CN113690433A - High-entropy prussian blue material and preparation method thereof - Google Patents
High-entropy prussian blue material and preparation method thereof Download PDFInfo
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- CN113690433A CN113690433A CN202110817643.5A CN202110817643A CN113690433A CN 113690433 A CN113690433 A CN 113690433A CN 202110817643 A CN202110817643 A CN 202110817643A CN 113690433 A CN113690433 A CN 113690433A
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- prussian blue
- precursor liquid
- equal
- salt
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- DCYOBGZUOMKFPA-UHFFFAOYSA-N iron(2+);iron(3+);octadecacyanide Chemical compound [Fe+2].[Fe+2].[Fe+2].[Fe+3].[Fe+3].[Fe+3].[Fe+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] DCYOBGZUOMKFPA-UHFFFAOYSA-N 0.000 title claims abstract description 113
- 229960003351 prussian blue Drugs 0.000 title claims abstract description 112
- 239000013225 prussian blue Substances 0.000 title claims abstract description 112
- 239000000463 material Substances 0.000 title claims abstract description 105
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims abstract description 76
- 229910001415 sodium ion Inorganic materials 0.000 claims abstract description 76
- 239000013078 crystal Substances 0.000 claims abstract description 35
- 239000007774 positive electrode material Substances 0.000 claims abstract description 27
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 16
- 239000002245 particle Substances 0.000 claims abstract description 15
- 230000008569 process Effects 0.000 claims abstract description 11
- 239000002243 precursor Substances 0.000 claims description 72
- 239000007788 liquid Substances 0.000 claims description 57
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 28
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 24
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 22
- 239000008367 deionised water Substances 0.000 claims description 22
- 229910021641 deionized water Inorganic materials 0.000 claims description 22
- 238000006243 chemical reaction Methods 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 18
- 239000008139 complexing agent Substances 0.000 claims description 14
- 239000002904 solvent Substances 0.000 claims description 14
- 239000012046 mixed solvent Substances 0.000 claims description 12
- 239000000725 suspension Substances 0.000 claims description 12
- 239000002270 dispersing agent Substances 0.000 claims description 11
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 9
- 230000032683 aging Effects 0.000 claims description 8
- -1 transition metal salts Chemical class 0.000 claims description 8
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- JFSUDVTVQZUDOP-UHFFFAOYSA-N tetrasodium;iron(2+);hexacyanide;decahydrate Chemical compound O.O.O.O.O.O.O.O.O.O.[Na+].[Na+].[Na+].[Na+].[Fe+2].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] JFSUDVTVQZUDOP-UHFFFAOYSA-N 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 239000001509 sodium citrate Substances 0.000 claims description 5
- 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 5
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 4
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 3
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 3
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 3
- 229940071106 ethylenediaminetetraacetate Drugs 0.000 claims description 3
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 claims description 3
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 3
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 3
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 3
- 238000004321 preservation Methods 0.000 claims description 3
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 3
- 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
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- 150000003842 bromide salts Chemical class 0.000 claims description 2
- 150000003841 chloride salts Chemical class 0.000 claims description 2
- 150000001868 cobalt Chemical class 0.000 claims description 2
- 150000001879 copper Chemical class 0.000 claims description 2
- 150000004673 fluoride salts Chemical class 0.000 claims description 2
- 235000019253 formic acid Nutrition 0.000 claims description 2
- XMBWDFGMSWQBCA-UHFFFAOYSA-M iodide Chemical compound [I-] XMBWDFGMSWQBCA-UHFFFAOYSA-M 0.000 claims description 2
- 150000002505 iron Chemical class 0.000 claims description 2
- 150000002696 manganese Chemical class 0.000 claims description 2
- 150000002815 nickel Chemical class 0.000 claims description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 2
- DZCAZXAJPZCSCU-UHFFFAOYSA-K sodium nitrilotriacetate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CN(CC([O-])=O)CC([O-])=O DZCAZXAJPZCSCU-UHFFFAOYSA-K 0.000 claims description 2
- 150000003608 titanium Chemical class 0.000 claims description 2
- 150000003681 vanadium Chemical class 0.000 claims description 2
- 150000001844 chromium Chemical class 0.000 claims 1
- 150000003751 zinc Chemical class 0.000 claims 1
- 238000000975 co-precipitation Methods 0.000 abstract description 10
- 239000012071 phase Substances 0.000 description 35
- 239000011734 sodium Substances 0.000 description 29
- 239000010406 cathode material Substances 0.000 description 18
- 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 description 17
- 229910052708 sodium Inorganic materials 0.000 description 17
- 238000012360 testing method Methods 0.000 description 13
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 12
- 238000004458 analytical method Methods 0.000 description 12
- 239000010949 copper Substances 0.000 description 11
- 239000011572 manganese Substances 0.000 description 11
- 229910021645 metal ion Inorganic materials 0.000 description 9
- 239000010936 titanium Substances 0.000 description 8
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 229910001416 lithium ion Inorganic materials 0.000 description 7
- 230000014759 maintenance of location Effects 0.000 description 7
- 239000003792 electrolyte Substances 0.000 description 6
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 150000003624 transition metals Chemical group 0.000 description 6
- 235000019441 ethanol Nutrition 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 4
- 239000011651 chromium Substances 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 229940078494 nickel acetate Drugs 0.000 description 4
- 230000002572 peristaltic effect Effects 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 239000000741 silica gel Substances 0.000 description 4
- 229910002027 silica gel Inorganic materials 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000003109 Disodium ethylene diamine tetraacetate Substances 0.000 description 3
- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical compound [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 description 3
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 description 3
- 239000010405 anode material Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 229910000365 copper sulfate Inorganic materials 0.000 description 3
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000018109 developmental process Effects 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 235000019301 disodium ethylene diamine tetraacetate Nutrition 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 238000004146 energy storage Methods 0.000 description 3
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 3
- 229910001414 potassium ion Inorganic materials 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 3
- 229910001428 transition metal ion Inorganic materials 0.000 description 3
- 229910000314 transition metal oxide Inorganic materials 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical compound N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 description 2
- 229910021555 Chromium Chloride Inorganic materials 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical group [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 229910021550 Vanadium Chloride Inorganic materials 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- QSWDMMVNRMROPK-UHFFFAOYSA-K chromium(3+) trichloride Chemical compound [Cl-].[Cl-].[Cl-].[Cr+3] QSWDMMVNRMROPK-UHFFFAOYSA-K 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229910021385 hard carbon Inorganic materials 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 229940099596 manganese sulfate Drugs 0.000 description 2
- 239000011702 manganese sulphate Substances 0.000 description 2
- 235000007079 manganese sulphate Nutrition 0.000 description 2
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000005486 organic electrolyte Substances 0.000 description 2
- 239000001301 oxygen Chemical group 0.000 description 2
- 229910052760 oxygen Chemical group 0.000 description 2
- RPESBQCJGHJMTK-UHFFFAOYSA-I pentachlorovanadium Chemical compound [Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[V+5] RPESBQCJGHJMTK-UHFFFAOYSA-I 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 229910021583 Cobalt(III) fluoride Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical group N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 1
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 1
- 229910019398 NaPF6 Inorganic materials 0.000 description 1
- 229910019441 NaTi2(PO4)3 Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 241000234314 Zingiber Species 0.000 description 1
- ACOUVIAARVCJGT-UHFFFAOYSA-N [acetyloxy-[2-(diacetyloxyamino)ethyl]amino] acetate;cobalt Chemical compound [Co].CC(=O)ON(OC(C)=O)CCN(OC(C)=O)OC(C)=O ACOUVIAARVCJGT-UHFFFAOYSA-N 0.000 description 1
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 1
- 239000003570 air Substances 0.000 description 1
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- YCYBZKSMUPTWEE-UHFFFAOYSA-L cobalt(ii) fluoride Chemical compound F[Co]F YCYBZKSMUPTWEE-UHFFFAOYSA-L 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- QYCVHILLJSYYBD-UHFFFAOYSA-L copper;oxalate Chemical compound [Cu+2].[O-]C(=O)C([O-])=O QYCVHILLJSYYBD-UHFFFAOYSA-L 0.000 description 1
- 239000008358 core component Substances 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000012983 electrochemical energy storage Methods 0.000 description 1
- 238000000635 electron micrograph Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003759 ester based solvent Substances 0.000 description 1
- ZQURKOAMICBVAW-UHFFFAOYSA-N ethene;manganese Chemical group [Mn].C=C ZQURKOAMICBVAW-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000011565 manganese chloride Substances 0.000 description 1
- 235000002867 manganese chloride Nutrition 0.000 description 1
- 229940099607 manganese chloride Drugs 0.000 description 1
- 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 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229920000447 polyanionic polymer Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- BAZAXWOYCMUHIX-UHFFFAOYSA-M sodium perchlorate Chemical compound [Na+].[O-]Cl(=O)(=O)=O BAZAXWOYCMUHIX-UHFFFAOYSA-M 0.000 description 1
- 229910001488 sodium perchlorate Inorganic materials 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 230000001360 synchronised effect Effects 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 239000004246 zinc acetate Substances 0.000 description 1
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C3/00—Cyanogen; Compounds thereof
- C01C3/08—Simple or complex cyanides of metals
- C01C3/12—Simple or complex iron cyanides
-
- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1397—Processes of manufacture of electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Organic Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Secondary Cells (AREA)
Abstract
The invention discloses a high-entropy prussian blue material, the molecular formula of which is NaxMyn [ Fe (CN)6]z•wH2And O, wherein M is n different transition metal elements, n is more than or equal to 5, yn is more than or equal to 0.01 and less than or equal to 0.90, y1+ y2+ y3+ y4+ y5 … + yn =1, w is more than or equal to 4.0, x is more than or equal to 1.40 and less than or equal to 1.95, and z is more than or equal to 0.90 and less than or equal to 0.98. The high-entropy Prussian blue material is of a monoclinic phase structure, the micro morphology of the high-entropy Prussian blue material is large-size crystal particles, and crystal grains are uniform in size and are in a regular polyhedral morphology with a single shape. The invention also provides application of the high-entropy Prussian blue material as a positive electrode material in a sodium ion battery and a preparation method thereof, wherein a coprecipitation method is adopted, and source materials are selected, designed in the process and manufactured in the preparation processThe high-entropy prussian blue material with high specific capacity, good rate capability and excellent cycle performance is obtained by selecting and controlling process parameters.
Description
Technical Field
The invention relates to the technical field of energy materials, in particular to a Prussian blue type sodium ion battery positive electrode material and a preparation method thereof.
Background
Environmental and energy problems are becoming more severe due to the excessive use of fossil energy, such as greenhouse effect, atmospheric pollution and energy exhaustion, which are gradually affecting the production and life of human beings. The emergence of new clean energy can mitigate the above-mentioned crisis to a great extent, and therefore has received attention from global researchers. However, the new clean energy, represented by solar energy, tidal energy, wind energy and heat energy, is severely limited by the time and space conditions, and is difficult to directly generate high-quality energy supply, so that energy storage equipment is required to solve the energy throughput problem. Among them, the development of large-scale and low-cost energy storage power stations has become the focus of the contemporary scientific and engineering communities, and electrochemical energy storage devices represented by lithium ion and sodium ion batteries are excellent and relatively cheap energy carriers. The development of lithium ion batteries in the last two decades has proven their success in portable electronics, electric vehicles, however, the limited lithium resource has severely hampered the sustainable development and large-scale application of lithium ion batteries. The sodium and the lithium which are the first main group have similar physicochemical properties, the working principle of corresponding electrode materials in the ion battery is very similar, and meanwhile, the sodium is used as a crustal high-abundance element, so that the cost is low and the sodium ion battery is easy to obtain, and the sodium ion battery has huge potential and advantage particularly in the large-scale energy storage direction.
The core component of the sodium ion battery generally consists of four parts, namely a positive electrode, an electrolyte, a diaphragm and a negative electrode. In the charging process, Na + is separated from the sodium-rich positive electrode and enters the negative electrode after passing through the diaphragm through the electrolyte; and the electrons move to the negative electrode along the external circuit for charge compensation. The discharging process is opposite to the former, and the two are highly reversible, so that the sodium ion battery has the charging and discharging functions.
The mainstream cathode materials of the sodium ion battery are hard carbon and NaTi2(PO4)3, the hard carbon and the NaTi2 are fully researched, and the sodium ion battery has the characteristics of long cycle, high capacity and the like. The electrolyte of the sodium ion battery is also well solved, mainly comprises sodium salts such as NaPF6 and NaClO4 and ester solvents, and has the property similar to that of the electrolyte of the lithium ion battery.
Unlike the negative electrode and electrolyte, the positive electrode material remains the bottleneck of the sodium ion battery. Among them, sodium-electric anodes widely studied can be classified into three types: transition metal oxides, polyanionic compounds, and prussian blue analogs. The transition metal oxide and polyanion compound contain fluorine and oxygen bonds in the crystal structure, so that the Na + is subjected to larger chemical constraint energy in the transmission process in the crystal lattice, thereby influencing the deintercalation on the anode and causing the low rate performance of the material. Moreover, the transition metal oxide is accompanied with uncontrollable phase change in the charging and discharging processes, thereby causing serious reduction of the cycle life of the material; polyanionic compounds generally have a low specific capacity due to the large molecular weight of the anion. The synthesis methods of both generally involve high temperature solid phase methods, which require enormous energy consumption.
The chemical formula of the Prussian blue material is AxMa [ Mb (CN)6]1-y, each transition metal atom is connected through a cyanide group to form a rigid and open cubic framework, and alkali metal ions can be freely transmitted and stored in the framework due to the large pore channel structure. Because no oxygen and fluorine elements are contained, the Na + is less in chemical constraint energy in the transmission process in the crystal lattice, and the rate capability is outstanding. The average sodium storage potential of the Prussian blue material is generally higher than 3V, and when the transition metals in the structure have electrochemical activity, the Prussian blue material has a theoretical capacity of 170 mAh/g. Meanwhile, the preparation of the prussian blue material is generally a coprecipitation method, a hydrothermal method and a ball milling method, and has low energy consumption and mild conditions, so the prussian blue material has a great commercial application prospect.
However, to be truly commercially viable, prussian blue-based materials still need to overcome the following obstacles: due to the existence of factors such as water and the like, the electrode material is easy to generate side reaction with electrolyte in the circulating process to damage the structure, and meanwhile, the circulating life of the material is also seriously reduced due to the dissolution of transition metal (particularly Mn); secondly, the electronic conductivity of the Prussian blue material is poor, and the Prussian blue material has the characteristics of high impedance, low rate performance and the like.
Disclosure of Invention
The object of the invention is therefore: the technical problems of short cycle life and poor rate capability when the existing Prussian blue materials are used as the positive electrode materials of the sodium ion battery are solved, and the high-entropy Prussian blue positive electrode materials of the sodium ion battery and the preparation method thereof are provided.
In order to achieve the above object, the present invention has the following technical solutions.
High-entropy pluuA material of the sky blue class, the molecular formula is NaxMyn[Fe(CN)6]z•wH2O, wherein M is n different transition metal elements; n is more than or equal to 5, yn is more than or equal to 0.01 and less than or equal to 0.90, y1+ y2+ y3+ y4+ y5 … + yn =1, z is more than or equal to 0.90 and less than or equal to 0.98, and w is more than or equal to 4.0.
The value of x in the formula for characterizing the sodium content is as follows: x is more than or equal to 1.40 and less than or equal to 1.95, the content of sodium in the structure of the high-entropy Prussian blue material can be increased, on one hand, the charge-discharge specific capacity of the material can be increased, the structural stability and the cycle performance are improved through the high entropy on the premise that the initial charge-discharge specific capacity of the obtained high-entropy material is improved, and the rate capability is increased; in addition, the increase of the sodium content also ensures that the high-entropy Prussian blue material can obtain a monoclinic-phase single-phase structure, the increase of the sodium content in the material structure causes lattice distortion, so that relative peaks are split, the monoclinic-phase single-phase structure is formed, and the initial charge-discharge specific capacity of the material is increased.
Wherein the transition metal elements are at least five of iron, manganese, cobalt, nickel, copper, titanium and vanadium; wherein, the transition metal is selected to provide necessary guarantee for realizing the following purposes: firstly, the high-entropy prussian blue material can be ensured to be uniformly mixed and arranged with different metal elements in a crystal structure when transition metals are 5 or more (n is more than or equal to 5) in the preparation process, especially when a low-temperature preparation method is selected, the dissolution of the metal elements is reduced, a stable integral structure frame of the high-entropy prussian blue is obtained, and the high cycle stability of the material in charge and discharge cycles is ensured; and the reasonable collocation between the transition metal element providing the redox site and the transition metal with a stable structure is ensured, the stability of the structural framework is ensured by obtaining high composition entropy, and the charge-discharge specific capacity can be improved.
Further, the high-entropy prussian blue material is of a single-phase structure and is in a monoclinic phase, and compared with a normal cubic phase single-phase structure, the single-phase structure with the monoclinic phase can obviously improve the charge-discharge specific capacity of the material, which is one reason for the invention to obtain the high-entropy prussian blue material with the monoclinic phase structure.
Furthermore, the microscopic morphology of the high-entropy prussian blue material is large-size crystal particles, crystal grains are uniform in size, single and regular in shape, the length size of the particles averagely reaches 4-8 mu m, and the large-size crystal grains meet the requirement of industrial production coating when being applied to the positive electrode material of the sodium-ion battery. However, when the high-entropy prussian blue material is prepared, it is not easy to obtain large-size crystal particles, and the growth process and the overall morphology of the crystal particles need to be regulated and controlled in the preparation process so as to improve the particle size. The invention controls the preparation process and obtains good effect. For example, Na obtained in example 11.9Mn0.2Fe0.2Co0.2Ni0.2Cu0.2[Fe(CN)6]0.96•1.2H2O is a single-phase structure of a monoclinic phase, the particles are in a regular spherical polyhedron shape, and the average length of single crystals is 6 mu m; na obtained in example 21.6Ti0.16Mn0.16Fe0.16Co0.2Ni0.16Cu0.16[Fe(CN)6]0.93·2.1H2O is a monoclinic phase single-phase structure, crystal particles are in a regular spheroidal shape, and the average length of single crystals is 8 mu m; na as obtained in example 31.4Mn0.20V0.20Ti0.20Ni0.1Cu0.1Cr0.20[Fe(CN)6]0.90·4H2And O is a single-phase structure with a high-crystallinity monoclinic phase, the single crystal presents a regular spherical polyhedron shape, and the average length of the single crystal is 4 mu m. The high-entropy Prussian blue material can be determined from the single-phase structure and the regular large-size crystal particle morphology, and has high crystallinity; in addition, each characteristic peak in XRD test results of the high-entropy Prussian blue materials prepared from the examples shows a sharp characteristic, and the fact that the materials have high crystallinity can be directly verified. Therefore, the high-entropy prussian blue material can be directly judged, and even if the mixed-arrangement metal is more than 5 (5 is less than or equal to n), the invention realizes the uniform mixed arrangement of different elements of each metal in the crystal structure.
Also, because the high-entropy prussian blue material of the invention realizes uniform mixing and arrangement of a plurality of metal elements in a crystal structure to achieve high crystallinity, and the introduction of vacancies and water is effectively reduced, the water content of the high-entropy prussian blue material of the invention is 4.0 or less (w is less than or equal to 4.0), the vacancies are less than 0.1 (the vacancy content is 1-Z, Z is 0.90 or less than or equal to Z in the molecular formula and less than or equal to 0.98), such as Na prepared in example 11.9Mn0.2Fe0.2Co0.2Ni0.2Cu0.2[Fe(CN)6]0.96·1.2H2O, with a water content as low as 1.2, with a vacancy of 0.04. The introduction of vacancies and water in the crystal structure of the high-entropy Prussian blue material is reduced, the integral structure frame of the high-entropy Prussian blue is further stabilized, and the high-entropy Prussian blue material has higher cycle stability in charge-discharge cycles; on the other hand, the reduction of the vacancy also improves the charge-discharge specific capacity.
The inventor applies the high-entropy Prussian blue material of the invention to a sodium-ion battery as a positive electrode material, and the cycle performance of the high-entropy Prussian blue material is as follows: the maximum discharge capacity of the material under the current density of 500 mA/g is more than 103mAh/g, the specific capacity retention rate of the battery after 1000 cycles reaches 78.8%, and excellent cycle performance is shown; the rate capability of the high-entropy Prussian blue material is that the discharge specific capacity of the high-entropy Prussian blue material is greater than 96.5mAh/g under the current density of 1000 mA/g, which shows that the high-entropy Prussian blue material has good rate capability and the specific capacity attenuation is reduced along with the increase of the current density. For example, Na obtained in example 2 of the present invention1.6Ti0.16Mn0.16Fe0.16Co0.2Ni0.16Cu0.16[Fe(CN)6]0.93·2.1H2O: the maximum discharge capacity of the material under the current density of 500 mA/g is 103mAh/g, and the specific capacity retention rate of the battery after 1000 cycles is 78.8%; the multiplying power performance is shown under the current density of 1000 mA/g, and the specific discharge capacity is 96.5 mAh/g. Na obtained in example 41.95Mn0.11Fe0.11Co0.11Ni0.12Cu0.11Ti0.11V0.11Cr0.11Zn0.11[Fe(CN)6]0.98·0.5H2O: at a current density of 500 mA/gThe maximum discharge capacity of the material is 120.2mAh/g, and the specific capacity retention rate of the battery after 1000 cycles is 82.5%; the multiplying power performance is shown under the current density of 1000 mA/g, and the specific discharge capacity is 116 mAh/g.
The high-entropy Prussian blue material obtained by the invention solves the technical problems of short cycle life and poor rate capability when the conventional Prussian blue material is used as a positive electrode material of a sodium ion battery, and further improves the cycle life and the rate capability on the premise of improving the initial charge-discharge specific capacity. Naturally, obtaining a high entropy prussian blue type material as described above is determined by the selection of source materials, the process design of the preparation process, the selection and control of process parameters when the inventors prepare the material.
Therefore, the invention also provides a preparation method of the high-entropy prussian blue material, which comprises the following steps:
(1) dissolving sodium ferrocyanide decahydrate, a complexing agent and a surface dispersing agent in a mixed solvent consisting of deionized water and an auxiliary solvent to obtain a precursor solution A for later use;
(2) dissolving 5 or more transition metal salts and complexing agents in a mixed solvent consisting of deionized water and an auxiliary solvent to obtain a precursor liquid B for later use;
(3) slowly dripping the precursor liquid B into the precursor liquid A for reaction, and then carrying out heat preservation stirring and aging treatment to obtain a suspension;
the precursor liquid B is added into the precursor liquid A in a slow dropwise adding mode, the reaction process is ensured to be that a small amount of the precursor liquid B is in the environment of a large amount of the precursor liquid A, so that various metal ions can be simultaneously and orderly released even under the condition that the precursor liquid B contains more than 5 metal ions, the metal ions can be orderly and uniformly mixed and arranged in a lattice structure, and uniform single-phase structure with high crystallinity and regular large-size crystals are obtained.
(4) And separating, washing and drying the suspension to obtain the high-entropy prussian blue material.
Further, the complexing agent is at least one of sodium citrate, 2' -bipyridine, 1-10-phenanthroline, ethylenediamine, disodium ethylene diamine tetraacetate and trisodium nitrilotriacetate; the use of the complexing agent also promotes the slow and synergistic rate release of transition metal ions of various metal ions, so that a more uniformly dispersed and equal-ratio reaction environment can be formed when the precursor is added dropwise, and the coprecipitation reaction is carried out with ferrocyanide, so that the slow growth of crystals is realized, the metal ions can be orderly and uniformly mixed and arranged in a lattice structure, and uniform single-phase structures with high crystallinity and regular large-size crystals are obtained. Further, the crystallinity of the material is improved, and sodium storage sites are increased, so that more sodium in the finally formed high-entropy prussian blue material structure is reserved, and the sodium content in the material structure is improved. More preferably, when the complexing agent itself is a sodium salt, such as sodium citrate, the reaction environment provides a sodium-rich reaction environment, thereby increasing the sodium content of the reaction product.
The surface dispersant is at least one of polyvinylpyrrolidone, cetyl trimethyl ammonium bromide, polycyclic aromatic hydrocarbon and sodium dodecyl benzene sulfonate. The use of the surface dispersing agent further promotes the ordered growth of crystal grains and promotes the ordered and uniform mixed arrangement of metal ions in a lattice structure; on the other hand, the addition of the surface dispersing agent has the effects of improving distribution, regulating and controlling the integral microscopic morphology of the material, enabling the material to reach a large size and increasing the particle size; thereby obtaining a uniform single-phase structure with high crystallinity and regular large-sized crystals.
The auxiliary solvent is at least one of ethanol, ethylene glycol, acetic acid, ethanolamine, n-butanol, methanol, formic acid and propanol.
Furthermore, the volume ratio of the deionized water to the auxiliary solvent in the precursor solutions a and B is any ratio, and the same auxiliary solvent and the same ratio are used in the precursor solutions a and B. Furthermore, the concentration of the complexing agent in the precursor solutions A and B is 0.1-3 mol/L, the concentration refers to the volume ratio of the molar quantity of the complexing agent to the deionized water in the solvent of the precursor solutions, and the same concentration is adopted in the precursor solutions A and B. When the precursor is dripped, the consistency and the uniformity of the reaction environment are ensured, the improvement of distribution is promoted, the integral microscopic appearance of the material is regulated and controlled, and the effects of large size and particle size increase are achieved.
Furthermore, the concentration of the surface dispersing agent in the precursor liquid A is 10-300 g/L, and the concentration refers to the volume ratio of the mass of the surface dispersing agent to the deionized water in the precursor liquid A.
Further, the transition metal salt is at least five of iron salt, manganese salt, cobalt salt, nickel salt, copper salt, titanium salt and vanadium salt;
the transition metal salt is at least one of fluoride salt, chloride salt, bromide salt, iodide salt, acetate, nitrate, sulfate, oxalate and ethylenediamine tetraacetate.
Further, the flow rate of the precursor liquid B dropwise added to the precursor liquid A in the step (3) is 1 mL/min-50 mL/min;
further, in the step (3), in the reaction process of dropwise adding the precursor liquid B into the precursor liquid A, heating the precursor liquid A to a target temperature and stirring simultaneously, introducing protective gas, keeping the temperature and stirring until the precursor liquid B is sufficiently and reversely added, and then carrying out aging treatment. Wherein the target temperature is 25-100 ℃; the protective gas is at least one of air, nitrogen and argon; the stirring speed is 200-1500 rpm, and the heat preservation stirring time is 1-48 h; the aging time is 1-48 h.
Further, the separation in the step (4) adopts a centrifugal method; the rotating speed of the centrifugation is 6000-10000 rpm, and the time is 5-10 minutes;
the drying in the step (4) is vacuum drying, and the vacuum degree is 10-6-10-2pa, drying temperature is 100-160 ℃, and drying time is 6-24 hours.
The technical scheme of the invention has the following advantages:
1. the high-entropy prussian blue material provided by the invention is prepared by adopting a coprecipitation method, more than 5 metal ions are used in the material, and the coprecipitation rates of various metal ions are different, so that how to realize orderly and synchronous release of various metal ions in a reaction is the key to realize high crystallinity of the high-entropy prussian blue material, obtain a uniform large-size single-phase crystal structure and finally obtain the high-cycle stability and good rate performance. According to the invention, the precursor liquid B is slowly dripped into the precursor liquid A, and the complexing agent and the dispersing agent are used in the precursor liquid A, B, so that more than 5 transition metal salts release transition metal ions at a slow and synergistic rate, and the transition metal ions and ferrocyanide are subjected to coprecipitation reaction, thereby realizing the slow growth of crystals and the uniform mixing of different elements in the crystal structure, and enabling the generated high-entropy Prussian blue sodium ion battery anode material to have high crystallinity, a single and consistent phase structure and a proper particle size. The high crystallinity reduces the introduction of vacancies and water, increases sodium storage sites, improves the specific capacity, stabilizes the integral structural framework of the high-entropy prussian blue and has higher cycle stability in charge-discharge cycles.
2. According to the preparation method of the high-entropy Prussian blue type sodium ion battery anode material, the selection and the usage amount of the complexing agent and the solvent in the precursor liquid A, B are consistent, the precursor liquid A, B is guaranteed to have the same liquid environment, and the precipitation of reaction substances caused by different liquid environments in the process of dripping the precursor liquid B into the precursor liquid is avoided; and the continuous and consistent reaction environment promotes the overall microcosmic appearance regulation of the material, so that the material achieves the effects of large size and particle size improvement. 3. The high-entropy Prussian blue type sodium ion battery positive electrode material provided by the invention has a single-phase structure of a monoclinic phase, has a structure mixed arrangement caused by high entropy, and greatly reduces the Zingiber Taylor effect of transition metal elements in the Prussian blue material on the premise of ensuring high specific capacity, so that the dissolution of the elements is reduced, and the long-term circulation stability of the corresponding sodium ion battery is greatly improved. And the cooperative work among various different transition metal elements can further ensure the specific capacity and simultaneously improve the multiplying power performance of the material structure.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without creative efforts.
Fig. 1 is a schematic diagram of a reaction apparatus of a preparation method of a prussian blue sodium-ion battery positive electrode material in an embodiment of the invention.
Fig. 2 is an SEM electron micrograph of the prussian blue-based sodium ion battery positive electrode material prepared in examples 1 to 4 of the present invention.
Fig. 3 is an XRD chart of the prussian blue sodium-ion battery cathode material prepared in examples 1-4 of the present invention.
Fig. 4 is a cycle performance diagram of the organic electrolyte system sodium ion half-cell with the prussian blue material as the positive electrode prepared in examples 1-4 of the present invention at a current density of 500 mA/g.
Fig. 5 is a rate performance graph of the organic electrolyte system sodium ion half-cell with the prussian blue material as the positive electrode prepared in examples 1-4 of the invention under current densities of 10, 100, 200, 500, 1000 and 1500 mA/g.
Fig. 6 is a charge-discharge curve diagram of the prussian blue sodium-ion battery cathode material prepared in example 1 of the present invention.
Detailed Description
The following examples are provided to better understand the present invention, not to limit the present invention to the best mode, and not to limit the content and protection scope of the present invention, and it is within the protection scope of the present invention that anyone can combine the features of the present invention with other prior art to obtain any product that is the same or similar to the present invention, and apply it to lithium ion battery, potassium ion battery, etc. similar to sodium ion battery.
The examples do not show the specific experimental steps or conditions, and can be performed according to the conventional experimental steps described in the literature in the field. The reagents or instruments used are not indicated by manufacturers, and are all conventional reagent products which can be obtained commercially.
Example 1
The embodiment provides a preparation method of a high-entropy Prussian blue type sodium ion battery positive electrode material, which comprises the following steps:
dissolving 3mol of sodium ferrocyanide decahydrate, 10g of polyvinylpyrrolidone and 2mol of sodium citrate in a mixed solvent consisting of 1L of deionized water and 100mL of absolute ethyl alcohol to obtain a precursor solution A;
dissolving 0.3mol of manganese sulfate, 0.3mol of copper sulfate, 0.3mol of nickel acetate, 0.3mol of cobalt chloride, 0.3mol of ferric nitrate and 2mol of sodium citrate in a mixed solvent consisting of 1L of deionized water and 100mL of absolute ethyl alcohol to obtain a precursor solution B;
the coprecipitation reaction is carried out by adopting the device shown in fig. 1, wherein a container A is filled with the precursor liquid A, a container B is filled with the precursor liquid B, the precursor liquid B is slowly dripped into the container A at the speed of 1mL/min by a peristaltic pump through a silica gel tube, the temperature of the liquid is raised to 90 ℃ by a temperature-controlled stirring device, and the stirring speed is 400 rpm. After the precursor B is dropwise added, keeping the temperature and stirring for 5 hours continuously, and then standing and aging for 40 hours to obtain a sample suspension;
and centrifuging the sample suspension at 6000rpm for 10min, washing the obtained sample precipitate for multiple times by using deionized water and ethanol, and drying the product in a vacuum oven with the temperature of 120 ℃ and the vacuum degree of 1pa for 10h to obtain the high-entropy Prussian blue type sodium-ion battery positive electrode material.
The molecular formula of the obtained material is Na through element analysis and ICP test1.9Mn0.2Fe0.2Co0.2Ni0.2Cu0.2[Fe(CN)6]0.96·1.2H2O。
According to SEM test analysis, the high-entropy Prussian blue sodium-ion battery cathode material prepared by the embodiment presents a spheroidal polyhedron shape, and the average length of a single crystal is 6 microns. The SEM spectrum is shown in FIG. 2 (a).
According to XRD test analysis, the high-entropy Prussian blue type sodium ion battery cathode material prepared by the embodiment presents an obvious monoclinic phase Prussian blue characteristic peak, and the high-entropy Prussian blue type sodium ion battery cathode material is high in crystallinity and is of a single-phase structure. The X-ray diffraction pattern is shown in fig. 3.
The high-entropy Prussian blue type sodium ion battery positive electrode material prepared by the example is assembled into a sodium ion half battery, and the cycle performance of the sodium ion half battery is tested. As shown in FIG. 4, the maximum discharge capacity of the material under the current density of 500 mA/g is 109mAh/g, the specific capacity retention rate of the battery after 1000 cycles is 84.2%, and excellent cycle performance is shown.
The high-entropy Prussian blue type sodium ion battery positive electrode material prepared by the example is assembled into a sodium ion half battery, and the rate capability of the sodium ion half battery is tested. As shown in FIG. 5, the specific discharge capacity was 99.5mAh/g at a current density of 1000 mA/g. The high-entropy prussian blue material prepared by the invention has good rate capability and small specific capacity attenuation along with the increase of current density.
Fig. 6 is a charge-discharge curve diagram of the prussian blue sodium-ion battery cathode material prepared in example 1 of the present invention. As can be seen from the figure, there are two voltage plateaus in the initial charge-discharge curves of about 3.3V and 2.7-2.8V, respectively. The voltage plateau between 2.7 and 2.8V is derived from the contribution of high spin Fe contrast capacity on one hand and the contribution of sodium content in the material structure on the other hand. This also confirms that the high-entropy prussian blue-type material obtained by the invention has a high sodium content in the structure and a real content of the high-spin Fe of the above formula. The guarantee of the sodium content also plays a key role in finally obtaining a monoclinic phase structure and further improving the specific capacity of the material.
Example 2
The embodiment provides a preparation method of a high-entropy Prussian blue type sodium ion battery positive electrode material, which comprises the following steps:
dissolving 4mol of sodium ferrocyanide decahydrate, 20g of hexadecyl trimethyl ammonium bromide and 1mol of 1-10-phenanthroline in a mixed solvent consisting of 1L of deionized water and 300mL of anhydrous n-butyl alcohol to obtain a precursor solution A;
dissolving 0.4mol of manganese chloride, 0.4mol of copper oxalate, 0.4mol of nickel acetate, 0.4mol of cobalt ethylenediamine tetraacetate, 0.4mol of ferric nitrate, 0.4mol of titanium chloride and 1mol of 1-10-phenanthroline in a mixed solvent consisting of 1L of deionized water to obtain a precursor solution B;
the coprecipitation reaction is carried out by adopting the device shown in fig. 1, wherein a container A is filled with the precursor liquid A, a container B is filled with the precursor liquid B, the precursor liquid B is slowly dripped into the container A at the speed of 5mL/min by a peristaltic pump through a silica gel tube, the temperature of the liquid is raised to 60 ℃ by a temperature-controlled stirring device, and the stirring speed is 200 rpm. After the precursor B is dropwise added, keeping the temperature and stirring for 10 hours continuously, and then standing and aging for 20 hours to obtain a sample suspension;
and centrifuging the sample suspension at 9000rpm for 15min, washing the obtained sample precipitate for multiple times by using deionized water and ethanol, and drying the product in a vacuum oven with the temperature of 120 ℃ and the vacuum degree of 0.001pa for 12h to obtain the high-entropy Prussian blue type sodium-ion battery positive electrode material.
The molecular formula of the obtained material is Na through element analysis and ICP test1.6Ti0.16Mn0.16Fe0.16Co0.2Ni0.16Cu0.16[Fe(CN)6]0.93·2.1H2O。
According to SEM test analysis, the high-entropy Prussian blue type sodium ion battery cathode material prepared by the example shows a spheroidal morphology, and the average length of a single crystal is 8 μm. The SEM spectrum is shown in FIG. 2 (b).
According to XRD test analysis, the high-entropy Prussian blue type sodium ion battery cathode material prepared by the embodiment presents an obvious monoclinic phase Prussian blue characteristic peak, and the high-entropy Prussian blue type sodium ion battery cathode material is high in crystallinity and is of a single-phase structure. The X-ray diffraction pattern is shown in fig. 3.
The high-entropy Prussian blue type sodium ion battery positive electrode material prepared by the example is assembled into a sodium ion half battery, and the cycle performance of the sodium ion half battery is tested. As shown in FIG. 4, the maximum discharge capacity of the material at a current density of 500 mA/g is 103mAh/g, the specific capacity retention rate of the battery after 1000 cycles is 78.8%, and excellent cycle performance is shown.
The high-entropy Prussian blue type sodium ion battery positive electrode material prepared by the example is assembled into a sodium ion half battery, and the rate capability of the sodium ion half battery is tested. As shown in FIG. 5, the specific discharge capacity was 96.5mAh/g at a current density of 1000 mA/g. The high-entropy prussian blue material prepared by the invention has good rate capability and small specific capacity attenuation along with the increase of current density.
Example 3
The embodiment provides a preparation method of a high-entropy Prussian blue type sodium ion battery positive electrode material, which comprises the following steps:
dissolving 1mol of sodium ferrocyanide decahydrate, 300g of sodium dodecyl benzene sulfonate and 0.1mol of disodium ethylene diamine tetraacetate in a mixed solvent consisting of 1L of deionized water and 100mL of anhydrous methanol to obtain a precursor solution A;
dissolving 0.2mol of manganese sulfate, 0.1mol of copper sulfate, 0.1mol of nickel acetate, 0.2mol of titanium chloride, 0.2mol of vanadium chloride, 0.2mol of chromium chloride and 0.001mol of disodium ethylene diamine tetraacetate in a mixed solvent consisting of 1L of deionized water and 500mL of absolute ethyl alcohol to obtain a precursor solution B;
the coprecipitation reaction is carried out by adopting the device shown in fig. 1, wherein a container A is filled with the precursor liquid A, a container B is filled with the precursor liquid B, the precursor liquid B is slowly dripped into the container A at the speed of 50mL/min by a peristaltic pump through a silica gel tube, the temperature of the liquid is raised to 30 ℃ by a temperature-controlled stirring device, and the stirring speed is 1000 rpm. After the precursor B is dropwise added, keeping the temperature and stirring for 1h continuously, and then standing and aging for 48h to obtain a sample suspension;
and centrifuging the sample suspension at 6000rpm for 10min, washing the obtained sample precipitate for multiple times by using deionized water and ethanol, and drying the product in a vacuum oven with the temperature of 120 ℃ and the vacuum degree of 10^ (-6) pa for 12h to obtain the high-entropy Prussian blue type sodium-ion battery anode material.
The molecular formula of the obtained material is Na through element analysis and ICP test1.4Mn0.20V0.20Ti0.20Ni0.1Cu0.1Cr0.20[Fe(CN)6]0.90·4H2O。
According to SEM test analysis, the high-entropy Prussian blue sodium-ion battery cathode material prepared by the embodiment presents a spheroidal polyhedron shape, and the average length of a single crystal is 4 microns. The SEM spectrum is shown in FIG. 2 (c).
According to XRD test analysis, the high-entropy Prussian blue type sodium ion battery cathode material prepared by the embodiment presents an obvious monoclinic phase Prussian blue characteristic peak, and the high-entropy Prussian blue type sodium ion battery cathode material is high in crystallinity and is of a single-phase structure. The X-ray diffraction pattern is shown in fig. 3.
The high-entropy Prussian blue type sodium ion battery positive electrode material prepared by the example is assembled into a sodium ion half battery, and the cycle performance of the sodium ion half battery is tested. As shown in FIG. 4, the maximum discharge capacity of the material at a current density of 500 mA/g is 116.4mAh/g, the specific capacity retention rate of the battery after 1000 cycles is 79.2%, and excellent cycle performance is shown.
The high-entropy Prussian blue type sodium ion battery positive electrode material prepared by the example is assembled into a sodium ion half battery, and the rate capability of the sodium ion half battery is tested. As shown in FIG. 5, the specific discharge capacity was 108mAh/g at a current density of 1000 mA/g. The high-entropy prussian blue material prepared by the invention has good rate capability and small specific capacity attenuation along with the increase of current density.
Example 4
The embodiment provides a preparation method of a high-entropy Prussian blue type sodium ion battery positive electrode material, which comprises the following steps:
dissolving 6mol of sodium ferrocyanide decahydrate, 10g of polycyclic aromatic hydrocarbon and 3mol of 2, 2' -bipyridine in a mixed solvent composed of 1L of deionized water and 100mL of anhydrous ethylene glycol to obtain a precursor solution A;
dissolving 0.3mol of manganese ethylene diamine tetraacetate, 0.3mol of copper sulfate, 0.3mol of nickel acetate, 0.3mol of cobalt fluoride, 0.3mol of ferric nitrate, 0.3mol of titanium chloride, 0.3mol of vanadium chloride, 0.3mol of zinc acetate, 0.3mol of chromium chloride and 3mol of 2, 2' -bipyridyl in a mixed solvent consisting of 1L of deionized water and 100mL of absolute ethyl alcohol to obtain a precursor solution B;
the device shown in fig. 1 is adopted to carry out coprecipitation reaction, wherein a container A is filled with a precursor liquid A, a container B is filled with a precursor liquid B, the precursor liquid B is slowly dripped into the container A at the speed of 2mL/min by a peristaltic pump through a silica gel tube, the liquid is heated to 25 ℃ by a temperature-controlled stirring device, and the stirring speed is 1500 rpm. After the precursor B is dropwise added, keeping the temperature and stirring for 20h, standing and aging for 1h to obtain a sample suspension;
and centrifuging the sample suspension at 6000rpm for 10min, washing the obtained sample precipitate for multiple times by using deionized water and ethanol, and drying the product in a vacuum oven with the temperature of 120 ℃ and the vacuum degree of 1pa for 24h to obtain the high-entropy Prussian blue type sodium-ion battery positive electrode material.
The molecular formula of the obtained material is Na through element analysis and ICP test1.95Mn0.11Fe0.11Co0.11Ni0.12Cu0.11Ti0.11V0.11Cr0.11Zn0.11[Fe(CN)6]0.98·0.5H2O。
According to SEM test analysis, the high-entropy Prussian blue sodium-ion battery cathode material prepared by the embodiment presents a spheroidal polyhedron crystal shape, and the average length of a single crystal is 4 μm. The SEM spectrum is shown in FIG. 2 (d).
According to XRD test analysis, the high-entropy Prussian blue type sodium ion battery cathode material prepared by the embodiment shows an obvious monoclinic phase Prussian blue characteristic peak, which indicates that the high-entropy Prussian blue type sodium ion battery cathode material has high crystallinity and is of a single-phase structure, and an X-ray diffraction pattern is shown in figure 3.
The high-entropy Prussian blue type sodium ion battery positive electrode material prepared by the example is assembled into a sodium ion half battery, and the cycle performance of the sodium ion half battery is tested. As shown in FIG. 4, the maximum discharge capacity of the material under the current density of 500 mA/g is 120.2mAh/g, the specific capacity retention rate of the battery after 1000 cycles is 82.5%, and excellent cycle performance is shown.
The high-entropy Prussian blue type sodium ion battery positive electrode material prepared by the example is assembled into a sodium ion half battery, and the rate capability of the sodium ion half battery is tested. As shown in FIG. 5, the specific discharge capacity was 116mAh/g at a current density of 1000 mA/g. The high-entropy prussian blue material prepared by the invention has good rate capability and small specific capacity attenuation along with the increase of current density.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications therefrom are within the scope of the invention. Naturally, although the invention exemplifies the application of the high-entropy prussian blue material prepared by the examples to the assembly of a sodium-ion battery cathode material into a sodium-ion half battery, the application cannot limit the possibility of applying the high-entropy prussian blue material to a lithium ion battery, a potassium ion battery and the like similar to the sodium-ion battery, and cannot limit the lithium ion battery and the potassium ion battery cathode material similar to the high-entropy prussian blue material of the invention, which is led out by the skilled person according to the preparation method of the examples of the invention, and the obvious changes are all within the scope of the invention.
Claims (9)
1. A high-entropy Prussian blue material is characterized in that: the molecular formula of the high-entropy Prussian blue material is NaxMyn [ Fe (CN)6]z•wH2And O, wherein M is n different transition metal elements, n is more than or equal to 5, yn is more than or equal to 0.01 and less than or equal to 0.90, y1+ y2+ y3+ y4+ y5 … + yn =1, w is more than or equal to 4.0, x is more than or equal to 1.40 and less than or equal to 1.95, z is more than or equal to 0.90 and less than or equal to 0.98, and the high-entropy Prussian blue material is in a monoclinic phase structure.
2. A high entropy prussian blue based material as claimed in claim 1, wherein: the high-entropy prussian blue material has a large-size crystal particle in a microscopic shape, crystal grains are uniform in size and are in a regular polyhedral shape with a single shape, and the length of the particle is 4-8 mu m on average.
3. A process for the preparation of a high entropy prussian blue based material as claimed in any of claims 1-2, comprising the steps of:
(1) dissolving sodium ferrocyanide decahydrate, a complexing agent and a surface dispersing agent in a mixed solvent consisting of deionized water and an auxiliary solvent to obtain a precursor solution A;
(2) dissolving 5 or more transition metal salts and complexing agents in a mixed solvent consisting of deionized water and an auxiliary solvent to obtain a precursor liquid B;
(3) dropwise adding the precursor liquid B into the precursor liquid A for reaction, and then carrying out heat preservation stirring and aging treatment to obtain a suspension;
and separating, washing and drying the suspension to obtain the high-entropy prussian blue material.
4. The preparation method of the high-entropy prussian blue material according to claim 3, characterized in that: the complexing agent is at least one of sodium citrate, 2' -bipyridyl, 1-10-phenanthroline, ethylenediamine tetraacetic acid and trisodium nitrilotriacetate; the volume ratio of the concentration of the complexing agent in the precursor liquid A and the precursor liquid B, namely the molar quantity of the complexing agent to the deionized water in the solvent of the precursor liquid is 0.001-3 mol/L, and the same concentration is adopted in the precursor liquid A and the precursor liquid B.
5. The preparation method of the high-entropy prussian blue material according to claim 3, characterized in that: the surface dispersant is at least one of polyvinylpyrrolidone, cetyl trimethyl ammonium bromide, polycyclic aromatic hydrocarbon and sodium dodecyl benzene sulfonate; the concentration of the surface dispersing agent in the precursor liquid A, namely the volume ratio of the mass of the surface dispersing agent to the deionized water in the solvent in the precursor liquid A is 10-300 g/L.
6. The preparation method of the high-entropy prussian blue material according to claim 3, characterized in that: and (3) dropwise adding the precursor liquid B to the precursor liquid A at a flow rate of 1-50 mL/min.
7. The preparation method of the high-entropy prussian blue material according to claim 3, characterized in that: the auxiliary solvent can be one of ethanol, ethylene glycol, acetic acid, ethanolamine, n-butanol, methanol, formic acid and propanol; the volume ratio of the deionized water to the auxiliary solvent in the precursor liquid A and the precursor liquid B is any ratio, and the same auxiliary solvent and the same ratio are adopted in the precursor liquid A and the precursor liquid B.
8. The preparation method of the high-entropy prussian blue material according to claim 3, characterized in that: the transition metal salt is at least five of iron salt, manganese salt, cobalt salt, nickel salt, copper salt, titanium salt, vanadium salt, zinc salt and chromium salt; the transition metal salt is at least one of fluoride salt, chloride salt, bromide salt, iodide salt, acetate, nitrate, sulfate, oxalate and ethylenediamine tetraacetate.
9. Use of a high entropy prussian blue based material according to any of claims 1-2, wherein: the high-entropy Prussian blue material is applied to a sodium ion battery and is used as a positive electrode material.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106920964A (en) * | 2017-04-05 | 2017-07-04 | 浙江大学 | A kind of prussian blue sodium-ion battery positive material and preparation method thereof |
| WO2018209653A1 (en) * | 2017-05-18 | 2018-11-22 | 宁德时代新能源科技股份有限公司 | Prussian blue positive electrode material, preparation method therefor, and electrochemical energy storage device |
| CN110199420A (en) * | 2018-05-30 | 2019-09-03 | 辽宁星空钠电电池有限公司 | Transient metal doped Prussian blue homologue and its preparation method and application and secondary ion battery |
| CN110510638A (en) * | 2019-08-12 | 2019-11-29 | 浙江大学 | A kind of prussian blue sodium-ion battery positive material and preparation method thereof of low latitude position |
| CN111377462A (en) * | 2019-07-05 | 2020-07-07 | 上海交通大学 | Prussian blue positive electrode material, sodium ion battery and preparation method and application of prussian blue positive electrode material and sodium ion battery |
| CN111525129A (en) * | 2020-04-22 | 2020-08-11 | 大连理工大学 | Water system sodium ion full battery based on nickel Prussian blue cathode material and preparation method and application thereof |
| CN111943225A (en) * | 2020-08-24 | 2020-11-17 | 全球能源互联网研究院有限公司 | Prussian blue type sodium ion battery positive electrode material and preparation method thereof |
| CN111943228A (en) * | 2020-08-24 | 2020-11-17 | 全球能源互联网研究院有限公司 | Prussian blue type sodium ion battery positive electrode material and preparation method thereof |
| CN112151804A (en) * | 2020-09-27 | 2020-12-29 | 广州大学 | Prussian blue analogue-based carbon-coated transition metal oxide and preparation method and application thereof |
| CN112174167A (en) * | 2020-08-13 | 2021-01-05 | 国网浙江省电力有限公司电力科学研究院 | Prussian blue material with core-shell structure and preparation method and application thereof |
| US20210043932A1 (en) * | 2019-08-07 | 2021-02-11 | Tsinghua University | Method for rapidly preparing prussian blue analogue with monoclinic crystal structure |
| CN112607748A (en) * | 2020-12-24 | 2021-04-06 | 三峡大学 | Multielement Prussian blue sodium ion battery positive electrode material and preparation method thereof |
| CN112928252A (en) * | 2021-01-22 | 2021-06-08 | 中国科学院过程工程研究所 | Sodium-ion battery positive electrode material and preparation method and application thereof |
-
2021
- 2021-07-20 CN CN202110817643.5A patent/CN113690433B/en active Active
Patent Citations (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106920964A (en) * | 2017-04-05 | 2017-07-04 | 浙江大学 | A kind of prussian blue sodium-ion battery positive material and preparation method thereof |
| WO2018209653A1 (en) * | 2017-05-18 | 2018-11-22 | 宁德时代新能源科技股份有限公司 | Prussian blue positive electrode material, preparation method therefor, and electrochemical energy storage device |
| CN110199420A (en) * | 2018-05-30 | 2019-09-03 | 辽宁星空钠电电池有限公司 | Transient metal doped Prussian blue homologue and its preparation method and application and secondary ion battery |
| WO2019227332A1 (en) * | 2018-05-30 | 2019-12-05 | 辽宁星空钠电电池有限公司 | Transitional metal-doped prussian blue homologous series, preparation method for same, applications thereof, and secondary ion battery |
| CN111377462A (en) * | 2019-07-05 | 2020-07-07 | 上海交通大学 | Prussian blue positive electrode material, sodium ion battery and preparation method and application of prussian blue positive electrode material and sodium ion battery |
| US20210043932A1 (en) * | 2019-08-07 | 2021-02-11 | Tsinghua University | Method for rapidly preparing prussian blue analogue with monoclinic crystal structure |
| CN110510638A (en) * | 2019-08-12 | 2019-11-29 | 浙江大学 | A kind of prussian blue sodium-ion battery positive material and preparation method thereof of low latitude position |
| CN111525129A (en) * | 2020-04-22 | 2020-08-11 | 大连理工大学 | Water system sodium ion full battery based on nickel Prussian blue cathode material and preparation method and application thereof |
| CN112174167A (en) * | 2020-08-13 | 2021-01-05 | 国网浙江省电力有限公司电力科学研究院 | Prussian blue material with core-shell structure and preparation method and application thereof |
| CN111943228A (en) * | 2020-08-24 | 2020-11-17 | 全球能源互联网研究院有限公司 | Prussian blue type sodium ion battery positive electrode material and preparation method thereof |
| CN111943225A (en) * | 2020-08-24 | 2020-11-17 | 全球能源互联网研究院有限公司 | Prussian blue type sodium ion battery positive electrode material and preparation method thereof |
| CN112151804A (en) * | 2020-09-27 | 2020-12-29 | 广州大学 | Prussian blue analogue-based carbon-coated transition metal oxide and preparation method and application thereof |
| CN112607748A (en) * | 2020-12-24 | 2021-04-06 | 三峡大学 | Multielement Prussian blue sodium ion battery positive electrode material and preparation method thereof |
| CN112928252A (en) * | 2021-01-22 | 2021-06-08 | 中国科学院过程工程研究所 | Sodium-ion battery positive electrode material and preparation method and application thereof |
Non-Patent Citations (4)
| Title |
|---|
| YANJIAO MA ET AL.: ""High-Entropy Metal–Organic Frameworks for Highly Reversible Sodium Storage"", 《ADVANCED MATERIALS》 * |
| YUE XU ET AL.: ""Structure Distortion Induced Monoclinic Nickel Hexacyanoferrate as High-Performance Cathode for Na-Ion Batteries"", 《ADVANCED ENERGY MATERIALS》 * |
| 刘欢庆等: "钠离子电池层状氧化物正极：层间滑移，相变与性能", 《储能科学与技术》 * |
| 龙宣有等: ""络合剂对铁基普鲁士蓝结构及储钠性能的影响"", 《储能科学与技术》 * |
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