CN114195193B - 掺杂型磷酸钒钠及其制备方法和应用 - Google Patents
掺杂型磷酸钒钠及其制备方法和应用 Download PDFInfo
- Publication number
- CN114195193B CN114195193B CN202111272724.8A CN202111272724A CN114195193B CN 114195193 B CN114195193 B CN 114195193B CN 202111272724 A CN202111272724 A CN 202111272724A CN 114195193 B CN114195193 B CN 114195193B
- Authority
- CN
- China
- Prior art keywords
- sodium
- doped
- peony
- molybdenum oxide
- phosphate
- 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.)
- Active
Links
- ZMVMBTZRIMAUPN-UHFFFAOYSA-H [Na+].[V+5].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O Chemical compound [Na+].[V+5].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O ZMVMBTZRIMAUPN-UHFFFAOYSA-H 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 229910000476 molybdenum oxide Inorganic materials 0.000 claims abstract description 66
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 claims abstract description 66
- 239000011734 sodium Substances 0.000 claims abstract description 33
- 238000010438 heat treatment Methods 0.000 claims abstract description 32
- 238000005406 washing Methods 0.000 claims abstract description 28
- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
- 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 14
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 14
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000011733 molybdenum Substances 0.000 claims abstract description 11
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 11
- 150000001412 amines Chemical class 0.000 claims abstract description 8
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 6
- 230000001105 regulatory effect Effects 0.000 claims abstract description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 30
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 18
- WGQKYBSKWIADBV-UHFFFAOYSA-N benzylamine Chemical compound NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 claims description 18
- 239000002243 precursor Substances 0.000 claims description 16
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims description 13
- 239000004280 Sodium formate Substances 0.000 claims description 9
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 9
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 claims description 9
- 235000019254 sodium formate Nutrition 0.000 claims description 9
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 8
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 8
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 8
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 8
- 229910052698 phosphorus Inorganic materials 0.000 claims description 8
- 239000011574 phosphorus Substances 0.000 claims description 8
- 239000001509 sodium citrate Substances 0.000 claims description 8
- 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 8
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 claims description 7
- 239000005695 Ammonium acetate Substances 0.000 claims description 7
- 235000019257 ammonium acetate Nutrition 0.000 claims description 7
- 229940043376 ammonium acetate Drugs 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 229910052720 vanadium Inorganic materials 0.000 claims description 7
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 7
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 6
- 238000001354 calcination Methods 0.000 claims description 6
- 239000001632 sodium acetate Substances 0.000 claims description 6
- 235000017281 sodium acetate Nutrition 0.000 claims description 6
- 238000000498 ball milling Methods 0.000 claims description 5
- TXCOQXKFOPSCPZ-UHFFFAOYSA-J molybdenum(4+);tetraacetate Chemical compound [Mo+4].CC([O-])=O.CC([O-])=O.CC([O-])=O.CC([O-])=O TXCOQXKFOPSCPZ-UHFFFAOYSA-J 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 4
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 claims description 4
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical group O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 4
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 claims description 4
- 229910000397 disodium phosphate Inorganic materials 0.000 claims description 4
- 235000019800 disodium phosphate Nutrition 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 claims description 4
- ZNCPFRVNHGOPAG-UHFFFAOYSA-L sodium oxalate Chemical compound [Na+].[Na+].[O-]C(=O)C([O-])=O ZNCPFRVNHGOPAG-UHFFFAOYSA-L 0.000 claims description 4
- 229940039790 sodium oxalate Drugs 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 3
- KWTSXDURSIMDCE-QMMMGPOBSA-N (S)-amphetamine Chemical compound C[C@H](N)CC1=CC=CC=C1 KWTSXDURSIMDCE-QMMMGPOBSA-N 0.000 claims description 2
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 claims description 2
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims description 2
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 claims description 2
- KWIPUXXIFQQMKN-UHFFFAOYSA-N 2-azaniumyl-3-(4-cyanophenyl)propanoate Chemical compound OC(=O)C(N)CC1=CC=C(C#N)C=C1 KWIPUXXIFQQMKN-UHFFFAOYSA-N 0.000 claims description 2
- WGTASENVNYJZBK-UHFFFAOYSA-N 3,4,5-trimethoxyamphetamine Chemical compound COC1=CC(CC(C)N)=CC(OC)=C1OC WGTASENVNYJZBK-UHFFFAOYSA-N 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 2
- YNNQORGFPVDZOI-UHFFFAOYSA-B C(CC(O)(C(=O)[O-])CC(=O)[O-])(=O)[O-].[Mo+4].C(CC(O)(C(=O)[O-])CC(=O)[O-])(=O)[O-].C(CC(O)(C(=O)[O-])CC(=O)[O-])(=O)[O-].C(CC(O)(C(=O)[O-])CC(=O)[O-])(=O)[O-].[Mo+4].[Mo+4] Chemical compound C(CC(O)(C(=O)[O-])CC(=O)[O-])(=O)[O-].[Mo+4].C(CC(O)(C(=O)[O-])CC(=O)[O-])(=O)[O-].C(CC(O)(C(=O)[O-])CC(=O)[O-])(=O)[O-].C(CC(O)(C(=O)[O-])CC(=O)[O-])(=O)[O-].[Mo+4].[Mo+4] YNNQORGFPVDZOI-UHFFFAOYSA-B 0.000 claims description 2
- 239000005696 Diammonium phosphate Substances 0.000 claims description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 2
- ITIONVBQFUNVJV-UHFFFAOYSA-N Etomidoline Chemical compound C12=CC=CC=C2C(=O)N(CC)C1NC(C=C1)=CC=C1OCCN1CCCCC1 ITIONVBQFUNVJV-UHFFFAOYSA-N 0.000 claims description 2
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 2
- 239000005708 Sodium hypochlorite Substances 0.000 claims description 2
- GKXVJHDEWHKBFH-UHFFFAOYSA-N [2-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC=C1CN GKXVJHDEWHKBFH-UHFFFAOYSA-N 0.000 claims description 2
- 229940090948 ammonium benzoate Drugs 0.000 claims description 2
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 2
- 239000011609 ammonium molybdate Substances 0.000 claims description 2
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 2
- 229940010552 ammonium molybdate Drugs 0.000 claims description 2
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 2
- 229940025084 amphetamine Drugs 0.000 claims description 2
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 2
- 229910000388 diammonium phosphate Inorganic materials 0.000 claims description 2
- 235000019838 diammonium phosphate Nutrition 0.000 claims description 2
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 claims description 2
- 229940012017 ethylenediamine Drugs 0.000 claims description 2
- 229940116007 ferrous phosphate Drugs 0.000 claims description 2
- 229910000155 iron(II) phosphate Inorganic materials 0.000 claims description 2
- SDEKDNPYZOERBP-UHFFFAOYSA-H iron(ii) phosphate Chemical compound [Fe+2].[Fe+2].[Fe+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O SDEKDNPYZOERBP-UHFFFAOYSA-H 0.000 claims description 2
- ALTWGIIQPLQAAM-UHFFFAOYSA-N metavanadate Chemical compound [O-][V](=O)=O ALTWGIIQPLQAAM-UHFFFAOYSA-N 0.000 claims description 2
- PSACBMCCZLGPIA-UHFFFAOYSA-J molybdenum(4+) tetraformate Chemical compound C(=O)[O-].[Mo+4].C(=O)[O-].C(=O)[O-].C(=O)[O-] PSACBMCCZLGPIA-UHFFFAOYSA-J 0.000 claims description 2
- 239000006012 monoammonium phosphate Substances 0.000 claims description 2
- 229910000403 monosodium phosphate Inorganic materials 0.000 claims description 2
- 235000019799 monosodium phosphate Nutrition 0.000 claims description 2
- 235000011007 phosphoric acid Nutrition 0.000 claims description 2
- HELHAJAZNSDZJO-OLXYHTOASA-L sodium L-tartrate Chemical compound [Na+].[Na+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O HELHAJAZNSDZJO-OLXYHTOASA-L 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 235000017550 sodium carbonate Nutrition 0.000 claims description 2
- 229960001790 sodium citrate Drugs 0.000 claims description 2
- 235000011083 sodium citrates Nutrition 0.000 claims description 2
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 claims description 2
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 2
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims description 2
- CMZUMMUJMWNLFH-UHFFFAOYSA-N sodium metavanadate Chemical compound [Na+].[O-][V](=O)=O CMZUMMUJMWNLFH-UHFFFAOYSA-N 0.000 claims description 2
- 239000011684 sodium molybdate Substances 0.000 claims description 2
- 235000015393 sodium molybdate Nutrition 0.000 claims description 2
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims description 2
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 2
- 229940006198 sodium phenylacetate Drugs 0.000 claims description 2
- 239000001488 sodium phosphate Substances 0.000 claims description 2
- 229910000162 sodium phosphate Inorganic materials 0.000 claims description 2
- 235000011008 sodium phosphates Nutrition 0.000 claims description 2
- JXKPEJDQGNYQSM-UHFFFAOYSA-M sodium propionate Chemical compound [Na+].CCC([O-])=O JXKPEJDQGNYQSM-UHFFFAOYSA-M 0.000 claims description 2
- 239000004324 sodium propionate Substances 0.000 claims description 2
- 235000010334 sodium propionate Nutrition 0.000 claims description 2
- 229960003212 sodium propionate Drugs 0.000 claims description 2
- 239000001433 sodium tartrate Substances 0.000 claims description 2
- 229960002167 sodium tartrate Drugs 0.000 claims description 2
- 235000011004 sodium tartrates Nutrition 0.000 claims description 2
- KKVTYAVXTDIPAP-UHFFFAOYSA-M sodium;methanesulfonate Chemical compound [Na+].CS([O-])(=O)=O KKVTYAVXTDIPAP-UHFFFAOYSA-M 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 2
- YWYZEGXAUVWDED-UHFFFAOYSA-N triammonium citrate Chemical compound [NH4+].[NH4+].[NH4+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O YWYZEGXAUVWDED-UHFFFAOYSA-N 0.000 claims description 2
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 2
- IHIXIJGXTJIKRB-UHFFFAOYSA-N trisodium vanadate Chemical compound [Na+].[Na+].[Na+].[O-][V]([O-])([O-])=O IHIXIJGXTJIKRB-UHFFFAOYSA-N 0.000 claims description 2
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 claims description 2
- 229910001415 sodium ion Inorganic materials 0.000 abstract description 18
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 abstract description 15
- 239000003792 electrolyte Substances 0.000 abstract description 5
- 238000009831 deintercalation Methods 0.000 abstract description 4
- 238000009792 diffusion process Methods 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract 1
- 238000001035 drying Methods 0.000 description 30
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 27
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 12
- 238000001816 cooling Methods 0.000 description 12
- 239000000203 mixture Substances 0.000 description 12
- 238000001704 evaporation Methods 0.000 description 11
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 9
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 7
- 239000002245 particle Substances 0.000 description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 239000007789 gas Substances 0.000 description 5
- 238000011282 treatment Methods 0.000 description 5
- 239000010406 cathode material Substances 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- FDPIMTJIUBPUKL-UHFFFAOYSA-N pentan-3-one Chemical compound CCC(=O)CC FDPIMTJIUBPUKL-UHFFFAOYSA-N 0.000 description 4
- 229920000447 polyanionic polymer Polymers 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 239000007774 positive electrode material Substances 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 229960004249 sodium acetate Drugs 0.000 description 2
- 229910000314 transition metal oxide Inorganic materials 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- DCYOBGZUOMKFPA-UHFFFAOYSA-N iron(2+);iron(3+);octadecacyanide Chemical class [Fe+2].[Fe+2].[Fe+2].[Fe+3].[Fe+3].[Fe+3].[Fe+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] DCYOBGZUOMKFPA-UHFFFAOYSA-N 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000007581 slurry coating method Methods 0.000 description 1
- -1 sodium hexafluorophosphate Chemical compound 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G39/00—Compounds of molybdenum
- C01G39/02—Oxides; Hydroxides
-
- 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
- C01B25/45—Phosphates containing plural metal, or metal and ammonium
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G39/00—Compounds of molybdenum
-
- 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
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
-
- 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
-
- 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
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/381—Alkaline or alkaline earth metals elements
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Secondary Cells (AREA)
Abstract
本发明属于钠离子电池技术领域,公开了掺杂型磷酸钒钠及其制备方法和应用,掺杂型磷酸钒钠的原料中的氮掺杂‑牡丹状氧化钼的制备步骤为向含钼溶液中加入调控剂进行反应,浓缩,热处理,得到牡丹状氧化钼;将牡丹状氧化钼溶于调节剂中,再加入胺源静置,离心,洗涤,热处理,即得。本发明的氮掺杂‑牡丹状氧化钼是通过加入调控剂制备得到,将其掺杂于磷酸钒钠,促使磷酸钒钠具有丰富的钠离子结合位点,结构稳定,能使得磷酸钒钠和电解质之间的接触范围扩大,合成的磷酸钒钠,其储钠位点也相应的增加,同时缩短钠离子扩散路径,提高了充放电时钠离子的脱嵌速率。
Description
技术领域
本发明属于钠离子电池技术领域,具体涉及掺杂型磷酸钒钠及其制备方法和应用。
背景技术
由于地壳中含有大量的钠,钠离子电池(NIBs)被认为是最有潜力替代锂离子电池(LIBs)的二次电池。近年来,人们为开发NIBs的负极材料、正极材料、电解液等关键技术做出了巨大的努力。然而NIBs的正极材料具有不可避免的缺点,例如比钠原子量较大、标准电化学势较低等,在钠的能量密度决定因素中起着最重要的作用。到目前为止,已经发现和开发了各种钠离子电池正极材料,包括层状型过渡金属氧化物、隧道型过渡金属氧化物、聚阴离子类化合物、混合聚阴离子类化合物、普鲁士蓝类化合物、非晶态类化合物等,而其中的聚阴离子型、混合聚阴离子型钠离子电池正极材料由于在充放电其结构的变化极小、性能佳、输出电压高等,因此其的循环稳定性很好,然而,由于聚阴离子基团特性,导致聚阴离子化合物的振实密度较低,钠离子电池的重量容量密度和体积能量密度都相对较低,倍率性能较差,导致其发展和应用受到很大的限制,因此开发性能更好的新型聚阴离子型钠离子正极材料仍然是当前研究的重点。
发明内容
本发明旨在至少解决上述现有技术中存在的技术问题之一。为此,本发明提出一种掺杂型磷酸钒钠及其制备方法和应用,该磷酸钒钠具有丰富的钠离子结合位点,结构稳定,能使得磷酸钒钠和电解质之间的接触范围扩大,合成的磷酸钒钠,其储钠位点也相应的增加,同时缩短钠离子扩散路径,提高了充放电时钠离子的脱嵌速率。
为实现上述目的,本发明采用以下技术方案:
一种氮掺杂-牡丹状氧化钼的制备方法,包括以下步骤:
(1)向含钼溶液中加入调控剂进行反应,浓缩,热处理,得到牡丹状氧化钼;
(2)将所述牡丹状氧化钼溶于调节剂中,再加入胺源静置,离心,洗涤,热处理,得到氮掺杂-牡丹状氧化钼;所述调控剂为硝酸、硝酸铵、过硫酸钠、过硫酸铵、硝酸、浓硫酸、H2O2、臭氧或次氯酸钠中的至少一种。
优选地,步骤(1)中,所述含钼溶液是由钼源溶于溶剂中,即得。
进一步优选地,所述钼源为钼酸钠、乙酸钼、甲酸钼、柠檬酸钼、钼酸铵、氧化钼、钼粉中的至少一种。
进一步优选地,所述溶剂为甲醇、乙醇、正丙醇、异丙醇、乙二醇、丙二醇、丙三醇、丙酮、乙酮、丁酮、二乙酮、二甲醚、乙醚或二乙醚中的至少一种。
进一步优选地,步骤(1)中,所述钼源和溶剂的固液比为(0.5-20):(10-40)g/mL;优选为(0.5-2):(10-15)。
优选地,所述调控剂为H2O2、硝酸中的至少一种。
优选地,步骤(1)中,所述调控剂的浓度为5-45wt%,优选为25-35wt%。
优选地,步骤(1)中,所述调控剂的加入量为含钼溶液的0.01-25v/v%,优选为0.01-15v/v%。
优选地,步骤(1)中,所述反应的温度为200-900℃,反应的时间为8-36h。
优选地,步骤(1)中,所述浓缩为将反应后的溶液蒸发脱水。
优选地,步骤(1)中,所述热处理的温度为400-600℃下,热处理的时间为3-8h。
优选地,步骤(1)中,所述热处理后还包括将热处理后的产物,进行降温洗涤、干燥。
优选地,步骤(2)中,所述调节剂为乙酸钠、乙酸铵、甲酸钠、乙酸钠、乙二铵、乙二酸钠、醋酸钠、醋酸铵、苯甲酸铵、苯乙酸钠、丙酸钠、酒石酸钠、柠檬酸钠或柠檬酸铵中的至少一种。
优选地,步骤(2)中,所述胺源为苯胺、二甲胺、三甲胺、苯甲胺、苯乙胺、乙胺、二乙胺、丙胺、苯二胺、苄胺、苯二甲胺或苯丙胺中的至少一种。
优选地,步骤(2)中,所述调节剂中调节物的浓度为0.001-2.0mol/L。
优选地,步骤(2)中,所述牡丹状氧化钼、调节剂、胺源的固液比为(0.1-10):(50-200):(0.01-5)g/mL/g。
优选地,步骤(2)中,所述热处理的气氛为Ne、Ar、Kr、Xe中的一种。
优选地,步骤(2)中,所述热处理的温度为300-700℃,热处理的时间为8-72h;优选热处理的温度为300-500℃,热处理的时间为24-36h。
一种氮掺杂-牡丹状氧化钼,是由上述的制备方法制备得到,所述氮掺杂-牡丹状氧化钼的化学式为N-MoO3。
一种掺杂型磷酸钒钠的制备方法,包括以下步骤:
(1)将钒源、钠源、磷源、所述氮掺杂-牡丹状氧化钼混合,球磨,洗涤,浓缩,得到前驱体;
(2)将所述前驱体进行煅烧,得到掺杂型磷酸钒钠Na3V2(PO4)3·mN-MoO3。
优选地,步骤(1)中,所述钒源为偏钒酸、偏钒酸钠、偏钒酸铵、正钒酸钠或正钒酸铵中的至少一种。
优选地,步骤(1)中,所述钠源为氢氧化钠、碳酸钠、磷酸氢钠、磷酸二氢钠、草酸钠、甲酸钠、柠檬酸钠、甲基磺酸钠或乙酸钠中的至少一种。
进一步优选地,步骤(1)中,所述钠源为氢氧化钠、甲酸钠中的至少一种。
优选地,步骤(1)中,所述磷源为磷酸钠、磷酸氢钠、磷酸亚铁、磷酸、磷酸、磷酸二氢铵、磷酸氢二氨中的至少一种。
进一步优选地,步骤(1)中,所述磷源为磷酸二氢铵、磷酸中的至少一种。
优选地,步骤(1)中,所述混合还包括加入分散剂进行混合。
进一步优选地,所述分散剂为三乙醇胺、丙三醇、甲醇、乙醇、聚合醇胺中的至少一种。
优选地,步骤(1)中,所述钠源、钒源、磷源的摩尔比为(0.01-60):(0.01-40):(0.01-60)。
优选地,步骤(1)中,所述氮掺杂-牡丹状氧化钼的加入量为钠源、钒源、磷源总质量的0.01-10%。
优选地,步骤(1)中,所述球磨的出料粒径<50μm,优选<10μm。
优选地,步骤(1)中,所述球磨的转速为100-2000r/min,球磨的时间为4-48h;转速优选为600-1000r/min。
优选地,步骤(1)中,所述煅烧的温度为300-1000℃,煅烧的时间为3-24h;优选为400-600℃下煅烧4-10h。
优选地,所述煅烧的的气氛为惰性气体;所述惰性气体为Ne、Ar、Kr、Xe中的一种。
一种掺杂型磷酸钒钠,是由上述的制备方法制得,所述掺杂型磷酸钒钠的化学式为Na3V2(PO4)3·mN-MoO3,其中0.0001≦m≦0.1。
一种电池,包括所述的掺杂型磷酸钒钠。
相对于现有技术,本发明的有益效果如下:
1、本发明的氮掺杂-牡丹状氧化钼是通过加入调控剂制备得到,牡丹状三维结构的氧化钼,能够增大正极材料的比表面积,增加电化学反应的化学反应位点,从而有效提升电极材料的可逆容量;进而将其掺杂于磷酸钒钠,促使磷酸钒钠具有丰富的钠离子结合位点,结构稳定,能使得磷酸钒钠和电解质之间的接触范围扩大,合成的磷酸钒钠,其储钠位点也相应的增加,同时缩短钠离子扩散路径,提高了充放电时钠离子的脱嵌速率。
2、本发明通过将氮掺杂-牡丹状氧化钼掺杂于磷酸钒钠,一是能减缓磷酸钒钠晶体畸变,提高了结构稳定性,有利于提高长循环、高电压放电条件下材料的稳定性。二是通过改性,能减少在充放电中钠离子脱嵌的表面损失,提升了磷酸钒钠材料表面的循环稳定性,导致充放电时表面还原磷酸钒钠的抗性得到了改善,增强了磷酸钒钠电化学性能。
附图说明
图1为本发明实施例1的工艺流程图;
图2实施例3牡丹状氧化钼SEM图;
图3实施例3磷酸钒钠的SEM图;
图4对比例1磷酸钒钠的SEM图。
具体实施方式
以下将结合实施例对本发明的构思及产生的技术效果进行清楚、完整地描述,以充分地理解本发明的目的、特征和效果。显然,所描述的实施例只是本发明的一部分实施例,而不是全部实施例,基于本发明的实施例,本领域的技术人员在不付出创造性劳动的前提下所获得的其他实施例,均属于本发明保护的范围。
实施例1
本实施例的掺杂型磷酸钒钠的制备方法,具体步骤如下:
(1)牡丹状三维结构氧化钼:将60g乙酸钼溶于400mL丙酮中,加入25mL质量分数为28%H2O2,进行反应,反应中除去气体,将反应后的溶液蒸发脱水,再在加热炉460℃下加热处理6h,降温、洗涤、干燥,得到21g牡丹状氧化钼;
(2)氮掺杂-牡丹状氧化钼(氮掺杂-牡丹状三维结构氧化钼):将8.3g牡丹状氧化钼加入到100mL的0.012mol/L乙酸铵溶液(乙酸铵pH=7.8),加入1.5mL苯甲胺,静置、离心、洗涤、干燥,送至Ar气氛加热炉中440℃高温处理10h,降温、洗涤、干燥,得到8.4g氮掺杂-牡丹状氧化钼;
(3)合成:将23.5g偏钒酸铵、12g氢氧化钠、300mL的11.5wt%磷酸、20mL甲醇混合,再加入1.2g氮掺杂-牡丹状氧化钼(氮掺杂-牡丹状氧化钼的加入量为偏钒酸铵、氢氧化钠、磷酸总质量的1.7%)得到混合物,Ar气氛下混合物在840r/min下球磨8h(出料粒径<50μm),完毕后洗涤、干燥除去甲醇,混合物蒸发、干燥,得到Na3V2(PO4)3前驱体;
(4)将前驱体送至加热炉中,通入Ar,并550℃下煅烧8h,降温,得到掺杂型的磷酸钒钠Na3V2(PO4)3·0.017N-MoO3。
实施例2
本实施例的掺杂型磷酸钒钠的制备方法,具体步骤如下:
(1)牡丹状三维结构氧化钼:将60g乙酸钼溶于400mL丙酮中,加入25mL质量分数为28%H2O2,进行反应,反应中除去气体,将反应后的溶液蒸发脱水,再在加热炉460℃下加热处理6h,降温、洗涤、干燥,得到21g牡丹状氧化钼;
(2)氮掺杂-牡丹状氧化钼(氮掺杂-牡丹状三维结构氧化钼):将10g牡丹状氧化钼加入到120mL的0.012mol/L乙酸铵溶液(乙酸铵pH=7.8)中,再加入1.5mL苯甲胺,静置、离心、洗涤、干燥,送至充Ar气氛的加热炉中485℃高温处理10h,降温、洗涤、干燥,得到10.3g氮掺杂-牡丹状氧化钼;
(3)合成:将23.5g偏钒酸铵、12g氢氧化钠、300mL的11.5wt%磷酸、25mL甲醇混合,再加1.8g氮掺杂-牡丹状氧化钼(氮掺杂-牡丹状氧化钼的加入量为偏钒酸铵、氢氧化钠、磷酸总质量的2.6%)得到混合物,Ar气氛下混合物在900r/min下球磨8h(出料粒径<50μm),完毕后洗涤、干燥除去甲醇,混合物蒸发、干燥,得到Na3V2(PO4)3前驱体;
(4)将前驱体送至加热炉中,通入Ar,并550℃下煅烧8h,降温,得到掺杂型的磷酸钒钠Na3V2(PO4)3·0.026N-MoO3。
实施例3
本实施例的掺杂型磷酸钒钠的制备方法,具体步骤如下:
(1)牡丹状三维结构氧化钼:25g氧化钼加入240mL丙三醇中,加入18mL质量分数为28%H2O2,进行反应,反应中除去气体,将反应后的溶液蒸发脱水,再在加热炉530℃下加热处理8h,降温、洗涤、干燥,得到25g牡丹状氧化钼;
(2)氮掺杂-牡丹状氧化钼(氮掺杂-牡丹状三维结构氧化钼):将10g牡丹状氧化钼加入到100mL的0.034mol/L柠檬酸钠溶液(调柠檬酸钠溶液pH=8.1),加入1.5mL苯甲胺,静置、离心、洗涤、干燥,送至充Ar气氛的加热炉中440℃高温处理10h,降温、洗涤、干燥,得到10.3g氮掺杂-牡丹状氧化钼;
(3)合成:将23.5g偏钒酸铵、20.4g甲酸钠、35g磷酸二氢铵、20mL三乙醇胺混合,再加1.7g氮掺杂-牡丹状氧化钼(氮掺杂-牡丹状氧化钼的加入量为偏钒酸铵、甲酸钠、磷酸二氢铵总质量的2.2%)得到混合物,Ar气氛下混合物在840r/min下球磨10h(出料粒径<50μm),完毕后洗涤、干燥除去三乙醇胺,混合物蒸发、干燥,得到Na3V2(PO4)3前驱体;
(4)将前驱体送至加热炉中,通入Ar,并660℃下煅烧8h,降温,得到掺杂型的磷酸钒钠Na3V2(PO4)3·0.022N-MoO3。
实施例4
本实施例的掺杂型磷酸钒钠的制备方法,具体步骤如下:
(1)牡丹状三维结构氧化钼:将25g氧化钼溶于240mL丙三醇中,加入20mL质量分数为28%H2O2,进行反应,反应中除去气体,将反应后的溶液蒸发脱水,再在加热炉530℃下加热处理8h,降温、洗涤、干燥,得到25g牡丹状氧化钼;
(2)氮掺杂-牡丹状氧化钼(氮掺杂-牡丹状三维结构氧化钼):将8.3g牡丹状氧化钼加入到100mL的0.034mol/L柠檬酸钠溶液(调柠檬酸钠溶液pH=8.1)中,再加入1.5mL苯甲胺,静置、离心、洗涤、干燥,送至充Ar气氛的加热炉中440℃高温处理10h,降温、洗涤、干燥,得到8.8g氮掺杂-牡丹状氧化钼;
(3)合成:将35g偏钒酸铵、20.4g甲酸钠、35g磷酸二氢铵、25mL三乙醇胺混合,再加2.0g氮掺杂-牡丹状氧化钼(氮掺杂-牡丹状氧化钼的加入量为偏钒酸铵、氢氧化钠、磷酸二氢铵总质量的2.5%)得到混合物,Ar气氛下混合物在720r/min下球磨12h(出料粒径<50μm),完毕后洗涤、干燥除去三乙醇胺,混合物蒸发、干燥,得到Na3V2(PO4)3前驱体;
(4)将前驱体送至加热炉中,通入Ar,并660℃下煅烧8h,降温,得到掺杂型的磷酸钒钠Na3V2(PO4)3·0.025N-MoO3。
对比例1
本对比例的磷酸钒钠的制备方法,具体步骤如下:
(1)合成:将23.5g偏钒酸铵、12g氢氧化钠、300mL的11.5wt%磷酸、9mL甲醇混合,Ar气氛下混合物在840r/min下球磨8h(出料粒径<50μm),完毕后洗涤、干燥除去甲醇,蒸发、干燥,得到Na3V2(PO4)3前驱体;
(2)将前驱体送至加热炉中,通入Ar,并550℃下煅烧8h,降温,得到磷酸钒钠Na3V2(PO4)3。
对比例2
本对比例的掺杂型磷酸钒钠的制备方法,具体步骤如下:
(1)合成:将35g偏钒酸铵、20.4g甲酸钠、35g磷酸二氢铵、25mL三乙醇胺混合,Ar气氛下混合物在840r/min下球磨8h(出料粒径<50μm),完毕后洗涤、干燥除去25mL三乙醇胺,蒸发、干燥,得到Na3V2(PO4)3前驱体;
(2)将前驱体送至加热炉中,通入Ar,660℃下煅烧8h,降温,得到磷酸钒钠Na3V2(PO4)3。
实施例1-4与对比例1-2分析:
实施例1-4与对比例1-2得到的掺杂型磷酸钒钠或磷酸钒钠、乙炔黑、PVDF以90:5:5的质量比配比溶于去离子水中配成浆料,搅拌成浆料,利用涂布机将浆料均匀涂布在铝箔上,烘干后制成正极片,电解液为1.1mol/L的六氟磷酸钠,DMC/EMC/PC溶剂以及其他添加剂,以石墨为负极,制成扣式电池。采用BTS电池测试仪对电池进行循环性能测试,测试电压为3.0~4.2V,电流密度为25mAh·g-1,采用FBT-9A单点法测试BET值。
表1实施例1-4与对比例1-2数据
从表1中可得,相较于对比例1-2,实施例1-4的在第1、20、50、100次放电容量保持率下降不明显,库仑效率均较高,实施例1-4的BET值分别为1.38m2/g、1.20m2/g、1.65m2/g、1.31m2/g,而对比例1-2的BET值为0.77、0.92,对比例的BET值较低。
图1为实施例1合成流程图:乙酸钼加入丙酮中,加入H2O2,进行反应,反应中除去气体,将反应后的溶液蒸发脱水,再加热处理,降温、洗涤、干燥,得到牡丹状氧化钼,将牡丹状氧化钼加入到乙酸铵溶液,加入苯甲胺,静置、离心、洗涤、干燥,高温处理后,降温、洗涤、干燥,得到氮掺杂-牡丹状氧化钼;偏钒酸铵、氢氧化钠、磷酸、甲醇混合,再加氮掺杂-牡丹状氧化钼,研磨、洗涤、干燥得到混合物,送至加热炉中,煅烧降温,得到掺杂型的磷酸钒钠Na3V2(PO4)3/N-MoO3。
图2为实施例3步骤(1)制得的牡丹状氧化钼,大小约为48μm。
图3为实施例3步骤(4)制得的掺杂型的磷酸钒钠Na3V2(PO4)3/N-MoO3,大部分牡丹状氧化钼大小在40-60μm。
图4为对比例步骤(2)制得的颗粒状磷酸钒钠Na3V2(PO4)3,大小约为2μm。
上面结合附图对本发明实施例作了详细说明,但是本发明不限于上述实施例,在所属技术领域普通技术人员所具备的知识范围内,还可以在不脱离本发明宗旨的前提下作出各种变化。此外,在不冲突的情况下,本发明的实施例及实施例中的特征可以相互组合。
Claims (9)
1.一种氮掺杂-牡丹状氧化钼的制备方法,其特征在于,包括以下步骤:
(1)向含钼溶液中加入调控剂进行反应,浓缩,热处理,得到牡丹状氧化钼;
(2)将所述牡丹状氧化钼溶于调节剂中,再加入胺源静置,离心,洗涤,热处理,得到氮掺杂-牡丹状氧化钼;所述调控剂为硝酸、硝酸铵、过硫酸钠、过硫酸铵、浓硫酸、H2O2、臭氧或次氯酸钠中的至少一种;
其中,
步骤(2)中,所述调节剂为乙酸钠、乙酸铵、甲酸钠、乙二铵、乙二酸钠、苯甲酸铵、苯乙酸钠、丙酸钠、酒石酸钠、柠檬酸钠或柠檬酸铵中的至少一种;
步骤(2)中,所述胺源为苯胺、二甲胺、三甲胺、苯甲胺、苯乙胺、乙胺、二乙胺、丙胺、苯二胺、苄胺、苯二甲胺或苯丙胺中的至少一种。
2.根据权利要求1所述的制备方法,其特征在于,步骤(1)中,所述含钼溶液是由钼源溶于溶剂中,即得;所述钼源为钼酸钠、乙酸钼、甲酸钼、柠檬酸钼、钼酸铵、氧化钼或钼粉中的至少一种。
3.根据权利要求1所述的制备方法,其特征在于,步骤(2)中,所述牡丹状氧化钼、调节剂、胺源的固液比为(0.1-10):(50-200):(0.01-5)g/mL/g。
4.一种氮掺杂-牡丹状氧化钼,其特征在于,是由权利要求1-3任一项所述的制备方法制备得到,所述氮掺杂-牡丹状氧化钼的化学式为N-MoO3。
5.一种掺杂型磷酸钒钠的制备方法,其特征在于,包括以下步骤:
(1)将钒源、钠源、磷源、权利要求4所述的氮掺杂-牡丹状氧化钼混合,球磨,洗涤,浓缩,得到前驱体;
(2)将所述前驱体进行煅烧,得到掺杂型磷酸钒钠Na3V2(PO4)3·N-MoO3。
6.根据权利要求5所述的制备方法,其特征在于,步骤(1)中,所述钒源为偏钒酸、偏钒酸钠、偏钒酸铵、正钒酸钠或正钒酸铵中的至少一种;所述钠源为氢氧化钠、碳酸钠、磷酸氢钠、磷酸二氢钠、草酸钠、甲酸钠、柠檬酸钠、甲基磺酸钠、乙酸钠中的至少一种。
7.根据权利要求5所述的制备方法,其特征在于,步骤(1)中,所述磷源为磷酸钠、磷酸氢钠、磷酸亚铁、磷酸、磷酸二氢铵、磷酸氢二铵中的至少一种;所述钠源、钒源、磷源的摩尔比为(0.01-60):(0.01-40):(0.01-60)。
8.一种掺杂型磷酸钒钠,其特征在于,是由权利要求5-7任一项所述的制备方法制得,所述掺杂型磷酸钒钠的化学式为Na3V2(PO4)3·mN-MoO3,其中0.0001≦m≦0.1。
9.一种电池,其特征在于,包括权利要求8所述的掺杂型磷酸钒钠。
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202111272724.8A CN114195193B (zh) | 2021-10-29 | 2021-10-29 | 掺杂型磷酸钒钠及其制备方法和应用 |
GB2309479.0A GB2616233A (en) | 2021-10-29 | 2022-08-12 | Doped sodium vanadium phosphate, preparation method therefor and use thereof |
US18/265,847 US11942643B2 (en) | 2021-10-29 | 2022-08-12 | Doped sodium vanadium phosphate and preparation method and application thereof |
PCT/CN2022/112241 WO2023071411A1 (zh) | 2021-10-29 | 2022-08-12 | 掺杂型磷酸钒钠及其制备方法和应用 |
DE112022000171.2T DE112022000171T5 (de) | 2021-10-29 | 2022-08-12 | Dotiertes natriumvanadiumphosphat, verfahren zur herstellung und seine verwendung |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202111272724.8A CN114195193B (zh) | 2021-10-29 | 2021-10-29 | 掺杂型磷酸钒钠及其制备方法和应用 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN114195193A CN114195193A (zh) | 2022-03-18 |
CN114195193B true CN114195193B (zh) | 2023-06-13 |
Family
ID=80646531
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202111272724.8A Active CN114195193B (zh) | 2021-10-29 | 2021-10-29 | 掺杂型磷酸钒钠及其制备方法和应用 |
Country Status (5)
Country | Link |
---|---|
US (1) | US11942643B2 (zh) |
CN (1) | CN114195193B (zh) |
DE (1) | DE112022000171T5 (zh) |
GB (1) | GB2616233A (zh) |
WO (1) | WO2023071411A1 (zh) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN114195193B (zh) | 2021-10-29 | 2023-06-13 | 广东邦普循环科技有限公司 | 掺杂型磷酸钒钠及其制备方法和应用 |
Family Cites Families (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US10676363B2 (en) * | 2017-04-06 | 2020-06-09 | Wisconsin Alumni Research Foundation | Reduced graphene oxide-metal oxynitride aerogel electrodes |
CN108539191A (zh) * | 2018-04-20 | 2018-09-14 | 合肥工业大学 | 一种纳米花状氧化钼锂离子电池负极材料及其制备方法 |
CN109244382B (zh) * | 2018-07-31 | 2020-09-22 | 华南理工大学 | 镍钛合金诱导生成花状多级结构三氧化钼材料及其制备方法与应用 |
CN111710867A (zh) * | 2020-06-29 | 2020-09-25 | 安徽大学 | 一种用于锂离子电池的新型正极材料及其制备方法 |
CN113198455B (zh) * | 2021-05-17 | 2022-12-09 | 南昌航空大学 | 一种三氧化钼/钼网光催化剂及其制备方法和应用 |
CN114195193B (zh) * | 2021-10-29 | 2023-06-13 | 广东邦普循环科技有限公司 | 掺杂型磷酸钒钠及其制备方法和应用 |
-
2021
- 2021-10-29 CN CN202111272724.8A patent/CN114195193B/zh active Active
-
2022
- 2022-08-12 US US18/265,847 patent/US11942643B2/en active Active
- 2022-08-12 DE DE112022000171.2T patent/DE112022000171T5/de active Pending
- 2022-08-12 GB GB2309479.0A patent/GB2616233A/en active Pending
- 2022-08-12 WO PCT/CN2022/112241 patent/WO2023071411A1/zh active Application Filing
Also Published As
Publication number | Publication date |
---|---|
GB2616233A (en) | 2023-08-30 |
WO2023071411A1 (zh) | 2023-05-04 |
CN114195193A (zh) | 2022-03-18 |
DE112022000171T5 (de) | 2023-07-27 |
US11942643B2 (en) | 2024-03-26 |
US20240038993A1 (en) | 2024-02-01 |
GB202309479D0 (en) | 2023-08-09 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN102856545B (zh) | 一种微纳米掺杂金属离子磷酸铁锂正极材料的制备方法 | |
JP7392132B2 (ja) | コバルトフリー正極材料およびその調製方法 | |
CN111916727B (zh) | 一种双离子湿法掺杂的三元高镍正极材料及其制备方法 | |
CN108767216B (zh) | 具有变斜率全浓度梯度的锂离子电池正极材料及其合成方法 | |
CN112164796B (zh) | 一种锂离子电池正极材料的预锂化添加剂及其制备方法和应用 | |
CN112271281B (zh) | 复合正极材料及其制备方法、应用和锂离子电池 | |
CN115432685B (zh) | 一种磷铁类锂离子电池正极材料及其制备方法和应用 | |
CN115101738A (zh) | 一种碳包覆的铁钒双金属磷酸焦磷酸钠复合材料及其制备方法和应用 | |
CN115832471A (zh) | 一种改性正极补锂添加剂及其制备方法和应用 | |
CN109950503B (zh) | 一种CoMoOx/碳/硫复合纳米材料的制备方法、锂离子电池负极及锂离子半电池 | |
CN114195193B (zh) | 掺杂型磷酸钒钠及其制备方法和应用 | |
CN111048766A (zh) | 一种硅酸铁锂/碳正极材料及其制备方法和用途 | |
WO2013146207A1 (ja) | 電極活物質、リチウムイオン電池、電極活物質の放電状態の検出方法及び電極活物質の製造方法 | |
CN112186191B (zh) | 一种汉堡包式2d-2d-2d结构的三元正极材料及其制备方法 | |
CN111668448B (zh) | 一种磷酸铁锂改性复合材料及其制备方法 | |
CN110660975A (zh) | 一种锇掺杂的LiAlSiO4包覆镍钴锰酸锂正极材料及其制备方法和应用 | |
CN113066988A (zh) | 一种负极极片及其制备方法和用途 | |
CN104393296B (zh) | 一种锂离子电池复合正极材料及其制备方法 | |
CN113745514B (zh) | 一种氟掺杂及硅酸锂包覆的富锂锰基正极材料及其制备方法与应用 | |
CN115911331A (zh) | 一种低镍铜锰基钠离子电池正极材料的制备方法 | |
CN114455563A (zh) | 一种改性磷酸铁锂材料及其制备方法和应用 | |
CN114212764A (zh) | 一种磷酸盐正极材料前驱体、其制备方法及应用 | |
JP2014194879A (ja) | 電極活物質及び電極並びにリチウムイオン電池 | |
CN115367723B (zh) | 一种LiFe2F6包覆磷酸铁锂正极材料的制备方法 | |
CN117012941A (zh) | 一种双层包覆球形磷酸锰铁锂正极材料及其制备方法和应用 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |