CN104810519B - A kind of lithium ion battery richness lithium manganese anode material and preparation method thereof - Google Patents
A kind of lithium ion battery richness lithium manganese anode material and preparation method thereof Download PDFInfo
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- CN104810519B CN104810519B CN201510184875.6A CN201510184875A CN104810519B CN 104810519 B CN104810519 B CN 104810519B CN 201510184875 A CN201510184875 A CN 201510184875A CN 104810519 B CN104810519 B CN 104810519B
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- lithium manganese
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- KLARSDUHONHPRF-UHFFFAOYSA-N [Li].[Mn] Chemical compound [Li].[Mn] KLARSDUHONHPRF-UHFFFAOYSA-N 0.000 title claims abstract description 104
- 239000010405 anode material Substances 0.000 title claims abstract description 81
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title claims abstract description 43
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 239000000463 material Substances 0.000 claims abstract description 64
- 239000011572 manganese Substances 0.000 claims abstract description 25
- 239000002245 particle Substances 0.000 claims abstract description 21
- 229910000473 manganese(VI) oxide Inorganic materials 0.000 claims abstract description 18
- 239000000126 substance Substances 0.000 claims abstract description 7
- 238000009826 distribution Methods 0.000 claims abstract description 5
- 239000007921 spray Substances 0.000 claims description 32
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical class [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 22
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 21
- 229910003002 lithium salt Inorganic materials 0.000 claims description 20
- 159000000002 lithium salts Chemical class 0.000 claims description 20
- 229910021645 metal ion Inorganic materials 0.000 claims description 20
- 238000001354 calcination Methods 0.000 claims description 18
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 16
- 238000010792 warming Methods 0.000 claims description 16
- 150000001455 metallic ions Chemical class 0.000 claims description 13
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 9
- 150000002696 manganese Chemical class 0.000 claims description 9
- 150000002815 nickel Chemical class 0.000 claims description 9
- 150000002505 iron Chemical class 0.000 claims description 8
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 7
- 239000012467 final product Substances 0.000 claims description 7
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 claims description 7
- 229910052744 lithium Inorganic materials 0.000 claims description 7
- 239000011259 mixed solution Substances 0.000 claims description 7
- 229910052759 nickel Inorganic materials 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 6
- 229940099596 manganese sulfate Drugs 0.000 claims description 6
- 235000007079 manganese sulphate Nutrition 0.000 claims description 6
- 239000011702 manganese sulphate Substances 0.000 claims description 6
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 6
- 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
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 5
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 5
- GLXDVVHUTZTUQK-UHFFFAOYSA-M lithium;hydroxide;hydrate Chemical compound [Li+].O.[OH-] GLXDVVHUTZTUQK-UHFFFAOYSA-M 0.000 claims description 4
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 4
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 4
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 3
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 3
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 3
- 229910000358 iron sulfate Inorganic materials 0.000 claims description 3
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 3
- 235000002867 manganese chloride Nutrition 0.000 claims description 3
- 239000011565 manganese chloride Substances 0.000 claims description 3
- 229940099607 manganese chloride Drugs 0.000 claims description 3
- 229940078494 nickel acetate Drugs 0.000 claims description 3
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 3
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 3
- 235000006408 oxalic acid Nutrition 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims 2
- 229910017604 nitric acid Inorganic materials 0.000 claims 2
- 229920000180 alkyd Polymers 0.000 claims 1
- 230000001717 pathogenic effect Effects 0.000 claims 1
- 239000000052 vinegar Substances 0.000 claims 1
- 235000021419 vinegar Nutrition 0.000 claims 1
- 239000003792 electrolyte Substances 0.000 abstract description 5
- 239000007774 positive electrode material Substances 0.000 abstract description 4
- 238000000034 method Methods 0.000 description 10
- 239000008187 granular material Substances 0.000 description 9
- 238000009413 insulation Methods 0.000 description 9
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 230000005611 electricity Effects 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 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 4
- 230000014759 maintenance of location Effects 0.000 description 4
- XMOKRCSXICGIDD-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O XMOKRCSXICGIDD-UHFFFAOYSA-N 0.000 description 3
- 235000014113 dietary fatty acids Nutrition 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 229930195729 fatty acid Natural products 0.000 description 3
- 239000000194 fatty acid Substances 0.000 description 3
- 150000004665 fatty acids Chemical class 0.000 description 3
- -1 glycolic Chemical compound 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 description 3
- 229910052748 manganese Inorganic materials 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 229910013191 LiMO2 Inorganic materials 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 229910016482 Ni0.4Co0.2Mn0.4 Inorganic materials 0.000 description 2
- 229910016771 Ni0.5Mn0.5 Inorganic materials 0.000 description 2
- 229910015177 Ni1/3Co1/3Mn1/3 Inorganic materials 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 235000019197 fats Nutrition 0.000 description 2
- 238000003837 high-temperature calcination Methods 0.000 description 2
- 229940071125 manganese acetate Drugs 0.000 description 2
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000001694 spray drying Methods 0.000 description 2
- OYHQOLUKZRVURQ-NTGFUMLPSA-N (9Z,12Z)-9,10,12,13-tetratritiooctadeca-9,12-dienoic acid Chemical compound C(CCCCCCC\C(=C(/C\C(=C(/CCCCC)\[3H])\[3H])\[3H])\[3H])(=O)O OYHQOLUKZRVURQ-NTGFUMLPSA-N 0.000 description 1
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- 229910000651 0.4Li2MnO3 Inorganic materials 0.000 description 1
- 229910001346 0.5Li2MnO3 Inorganic materials 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical class [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 1
- 229910032387 LiCoO2 Inorganic materials 0.000 description 1
- 229910052493 LiFePO4 Inorganic materials 0.000 description 1
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 239000005030 aluminium foil Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 239000004531 microgranule Substances 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 235000021313 oleic acid Nutrition 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 229910006525 α-NaFeO2 Inorganic materials 0.000 description 1
- 229910006596 α−NaFeO2 Inorganic materials 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- 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
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a kind of lithium ion battery richness lithium manganese anode material and preparation method thereof, belong to technical field of lithium ion battery positive pole material preparation.The chemical formula of the rich lithium manganese anode material of the present invention is xLi2MnO3·(1‑x)LiNi0.5‑a/2Mn0.5‑a/2FeaO2, wherein, 0.1≤x≤0.9,0.002≤a≤0.08；The accumulative particle size distribution in percentage of described richness lithium manganese anode material reaches corresponding particle diameter when 50% and is 0.1～0.8 μm.The particle diameter of the rich lithium manganese anode material of the present invention is submicron order, and less particle diameter enables rich lithium manganese anode material to be fully contacted with electrolyte, and can shorten Li+The evolving path, make the lithium ion battery using the rich lithium manganese anode material of the present invention as positive electrode active materials have good high rate performance, the specific discharge capacity under 5C multiplying power can be maintained at more than 150mAh/g.
Description
Technical field
The present invention relates to technical field of lithium ion battery positive pole material preparation, particularly to a kind of lithium ion battery richness lithium manganese
Positive electrode and preparation method thereof.
Background technology
Lithium ion battery, as a kind of high-energy battery, has energy density height, long service life, good cycle and nothing
The advantages of memory effect.Anode material for lithium-ion batteries is the important component part in lithium ion battery, and it is for lithium-ion electric
The chemical property in pond has important impact.General anode material for lithium-ion batteries (LiCoO2、LiMn2O4、LiFePO4)
Through the demand to high power capacity, high-energy-density electronic product for the people can not be met.Stratiform richness lithium manganese anode material xLi2MnO3·
(1-x)LiMO2(M=Mn, Ni, Co, Ni0.5Mn0.5, Cr, Ni1/3Co1/3Mn1/3, Fe ...) and it is a kind of α-NaFeO2Type solid solution material
Material, by the Li of stratiform2MnO3And LiMO2(M=Mn, Ni, Co, Ni0.5Mn0.5, Cr, Ni1/3Co1/3Mn1/3, Fe ...) formed, with it
The performances such as distinctive height ratio capacity (200～300mAh/g), outstanding circulation ability, become current lithium ion secondary battery positive electrode
The study hotspot of material.For example, CN102013481A (application number：201010522413.8) disclose a kind of spherical gradient richness lithium
Manganese anode material xLi2MnO3·(1-x)Li[Ni0.4Co0.2Mn0.4]O2The synthetic method of (0.1≤x≤0.4), uses existing business
Industry spherical precursor [Ni0.4Co0.2Mn0.4](OH)2Carry out Mn element cladding, then with Lithium hydrate mixing heat treatment.Gained
The particle diameter of positive electrode is 10 μm about, 0.2C multiplying power current charge-discharge electricity, and electric discharge specific capacitance is 242mAh/g first；At 1C times
Under rate, electric discharge specific capacitance is 171mAh/g first；Under 2C multiplying power, electric discharge specific capacitance is 162mAh/g first.
During realizing the present invention, the inventors discovered that at least there is problems with prior art：Existing richness
Specific discharge capacity under compared with high magnification for the lithium manganese anode material is relatively low, and high rate performance is poor.
Content of the invention
In order to solve above-mentioned technical problem, the present invention provides a kind of lithium ion battery richness lithium with good high rate performance
Manganese anode material and preparation method thereof.
Specifically, including following technical scheme：
First aspect present invention provides a kind of lithium ion battery richness lithium manganese anode material, the change of described richness lithium manganese anode material
Formula is xLi2MnO3·(1-x)LiNi0.5-a/2Mn0.5-a/2FeaO2, wherein, 0.1≤x≤0.9,0.002≤a≤0.08；Described
The accumulative particle size distribution in percentage of rich lithium manganese anode material reaches corresponding particle diameter when 50% and is 0.1～0.8 μm.
Further, the specific surface area of described richness lithium manganese anode material is 0.8～2.0m2/ g, tap density be 1.8～
2.3g/cm3.
Second aspect present invention provides a kind of preparation of the lithium ion battery richness lithium manganese anode material of first aspect present invention
Method, described preparation method comprises the following steps：
Step (1), according to xLi2MnO3·(1-x)LiNi0.5-a/2Mn0.5-a/2FeaO2Stoichiometric proportion by lithium salts, nickel
Salt, iron salt and manganese salt is soluble in water obtains aqueous metallic ions, metal ion total concentration in described aqueous metallic ions
For 0.2～3mol/L；
Step (2), chelating agen is added in described aqueous metallic ions, dispersed with stirring is uniform；The thing of described chelating agen
The ratio of the amount of the amount of matter and described metal ion total material is 1～1.2:1；
Step (3), is dried to step (2) gained mixed solution with spray dryer, obtains described richness lithium manganese positive pole
The persursor material of material；The inlet temperature of described spray dryer is 180～220 DEG C, the going out of described spray dryer
Air temperature is 100～120 DEG C；
Step (4), calcines after step (3) gained persursor material is compacted in air atmosphere；Calcination condition is：First
Insulation 3～15h after 350～500 DEG C is warming up to the speed of 0.5～10 DEG C/min, then again with the speed liter of 1～10 DEG C/min
Temperature is incubated 5～24h to after 650～900 DEG C；Described richness lithium manganese anode material is obtained final product after being cooled to room temperature.
Preferably, in step (3), the inlet temperature of described spray dryer is 180～210 DEG C, described spray dryer
Leaving air temp be 100～110 DEG C.
Preferably, the calcination condition in step (4) is：It is warming up to after 350～450 DEG C with the speed of 2～6 DEG C/min first
Insulation 3～10h, is then warming up to insulation 5～15h after 750～900 DEG C with the speed of 1～6 DEG C/min again.
Preferably, lithium salts described in step (1) is selected from Lithium hydrate, lithium acetate, lithium nitrate and lithium chloride at least
A kind of.
Preferably, manganese salt described in step (1) is selected from least one of manganese nitrate, manganese acetate, manganese sulfate and manganese chloride.
Preferably, iron salt described in step (1) is selected from least one of iron sulfate, ferric nitrate and iron chloride.
Preferably, nickel salt described in step (1) is selected from least in nickel sulfate, nickel nitrate, Nickel dichloride. and nickel acetate
Kind.
Preferably, chelating agen described in step (2) be selected from citric acid, glycolic, triethanolamine, acrylic acid, fatty acid with
And at least one in oxalic acid.
The beneficial effect of technical scheme provided in an embodiment of the present invention：
1st, the embodiment of the present invention lithium ion battery richness lithium manganese anode material preparation process in, using spray dryer pair
Metal ion solution is spray-dried, and is calcined after obtaining persursor material, and to the inlet temperature of spray dryer, go out
Air temperature and calcination condition are optimized, and have obtained the submicron order richness lithium manganese anode material of 0.1～0.8 μm of particle diameter.Due to
Gained richness lithium manganese anode material particle diameter is little, can be fully contacted with electrolyte, and less granule shortens Li+Diffusion road
Footpath, makes the lithium ion battery using richness lithium manganese anode material provided in an embodiment of the present invention as positive electrode active materials have good
High rate performance, the specific discharge capacity under 5C multiplying power can be maintained at more than 150mAh/g.
2nd, the method due to employing spray drying, make gained richness lithium manganese anode material in metallic elements of ferrum, manganese,
Nickel and lithium can uniformly be distributed so that the ferrum in rich lithium manganese anode material, the ratio of manganese, nickel and lithium can accurately accord with
Close xLi2MnO3·(1-x)LiNi0.5-a/2Mn0.5-a/2FeaO2The chemistry meter of (wherein, 0.1≤x≤0.9,0.002≤a≤0.08)
Amount ratio.
3rd, do not contain metallic cobalt in the lithium ion battery richness lithium manganese anode material of the embodiment of the present invention, and ferrum, manganese, nickel, lithium
Abundance, reduces the cost of rich lithium manganese anode material.Simultaneously as being doped with ferrum, improve rich lithium manganese anode material knot
The stability of structure, thus improve its cyclical stability in coulombic efficiency and charge and discharge process first.
4th, the preparation process is simple of lithium ion battery provided in an embodiment of the present invention richness lithium manganese anode material is it is easy to industrialization
Produce.
Brief description
For the technical scheme being illustrated more clearly that in the embodiment of the present invention, will make to required in embodiment description below
Accompanying drawing be briefly described it should be apparent that, drawings in the following description are only some embodiments of the present invention, for
For those of ordinary skill in the art, on the premise of not paying creative work, other can also be obtained according to these accompanying drawings
Accompanying drawing.
Fig. 1 is the scanning electron microscope (SEM) photograph of the embodiment of the present invention 1 gained lithium ion battery richness lithium manganese anode material；
Fig. 2 is the embodiment of the present invention 1 gained lithium ion battery richness lithium manganese anode material first charge-discharge cycle performance curve；
Fig. 3 is the cycle performance that discharges under the embodiment of the present invention 1 gained lithium ion battery richness lithium manganese anode material different multiplying
Curve；
Fig. 4 is the embodiment of the present invention 1 gained lithium ion battery richness lithium manganese anode material discharge cycles performance curve.
Specific embodiment
For making technical scheme and advantage clearer, below in conjunction with accompanying drawing embodiment of the present invention is made into
One step ground describes in detail.
First aspect present invention provides a kind of lithium ion battery richness lithium manganese anode material, the change of described richness lithium manganese anode material
Formula is xLi2MnO3·(1-x)LiNi0.5-a/2Mn0.5-a/2FeaO2, wherein, 0.1≤x≤0.9,0.002≤a≤0.08；Described
The accumulative particle size distribution in percentage of rich lithium manganese anode material reaches corresponding particle diameter when 50% and is 0.1～0.8 μm.
The accumulative particle size distribution in percentage of richness lithium manganese anode material provided in an embodiment of the present invention reaches corresponding when 50%
Particle diameter (hereinafter referred to as D50) be 0.1～0.8 μm, reached submicron rank, because particle diameter is little, made rich lithium manganese anode material
Can be fully contacted with electrolyte, and less granule shortens Li+The evolving path, make with above-mentioned richness lithium manganese anode material
Lithium ion battery as positive electrode active materials has good high rate performance, and the specific discharge capacity under 5C multiplying power can keep
In more than 150mAh/g.Additionally, not containing metallic cobalt in the rich lithium manganese anode material of the embodiment of the present invention, reduce rich lithium manganese positive pole
The cost of material.And due to being doped with ferrum, improve the stability of rich lithium manganese anode material structure, thus improve its storehouse first
Cyclical stability in human relations efficiency and charge and discharge process.
In above-mentioned rich lithium manganese anode material, the specific surface area of described richness lithium manganese anode material is 0.8～2.0m2/ g,
Tap density is 1.8～2.3g/cm3, larger specific surface area is conducive to increasing the contact with electrolyte for the rich lithium manganese anode material
Area, improves the performance of lithium ion battery；Higher tap density can make to accommodate in the lithium ion battery of unit volume more
Rich lithium manganese anode material, be conducive to improve lithium ion battery capacity.
Second aspect present invention provides a kind of preparation of the lithium ion battery richness lithium manganese anode material of first aspect present invention
Method, described preparation method comprises the following steps：
Step (1), according to xLi2MnO3·(1-x)LiNi0.5-a/2Mn0.5-a/2FeaO2Stoichiometric proportion by lithium salts, nickel
Salt, iron salt and manganese salt is soluble in water obtains aqueous metallic ions, metal ion total concentration in described aqueous metallic ions
For 0.2～3mol/L；
Step (2), chelating agen is added in described aqueous metallic ions, dispersed with stirring is uniform；The thing of described chelating agen
The ratio of the amount of the amount of matter and described metal ion total material is 1～1.2:1；
Step (3), is dried to step (2) gained mixed solution with spray dryer, obtains described richness lithium manganese positive pole
The persursor material of material；The inlet temperature of described spray dryer is 180～220 DEG C, the going out of described spray dryer
Air temperature is 100～120 DEG C；
Step (4), calcines after step (3) gained persursor material is compacted in air atmosphere；Calcination condition is：First
Insulation 3～15h after 350～500 DEG C is warming up to the speed of 0.5～10 DEG C/min, then again with the speed liter of 1～10 DEG C/min
Temperature is incubated 5～24h to after 650～900 DEG C；Described richness lithium manganese anode material is obtained final product after being cooled to room temperature.
In preparation method provided in an embodiment of the present invention, using spray dryer, metal ion solution is dried and obtains
Persursor material, obtains the rich lithium manganese anode material of first aspect present invention after persursor material is calcined.The work being spray-dried
As principle it is：By mechanism it would be desirable to the material dispersion being dried becomes the very thin microgranule as mist, connect with hot-air
Touch, because disengagement area is big, in moment, most of moisture can be removed, thus the solid matter in material is dried to powder
End.The spray-dried solid powder particle obtaining is less and is uniformly dispersed.In spray-drying process, spray dryer
The rate of drying of inlet temperature and leaving air temp impact material and drying effect, and then affect the property of final gained pressed powder
Matter.Therefore, the embodiment of the present invention, on the basis of using being spray-dried, is entered to the inlet temperature and leaving air temp of spray dryer
Row optimize, make gained richness lithium manganese anode material persursor material particle diameter little, ferrum, manganese, nickel and lithium are uniformly dispersed and they
Ratio can accurately meet xLi2MnO3·(1-x)LiNi0.5-a/2Mn0.5-a/2FeaO2Stoichiometric ratio.The present invention is real
Apply example also the calcination condition in rich lithium manganese anode material preparation process to be optimized.It is rich that the condition of calcining can affect final gained
The properties such as the pattern of lithium manganese anode material, crystal structure, and then affect the high rate performance of rich lithium manganese anode material, cyclical stability
The electric properties such as energy.To sum up, pass through in the embodiment of the present invention to optimize the technological parameter being spray-dried with calcination process, obtain
D50 is the rich lithium manganese anode material of 0.1～0.8 μm of submicron order.And the preparation method process is simple of the embodiment of the present invention,
Be conducive to industrialized production.
In above-mentioned preparation method, in step (3), preferably 180～210 DEG C of the inlet temperature of described spray dryer,
For example, it is possible to for 185 DEG C, 190 DEG C, 200 DEG C, 205 DEG C etc.；Preferably 100～110 DEG C of the leaving air temp of described spray dryer,
Can it be for example 102 DEG C, 104 DEG C, 105 DEG C, 106 DEG C, 108 DEG C etc..
In above-mentioned preparation method, in step (4), preferred calcination condition is：First with the speed liter of 2～6 DEG C/min
Temperature is incubated 3～10h to after 350～450 DEG C, then again with the speed of 1～6 DEG C/min be warming up to after 750～900 DEG C insulation 5～
15h.Wherein, temperature when being incubated for the first time can be 360 DEG C, 380 DEG C, 400 DEG C, 420 DEG C etc.；Temperature when being incubated for second
Can it be 760 DEG C, 780 DEG C, 800 DEG C, 820 DEG C, 840 DEG C, 850 DEG C, 860 DEG C, 880 DEG C etc..
In above-mentioned preparation method, described in step (1), lithium salts does not have strict restriction, as long as can soluble in water be
Can, can be for example Lithium hydrate, lithium acetate, lithium nitrate or lithium chloride etc., can be used alone with every kind of lithium salts it is also possible to two
Plant or two or more lithium salts is used in mixed way.
In above-mentioned preparation method, described in step (1), manganese salt does not have strict restriction yet, can be arbitrarily solvable
Property, such as manganese nitrate, manganese acetate, manganese sulfate or manganese chloride etc., can be used alone it is also possible to two kinds or two with every kind of manganese salt
Plant above manganese salt to be used in mixed way.
In above-mentioned preparation method, described in step (1), iron salt does not have considered critical yet, as long as soluble ferric iron salt is
Can, can be iron sulfate, ferric nitrate or iron chloride etc., can be used alone with every kind of iron salt it is also possible to two kinds or two kinds with
On iron salt be used in mixed way.
In above-mentioned preparation method, nickel salt described in step (1) also without considered critical, soluble nickel salt,
Such as nickel sulfate, nickel nitrate, Nickel dichloride. or nickel acetate etc., similar with above-mentioned lithium salts, manganese salt, iron salt, can be with every kind of nickel salt
It is used alone it is also possible to two kinds or two or more nickel salts are used in mixed way.
In above-mentioned preparation method, the chelating agen in step (2) can be any chelating agen commonly used in the art, for example
Citric acid, glycolic, triethanolamine, acrylic acid, fatty acid, oxalic acid etc., can be used alone it is also possible to two kinds with every kind of chelating agen
Or two or more chelating agen is used in mixed way.Wherein, the concrete species of fatty acid does not particularly require, fat commonly used in the art
Fat acid, such as Oleic acid, linoleic acid, stearic acid etc..
In above-mentioned preparation method, in step (4), compacted density can be compacted to for 0.5 by just described persursor material
～1.8g/cm3After calcined.
In above-mentioned preparation method, because lithium salts has a small amount of volatilization in high-temperature calcination, therefore in order that final
In gained richness lithium manganese anode material, each constituent content is more accurate, in step (1) during preparing metal deionized water solution, can make lithium
Salt excessive 1%～8% is compensating a small amount of volatilization in high-temperature calcination for the lithium salts.
Lithium ion battery richness lithium manganese anode material is prepared according to the preparation method that the present invention provides in example 1 below～4, will
Gained richness lithium manganese anode material is assembled in lithium ion battery, and to the high rate performance of gained lithium ion battery, first coulomb effect
The property such as rate and cyclical stability is tested.Wherein, the assembly method of lithium ion battery is as follows：
By the rich lithium manganese anode material of gained in embodiment 1～4 and conductive agent acetylene black, binding agent PVDF (polyvinylidene fluoride
Alkene) according to mass ratio 8:1:Said mixture is modulated into slurry with NMP (1-Methyl-2-Pyrrolidone), all by 1 mix homogeneously
Even be coated on aluminium foil, put in baking oven, 110 DEG C drying 3h, take out be washed into pole piece；85 DEG C vacuum drying 12 hours after pressed
Piece, is vacuum dried 12 hours after tabletting, prepared experimental cell pole piece at 85 DEG C again.It is to electrode with lithium piece, electrolyte is
1.0mol/L LiPF6EC (ethyl carbonate ester)+DMC (dimethyl carbonate) (volume ratio 1:1) solution, barrier film is
Celgard2325 film, is assembled into CR2025 type button cell in the glove box full of argon gas atmosphere.
Embodiment 1
The present embodiment provides a kind of lithium ion battery richness lithium manganese anode material and preparation method thereof, and prepared rich lithium manganese is just
The chemical formula of pole material is：0.5Li2MnO3·0.5LiNi0.49Mn0.49Fe0.02O2, preparation method is as follows：
Step (1), according to Li:Ni:Fe:Mn=1.575:0.245:0.01:The ratio of 0.745 (mol ratio, similarly hereinafter) will
Lithium acetate, Nickel dichloride., iron chloride and manganese nitrate are dissolved in the metal obtaining in deionized water that metal ion total concentration is 1mol/L
Deionized water solution；Wherein, lithium salts excessive 5%, to compensate a small amount of volatilization when lithium salts is calcined at high temperature；
Step (2), citric acid is added in described aqueous metallic ions, dispersed with stirring is uniform；The material of citric acid
Amount is 1.05 with the ratio of the amount of described metal ion total material:1；
Step (3), is dried to step (2) gained mixed solution with spray dryer, obtains described richness lithium manganese positive pole
The persursor material of material；The inlet temperature of described spray dryer is 180 DEG C, the leaving air temp of described spray dryer
For 100 DEG C；
Step (4), it is 0.5g/cm that step (3) gained persursor material is compacted to compacted density3Afterwards in air atmosphere
Calcining；Calcination condition is：First insulation 4h after 400 DEG C is warming up to the speed of 5 DEG C/min, then again with the speed of 2 DEG C/min
It is incubated 5h after being warming up to 750 DEG C；0.5Li is obtained final product after being cooled to room temperature2MnO3·0.5LiNi0.49Mn0.49Fe0.02O2Rich lithium manganese is just
Pole material.
Electronic Speculum test is scanned to gained richness lithium manganese anode material, gained stereoscan photograph is as shown in Figure 1.From Fig. 1
As can be seen that gained richness lithium manganese anode material is spherical or spherical shape granule, even particle size, D50 is 0.6 μm.Institute
The specific surface area obtaining rich lithium manganese anode material is 0.85m2/ g, tap density is 1.98g/cm3.
First charge-discharge loop test, test strip are carried out to the button cell using above-mentioned richness lithium manganese material as positive electrode
Part：Charging/discharging voltage scope is 4.8～2.0V, is 0.1C (1C=250mA/g, similarly hereinafter), result such as Fig. 2 in charging and discharging currents
Shown.It is respectively using above-mentioned richness lithium manganese material as the first charge-discharge specific capacity of the button cell of positive electrode
278.337mAh/g, 247.162mAh/g, initial coulomb efficiency is 88.8%, and efficiency is higher first.
High rate performance using above-mentioned richness lithium manganese material as the button cell of positive electrode is tested, charging/discharging voltage
Scope is 4.8～2.0V, and charging current is 0.1C, and discharge current is respectively 0.1C, 0.2C, 0.5C, 1C, 2C, 5C, each multiplying power
Circulation 5 times.As shown in figure 3, under 1C multiplying power, specific discharge capacity is maintained at 200mAh/g to high rate performance test result；?
Under 2C multiplying power, specific discharge capacity is maintained at 180mAh/g；Under 5C multiplying power, specific discharge capacity still is able to be maintained at
More than 154mAh/g.As can be seen here, the rich lithium manganese anode material of submicron order can shorten Li+The evolving path, make gained electricity
Pond has good high rate performance.
Stable circulation performance using above-mentioned richness lithium manganese material as the button cell of positive electrode is tested, discharge and recharge
Electric current is 0.2C.As shown in figure 4, first discharge specific capacity is 243.236mAh/g, 50 specific capacities of circulation are
241.63mAh/g, capability retention is 99.34%, and cyclical stability is preferable.
Embodiment 2
The present embodiment provides a kind of lithium ion battery richness lithium manganese anode material and preparation method thereof, and prepared rich lithium manganese is just
The chemical formula of pole material is：0.2Li2MnO3·0.8LiNi0.48Mn0.48Fe0.04O2, preparation method is as follows：
Step (1), according to Li:Ni:Fe:Mn=1.224:0.384:0.032:0.584 ratio is by lithium nitrate, acetic acid
Nickel, iron chloride and manganese sulfate be dissolved in obtain in deionized water metal ion total concentration be 2.0mol/L metal ion water-soluble
Liquid；Wherein, lithium salts excessive 2%, to compensate a small amount of volatilization when lithium salts is calcined at high temperature；
Step (2), acrylic acid is added in described aqueous metallic ions, dispersed with stirring is uniform；Acrylic acid material
Amount is 1.01 with the ratio of the amount of described metal ion total material:1；
Step (3), is dried to step (2) gained mixed solution with spray dryer, obtains described richness lithium manganese positive pole
The persursor material of material；The inlet temperature of described spray dryer is 195 DEG C, the leaving air temp of described spray dryer
For 105 DEG C；
Step (4), it is 1.0g/cm that step (3) gained persursor material is compacted to compacted density3Afterwards in air atmosphere
Calcining；Calcination condition is：First insulation 6h after 350 DEG C is warming up to the speed of 3 DEG C/min, then again with the speed of 3 DEG C/min
It is incubated 8h after being warming up to 850 DEG C；0.2Li is obtained final product after being cooled to room temperature2MnO3·0.8LiNi0.48Mn0.48Fe0.04O2Rich lithium manganese is just
Pole material.
Scanning electron microscope result shows, the present embodiment gained richness lithium manganese material is spherical or spherical shape granule, and granule is big
Little uniform, D50 is 0.4 μm.The specific surface area of gained richness lithium manganese anode material is 0.96m2/ g, tap density is 2.1g/cm3.
According to the test condition of embodiment 1, to the button electricity using the present embodiment gained richness lithium manganese material as positive electrode
The first charge-discharge cycle performance in pond, high rate performance and cyclical stability are tested.Result shows, first discharge specific capacity
For 266.68mAh/g, coulombic efficiency 85.68% first；Specific discharge capacity under 5C multiplying power is maintained at more than 148mAh；Circulation 50
Secondary capability retention is 98.45%, and cyclical stability is preferable.As can be seen here, the rich lithium manganese anode material of submicron order can contract
Short Li+The evolving path, make gained battery have good high rate performance.
Embodiment 3
The present embodiment provides a kind of lithium ion battery richness lithium manganese anode material and preparation method thereof, and prepared rich lithium manganese is just
The chemical formula of pole material is：0.7Li2MnO3·0.3LiNi0.495Mn0.495Fe0.01O2, preparation method is as follows：
Step (1), according to Li:Ni:Fe:Mn=1.717:0.1485:0.003:0.8485 ratio is by lithium nitrate, acetic acid
Nickel, iron chloride and manganese sulfate be dissolved in obtain in deionized water metal ion total concentration be 1.5mol/L metal ion water-soluble
Liquid；Wherein, lithium salts excessive 1%, to compensate a small amount of volatilization when lithium salts is calcined at high temperature；
Step (2), citric acid is added in described aqueous metallic ions, dispersed with stirring is uniform；The material of citric acid
Amount is 1.05 with the ratio of the amount of described metal ion total material:1；
Step (3), is dried to step (2) gained mixed solution with spray dryer, obtains described richness lithium manganese positive pole
The persursor material of material；The inlet temperature of described spray dryer is 200 DEG C, the leaving air temp of described spray dryer
For 100 DEG C；
Step (4), it is 1.5g/cm that step (3) gained persursor material is compacted to compacted density3Afterwards in air atmosphere
Calcining；Calcination condition is：First insulation 4h after 400 DEG C is warming up to the speed of 5 DEG C/min, then again with the speed of 5 DEG C/min
It is incubated 10h after being warming up to 900 DEG C；0.7Li is obtained final product after being cooled to room temperature2MnO3·0.3LiNi0.495Mn0.495Fe0.01O2Rich lithium manganese
Positive electrode.
Scanning electron microscope result shows, the present embodiment gained richness lithium manganese material is spherical or spherical shape granule, and granule is big
Little uniform, D50 is 0.7 μm.The specific surface area of gained richness lithium manganese anode material is 1.06m2/ g, tap density is 2.05g/cm3.
According to the test condition of embodiment 1, to the button electricity using the present embodiment gained richness lithium manganese material as positive electrode
The first charge-discharge cycle performance in pond, high rate performance and cyclical stability are tested.Result shows, first discharge specific capacity
For 215.235mAh/g, coulombic efficiency 83.2% first；Specific discharge capacity under 5C multiplying power is maintained at more than 165mAh；Circulation 50
Secondary capability retention is 97.62%, and cyclical stability is preferable.As can be seen here, the rich lithium manganese anode material of submicron order can contract
Short Li+The evolving path, make gained battery have good high rate performance.
Embodiment 4
The present embodiment provides a kind of lithium ion battery richness lithium manganese anode material and preparation method thereof, and prepared rich lithium manganese is just
The chemical formula of pole material is：0.4Li2MnO3·0.6LiNi0.47Mn0.47Fe0.06O2, preparation method is as follows：
Step (1), according to Li:Ni:Fe:Mn=1.484:0.282:0.036:0.682 ratio is by lithium nitrate, acetic acid
Nickel, iron chloride and manganese sulfate be dissolved in obtain in deionized water metal ion total concentration be 2.1mol/L metal ion water-soluble
Liquid；Wherein, lithium salts excessive 6%, to compensate a small amount of volatilization when lithium salts is calcined at high temperature；
Step (2), triethanolamine is added in described aqueous metallic ions, dispersed with stirring is uniform；The thing of triethanolamine
The ratio of the amount of the amount of matter and described metal ion total material is 1:1；
Step (3), is dried to step (2) gained mixed solution with spray dryer, obtains described richness lithium manganese positive pole
The persursor material of material；The inlet temperature of described spray dryer is 205 DEG C, the leaving air temp of described spray dryer
For 110 DEG C；
Step (4), it is 1.8g/cm that step (3) gained persursor material is compacted to compacted density3Afterwards in air atmosphere
Calcining；Calcination condition is：First insulation 6h after 500 DEG C is warming up to the speed of 5 DEG C/min, then again with the speed of 3 DEG C/min
It is incubated 8h after being warming up to 750 DEG C；0.4Li is obtained final product after being cooled to room temperature2MnO3·0.6LiNi0.47Mn0.47Fe0.06O2Rich lithium manganese is just
Pole material.
Scanning electron microscope result shows, the present embodiment gained richness lithium manganese material is spherical or spherical shape granule, and granule is big
Little uniform, D50 is 0.75 μm.The specific surface area of gained richness lithium manganese anode material is 1.65m2/ g, tap density is 2.2g/cm3.
According to the test condition of embodiment 1, to the button electricity using the present embodiment gained richness lithium manganese material as positive electrode
The first charge-discharge cycle performance in pond, high rate performance and cyclical stability are tested.Result shows, first discharge specific capacity
For 257.652mAh/g, coulombic efficiency 87.51% first；Specific discharge capacity under 5C multiplying power is maintained at more than 158mAh；Circulation
50 times capability retention is 98.75%, and cyclical stability is preferable.As can be seen here, the rich lithium manganese anode material of submicron order can
Shorten Li+The evolving path, make gained battery have good high rate performance.
Table 1 embodiment 1～4 gained richness lithium manganese anode material performance collects
To sum up, the embodiment of the present invention obtains forerunner by being dried to metal ion solution using the method being spray-dried
Body material, and the condition being spray-dried and persursor material is calcined is optimized, having obtained particle diameter is 0.1～0.8 μm
Submicron order richness lithium manganese anode material.Because less particle diameter can shorten Li+The evolving path, therefore with the embodiment of the present invention
The rich lithium manganese anode material providing has good high rate performance as the lithium ion battery of positive electrode active materials, under 5C multiplying power
Specific discharge capacity can be maintained at more than 150mAh/g.
The above is for only for ease of those skilled in the art and understands technical scheme, not in order to limit
The present invention.All any modification, equivalent substitution and improvement within the spirit and principles in the present invention, made etc., should be included in this
Within the protection domain of invention.
Claims (8)
1. a kind of preparation method of lithium ion battery richness lithium manganese anode material is it is characterised in that described richness lithium manganese anode material
Chemical formula is xLi2MnO3·(1-x)LiNi0.5-a/2Mn0.5-a/2FeaO2, wherein, 0.1≤x≤0.9,0.002≤a≤0.08；Institute
The accumulative particle size distribution in percentage stating rich lithium manganese anode material reaches corresponding particle diameter when 50% for 0.1～0.8 μm；Described richness
The specific surface area of lithium manganese anode material is 0.8～2.0m2/ g, tap density is 1.8～2.3g/cm3；Described preparation method includes
Following steps：
Step (1), according to xLi2MnO3·(1-x)LiNi0.5-a/2Mn0.5-a/2FeaO2Stoichiometric proportion by lithium salts, nickel salt, ferrum
Salt and manganese salt is soluble in water obtains aqueous metallic ions, in described aqueous metallic ions, metal ion total concentration is 0.2
～3mol/L；
Step (2), chelating agen is added in described aqueous metallic ions, dispersed with stirring is uniform；The material of described chelating agen
The ratio of the amount of amount and described metal ion total material is 1～1.2:1；
Step (3), is dried to step (2) gained mixed solution with spray dryer, obtains described richness lithium manganese anode material
Persursor material；The inlet temperature of described spray dryer is 180～220 DEG C, and the leaving air temp of described spray dryer is
100～120 DEG C；
Step (4), calcines after step (3) gained persursor material is compacted in air atmosphere；Calcination condition is：First with
The speed of 0.5～10 DEG C/min is incubated 3～15h after being warming up to 350～500 DEG C, is then heated up with the speed of 1～10 DEG C/min again
It is incubated 5～24h to after 650～900 DEG C；Described richness lithium manganese anode material is obtained final product after being cooled to room temperature.
2. preparation method according to claim 1 is it is characterised in that in step (3), described spray dryer enter pathogenic wind-warm
Spend for 180～210 DEG C, the leaving air temp of described spray dryer is 100～110 DEG C.
3. preparation method according to claim 1 is it is characterised in that the calcination condition in step (4) is：First with 2～6
DEG C/speed of min is incubated 3～10h after being warming up to 350～450 DEG C, then it is warming up to 750 with the speed of 1～6 DEG C/min again～
It is incubated 5～15h after 900 DEG C.
4. preparation method according to claim 1 is it is characterised in that lithium salts described in step (1) is selected from Lithium hydrate, vinegar
At least one in sour lithium, lithium nitrate and lithium chloride.
5. preparation method according to claim 1 is it is characterised in that manganese salt described in step (1) is selected from manganese nitrate, acetic acid
At least one of manganese, manganese sulfate and manganese chloride.
6. preparation method according to claim 1 is it is characterised in that iron salt described in step (1) is selected from iron sulfate, nitric acid
At least one of ferrum and iron chloride.
7. preparation method according to claim 1 is it is characterised in that nickel salt described in step (1) is selected from nickel sulfate, nitric acid
At least one in nickel, Nickel dichloride. and nickel acetate.
8. preparation method according to claim 1 is it is characterised in that chelating agen described in step (2) is selected from citric acid, second
At least one in alkyd, triethanolamine, acrylic acid and oxalic acid.
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| CN111600012B (en) * | 2020-04-30 | 2023-09-26 | 孚能科技(赣州)股份有限公司 | Cobalt-free lithium-rich manganese-based positive electrode material, composite positive electrode plate and lithium ion battery |
| CN113097475A (en) * | 2021-04-02 | 2021-07-09 | 上海科技大学 | Lithium-rich layered cathode material, preparation method thereof, battery cathode formed by lithium-rich layered cathode material and battery |
| CN113991102B (en) * | 2021-12-29 | 2022-03-22 | 蜂巢能源科技股份有限公司 | Cobalt-free lithium-rich cathode material and preparation method and application thereof |
| CN116344791B (en) * | 2023-05-26 | 2023-08-08 | 天津巴莫科技有限责任公司 | Positive electrode material, preparation method thereof, positive electrode plate and battery |
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