CN103490058A - Preparation method of doped layered lithium manganate - Google Patents
Preparation method of doped layered lithium manganate Download PDFInfo
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- CN103490058A CN103490058A CN201310464905.XA CN201310464905A CN103490058A CN 103490058 A CN103490058 A CN 103490058A CN 201310464905 A CN201310464905 A CN 201310464905A CN 103490058 A CN103490058 A CN 103490058A
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- manganese
- lithium manganate
- layered lithium
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- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000000203 mixture Substances 0.000 claims abstract description 34
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 21
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims abstract description 18
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 18
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000011572 manganese Substances 0.000 claims abstract description 15
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000000227 grinding Methods 0.000 claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims abstract description 7
- 238000001816 cooling Methods 0.000 claims abstract description 7
- 238000007603 infrared drying Methods 0.000 claims abstract description 7
- VASIZKWUTCETSD-UHFFFAOYSA-N oxomanganese Chemical compound [Mn]=O VASIZKWUTCETSD-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000005406 washing Methods 0.000 claims abstract description 7
- 150000001449 anionic compounds Chemical class 0.000 claims abstract description 6
- 150000001767 cationic compounds Chemical class 0.000 claims abstract description 6
- 238000001354 calcination Methods 0.000 claims abstract description 4
- 239000007788 liquid Substances 0.000 claims abstract description 4
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 9
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 6
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 claims description 6
- HSZCZNFXUDYRKD-UHFFFAOYSA-M lithium iodide Chemical compound [Li+].[I-] HSZCZNFXUDYRKD-UHFFFAOYSA-M 0.000 claims description 6
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 5
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 4
- -1 Schweinfurt green Chemical compound 0.000 claims description 4
- VGBWDOLBWVJTRZ-UHFFFAOYSA-K cerium(3+);triacetate Chemical compound [Ce+3].CC([O-])=O.CC([O-])=O.CC([O-])=O VGBWDOLBWVJTRZ-UHFFFAOYSA-K 0.000 claims description 3
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 3
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 3
- XKPJKVVZOOEMPK-UHFFFAOYSA-M lithium;formate Chemical compound [Li+].[O-]C=O XKPJKVVZOOEMPK-UHFFFAOYSA-M 0.000 claims description 3
- 229940071125 manganese acetate Drugs 0.000 claims description 3
- 239000011656 manganese carbonate Substances 0.000 claims description 3
- 229940093474 manganese carbonate Drugs 0.000 claims description 3
- 235000006748 manganese carbonate Nutrition 0.000 claims description 3
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 3
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 claims description 3
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 claims description 3
- 229960004643 cupric oxide Drugs 0.000 claims description 2
- TYTHZVVGVFAQHF-UHFFFAOYSA-N manganese(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Mn+3].[Mn+3] TYTHZVVGVFAQHF-UHFFFAOYSA-N 0.000 claims description 2
- GEYXPJBPASPPLI-UHFFFAOYSA-N manganese(III) oxide Inorganic materials O=[Mn]O[Mn]=O GEYXPJBPASPPLI-UHFFFAOYSA-N 0.000 claims description 2
- 230000003647 oxidation Effects 0.000 claims description 2
- 238000007254 oxidation reaction Methods 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 10
- 238000000034 method Methods 0.000 abstract description 9
- 239000000126 substance Substances 0.000 abstract description 6
- 238000002156 mixing Methods 0.000 abstract description 5
- 230000008901 benefit Effects 0.000 abstract description 4
- 229910016141 LiMn1-x Inorganic materials 0.000 abstract description 3
- 239000002243 precursor Substances 0.000 abstract 3
- 239000007795 chemical reaction product Substances 0.000 abstract 1
- 238000011031 large-scale manufacturing process Methods 0.000 abstract 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 9
- 239000004570 mortar (masonry) Substances 0.000 description 9
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 6
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 6
- 238000013019 agitation Methods 0.000 description 6
- 239000010406 cathode material Substances 0.000 description 6
- 239000002131 composite material Substances 0.000 description 6
- 229910001416 lithium ion Inorganic materials 0.000 description 6
- LBSANEJBGMCTBH-UHFFFAOYSA-N manganate Chemical compound [O-][Mn]([O-])(=O)=O LBSANEJBGMCTBH-UHFFFAOYSA-N 0.000 description 6
- 229910002993 LiMnO2 Inorganic materials 0.000 description 4
- 229910017052 cobalt Inorganic materials 0.000 description 4
- 239000010941 cobalt Substances 0.000 description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 3
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 3
- 239000002033 PVDF binder Substances 0.000 description 3
- 239000006230 acetylene black Substances 0.000 description 3
- 239000005030 aluminium foil Substances 0.000 description 3
- 230000004888 barrier function Effects 0.000 description 3
- 230000004087 circulation Effects 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 3
- 235000011837 pasties Nutrition 0.000 description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000010189 synthetic method Methods 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- 239000002253 acid Substances 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 229910052596 spinel Inorganic materials 0.000 description 2
- 239000011029 spinel Substances 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- AMWRITDGCCNYAT-UHFFFAOYSA-L manganese oxide Inorganic materials [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 238000003836 solid-state method Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—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
- 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
-
- 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)
- Composite Materials (AREA)
- Inorganic Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention relates to a preparation method of doped layered lithium manganate. The layered lithium manganate made by the method provided in the invention has a chemical formula shown as LiMn1-x(M)xO2-y(N)y. The making steps include: (1) making a precursor: mixing a manganese source, a cationic compound, and an anionic compound uniformly in a ratio of (0.95-1):(0-0.05):(0-0.02), then calcining the mixture at a high temperature of 500-900DEG C for 4-6h to generate a doped manganese oxygen compound, performing natural cooling, then taking it out, and conducting fully grinding again for 30min, thus obtaining the precursor; (2) mixing the lithium source with the precursor obtained in step (1) in a ratio of 1:(0.95-0.98), carrying out grinding for 30min, then adding sodium hydroxide or potassium hydroxide to further perform grinding for 10min, thus obtaining a mixture A; (3) dissolving the mixture A made in step (2) with ethanol absolute, adding the dissolved liquid into a high-pressure reaction kettle to let it react for 2-10h at 180-300DEG C in an infrared drying box, then taking the reaction product out and performing centrifugal washing, thus obtaining the doped layered lithium manganate. The battery manufactured from the material provided in the invention has the advantage of stable performance, is suitable for large-scale production and use.
Description
Technical field
The invention belongs to lithium ion battery material and manufacture field, be specifically related to a kind of preparation method and application thereof of the stratiform manganate cathode material for lithium that adulterates.
Background technology
Along with economic development, people more and more pay close attention to for energy problem, oil price rises violently and makes people, to new forms of energy, darker understanding arranged, the preferred material of 2008 year country's " 863 Program " Modern Transportation Technology field " energy-conservation and new-energy automobile " major projects using manganate cathode material for lithium as electrokinetic cell particularly, lithium ion battery material faces an opportunity to develop.Take electric automobile power battery as representative, and the lithium ion battery field forms.The staple lithium ion anode material is mainly cobalt acid lithium at present, the technology comparative maturity, and chemical property is best, be to use at present maximum materials, but cobalt resource is rare, price, it is poor that battery security is compared other materials.The cobalt resource of China is relatively less in addition, is unfavorable for the sustainable development of cobalt acid lithium.China has abundant manganese resource, it is reported with regard to pyrolusite, abundant at ground reserves such as Hunan, Guangxi, approximately has several ten million tons, so LiMn2O4 has advantage as following electrokinetic cell.
LiMn2O4 has spinelle and two kinds of configurations of stratiform, and for spinel lithium manganate (LiMn2O4), although applied, because its cycle performance is poor, particularly at high temperature capacity attenuation is serious, fails to widely apply in reality.And the theoretical specific capacity of layered lithium manganate (LiMnO2) is up to 285mAh/g, it is the spinel-type twice, layered lithium manganate is divided into three kinds of crystal formation: γ-LiMnO2, m-LiMnO2, ο-LiMnO2, but layered lithium manganate exists a lot of distinct issues (as poor as the high-temperature thermal stability performance when application, the Stability Analysis of Structures performance is poor, the high temperature capacity attenuation is serious), therefore how to solve the direction that these outstanding problems are layered lithium manganate development.
The layered lithium manganate compound has nontoxic, low cost and other advantages, be considered to have most the positive electrode of development potentiality, main synthetic method has: high temperature solid-state method, low temperature synthetic method, ion-exchange, chemical reduction method etc., but prior art can't be brought into play the excellent properties of layered lithium manganate itself, sometimes also can affect its electrical stability energy, cause the problems such as capacity attenuation.
Summary of the invention
The present invention is directed to the shortcoming of traditional synthetic method, the preparation method of involutory one-tenth layered lithium manganate carries out technological improvement, optimize the architectural characteristic of LiMn2O4, the variation of structure after minimizing lithium ion desorption, stable laminated structure carries out the doping of anion on the basis of cation doping simultaneously, increases initial capacity, reduce capacity attenuation, to improve the chemical property of material.
For achieving the above object, the invention provides a kind of preparation method of the layered lithium manganate that adulterates, utilizing its chemical formula of layered lithium manganate that this method is made is LiMn1-x (M) xO2-y (N) y, and its making step comprises:
1. make presoma: by manganese source, cationic compound, anionic compound (0.95-1) in molar ratio: (0-0.05): ratio (0-0.02) is evenly mixed, then mixture is placed under 500-900 ℃ of high temperature, calcining mixt 4-6 hour, generate doped with manganese oxygen compound, naturally cooling rear taking-up, again fully grind and within 30 minutes, make presoma;
2. by the lithium source with step presoma 1. according to mol ratio 1:(0.95-0.98) ratio mixed rear grinding 30 minutes, then add NaOH or potassium hydroxide to proceed to grind and within 10 minutes, make mixture A;
3. the mixture A anhydrous alcohol solution 2. step made, the liquid after dissolving joins in autoclave, in infrared drying oven at the temperature of 180-300 ℃ reaction 2-10 hour, then take out and carry out centrifuge washing and obtain the layered lithium manganate that adulterates.
Further, described manganese source is electrolytic manganese dioxide, four oxidations three, manganese sesquioxide managnic oxide, manganese carbonate, the mixture of one or both in manganese acetate.
Further, described cationic compound is a kind of or two kinds of mixtures in cerous acetate, cerous nitrate, Schweinfurt green, cupric oxide.
Further, the mixture that described anionic compound is a kind of in lithium fluoride, lithium chloride, lithium iodide or two kinds.
Further, described mineralizer is NaOH, potassium hydroxide.
Further, the mass ratio of described absolute ethyl alcohol and mixture A is 1:(0.05-0.1).
Further, described lithium source is a kind of or two kinds of mixtures wherein in lithium acetate, lithium formate, lithium hydroxide.
Further, in described lithium source and doped with manganese oxygen compound, the mol ratio of Li/Mn is 1:(0.95-0.98), in foreign cation and doped with manganese oxygen compound, the mol ratio of manganese is (0-0.05): 1, and in doping anion and doped with manganese oxygen compound, the mol ratio of oxygen is: (0-0.02): 2.
The doping layered lithium manganate that the present invention adopts above scheme to prepare is compared with existing preparation method, has advantages of following:
1. by doped and compounded, make positive electrode there is high initial discharge capacity, after discharge test, discharge capacitance is more than 94%, cycle performance is good, makes and to become stable performance after lithium ion anode material, the demand of satisfying the market to manganate cathode material for lithium;
2. by adding compound ion to suppress positive electrode transformation to spinel structure by layer structure, the quick decay of the capacity that slows down, significantly improve the chemical property of material, improves the stability of material, keeps the good structure of material;
3. this method is compared with traditional handicraft, and technological process is simple, avoids too much high-temperature calcination, and condition is gentleer, is applicable to large-scale industrial production.
The accompanying drawing explanation
The cyclic curve that Fig. 1 embodiment of the present invention 1 battery is 25 ℃.
Embodiment
For the present invention will be further described, below in conjunction with accompanying drawing 1 and embodiment, the present invention is further elaborated.
A kind of preparation method of the layered lithium manganate that adulterates, utilizing its chemical formula of layered lithium manganate that this method is made is LiMn1-x (M) xO2-y (N) y, its making step comprises:
1. make presoma: by manganese source, cationic compound, anionic compound (0.95-1) in molar ratio: (0-0.05): ratio (0-0.02) is evenly mixed, then mixture is placed under 500-900 ℃ of high temperature, calcining mixt 4-6 hour, generate doped with manganese oxygen compound, naturally cooling rear taking-up, again fully grind and within 30 minutes, make presoma;
2. by the lithium source with step presoma 1. according to mol ratio 1:(0.95-0.98) ratio mixed rear grinding 30 minutes, then add NaOH or potassium hydroxide to proceed to grind and within 10 minutes, make mixture A;
3. the mixture A anhydrous alcohol solution 2. step made, the liquid after dissolving joins in autoclave, in infrared drying oven at the temperature of 180-300 ℃ reaction 2-10 hour, then take out and carry out centrifuge washing and obtain the layered lithium manganate that adulterates.
Below in conjunction with embodiment, the present invention will be further described.
Embodiment 1:1. takes a certain amount of manganese acetate, cerous acetate and a small amount of lithium fluoride and is placed in fully mixed grinding of agate mortar, the mol ratio that makes Mn:Ce:F in mixture is 0.097:0.03:0.01, be positioned in the Muffle furnace of 550 ℃ and calcine 4h, cooling rear taking-up is again ground and is obtained the presoma composite oxides in agate mortar;
2. by the mol ratio of manganese in the composite oxides of lithium acetate and gained, be 1:0.97, add a small amount of NaOH after mixing, in agate mortar, mixture is ground evenly, then add absolute ethyl alcohol under mechanical agitation, to make mixture dissolve, mechanical agitation 2h, after stirring, pack in autoclave, react 4h in infrared drying oven, 200 ℃ of reaction temperatures, after taking out, centrifuge washing is for several times, at the dry 8h of vacuum drying chamber, process grinds, sub-sieve obtains complex layered manganate cathode material for lithium;
3. the layered lithium manganate positive electrode of gained, acetylene black and PVDF are mixed, take 1-METHYLPYRROLIDONE (NMP) as solvent by mixture furnishing pasty state, then be coated in uniformly on the collector aluminium foil, roll extrusion after dry, make positive plate, negative pole is the disc-shaped lithium metal, and diameter is 12mm; Barrier film is the PE film, and diameter is 14mm; 1.0MLiPF6 ethylene carbonate and diethyl carbonate mixed liquor, mol ratio is 3:7, the electrolyte moisture is less than 30ppm; Test battery adopts 2032 type button cells.After tested, discharge capacity specific capacity 261mAh/g first, after 250 circulations, discharge capacitance is 95%.
Embodiment 2:1. takes a certain amount of mangano-manganic oxide, cerous nitrate and a small amount of lithium iodide and is placed in fully mixed grinding of agate mortar, the mol ratio that makes Mn:Ce:I in mixture is 0.096:0.04:0.02, be positioned in the Muffle furnace of 850 ℃ and calcine 6h, cooling rear taking-up is again ground and is obtained the presoma composite oxides in agate mortar;
2. by the mol ratio of manganese in the composite oxides of lithium formate and gained, be 1:0.96, add a small amount of NaOH after mixing, in agate mortar, mixture is ground evenly, then add absolute ethyl alcohol under mechanical agitation, to make mixture dissolve, mechanical agitation 2h, after stirring, pack in autoclave, react 6h in infrared drying oven, 220 ℃ of reaction temperatures, after taking out, centrifuge washing for several times, at the dry 12h of vacuum drying chamber, process grinds, sub-sieve obtains complex layered manganate cathode material for lithium;
3. the layered lithium manganate positive electrode of gained, acetylene black and PVDF are mixed, take 1-METHYLPYRROLIDONE (NMP) as solvent by mixture furnishing pasty state, then be coated in uniformly on the collector aluminium foil, roll extrusion after dry, make positive plate, negative pole is the disc-shaped lithium metal, and diameter is 12mm; Barrier film is the PE film, and diameter is 14mm; 1.0MLiPF6 ethylene carbonate and diethyl carbonate mixed liquor, mol ratio is 3:7, the electrolyte moisture is less than 30ppm; Test battery adopts 2032 type button cells.After tested, discharge capacity specific capacity 265mAh/g first, after 250 circulations, discharge capacitance is 94%.
Embodiment 3:1. takes a certain amount of manganese carbonate, Schweinfurt green and a small amount of lithium chloride and is placed in fully mixed grinding of agate mortar, the mol ratio that makes Mn:Cu:Cl in mixture is 0.098:0.02:0.02, be positioned in the Muffle furnace of 750 ℃ and calcine 5h, cooling rear taking-up is again ground and is obtained the presoma composite oxides in agate mortar;
2. by the mol ratio of manganese in the composite oxides of lithium hydroxide and gained, be 1:0.98, add a small amount of potassium hydroxide after mixing, in agate mortar, mixture is ground evenly, then add absolute ethyl alcohol under mechanical agitation, to make mixture dissolve, mechanical agitation 2h, after stirring, pack in autoclave, react 8h in infrared drying oven, 250 ℃ of reaction temperatures, after taking out, centrifuge washing for several times, at the dry 10h of vacuum drying chamber, process grinds, sub-sieve obtains complex layered manganate cathode material for lithium
3. the layered lithium manganate positive electrode of gained, acetylene black and PVDF are mixed, take 1-METHYLPYRROLIDONE (NMP) as solvent by mixture furnishing pasty state, then be coated in uniformly on the collector aluminium foil, roll extrusion after dry, make positive plate, negative pole is the disc-shaped lithium metal, and diameter is 12mm; Barrier film is the PE film, and diameter is 14mm; 1.0MLiPF6 ethylene carbonate and diethyl carbonate mixed liquor, mol ratio is 3:7, the electrolyte moisture is less than 30ppm; Test battery adopts 2032 type button cells.After tested, discharge capacity specific capacity 264mAh/g first, after 250 circulations, discharge capacitance is 95%.
Apparent, above-described embodiment, be only one or more execution modes of the present invention, and any simple modifications of doing on basis of the present invention all belongs to protection scope of the present invention.
Claims (4)
1. the preparation method of the layered lithium manganate that adulterates comprises following steps:
1. make presoma: by manganese source, cationic compound, anionic compound (0.95-1) in molar ratio: (0-0.05): ratio (0-0.02) is evenly mixed, then mixture is placed under 500-900 ℃ of high temperature, calcining mixt 4-6 hour, generate doped with manganese oxygen compound, naturally cooling rear taking-up, again fully grind and within 30 minutes, make presoma;
2. by the lithium source with step presoma 1. according to mol ratio 1:(0.95-0.98) ratio mixed rear grinding 30 minutes, then add NaOH or potassium hydroxide to proceed to grind and within 10 minutes, make mixture A;
3. the mixture A anhydrous alcohol solution 2. step made, the liquid after dissolving joins in autoclave, in infrared drying oven at the temperature of 180-300 ℃ reaction 2-10 hour, then take out and carry out centrifuge washing and obtain the layered lithium manganate that adulterates.
2. the preparation method of a kind of layered lithium manganate that adulterates according to claim 1, is characterized in that the manganese source is electrolytic manganese dioxide, four oxidations three, manganese sesquioxide managnic oxide, manganese carbonate, the mixture of one or both in manganese acetate; The lithium source is a kind of or two kinds of mixtures wherein in lithium acetate, lithium formate, lithium hydroxide.
3. the preparation method of a kind of layered lithium manganate that adulterates according to claim 1, is characterized in that cationic compound is a kind of or two kinds of mixtures in cerous acetate, cerous nitrate, Schweinfurt green, cupric oxide; The mixture that anionic compound is a kind of in lithium fluoride, lithium chloride, lithium iodide or two kinds.
4. the preparation method of a kind of layered lithium manganate that adulterates according to claim 1, the mass ratio that it is characterized in that absolute ethyl alcohol and mixture A is 1:(0.05-0.1).
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| TW500697B (en) * | 1998-09-11 | 2002-09-01 | Accentus Plc | Method for making manganese oxide-based material |
| CN1770513A (en) * | 2004-11-03 | 2006-05-10 | 深圳市比克电池有限公司 | Manganese-included multi-element metal oxide, lithium ion secondary battery anode material and its preparing method |
| CN101510603A (en) * | 2009-03-20 | 2009-08-19 | 吉林吉恩镍业股份有限公司 | Method for preparing anode material lithium nickle cobalt manganic acid of lithium ion battery |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| TW500697B (en) * | 1998-09-11 | 2002-09-01 | Accentus Plc | Method for making manganese oxide-based material |
| CN1770513A (en) * | 2004-11-03 | 2006-05-10 | 深圳市比克电池有限公司 | Manganese-included multi-element metal oxide, lithium ion secondary battery anode material and its preparing method |
| CN101510603A (en) * | 2009-03-20 | 2009-08-19 | 吉林吉恩镍业股份有限公司 | Method for preparing anode material lithium nickle cobalt manganic acid of lithium ion battery |
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