CN112993241A - Preparation method of single-crystal lithium manganate material - Google Patents
Preparation method of single-crystal lithium manganate material Download PDFInfo
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- CN112993241A CN112993241A CN202110362475.5A CN202110362475A CN112993241A CN 112993241 A CN112993241 A CN 112993241A CN 202110362475 A CN202110362475 A CN 202110362475A CN 112993241 A CN112993241 A CN 112993241A
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- lithium manganate
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- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 title claims abstract description 80
- 239000013078 crystal Substances 0.000 title claims abstract description 60
- 239000000463 material Substances 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 24
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 16
- 239000000843 powder Substances 0.000 claims description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- 238000001816 cooling Methods 0.000 claims description 20
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 16
- GEYXPJBPASPPLI-UHFFFAOYSA-N manganese(III) oxide Inorganic materials O=[Mn]O[Mn]=O GEYXPJBPASPPLI-UHFFFAOYSA-N 0.000 claims description 15
- 238000007873 sieving Methods 0.000 claims description 15
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 14
- 239000001301 oxygen Substances 0.000 claims description 14
- 229910052760 oxygen Inorganic materials 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 13
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 8
- 235000019270 ammonium chloride Nutrition 0.000 claims description 8
- 150000003863 ammonium salts Chemical class 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- 239000007789 gas Substances 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 8
- 229910052744 lithium Inorganic materials 0.000 claims description 8
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 8
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 8
- 238000000926 separation method Methods 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 7
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 7
- 230000002950 deficient Effects 0.000 claims description 7
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 5
- 239000001099 ammonium carbonate Substances 0.000 claims description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-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
- 238000000498 ball milling Methods 0.000 claims description 4
- 239000011575 calcium Substances 0.000 claims description 4
- 230000007547 defect Effects 0.000 claims description 4
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 4
- 239000011812 mixed powder Substances 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 230000001590 oxidative effect Effects 0.000 claims description 4
- 238000001556 precipitation Methods 0.000 claims description 4
- 239000012716 precipitator Substances 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 3
- 229910017052 cobalt Inorganic materials 0.000 claims description 3
- 239000010941 cobalt Substances 0.000 claims description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 3
- 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
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 2
- 229910052684 Cerium Inorganic materials 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 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
- 229910052772 Samarium Inorganic materials 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 2
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 2
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 2
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 2
- 229910052788 barium Inorganic materials 0.000 claims description 2
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052796 boron Inorganic materials 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 239000011651 chromium Substances 0.000 claims description 2
- 229910052746 lanthanum Inorganic materials 0.000 claims description 2
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 2
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 239000011777 magnesium Substances 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 229910052758 niobium Inorganic materials 0.000 claims description 2
- 239000010955 niobium Substances 0.000 claims description 2
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 2
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 235000017550 sodium carbonate Nutrition 0.000 claims description 2
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 2
- 229910052712 strontium Inorganic materials 0.000 claims description 2
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims description 2
- 239000011135 tin Substances 0.000 claims description 2
- 229910052718 tin Inorganic materials 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- 239000002245 particle Substances 0.000 abstract description 18
- 239000011164 primary particle Substances 0.000 abstract description 9
- 238000005054 agglomeration Methods 0.000 abstract description 6
- 230000002776 aggregation Effects 0.000 abstract description 6
- 238000004090 dissolution Methods 0.000 abstract description 4
- 229910052748 manganese Inorganic materials 0.000 abstract description 4
- 239000011572 manganese Substances 0.000 abstract description 4
- 239000011163 secondary particle Substances 0.000 abstract description 4
- 239000007790 solid phase Substances 0.000 abstract description 3
- 230000005536 Jahn Teller effect Effects 0.000 abstract description 2
- 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 abstract description 2
- 239000002243 precursor Substances 0.000 abstract description 2
- 230000004907 flux Effects 0.000 abstract 1
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 abstract 1
- 229910001947 lithium oxide Inorganic materials 0.000 abstract 1
- 238000010438 heat treatment Methods 0.000 description 46
- 230000000052 comparative effect Effects 0.000 description 16
- 230000014759 maintenance of location Effects 0.000 description 12
- 238000005245 sintering Methods 0.000 description 10
- 239000007774 positive electrode material Substances 0.000 description 9
- 229910015645 LiMn Inorganic materials 0.000 description 8
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 7
- 238000000227 grinding Methods 0.000 description 7
- 229910001416 lithium ion Inorganic materials 0.000 description 7
- 238000005303 weighing Methods 0.000 description 6
- 229910014078 LiMn1.9Al0.1O4 Inorganic materials 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
- 239000002033 PVDF binder Substances 0.000 description 3
- 239000010405 anode material Substances 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000000840 electrochemical analysis Methods 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 3
- 238000004321 preservation Methods 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 2
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 description 2
- 239000013543 active substance Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 description 2
- 229910002102 lithium manganese oxide Inorganic materials 0.000 description 2
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 description 2
- VLXXBCXTUVRROQ-UHFFFAOYSA-N lithium;oxido-oxo-(oxomanganiooxy)manganese Chemical compound [Li+].[O-][Mn](=O)O[Mn]=O VLXXBCXTUVRROQ-UHFFFAOYSA-N 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 description 1
- 229910001863 barium hydroxide Inorganic materials 0.000 description 1
- OJIJEKBXJYRIBZ-UHFFFAOYSA-N cadmium nickel Chemical compound [Ni].[Cd] OJIJEKBXJYRIBZ-UHFFFAOYSA-N 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000005056 compaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000009766 low-temperature sintering Methods 0.000 description 1
- PPNAOCWZXJOHFK-UHFFFAOYSA-N manganese(2+);oxygen(2-) Chemical compound [O-2].[Mn+2] PPNAOCWZXJOHFK-UHFFFAOYSA-N 0.000 description 1
- VASIZKWUTCETSD-UHFFFAOYSA-N manganese(II) oxide Inorganic materials [Mn]=O VASIZKWUTCETSD-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 230000036314 physical performance Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B35/00—Boron; Compounds thereof
- C01B35/08—Compounds containing boron and nitrogen, phosphorus, oxygen, sulfur, selenium or tellurium
- C01B35/10—Compounds containing boron and oxygen
- C01B35/12—Borates
- C01B35/128—Borates containing plural metal or metal and ammonium
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G45/00—Compounds of manganese
- C01G45/02—Oxides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G45/00—Compounds of manganese
- C01G45/12—Complex oxides containing manganese and at least one other metal element
- C01G45/1221—Manganates or manganites with trivalent manganese, tetravalent manganese or mixtures thereof
- C01G45/1242—Manganates or manganites with trivalent manganese, tetravalent manganese or mixtures thereof of the type (Mn2O4)-, e.g. LiMn2O4 or Li(MxMn2-x)O4
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G51/00—Compounds of cobalt
- C01G51/40—Complex oxides containing cobalt and at least one other metal element
- C01G51/42—Complex oxides containing cobalt and at least one other metal element containing alkali metals, e.g. LiCoO2
- C01G51/44—Complex oxides containing cobalt and at least one other metal element containing alkali metals, e.g. LiCoO2 containing manganese
- C01G51/54—Complex oxides containing cobalt and at least one other metal element containing alkali metals, e.g. LiCoO2 containing manganese of the type (Mn2O4)-, e.g. Li(CoxMn2-x)O4 or Li(MyCoxMn2-x-y)O4
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B1/00—Single-crystal growth directly from the solid state
- C30B1/10—Single-crystal growth directly from the solid state by solid state reactions or multi-phase diffusion
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/10—Inorganic compounds or compositions
- C30B29/16—Oxides
- C30B29/22—Complex oxides
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- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- 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
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
本发明公开了一种单晶锰酸锂材料的制备方法，该方法中采用的掺杂元素M，有两方面作用：一是作为助熔剂，能够在更低温度或保温时间下形成单晶锰酸锂颗粒，甚至形成不同形貌的单晶锰酸锂颗粒；二是掺杂元素可以减少锰酸锂循环过程中的Jahn‑Teller效应、减少锰的溶解、稳定晶格结构从而提高锰酸锂的循环、倍率性能。本发明掺杂四氧化三锰具有较大的八面体一次颗粒团聚而成的二次颗粒，掺杂元素均匀沉淀或吸附在前驱体颗粒的缝隙或表面的特点，可以使锰酸锂性能和形貌的一致性将大大提升，此外可以用更低的温度或保温时间固相合成单晶锰酸锂，甚至形成不同形貌的单晶锰酸锂颗粒，从而得到物理性能、电化学性能兼具的单晶锰酸锂材料。
The invention discloses a preparation method of a single crystal lithium manganate material. The doping element M used in the method has two functions: first, as a flux, it can form single crystal manganese at a lower temperature or a holding time. Lithium oxide particles, and even single-crystal lithium manganate particles with different morphologies; second, doping elements can reduce the Jahn-Teller effect during the cycle of lithium manganate, reduce the dissolution of manganese, and stabilize the lattice structure to improve lithium manganate. cycle and rate performance. The doped manganese tetroxide of the invention has the characteristics of secondary particles formed by agglomeration of larger octahedral primary particles, and the doping elements are uniformly precipitated or adsorbed on the gaps or surfaces of the precursor particles, which can improve the performance and shape of lithium manganate. The consistency of the morphology will be greatly improved. In addition, single-crystal lithium manganate can be solid-phase synthesized at a lower temperature or holding time, and even single-crystal lithium manganate particles with different morphologies can be formed, so as to obtain both physical and electrochemical properties. single crystal lithium manganate material.
Description
Technical Field
The invention belongs to the technical field of lithium ion battery anode materials, and particularly relates to a preparation method of a single-crystal lithium manganate material.
Background
With the increasing environmental problems of exhaustion of fossil energy such as petroleum, air pollution and the like and the improvement of performance requirements of people on various aspects of secondary batteries, lithium ion batteries attract attention of people with the advantages of high energy density, long service life, small pollution and the like, and in the development process of nearly thirty years, the occupancy rate of the lithium ion batteries in the market by the advantages of multiple aspects of the lithium ion batteries gradually catches up and exceeds that of the traditional secondary batteries such as: lead-acid batteries, nickel-hydrogen batteries and nickel-cadmium batteries, and are widely applied to new energy automobiles, smart phones, notebook computers and other products.
At present, many reports have been made on positive electrode materials of lithium ion batteries, and particularly, lithium cobalt oxide has been used as a positive electrode material, and the lithium ion batteries have a relatively mature technology and are widely used, but with shortage of cobalt resources and soaring price, people gradually find new positive electrode materials which can be used for lithium ion batteries, and compared with lithium cobalt oxide, lithium manganese oxide positive electrode materials have an absolute advantage in price, and in addition, the lithium manganese oxide positive electrode materials have the characteristics of high discharge voltage, low pollution, high safety performance and the like, and are also greatly concerned. However, the cycle performance of lithium manganate needs to be improved, and the development of lithium manganate is greatly limited by the problem that the capacity of lithium manganate is rapidly attenuated particularly at high temperature (55 ℃).
The single crystal lithium manganate material has the characteristics of small specific surface area, good crystallinity, good lattice orientation consistency and the like, can effectively reduce the side reaction of the material with electrolyte when being used as an electrode active substance, and reduce the dissolution of manganese, thereby maintaining a stable lattice structure and improving the cycle performance; in addition, the compaction density and the tap density of the single-crystal lithium manganate are greatly higher than those of polycrystalline lithium manganate with serious primary particle agglomeration, so that the single-crystal lithium manganate has excellent physical properties and also improves the volume energy density; in addition, the condition that the particles are broken after rolling can be effectively avoided in the processing process of the single crystal lithium manganate with large-size primary particles, and the single crystal lithium manganate has good processing performance.
In order to improve the electrochemical performance of the lithium manganate anode material or to synthesize a single-crystal lithium manganate material more easily, doping elements are usually added in the process of synthesizing lithium manganate at a high temperature in the prior art, but only the doping elements are usually concerned to improve the cycle and rate performance of lithium manganate. The change of doping elements on the appearance of the lithium manganate material and the change of a preparation process of the lithium manganate material are not concerned; at present, solid-phase mixing is mainly adopted for doping elements, so that the doping elements are not uniformly mixed with a manganese source and a lithium source, and the consistency of the particle appearance and performance is directly influenced; therefore, how to ensure the uniformity of the doping elements is an urgent problem to be solved.
Disclosure of Invention
The invention aims to provide a preparation method of a single-crystal lithium manganate material, which can ensure the uniformity of doped elements, reduce the synthesis temperature and shorten the time.
The preparation method of the single-crystal lithium manganate material comprises the following steps:
A) adding ammonium salt and soluble doping element M into deionized water, continuously stirring and introducing oxidizing gas at a set temperature, adding manganese powder under the condition of keeping the gas introduction, continuously and slowly adding the manganese powder, continuing to react after the addition is finished, stopping the gas introduction after the reaction is finished, cooling to room temperature, then adding a precipitator, carrying out stirring and precipitation reaction, carrying out solid-liquid separation after the reaction is finished, and washing and drying the solid to obtain uniformly doped trimanganese tetroxide powder;
B) uniformly mixing the uniformly doped manganous-manganic oxide powder obtained in the step A) and a lithium source to obtain mixed powder;
C) and C), firstly roasting the mixed powder in the step B) at 400-550 ℃, then roasting at 600-680 ℃, finally roasting at 800-950 ℃ in a third stage, cooling and crushing to obtain the defective single crystal lithium manganate powder material.
D) And C), continuously roasting the defect type single crystal lithium manganate powder material in the step C) at 350-520 ℃ for the first time, then roasting at 580-650 ℃ for the second time, finally roasting at 700-850 ℃ for the third time, and cooling and crushing to obtain the single crystal lithium manganate powder material with a complete crystal structure.
In the step A), the ammonium salt is one or more of ammonium nitrate, ammonium chloride and ammonium sulfate; the doping element M is at least one of nitrate, sulfate, acetate and chloride of cobalt, nickel, calcium, tin, zirconium, chromium, titanium, lanthanum, barium, aluminum, magnesium, boron, strontium, niobium, samarium and cerium; the concentration of ammonium salt in deionized water is 5-100 g/L, and the concentration of doping element M in deionized water is 5-30 g/L; setting the temperature to be 50-90 ℃; the oxidizing gas is oxygen or air; the mass ratio of the manganese powder to the ammonium salt is (3-20): 1, the adding speed of the manganese powder is 20-30 g/h, and the continuous reaction time is 5-12 h; the precipitator is one or more of ammonium carbonate, ammonium bicarbonate, ammonia water, sodium carbonate and sodium hydroxide, and the precipitation reaction time is 1-12 h; in the reaction process, the stirring speed is 300-1000 r/min.
The doping element M adopted in the method has two functions: the lithium manganate particles can be used as a fluxing agent, and can be formed at lower temperature or in heat preservation time, even can be formed into single-crystal lithium manganate particles with different shapes; and secondly, the doping element can reduce the Jahn-Teller effect in the lithium manganate circulation process, reduce the dissolution of manganese and stabilize the lattice structure, thereby improving the circulation and rate capability of the lithium manganate.
Compared with the prior art, the uniformly doped manganous-manganic oxide obtained by the method has secondary particles formed by agglomeration of large octahedral primary particles, and can be used for solid-phase synthesis of a single-crystal lithium manganate material at lower temperature and with shorter heat preservation time, so that the energy consumption is reduced, the interior of the lithium manganate material is more complete, and the excellent electrochemical performance is obtained.
In the step B), the lithium source comprises one or more of lithium carbonate, lithium hydroxide, lithium acetate and lithium nitrate, and the uniformly doped manganous-manganic oxide powder and the lithium source are proportioned according to the structural formula of the doped lithium manganate.
In the step C), all heating rates are 1-8 ℃/min, the first-stage roasting time is 2-6 h, the second-stage roasting time is 4-9 h, and the third-stage roasting time is 8-16 h; and (3) crushing by adopting roller crushing or ball milling crushing, wherein the crushing time is 10-60 min, and sieving by using a 100-300-mesh sieve.
In the step D), all the heating rates are 1-6 ℃/min, the first-stage roasting time is 2-5 h, the second-stage roasting time is 4-8 h, and the third-stage roasting time is 8-14 h; and (3) crushing by adopting roller crushing or ball milling crushing, wherein the crushing time is 10-60 min, and sieving by using a 100-300-mesh sieve.
The method of the invention utilizes the defect type single crystal lithium manganate material with uniform particles, proper size and few defects obtained at the higher synthesis temperature of the step C), and utilizes the sintering at the lower synthesis temperature of the step D) to ensure that the lithium manganate material in the step D) has more complete and stable structure.
The single-crystal lithium manganate material is prepared according to the method.
The invention has the beneficial effects that:
1) the doped mangano-manganic oxide has the characteristics that secondary particles are formed by agglomeration of larger octahedral primary particles, doping elements are uniformly precipitated or adsorbed in gaps or surfaces of precursor particles, so that the consistency of the performance and the appearance of the lithium manganate can be greatly improved, in addition, the single crystal lithium manganate can be synthesized in a solid phase mode at lower temperature or in heat preservation time, and even single crystal lithium manganate particles with different appearances are formed, so that the single crystal lithium manganate material with both physical properties and electrochemical properties can be obtained.
2) The single crystal lithium manganate anode material is synthesized by two times of low-temperature sintering after high-temperature sintering and cooling, mainly comprises large single crystal primary particles, has the characteristics of uniform particles, proper size, small specific surface area, good crystallinity, difficult breakage during particle processing, complete and stable structure, can show larger tap density and compacted density when being used as an active substance, has small side reaction with electrolyte, can effectively inhibit the dissolution of divalent manganese in a circulating process, and is an energy storage material with excellent physical performance and electrochemical performance.
3) The preparation process of the manganous-manganic oxide doped and synthesized monocrystal lithium manganate material is simple, has low cost and is beneficial to large-scale production.
Drawings
FIG. 1 is an SEM photograph of Al-doped manganomanganic oxide in example 1 of the present invention.
FIG. 2 is an SEM photograph of trimanganese tetroxide in comparative example 1 of the present invention.
FIG. 3 is an SEM photograph of a single crystalline lithium manganate material according to example 1 of the present invention.
FIG. 4 is a comparison graph showing the normal temperature cycle of lithium manganate 1C according to example 1 of the present invention and comparative example 2.
FIG. 5 is a graph showing a comparison of high temperature (55 ℃ C.) cycles of lithium manganate 1C according to example 1 of the present invention and comparative example 2.
Detailed description of the invention
In order to make the objects, technical solutions and effects of the present invention clearer and clearer, the present invention is described in further detail below. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
In the following examples and comparative examples, crushing was effected by roller crushing for a crushing time of 30 min.
The 100-300 mesh sieve used for sieving in the following examples and comparative examples.
In the roasting in the following examples and comparative examples, the temperature rise rate of the first high-temperature sintering is 1-8 ℃/min; the first-stage roasting time is 2-6 hours, the second-stage roasting time is 4-9 hours, and the third-stage roasting time is 8-16 hours. And after crushing and cooling, carrying out second-time lower-temperature sintering at a temperature rise rate of 1-6 ℃/min, wherein the first-stage roasting time is 2-5 h, the second-stage roasting time is 4-8 h, and the third-stage roasting time is 8-14 h.
The invention will be further illustrated with reference to the following specific examples and the accompanying drawings:
example 1
Preparation of Al-doped mangano-manganic oxide and LiMn synthesized by same1.9Al0.1O4A single-crystal lithium manganate material: adding 20g of ammonium chloride and 20g of aluminum nitrate into 1L of constant-temperature deionized water, keeping the water temperature at 65 ℃, continuously introducing oxygen, continuously stirring at 400r/min, uniformly and slowly adding 100g of manganese powder into the water within 4h, continuously reacting for 10h after the manganese powder is added, stopping introducing the oxygen, cooling to room temperature, adding 10g of ammonia water, continuously reacting for 3h, performing solid-liquid separation, washing and drying the obtained solid to obtain the uniform Al-doped manganous manganic oxide powder.
Weighing lithium carbonate and Al-doped manganous-manganic oxide according to a stoichiometric ratio, uniformly grinding to obtain a mixture, heating to 500 ℃ at the heating rate of 3 ℃/min, and roasting for a period of 4 hours; heating to 700 ℃ according to the heating rate of 3 ℃/min, and carrying out secondary roasting for 6 h; heating to 850 ℃ according to the heating rate of 3 ℃/min, carrying out three-stage roasting for 12h, crushing for 30min by adopting a crushing roller after roasting is finished, and then sieving by using a 200-mesh sieve to obtain the defective monocrystal lithium manganate powder. Finally, roasting the powder at a lower temperature for the second time, wherein the sintering system is to carry out first-stage roasting for 3h when the temperature is raised to 450 ℃ according to the temperature raising rate of 3 ℃/min, and carry out second-stage roasting for 5h when the temperature is raised to 600 ℃ according to the temperature raising rate of 3 ℃/min; heating to 770 ℃ at a heating rate of 3 ℃/min, and carrying out three-stage roasting for 8 h; crushing for 30min by adopting a crushing roller, sieving by a 200-mesh sieve, and cooling to obtain the single crystal LiMn1.9Al0.1O4。
The charge and discharge performance test of the products obtained in all the examples and comparative examples was carried out according to the following method:
uniformly mixing the obtained lithium manganate, acetylene black and PVDF in a mass ratio of 8:1:1, adding NMP, grinding into uniform slurry, coating the uniform slurry on an aluminum foil, standing in a vacuum drying phase at 120 ℃ for 10 hours, and preparing the CR2025 button cell by taking a metal lithium sheet as a negative electrode and 1M LiPF6 as electrolyte. The electrochemical test voltage range is 3-4.3V, and 1C cycle is carried out after 2 cycles of 0.2C (1C: 148mAh/g) (NMP: N-methyl-2-pyrrolidone; PVDF: polyvinylidene fluoride).
In the embodiment 1, the 1C first discharge specific capacity of the single-crystal lithium manganate material at normal temperature is 115.7mAh/g, and the capacity retention rate after 200 cycles is 93.9%; under the condition of 1C at high temperature (55 ℃), the first discharge specific capacity is 117.4mAh/g, and the capacity retention rate after 200 cycles is 93.2%.
TABLE 1 electrochemical Performance test results of the positive electrode materials obtained in examples 1 to 2 and comparative examples 1 to 2
Example 2
Preparation of Al-doped mangano-manganic oxide and LiMn synthesized by same1.9Al0.1O4A single-crystal lithium manganate material: adding 20g of ammonium chloride and 20g of aluminum nitrate into 1L of constant-temperature deionized water, keeping the temperature of the water at 65 ℃, continuously introducing oxygen, continuously stirring at 400r/min, uniformly and slowly adding 100g of manganese powder into the water within 4h, continuously reacting for 10h after the manganese powder is added, stopping introducing the oxygen, cooling to room temperature, adding 10g of ammonia water, continuously reacting for 3h, performing solid-liquid separation, washing and drying the obtained solid to obtain the uniform Al-doped manganous manganic oxide powder.
Weighing lithium carbonate and Al-doped manganous-manganic oxide according to the stoichiometric ratio, grinding uniformly to obtain a mixture, heating to 500 ℃ according to the heating rate of 5 ℃/min, and roasting for a period of 5 hours; heating to 700 ℃ according to the heating rate of 5 ℃/min, and carrying out secondary roasting for 8 h; and heating to 950 ℃ according to the heating rate of 5 ℃/min, carrying out three-stage roasting for 14h, crushing for 30min by adopting a crushing roller after roasting is finished, and then sieving by using a 200-mesh sieve to obtain the defective monocrystal lithium manganate powder. Finally, roasting the powder at a lower temperature for the second time, wherein the sintering system is to perform first-stage roasting for 5 hours by heating to 450 ℃ according to the heating rate of 5 ℃/min, and perform second-stage roasting for 6 hours by heating to 600 ℃ according to the heating rate of 5 ℃/min; heating to 770 ℃ according to the heating rate of 5 ℃/min, and carrying out three-section roasting for 12 h; crushing for 30min by adopting a crushing roller, sieving by a 200-mesh sieve, and cooling to obtain the single crystal LiMn1.9Al0.1O4。
In the embodiment 2, the 1C first discharge specific capacity of the single-crystal lithium manganate material at normal temperature is 112.1mAh/g, and the capacity retention rate after 200 cycles is 92.3%; under the condition of 1C at high temperature (55 ℃), the first discharge specific capacity is 116.4mAh/g, and the capacity retention rate after 200 cycles is 88.4%.
Example 3
Preparation of Ba-doped mangano-manganic oxide and synthesized LiMn thereof1.9Ba0.1O4A single-crystal lithium manganate material: adding 20g of ammonium chloride and 13.12g of barium hydroxide into 1L of constant-temperature deionized water, keeping the temperature of the water at 65 ℃, continuously introducing oxygen, continuously stirring at 400r/min, uniformly and slowly adding 100g of manganese powder into the water within 4h, continuously reacting for 10h after the manganese powder is added, stopping introducing the oxygen, cooling to room temperature, adding 10g of ammonia water, continuously reacting for 3h, performing solid-liquid separation, washing and drying the obtained solid to obtain the uniformly Ba-doped mangano-manganic oxide powder.
Weighing lithium carbonate and Ba-doped manganous-manganic oxide according to a stoichiometric ratio, uniformly grinding to obtain a mixture, heating to 500 ℃ at a heating rate of 3 ℃/min, and roasting for a period of 4 hours; heating to 700 ℃ according to the heating rate of 3 ℃/min, and carrying out secondary roasting for 6 h; heating to 850 ℃ according to the heating rate of 3 ℃/min, carrying out three-stage roasting for 12h, crushing for 30min by adopting a crushing roller after roasting is finished, and then sieving by using a 200-mesh sieve to obtain the defective monocrystal lithium manganate powder. Finally, roasting the powder at a lower temperature for the second time, wherein the sintering system is to carry out first-stage roasting for 3h when the temperature is raised to 450 ℃ according to the temperature raising rate of 3 ℃/min, and carry out second-stage roasting for 5h when the temperature is raised to 600 ℃ according to the temperature raising rate of 3 ℃/min; heating to 770 ℃ at a heating rate of 3 ℃/min, and carrying out three-stage roasting for 8 h; crushing for 30min by adopting a crushing roller, sieving by a 200-mesh sieve, and cooling to obtain the single crystal LiMn1.9Ba0.1O4。
Example 3 the 1C first discharge specific capacity of the single crystal lithium manganate material at normal temperature is 112.2mAh/g, and the capacity retention rate after 200 cycles is 93.4%; under the condition of 1C at high temperature (55 ℃), the first discharge specific capacity is 116.8mAh/g, and the capacity retention rate after 200 cycles is 91.8%.
Example 4
Preparation of Ca-doped mangano-manganic oxide and LiMn synthesized by same1.9Ca0.1O4A single-crystal lithium manganate material: adding 20g of ammonium chloride and 10.7g of calcium chloride into 1L of constant-temperature deionized water, keeping the temperature of the water at 65 ℃, continuously introducing oxygen, continuously stirring at 400r/min, uniformly and slowly adding 100g of manganese powder into the water within 4h, continuously reacting for 10h after the manganese powder is added, stopping introducing the oxygen, cooling to room temperature, adding 10g of ammonium bicarbonate, continuously reacting for 3h, performing solid-liquid separation, washing and drying the obtained solid to obtain the uniform Ca-doped mangano-manganic oxide powder.
Weighing lithium carbonate and Ca-doped manganous-manganic oxide according to a stoichiometric ratio, uniformly grinding to obtain a mixture, heating to 500 ℃ at the heating rate of 3 ℃/min, and roasting for a period of 4 hours; heating to 700 ℃ according to the heating rate of 3 ℃/min, and carrying out secondary roasting for 6 h; heating to 850 ℃ according to the heating rate of 3 ℃/min, carrying out three-stage roasting for 12h, crushing for 30min by adopting a crushing roller after roasting is finished, and then sieving by using a 200-mesh sieve to obtain the defective monocrystal lithium manganate powder. Finally, roasting the powder at a lower temperature for the second time, wherein the sintering system is to carry out first-stage roasting for 3h when the temperature is raised to 450 ℃ according to the temperature raising rate of 3 ℃/min, and carry out second-stage roasting for 5h when the temperature is raised to 600 ℃ according to the temperature raising rate of 3 ℃/min; heating to 770 ℃ at a heating rate of 3 ℃/min, and carrying out three-stage roasting for 8 h; crushing for 30min by adopting a crushing roller, sieving by a 200-mesh sieve, and cooling to obtain the single crystal LiMn1.9Ca0.1O4. The electrochemical test method of the product is the same as that of the example 1.
Example 4, the 1C first discharge specific capacity of the single-crystal lithium manganate material at normal temperature is 112.4mAh/g, and the capacity retention rate after 200 cycles is 93.2%; under the condition of 1C at high temperature (55 ℃), the first discharge specific capacity is 116.3mAh/g, and the capacity retention rate after 200 cycles is 92.1%.
Comparative example 1
Preparation of mangano-manganic oxide and LiMn synthesized by same2O4Adding 20g of ammonium chloride into 1L of constant-temperature deionized water, keeping the temperature of the water at 65 ℃, continuously introducing oxygen, and continuously stirring at 400r/minAnd (3) stirring, uniformly and slowly adding 100g of manganese powder into water within 4h, continuously reacting for 10h after the manganese powder is added, stopping introducing oxygen, cooling to room temperature, adding 10g of ammonia water, continuously reacting for 3h, performing solid-liquid separation, washing and drying the obtained solid to obtain the trimanganese tetroxide powder. Weighing lithium carbonate and Al-doped manganous-manganic oxide according to the stoichiometric ratio, uniformly grinding to obtain a mixture, heating to 500 ℃ at the heating rate of 3 ℃/min, and roasting for a period of 4 hours; heating to 700 ℃ according to the heating rate of 3 ℃/min, and carrying out secondary roasting for 6 h; heating to 850 ℃ according to the heating rate of 3 ℃/min, carrying out three-stage roasting for 12h, crushing for 30min by adopting a crushing roller after roasting is finished, and then sieving by using a 200-mesh sieve to obtain the defective monocrystal lithium manganate powder. Finally, roasting the powder at a lower temperature for the second time, wherein the sintering system is to carry out first-stage roasting for 3h when the temperature is raised to 450 ℃ according to the temperature raising rate of 3 ℃/min, and carry out second-stage roasting for 5h when the temperature is raised to 600 ℃ according to the temperature raising rate of 3 ℃/min; heating to 770 ℃ at a heating rate of 3 ℃/min, and carrying out three-stage roasting for 8 h; crushing for 30min by adopting a crushing roller, sieving by a 200-mesh sieve, and cooling to obtain the single crystal LiMn2O4。
Comparative example 1 the 1C first discharge specific capacity of the single crystal lithium manganate material at normal temperature is 115.2mAh/g, and the capacity retention rate after 200 cycles is 87.1%; under the condition of 1C at high temperature (55 ℃), the first discharge specific capacity is 119.5mAh/g, and the capacity retention rate after 200 cycles is 85.8%.
Comparative example 2
Preparation of mangano-manganic oxide and LiMn synthesized by same2O4Adding 20g of ammonium chloride into 1L of constant-temperature deionized water, keeping the temperature of the water at 65 ℃, continuously introducing oxygen, continuously stirring at 400r/min, uniformly and slowly adding 100g of manganese powder into the water within 4h, continuously reacting for 10h after the manganese powder is added, stopping introducing the oxygen, cooling to room temperature, adding 10g of ammonia water, continuously reacting for 3h, performing solid-liquid separation, washing and drying the obtained solid to obtain manganous oxide powder. Then weighing lithium carbonate and mangano-manganic oxide according to the stoichiometric ratio, grinding uniformly, and roasting at a second lower temperature, wherein the sintering system is to firstly roast at a first stage at 450 ℃, then roast at a second stage at 600 ℃, and finally roast at the second stageThree-stage roasting at 770 ℃, crushing and cooling to obtain polycrystalline LiMn2O4(ii) a The electrochemical test method of the product is the same as that of the example 1.
Comparative example 2 the first discharge specific capacity of the polycrystalline lithium manganate material at room temperature under 1C is 115.1mAh/g, and the capacity retention rate after 200 cycles is 73.2%; under the condition of 1C at high temperature (55 ℃), the first discharge specific capacity is 116.4mAh/g, and the capacity retention rate after 200 cycles is 72.8%.
FIG. 1 is an SEM image of Al-doped manganous-manganic oxide in the embodiment of the invention, and it can be seen from FIG. 1 that the Al-doped manganous-manganic oxide is formed by more large octahedral primary particles, has uniform particle size, less agglomeration and smaller specific surface area, and the particle size is 0.2-0.5 μm.
Fig. 2 is an SEM image of the manganomanganic oxide in the comparative example of the present invention, and it can be seen from fig. 2 that the manganomanganic oxide is secondary particles in which a small amount of octahedral primary particles are present, which are formed by agglomeration of primary particles.
FIG. 3 is an SEM photograph of a single-crystal lithium manganate material of example 1 of the present invention, and from FIG. 3, it can be seen that synthesized LiMn1.9Al0.1O4The single crystal particle consists of primary single crystal particles with truncated octahedron shapes, and the particle size is approximately 0.5-2 mu m.
FIG. 4 is a comparison of the normal temperature cycle of lithium manganate 1C of example 1 of the present invention and comparative example 2, and from FIG. 4, it can be seen that single crystal LiMn1.9Al0.1O4The cycle performance of the material is superior to that of polycrystalline LiMn without doping Al element2O4And (3) a positive electrode material.
FIG. 5 is a comparison of high temperature (55 ℃ C.) cycles of lithium manganate 1C according to example 1 and comparative example 2 of the present invention, and it can be seen from FIG. 5 that single crystal LiMn1.9Al0.1O4The cycle performance of the material is superior to that of polycrystalline LiMn without doping Al element2O4And (3) a positive electrode material.
TABLE 1 electrochemical Performance test results of the positive electrode materials obtained in examples 1 to 2 and comparative examples 1 to 2
The above-mentioned application examples are only illustrative and the present invention is described in detail by examples, which are only used for further illustration of the present invention and are not intended to limit the scope of the present invention, and those skilled in the art can make some insubstantial modifications and adaptations of the present invention.
Claims (7)
1. The preparation method of the single-crystal lithium manganate material is characterized by comprising the following steps of:
A) adding ammonium salt and soluble doping element M into deionized water, continuously stirring and introducing oxidizing gas at a set temperature, adding manganese powder under the condition of keeping the gas introduction, continuously and slowly adding the manganese powder, continuing to react after the addition is finished, stopping the gas introduction after the reaction is finished, cooling to room temperature, then adding a precipitator, carrying out stirring and precipitation reaction, carrying out solid-liquid separation after the reaction is finished, and washing and drying the solid to obtain uniformly doped trimanganese tetroxide powder;
B) uniformly mixing the uniformly doped manganous-manganic oxide powder obtained in the step A) and a lithium source to obtain mixed powder;
C) performing primary roasting on the mixed powder in the step B) at 400-550 ℃, performing secondary roasting at 600-680 ℃, finally performing third-stage roasting at 800-950 ℃, cooling and crushing to obtain a defective single-crystal lithium manganate powder material;
D) and C), continuously roasting the defect type single crystal lithium manganate powder material in the step C) at 350-520 ℃ for the first time, then roasting at 580-650 ℃ for the second time, finally roasting at 700-850 ℃ for the third time, and cooling and crushing to obtain the single crystal lithium manganate powder material with a complete crystal structure.
2. The method for preparing a single-crystal lithium manganate material of claim 1, wherein in the step A), the ammonium salt is one or more of ammonium nitrate, ammonium chloride and ammonium sulfate; the doping element M is at least one of nitrate, sulfate, acetate and chloride of cobalt, nickel, calcium, tin, zirconium, chromium, titanium, lanthanum, barium, aluminum, magnesium, boron, strontium, niobium, samarium and cerium; the concentration of ammonium salt in deionized water is 5-100 g/L, and the concentration of doping element M in deionized water is 5-30 g/L; the temperature is set to 50-90 ℃.
3. The method of producing a single-crystal lithium manganate material of claim 1, characterized in that the oxidizing gas is oxygen or air; the mass ratio of the manganese powder to the ammonium salt is (3-20): 1, the adding speed of the manganese powder is 20-30 g/h, and the continuous reaction time is 5-12 h; the precipitator is one or more of ammonium carbonate, ammonium bicarbonate, ammonia water, sodium carbonate and sodium hydroxide, and the precipitation reaction time is 1-12 h; in the reaction process, the stirring speed is 300-1000 r/min.
4. The method for preparing a single-crystal lithium manganate material of claim 1, wherein in the step B), the lithium source comprises one or more of lithium carbonate, lithium hydroxide, lithium acetate and lithium nitrate, and the uniform manganous manganic oxide powder and the lithium source are proportionally doped according to the structural formula of the doped lithium manganate.
5. The preparation method of the single-crystal lithium manganate material of claim 1, characterized in that in the step C), all temperature rise rates are 1-8 ℃/min, the time of the first-stage roasting is 2-6 h, the time of the second-stage roasting is 4-9 h, and the time of the third-stage roasting is 8-16 h; and (3) crushing by adopting roller crushing or ball milling crushing, wherein the crushing time is 10-60 min, and sieving by using a 100-300-mesh sieve.
6. The preparation method of the single-crystal lithium manganate material of claim 1, characterized in that in the step D), all the temperature rise rates are 1-6 ℃/min, the time of the first-stage roasting is 2-5 h, the time of the second-stage roasting is 4-8 h, and the time of the third-stage roasting is 8-14 h; and (3) crushing by adopting roller crushing or ball milling crushing, wherein the crushing time is 10-60 min, and sieving by using a 100-300-mesh sieve.
7. The single-crystal lithium manganate material prepared by the preparation method of any one of claims 1 to 6.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114084908A (en) * | 2021-10-28 | 2022-02-25 | 江苏大学 | Chamfered octahedral monocrystal lithium manganate, electrode for extracting lithium from salt lake and preparation method |
| CN114678525A (en) * | 2022-04-12 | 2022-06-28 | 浙江极氪智能科技有限公司 | Ternary cathode material and preparation method thereof, and lithium ion battery |
| CN116247197A (en) * | 2023-02-15 | 2023-06-09 | 安徽博石高科新材料股份有限公司 | Spherical high-voltage lithium nickel manganese oxide positive electrode material, preparation method thereof and lithium ion battery |
| CN116425204A (en) * | 2023-04-28 | 2023-07-14 | 巴斯夫杉杉电池材料有限公司 | Spinel type lithium manganate, preparation method thereof and lithium ion battery |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004292264A (en) * | 2003-03-27 | 2004-10-21 | Toda Kogyo Corp | Trimanganese tetroxide particle, its production method, nonaqueous electrolyte secondary battery, positive electrode active substance therefor and its preparation method |
| CN101841018A (en) * | 2010-06-22 | 2010-09-22 | 湖南杉杉新材料有限公司 | Single crystal lithium manganese oxide for lithium ion battery and preparation method thereof |
| KR20110111057A (en) * | 2010-04-02 | 2011-10-10 | 주식회사 이엔드디 | Crystalline trimanganese tetraoxide, lithium manganese oxide for lithium secondary battery and manufacturing method |
| CN102336441A (en) * | 2011-06-29 | 2012-02-01 | 金瑞新材料科技股份有限公司 | Method for preparing lithium manganate used as lithium ion battery anode material by using trimanganese tetroxide |
| US20130108542A1 (en) * | 2011-10-28 | 2013-05-02 | Dongguk University Industry-Academic Cooperation Foundation | Method for MN3O4 nanoparticles by solid-state decomposition of exfoliated MNO2 nanosheet |
| CN107482213A (en) * | 2017-07-27 | 2017-12-15 | 湖南长远锂科有限公司 | A kind of nickel-aluminum co-doped trimanganese tetraoxide and preparation method thereof |
| CN110336016A (en) * | 2019-07-16 | 2019-10-15 | 中钢集团南京新材料研究院有限公司 | A kind of preparation method for mixing aluminium LiMn2O4 |
| CN110904495A (en) * | 2019-12-02 | 2020-03-24 | 中南大学 | Preparation method of monocrystal polyhedral lithium manganate positive electrode material |
| CN112390292A (en) * | 2020-11-13 | 2021-02-23 | 贵州大龙汇成新材料有限公司 | Bulk phase doped manganous-manganic oxide and preparation method and application thereof |
-
2021
- 2021-04-02 CN CN202110362475.5A patent/CN112993241B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004292264A (en) * | 2003-03-27 | 2004-10-21 | Toda Kogyo Corp | Trimanganese tetroxide particle, its production method, nonaqueous electrolyte secondary battery, positive electrode active substance therefor and its preparation method |
| KR20110111057A (en) * | 2010-04-02 | 2011-10-10 | 주식회사 이엔드디 | Crystalline trimanganese tetraoxide, lithium manganese oxide for lithium secondary battery and manufacturing method |
| CN101841018A (en) * | 2010-06-22 | 2010-09-22 | 湖南杉杉新材料有限公司 | Single crystal lithium manganese oxide for lithium ion battery and preparation method thereof |
| CN102336441A (en) * | 2011-06-29 | 2012-02-01 | 金瑞新材料科技股份有限公司 | Method for preparing lithium manganate used as lithium ion battery anode material by using trimanganese tetroxide |
| US20130108542A1 (en) * | 2011-10-28 | 2013-05-02 | Dongguk University Industry-Academic Cooperation Foundation | Method for MN3O4 nanoparticles by solid-state decomposition of exfoliated MNO2 nanosheet |
| CN107482213A (en) * | 2017-07-27 | 2017-12-15 | 湖南长远锂科有限公司 | A kind of nickel-aluminum co-doped trimanganese tetraoxide and preparation method thereof |
| CN110336016A (en) * | 2019-07-16 | 2019-10-15 | 中钢集团南京新材料研究院有限公司 | A kind of preparation method for mixing aluminium LiMn2O4 |
| CN110904495A (en) * | 2019-12-02 | 2020-03-24 | 中南大学 | Preparation method of monocrystal polyhedral lithium manganate positive electrode material |
| CN112390292A (en) * | 2020-11-13 | 2021-02-23 | 贵州大龙汇成新材料有限公司 | Bulk phase doped manganous-manganic oxide and preparation method and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| JIANBING JIANG等: "Syntheses of spherical LiMn2O4 with Mn3O4 and its electrochemistry performance", 《JOURNAL OF ALLOYS AND COMPOUNDS》 * |
| 赵陈浩等: "钴掺杂Mn3O4作为模板制备锂离子电池正极LiMn2O4", 《井冈山大学学报(自然科学版)》 * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114084908A (en) * | 2021-10-28 | 2022-02-25 | 江苏大学 | Chamfered octahedral monocrystal lithium manganate, electrode for extracting lithium from salt lake and preparation method |
| CN114084908B (en) * | 2021-10-28 | 2023-12-15 | 江苏大学 | Shaved octahedral single crystal lithium manganate, electrode for lithium extraction from salt lakes and preparation method |
| CN114678525A (en) * | 2022-04-12 | 2022-06-28 | 浙江极氪智能科技有限公司 | Ternary cathode material and preparation method thereof, and lithium ion battery |
| CN114678525B (en) * | 2022-04-12 | 2023-08-18 | 浙江极氪智能科技有限公司 | Ternary cathode material and preparation method thereof, lithium ion battery |
| CN116247197A (en) * | 2023-02-15 | 2023-06-09 | 安徽博石高科新材料股份有限公司 | Spherical high-voltage lithium nickel manganese oxide positive electrode material, preparation method thereof and lithium ion battery |
| CN116247197B (en) * | 2023-02-15 | 2023-09-26 | 安徽博石高科新材料股份有限公司 | Spherical high-voltage lithium nickel manganese oxide positive electrode material, preparation method thereof and lithium ion battery |
| CN116425204A (en) * | 2023-04-28 | 2023-07-14 | 巴斯夫杉杉电池材料有限公司 | Spinel type lithium manganate, preparation method thereof and lithium ion battery |
| CN116425204B (en) * | 2023-04-28 | 2024-03-22 | 巴斯夫杉杉电池材料有限公司 | Spinel type lithium manganate, preparation method thereof and lithium ion battery |
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