GB2619230A - Nickel-rich high-voltage sodium-ion positive electrode material for battery, preparation method therefor, and application thereof - Google Patents
Nickel-rich high-voltage sodium-ion positive electrode material for battery, preparation method therefor, and application thereof Download PDFInfo
- Publication number
- GB2619230A GB2619230A GB2313956.1A GB202313956A GB2619230A GB 2619230 A GB2619230 A GB 2619230A GB 202313956 A GB202313956 A GB 202313956A GB 2619230 A GB2619230 A GB 2619230A
- Authority
- GB
- United Kingdom
- Prior art keywords
- sodium
- positive electrode
- electrode material
- nickel
- sulfate
- 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.)
- Pending
Links
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 85
- 229910001415 sodium ion Inorganic materials 0.000 title claims abstract description 70
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title claims abstract description 68
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 20
- 239000003381 stabilizer Substances 0.000 claims abstract description 10
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims abstract description 6
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052802 copper Inorganic materials 0.000 claims abstract description 4
- 239000010949 copper Substances 0.000 claims abstract description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims abstract description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 3
- 239000011575 calcium Substances 0.000 claims abstract description 3
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 3
- 239000011651 chromium Substances 0.000 claims abstract description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 3
- 239000011733 molybdenum Substances 0.000 claims abstract description 3
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 3
- 239000011701 zinc Substances 0.000 claims abstract description 3
- 229910019142 PO4 Inorganic materials 0.000 claims description 40
- 235000002639 sodium chloride Nutrition 0.000 claims description 35
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 33
- 239000002243 precursor Substances 0.000 claims description 33
- 150000003839 salts Chemical class 0.000 claims description 33
- 239000011734 sodium Substances 0.000 claims description 32
- 238000010438 heat treatment Methods 0.000 claims description 26
- 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 25
- 229910052708 sodium Inorganic materials 0.000 claims description 25
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 24
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 18
- 238000005406 washing Methods 0.000 claims description 13
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 12
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 12
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 10
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 10
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 9
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 9
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 9
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 8
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 8
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 5
- 229910000388 diammonium phosphate Inorganic materials 0.000 claims description 5
- 235000019838 diammonium phosphate Nutrition 0.000 claims description 5
- 150000007524 organic acids Chemical class 0.000 claims description 5
- 238000002791 soaking Methods 0.000 claims description 5
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 4
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 4
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 4
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims description 4
- 239000011737 fluorine Substances 0.000 claims description 4
- 229910052731 fluorine Inorganic materials 0.000 claims description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 4
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 claims description 4
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 claims description 4
- 238000005245 sintering Methods 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 4
- 239000001488 sodium phosphate Substances 0.000 claims description 4
- 229910000162 sodium phosphate Inorganic materials 0.000 claims description 4
- 235000011008 sodium phosphates Nutrition 0.000 claims description 4
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 4
- 235000011152 sodium sulphate Nutrition 0.000 claims description 4
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 4
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 claims description 3
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 3
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 3
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 3
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 3
- 235000006408 oxalic acid Nutrition 0.000 claims description 3
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 3
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 3
- 229960001763 zinc sulfate Drugs 0.000 claims description 3
- WWILHZQYNPQALT-UHFFFAOYSA-N 2-methyl-2-morpholin-4-ylpropanal Chemical compound O=CC(C)(C)N1CCOCC1 WWILHZQYNPQALT-UHFFFAOYSA-N 0.000 claims description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 2
- 239000004254 Ammonium phosphate Substances 0.000 claims description 2
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 2
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 2
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 2
- 235000011054 acetic acid Nutrition 0.000 claims description 2
- 229940010048 aluminum sulfate Drugs 0.000 claims description 2
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 2
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 2
- 229910000148 ammonium phosphate Inorganic materials 0.000 claims description 2
- 235000019289 ammonium phosphates Nutrition 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
- 235000015165 citric acid Nutrition 0.000 claims description 2
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 claims description 2
- 229910000397 disodium phosphate Inorganic materials 0.000 claims description 2
- 235000019800 disodium phosphate Nutrition 0.000 claims description 2
- 235000019253 formic acid Nutrition 0.000 claims description 2
- 229910000040 hydrogen fluoride Inorganic materials 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 229940099596 manganese sulfate Drugs 0.000 claims description 2
- 239000011702 manganese sulphate Substances 0.000 claims description 2
- 235000007079 manganese sulphate Nutrition 0.000 claims description 2
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 2
- ICYJJTNLBFMCOZ-UHFFFAOYSA-J molybdenum(4+);disulfate Chemical compound [Mo+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ICYJJTNLBFMCOZ-UHFFFAOYSA-J 0.000 claims description 2
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 2
- 229910000159 nickel phosphate Inorganic materials 0.000 claims description 2
- 229940053662 nickel sulfate Drugs 0.000 claims description 2
- JOCJYBPHESYFOK-UHFFFAOYSA-K nickel(3+);phosphate Chemical compound [Ni+3].[O-]P([O-])([O-])=O JOCJYBPHESYFOK-UHFFFAOYSA-K 0.000 claims description 2
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 claims description 2
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 claims description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 2
- 235000011007 phosphoric acid Nutrition 0.000 claims description 2
- 239000011698 potassium fluoride Substances 0.000 claims description 2
- 235000003270 potassium fluoride Nutrition 0.000 claims description 2
- 239000001632 sodium acetate Substances 0.000 claims description 2
- 235000017281 sodium acetate Nutrition 0.000 claims description 2
- WBHQBSYUUJJSRZ-UHFFFAOYSA-M sodium bisulfate Chemical compound [Na+].OS([O-])(=O)=O WBHQBSYUUJJSRZ-UHFFFAOYSA-M 0.000 claims description 2
- 229910000342 sodium bisulfate Inorganic materials 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 235000017550 sodium carbonate Nutrition 0.000 claims description 2
- 239000011780 sodium chloride Substances 0.000 claims description 2
- 239000001509 sodium citrate Substances 0.000 claims description 2
- 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 2
- 239000011775 sodium fluoride Substances 0.000 claims description 2
- 235000013024 sodium fluoride 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
- 239000011975 tartaric acid Substances 0.000 claims description 2
- 235000002906 tartaric acid Nutrition 0.000 claims description 2
- 239000002245 particle Substances 0.000 abstract description 11
- 239000000463 material Substances 0.000 abstract description 10
- 239000011247 coating layer Substances 0.000 abstract description 3
- 125000004122 cyclic group Chemical group 0.000 abstract description 2
- 150000002500 ions Chemical class 0.000 abstract description 2
- 229910044991 metal oxide Inorganic materials 0.000 abstract description 2
- 150000004706 metal oxides Chemical class 0.000 abstract description 2
- 238000005054 agglomeration Methods 0.000 abstract 1
- 230000002776 aggregation Effects 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 17
- 239000012300 argon atmosphere Substances 0.000 description 13
- 238000003756 stirring Methods 0.000 description 12
- 239000000203 mixture Substances 0.000 description 11
- 230000015572 biosynthetic process Effects 0.000 description 10
- 229910052744 lithium Inorganic materials 0.000 description 10
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 9
- 238000003786 synthesis reaction Methods 0.000 description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- 229910020665 Na3Ni Inorganic materials 0.000 description 8
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 7
- 238000000498 ball milling Methods 0.000 description 7
- 239000000919 ceramic Substances 0.000 description 7
- 229910001416 lithium ion Inorganic materials 0.000 description 7
- 238000001704 evaporation Methods 0.000 description 6
- 230000008020 evaporation Effects 0.000 description 6
- 239000002002 slurry Substances 0.000 description 6
- 238000001035 drying Methods 0.000 description 5
- 229910052786 argon Inorganic materials 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 229910021645 metal ion Inorganic materials 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 239000002253 acid Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 230000006641 stabilisation Effects 0.000 description 2
- 238000011105 stabilization Methods 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229910020685 Na4Co3 Inorganic materials 0.000 description 1
- 229910020939 NaC104 Inorganic materials 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002484 cyclic voltammetry Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 230000017525 heat dissipation Effects 0.000 description 1
- 238000010335 hydrothermal treatment Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- -1 polytetrafluoroethylene Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- KEAYESYHFKHZAL-BJUDXGSMSA-N sodium-22 Chemical compound [22Na] KEAYESYHFKHZAL-BJUDXGSMSA-N 0.000 description 1
- AWRQDLAZGAQUNZ-UHFFFAOYSA-K sodium;iron(2+);phosphate Chemical compound [Na+].[Fe+2].[O-]P([O-])([O-])=O AWRQDLAZGAQUNZ-UHFFFAOYSA-K 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/455—Phosphates containing halogen
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- 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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/54—Reclaiming serviceable parts of waste accumulators
-
- 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
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The present invention relates to the technical field of sodium-ion batteries, and disclosed are a nickel-rich high-voltage sodium-ion positive electrode material, a preparation method therefor, and an application thereof. The general formula of the sodium-ion positive electrode material is NasNit(PO4)(SO4)/F@M-C, 2≤s≤4, and 0.5≤t≤1.5; and M is an oxide of at least one of zinc, nickel, aluminum, manganese, chromium, molybdenum, manganese, copper, and calcium. In the sodium-ion positive electrode material of the present invention, a stabilizer is added so that the structural stability of the positive electrode material is strengthened, and cyclic discharge performance of the material is improved; a coating layer (formed by tightly combining a metal oxide and the positive electrode material) in the sodium-ion positive electrode material can stabilize ion and electron transport kinetic properties of the material, improve cycle performance of the positive electrode material, hinder the material from continuing agglomeration, and control a particle size.
Description
NICKEL-RICH HIGH-VOLTAGE SODIUM-ION POSITIVE ELECTRODE MATERIAL FOR BATTERY, PREPARATION METHOD THEREFOR, AND APPLICATION
THEREOF
FIELD
[00011 The present disclosure belongs to the technical field of sodium-ion batteries, and specifically relates to a positive electrode material for a nickel-rich high-voltage sodium-ion battery and a preparation method and application thereof.
to BACKGROUND
[0002] Lithium-ion batteries have satisfactory properties, such as high energy density and excellent cycle life, and are successfully applied in mobile electronic devices, transportation power, and energy storage power. At present, thanks to the vigorous development of new energy sources, there is more demand for lithium battery energy storage equipment in fields such as hybrid electric vehicles (HEV), electric vehicles (EV), and smart grids. The current conundrum is that the sharp rise in the cost of lithium and the materials associated with the manufacture of lithium-ion batteries has led to an increase in the price of lithium-ion batteries. The lack of resource prospects and uneven distribution of lithium, therefore, has prompted research into more sustainable and lower-cost, more efficient options.
[0003] Sodium-ion batteries would be a suitable alternative. Sodium is more abundant in the earth's crust; the standard redox potential of sodium is only 0.326V higher than that of lithium metal, and its electronegativity is only 0.05V lower than that of lithium. However, the theoretical mass specific capacity (3860 mAh-g-I) and the theoretical volume specific capacity (2060 mAh-cm') of lithium is much higher than the theoretical mass specific capacity (1160 mAh-g-1) and the theoretical volume specific capacity (1130 mAh-cm-3) of sodium. It can be seen that the performance of sodium-ion battery is inferior to that of lithium-ion battery. Therefore, since 2001, researchers have carried out a lot of research on improving the electrochemical performance of sodium, such as developing high-performance electrode materials, providing superior operating voltage, ascertaining the decomposition reaction of the electrode in the electrolyte and the
-I -
formation of products, and enhancing the electrochemical cycle stability, which will be beneficial to solve the problems of energy density and lifespan of sodium-ion batteries.
[0004] In recent years, with the continuous increase in the price of lithium-ion batteries, especially the consumption of lithium resources and not abundant lithium reserves in the world, we will have to face the dilemma of lithium shortage in the future. The study indicates that sodium, which has similar chemical properties to lithium, is very promising to become the next-generation secondary battery after lithium-ion batteries. Nevertheless, because the larger radius of the sodium ions, the heavier the atomic weight, and the higher standard potential of sodium usually leads to poor reversibility and lower energy density, in general the performance of sodium-ion batteries is not as good as that of lithium-ion batteries. For example, the electrochemical performance of sodium iron phosphate positive electrode materials in terms of capacity, voltage, and cycle ability is lower than that of lithium iron phosphate positive electrode materials.
[0005] Currently, Na4MP207 (M=Fe, Co, Mn, Cu, PO4, 504, CO3) polyanionic positive electrode material, capable of operating at high voltages >3.5 V (vs Na/Na) and exhibiting excellent cycling stability, is a promising positive electrode material. For example, Na4Co3(PO4)2P207 provides a capacity of 95 mAh-g-1 at 0.2C rate in the 3.0-4.4 V (vs Na/Na) voltage window and a capacity retention of >95% over 100 cycles; Na4Fe3(PO4)2(P207), as a positive electrode material for sodium-ion batteries, releases a reversible capacity of 129 mAh-g-1, and the average operating voltage exceeds 3.2 V (vs Nat/Na) electrodes. Nevertheless, for Na4MP04-type sodium-ion batteries, low energy density and poor cycle performance are still the biggest shortcomings, and the energy density of batteries depends on the specific capacity and operating voltage of the material. Therefore, it is urgent to develop a positive electrode material with high specific capacity and high initial operating voltage.
SUMMARY
[0006] The present disclosure aims to solve at least one of the above-mentioned technical problems existing in the prior art. To this end, the present disclosure proposes a nickel-rich high-voltage sodium-ion positive electrode material and a preparation method and application thereof, and the sodium-ion positive electrode material has excellent cycle performance, high specific capacity and an initial operating voltage of up to 3.8V.
[0007] To achieve the above object, the present disclosure adopts the following technical solutions: [0008] A sodium-ion positive electrode material with a general formula of NasNit(PO4)(504)/F@M-C, 2<scl, 0.5<t< I.5; wherein M is oxide of at least one of zinc, nickel, aluminum, manganese, chromium, molybdenum, manganese, copper and calcium.
[0009] Preferably, a value range of s is 2.5<s<3.5, and a value range of t is 0.5<t<1.2.
[0010] Preferably, a formula of the sodium-ion positive electrode material is at least one of Na2.6Nii.2(PO4)(804)/F@A1203-C, Na3.4Nio.s(PO4)(804)/F@CuO-C, and Na3Ni(PO4)(SO4)/F@ZnO-C.
[0011] A preparation method of a sodium-ion positive electrode material, comprising steps of: [0012] mixing a nickel source solution, sulfuric acid source, phosphoric acid source and fluorine source for a microwave hydrothermal reaction, and performing concentration to obtain a triacid salt precursor; [0013] mixing the triacid salt precursor with sodium source and a stabilizer, and heating for reaction to obtain Na,Nit(PO4)(SO4)/F; and [0014] adding a sodium washing agent to the NasNit(PO4)(804)/F for soaking, and sintering to obtain the sodium-ion positive electrode material.
[0015] Preferably, the nickel source solution is obtained by mixing nickel source and an organic acid.
[0016] Further preferably, the organic acid is at least one of tartaric acid, oxalic acid, citric acid, formic acid and acetic acid.
[0017] Further preferably, a concentration of the organic acid is 0.01-12 wt%.
[0018] Further preferably, the nickel source is at least one of nickel sulfate, nickel hydroxide, nickel nitrate, nickel chloride and nickel carbonate.
[0019] Preferably, the sulfuric acid source is at least one of sulfuric acid, sodium sulfate, -3 -ammonium sulfate, ammonium hydrogen sulfate, sodium hydrogen sulfate and nickel sulfate.
[9029] Preferably, the phosphoric acid source is at least one of phosphoric acid, sodium phosphate, ammonium phosphate, di ammonium hydrogen phosphate, ammonium dihydrogen phosphate, sodium hydrogen phosphate and nickel phosphate.
[9021] Preferably, the fluorine source is at least one of ammonium fluoride, potassium fluoride, sodium fluoride and hydrogen fluoride.
[0022] Preferably, a temperature of the microwave hydrothermal reaction is 100-300°C, and a duration of the microwave hydrothermal reaction is 1-60 min: the temperature is preferably 120-240°C, and the duration is preferably 5-300 min [9023] Preferably, after the concentration, it further comprises soaking and drying the triacid salt precursor.
[9024] Preferably, before the mixing, it further comprises hall-milling the triacid salt precursor for 0.5-12 h, and the particle size after ball-milling is <50 p.m.
[9025] Preferably, the sodium source is at least one of sodium hydroxide, sodium citrate, sodium oxalate, sodium acetate, sodium phosphate, sodium sulfate, sodium carbonate and sodium chloride.
[0026] Preferably, the stabilizer is at least one of 1.4-benzenedicarboxylic acid 2,5-dipropoxy-1.4-dihyclrazide, N,N,N-,N.-tetrakis(4-methoxypheny1)-9H-carbazole-3,6-diamine, and 4,4',4-trimethy1-2,2":6',2-terpyridine.
[0027] Preferably, the stabilizer is 0.01-5 wt% of a total mass of the triacid salt precursor and the sodium source.
[9028] Preferably, after the soaking, it further comprises drying, and a temperature of the drying is 60-150°C.
[9029] Preferably, a temperature of the heating reaction is 300-800°C, and a duration of the heating reaction is 0.5-24 h. [9039] Preferably, a solid-liquid ratio of the NasNi1(PO4)(804)/F to the sodium washing agent is (0.1-3): (1-5) g/ml. -4 -
[90311 Preferably, the sodium washing agent is at least one of zinc sulfate, nickel sulfate, aluminum sulfate, manganese sulfate, chromium sulfate, molybdenum sulfate, copper sulfate and calcium sulfate.
[9032] On the one hand, the sodium washing agent can wash away the residual sodium hydroxide on the surface of the positive electrode material, reduce the residual sodium in the positive electrode material, and reduce the side reactions on the surface of the positive electrode material. On the other hand, the sodium ions in the sodium hydroxide on the surface of the positive electrode material are exchanged with acid salts. Some metal ions are added to be hydrolyzed and deposited on the surface of the positive electrode material, dehydrated after drying, and become metal oxides and deposit on the surface of the positive electrode material.
[0033] Preferably, a temperature of the sintering is 400-800'C., and an atmosphere of the sintering is an inert gas.
[9034] A battery, comprising the sodium-ion positive electrode material.
[0035] Preferably, a battery prepared by the sodium-ion positive electrode material has an operating platform voltage of greater than 3.8V during the first discharge.
[9036] With respect to the prior art, the present disclosure has the following beneficial effects: [9037] 1. In the sodium-ion positive electrode material of the present disclosure, by adding a stabilizer, the structural stability of the positive electrode material is strengthened and the cyclic discharge performance of the material is improved; the coating layer (after the sodium washing agent treatment, the metal ions are hydrolyzed and deposited on the surface of the positive electrode material, and are dehydrated to become metal ions, and the metal ions tightly combine with the positive electrode material to form the coating layer) in the sodium-ion positive electrode material can improve the ion and electron transport kinetic properties of the material, improve the cycling performance of the positive electrode material, prevent the nickel-rich high-voltage sodium-ion positive electrode material from continuing to agglomerate and grow, and control the particle size.
[0038] 2. In the preparation method of the present disclosure, the internal particle distribution of the triacid salt precursor synthesized by the microwave method is more uniform, and the electron transfer rate and heat transfer efficiency inside the obtained nickel-rich high-voltage -5 -positive electrode material are of high consistency, which is conducive to the stability of the internal structure of the material. In addition, as a stabilizer is conductive to the stabilized structure and good heat dissipation characteristics, a stabilizer is added to the positive electrode material, so that the stability of the structure of the positive electrode material is strengthened and the cycle discharge performance of the material is improved.
[00391 3. In the present disclosure, during the preparation of a precursor of the nickel-rich high-voltage sodium-ion positive electrode material, the triacid salt precursor is synthesized using microwave, in which the temperature rises rapidly, and the reaction is generally completed within 3-20 minutes. Therefore, the reaction process is very fast and the reaction time is shortened by more than 90%. In addition, the synthesis temperature is controlled at 100-300°C, which is much lower than the conventional high-temperature treatment of 400-800°C, so the reaction temperature of microwave synthesis of triacid salt precursors is lower. In a controlled electromagnetic environment, the crystal nucleation and growth of the triacid salt precursor are accelerated, the grain morphology is controllable, and the uniformity of the triacid salt precursor is good, which is conducive to the synthesis of a material with high crystallinity and uniform and complete particles.
BRIEF DESCRIPTION OF DRAWINGS
[00401 FIG. 1 is a process flow diagram of preparing a sodium-ion positive electrode material
in Example 1 of the present disclosure;
[00411 FIG. 2 is a schematic diagram of the sodium-ion positive electrode material prepared in Example 1 of the present disclosure; [0042] FIG. 3 is an SEM image of the sodium-ion positive electrode material prepared in Example 1 of the present disclosure; [0043] FIG. 4 is a TEM image of the sodium-ion positive electrode material prepared in
Example 1 of the present disclosure.
DETAILED DESCRIPTION -6 -
l00441 The concept of the present disclosure and the technical effects produced thereby will be clearly and completely described below in conjunction with the examples, so as to fully understand the purpose, characteristics and effects of the present disclosure. Obviously, the described examples are only a part of the embodiments of the present disclosure, rather than all the embodiments. Based on the embodiments of the present disclosure, other embodiments obtained by those skilled in the art without creative efforts are all within the scope of protection of the present disclosure.
Example 1
[9045] The sodium-ion positive electrode material of this example has a formula of Na2oNlii.2(PO4)(SO4)/F@A1203-C.
[0046] The process flow diagram of the sodium-ion positive electrode material prepared in this example is shown in FIG. 1. In FIG. 1, nickel hydroxide and citric acid were mixed to obtain solution A; ammonium sulfate, phosphoric acid, and ammonium fluoride were mixed to obtain solution B; under stirring, solution B was added to solution A to obtain solution C; and solution C was placed in a ceramic crucible, sent to a microwave reactor, heated and cooled to obtain a triacid salt precursor. After ball-milling the triacid salt precursor, it was mixed with sodium hydroxide, N,N,N',N'-tetrakis(4-methoxypheny1)-9H-carbazole-3,6-diamine slurry evenly, and the mixture was heated to obtain Na2.6Nii.2(PO4)(SO4)/F. Aluminum sulfate and Na2isNii.2(PO4)(SO4)/F were soaked, heated and cooled to obtain N a2.6Ni.2(PO4)(S 04)/F (9)A1203-C.
[0047] The specific steps for the preparation of the sodium-ion positive electrode material in this example are as follows: l00481 (1) Microwave hydrothermal synthesis of triacid salt precursor: 1.12 g of nickel hydroxide was mixed with 150 nth of 5.5w% citric acid to obtain solution A. 19 mL of 0.53 mol/L ammonium sulfate, 14.9 mL of 0.67 mol/L phosphoric acid, and 9 mL of 0.17 mol/L ammonium fluoride were mixed to obtain solution B. Under stirring, solution B was gradually added dropwise to solution A to obtain solution C. 20 mL of solution C was taken and placed in a ceramic crucible, which was sent to a microwave reactor filled with argon gas at 350W. The microwave reactor was set as follows: the first stage was heating at 110°C and stable evaporation -7 -for 6 mm, the second stage was heating at 275°C and stable evaporation for 25 min, the heating time between the two stages was 180 s, and the temperature was lowered. A triacid salt precursor was obtained.
[9049] (2) Synthesis of Na,6Nii2(PO4)(SO4)/F: After ball-milling the triacid salt precursor for 7.5 h, it was mixed with 17.5 mL of 1.5 mol/L sodium hydroxide and 18 mL of 1.66 wt% N,N,N ',N '-tetrakis(4-methoxypheny1)-9H-carbazole-3,6-diamine slurry evenly under stirring. The mixture was heated in a heating furnace at 300°C for 8h under the argon atmosphere to obtain a sodium-ion positive electrode material Nao 6Nii.2(PO4)(SO4)/F.
[9059] (3) Sodium washing treatment: 4.5 mL of 0.019 mol/L aluminum sulfate was divided 10 into three equal parts, mixed with 1.5 g of sodium-ion positive electrode material Na26Nit2(PO4)(504)/F. The mixture was soaked for three times, and dried in an oven at 110°C for 10 h overnight. It was sintered in the heating furnace at 470°C for 8 h under the argon atmosphere, and cooled to obtain a sodium-ion positive electrode material N a2.6Nii2(PO4)(SO4)/F@ A1203-C.
Example 2
[9051] The sodium-ion positive electrode material of this example has a formula of Na3.4Nio.s(PO4)(S 04)/F @ Cu O-C.
[00521 The specific steps for the preparation of the sodium-ion positive electrode material in this example are as follows: [0053] (I) Microwave hydrothermal synthesis of triacid salt precursor: 1.24 g of nickel sulfate was dissolved in 150 mL of 7.1 w% oxalic acid to obtain solution A. 19 mL of (153 mol/L ammonium sulfate, 1.33 g of diammonium hydrogen phosphate, and 12 mL of (118 mol/L ammonium fluoride were mixed to obtain solution B. Under stirring, solution B was gradually added dropwise to solution A to obtain solution C. 20 mL of solution C was taken and placed in a ceramic crucible, which was sent to a microwave reactor filled with argon gas at 500W. The microwave reactor was set as follows: the first stage was heating at 115°C and stabilization for 3 mm, the second stage was heating at 240°C and stabilization for 20 min, the heating time between the two stages was 180 s, and the temperature was lowered. A triacid salt precursor was obtained. -s -
[00541 (2) Synthesis of Na3.4Nio.8(PO4)(504)/F: After ball-milling the triacid salt precursor to a particle size of <50 pm, it was mixed with 22.7 mL of 1.5 mol/L sodium hydroxide and 18 mL of 1.5 wt% 1,4-benzenedicarboxylic acid 2,5-dipropoxy-1,4-dihydrazide slurry evenly under stirring. The mixture was heated in a heating furnace at 540°C for 6.5h under the argon atmosphere to obtain a sodium-ion positive electrode material Na3.4Nio.s(PO4)(SO4)/F.
[00551 (3) Sodium washing treatment: 4.5 mL of 0.032 mol/L copper sulfate was divided into three equal parts, mixed with 1.5 g of sodium-ion positive electrode material Na3.4Nio.s(PO4)(504)/F. The mixture was soaked for three times, and dried in an oven at 150°C for 4 h. It was sintered in the heating furnace at 590°C for 6.5 h under the argon atmosphere, and cooled to obtain a sodium-ion positive electrode material Na3ANio.s(PO4)(SO4)/F@CuO-C.
Example 3
[00561 The sodium-ion positive electrode material of this example has a formula of Na3Ni(PO4)(SO4)/F@ZnO-C.
[0057] The specific steps for the preparation of the sodium-ion positive electrode material in this example are as follows: [0058] (1) Microwave hydrothermal synthesis of triacid salt precursor: 1.3 g of nickel chloride was dissolved in 500 mL of 0.317mo1/Lw% citric acid to obtain solution A. 19 mL of 0.53 mol/L ammonium sulfate, 1.33 g of diammonium hydrogen phosphate, and 17 mL of 0.18 mol/L ammonium fluoride were mixed to obtain solution B. Under stirring, solution B was gradually added dropwise to solution A to obtain solution C. 200 mL of solution C was taken and placed in a ceramic crucible, which was sent to a microwave reactor filled with argon gas at 350W. The microwave reactor was set as follows: the first stage was heating at 115°C and stable evaporation for 3 mm, the second stage was heating at 275°C and stable evaporation for 20 min, the heating time between the two stages was 180 s, and the temperature was lowered. A triacid salt precursor was obtained.
[0059] (2) Synthesis of Na3Ni(PO4)(504)/F: After ball-milling the triacid salt precursor to a particle size of <50 gm, it was mixed with 20 mL of 1.5 mol/L sodium hydroxide and 22 mL of 1.5 wt% 4,4',4-trimethy1-2,2':6',2-terpyridine slurry evenly under stirring. The mixture was heated in a heating furnace at 620°C for 8h under the argon atmosphere to obtain a sodium-ion positive electrode material Na3Ni(PO4)(SO4)/E [9069] (3) Sodium washing treatment: 6 mL of 0.063 mol/L zinc sulfate was divided into three equal parts, mixed with 2.0 g of sodium-ion positive electrode material Na3Ni(PO4)(SO4)/F. The mixture was soaked for three times, and dried in an oven at 125°C for 3 11. It was sintered in the heating furnace at 470°C for 6.5 h under the argon atmosphere, and cooled to obtain a sodium-ion positive electrode material Na3Ni(PO4)(SO4)/F@ZnO-C.
Comparative Example 1 [9061] The sodium-ion positive electrode material of this comparative example has a formula of Na34Ni0.8(1)04)(SO4)/F@A1203.
[0062] The specific steps for the preparation of the sodium-ion positive electrode material in this comparative example are as follows: [9063] (1) Microwave hydrothermal synthesis of triacid salt precursor: 1.24 g of nickel sulfate was dissolved in 50 mL of 5.5w% citric acid to obtain solution A. 19 mL of 0.53 mol/L ammonium sulfate, 16 mL of 0.67 mol/L phosphoric acid, and 12 mL of 0.18 mol/L ammonium fluoride were mixed to obtain solution B. Under stirring, solution B was gradually added dropwise to solution A to obtain solution C. 200 mL of solution C was taken and placed in a ceramic crucible, which was heated at 540°C for 8 h under argon atmosphere and cooled to obtain a triacid salt precursor.
[9064] (2) Synthesis of Na3.4Nius(PO4)(SO4)/F: After ball-milling the triacid salt precursor to a particle size of <50 pm, it was mixed with 22.7 mL of 1.5 mol/L sodium hydroxide and 18 mL, of L5 wt% 4,4',4-trimethyl-2,2':6',2-terpyridine slurry evenly under stirring. The mixture was heated in a heating furnace at 540°C for 6.5h under the argon atmosphere to obtain a sodium-ion positive electrode material Na3.4Nio.s(PO4)(SOL)/F-C.
Comparative Example 2 [00651 The sodium-ion positive electrode material of this comparative example has a formula of Na3.4Ni0.4PO4)(SO4)/F@A1203.
[0066] The specific steps for the preparation of the sodium-ion positive electrode material in this comparative example are as follows: [00671 (1) Microwave hydrothermal synthesis of triacid salt precursor: 1.24 g of nickel sulfate was dissolved in 50 mL of 5.5w% citric acid to obtain solution A. 19 mL of 0.53 mol/L ammonium sulfate, 1.42 g of diammonium hydrogen phosphate, and 12 mL of 0.18 mol/L ammonium fluoride were mixed to obtain solution B. Under stirring, solution B was gradually added dropwi se to solution A to obtain solution C. 200 mL of solution C was taken and placed in a ceramic crucible, which was heated at 540°C for 8 h under argon atmosphere and cooled to obtain a triacid salt precursor.
[00681 (2) Synthesis of Na34Nios(PO4)(SO4)/F: After ball-milling the triacid salt precursor to a particle size of <50 p.m, it was mixed with 22.7 mL of 1.5 mol/L sodium hydroxide evenly under stirring. The mixture was heated in a heating furnace at 540°C for 6.5h under the argon atmosphere to obtain a sodium-ion positive electrode material Na34Nios(PO4)(504)/F.
[00691 (3) Sodium washing treatment: 6 mL of 0.022 mol/L aluminum sulfate was divided into three equal parts, mixed with 2.0 g of sodium-ion positive electrode material Na3.4Ni0.8(PO4)(SO4)/F. The mixture was soaked for three times, and dried in an oven at 95°C to constant weight. It was sintered in the heating furnace at 540°C for 6.5 h under the argon atmosphere, and cooled to obtain a sodium-ion positive electrode material Na3.4Nio.8(1)04)(504)/F@ A1203.
Comparative Example 3 [00701 The sodium-ion positive electrode material of this comparative example has a formula 20 of Na3Ni(PO4)(SO4)/F.
[00711 The specific steps for the preparation of the sodium-ion positive electrode material in this comparative example are as follows: [0072] (I) Microwave hydrothermal synthesis of triacid salt precursor: 1.55 g of nickel sulfate was dissolved in 50 mL of 5.5w% citric acid to obtain solution A. 19 mL of 0.53 mol/L ammonium sulfate, 1.53 g of diammonium hydrogen phosphate, and 12 mi. of 0.18 mol/L ammonium fluoride were mixed to obtain solution B. Under stirring, solution B was gradually added dropwise to solution A to obtain solution C. 200 mL of solution C was taken and placed in a ceramic crucible, which was sent to a microwave reactor filled with argon gas at 350W. The microwave reactor was set as follows: the first stage was heating at 90°C and stable evaporation for 6 min, the second stage was heating at 275°C and stable evaporation for 25 min, the heating time between the two stages was 180 s, and the temperature was lowered. A triacid salt precursor was obtained.
i90731 (2) Synthesis of NaiNi(PO4)(SO4)/F: The triacid salt precursor was ball-milled to a 5 particle size of <50 pm, mixed with 20 mL of 1.5 mol/L sodium hydroxide, and dried in an oven at 125°C for 3h. The mixture was heated in a heating furnace at 540°C for 8h under the argon atmosphere to obtain a sodium-ion positive electrode material Na3Ni(PO4)(SO4)/F.
Analysis of Examples 1-3 and Comparative Examples 1-3: [00741 The sodium-ion positive electrode material prepared in Examples 1-3 and Comparative Examples 1-3, carbon black conductive agent, and polytetrafluoroethylene were mixed and dissolved in deionized water in a mass ratio of 80:10:10 to prepare a slurry, which was then coated on aluminum foil to form electrode sheet. The electrode sheet was placed in a drying box to dry at 80°C for 12 h, and stamped into a disc in a mold. The disc was cut into a counter electrode sheet with a diameter of 10 mm. 1.0 mol/L NaC104 as electrolyte was added to carbonate. Celgard2400 was used as separator. The battery was assembled in a vacuum glove box under argon atmosphere. The AC impedance and cyclic voltammetry of the button battery were tested by electrochemical workstation, and the charge and discharge of the button battery was tested by the LAND battery test system. The current density of the test was 30 mAig-l.
Table 1 Test data of battery obtained from the positive electrode materials prepared in Examples 1-3 and Comparative Examples 1-3 Sample Discharge Capacity Discharge Efficiency (To) Operating (mAh-g-i) Platform Voltage at First Discharge (V) tsi 1011 tooth 1st win 100th Example 1 132.6 121.3 108.7 981 89.9 80.5 3.8 Example 2 131.4 122.9 108.2 97.3 91.3 80.1 3.8 Example 3 128.3 119.8 107.5 95.1 88.7 79.6 3.8 12 -Comparative 117.7 110.8 91.3 92.7 87.2 71.9 3.7
Example I
Comparative 117.5 109.1 93.2 92.5 86.3 70.8 3.6
Example 2
Comparative 115.6 107.6 89.8 91.0 88.0 73.5 3.7
Example 3
[0075] In Table 1, the first discharge capacity of Examples 1-3 was 128.3-132.6 inAh-g-1 and the platform voltage at the first discharge was 3.8V, whereas the first discharge capacity of Comparative Examples 1-3 was 115.6-117.7 mAh-g-1 and the platform voltage at the first discharge was 3.6-3.7V. In addition, at the 100th discharge; the discharge capacity of Examples 1-3 was still 107.5-108.7 mAh-g-1, and the first discharge capacity of Comparative Examples 1-3 was 89.8-93.2 mAh-g-1. The discharge efficiency of the battery obtained from the positive electrode material prepared in Examples 1-3 was also higher than that of the battery obtained from the positive electrode material prepared in Comparative Examples 1-3 in the first, 10th, and 1001h discharge, respectively. It shows that the electrochemical performance of nickel-rich high-voltage sodium-ion positive electrode material has been improved after microwave hydrothermal treatment, addition of stabilizer, and soaking with sodium washing agent.
[0076] From FIG. 2 and FIG. 4, the surface of the sodium-ion positive electrode material prepared in Example 1 was coated with a layer of aluminium oxide, which was closely combined with the sodium-ion positive electrode material. In FIG. 3, the surface of the nickel-rich high-voltage sodium-ion positive electrode material was relatively rough, and the particle size was about 12 p.m.
[0077] The embodiments of the present disclosure have been described in detail above in conjunction with the drawings. However, the present disclosure is not limited to the above-mentioned embodiments, and various modifications can be made without departing from the purpose of the present disclosure within the scope of knowledge possessed by those of ordinary skill in the art. In addition, in the case of no conflict, the embodiments of the present disclosure and the features in the embodiments may be combined with each other.
Claims (10)
- CLAIMS1. A sodium-ion positive electrode material with a general formula of NasNii(PO4)(SO4)/F@M-C; wherein M is oxide of at least one of zinc, nickel, aluminum, manganese, chromium, molybdenum, manganese, copper and calcium, and 2<s<4, 0.5<t< I.5.
- 2. The sodium-ion positive electrode material according to claim I, wherein a value range of s is 2.5<s<3.5, and a value range of t is 0.54<1.2.
- 3. A preparation method of the sodium-ion positive electrode material according to any one of claims 1-2, comprising steps of: mixing a nickel source solution, sulfuric acid source, phosphoric acid source and fluorine source for a microwave hydrothermal reaction, and performing concentration to obtain a triacid salt precursor; mixing the triacid salt precursor with sodium source and a stabilizer, and heating for reaction to obtain NasNii(PO4)(Sa4)/F; and adding a sodium washing agent to the NasNit(PO4)(SO4)/F for soaking, and sintering to obtain the sodium-ion positive electrode material.
- 4. The preparation method according to claim 3, wherein the nickel source solution is obtained by dissolving nickel source in an organic acid; the organic acid is at least one of tartaric acid, oxalic acid, citric acid, formic acid, and acetic acid; and the nickel source is at least one of nickel sulfate, nickel hydroxide, nickel nitrate, nickel chloride and nickel carbonate.
- 5. The preparation method according to claim 3, wherein the sulfuric acid source is at least one of sulfuric acid, sodium sulfate, ammonium sulfate, ammonium hydrogen sulfate, sodium hydrogen sulfate and nickel sulfate.
- -14 - 6. The preparation method according to claim 3, wherein the phosphoric acid source is at least one of phosphoric acid, sodium phosphate, ammonium phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, sodium hydrogen phosphate and nickel phosphate.
- 7. The preparation method according to claim 3, wherein the fluorine source is at least one of ammonium fluoride, potassium fluoride, sodium fluoride and hydrogen fluoride; the sodium source is at least one of sodium hydroxide, sodium citrate, sodium oxalate, sodium acetate, sodium phosphate, sodium sulfate, sodium carbonate and sodium chloride; the stabilizer is at least one of 1,4-benzenedicarboxylic acid 2,5-dipropoxy-1,4-dihydrazide, N,N,N',N.-tetralcis(4-methoxypheny1)-9H-carbazole-3,6-diamine, and 4,4',4-trimethy1-2,2':6',2-terpyridine.
- 8. The preparation method according to claim 3, wherein a temperature of the microwave hydrothermal reaction is 100-300°C, and a duration of the microwave hydrothermal reaction is 1-60 mm; and a solid-liquid ratio of the NaNiu(PO4)(804)/F to the sodium washing agent is (0.1-3): (1-5) g/ml.
- 9. The preparation method according to claim 3, wherein the sodium washing agent is at least one of zinc sulfate, nickel sulfate, aluminum sulfate, manganese sulfate, chromium sulfate, molybdenum sulfate, copper sulfate and calcium sulfate.
- 10. A battery, comprising the sodium-ion positive electrode material according to any one of claims 1-2.-15 -
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111424144.6A CN114242972A (en) | 2021-11-26 | 2021-11-26 | Nickel-rich high-voltage sodium ion battery positive electrode material and preparation method and application thereof |
| PCT/CN2022/115953 WO2023093180A1 (en) | 2021-11-26 | 2022-08-30 | Nickel-rich high-voltage sodium-ion positive electrode material for battery, preparation method therefor, and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| GB202313956D0 GB202313956D0 (en) | 2023-10-25 |
| GB2619230A true GB2619230A (en) | 2023-11-29 |
Family
ID=80751465
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB2313956.1A Pending GB2619230A (en) | 2021-11-26 | 2022-08-30 | Nickel-rich high-voltage sodium-ion positive electrode material for battery, preparation method therefor, and application thereof |
Country Status (3)
| Country | Link |
|---|---|
| CN (1) | CN114242972A (en) |
| GB (1) | GB2619230A (en) |
| WO (1) | WO2023093180A1 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114242972A (en) * | 2021-11-26 | 2022-03-25 | 广东邦普循环科技有限公司 | Nickel-rich high-voltage sodium ion battery positive electrode material and preparation method and application thereof |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104364946A (en) * | 2012-06-12 | 2015-02-18 | 丰田自动车株式会社 | Positive electrode material for sodium batteries and method for producing same |
| CN106328911A (en) * | 2016-11-30 | 2017-01-11 | 合肥工业大学 | Material with mixture of ions with sodium vanadium phosphate cathode material coated by carbon and preparing method thereof |
| CN109065855A (en) * | 2018-07-12 | 2018-12-21 | 合肥国轩高科动力能源有限公司 | A kind of oxide and carbon coat sodium-ion battery positive material vanadium phosphate sodium of cation doping and preparation method thereof altogether |
| JP2020027734A (en) * | 2018-08-10 | 2020-02-20 | 太平洋セメント株式会社 | Negative electrode active material particle for sodium ion secondary battery and method of producing the same |
| CN110875473A (en) * | 2018-09-03 | 2020-03-10 | 宁德时代新能源科技股份有限公司 | Positive electrode active material, preparation method thereof and sodium ion battery |
| CN112447947A (en) * | 2019-08-28 | 2021-03-05 | 宁德时代新能源科技股份有限公司 | Positive electrode material for sodium ion battery and preparation method thereof |
| CN113422043A (en) * | 2021-07-19 | 2021-09-21 | 中国科学院过程工程研究所 | Modified titanium manganese sodium phosphate cathode material and preparation method and application thereof |
| CN114242972A (en) * | 2021-11-26 | 2022-03-25 | 广东邦普循环科技有限公司 | Nickel-rich high-voltage sodium ion battery positive electrode material and preparation method and application thereof |
-
2021
- 2021-11-26 CN CN202111424144.6A patent/CN114242972A/en active Pending
-
2022
- 2022-08-30 WO PCT/CN2022/115953 patent/WO2023093180A1/en active Application Filing
- 2022-08-30 GB GB2313956.1A patent/GB2619230A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104364946A (en) * | 2012-06-12 | 2015-02-18 | 丰田自动车株式会社 | Positive electrode material for sodium batteries and method for producing same |
| CN106328911A (en) * | 2016-11-30 | 2017-01-11 | 合肥工业大学 | Material with mixture of ions with sodium vanadium phosphate cathode material coated by carbon and preparing method thereof |
| CN109065855A (en) * | 2018-07-12 | 2018-12-21 | 合肥国轩高科动力能源有限公司 | A kind of oxide and carbon coat sodium-ion battery positive material vanadium phosphate sodium of cation doping and preparation method thereof altogether |
| JP2020027734A (en) * | 2018-08-10 | 2020-02-20 | 太平洋セメント株式会社 | Negative electrode active material particle for sodium ion secondary battery and method of producing the same |
| CN110875473A (en) * | 2018-09-03 | 2020-03-10 | 宁德时代新能源科技股份有限公司 | Positive electrode active material, preparation method thereof and sodium ion battery |
| CN112447947A (en) * | 2019-08-28 | 2021-03-05 | 宁德时代新能源科技股份有限公司 | Positive electrode material for sodium ion battery and preparation method thereof |
| CN113422043A (en) * | 2021-07-19 | 2021-09-21 | 中国科学院过程工程研究所 | Modified titanium manganese sodium phosphate cathode material and preparation method and application thereof |
| CN114242972A (en) * | 2021-11-26 | 2022-03-25 | 广东邦普循环科技有限公司 | Nickel-rich high-voltage sodium ion battery positive electrode material and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114242972A (en) | 2022-03-25 |
| WO2023093180A1 (en) | 2023-06-01 |
| GB202313956D0 (en) | 2023-10-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111082058B (en) | Nasicon structure sodium titanium phosphate surface modified P2 type manganese-based sodium ion battery positive electrode material and preparation method thereof | |
| CN107403913A (en) | A kind of nickel cobalt lithium aluminate cathode material of surface modification and preparation method thereof | |
| CN1907844A (en) | High density ultrafine composite ferric lithium phosphate anode material and preparation method | |
| CN111180709A (en) | Carbon nano tube and metal copper co-doped ferrous oxalate lithium battery composite negative electrode material and preparation method thereof | |
| CN111162256A (en) | Mixed polyanion type sodium ion battery positive electrode material and preparation thereof | |
| WO2023193372A1 (en) | Binary-doped iron-based fluorophosphate sodium ion positive electrode material and preparation method therefor | |
| CN111029560A (en) | Spinel structure positive active material doped with sodium ions in gradient manner and preparation method thereof | |
| CN110790248B (en) | Iron-doped cobalt phosphide microsphere electrode material with flower-shaped structure and preparation method and application thereof | |
| CN116169260A (en) | β”-Al 2 O 3 And N-doped C composite coated Na 3 V 2 (PO 4 ) 2 F 3 Electrode material | |
| CN111403703A (en) | Method for double coating of ternary positive electrode material by fluoride and sulfide | |
| CN114620702A (en) | Preparation method of positive electrode material, positive plate and sodium ion battery | |
| GB2619230A (en) | Nickel-rich high-voltage sodium-ion positive electrode material for battery, preparation method therefor, and application thereof | |
| CN112938952A (en) | Preparation and application of cathode material with two-dimensional structure tungsten trioxide coated with graphene | |
| CN112952063A (en) | Lithium-rich manganese-based composite cathode material and preparation method and application thereof | |
| CN111463406A (en) | Preparation method of cobalt-doped zinc-based metal selenide composite electrode for lithium ion battery | |
| CN108023079B (en) | Mixed transition metal borate anode material and preparation method thereof | |
| CN113517438B (en) | Internal confinement heterojunction yolk-shell electrode material and preparation method and application thereof | |
| CN115893503A (en) | Preparation method and application of carbon-coated lithium ferrite | |
| CN114864945A (en) | Preparation method and application of high-conductivity lithium iron phosphate | |
| CN113991103A (en) | Aqueous lithium ion battery NaTi2(PO4)3Preparation method of/C negative electrode material | |
| CN108400319B (en) | Preparation method of nano-structure cobalt molybdate electrode material | |
| JP2013069567A (en) | Electrode active material and method for manufacturing the same, and lithium ion battery | |
| CN112993246A (en) | High-performance sodium-ion battery negative electrode material and preparation method thereof | |
| CN107394177B (en) | Nickel bicarbonate/graphene composite material for sodium-ion battery cathode and preparation method and application thereof | |
| CN111403725A (en) | Aluminum oxide coated hafnium/nitrogen co-doped lithium iron phosphate cathode material and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| 789A | Request for publication of translation (sect. 89(a)/1977) |
Ref document number: 2023093180 Country of ref document: WO |