CN100373671C - Positive electrode material (Li-Mn-Co-O) of lithium ion cell and its preparation method - Google Patents
Positive electrode material (Li-Mn-Co-O) of lithium ion cell and its preparation method Download PDFInfo
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- CN100373671C CN100373671C CNB2005100311730A CN200510031173A CN100373671C CN 100373671 C CN100373671 C CN 100373671C CN B2005100311730 A CNB2005100311730 A CN B2005100311730A CN 200510031173 A CN200510031173 A CN 200510031173A CN 100373671 C CN100373671 C CN 100373671C
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- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000007774 positive electrode material Substances 0.000 title claims description 11
- 229910020647 Co-O Inorganic materials 0.000 title claims 5
- 229910020704 Co—O Inorganic materials 0.000 title claims 5
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000002243 precursor Substances 0.000 claims abstract description 20
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims abstract description 14
- 229910052808 lithium carbonate Inorganic materials 0.000 claims abstract description 14
- 239000000463 material Substances 0.000 claims abstract description 9
- 229910001404 rare earth metal oxide Inorganic materials 0.000 claims abstract description 7
- 150000003839 salts Chemical class 0.000 claims abstract description 7
- 238000009413 insulation Methods 0.000 claims description 26
- 238000010792 warming Methods 0.000 claims description 26
- 239000013067 intermediate product Substances 0.000 claims description 21
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(2+);cobalt(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 claims description 18
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 12
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 12
- 239000011572 manganese Substances 0.000 claims description 9
- 238000000498 ball milling Methods 0.000 claims description 7
- 239000003960 organic solvent Substances 0.000 claims description 7
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 claims description 6
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- VIEVWNYBKMKQIH-UHFFFAOYSA-N [Co]=O.[Mn].[Li] Chemical compound [Co]=O.[Mn].[Li] VIEVWNYBKMKQIH-UHFFFAOYSA-N 0.000 claims description 5
- 238000009826 distribution Methods 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 5
- 229910052684 Cerium Inorganic materials 0.000 claims description 4
- 229910052691 Erbium Inorganic materials 0.000 claims description 4
- 229910052693 Europium Inorganic materials 0.000 claims description 4
- 229910052688 Gadolinium Inorganic materials 0.000 claims description 4
- 229910052689 Holmium Inorganic materials 0.000 claims description 4
- 229910052765 Lutetium Inorganic materials 0.000 claims description 4
- 229910052779 Neodymium Inorganic materials 0.000 claims description 4
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 4
- 229910052772 Samarium Inorganic materials 0.000 claims description 4
- 229910052776 Thorium Inorganic materials 0.000 claims description 4
- 229910052775 Thulium Inorganic materials 0.000 claims description 4
- 229910052769 Ytterbium Inorganic materials 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- 229910052746 lanthanum Inorganic materials 0.000 claims description 4
- 239000000320 mechanical mixture Substances 0.000 claims description 4
- 229910052706 scandium Inorganic materials 0.000 claims description 4
- 229910052692 Dysprosium Inorganic materials 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- 239000007791 liquid phase Substances 0.000 claims 2
- 239000008367 deionised water Substances 0.000 claims 1
- 229910021641 deionized water Inorganic materials 0.000 claims 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 6
- 239000010405 anode material Substances 0.000 abstract description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract 2
- 229910017052 cobalt Inorganic materials 0.000 abstract 2
- 239000010941 cobalt Substances 0.000 abstract 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 abstract 2
- 229910052744 lithium Inorganic materials 0.000 abstract 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 abstract 2
- 229910052760 oxygen Inorganic materials 0.000 abstract 2
- 239000001301 oxygen Substances 0.000 abstract 2
- GPKIXZRJUHCCKX-UHFFFAOYSA-N 2-[(5-methyl-2-propan-2-ylphenoxy)methyl]oxirane Chemical compound CC(C)C1=CC=C(C)C=C1OCC1OC1 GPKIXZRJUHCCKX-UHFFFAOYSA-N 0.000 abstract 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 abstract 1
- 229910021502 aluminium hydroxide Inorganic materials 0.000 abstract 1
- 238000001354 calcination Methods 0.000 abstract 1
- 229910001679 gibbsite Inorganic materials 0.000 abstract 1
- 239000000047 product Substances 0.000 description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- 238000004513 sizing Methods 0.000 description 8
- 239000007789 gas Substances 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 6
- 230000004087 circulation Effects 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 101100437991 Oryza sativa subsp. japonica BURP17 gene Proteins 0.000 description 5
- GOPYZMJAIPBUGX-UHFFFAOYSA-N [O-2].[O-2].[Mn+4] Chemical class [O-2].[O-2].[Mn+4] GOPYZMJAIPBUGX-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- CPABIEPZXNOLSD-UHFFFAOYSA-N lithium;oxomanganese Chemical compound [Li].[Mn]=O CPABIEPZXNOLSD-UHFFFAOYSA-N 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- IDSMHEZTLOUMLM-UHFFFAOYSA-N [Li].[O].[Co] Chemical compound [Li].[O].[Co] IDSMHEZTLOUMLM-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000000634 powder X-ray diffraction Methods 0.000 description 2
- 229910001954 samarium oxide Inorganic materials 0.000 description 2
- 229940075630 samarium oxide Drugs 0.000 description 2
- FKTOIHSPIPYAPE-UHFFFAOYSA-N samarium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[Sm+3].[Sm+3] FKTOIHSPIPYAPE-UHFFFAOYSA-N 0.000 description 2
- -1 D y Inorganic materials 0.000 description 1
- 101150058910 RDS1 gene Proteins 0.000 description 1
- 101100219167 Saccharomyces cerevisiae (strain ATCC 204508 / S288c) BUL1 gene Proteins 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 229910001940 europium oxide Inorganic materials 0.000 description 1
- AEBZCFFCDTZXHP-UHFFFAOYSA-N europium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Eu+3].[Eu+3] AEBZCFFCDTZXHP-UHFFFAOYSA-N 0.000 description 1
- URIIGZKXFBNRAU-UHFFFAOYSA-N lithium;oxonickel Chemical compound [Li].[Ni]=O URIIGZKXFBNRAU-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- 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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- Battery Electrode And Active Subsutance (AREA)
Abstract
The present invention relates to an anode material (lithium, manganese, cobalt and oxygen) of a lithium ion battery and a preparation method thereof. A precursor made of battery pole lithium carbonate, electrolytic manganese dioxide, tricobalt tetraoxide, rare-earth oxides or salt mixing materials is made into a middle product through calcination and post treatment, the middle product is mixed with LiX and the electrolytic manganese dioxide and Al(OH)3, and the double-compound lithium, manganese, cobalt and oxygen material mixed and doped with zwitterions is obtained through treatment at certain temperature. The product of the anode material has the advantages of uniform granularity, large tap density, stable performance, good uniformity, good charge and discharge capacity and good charge and discharge cycle performance.
Description
Technical field:
The present invention relates to a kind of battery material, be specifically related to a kind of positive electrode material (Li-Mn-Co-O) of lithium ion cell and preparation method thereof.
Background technology:
As three kinds of positive electrodes the most representative of lithium ion battery, lithium cobalt oxygen, lithium nickel oxygen and lithium manganese oxygen respectively have quality.Wherein lithium manganese oxygen number lattice are minimum, pollution-free, prepare also relatively easy, and its overcharging resisting security performance is good, as a kind of anode material for lithium-ion batteries, caused at present the extensive concern of numerous battery producer, but the capacitance of pure lithium manganese oxygen is lower with great potential.On the contrary, lithium cobalt oxygen be the lithium ion battery open circuit voltage height, specific energy of positive electrode big, have extended cycle life, can fast charging and discharging, but cost an arm and a leg.
Summary of the invention:
Technical problem to be solved by this invention is: solving three kinds of anode material for lithium-ion batteries the most representative of prior art respectively has quality or the lower or expensive problem of capacitance; And provide a kind of preparation technology simple and convenient, easily carry out large-scale industrialization production, greatly reduce the anode material for lithium-ion batteries cost, can guarantee positive electrode material (Li-Mn-Co-O) of lithium ion cell that charge/discharge capacity and charge-discharge performance are good and preparation method thereof.
The technical solution used in the present invention is: this positive electrode material (Li-Mn-Co-O) of lithium ion cell is prepared from by following component: battery-level lithium carbonate, cobaltosic oxide, rare earth oxide or salt, electrolytic manganese dioxide, Al (OH)
3, one or more among LiCl, LiF, LiBr, the LiOH; Above-mentioned battery-level lithium carbonate, part electrolytic manganese dioxide, cobaltosic oxide, rare earth oxide or salt are pressed Li
xMn
2-yCo
yMe
zO
4The batching batch mixing gets precursor, in the formula, and 0.95≤x≤1.2,0＜y≤0.3,0＜z≤0.3, Me is one or more among La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Th, Dy, Ho, Er, Tm, Yb, Lu, Sc, the Y; The positive electrode material (Li-Mn-Co-O) of lithium ion cell that makes is the lithium manganese cobalt oxygen material Li of two compound zwitterion mixing and dopings
xMn
2-z-m-nCo
zRE
mAl
nO
4-0.5bX
b, in the formula, 0.95≤x≤1.2,0＜z≤0.3,0＜m≤0.3,0＜n≤0.3,0＜b≤0.3, X is Cl
-, F
-, Br
-, OH
-In one or more.
The preparation method of positive electrode material (Li-Mn-Co-O) of lithium ion cell of the present invention is: battery-level lithium carbonate, electrolytic manganese dioxide, cobaltosic oxide and rare earth oxide or salt are pressed Li
xMn
2-yCo
yMe
zO
4Molecule mol ratio metering proportioning, batch mixing get precursor, in the formula, and 0.95≤x≤1.2,0＜y≤0.3,0＜z≤0.3, Me is one or more among La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Th, D y, Ho, Er, Tm, Yb, Lu, Sc, the Y; With precursor earlier through roasting, classified again screen intermediate products, again with one or more and electrolytic manganese dioxide and Al (OH) among intermediate products and LiCl, LiF, LiBr, the LiOH
3Mix, handle at a certain temperature then, obtain the lithium manganese cobalt oxygen material Li of two compound zwitterion mixing and dopings
xMn
2-z-m-nCo
zRE
mAl
nO
4-0.5bX
b, in the formula, 0.95≤x≤1.2,0＜z≤0.3,0＜m≤0.3,0＜n≤0.3,0＜b≤0.3, X is Cl
-, F
-, Br
-, OH
-In one or more.
Concrete preparation technology's method is as follows:
1. be 99.5% or 99.9% with battery-level lithium carbonate purity respectively, average grain diameter is 3-10 μ m; Cobaltosic oxide purity is greater than 99.0%, and average grain diameter is 3-10 μ m; Rare earth oxide or purity salt are greater than 99.5%, and average grain diameter is 3-10 μ m, and electrolytic manganese dioxide purity is greater than 92%, and particle size distribution is between 1-45 μ m, and average grain diameter is 10-25 μ m.Press Li
xMn
2-yCo
yMe
zO
4(0.95≤x≤1.2,0＜y≤0.3,0＜z≤0.3) batching, wherein Me is one or more among La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Th, Dy, Ho, Er, Tm, Yb, Lu, Sc, the Y.
With various raw materials by conical double ribbon revolve the batch mixer mechanical mixture get precursor or by high energy ball mill or agitating ball mill with water or organic solvent such as ethanol or acetone or wherein one or more mixing make medium, even through mixing and ball milling, get precursor through vacuumize again.
3. in the tunnel pushed bat kiln that advances continuously, control different flat-temperature zone length of fields and control different propelling speed, make precursor be warming up to 350 ℃-450 ℃ insulations 3-8 hour with 50 ℃-100 ℃/hour, the back is warming up to 550 ℃-650 ℃ insulations 5-10 hour with 50 ℃-100 ℃/hour, be warming up to 750 ℃-850 ℃ insulations 12-24 hour with 50 ℃-100 ℃/hour again, drop to room temperature with 50 ℃-100 ℃/hour at last.Or with precursor directly in the clearance-type kiln control temperature with 50 ℃/hour be warming up to 350 ℃-450 ℃ the insulation 3-8 hour, the back is warming up to 550 ℃-650 ℃ insulations 5-10 hour with 50 ℃/hour, be warming up to 750 ℃-850 ℃ insulations 12-24 hour with 50 ℃/hour again, drop to room temperature with 50 ℃/hour at last.
4. utilize gas flow sizing machine that product is carried out sizing screening, obtain the intermediate products of different average grain diameters.
5. again with intermediate products and LiX (X=Cl
-, F
-, Br
-, OH
-) in one or more and electrolytic manganese dioxide and Al (OH)
3Mix, be warming up to 750 ℃-850 ℃ insulations 12-24 hour with 50 ℃/hour then, drop to room temperature with 50 ℃/hour at last, obtain the lithium manganese cobalt oxygen material Li of two compound zwitterion mixing and dopings
xMn
2-z-m-nCo
zRE
mAl
nO
4-0.5bX
b(0.95≤x≤1.2,0＜z≤0.3,0＜m≤0.3,0＜n≤0.3,0＜b≤0.3).
Utilize the product of prescription of the present invention and preparation method preparation to have good physical property and chemical property.Product granularity is even, and average grain diameter is 10-20 μ m, and can adjust according to the requirement of different user, and the product tap density is big, greater than 2.2g/cm
3And the lithium manganese cobalt oxygen product stable performance of the present invention's preparation, good product consistency, charge/discharge capacity and charge-discharge performance are all better.
Description of drawings:
Fig. 1 is the X-ray powder diffraction figure of intermediate products RDB1.
Fig. 2 is the X-ray powder diffraction figure of embodiment 1 product.
Fig. 3 is the sem photograph of intermediate products RDB1 and embodiment 1 product, and figure middle and upper part curve is the scanning curve of embodiment 1 product, and lower curve is the scanning curve of intermediate products RDB1.
Embodiment:
Embodiment 1
Taking by weighing average grain diameter is 3-5 μ m, and purity is 99.5% battery-level lithium carbonate 18.66Kg; Purity is 99.0%, and average grain diameter is the cobaltosic oxide 2.5Kg of 3-5 μ m, and purity is 99.9%, and average grain diameter is the samarium oxide 582.5g of 3-5 μ m; Purity is 95.2%, and particle size distribution is between 1-45 μ m, and average grain diameter is the electrolytic manganese dioxide 80Kg of 22.5 μ m.Make medium by agitating ball mill with organic solvent ethanol, even through the 60min mixing and ball milling, get precursor through vacuumize again.In the tunnel pushed bat kiln that advances continuously, control different flat-temperature zone length of fields and control different propelling speed, make precursor be warming up to 450 ℃ of insulations 4 hours with 100 ℃/hour, the back is warming up to 600 ℃ of insulations 6 hours with 100 ℃/hour, be warming up to 750 ℃ of insulations 24 hours with 100 ℃/hour again, drop to room temperature with 100 ℃/hour at last.Cooled powder is obtained intermediate products through the gas flow sizing machine classification.The intermediate products average grain diameter is 13.5 μ m, tap density 2.25g/cm
3, make negative pole with carbon, discharge capacity is 105mAh/g first, after 200 circulations, capacity attenuation is less than 15%.With this intermediate products numbering RDB1.
Get 20 kilograms in above-mentioned intermediate products RDB1 sample, 2 kilograms of electrolytic manganese dioxides, lithium carbonate 200 grams, LiCl sample 48 grams, LiOH.H
2O sample 230 grams, Al (OH), sample 75 grams, pass through agitating ball mill with organic solvent ethanol as medium, even through the 30min mixing and ball milling, again through vacuumize, dried sample is warming up to 750 ℃ of insulations 15 hours with 50 ℃/hour then, drop to room temperature with 50 ℃/hour at last, cooled powder is promptly obtained final products of the present invention through the gas flow sizing machine classification.This product average grain diameter of the present invention is 12.5 μ m, tap density 2.2g/cm
3, make negative pole with carbon, discharge capacity is 110mAh/g first, after 200 circulations, capacity attenuation is less than 10%.Numbering RDS1
Embodiment 2:
Taking by weighing average grain diameter is 3-5 μ m, and purity is 99.5% battery-level lithium carbonate 16.46Kg; Purity is 99.0%, and average grain diameter is the cobaltosic oxide 2.0Kg of 3-5 μ m, and purity is 99.9%, and average grain diameter is the europium oxide 350.5g of 3-5 μ m; Purity is 96.2%, and particle size distribution is between 1-35 μ m, and average grain diameter is the electrolytic manganese dioxide 84Kg of 14.5 μ m.By twin-screw mixing procedure machine mechanical mixture 30min, get precursor through twin-screw mixing procedure machine mechanical mixture 30min again behind 200 mesh sieves excessively.In the Muffle furnace of clearance-type, make precursor be warming up to 400 ℃ of insulations 5 hours with 100 ℃/hour, the back is warming up to 550 ℃ of insulations 6 hours with 100 ℃/hour, is warming up to 750 ℃ of insulations 20 hours with 100 ℃/hour again, drops to room temperature with 100 ℃/hour at last.Cooled powder is obtained intermediate products through the gas flow sizing machine classification.The intermediate products average grain diameter is 14.2 μ m, tap density 2.3g/cm
3, make negative pole with carbon, discharge capacity is 102mAh/g first, after 200 circulations, capacity attenuation is less than 15%.With this intermediate products numbering RDB2.
Get 20 kilograms in above-mentioned intermediate products RDB2 sample, 2 kilograms of electrolytic manganese dioxides, lithium carbonate 200 grams, LiCl sample 24 grams, LiF sample 24 grams, LiOH.H
2O sample 230 grams, A l (OH)
3 Sample 75 grams, pass through agitating ball mill with organic solvent ethanol as medium, even through the 30min mixing and ball milling, again through vacuumize, dried sample is warming up to 750 ℃ of insulations 15 hours with 50 ℃/hour then, drop to room temperature with 50 ℃/hour at last, cooled powder is promptly obtained final products of the present invention through the gas flow sizing machine classification.This product average grain diameter is 13.5 μ m, tap density 2.25g/cm
3, make negative pole with carbon, discharge capacity is 105mAh/g first, after 200 circulations, capacity attenuation is less than 12%.
Taking by weighing average grain diameter is 3-5 μ m, and purity is 99.9% battery-level lithium carbonate 18.56Kg; Purity is 99.0%, and average grain diameter is the cobaltosic oxide 1.55Kg of 3-5 μ m, and purity is 99.9%, and average grain diameter is the samarium oxide 545.5g of 3-5 μ m; Purity is 97.5%, and particle size distribution is between 1-45 μ m, and average grain diameter is the electrolytic manganese dioxide 82.5Kg of 23.5 μ m.Make medium with organic solvent ethanol, even by agitating ball mill through the 45min mixing and ball milling, get precursor through vacuumize again.In the tunnel pushed bat kiln that advances continuously, control different flat-temperature zone length of fields and control different propelling speed, make precursor be warming up to 480 ℃ of insulations 4 hours with 100 ℃/hour, the back is warming up to 650 ℃ of insulations 6 hours with 100 ℃/hour, be warming up to 800 ℃ of insulations 18 hours with 100 ℃/hour again, drop to room temperature with 100 ℃/hour at last.Cooled powder is obtained intermediate products through the gas flow sizing machine classification.The intermediate products average grain diameter is 15.5 μ m, tap density 2.35g/cm
3, make negative pole with carbon, discharge capacity is 110mAh/g first, after 200 circulations, capacity attenuation is less than 12%.With this intermediate products numbering RDB3.
Get 20 kilograms in above-mentioned intermediate products RDB3 sample, 2 kilograms of electrolytic manganese dioxides, lithium carbonate 200 grams, LiCl sample 48 grams, LiF sample 24 grams, LiOH.H
2O sample 230 grams, Al (OH)
3Sample 150 grams, pass through agitating ball mill with organic solvent ethanol as medium, even through the 30min mixing and ball milling, again through vacuumize, dried sample is warming up to 750 ℃ of insulations 15 hours with 50 ℃/hour then, drop to room temperature with 50 ℃/hour at last, cooled powder is promptly obtained final products of the present invention through the gas flow sizing machine classification.This product average grain diameter is 14.0 μ m, tap density 2.30g/cm
3, make negative pole with carbon, discharge capacity is 115mAh/g first, after 200 circulations, capacity attenuation is less than 8%.
Claims (4)
1. the preparation method of a positive electrode material (Li-Mn-Co-O) of lithium ion cell is characterized in that battery-level lithium carbonate, electrolytic manganese dioxide, cobaltosic oxide and rare earth oxide or salt by Li
xMn
2-yCo
yRE
zO
4Molecule mol ratio metering proportioning, batch mixing get precursor, in the formula, and 0.95≤x≤1.2,0＜y≤0.3,0＜z≤0.3, RE is one or more among La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Th, Dy, Ho, Er, Tm, Yb, Lu, Sc, the Y; With precursor process roasting earlier, described roasting refers in the tunnel pushed bat kiln that advances continuously, control different flat-temperature zone length of fields and control different propelling speed, make precursor be warming up to 350 ℃-450 ℃ insulations 3-8 hour with 50 ℃-100 ℃/hour, the back is warming up to 550 ℃-650 ℃ insulations 5-10 hour with 50 ℃-100 ℃/hour, be warming up to 750 ℃-850 ℃ insulations 12-24 hour with 50 ℃-100 ℃/hour again, drop to room temperature with 50 ℃-100 ℃/hour at last, or with precursor directly in the clearance-type kiln control temperature with 50 ℃/hour be warming up to 350 ℃-450 ℃ the insulation 3-8 hour, the back is warming up to 550 ℃-650 ℃ insulations 5-10 hour with 50 ℃/hour, be warming up to 750 ℃-850 ℃ insulations 12-24 hour with 50 ℃/hour again, drop to room temperature with 50 ℃/hour at last; After the roasting, classified again screen intermediate products, again with one or more and electrolytic manganese dioxide, lithium carbonate and Al (OH) among intermediate products and LiCl, LiF, LiBr, the LiOH
3Press Li
xMn
2-z-m-nCo
zRE
mAl
nO
4-0.5bX
bMolecule mol ratio metering proportioning is mixed, in the formula, and 0.95≤x≤1.2,0＜z≤0.3,0＜m≤0.3,0＜n≤0.3,0＜b≤0.3, X is Cl
-, F
-, Br
-, OH
-In one or more, handle at a certain temperature then, the described processing at a certain temperature refers to be warming up to 750 ℃-850 ℃ insulations 12-24 hour with 50 ℃/hour, reduces to room temperature with 50 ℃/hour at last, obtains the lithium manganese cobalt oxygen material Li of two compound zwitterion mixing and dopings at last
xMn
2-z-m-nCo
zRE
mAl
nO
4-0.5bX
bIn the formula, 0.95≤X≤1.2,0＜z≤0.3,0＜m≤0.3,0＜n≤0.3,0＜b≤0.3, X is Cl
-, F
-, Br
-, OH
-In one or more.
2. the preparation method of positive electrode material (Li-Mn-Co-O) of lithium ion cell according to claim 1 is characterized in that described battery-level lithium carbonate purity is 99.5% or 99.9%, and average grain diameter is 3-10 μ m; Cobaltosic oxide purity is greater than 99.0%, and average grain diameter is 3-10 μ m; Rare earth oxide or purity salt are greater than 99.5%, and average grain diameter is 3-10 μ m; Electrolytic manganese dioxide purity is greater than 92%, and particle size distribution is between 1-45 μ m, and average grain diameter is 10-25 μ m.
3. the preparation method of positive electrode material (Li-Mn-Co-O) of lithium ion cell according to claim 1 is characterized in that described batch mixing comprises dry method batch mixing and material by wet type mixing; The dry method batch mixing refers to that revolving batch mixer by conical double ribbon gets precursor with the plurality of raw materials mechanical mixture; Material by wet type mixing refers to make medium by high energy ball mill or agitating ball mill with liquid phase, and the plurality of raw materials mixing and ball milling is even, gets precursor through vacuumize again.
4. the preparation method of positive electrode material (Li-Mn-Co-O) of lithium ion cell according to claim 3 is characterized in that described liquid phase medium refers to deionized water or organic solvent.
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| CN102723494A (en) * | 2012-07-05 | 2012-10-10 | 河北善鑫泰瑞电池科技有限公司 | Doped and modified high-temperature lithium manganate cathode material and preparation method thereof |
| CN103943824B (en) * | 2014-04-08 | 2016-06-29 | 贵州中伟正源新材料有限公司 | A kind of preparation method of rare earth doped ternary composite cathode material of lithium ion battery |
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| JPH09245796A (en) * | 1996-03-07 | 1997-09-19 | Toyota Central Res & Dev Lab Inc | Positive electrode material for lithium secondary battery |
| US5759720A (en) * | 1997-06-04 | 1998-06-02 | Bell Communications Research, Inc. | Lithium aluminum manganese oxy-fluorides for Li-ion rechargeable battery electrodes |
| CN1267096A (en) * | 1999-03-10 | 2000-09-20 | 三星电管株式会社 | Positive active matter for rechargeable Li cell and mfg. method thereof |
| CN1472830A (en) * | 2003-06-05 | 2004-02-04 | 上海交通大学 | Anode material of lithium ion battery and preparing method thereof |
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| JPH09245796A (en) * | 1996-03-07 | 1997-09-19 | Toyota Central Res & Dev Lab Inc | Positive electrode material for lithium secondary battery |
| US5759720A (en) * | 1997-06-04 | 1998-06-02 | Bell Communications Research, Inc. | Lithium aluminum manganese oxy-fluorides for Li-ion rechargeable battery electrodes |
| CN1267096A (en) * | 1999-03-10 | 2000-09-20 | 三星电管株式会社 | Positive active matter for rechargeable Li cell and mfg. method thereof |
| CN1472830A (en) * | 2003-06-05 | 2004-02-04 | 上海交通大学 | Anode material of lithium ion battery and preparing method thereof |
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