CN102088085B - Lithium ion battery positive material and preparation method thereof - Google Patents
Lithium ion battery positive material and preparation method thereof Download PDFInfo
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- CN102088085B CN102088085B CN2010106098876A CN201010609887A CN102088085B CN 102088085 B CN102088085 B CN 102088085B CN 2010106098876 A CN2010106098876 A CN 2010106098876A CN 201010609887 A CN201010609887 A CN 201010609887A CN 102088085 B CN102088085 B CN 102088085B
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000000463 material Substances 0.000 title abstract description 43
- 238000000034 method Methods 0.000 claims abstract description 22
- 238000001035 drying Methods 0.000 claims abstract description 15
- 239000002002 slurry Substances 0.000 claims abstract description 15
- 238000005245 sintering Methods 0.000 claims abstract description 6
- 239000000178 monomer Substances 0.000 claims description 29
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 18
- 229910052760 oxygen Inorganic materials 0.000 claims description 17
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 15
- 239000010405 anode material Substances 0.000 claims description 14
- 239000000499 gel Substances 0.000 claims description 14
- -1 rare earth ion Chemical class 0.000 claims description 13
- 238000000498 ball milling Methods 0.000 claims description 11
- 238000005303 weighing Methods 0.000 claims description 11
- 239000003054 catalyst Substances 0.000 claims description 10
- 239000003431 cross linking reagent Substances 0.000 claims description 10
- 239000002270 dispersing agent Substances 0.000 claims description 10
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 9
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 7
- 239000001301 oxygen Substances 0.000 claims description 7
- 229920001223 polyethylene glycol Polymers 0.000 claims description 7
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 5
- 239000002202 Polyethylene glycol Substances 0.000 claims description 5
- GNWBLLYJQXKPIP-ZOGIJGBBSA-N (1s,3as,3bs,5ar,9ar,9bs,11as)-n,n-diethyl-6,9a,11a-trimethyl-7-oxo-2,3,3a,3b,4,5,5a,8,9,9b,10,11-dodecahydro-1h-indeno[5,4-f]quinoline-1-carboxamide Chemical compound CN([C@@H]1CC2)C(=O)CC[C@]1(C)[C@@H]1[C@@H]2[C@@H]2CC[C@H](C(=O)N(CC)CC)[C@@]2(C)CC1 GNWBLLYJQXKPIP-ZOGIJGBBSA-N 0.000 claims description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 4
- 229910052692 Dysprosium Inorganic materials 0.000 claims description 4
- 229910052691 Erbium Inorganic materials 0.000 claims description 4
- 229910052693 Europium Inorganic materials 0.000 claims description 4
- 229910052688 Gadolinium Inorganic materials 0.000 claims description 4
- 108010010803 Gelatin Proteins 0.000 claims description 4
- 229910052689 Holmium Inorganic materials 0.000 claims description 4
- 229910052765 Lutetium Inorganic materials 0.000 claims description 4
- 229910052779 Neodymium Inorganic materials 0.000 claims description 4
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 4
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 4
- 229910052772 Samarium Inorganic materials 0.000 claims description 4
- 229920002125 Sokalan® Polymers 0.000 claims description 4
- 229910052771 Terbium Inorganic materials 0.000 claims description 4
- 229910052775 Thulium Inorganic materials 0.000 claims description 4
- 229910052769 Ytterbium Inorganic materials 0.000 claims description 4
- 239000008273 gelatin Substances 0.000 claims description 4
- 229920000159 gelatin Polymers 0.000 claims description 4
- 235000019322 gelatine Nutrition 0.000 claims description 4
- 235000011852 gelatine desserts Nutrition 0.000 claims description 4
- 229910052746 lanthanum Inorganic materials 0.000 claims description 4
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 claims description 4
- 239000004584 polyacrylic acid Substances 0.000 claims description 4
- 229920000193 polymethacrylate Polymers 0.000 claims description 4
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 4
- 229910052706 scandium Inorganic materials 0.000 claims description 4
- YWYZEGXAUVWDED-UHFFFAOYSA-N triammonium citrate Chemical compound [NH4+].[NH4+].[NH4+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O YWYZEGXAUVWDED-UHFFFAOYSA-N 0.000 claims description 4
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 claims description 3
- DIHKMUNUGQVFES-UHFFFAOYSA-N n,n,n',n'-tetraethylethane-1,2-diamine Chemical group CCN(CC)CCN(CC)CC DIHKMUNUGQVFES-UHFFFAOYSA-N 0.000 claims description 3
- 150000002910 rare earth metals Chemical class 0.000 claims description 3
- 238000012545 processing Methods 0.000 claims description 2
- 238000005516 engineering process Methods 0.000 abstract description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 34
- 239000011572 manganese Substances 0.000 description 32
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 description 14
- 239000002245 particle Substances 0.000 description 14
- 238000002156 mixing Methods 0.000 description 10
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical group [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 9
- 230000014759 maintenance of location Effects 0.000 description 8
- 239000012071 phase Substances 0.000 description 8
- 229910001220 stainless steel Inorganic materials 0.000 description 8
- 239000010935 stainless steel Substances 0.000 description 8
- 235000015110 jellies Nutrition 0.000 description 7
- 239000008274 jelly Substances 0.000 description 7
- 239000000843 powder Substances 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 6
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 229910052744 lithium Inorganic materials 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 229910015645 LiMn Inorganic materials 0.000 description 4
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 4
- 229910014689 LiMnO Inorganic materials 0.000 description 3
- 229910013553 LiNO Inorganic materials 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 229910052748 manganese Inorganic materials 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- 229920002635 polyurethane Polymers 0.000 description 3
- 239000004814 polyurethane Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000010189 synthetic method Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 229910015118 LiMO Inorganic materials 0.000 description 2
- 229910052773 Promethium Inorganic materials 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 238000000975 co-precipitation Methods 0.000 description 2
- 229910052593 corundum Inorganic materials 0.000 description 2
- 239000010431 corundum Substances 0.000 description 2
- KBQHZAAAGSGFKK-UHFFFAOYSA-N dysprosium atom Chemical compound [Dy] KBQHZAAAGSGFKK-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- UYAHIZSMUZPPFV-UHFFFAOYSA-N erbium Chemical compound [Er] UYAHIZSMUZPPFV-UHFFFAOYSA-N 0.000 description 2
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- KJZYNXUDTRRSPN-UHFFFAOYSA-N holmium atom Chemical compound [Ho] KJZYNXUDTRRSPN-UHFFFAOYSA-N 0.000 description 2
- 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 2
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 2
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 description 2
- OHSVLFRHMCKCQY-UHFFFAOYSA-N lutetium atom Chemical compound [Lu] OHSVLFRHMCKCQY-UHFFFAOYSA-N 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 description 2
- VQMWBBYLQSCNPO-UHFFFAOYSA-N promethium atom Chemical compound [Pm] VQMWBBYLQSCNPO-UHFFFAOYSA-N 0.000 description 2
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 description 2
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000003746 solid phase reaction Methods 0.000 description 2
- GZCRRIHWUXGPOV-UHFFFAOYSA-N terbium atom Chemical compound [Tb] GZCRRIHWUXGPOV-UHFFFAOYSA-N 0.000 description 2
- FRNOGLGSGLTDKL-UHFFFAOYSA-N thulium atom Chemical compound [Tm] FRNOGLGSGLTDKL-UHFFFAOYSA-N 0.000 description 2
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 description 2
- BCNBMSZKALBQEF-UHFFFAOYSA-N 1,3-dimethylpyrrolidin-2-one Chemical compound CC1CCN(C)C1=O BCNBMSZKALBQEF-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 206010013786 Dry skin Diseases 0.000 description 1
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- 101100513612 Microdochium nivale MnCO gene Proteins 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- DQMUQFUTDWISTM-UHFFFAOYSA-N O.[O-2].[Fe+2].[Fe+2].[O-2] Chemical compound O.[O-2].[Fe+2].[Fe+2].[O-2] DQMUQFUTDWISTM-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000005030 aluminium foil Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- VEPSWGHMGZQCIN-UHFFFAOYSA-H ferric oxalate Chemical compound [Fe+3].[Fe+3].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O VEPSWGHMGZQCIN-UHFFFAOYSA-H 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 235000014413 iron hydroxide Nutrition 0.000 description 1
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 1
- YPJCVYYCWSFGRM-UHFFFAOYSA-H iron(3+);tricarbonate Chemical compound [Fe+3].[Fe+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O YPJCVYYCWSFGRM-UHFFFAOYSA-H 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 description 1
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical group [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- 229910002102 lithium manganese oxide Inorganic materials 0.000 description 1
- VLXXBCXTUVRROQ-UHFFFAOYSA-N lithium;oxido-oxo-(oxomanganiooxy)manganese Chemical compound [Li+].[O-][Mn](=O)O[Mn]=O VLXXBCXTUVRROQ-UHFFFAOYSA-N 0.000 description 1
- 229940071125 manganese acetate Drugs 0.000 description 1
- 235000006748 manganese carbonate Nutrition 0.000 description 1
- 239000011656 manganese carbonate Substances 0.000 description 1
- 229940093474 manganese carbonate Drugs 0.000 description 1
- IPJKJLXEVHOKSE-UHFFFAOYSA-L manganese dihydroxide Chemical compound [OH-].[OH-].[Mn+2] IPJKJLXEVHOKSE-UHFFFAOYSA-L 0.000 description 1
- 229940099594 manganese dioxide Drugs 0.000 description 1
- 229940099596 manganese sulfate Drugs 0.000 description 1
- 235000007079 manganese sulphate Nutrition 0.000 description 1
- 239000011702 manganese sulphate Substances 0.000 description 1
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 1
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 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
- RGVLTEMOWXGQOS-UHFFFAOYSA-L manganese(2+);oxalate Chemical compound [Mn+2].[O-]C(=O)C([O-])=O RGVLTEMOWXGQOS-UHFFFAOYSA-L 0.000 description 1
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 description 1
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 1
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical group [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000003836 solid-state method Methods 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The purpose of the invention is to provide a lithium ion battery positive material of high specific capacity, good multiplying power performance, good cycle performance, compatible high and low temperature performance and low technology cost, and a preparation method of the lithium ion battery positive material of high specific capacity. The molecule structural formula of the lithium ion battery positive material is LiaMnbFecMdO2, and the method comprises the preparing steps: (1) preparing slurry; (2) preparing gel; (3) drying the gel, and sintering. Compared with the prior art, the invention has significant advantages of high specific capacity, good multiplying power performance, good cycle performance, compatible high and low temperature performance(from -20 DEG C to +50 DEG C), simple process and low process cost.
Description
Technical field:
The present invention relates to a kind of lithium ion battery material, particularly a kind of anode material for lithium-ion batteries and preparation method thereof.
Background technology:
The actual discharge capacity of present commercial anode material for lithium-ion batteries is lower, can not satisfy the demand of electric automobile and hybrid power electric car.Lithium manganese oxide anode material mainly is divided into spinel-type LiMn because of aboundresources, the low favor that enjoys the researcher of cost
2O
4, stratiform LiMnO
2With stratiform Li
2MnO
3Spinel-type LiMn
2O
4Theoretical discharge capacity 148mAh/g, the actual discharge capacity has only about 120mAh/g, simultaneously because shortcomings such as cyclical stability difference and high temperature capacity attenuation have restricted its development to a certain extent.The LiMnO of layer structure
2Theoretical discharge capacity is 285mAh/g, and actual capacity can reach 190mAh/g, but since this material be difficult to synthesize, and in cyclic process because of Mn
3+The Jahn-Teller distortion taking place material structure is changed to spinel-type, cause the battery capacity decay, makes stratiform LiMnO
2Research and use and once once to stagnate.Stratiform Li
2MnO
3(also can be write as rich lithium material Li[Li
1/3Mn
2/3] O
2) in Mn be+4 valencys, can not continue oxidized, Li
2MnO
3Material once was considered to the non-electrochemical activity, and+the Jahn-Teller distortion do not take place in the Mn of 4 valencys, so the layer structure of this material is highly stable.In recent years, the researcher proposes with Li
2MnO
3Be the complex layered positive electrode xLi of the rich lithium of stable phase
2MnO
3(1-x) LiMO
2(wherein M=Mn, Ni, Co, Fe etc.) (as document J.Mater.Chem., 2007,17,3112; Adv.Mater., 2001,13,943; J.Electrochem.Soc., 2002,149, A778; J.Power Sources, 2003,124,533; J.Electrochem.Soc., 2005,152, A1879; J.Power Sources, 2005,146,598; J.Power Sources, 2010,195,834; US2002/0064498A1), it has Stability Analysis of Structures, advantage that specific capacity is high, and the manganese aboundresources, and cheap and environmental friendliness becomes the most potential power lithium-ion battery positive electrode.
But in the application of reality, because material is synthetic difficult, conductivity is lower, causes the cycle life of material poor, and capacity attenuation is fast, and high rate performance is bad, and first charge-discharge efficiency is lower, poor performance at low temperatures.Therefore, urgently seek the complex layered xLi of the rich lithium of a kind of preparation and modification
2MnO
3(1-x) LiMO
2The new method of compound make it have reversible capacity, cycle performance and rate charge-discharge performance preferably, and synthetic manufacturing process is simple, and with low cost, batch good stability is to satisfy the electrokinetic cell performance requirement.
At present, the preparation method that complex layered positive electrode is commonly used mainly contains coprecipitation (as US2009/0297947A1, US2002/0064498A1, CN100426569C, Journal of Power Sources.2007,174 (2): 565), sol-gel process is (as Journal of Power Sources.2002,112 (2): 634; J.Phys.Chem.C.2009,113:17936; Journal of Power Sources.2010,195 (21): 7391), high temperature solid-state method is (as Journal of The Electrochemical Society, 2005,152 (1): A171; Solid State Ionics, 1999,117:257; Journal of Power Sources, 2006,162:629), firing method (as Solid State Ionics.2005,176 (11-12): 1035; Journal of Power Sources.2004,129 (2): 288; Journal of Power Sources.2009,189 (1): 248) etc.In these synthetic methods, all there are pluses and minuses separately, simple such as solid phase reaction process, but energy consumption is big, and raw material mixes inhomogeneous; Other soft chemical method such as coprecipitation, sol-gal process can make the mixing of raw material reach the atom level level, but course of reaction wants strictness to control conditions such as the pH value of solution, concentration, reaction temperature, and technology is very complicated.Firing method technology is simple relatively, also can guarantee the even mixing of raw material, but owing to can emit a large amount of gases in the course of reaction, product is collected difficulty.In sum, present soft chemical method all is not suitable for suitability for industrialized production.
Summary of the invention:
The purpose of this invention is to provide a kind of specific capacity height, a kind of anode material for lithium-ion batteries that high rate performance and good cycle and high temperature performance compatibility and technology cost are low and preparation method thereof.Technical scheme of the present invention is that a kind of anode material for lithium-ion batteries is characterized in that: the molecular structural formula of described anode material for lithium-ion batteries is Li
aMn
bFe
cM
dO
2, M is one or more of rare earth Sc, La, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu in the formula, and 1≤a≤1.5,0＜b≤1,0＜c≤1,0＜d≤0.1, and a+b+c+d=2.A kind of method for preparing anode material for lithium-ion batteries, it is characterized in that following steps are arranged: (1) is according to 1～1.5: 0～1: 0～1: 0～0.1 ratio takes by weighing in Li source, Mn source, Fe source, the rare earth ion doped source adding ball grinder, add organic monomer and dispersant ball milling again and be mixed into uniform slurry in 12-48 hour, described organic monomer is a kind of in acrylamide, Methacrylamide, DMAA, the acrylic acid, and wherein the addition of monomer is the 2wt～20wt% of Li source, Mn source, Fe source and rare earth ion doped source gross mass; Described dispersant is one or more in polyethylene glycol, ethanol, water, polyacrylic acid, ammonium polymethacrylate, ammonium citrate, the polyvinyl alcohol, and the dispersant addition is the 1wt～20wt% of Li source, Mn source, Fe source and rare earth ion doped source gross mass; (2) add crosslinking agent, initator, catalyst in the slurry of above-mentioned steps (1), the preparation gel, described crosslinking agent is N, a kind of in N ' methylene-bisacrylamide, the gelatin, wherein the addition of crosslinking agent is the 2wt%～10wt% of monomer mass; Described initator is a kind of in ammonium persulfate, the hydrogen peroxide, and the addition of initator is the 1wt%～10wt% of organic monomer quality; Described catalyst is tetraethylethylenediamine, and the amount of catalyst is the 1wt%～5wt% of the amount of monomer; (3) gel with above-mentioned processing step (2) places drying box, carries out drying under 60 ℃～150 ℃, obtains xerogel; (4) xerogel with step (3) places microwave oven, low fire, moderate heat or high fire were handled 1～60 minute, place Muffle furnace again, in oxygen enrichment or air atmosphere in 500 ℃～900 ℃ sintering 2-12 hour, can obtain anode material for lithium-ion batteries of the present invention.The present invention has the specific capacity height compared with the prior art, high rate performance and good cycle, and high temperature performance compatibility (20 ℃～+ 50 ℃) and technology simply reach the low remarkable advantage of cost.
Embodiment:
Embodiment of the present invention are:
Consisting of of positive electrode provided by the invention: Li
aMn
bFe
cM
dO
2, wherein M is one or more of rare earth element scandium Sc, lanthanum La, praseodymium Pr, neodymium Nd, promethium Pm, samarium Sm, europium Eu, gadolinium Gd, terbium Tb, dysprosium Dy, holmium Ho, erbium Er, thulium Tm, ytterbium Yb, lutetium Lu, and 1≤a≤1.5,0＜b≤1,0＜c≤1,0＜d≤0.1, and a+b+c+d=2.
Positive electrode of the present invention has the stratiform rock salt structure.
Preparation method of the present invention may further comprise the steps:
(1) according to 1～1.5: 0～1: 0～1: 0～0.1 ratio takes by weighing in Li source, Mn source, Fe source, the rare earth ion doped source adding ball grinder, adds organic monomer and dispersant again.Wherein organic monomer and dispersant addition are respectively 2～20wt% and the 1～20wt% of Li source, Mn source, Fe source, rare earth ion doped source quality;
(2) above-mentioned material ball milling in ball grinder was mixed into uniform slurry in 12～48 hours;
(3) in slurry, add crosslinking agent, initator, catalyst, the preparation gel.Wherein the addition of crosslinking agent is the 2wt%～10wt% of monomer mass, and the addition of initator is the 1wt%～10wt% of monomer mass, and the addition of catalyst is the 1wt%～5wt% of the quality of monomer;
(4) gel places drying box after 60 ℃～150 ℃ dryings, place the low fire of microwave oven, moderate heat or high fire to handle 1～60 minute, obtain fluffy presoma, 500～900 ℃ of sintering 2～12 hours in oxygen enrichment or air atmosphere can obtain target product again.
Lithium of the present invention source is lithium carbonate, lithium hydroxide, lithium nitrate, lithium acetate, lithium chloride; Described manganese source is manganese carbonate, manganese acetate, manganese dioxide, manganese nitrate, manganese sulfate, manganese oxalate or manganous hydroxide; Described source of iron is ferric oxalate, ferric carbonate, ferric sulfate, di-iron trioxide, ferric nitrate or iron hydroxide.
Ion doping of the present invention source can be among rare earth element scandium Sc, lanthanum La, praseodymium Pr, neodymium Nd, promethium Pm, samarium Sm, europium Eu, gadolinium Gd, terbium Tb, dysprosium Dy, holmium Ho, erbium Er, thulium Tm, ytterbium Yb, the lutetium Lu one or more, and its raw material can be one or more in oxide, hydroxide, chloride, nitrate, carbonate, the sulfate.
Organic monomer of the present invention is a kind of in acrylamide, Methacrylamide, DMAA, the acrylic acid.Wherein the addition of monomer is the 2wt～20wt% of Li source, Mn source, Fe source, rare earth ion doped source gross mass.
Crosslinking agent of the present invention is N, a kind of in N ' methylene-bisacrylamide, the gelatin.Wherein the addition of crosslinking agent is the 2wt%～10wt% of monomer mass.
Dispersant of the present invention is one or more in polyethylene glycol, ethanol, water, polyacrylic acid, ammonium polymethacrylate, ammonium citrate, the polyvinyl alcohol.The addition of dispersant is the 1wt～20wt% of Li source, Mn source, Fe source, rare earth ion doped source gross mass
Initator of the present invention is a kind of in ammonium persulfate, the hydrogen peroxide.The addition of initator is the 1wt%～10wt% of monomer mass.
Catalyst of the present invention is tetraethylethylenediamine.The addition of catalyst is the 1wt%～5wt% of monomer mass.
Ball mill container of the present invention is a kind of in agate jar, polyurethane ball grinder, stainless steel jar mill, the corundum ball grinder.Be situated between a kind of in alumina balls, zirconia ball, agate ball, the stainless steel ball of mill.The ball milling time is 12～48 hours.
Synthetic method Drying of gels temperature of the present invention is 60 ℃～150 ℃, and the microwave treatment conditions of xerogel is low fire, moderate heat or high fiery 1～60 minute, and the sintering temperature in the Muffle furnace is 500 ℃～900 ℃, and temperature retention time is 2～12 hours.
Sintering atmosphere of the present invention is air or oxygen.
Usefulness of the present invention is:
(1) material is formed manganese, the iron based on cheapness, and is in addition rare earth doped on a small quantity, do not contain cobalt and nickel, so cost is very low, and environmental friendliness.
(2) Li of gained of the present invention
aMn
bFe
cM
dO
2Material belongs to the stratiform rock salt structure, and material granule is agglomerated into submicron order sphere or class spherical structure by nano particle, has both possessed the good electrochemical properties of nano material, has the good electrode processability of submicron order material again.
(3) the specific discharge capacity height of material, high rate performance and good cycling stability, the high temperature performance compatibility can satisfy the performance requirement of power lithium-ion battery.
(4) synthetic method of material combines the advantage of solid phase reaction and soft chemical method, the macromolecule that adopts in-situ polymerization to form is the template agent, utilize its formed macromolecule network to the complexing anchorage effect of metal ion, make the mixing of raw material full and uniform, the nucleation mode of limiting material simultaneously, thus reach the purpose of grain-size.The gas that produces in the calcination process is conducive to make material granule to form loose structure, and the existence of a large amount of pore structures is more conducive to the infiltration of electrolyte, can fundamentally improve the electrical property of material.
Embodiments of the invention:
Embodiment 1:
By Mn (CH
3COO)
24H
2O, Fe
2O
3, LiCO
3And Sm
2(CO
3)
3, Tb
2(CO
3)
3, the preparation Li
1.1Mn
0.58Fe
0.28Sm
0.01Tb
0.01O
2
Put into stainless steel jar mill (stainless steel ball) according to the above-mentioned five kinds of materials of product stoichiometric proportion weighing, the acrylic acid that adds material gross mass 2wt% again, the polyvinyl alcohol of 1wt% and appropriate amount of deionized water, mixing and ball milling 12 hours, take out slurry, the N-N-methylene diacrylamine (MBAM) that adds monomer mass 2wt% while stirring, the aqueous hydrogen peroxide solution of 1wt%, 1wt% tetramethylethylenediamine (TEMED), continue to be stirred to generation jelly shape gel, after being put in 60 ℃ of drying boxes oven dry, the high fire of microwave was handled 1 minute, 600 ℃ of constant temperature 2 hours in the Muffle furnace under the oxygen atmosphere, cool to room temperature with the furnace, get Li
1.1Mn
0.58Fe
0.28Sm
0.01Tb
0.01O
2Black powder.Products therefrom is rock salt structure, has higher phase purity.Particle is regular sphere, and particle diameter is about 400nm.
Take by weighing the Li that 0.85g prepares as stated above
1.1Mn
0.58Fe
0.28Sm
0.01Tb
0.01O
2, adding 0.1g acetylene black, 0.05g is dissolved in the polyvinylidene fluoride adhesive of N-N ' dimethyl pyrrolidone, mix the formation slurry, be evenly coated on the aluminium foil, in the argon gas atmosphere glove box, be to electrode with metal lithium sheet, celgard2400 is barrier film, the LiPF of 1mol/L
6-EC+DEC (1: 1) is electrolyte, is assembled into CR2016 type button cell, and tester is LAND CT2001 type battery test system.In the 2.0V-4.9V voltage range, battery is carried out the charge and discharge cycles experiment.Battery is at normal temperature, 0.5C, 5C, and under the discharge-rate of 10C, specific capacity is respectively 260mAh/g
-1, 214mAh/g
-1, 180mAh/g
-1Discharge capacity is 207mAh/g in the time of-20 ℃
-1, discharge capacity is 299mAh/g when being 80%, 50 ℃ of normal temperature discharge capacity
-1, be 115% of normal temperature discharge capacity.The capability retention of material is all between 81%～99% under different temperatures, the different multiplying.
Embodiment 2:
By Mn (NO
3)
24H
2O, Fe (NO
3)
29H
2O, NdCl
3, LiOHH
2O prepares Li
1.2Mn
0.5Fe
0.2Nd
0.1O
2
Put into agate jar (agate ball) by the above-mentioned four kinds of materials of product stoichiometric proportion weighing, the acrylamide (AM) that adds material gross mass 8wt% again, the polyethylene glycol of 5wt% (PEG) and appropriate amount of deionized water, mixing and ball milling 48 hours, take out slurry, the N-N-methylene diacrylamine (MBAM) that adds monomer mass 4wt% while stirring, the ammonium persulfate solution of 2wt%, 2wt% tetramethylethylenediamine (TEMED), continue to be stirred to generation jelly shape gel, after being put in 80 ℃ of drying boxes oven dry, the microwave moderate heat was handled 40 minutes, 700 ℃ of constant temperature 12 hours in the Muffle furnace under the air atmosphere, cool to room temperature with the furnace, get Li
1.2Mn
0.5Fe
0.2Nd
0.1O
2Black powder.Products therefrom is the rock salt structure, has higher phase purity.Particle is porous class sphere, and particle diameter is about 600nm.Prepare battery by embodiment 1 method, test its charge-discharge performance.Battery at normal temperatures, the specific capacity under 0.5C, 5C and the 10C discharge-rate is respectively 232mAh/g
-1, 201mAh/g
-1And 173mAh/g
-1Discharge capacity is 183mAh/g in the time of-20 ℃
-1, discharge capacity is 255mAh/g when being 79%, 50 ℃ of normal temperature discharge capacity
-1, be 110% of normal temperature discharge capacity; The capability retention of material is between 80%～96% under different temperatures, the different multiplying.
Embodiment 3:
By MnO
2, Fe
2(C
2O
4)
35H
2O, La (OH)
3, CH
3COOLi2H
2O prepares LiMn
0.6Fe
0.39La
0.01O
2Put into polyurethane ball grinder (zirconia ball) by the above-mentioned four kinds of materials of product stoichiometric proportion weighing, the Methacrylamide that adds material gross mass 15wt% again, the ethanol of 10wt%, mixing and ball milling 36 hours, take out slurry, the N-N-methylene diacrylamine (MBAM) that adds monomer mass 8wt% while stirring, the ammonium persulfate solution of 7wt%, the tetramethylethylenediamine of 4wt% (TEMED), continue to be stirred to generation jelly shape gel, after being put in 100 ℃ of drying boxes oven dry, the low fire of microwave was handled 60 minutes, 500 ℃ of constant temperature 5 hours in the Muffle furnace under the oxygen atmosphere, cool to room temperature with the furnace, get LiMn
0.6Fe
0.39La
0.01O
2Black powder.Products therefrom is the rock salt structure, has higher phase purity.Particle is the class sphere, and particle diameter is about 300nm.Prepare battery by embodiment 1 method, test its charge-discharge performance.Battery at normal temperatures, the specific capacity under 0.5C, 5C and the 10C discharge-rate is respectively 236mAh/g
-1, 200mAh/g
-1And 180mAh/g
-1Discharge capacity is 189mAh/g in the time of-20 ℃
-1, discharge capacity is 260mAh/g when being 80%, 50 ℃ of normal temperature discharge capacity
-1, be 110% of normal temperature discharge capacity; The capability retention of material is between 80%～95% under different temperatures, the different multiplying.
Embodiment 4:
By MnCO
3H
2O, Fe (OH)
3, Gd (NO
3)
26H
2O, Yb (NO
3)
26H2O, Er (NO
3)
26H
2O, Eu (NO
3)
2And LiNO
3Preparation Li
1.3Mn
0.46Fe
0.16Gd
0.01Yb
0.01Er
0.01Eu
0.01O
2Put into stainless steel jar mill (stainless steel ball) by the above-mentioned seven kinds of materials of product stoichiometric proportion weighing, the acrylic acid that adds material gross mass 20wt% again, the ammonium citrate of 15wt%, mixing and ball milling 24 hours, take out slurry, the N-N-methylene diacrylamine (MBAM) that adds monomer mass 10wt% while stirring, the ammonium persulfate solution of 10wt%, the tetramethylethylenediamine of 5wt% (TEMED), continue to be stirred to generation jelly shape gel, after being put in 120 ℃ of drying boxes oven dry, the high fire of microwave was handled 20 minutes, 900 ℃ of constant temperature 6 hours in the Muffle furnace under the air atmosphere, cool to room temperature with the furnace, get Li
1.3Mn
0.46Fe
0.16Gd
0.01Yb
0.01Er
0.01Eu
0.01O
2Black powder.Products therefrom is the rock salt structure, has higher phase purity.Particle is porous spherical, and particle diameter is about 700nm.Prepare battery by embodiment 1 method, test its charge-discharge performance.Battery at normal temperatures, the specific capacity under 0.5C, 5C and the 10C discharge-rate is respectively 210mAh/g
-1, 191mAh/g
-1And 167mAh/g
-1Discharge capacity is 163mAh/g in the time of-20 ℃
-1, discharge capacity is 225mAh/g when being 78%, 50 ℃ of normal temperature discharge capacity
-1, be 107% of normal temperature discharge capacity; The capability retention of material is between 85%～95% under different temperatures, the different multiplying.
Embodiment 5:
By MnSO
4H
2O, Fe
2(SO
4)
39H
2O, Eu
2O
3, Dy
2O
3, Lu
2O
3, Ho
2O
3, Tm
2O
3, and LiNO
3Preparation Li
1.4Mn
0.45Fe
0.1Eu
0.01Dy
0.01Lu
0.01Ho
0.01Tm
0.01O
2Put into stainless steel jar mill (stainless steel ball) by the above-mentioned eight kinds of materials of product stoichiometric proportion weighing, the acrylamide (AM) that adds material gross mass 10wt% again, the ammonium polymethacrylate of 20wt% and appropriate amount of deionized water, mixing and ball milling 24 hours, take out slurry, the N-N-methylene diacrylamine (MBAM) that adds monomer mass 6wt% while stirring, the ammonium persulfate solution of 5wt%, 3wt% tetramethylethylenediamine (TEMED), continue to be stirred to generation jelly shape gel, after being put in 150 ℃ of drying boxes oven dry, the low fire of microwave was handled 50 minutes, 800 ℃ of constant temperature 8 hours in the Muffle furnace under the air atmosphere, cool to room temperature with the furnace, get Li
1.4Mn
0.45Fe
0.1Eu
0.01Dy
0.01Lu
0.01Ho
0.01Tm
0.01O
2Black powder.Products therefrom is the rock salt structure, has higher phase purity.Particle is porous class sphere, and particle diameter is about 700nm.Prepare battery by embodiment 1 method, test its charge-discharge performance.Battery at normal temperatures, the specific capacity under 0.5C, 5C and the 10C discharge-rate is respectively 277mAh/g
-1, 254mAh/g
-1And 221mAh/g
-1Discharge capacity is 227mAh/g in the time of-20 ℃
-1, discharge capacity is 298mAh/g when being 82%, 50 ℃ of normal temperature discharge capacity
-1, be 107% of normal temperature discharge capacity; The capability retention of material is between 80%～95% under different temperatures, the different multiplying.
Embodiment 6:
By Mn (CH
3COO)
24H
2O, Fe
2(CO
3)
3, Pr
2(SO
4)
3, Pm
2(SO
4)
3Prepare Li with LiCl
1.5Mn
0.32Fe
0.1Pr
0.03Pm
0.05O
2Put into polyurethane ball grinder (zirconia ball) by the above-mentioned five kinds of materials of product stoichiometric proportion weighing, the DMAA that adds material gross mass 8wt% again, the polyacrylic acid of 5wt% and appropriate amount of deionized water, mixing and ball milling 48 hours, take out slurry, the gelatin that adds monomer mass 4wt% while stirring, 2wt% ammonium persulfate solution, 2wt% tetramethylethylenediamine (TEMED) continues to be stirred to and generates jelly shape gel, is put in 80 ℃ of drying boxes after the oven dry, the microwave moderate heat was handled 30 minutes, 700 ℃ of constant temperature 10 hours in the Muffle furnace cools to room temperature with the furnace under the air atmosphere, gets Li
1.5Mn
0.32Fe
0.1Pr
0.03Pm
0.05O
2Black powder.Products therefrom is the rock salt structure, has higher phase purity.Particle is porous class sphere, and particle diameter is about 500nm.Prepare battery by embodiment 1 method, test its charge-discharge performance.Battery at normal temperatures, the specific capacity under 0.5C, 5C and the 10C discharge-rate is respectively 269mAh/g
-1, 244mAh/g
-1And 200mAh/g
-1Discharge capacity is 218mAh/g in the time of-20 ℃
-1, discharge capacity is 278mAh/g when being 81%, 50 ℃ of normal temperature discharge capacity
-1, be 104% of normal temperature discharge capacity; The capability retention of material is between 80%～96% under different temperatures, the different multiplying.
Embodiment 7:
By Mn (OH)
2, Fe
2(C
2O
4)
35H
2O, Sc
2O
3And LiNO
3Preparation Li
1.25Mn
0.39Fe
0.3Sc
0.06O
2The above-mentioned four kinds of materials of product stoichiometric proportion weighing are put into corundum ball grinder (alumina balls), the acrylamide (AM) that adds material gross mass 5wt% again, the polyethylene glycol of 4wt% (PEG) and appropriate amount of deionized water, mixing and ball milling 48 hours, take out slurry, the N-N-methylene diacrylamine (MBAM) that adds monomer mass 3wt% while stirring, the ammonium persulfate solution of 2wt%, the tetramethylethylenediamine of 1wt% (TEMED), continue to be stirred to generation jelly shape gel, after being put in 80 ℃ of drying boxes oven dry, the microwave moderate heat was handled 30 minutes, 700 ℃ of constant temperature 10 hours in the Muffle furnace under the air atmosphere, cool to room temperature with the furnace, get Li
1.25Mn
0.39Fe
0.3Sc
0.06O
2Black powder.Products therefrom is the rock salt structure, has higher phase purity.Particle is porous class sphere, and particle diameter is about 500nm.Prepare battery by embodiment 1 method, test its charge-discharge performance.Battery at normal temperatures, the specific capacity under 0.5C, 5C and the 10C discharge-rate is respectively 289mAh/g
-1, 251mAh/g
-1And 230mAh/g
-1Discharge capacity is 231mAh/g in the time of-20 ℃
-1, discharge capacity is 299mAh/g when being 80%, 50 ℃ of normal temperature discharge capacity
-1, be 103% of normal temperature discharge capacity; The capability retention of material is between 82%～95% under different temperatures, the different multiplying.
Claims (3)
1. anode material for lithium-ion batteries, it is characterized in that: the molecular structural formula of described anode material for lithium-ion batteries is Li
aMn
bFe
cM
dO
2, M is one or more of rare earth Sc, La, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu in the formula, and 1≤a≤1.25,0.39≤b≤0.6,0.2≤c≤0.39,0.01≤d≤0.1, and a+b+c+d=2.
2. method for preparing the described anode material for lithium-ion batteries of claim 1 is characterized in that following steps are arranged:
1) according to 1～1.25: 0.39～0.6: 0.2～0.39: 0.01～0.1 ratio takes by weighing in Li source, Mn source, Fe source, the rare earth ion doped source adding ball grinder, add organic monomer and dispersant ball milling again and be mixed into uniform slurry in 12-48 hour, described organic monomer is a kind of in acrylamide, Methacrylamide, DMAA, the acrylic acid, and wherein the addition of organic monomer is the 2wt～20wt% of Li source, Mn source, Fe source and rare earth ion doped source gross mass; Described dispersant is one or more in polyethylene glycol, ethanol, water, polyacrylic acid, ammonium polymethacrylate, ammonium citrate, the polyvinyl alcohol, and the dispersant addition is the 1wt～20wt% of Li source, Mn source, Fe source and rare earth ion doped source gross mass;
2) above-mentioned steps 1) slurry in add crosslinking agent, initator, catalyst, the preparation gel, described crosslinking agent is N, a kind of in N ' methylene-bisacrylamide, the gelatin, wherein the addition of crosslinking agent is the 2wt%～10wt% of organic monomer quality; Described initator is a kind of in ammonium persulfate, the hydrogen peroxide, and the addition of initator is the 1wt%～10wt% of organic monomer quality; Described catalyst is tetraethylethylenediamine, and the amount of catalyst is the 1wt%～5wt% of organic monomer quality:
3) with above-mentioned processing step 2) gel place drying box, under 60 ℃～150 ℃, carry out drying, obtain xerogel;
4) xerogel with step 3) places microwave oven, and low fire, moderate heat or high fire were handled 1～60 minute, placed Muffle furnace again, in oxygen-enriched atmosphere in 500 ℃～900 ℃ sintering 2-12 hour, can obtain anode material for lithium-ion batteries.
3. the method for anode material for lithium-ion batteries according to claim 2, it is characterized in that: the oxygen-enriched atmosphere in the described step 4) is air atmosphere.
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| CN102646827A (en) * | 2012-05-16 | 2012-08-22 | 中国第一汽车股份有限公司 | Preparation method of high-capacity lithium-ion battery anode material |
| CN104112860B (en) * | 2013-04-22 | 2017-02-08 | 万向电动汽车有限公司 | Preparation method of lithium ion battery positive electrode modified material |
| CN103413932B (en) * | 2013-08-19 | 2015-07-29 | 北大先行科技产业有限公司 | A kind of modification single crystal type multielement anode material and preparation method thereof |
| CN103474640B (en) * | 2013-09-21 | 2015-11-18 | 中南大学 | A kind of preparation method of lithium ion battery lithium-rich manganese-based anode material |
| CN103606697A (en) * | 2013-11-15 | 2014-02-26 | 江苏天鹏电源有限公司 | Low-cost high-specific-capacity lithium ion battery |
| CN104766987A (en) * | 2015-04-02 | 2015-07-08 | 青海绿草地新能源科技有限公司 | Conveniently-dismounted high-capacity rare-earth lithium battery module used in high-low-temperature range |
| CN106410180A (en) * | 2016-11-11 | 2017-02-15 | 河南师范大学 | Lithium ion battery positive pole material, and preparation method and application thereof |
| CN107887601A (en) * | 2017-11-09 | 2018-04-06 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of lithium ion battery negative material zinc-manganese oxygen and products thereof and application |
| JP6674580B2 (en) * | 2018-09-14 | 2020-04-01 | 花王株式会社 | Method for producing positive electrode active material for lithium ion secondary battery |
| CN111048322B (en) * | 2018-10-14 | 2021-07-13 | 天津大学 | Carbon nanotube-polyaniline-gelatin semi-interpenetrating network flexible electrode and preparation method and application thereof |
| CN110518239A (en) * | 2019-09-02 | 2019-11-29 | 梅州市量能新能源科技有限公司 | A kind of anode material for lithium-ion batteries and lithium ion battery |
| CN111592028A (en) * | 2020-04-24 | 2020-08-28 | 广西科学院 | Microwave calcination preparation method of rare earth oxide superfine powder |
| CN113285051B (en) * | 2021-05-19 | 2022-04-12 | 蜂巢能源科技有限公司 | Iron-manganese-based cathode material and preparation method and application thereof |
| CN113443653A (en) * | 2021-06-29 | 2021-09-28 | 哈尔滨工业大学 | Ball milling-heat treatment activation method for lithium dimanganese oxide three-positive electrode material |
| CN113603146B (en) * | 2021-07-30 | 2023-05-09 | 蜂巢能源科技有限公司 | Iron-manganese-based positive electrode material and preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101121508A (en) * | 2006-08-08 | 2008-02-13 | 新疆大学 | Method for synthesizing lithium iron phosphate battery anode material by microwave |
| CN101913655A (en) * | 2010-09-10 | 2010-12-15 | 河南联合新能源有限公司 | Method for preparing lithium manganate cathode material by microwave sintering |
-
2010
- 2010-12-29 CN CN2010106098876A patent/CN102088085B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101121508A (en) * | 2006-08-08 | 2008-02-13 | 新疆大学 | Method for synthesizing lithium iron phosphate battery anode material by microwave |
| CN101913655A (en) * | 2010-09-10 | 2010-12-15 | 河南联合新能源有限公司 | Method for preparing lithium manganate cathode material by microwave sintering |
Non-Patent Citations (4)
| Title |
|---|
| A.Robert Armstrong et al.Synthesis of layered LiMnO2 as an electrode for rechargeable lithium batteries.《Nature》.1996,第381卷499-500. |
| Synthesis of layered LiMnO2 as an electrode for rechargeable lithium batteries;A.Robert Armstrong et al;《Nature》;19960606;第381卷;499-500 * |
| 杨书廷 et al.稀土掺杂锂锰氧化物LiMn2-xNdxO4(x=0.005-0.1)的结构和电性能研究.《无机材料学报》.2003,第18卷(第2期),301-306. |
| 稀土掺杂锂锰氧化物LiMn2-xNdxO4(x=0.005-0.1)的结构和电性能研究;杨书廷 et al;《无机材料学报》;20030331;第18卷(第2期);301-306 * |
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