CN104241634A - Lithium and manganese-rich cathode material of lithium ion battery and preparation method of cathode material - Google Patents
Lithium and manganese-rich cathode material of lithium ion battery and preparation method of cathode material Download PDFInfo
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- CN104241634A CN104241634A CN201410513820.0A CN201410513820A CN104241634A CN 104241634 A CN104241634 A CN 104241634A CN 201410513820 A CN201410513820 A CN 201410513820A CN 104241634 A CN104241634 A CN 104241634A
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- manganese
- lithium
- nickel
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- rich
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- 238000002360 preparation method Methods 0.000 title claims abstract description 36
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 29
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 27
- 239000011572 manganese Substances 0.000 title claims abstract description 19
- 229910052748 manganese Inorganic materials 0.000 title claims abstract description 15
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 title abstract description 6
- 239000010406 cathode material Substances 0.000 title abstract 7
- 239000000463 material Substances 0.000 claims abstract description 50
- 238000005245 sintering Methods 0.000 claims abstract description 23
- 150000001875 compounds Chemical class 0.000 claims abstract description 20
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 14
- 229910013716 LiNi Inorganic materials 0.000 claims abstract description 11
- 238000001354 calcination Methods 0.000 claims abstract description 11
- 238000000975 co-precipitation Methods 0.000 claims abstract description 6
- 239000002904 solvent Substances 0.000 claims abstract description 4
- KLARSDUHONHPRF-UHFFFAOYSA-N [Li].[Mn] Chemical compound [Li].[Mn] KLARSDUHONHPRF-UHFFFAOYSA-N 0.000 claims description 58
- ZAUUZASCMSWKGX-UHFFFAOYSA-N manganese nickel Chemical compound [Mn].[Ni] ZAUUZASCMSWKGX-UHFFFAOYSA-N 0.000 claims description 37
- 239000000126 substance Substances 0.000 claims description 37
- 239000010405 anode material Substances 0.000 claims description 31
- 229910052782 aluminium Inorganic materials 0.000 claims description 26
- 239000000243 solution Substances 0.000 claims description 22
- 238000009413 insulation Methods 0.000 claims description 21
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 19
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 19
- 239000004411 aluminium Substances 0.000 claims description 18
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 18
- 239000002131 composite material Substances 0.000 claims description 18
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 150000001399 aluminium compounds Chemical class 0.000 claims description 14
- 239000012153 distilled water Substances 0.000 claims description 14
- 229910021645 metal ion Inorganic materials 0.000 claims description 14
- 239000002245 particle Substances 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 14
- 238000005406 washing Methods 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 13
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 229910052759 nickel Inorganic materials 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 10
- 238000001914 filtration Methods 0.000 claims description 9
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 8
- 239000003153 chemical reaction reagent Substances 0.000 claims description 8
- 238000001556 precipitation Methods 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 7
- 239000011259 mixed solution Substances 0.000 claims description 7
- 159000000013 aluminium salts Chemical class 0.000 claims description 6
- 229910000329 aluminium sulfate Inorganic materials 0.000 claims description 6
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 6
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 6
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 6
- 150000002696 manganese Chemical class 0.000 claims description 6
- 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 6
- 150000002815 nickel Chemical class 0.000 claims description 6
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 5
- UQZIWOQVLUASCR-UHFFFAOYSA-N alumane;titanium Chemical compound [AlH3].[Ti] UQZIWOQVLUASCR-UHFFFAOYSA-N 0.000 claims description 5
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 5
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 4
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 4
- 230000007062 hydrolysis Effects 0.000 claims description 4
- 238000006460 hydrolysis reaction Methods 0.000 claims description 4
- 229940071125 manganese acetate Drugs 0.000 claims description 4
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 4
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 4
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 4
- 229910000363 nickel(II) sulfate Inorganic materials 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
- 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
- 229940099596 manganese sulfate Drugs 0.000 claims description 3
- 235000007079 manganese sulphate Nutrition 0.000 claims description 3
- 239000011702 manganese sulphate Substances 0.000 claims description 3
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 3
- 229940078494 nickel acetate Drugs 0.000 claims description 3
- 230000004087 circulation Effects 0.000 abstract description 5
- -1 nickel manganese aluminum Chemical compound 0.000 abstract description 4
- 238000002156 mixing Methods 0.000 abstract description 3
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 abstract description 2
- 150000002642 lithium compounds Chemical class 0.000 abstract description 2
- 239000002243 precursor Substances 0.000 abstract description 2
- 229910007848 Li2TiO3 Inorganic materials 0.000 abstract 1
- 230000003301 hydrolyzing effect Effects 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 9
- 230000008569 process Effects 0.000 description 7
- 239000008187 granular material Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 238000007599 discharging Methods 0.000 description 5
- 230000002427 irreversible effect Effects 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 3
- 239000012798 spherical particle Substances 0.000 description 3
- 238000010998 test 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
- 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
- 229910015177 Ni1/3Co1/3Mn1/3 Inorganic materials 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 238000003487 electrochemical reaction Methods 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- 229910021314 NaFeO 2 Inorganic materials 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 239000006230 acetylene black Substances 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
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000010416 ion conductor Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 238000003913 materials processing Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 239000002195 soluble material Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910001170 xLi2MnO3-(1−x)LiMO2 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
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- 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
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
-
- 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
- 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
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Composite Materials (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention relates to a lithium and manganese-rich cathode material of a lithium ion battery and a preparation method of the cathode material. The lithium and manganese-rich cathode material is a Li2TiO3-coated xLi2MnO3.(1-x)LiNi[0.5-a/2]Mn[0.5-a/2]AlaO2 (wherein x is not less than 0.1 and not more than 0.9 and a is not less than 0.002 and not more than 0.1) material. The preparation method comprises the following steps: preparing a nickel manganese aluminum compound carbonate precursor by a coprecipitation method, sintering at the high temperature to obtain spherical or quasi-spherical nickel manganese aluminum compound oxide, adding into a solvent, uniformly dispersing, adding tetrabutyl titanate, hydrolyzing to obtain a nickel manganese aluminum titanium compound, mixing with a lithium compound, and calcining to obtain the lithium and manganese-rich cathode material. The lithium and manganese-rich cathode material prepared by the method is high in first coulombic efficiency, good in circulation stability and high in rate performance.
Description
Technical field
The present invention relates to field of lithium ion battery material, be specifically related to rich lithium manganese anode material of a kind of lithium ion battery and preparation method thereof.
Background technology
Lithium ion battery due to its energy density high, advantages such as operating voltage is high, good cycle, and be widely used in mobile phone, notebook computer, the fields such as electric automobile.Along with lithium ion battery applications field expands, higher requirement be it is also proposed to anode material for lithium-ion batteries, as higher energy density, cheap price, excellent cycle life, higher high rate performance etc.Stratiform rich lithium manganese anode material xLi
2mnO
3(1-x) LiMO
2(M=Mn, Ni, Co, Ni
0.5mn
0.5, Cr, Ni
1/3co
1/3mn
1/3, Fe ...) be a kind of α-NaFeO
2type solid-solution material, by the Li of stratiform
2mnO
3and LiMO
2(M=Mn, Ni, Co, Ni
0.5mn
0.5, Cr, Ni
1/3co
1/3mn
1/3, Fe ...) formed, with performances such as its distinctive height ratio capacity (200 ~ 300mAh/g), outstanding circulation ability and new charge discharge mechanism, become the study hotspot of current lithium ion secondary battery anode material.
Chinese patent (Zhao Yujuan, Sun Zhaoqin, Feng Hailan etc., a kind of synthetic method of spherical gradient lithium-rich anode material, China Patent No.: CN201010522413.8) discloses a kind of spherical gradient lithium-rich anode material xLi
2mnO
3(1-x) Li [Ni
0.4co
0.2mn
0.4] O
2the synthetic method of (0.1≤x≤0.4), with existing commercialization spherical precursor [Ni
0.4co
0.2mn
0.4] (OH)
2carry out Mn element coated, then with the process of the lithium hydroxide heat of mixing, 0.2C multiplying power current charge-discharge electricity, the specific capacitance that discharges first is 242mAh/g, and after 50 circulations, specific capacity is 221mAh/g.Chinese patent (Zhong Shengwen, Hu Wei, Zhang Qian, lithium-rich manganese-based anode material and preparation method thereof, China Patent No.: CN200910186311.0) discloses rich lithium base anode material Li [Li
(1-2x)/3ni
x-am
ymn
(2-x)/3-b] O
2(M=Co, Al, Ti, Mg, Cu) and preparation method thereof, adopts reactor Co deposited synthesis presoma [Ni
(x-a)/[x+ (2-x)/3]m
y/ [x+ (2-x)/3] Mn
[(2-x)/3-b]/[x+ (2-x)/3]] (OH)
2, then with lithium compound mixing high temperature sintering, 0.1C multiplying power current charge-discharge electricity, putting specific capacitance is first 250mAh/g, and under the discharge and recharge condition of 2.75-4.2V, 1C, putting specific capacitance is first 144mAh/g, and after 300 circulations, capability retention is 97%.
These materials have excellent chemical property, but the maximum problem of this kind of positive electrode one of existing is exactly when initial charge is to more than 4.5V, irreversible electrochemical reaction occurs: xLi
2mn O
3(1-x) MO
2→ xMnO
2(1-x) MO
2+ xLi
2(there is reversible de-lithium reaction when charging is less than 4.5V: xLi in O
2mnO
3(1-x) LiMO
2→ xLi
2mnO
3(1-x) MO
2+ (1-x) Li.), the Li namely in material
+with Li
2the form of O is deviate from from structure cell, and during electric discharge, this part lithium ion all cannot be embedded into original structure cell again, and cause material to have larger irreversible capacity first, coulombic efficiency is lower, and cyclical stability is poor.
In order to address this problem, a lot of researcher carries out Surface coating process to it, mainly utilizes other metal or nonmetal oxide (such as, MgO, SiO
2, ZnO, Al
2o
3, ZrO
2deng) carry out Surface coating, improve coulombic efficiency first, improve cycle performance.Coating layer and rich lithium manganese material poor compatibility, interface impedance obviously increases; After coated, resistance increases more, and high rate performance declines many; And the material granule of some preparations is little, specific area is comparatively large, poor processability.Therefore the more difficult application of rich lithium material of preparation at present.
In sum, following technical problem is there is: the maximum problem that positive electrode exists is exactly when initial charge is to more than 4.5V in prior art, there is irreversible electrochemical reaction, material is caused to have larger irreversible capacity first, coulombic efficiency is lower first, and cyclical stability is poor.
Summary of the invention
The object of the invention is to the shortcoming overcoming prior art existence, adopt a kind of new technique, the preparation method of the rich lithium manganese anode material of a kind of lithium ion battery is provided, preparation Li
2tiO
3coated xLi
2mnO
3(1-x) LiNi
0.5-a/2mn
0.5-a/2al
ao
2material, technique is simple, is easy to suitability for industrialized production.Utilize co-precipitation slow reaction to prepare spherical or class spherical nickel-manganese aluminium compound carbonate, sintering obtain nickel manganese aluminium composite oxide, then carry out tetrabutyl titanate hydrolysis coated, join lithium sintering obtain rich lithium manganese material.Concrete technical scheme is as follows:
A preparation method for the rich lithium manganese anode material of lithium ion battery, comprises the steps:
(1) nickel manganese aluminium compound carbonate presoma is prepared;
(2) sinter under high temperature, obtain spherical or class spherical nickel-manganese aluminium composite oxide;
(3) obtained for step (2) thing is added in solvent be uniformly dispersed, add butyl titanate, through hydrolysis, obtain nickel manganese aluminium titanium complex chemical compound;
(4) by the compound of nickel manganese aluminium titanium complex chemical compound and lithium, through calcining, rich lithium manganese anode material is obtained.
Further, nickel manganese aluminium compound carbonate presoma is prepared by coprecipitation in step (1).
Further, rich lithium manganese material is Li
2tiO
3coated xLi
2mnO
3(1-x) LiNi
0.5-a/2mn
0.5-a/2al
ao
2material, 0.1≤x≤0.9,0.002≤a≤0.1.
Further, step (1) specifically comprises the steps:
(1-1) according to xLi
2mnO
3(1-x) LiNi
0.5-a/2mn
0.5-a/2al
ao
2in chemical formula, Ni, Mn, Al stoichiometric proportion takes nickel salt, manganese salt, aluminium salt is made into uniform mixed aqueous solution;
(1-2) under stirring, in mixed solution, precipitation reagent lithium carbonate is added;
(1-3) after filtration or centrifugal, washing, drying obtains nickel manganese aluminium compound carbonate presoma.
Further, in step (1-1), metal ion total concentration is 0.2mol/L ~ 2.5mol/L, controlling solution temperature is 25 ~ 75 DEG C of constant temperature, and/or, the amount of substance that in step (1-2), the amount of substance of lithium carbonate is total with metal ion is identical, reaction 4 ~ 24h, and/or, the middle presoma pattern of step (1-3) is spherical or class is spherical, and particle diameter D50 is 3 ~ 25um.
Further, step (2) specifically comprises the steps: that presoma step (1) obtained is broken, then temperature programmed control air atmosphere sintering, 350 ~ 650 DEG C are heated to 0.2 ~ 10 DEG C/min programming rate, insulation 3 ~ 24h, obtains spherical or class spherical nickel-manganese aluminium composite oxide.
Further, step (3) specifically comprises the steps:
(3-1) spherical or class spherical nickel-manganese aluminium composite oxide adds in ethanol, is uniformly dispersed;
(3-2) under stirring, in solution, a certain amount of butyl titanate is added;
(3-3) drip distilled water, the amount of substance of distilled water is 4-10 times of the amount of substance of butyl titanate;
(3-4) airtight, controlling solution temperature is 90 ~ 180 DEG C of constant temperature, insulation 2-24h;
(3-5) to filter or centrifugal, washing, dry.
Further, step (4) specifically comprises the steps:
(4-1) even with the compound of lithium;
(4-2) temperature programmed control air atmosphere sintering, is heated to 450 ~ 650 DEG C with 0.2 ~ 10 DEG C/min programming rate, insulation 1 ~ 8h;
(4-3) 750 ~ 1000 DEG C are heated to 0.2 ~ 10 DEG C/min programming rate, calcining 5 ~ 48h;
(4-4) Temperature fall is to room temperature, namely obtains rich lithium manganese material.
Further, described nickel salt is one or more in nickel nitrate, nickel acetate, nickelous sulfate, nickel chloride; And/or described manganese salt is one or more in manganese nitrate, manganese acetate, manganese sulfate, manganese chloride; And/or described aluminium salt is one or more in aluminum nitrate, aluminum sulfate, aluminium chloride; And/or the compound of described lithium is one or more in lithium carbonate, lithium hydroxide, lithium acetate, lithium nitrate, lithium chloride; And/or the rich lithium manganese material particle diameter D50 of described preparation is 5-20um, and tap density is>=2.05g/cm
3.
The rich lithium manganese anode material of a kind of lithium ion battery, adopts above-mentioned any one method to obtain.
Compared with currently available technology, the coulombic efficiency first of rich lithium manganese material prepared by the present invention is high, and good cycling stability, high rate performance is high.Specifically: utilize co-precipitation slow reaction (micro-soluble material lithium carbonate is as precipitation reagent) to prepare spherical or class spherical nickel-manganese aluminium compound carbonate.Li
2tiO
3there is wider electrochemical window, having good stability in the electrolytic solution; With xLi
2mnO
3(1-x) LiNi
0.5-a/2mn
0.5-a/2al
ao
2have identical layer structure, both compatibility are good; It is monoclinic crystal structure, is commonly called as fast-ionic conductor, has quick deintercalate lithium ions diffusion admittance, therefore the rich lithium manganese of preparation has higher electric conductivity, high rate performance.And xLi
2mnO
3(1-x) LiNi
0.5-a/2mn
0.5-a/2al
ao
2containing Al
3+ion, identical number replaces Ni
2+, Mn
4+, strengthen the stability of its structure, thus improve the chemical property of material; xLi
2mnO
3(1-x) LiNi
0.5-a/2mn
0.5-a/2al
ao
2material is through Li
2tiO
3coated, suppress the generation of its initial charge process irreversible chemical reaction, coulombic efficiency is high first.Rich lithium manganese material, moderate in grain size, tap density is high, and materials processing performance is good, and preparation technology is simple, is easy to suitability for industrialized production and application.
Accompanying drawing explanation
The rich lithium manganese material SEM of Fig. 1 prepared by the embodiment of the present invention 1 schemes.
The rich lithium manganese material first charge-discharge cycle performance curve of Fig. 2 prepared by the embodiment of the present invention 1.
The rich lithium manganese material discharge cycles performance curve of Fig. 3 prepared by the embodiment of the present invention 1.
The rich lithium manganese material of Fig. 4 prepared by the embodiment of the present invention 1 discharges cycle performance curve under different discharge-rate.
Embodiment
Describe the present invention with reference to the accompanying drawings below, it is a kind of preferred embodiment in numerous embodiments of the present invention.
A preparation method for the rich lithium manganese anode material of lithium ion battery, this rich lithium manganese material is Li
2tiO
3coated xLi
2mnO
3(1-x) LiNi
0.5-a/2mn
0.5-a/2al
ao
2(wherein, 0.1≤x≤0.9,0.002≤a≤0.1) material, nickel manganese aluminium compound carbonate presoma is prepared by coprecipitation, then at high temperature sinter, obtain spherical or class spherical nickel-manganese aluminium composite oxide, added in solvent and be uniformly dispersed, add butyl titanate, through hydrolysis, obtain nickel manganese aluminium titanium complex chemical compound, with the compound of lithium, through calcining, obtain rich lithium manganese anode material.Specifically:
Step 1. prepares presoma
According to xLi
2mnO
3(1-x) LiNi
0.5-a/2mn
0.5-a/2al
ao
2in chemical formula, Ni, Mn, Al stoichiometric proportion takes nickel salt, manganese salt, aluminium salt is made into uniform mixed aqueous solution, metal ion total concentration is 0.2mol/L ~ 2.5mol/L, controlling solution temperature is 25 ~ 75 DEG C of constant temperature, under stirring, precipitation reagent lithium carbonate is added in mixed solution, the amount of substance that the amount of substance of lithium carbonate is total with metal ion is identical, reaction 4 ~ 24h, after filtration or centrifugal, washing, drying obtains nickel manganese aluminium compound carbonate presoma, pattern is spherical or class is spherical, and particle diameter D50 is 3 ~ 25um.
Step 2. presoma is through sintering processes
Above-mentioned presoma is broken, and then temperature programmed control air atmosphere sintering, is heated to 350 ~ 650 DEG C with 0.2 ~ 10 DEG C/min programming rate, and insulation 3 ~ 24h, obtains spherical or class spherical nickel-manganese aluminium composite oxide.
The preparation of the rich lithium manganese material of step 3.
Spherical or class spherical nickel-manganese aluminium composite oxide adds in ethanol, be uniformly dispersed, under stirring, a certain amount of butyl titanate is added in solution, drip distilled water, the amount of substance of distilled water is 4-10 times of the amount of substance of butyl titanate, airtight, controlling solution temperature is 90 ~ 180 DEG C of constant temperature, insulation 2-24h, after filtration or centrifugal, washing, dry, with compound (the slightly excessive 2-10% of Li of lithium, in order to the compound compensating lithium at high temperature volatilizees on a small quantity) mix, then temperature programmed control air atmosphere sintering, 450 ~ 650 DEG C are heated to 0.2 ~ 10 DEG C/min programming rate, insulation 1 ~ 8h, be heated to 750 ~ 1000 DEG C with 0.2 ~ 10 DEG C/min programming rate, calcining 5 ~ 48h, then Temperature fall is to room temperature, namely obtains rich lithium manganese material.Wherein, Li
2tiO
3account for the 0.2%-10% of rich lithium manganese gross mass.Described nickel salt is one or more in nickel nitrate, nickel acetate, nickelous sulfate, nickel chloride.Described manganese salt is one or more in manganese nitrate, manganese acetate, manganese sulfate, manganese chloride.Described aluminium salt is one or more in aluminum nitrate, aluminum sulfate, aluminium chloride.The compound of described lithium is one or more in lithium carbonate, lithium hydroxide, lithium acetate, lithium nitrate, lithium chloride.The rich lithium manganese material particle diameter D50 of described preparation is 5-20um, and tap density is>=2.05g/cm
3.
Embodiment 1
The present embodiment provides the preparation method of the rich lithium manganese anode material of a kind of lithium ion battery, and this material is Li
2tiO
3coated 0.5Li
2mnO
30.5LiNi
0.485mn
0.485al
0.03o
2material, Li
2tiO
3account for 3.5% of rich lithium manganese gross mass.It comprises the following steps.
Step 1. prepares presoma
According to 0.5Li
2mnO
30.5LiNi
0.485mn
0.485al
0.03o
2in chemical formula, Ni, Mn, Al stoichiometric proportion takes nickelous sulfate, manganese nitrate, aluminum sulfate is made into uniform mixed aqueous solution, metal ion total concentration is 0.5mol/L, controlling solution temperature is 40 DEG C of constant temperature, under stirring, add precipitation reagent lithium carbonate in mixed solution, the amount of substance that the amount of substance of lithium carbonate is total with metal ion is identical, reaction 8h, after filtration, washing, drying obtains nickel manganese aluminium compound carbonate presoma, and pattern is spheric granules, and particle diameter D50 is 13.2um.
Step 2. presoma is through sintering processes
Above-mentioned presoma is broken, and then temperature programmed control air atmosphere sintering, is heated to 400 DEG C with 6 DEG C/min programming rate, and insulation 6h, obtains spherical or class spherical nickel-manganese aluminium composite oxide.
The preparation of the rich lithium manganese material of step 3.
Spherical or class spherical nickel-manganese aluminium composite oxide adds in ethanol, be uniformly dispersed, under stirring, a certain amount of butyl titanate is added in solution, drip distilled water, the amount of substance of distilled water is 4 times of the amount of substance of butyl titanate, airtight, controlling solution temperature is 120 DEG C, insulation 5h, after filtration, washing, drying, mix with lithium carbonate (Li slightly excessive 6%, in order to the compound compensating lithium at high temperature volatilizees on a small quantity), then temperature programmed control air atmosphere sintering, 550 DEG C are heated to, insulation 2h with 5 DEG C/min programming rate; Be heated to 800 DEG C with 6 DEG C/min programming rate, calcining 12h, then Temperature fall is to room temperature, namely obtains rich lithium manganese material.
SEM test result shows that product is spheric granules as shown in Figure 1, and particle diameter D50 is 12.5um, and tap density is detected as 2.4g/cm
3.
Button cell makes:
Rich lithium manganese material is mixed according to mass ratio 8:1:1 with conductive agent acetylene black, binding agent PVDF (Kynoar), with NMP (1-Methyl-2-Pyrrolidone), this mixture is modulated into slurry, evenly be coated on aluminium foil, put into baking oven, dry 1h for 80-120 DEG C, take out and be washed into circular pole piece, 85 DEG C of vacuumize 12 hours, carry out compressing tablet, 85 DEG C of vacuumize 12 hours, obtained experimental cell pole piece.Be to electrode with lithium sheet, electrolyte is 1.5mol/L LiPF
6eC (ethyl carbonate ester)+DMC (dimethyl carbonate) (volume ratio 1:3) solution, barrier film is celgard2325 film, is assembled into CR2025 type button cell in the glove box being full of argon gas atmosphere.Be washed into circular pole piece, 85 DEG C of vacuumize 12 hours, carries out compressing tablet, 85 DEG C of vacuumize 12 hours, obtained experimental cell pole piece.
As shown in Figure 2, first charge-discharge loop test is carried out to this button cell: charging/discharging voltage scope is 4.8 ~ 2.0V, be the condition of 0.1C (1C=250mA/g) at charging and discharging currents under, first charge-discharge specific capacity is respectively 283.191mAh/g, 256.045mAh/g, initial coulomb efficiency is 90.4%, and efficiency is higher first.
As shown in Figure 3, be the condition of 0.2C at charging and discharging currents under, first discharge specific capacity is 248.57mAh/g, and 100 specific capacities that circulate are 238.01mAh/g, and capability retention is 95.75%, and cyclical stability is better.
As shown in Figure 4, high rate performance test is carried out to this button cell: charging/discharging voltage scope is 4.8 ~ 2.0V, and charging current is 0.1C, and discharging current is respectively 0.1C, 0.2C, 0.5C, 1C, 2C, 5C, each circulation 5 times.Wherein, 1C=250mA/g.High rate performance test result shows, 5C specific discharge capacity is still at more than 150mAh, and high rate performance is better.
Embodiment 2
The present embodiment provides the preparation method of the rich lithium manganese anode material of a kind of lithium ion battery, and this material is Li
2tiO
3coated 0.3Li
2mnO
30.7LiNi
0.47mn
0.47al
0.06o
2material, Li
2tiO
3account for 0.3% of rich lithium manganese gross mass.It comprises the following steps.
Step 1. prepares presoma
According to 0.3Li
2mnO
30.7LiNi
0.47mn
0.47al
0.06o
2in chemical formula, Ni, Mn, Al stoichiometric proportion takes nickel nitrate, manganese nitrate, aluminum nitrate be made into uniform mixed aqueous solution, metal ion total concentration is 2.0mol/L, controlling solution temperature is 65 DEG C of constant temperature, under stirring, add precipitation reagent lithium carbonate in mixed solution, the amount of substance that the amount of substance of lithium carbonate is total with metal ion is identical, reaction 15h, after filtration, washing, drying obtains nickel manganese aluminium compound carbonate presoma, and pattern is spheric granules, and particle diameter D50 is 10.4um.
Step 2. presoma is through sintering processes
Above-mentioned presoma is broken, and then temperature programmed control air atmosphere sintering, is heated to 480 DEG C with 2 DEG C/min programming rate, and insulation 15h, obtains spherical or class spherical nickel-manganese aluminium composite oxide.
The preparation of the rich lithium manganese material of step 3.
Spherical or class spherical nickel-manganese aluminium composite oxide adds in ethanol, be uniformly dispersed, under stirring, a certain amount of butyl titanate is added in solution, drip distilled water, the amount of substance of distilled water is 6 times of the amount of substance of butyl titanate, airtight, controlling solution temperature is 90 DEG C, insulation 18h, through centrifugal, washing, drying, mix with lithium acetate (Li slightly excessive 2%, in order to the compound compensating lithium at high temperature volatilizees on a small quantity), then temperature programmed control air atmosphere sintering, 650 DEG C are heated to, insulation 1h with 2 DEG C/min programming rate; Be heated to 950 DEG C with 3 DEG C/min programming rate, calcining 18h, then Temperature fall is to room temperature, namely obtains rich lithium manganese material.
SEM test result shows that product is spherical or spherical particle, and particle diameter D50 is 8.6um, and tap density is detected as 2.3g/cm
3.
Assembled battery method of testing is all with embodiment 1, and discharge cycles test data is in table 1.
Embodiment 3
The present embodiment provides the preparation method of the rich lithium manganese anode material of a kind of lithium ion battery, and this material is Li
2tiO
3coated 0.8Li
2mnO
30.2LiNi
0.49mn
0.49al
0.02o
2material, Li
2tiO
3account for 8.5% of rich lithium manganese gross mass.It comprises the following steps.
Step 1. prepares presoma
According to 0.8Li
2mnO
30.2LiNi
0.49mn
0.49al
0.02o
2in chemical formula, Ni, Mn, Al stoichiometric proportion takes nickel nitrate, manganese nitrate, aluminum nitrate be made into uniform mixed aqueous solution, metal ion total concentration is 0.8mol/L, controlling solution temperature is 28 DEG C of constant temperature, under stirring, add precipitation reagent lithium carbonate in mixed solution, the amount of substance that the amount of substance of lithium carbonate is total with metal ion is identical, reaction 10h, after filtration, washing, drying obtains nickel manganese aluminium compound carbonate presoma, and pattern is spheric granules, and particle diameter D50 is 6.2um.
Step 2. presoma is through sintering processes
Above-mentioned presoma is broken, and then temperature programmed control air atmosphere sintering, is heated to 350 DEG C with 8 DEG C/min programming rate, and insulation 5h, obtains spherical or class spherical nickel-manganese aluminium composite oxide.
The preparation of the rich lithium manganese material of step 3.
Spherical or class spherical nickel-manganese aluminium composite oxide adds in ethanol, be uniformly dispersed, under stirring, a certain amount of butyl titanate is added in solution, drip distilled water, the amount of substance of distilled water is 4.2 times of the amount of substance of butyl titanate, airtight, controlling solution temperature is 100 DEG C, insulation 20h, through centrifugal, washing, dry, with lithium acetate (Li slightly excessive 4%, in order to the compound compensating lithium at high temperature volatilizees on a small quantity) mix, then temperature programmed control air atmosphere sintering, 450 DEG C are heated to 3 DEG C/min programming rate, insulation 1.5h, be heated to 750 DEG C with 10 DEG C/min programming rate, calcining 30h, then Temperature fall is to room temperature, namely obtains rich lithium manganese material.
SEM test result shows that product is spherical or spherical particle, and particle diameter D50 is 14.8um, and tap density is detected as 2.52g/cm
3.
Assembled battery method of testing is all with embodiment 1, and discharge cycles test data is in table 1.
Embodiment 4
The present embodiment provides the preparation method of the rich lithium manganese anode material of a kind of lithium ion battery, and this material is Li
2tiO
3coated 0.25Li
2mnO
30.75LiNi
0.46mn
0.46al
0.08o
2material, Li
2tiO
3account for 1.9% of rich lithium manganese gross mass.It comprises the following steps.
Step 1. prepares presoma
According to 0.25Li
2mnO
30.75LiNi
0.46mn
0.46al
0.08o
2in chemical formula, Ni, Mn, Al stoichiometric proportion takes nickel chloride, manganese acetate, aluminium chloride is made into uniform mixed aqueous solution, metal ion total concentration is 1.5mol/L, controlling solution temperature is 50 DEG C of constant temperature, under stirring, add precipitation reagent lithium carbonate in mixed solution, the amount of substance that the amount of substance of lithium carbonate is total with metal ion is identical, reaction 15h, after filtration, washing, drying obtains nickel manganese aluminium compound carbonate presoma, and pattern is spheric granules, and particle diameter D50 is 16.53um.
Step 2. presoma is through sintering processes
Above-mentioned presoma is broken, and then temperature programmed control air atmosphere sintering, is heated to 620 DEG C with 6 DEG C/min programming rate, and insulation 10h, obtains spherical or class spherical nickel-manganese aluminium composite oxide.
The preparation of the rich lithium manganese material of step 3.
Spherical or class spherical nickel-manganese aluminium composite oxide adds in ethanol, be uniformly dispersed, under stirring, a certain amount of butyl titanate is added in solution, drip distilled water, the amount of substance of distilled water is 9.5 times of the amount of substance of butyl titanate, airtight, controlling solution temperature is 95 DEG C, insulation 11h, through centrifugal, washing, drying, mix with lithium acetate (Li slightly excessive 5%, in order to the compound compensating lithium at high temperature volatilizees on a small quantity), then temperature programmed control air atmosphere sintering, 520 DEG C are heated to, insulation 2h with 4 DEG C/min programming rate; Be heated to 900 DEG C with 6 DEG C/min programming rate, calcining 14h, then Temperature fall is to room temperature, namely obtains rich lithium manganese material.
SEM test result shows that product is spherical or spherical particle, and particle diameter D50 is 18.5um, and tap density is detected as 2.48g/cm
3.
Assembled battery method of testing is all with embodiment 1, and discharge cycles test data is in table 1.
The rich lithium manganese anode material discharge cycles test data of table 1 prepared by the embodiment of the present invention.
Above by reference to the accompanying drawings to invention has been exemplary description; obvious specific implementation of the present invention is not subject to the restrictions described above; as long as have employed the various improvement that method of the present invention is conceived and technical scheme is carried out; or directly apply to other occasion, all within protection scope of the present invention without improving.
Claims (10)
1. a preparation method for the rich lithium manganese anode material of lithium ion battery, is characterized in that, comprise the steps:
(1) nickel manganese aluminium compound carbonate presoma is prepared;
(2) sinter under high temperature, obtain spherical or class spherical nickel-manganese aluminium composite oxide;
(3) obtained for step (2) thing is added in solvent be uniformly dispersed, add butyl titanate, through hydrolysis, obtain nickel manganese aluminium titanium complex chemical compound;
(4) by the compound of nickel manganese aluminium titanium complex chemical compound and lithium, through calcining, rich lithium manganese anode material is obtained.
2. the preparation method of the rich lithium manganese anode material of lithium ion battery as claimed in claim 1, is characterized in that, prepare nickel manganese aluminium compound carbonate presoma in step (1) by coprecipitation.
3. the preparation method of the rich lithium manganese anode material of lithium ion battery as claimed in claim 1 or 2, it is characterized in that, rich lithium manganese material is Li
2tiO
3coated xLi
2mnO
3(1-x) LiNi
0.5-a/2mn
0.5-a/2al
ao
2material, 0.1≤x≤0.9,0.002≤a≤0.1.
4. the preparation method of the rich lithium manganese anode material of the lithium ion battery according to any one of claim 1-3, it is characterized in that, step (1) specifically comprises the steps:
(1-1) according to xLi
2mnO
3(1-x) LiNi
0.5-a/2mn
0.5-a/2al
ao
2in chemical formula, Ni, Mn, Al stoichiometric proportion takes nickel salt, manganese salt, aluminium salt is made into uniform mixed aqueous solution;
(1-2) under stirring, in mixed solution, precipitation reagent lithium carbonate is added;
(1-3) after filtration or centrifugal, washing, drying obtains nickel manganese aluminium compound carbonate presoma.
5. the preparation method of the rich lithium manganese anode material of lithium ion battery as claimed in claim 4, it is characterized in that, in step (1-1), metal ion total concentration is 0.2mol/L ~ 2.5mol/L, controlling solution temperature is 25 ~ 75 DEG C of constant temperature, and/or the amount of substance that in step (1-2), the amount of substance of lithium carbonate is total with metal ion is identical, reaction 4 ~ 24h, and/or the middle presoma pattern of step (1-3) is spherical or class is spherical, and particle diameter D50 is 3 ~ 25um.
6. the preparation method of the rich lithium manganese anode material of the lithium ion battery according to any one of claim 1-5, it is characterized in that, step (2) specifically comprises the steps: that presoma step (1) obtained is broken, then temperature programmed control air atmosphere sintering, 350 ~ 650 DEG C are heated to 0.2 ~ 10 DEG C/min programming rate, insulation 3 ~ 24h, obtains spherical or class spherical nickel-manganese aluminium composite oxide.
7. the preparation method of the rich lithium manganese anode material of the lithium ion battery according to any one of claim 1-6, it is characterized in that, step (3) specifically comprises the steps:
(3-1) spherical or class spherical nickel-manganese aluminium composite oxide adds in ethanol, is uniformly dispersed;
(3-2) under stirring, in solution, a certain amount of butyl titanate is added;
(3-3) drip distilled water, the amount of substance of distilled water is 4-10 times of the amount of substance of butyl titanate;
(3-4) airtight, controlling solution temperature is 90 ~ 180 DEG C of constant temperature, insulation 2-24h;
(3-5) to filter or centrifugal, washing, dry.
8. the preparation method of the rich lithium manganese anode material of the lithium ion battery according to any one of claim 1-7, it is characterized in that, step (4) specifically comprises the steps:
(4-1) even with the compound of lithium;
(4-2) temperature programmed control air atmosphere sintering, is heated to 450 ~ 650 DEG C with 0.2 ~ 10 DEG C/min programming rate, insulation 1 ~ 8h;
(4-3) 750 ~ 1000 DEG C are heated to 0.2 ~ 10 DEG C/min programming rate, calcining 5 ~ 48h;
(4-4) Temperature fall is to room temperature, namely obtains rich lithium manganese material.
9. the preparation method of the rich lithium manganese anode material of the lithium ion battery according to any one of claim 1-8, it is characterized in that, described nickel salt is one or more in nickel nitrate, nickel acetate, nickelous sulfate, nickel chloride; And/or described manganese salt is one or more in manganese nitrate, manganese acetate, manganese sulfate, manganese chloride; And/or described aluminium salt is one or more in aluminum nitrate, aluminum sulfate, aluminium chloride; And/or the compound of described lithium is one or more in lithium carbonate, lithium hydroxide, lithium acetate, lithium nitrate, lithium chloride; And/or the rich lithium manganese material particle diameter D50 of described preparation is 5-20um, and tap density is>=2.05g/cm
3.
10. the rich lithium manganese anode material of lithium ion battery, is characterized in that, adopts method any one of claim 1-9 to obtain.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104617286A (en) * | 2015-01-18 | 2015-05-13 | 北京工业大学 | Simple surface modification method of Li-rich cathode material |
| CN110911663A (en) * | 2019-11-13 | 2020-03-24 | 惠州学院 | Lithium-rich manganese-based composite lithium battery positive electrode material and manufacturing method thereof |
| CN111115714A (en) * | 2019-12-30 | 2020-05-08 | 北京机科国创轻量化科学研究院有限公司 | Micron-sized non-agglomerated primary particle lithium-rich manganese-based material and preparation method thereof |
| CN111740085A (en) * | 2020-06-19 | 2020-10-02 | 贵州梅岭电源有限公司 | Coating modification method of lithium-rich manganese-based positive electrode material |
| CN111785913A (en) * | 2020-07-01 | 2020-10-16 | 厦门大学 | Preparation method of waxberry-shaped lithium-rich cathode material for lithium battery |
| CN113871589A (en) * | 2021-09-16 | 2021-12-31 | 南开大学 | Lithium-rich manganese-based positive electrode material coated with lithium titanate assisted by molten salt and preparation method thereof |
| CN116682972A (en) * | 2023-06-16 | 2023-09-01 | 长沙理工大学 | Selenium and titanium aluminum lithium phosphate double-modified lithium-rich manganese anode material and preparation method thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102054976A (en) * | 2010-12-10 | 2011-05-11 | 王志勇 | Preparation method of lithium ion battery cathode material |
| CN103247797A (en) * | 2013-05-20 | 2013-08-14 | 深圳市贝特瑞新能源材料股份有限公司 | Positive pole material for lithium ion battery and preparation method of positive pole material |
| CN103500827A (en) * | 2013-10-11 | 2014-01-08 | 宁德新能源科技有限公司 | Lithium ion battery and multi-element positive material thereof as well as preparation method of multi-element positive material |
| CN103700833A (en) * | 2012-09-27 | 2014-04-02 | 清华大学 | Lithium ion battery anode composite material |
| CN103943846A (en) * | 2014-04-18 | 2014-07-23 | 江苏大学 | Preparation method of lithium ion battery positive-electrode material precursor |
| CN104022276A (en) * | 2014-06-09 | 2014-09-03 | 南京航空航天大学 | Clad modified layered cathode material of lithium-ion battery and preparation method of layered cathode material |
-
2014
- 2014-09-29 CN CN201410513820.0A patent/CN104241634B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102054976A (en) * | 2010-12-10 | 2011-05-11 | 王志勇 | Preparation method of lithium ion battery cathode material |
| CN103700833A (en) * | 2012-09-27 | 2014-04-02 | 清华大学 | Lithium ion battery anode composite material |
| CN103247797A (en) * | 2013-05-20 | 2013-08-14 | 深圳市贝特瑞新能源材料股份有限公司 | Positive pole material for lithium ion battery and preparation method of positive pole material |
| CN103500827A (en) * | 2013-10-11 | 2014-01-08 | 宁德新能源科技有限公司 | Lithium ion battery and multi-element positive material thereof as well as preparation method of multi-element positive material |
| CN103943846A (en) * | 2014-04-18 | 2014-07-23 | 江苏大学 | Preparation method of lithium ion battery positive-electrode material precursor |
| CN104022276A (en) * | 2014-06-09 | 2014-09-03 | 南京航空航天大学 | Clad modified layered cathode material of lithium-ion battery and preparation method of layered cathode material |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104617286A (en) * | 2015-01-18 | 2015-05-13 | 北京工业大学 | Simple surface modification method of Li-rich cathode material |
| CN110911663A (en) * | 2019-11-13 | 2020-03-24 | 惠州学院 | Lithium-rich manganese-based composite lithium battery positive electrode material and manufacturing method thereof |
| CN111115714A (en) * | 2019-12-30 | 2020-05-08 | 北京机科国创轻量化科学研究院有限公司 | Micron-sized non-agglomerated primary particle lithium-rich manganese-based material and preparation method thereof |
| CN111740085A (en) * | 2020-06-19 | 2020-10-02 | 贵州梅岭电源有限公司 | Coating modification method of lithium-rich manganese-based positive electrode material |
| CN111740085B (en) * | 2020-06-19 | 2022-02-01 | 贵州梅岭电源有限公司 | Coating modification method of lithium-rich manganese-based positive electrode material |
| CN111785913A (en) * | 2020-07-01 | 2020-10-16 | 厦门大学 | Preparation method of waxberry-shaped lithium-rich cathode material for lithium battery |
| CN111785913B (en) * | 2020-07-01 | 2021-11-16 | 厦门大学 | Preparation method of waxberry-shaped lithium-rich cathode material for lithium battery |
| CN113871589A (en) * | 2021-09-16 | 2021-12-31 | 南开大学 | Lithium-rich manganese-based positive electrode material coated with lithium titanate assisted by molten salt and preparation method thereof |
| CN113871589B (en) * | 2021-09-16 | 2023-10-24 | 南开大学 | Lithium-rich manganese-based positive electrode material coated by molten salt-assisted lithium titanate and preparation method thereof |
| CN116682972A (en) * | 2023-06-16 | 2023-09-01 | 长沙理工大学 | Selenium and titanium aluminum lithium phosphate double-modified lithium-rich manganese anode material and preparation method thereof |
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