 1, it was found that the overall structure of the material was not substantially changed significantly.
Example 3
The preparation of the coated oxygen-site doped modified sodium ion battery anode material comprises the following steps:
s1, nickel acetate, ferrous acetate, manganese acetate and cobalt acetate are mixed according to the following ratio of 1:4:4:1 in the molar ratio of deionized water to prepare a mixed solution with the total metal ion concentration of 2 mol/L; simultaneously preparing a sodium citrate complexing agent solution with the concentration of 1mol/L and a potassium hydroxide precipitant solution with the concentration of 2 mol/L. The reaction vessel is prepared by adopting a reaction kettle as a precursor, and argon is introduced in advance as a protective gas. Adding a base solution consisting of deionized water, a complexing agent solution and a precipitant solution into a reaction kettle, controlling the pH value to be in a range of 12-13, and then pumping a metal salt mixed solution, a complex solution and the precipitant solution into the reaction kettle at the same time through peristaltic pumps according to a certain flow rate, wherein the reaction temperature is controlled to be 50 ℃, and the stirring rate is 400r/min. After the addition is completed, the reaction temperature is maintained and the mixture is aged for 18 hours for one time of coprecipitation. Filtering, washing and drying, and separating the precursor from the solution to obtain a transition metal hydroxide precursor product;
s2, mixing the prepared transition metal hydroxide precursor with sodium carbonate and ferrous chloride according to the following ratio of 2:1: the mixture was placed in a ball mill vessel at a molar ratio of 0.01 for ball milling for 6 hours. After the mixture is uniformly mixed, the mixture is placed in a corundum crucible and transferred to a muffle furnace, and two-step sintering treatment is carried out in an air atmosphere. The temperature is raised to 500 ℃ at a heating rate of 5 ℃/min, the constant temperature sintering is carried out for 6 hours at the temperature, the temperature is further raised to 920 ℃ from 500 ℃ at a heating rate of 5 ℃/min, and the constant temperature sintering is carried out for 12 hours at the temperature. Cooling to room temperature at a cooling rate of 5 ℃/min under an air atmosphere. The material is crushed and sieved to obtain the oxygen-doped modified sodium ion battery anode material.
S3, mixing oxygen-site doped modified sodium ion battery anode material with 0.4% of B 2 O 3 Dispersing in ethanol solution, stirring the system at normal temperature for 2 hours, heating to 70 ℃ and evaporating the solvent, and heating the obtained solid mixture to 600 ℃ at a heating rate of 3 ℃/min under air atmosphere to perform one-step sintering treatment. And (3) sintering for 4 hours at constant temperature, and cooling to room temperature at a cooling rate of 3 ℃/min to obtain the coated oxygen-doped modified sodium ion battery anode material. The chemical composition formula of the positive electrode material is as follows: na (Ni) 0.1 Fe 0.4 Mn 0.4 Co 0.1 )O 1.99 Cl 0.01 @0.4-Na 2 B 8 O 13 。
Example 4
The preparation of the coated oxygen-site doped modified sodium ion battery anode material comprises the following steps:
s1, nickel sulfate, ferrous sulfate, manganese sulfate, copper sulfate and zinc sulfate are mixed according to the following ratio of 1.5:3:4:1: dissolving the mixture in deionized water according to a molar ratio of 0.5 to prepare a mixed solution with the total metal ion concentration of 1 mol/L; simultaneously preparing a sodium citrate complexing agent solution with the concentration of 0.6mol/L and a potassium hydroxide precipitant solution with the concentration of 1.5 mol/L. The reaction vessel is prepared by adopting a reaction kettle as a precursor, and argon is introduced in advance as a protective gas. Adding a base solution consisting of deionized water, a complexing agent solution and a precipitant solution into a reaction kettle, controlling the pH value to be within a range of 10.5-13, and then pumping the metal salt mixed solution, the complex solution and the precipitant solution into the reaction kettle respectively through peristaltic pumps according to a certain flow rate, wherein the reaction temperature is controlled to be 55 ℃, and the stirring speed is controlled to be 800r/min. After the addition is completed, the reaction temperature is maintained and the reaction is continued to age for 12 hours for one coprecipitation. Filtering, washing and drying, and separating the precursor from the solution to obtain a transition metal hydroxide precursor product;
s2, mixing the prepared transition metal hydroxide precursor with sodium carbonate and zinc chloride according to the following ratio of 2:1: the mixture was placed in a ball mill vessel at a molar ratio of 0.02 for ball milling for 8 hours. After the mixture is uniformly mixed, the mixture is placed in a corundum crucible and transferred to a muffle furnace, and two-step sintering treatment is carried out in an air atmosphere. The temperature is raised to 500 ℃ at a heating rate of 3 ℃/min, the constant temperature sintering is carried out for 2 hours at the temperature, the temperature is further raised to 800 ℃ from 500 ℃ at a heating rate of 3 ℃/min, and the constant temperature sintering is carried out for 15 hours at the temperature. Cooling to room temperature at a cooling rate of 3 ℃/min under an air atmosphere. The material is crushed and sieved to obtain the oxygen-doped modified sodium ion battery layered oxide anode material.
S3, mixing the oxygen-site doped modified sodium ion battery anode material with Bi in a mass ratio of 0.5% 2 O 3 Dispersing in ethanol solution, stirring the system at normal temperature for 4 hours, heating to 70 ℃ and evaporating the solvent, and heating the obtained solid mixture to 700 ℃ at a heating rate of 5 ℃/min under air atmosphere for one-step sintering treatment. And (3) sintering for 2 hours at constant temperature, and cooling to room temperature at a cooling rate of 5 ℃/min to obtain the coated oxygen-site doped modified sodium ion battery anode material. According to Bi 2 O 3 With surface residual alkali (Na) 2 CO 3 NaOH) to form single NaBiO 2 As a principle of the coating layer, the chemical composition formula of the positive electrode material is as follows: na (Ni) 0.15 Fe 0.3 Mn 0.4 Co 0.1 Zn 0.05 )O 1.98 Cl 0.02 @0.5-NaBiO 2 。
Example 5
Based on the example 1, only the oxygen site doping modified sodium ion battery positive electrode material in the step S3 was mixed with 0.2% by mass of B 2 O 3 Dispersing in ethanol solution, and other steps and conditions are the same as those of the embodiment 1, wherein the chemical composition formula of the positive electrode material is as follows: na (Ni) 1/3 Fe 1/3 Mn 1/3 )O 1.99 Cl 0.01 @0.2-Na 2 B 8 O 13 . As can be seen from the data in Table 1, the gram capacity (123 mAh/g) of the sample of example 5 after being left in an air environment (25 ℃ C., 50% RH) for 48 hours is smaller than the data (130 mAh/g) obtained under the same conditions for the sample of example 1, but is higher than the result (115 mAh/g) of comparative example 2. Indicating that the addition amount of the oxide is insufficientSome residual alkali does not participate in the reaction to affect the air stability of the material, so that the gram capacity is reduced.
Example 6
Based on the example 1, only the oxygen-site doped and modified sodium ion battery cathode material in the step S3 is mixed with ZrO 1 in mass ratio 2 Dispersing in ethanol solution, and other steps and conditions are the same as those of the embodiment 1, wherein the chemical composition formula of the positive electrode material is as follows: na (Ni) 1/3 Fe 1/3 Mn 1/3 )O 1.99 Cl 0.01 @1-Na 2 ZrO 3 . As can be seen from the data in Table 1, the gram capacity (128 mAh/g) of the sample of example 6 after being placed in an air environment (25 ℃ C., 50% RH) for 48 hours is slightly smaller than the data (130 mAh/g) obtained under the same conditions for the sample of example 1, indicating that the type of oxide selected has an effect on the improvement of the air stability of the material, but to a lesser extent. Overall, the gram capacity of the samples of example 1 and example 6 showed better retention than the uncoated material (sample of comparative example 2, which had a gram capacity of 115mAh/g after 48 hours in air) demonstrating a significant improvement in air stability of the coated material.
Comparative example 1
The preparation of the coated oxygen-site doped modified sodium ion battery anode material comprises the following steps:
s1, nickel sulfate, ferrous sulfate and manganese sulfate are mixed according to the following ratio of 1:1:1 in the molar ratio of deionized water to prepare a mixed solution with the total metal ion concentration of 2 mol/L; simultaneously preparing 1mol/L ammonia water complexing agent solution and 2mol/L sodium hydroxide precipitant solution. The reaction vessel is prepared by adopting a reaction kettle as a precursor, and nitrogen is introduced in advance as protective gas. Adding a base solution consisting of deionized water, a complexing agent solution and a precipitant solution into a reaction kettle, controlling the pH value to be 11-12, and then pumping a metal salt mixed solution, a complex solution and the precipitant solution into the reaction kettle at the same time through peristaltic pumps according to a certain flow rate, wherein the reaction temperature is controlled to be 50 ℃, and the stirring rate is controlled to be 400r/min. After the addition is completed, the reaction temperature is maintained and the reaction is continued to age for 24 hours for one coprecipitation. Filtering, washing and drying, and separating the precursor from the solution to obtain a transition metal hydroxide precursor product;
s2, mixing the prepared transition metal hydroxide precursor with sodium carbonate according to the following ratio of 2: the molar ratio of 1 is put into a ball milling container for ball milling treatment, and the ball milling time is 4 hours. After the mixture is uniformly mixed, the mixture is placed in a corundum crucible and transferred to a muffle furnace, and two-step sintering treatment is carried out in an air atmosphere. The temperature is raised to 500 ℃ at a heating rate of 3 ℃/min, the constant temperature sintering is carried out for 5 hours at the temperature, and the temperature is raised to 880 ℃ from 500 ℃ at a heating rate of 3 ℃/min, and the constant temperature sintering is carried out for 10 hours at the temperature. Cooling to room temperature at a cooling rate of 5 ℃/min under an air atmosphere. The material is crushed and sieved to obtain the oxygen-doped modified sodium ion battery layered oxide anode material.
The chemical composition formula of the positive electrode material is as follows: na (Ni) 1/3 Fe 1/3 Mn 1/3 )O 2 The structure is characterized in fig. 1. From the results, it can be seen that successful sintering yields the desired structure. FIG. 3 further illustrates the microstructure of the material, which can be found by scanning electron microscopy to be a polycrystalline material with a particle size D50 of about 3 μm, agglomerated from nanoscale particles, similar to example 1. FIG. 4 shows the specific capacity of the material, the specific discharge capacity of the material is 120mAh/g, the initial effect is 84.6%, and the performance result is inferior to that of the modified sample. FIG. 5 shows the results of the rate performance test, and it can be seen that the rate performance of the modified sample exceeds that of the unmodified sample, particularly at a larger rate of 5C, the specific capacity of the unmodified sample is 63mAh/g, which is lower than that of the sample of example 1 (90 mAh/g) at 5C. From the cyclic voltammograms of fig. 6 and 7, it can be seen that the anions cause less potential difference in oxidation-reduction of the material after oxygen doping and surface coating, and the polarization phenomenon is relieved, which is beneficial to the charge-discharge process of the battery.
Comparative example 2
The coating step in the step S3 was not performed in the same manner as in example 1, except that the chemical composition formula of the positive electrode material was as follows: na (Ni) 1/3 Fe 1/3 Mn 1/3 )O 1.99 Cl 0.01 . As can be seen from the data in Table 1, the sample of comparative example 2 had a gram capacity of 131mAh/g before being left in an air environment (25 ℃ C., 50% RH) for 48 hours and a gram capacity of 115mAh/g after being left for 48 hours, indicating that the non-surface-coated material had poor air stability.
Table 1 gram volume data for different samples before and after 48 hours of exposure to air
| Sample name | Gram Capacity before Placement (mAh/g) | Gram Capacity after standing (mAh/g) |
| Example 1 | 132 | 130 |
| Example 2 | 125 | 124 |
| Example 3 | 135 | 127 |
| Example 4 | 126 | 125 |
| Example 5 | 132 | 123 |
| Example 6 | 130 | 128 |
| Comparative example 1 | 120 | 101 |
| Comparative example 2 | 131 | 115 |
While the foregoing is directed to the preferred embodiments of the present invention, it will be appreciated by those skilled in the art that various modifications and adaptations can be made without departing from the principles of the present invention, and such modifications and adaptations are intended to be comprehended within the scope of the present invention.
Claims (10)
1. The coated oxygen-site doped modified sodium ion battery anode material is characterized by having a chemical formula as follows: na (Ni) x Fe y Mn z M 1-x-y-z )O 2-a X a @Na b Y c O d The method comprises the steps of carrying out a first treatment on the surface of the Wherein M is V 3+ 、Cr 3+ 、Co 3+ 、Cu 2+ 、Zn 2+ 、Zr 4+ 、Al 3+ 、Sb 3+ 、Bi 3+ 、La 3+ 、Ti 4+ 、Mg 2+ 、Nb 5+ 、Ta 5+ 、W 6+ 、Mo 6+ At least one of (a) and (b); x is F - 、Cl - 、Br - At least one of (a) and (b); y is at least one of B, bi, zr, mo; each component in the chemical formula meets the conservation of charge and the conservation of stoichiometry; and 0 is<x+y+z≤1；0≤a≤0.1。
2. The method for preparing the coated oxygen-site doped modified sodium ion battery positive electrode material as claimed in claim 1, comprising the following steps:
s1: introducing inert gas in advance, adding a transition metal salt mixed solution, a complex and a precipitant into a reaction kettle at the same time according to a certain flow rate, controlling the pH value, the reaction temperature and the stirring rate, performing coprecipitation reaction, and performing suction filtration, washing, drying and separation to obtain a transition metal hydroxide precursor;
s2: placing the transition metal hydroxide precursor, a sodium source and a doping agent in a ball milling container for ball milling treatment to obtain a mixture; placing the mixture into a corundum crucible, transferring the corundum crucible into a muffle furnace, and performing one-step or two-step heat treatment in an oxygen atmosphere to obtain an oxygen-doped modified sodium ion battery anode material;
s3: and mixing and stirring the oxygen-doped modified sodium ion battery anode material, oxide and solvent uniformly, and performing sintering treatment to obtain the cathode material.
3. The method for preparing a coated oxygen-doped modified sodium ion battery positive electrode material according to claim 2, wherein the transition metal salt is at least one of sulfate, nitrate, chloride, oxalate, acetate and carbonate, and the transition metal is at least three or more transition metals including Ni, fe and Mn; the total concentration of transition metal ions in the transition metal salt mixed solution is 0.5-5 mol/L; the complexing agent is at least one of ammonia water, sodium citrate solution, ethylene diamine tetraacetic acid tetrasodium solution and ethylene diamine tetraacetic acid disodium solution, and the concentration is 0.2-3 mol/L; the precipitant is at least one of sodium hydroxide and potassium hydroxide, and the concentration is 0.5-5 mol/L.
4. The method for preparing a coated oxygen-site doped modified sodium ion battery positive electrode material according to claim 3, wherein the oxygen-site doped modified sodium ion battery positive electrode material has a chemical composition formula: na (Ni) x Fe y Mn z M 1-x-y-z )O 2-a X a The method comprises the steps of carrying out a first treatment on the surface of the Wherein M is V 3+ 、Cr 3+ 、Co 3+ 、Cu 2+ 、Zn 2+ 、Zr 4+ 、Al 3+ 、Sb 3+ 、Bi 3+ 、La 3+ 、Ti 4+ 、Mg 2+ 、Nb 5+ 、Ta 5+ 、W 6+ 、Mo 6+ At least one of (a) and (b); x is F - 、Cl - 、Br - At least one of (a) and (b); wherein 0 is<x+y+z≤1；0≤a≤0.1。
5. The method for preparing a coated oxygen-doped modified positive electrode material of a sodium ion battery according to claim 4, wherein the sodium source is at least one of sodium oxide, sodium carbonate, sodium bicarbonate, sodium acetate, sodium nitrate, sodium citrate, sodium sulfate and sodium oxalate; the dopant is sodium salt or transition metal salt of fluorine, chlorine or bromine.
6. The preparation method of the coated oxygen-doped modified sodium ion battery anode material according to claim 5, wherein in the step S1, the pH is 9-13, the reaction temperature is 50 ℃, the stirring rate is 400r/min, and the reaction time is 12-48 h.
7. The method for preparing the coated oxygen-site doped modified sodium ion battery positive electrode material according to claim 6, wherein the one-step or two-step heat treatment in the step S2 is as follows:
(1) The one-step heat treatment process comprises the following steps: heating to 700-1000 ℃ at a heating rate of 2-10 ℃/min in air or oxygen atmosphere, and sintering at constant temperature for 5-30 hours; cooling to room temperature at a cooling rate of 2-10 ℃/min;
(2) The two-step heat treatment process comprises the following steps: in air or oxygen atmosphere, heating to 300-600 ℃ at a heating rate of 2-10 ℃/min, and presintering for 2-8 hours at constant temperature; further heating to 700-1000 ℃ at a heating rate of 2-10 ℃/min, and sintering at constant temperature for 5-30 hours; and then cooling to room temperature at a cooling rate of 2-10 ℃/min.
8. The method for preparing a coated oxygen-site doped modified sodium ion battery positive electrode material according to claim 7, wherein the oxide is B 2 O 3 、Bi 3 O 3 、MoO 2 、ZrO 2 At least one of (a) and (b); the solvent is any one of methanol, ethanol and propanol.
9. The method for preparing a coated oxygen-site doped modified sodium ion battery positive electrode material according to claim 8, wherein the mass of the oxide is 0.1-2% of the mass of the oxygen-site doped modified sodium ion battery positive electrode material.
10. The preparation method of the coated oxygen-site doped modified sodium ion battery positive electrode material according to claim 1, wherein the sintering process in the step S3 is specifically: heating to 400-800 ℃ at a heating rate of 2-10 ℃/min in air or oxygen atmosphere, and sintering at constant temperature for 1-12 hours; and then cooling to room temperature at a cooling rate of 2-10 ℃/min.
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| CN117497728B (en) * | 2023-12-04 | 2024-06-11 | 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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| CN117497728B (en) * | 2023-12-04 | 2024-06-11 | 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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