CN103490058B - A kind of preparation method of the layered lithium manganate that adulterates - Google Patents
A kind of preparation method of the layered lithium manganate that adulterates Download PDFInfo
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- CN103490058B CN103490058B CN201310464905.XA CN201310464905A CN103490058B CN 103490058 B CN103490058 B CN 103490058B CN 201310464905 A CN201310464905 A CN 201310464905A CN 103490058 B CN103490058 B CN 103490058B
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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
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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
- H01M4/48—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
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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
- 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
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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
Abstract
A kind of preparation method of the layered lithium manganate that adulterates, its chemical formula of the layered lithium manganate utilizing this method to make is LiMn1-x (M) xO2-y (N) y, its making step comprises: 1. make presoma: by manganese source, cationic compound, anionic compound in molar ratio (0.95-1): (0-0.05): the ratio of (0-0.02) carries out Homogeneous phase mixing, then under mixture being placed in 500-900 DEG C of high temperature, calcining mixt 4-6 hour, generate doped with manganese oxygen compound, naturally take out after cooling, again fully grind 30 minutes obtained presomas; 2. by lithium source and step presoma 1. according to mol ratio 1:(0.95-0.98) ratio carry out mixing rear grinding 30 minutes, then add NaOH or potassium hydroxide proceeds grinding 10 minutes obtained mixture A; 3. the mixture A anhydrous alcohol solution 2. step obtained, the liquid after dissolving joins in autoclave, in infrared drying oven, react 2-10 hour at the temperature of 180-300 DEG C, then take out carry out centrifuge washing obtain adulterate layered lithium manganate.The battery utilizing the material made by the present invention to produce, has the advantage of stable performance, is applicable to 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 the development of economy, people more and more pay close attention to for energy problem, oil price rises violently and makes people have darker understanding to new forms of energy, particularly 2008 annual country " 863 Program " technical field of modern transportation " energy-conservation and new-energy automobile " major projects are using the preferred material of manganate cathode material for lithium as electrokinetic cell, and lithium ion battery material faces an opportunity to develop.Be representative with electric automobile power battery, field of lithium ion battery is formed.Current staple lithium ion anode material is cobalt acid lithium mainly, and Technical comparing is ripe, and chemical property is best, is to use maximum materials at present, but cobalt resource is rare, price, and battery security compares other materials difference.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, at the ground such as Hunan, Guangxi rich reserves, about has several ten million tons, so LiMn2O4 has advantage as the electrokinetic cell in future.
LiMn2O4 has spinelle and stratiform two kinds of configurations, 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 spinel-type twice, layered lithium manganate is divided into three kinds of crystal formations: γ-LiMnO2, m-LiMnO2, ο-LiMnO2, but it is (as poor in high-temperature thermal stability performance to there are a lot of distinct issues when applying in layered lithium manganate, Stability Analysis of Structures performance is poor, high temperature capacity attenuation is serious), therefore how to solve the direction that these outstanding problems are layered lithium manganate development.
Layered lithium manganate compound has nontoxic, low cost and other advantages, be considered to the positive electrode most with development potentiality, main synthetic method has: high temperature solid-state method, low temperature synthetic method, ion-exchange, chemical reduction method etc., but prior art cannot 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 layered LiMn2O4 carries out technological improvement, optimize the architectural characteristic of LiMn2O4, the change of structure after minimizing lithium ion desorption, stable laminated structure, the basis of cation doping is carried out the doping of anion 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, its chemical formula of the layered lithium manganate utilizing this method to make is LiMn1-x (M) xO2-y (N) y, and its making step comprises:
1. presoma is made: by manganese source, cationic compound, anionic compound in molar ratio (0.95-1): (0-0.05): the ratio of (0-0.02) carries out Homogeneous phase mixing, then under mixture being placed in 500-900 DEG C of high temperature, calcining mixt 4-6 hour, generate doped with manganese oxygen compound, naturally take out after cooling, again fully grind 30 minutes obtained presomas;
2. by lithium source and step presoma 1. according to mol ratio 1:(0.95-0.98) ratio carry out mixing rear grinding 30 minutes, then add NaOH or potassium hydroxide proceeds grinding 10 minutes obtained mixture A;
3. the mixture A anhydrous alcohol solution 2. step obtained, the liquid after dissolving joins in autoclave, in infrared drying oven, react 2-10 hour at the temperature of 180-300 DEG C, then take out carry out centrifuge washing obtain adulterate layered lithium manganate.
Further, described manganese source is electrolytic manganese dioxide, mangano-manganic oxide, manganese sesquioxide managnic oxide, manganese carbonate, one or both the mixture in manganese acetate.
Further, described cationic compound is one in cerous acetate, cerous nitrate, Schweinfurt green, cupric oxide or two kinds of mixtures.
Further, described anionic compound is the mixture of 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 in lithium acetate, lithium formate, lithium hydroxide or two kinds of mixtures wherein.
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 Doped anions 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, compared with existing preparation method, has following advantage:
1., by doped and compounded, make positive electrode have high initial discharge capacity, after discharge test, discharge capacitance is more than 94%, cycle performance is excellent, makes and becomes stable performance after lithium ion anode material, meet the demand of market to manganate cathode material for lithium;
2. suppress positive electrode by the transformation of layer structure to spinel structure by adding compound ion, the rapid decay of the capacity that slows down, makes the chemical property of material significantly improve, and improves the stability of material, keeps the structure that material is good;
3. this method is compared with traditional handicraft, and technological process is simple, and avoid too much high-temperature calcination, condition is gentleer, is applicable to large-scale industrial production.
Accompanying drawing explanation
The cyclic curve of 25 DEG C, Fig. 1 embodiment of the present invention 1 battery.
Embodiment
For the present invention will be further described, below in conjunction with accompanying drawing 1 and embodiment, the present invention is further elaborated.
Adulterate the preparation method of layered lithium manganate, and its chemical formula of the layered lithium manganate utilizing this method to make is LiMn1-x (M) xO2-y (N) y, and its making step comprises:
1. presoma is made: by manganese source, cationic compound, anionic compound in molar ratio (0.95-1): (0-0.05): the ratio of (0-0.02) carries out Homogeneous phase mixing, then under mixture being placed in 500-900 DEG C of high temperature, calcining mixt 4-6 hour, generate doped with manganese oxygen compound, naturally take out after cooling, again fully grind 30 minutes obtained presomas;
2. by lithium source and step presoma 1. according to mol ratio 1:(0.95-0.98) ratio carry out mixing rear grinding 30 minutes, then add NaOH or potassium hydroxide proceeds grinding 10 minutes obtained mixture A;
3. the mixture A anhydrous alcohol solution 2. step obtained, the liquid after dissolving joins in autoclave, in infrared drying oven, react 2-10 hour at the temperature of 180-300 DEG C, then take out carry out centrifuge washing obtain adulterate layered lithium manganate.
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 agate mortar fully mixed grinding, the mol ratio of Mn:Ce:F in mixture is made to be 0.097:0.03:0.01, be positioned in the Muffle furnace of 550 DEG C and calcine 4h, take out after cooling, in agate mortar, grinding obtains presoma composite oxides again;
2. be 1:0.97 by the mol ratio of manganese in the composite oxides of lithium acetate and gained, a small amount of NaOH is added after mixing, in agate mortar by mixture grinding evenly, then add absolute ethyl alcohol and make mixture dissolve under mechanical stirring, mechanical agitation 2h, load after stirring in autoclave, in infrared drying oven, react 4h, reaction temperature 200 DEG C, after taking out, centrifuge washing 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, with 1-METHYLPYRROLIDONE (NMP) for solvent is by mixture furnishing pasty state, be then coated in uniformly in current collector aluminum foil, roll extrusion after dry, make positive plate, negative pole is disc-shaped lithium metal, and diameter is 12mm; Barrier film is PE film, and diameter is 14mm; The ethylene carbonate of 1.0MLiPF6 and diethyl carbonate mixed liquor, mol ratio is 3:7, and 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 agate mortar fully mixed grinding, the mol ratio of Mn:Ce:I in mixture is made to be 0.096:0.04:0.02, be positioned in the Muffle furnace of 850 DEG C and calcine 6h, take out after cooling, in agate mortar, grinding obtains presoma composite oxides again;
2. be 1:0.96 by the mol ratio of manganese in the composite oxides of lithium formate and gained, a small amount of NaOH is added after mixing, in agate mortar by mixture grinding evenly, then adding absolute ethyl alcohol makes mixture dissolve under mechanical stirring, mechanical agitation 2h, load after stirring in autoclave, 6h is reacted in infrared drying oven, reaction temperature 220 DEG C, 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, with 1-METHYLPYRROLIDONE (NMP) for solvent is by mixture furnishing pasty state, be then coated in uniformly in current collector aluminum foil, roll extrusion after dry, make positive plate, negative pole is disc-shaped lithium metal, and diameter is 12mm; Barrier film is PE film, and diameter is 14mm; The ethylene carbonate of 1.0MLiPF6 and diethyl carbonate mixed liquor, mol ratio is 3:7, and 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 agate mortar fully mixed grinding, the mol ratio of Mn:Cu:Cl in mixture is made to be 0.098:0.02:0.02, be positioned in the Muffle furnace of 750 DEG C and calcine 5h, take out after cooling, in agate mortar, grinding obtains presoma composite oxides again;
2. be 1:0.98 by the mol ratio of manganese in the composite oxides of lithium hydroxide and gained, a small amount of potassium hydroxide is added after mixing, in agate mortar by mixture grinding evenly, then adding absolute ethyl alcohol makes mixture dissolve under mechanical stirring, mechanical agitation 2h, load after stirring in autoclave, 8h is reacted in infrared drying oven, reaction temperature 250 DEG C, 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, with 1-METHYLPYRROLIDONE (NMP) for solvent is by mixture furnishing pasty state, be then coated in uniformly in current collector aluminum foil, roll extrusion after dry, make positive plate, negative pole is disc-shaped lithium metal, and diameter is 12mm; Barrier film is PE film, and diameter is 14mm; The ethylene carbonate of 1.0MLiPF6 and diethyl carbonate mixed liquor, mol ratio is 3:7, and 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, is only one or more execution modes of the present invention, and any simple modifications done on basis of the present invention all belongs to protection scope of the present invention.
Claims (3)
1. adulterate the preparation method of layered lithium manganate, comprises following steps:
1. presoma is made: by manganese source, cationic compound, anionic compound in molar ratio (0.95-1): (0-0.05): the ratio of (0-0.02) carries out Homogeneous phase mixing, then under mixture being placed in 500-900 DEG C of high temperature, calcining mixt 4-6 hour, generate doped with manganese oxygen compound, naturally take out after cooling, again fully grind 30 minutes obtained presomas, described cationic compound is one in cerous acetate, cerous nitrate, Schweinfurt green, cupric oxide or two kinds of mixtures; Described anionic compound is the mixture of a kind of in lithium fluoride, lithium chloride, lithium iodide or two kinds;
2. by lithium source and step presoma 1. according to mol ratio 1:(0.95-0.98) ratio carry out mixing rear grinding 30 minutes, then add NaOH or potassium hydroxide proceeds grinding 10 minutes obtained mixture A;
3. the mixture A anhydrous alcohol solution 2. step obtained, the liquid after dissolving joins in autoclave, in infrared drying oven, react 2-10 hour at the temperature of 180-300 DEG C, then take out carry out centrifuge washing obtain adulterate layered lithium manganate.
2. the preparation method of a kind of layered lithium manganate that adulterates according to claim 1, is characterized in that manganese source is electrolytic manganese dioxide, mangano-manganic oxide, manganese sesquioxide managnic oxide, manganese carbonate, one or both the mixture in manganese acetate; Lithium source is a kind of in lithium acetate, lithium formate, lithium hydroxide or two kinds of mixtures wherein.
3. the preparation method of a kind of layered lithium manganate that adulterates according to claim 1, is characterized in that the mass ratio of absolute ethyl alcohol and mixture A is 1:(0.05-0.1).
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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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Address after: 277600 Runfeng Industrial Park, Weishan Economic Development Zone, Jining City, Shandong Province Patentee after: SHANDONG JAYU & REALFORCE ENTERPRISES Co.,Ltd. Address before: 277600 Runfeng Industrial Park, Weishan Economic Development Zone, Weishan County, Jining City, Shandong Province Patentee before: SHANDONG REALFORCE ENTERPRISES Co.,Ltd. |
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Effective date of registration: 20220425 Address after: 610000 No. 1537, middle section of Jiannan Avenue, high tech Zone, Chengdu, Sichuan Patentee after: Yu Yongbo Address before: 277600 Runfeng Industrial Park, Weishan Economic Development Zone, Jining City, Shandong Province Patentee before: SHANDONG JAYU & REALFORCE ENTERPRISES CO.,LTD. |