CN102173456A - Preparation method of conglobate lithium manganate aggregates - Google Patents
Preparation method of conglobate lithium manganate aggregates Download PDFInfo
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- CN102173456A CN102173456A CN 201010609865 CN201010609865A CN102173456A CN 102173456 A CN102173456 A CN 102173456A CN 201010609865 CN201010609865 CN 201010609865 CN 201010609865 A CN201010609865 A CN 201010609865A CN 102173456 A CN102173456 A CN 102173456A
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Abstract
The invention provides a preparation method of conglobate lithium manganate, particularly relates to a preparation method of conglobate lithium manganate which has high tap density, high specific capacity and good recycling property, moreover, the preparation method has simple process and is suitable for industrial production. In the technical scheme of the invention, the preparation method comprises the following steps of: (1) slurry preparing, (2) gel preparing and (3) gel drying and sintering. Compared with the prior art, the preparation method has the obvious advantages that the prepared conglobate lithium manganate has high tap density, high specific capacity and good recycling property; and the method is simple and suitable for industrial production.
Description
Technical field:
The present invention relates to a kind of anode material for lithium-ion batteries, particularly a kind of preparation method of conglobation lithium manganate.
Background technology:
At present, commercial positive electrode material LiCoO
2Have relative higher cost and overcharge insecurity, and actual capacity (130～140mAh/g) shortcomings such as on the low side, its large-scale application is restricted always.LiMn
2O
4Material is LiCoO
2One of equivalent material cheap because its safety performance is good, and the manganese aboundresources, nontoxic pollution-free, so be lithium ion battery always, electric vehicle power lithium-ion battery one of the most promising positive electrode material particularly.But with LiCoO
2Compare LiMn
2O
4Material specific capacity is lower, tap density is less (present commercially available LiMn
2O
4Tap density be 1.8～2.0g/cm
3), particularly high temperature cyclic performance is relatively poor for cycle performance, these shortcomings have seriously limited LiMn
2O
4Practical application.Can effectively improve the tap density of material by the synthesizing spherical material.Present synthesizing spherical LiMn
2O
4The method that material is commonly used is to utilize ball milling or coprecipitation method, perhaps utilizes collosol and gel to obtain spherical presoma in conjunction with spray drying technology, then by the synthetic target product of high temperature solid state reaction.As at CN1447464A, CN1562771A, among the CN1783550A, the applicant utilizes the liquid phase coprecipitation method to synthesize spherical presoma trimanganese tetroxide respectively, Manganse Dioxide, manganous oxalate, and then obtain the spherical lithium manganate particle by high temperature sintering with lithium salts.The synthesis technique of spherical presoma is very complicated in this method, the concentration of strict control solution, pH value, temperature of reaction, stirring velocity etc., and the later stage with still to adopt solid state reaction preparation mixing of lithium salts, this just causes the raw material blended inhomogeneous easily, thereby has influence on the performance of material.At J.Applied Electrochemistry.2003,33 (1): in 107, the author adopts soluble manganese salt and solubility lithium salts prepared in reaction sol gel solution, obtains spherical presoma by spraying drying then, and high-temperature calcination obtains spherical lithium manganate again.The ratio of mixture of raw material is more even in this method, but the same more complicated of preparation process of precursor, and also cost is higher, is not suitable for suitability for industrialized production.
Summary of the invention:
The purpose of this invention is to provide a kind of tap density height, the specific storage height, good cycle and technology simply are suitable for the preparation method of industrial a kind of conglobation lithium manganate.Technical scheme of the present invention is, a kind of preparation method of conglobation lithium manganate, it is characterized in that following steps are arranged: (1) is the lithium source, the manganese source, organic monomer, dispersion agent places the ball grinder ball milling to be mixed into uniform slurry, the ball milling time is 12～48 hours, described lithium source is a Quilonum Retard, lithium hydroxide, lithium nitrate, Lithium Acetate, lithium chloride, described manganese source is a manganous carbonate, manganese acetate, Manganse Dioxide, manganous nitrate, Manganous chloride tetrahydrate, or manganous hydroxide, described organic monomer is an acrylamide, Methacrylamide, DMAA, a kind of in the vinylformic acid, wherein monomeric add-on is 2～20wt% of lithium source and manganese source total mass, described dispersion agent is a polyoxyethylene glycol, ethanol, water, polyacrylic acid, ammonium polymethacrylate, in the polyvinyl alcohol one or more, dispersion agent add-on are 1～20wt% of lithium source and manganese source total mass; (2) in the formed slurry of step (1), add linking agent, initiator, catalyzer, the preparation gel, described linking agent is N, a kind of in N ' methylene-bisacrylamide, the gelatin, the add-on of linking agent is 2%～10wt% of monomer mass; Initiator is a kind of in ammonium persulphate, the hydrogen peroxide, and the add-on of initiator is 1%～10wt% of monomer mass; Catalyzer is a tetraethylethylenediamine, and the add-on of catalyzer is 1%～5wt% of monomer mass; (3) gel with step (2) places loft drier to obtain xerogel after 60 ℃～150 ℃ oven dry, xerogel places microwave oven, low fire, moderate heat or high fire were handled 1～60 minute, place retort furnace again, the conglobation lithium manganate was made in insulation in 4-10 hour after 600 ℃～800 ℃ calcinings in air atmosphere.The present invention has the tap density height compared with the prior art, the specific storage height, and good cycle and technology are simple and be suitable for the remarkable advantage of suitability for industrialized production.
Embodiment:
Embodiment of the present invention are:
A kind of synthetic method of Conglobation type spherical lithium manganate comprises the steps:
(1) place lithium source, manganese source, organic monomer, dispersion agent the ball grinder ball milling to be mixed into uniform slurry;
(2) in the formed slurry of step (1), add linking agent, initiator, catalyzer, the preparation gel.
Place vacuum drying oven 60～150 ℃ of dryings then, obtain xerogel;
(3) xerogel with step (2) preparation places the low fire of microwave oven, moderate heat or high fire to handle 1～60 minute, obtains fluffy presoma, place again 600～800 ℃ of calcinings of retort furnace get final product product.
Lithium of the present invention source is Quilonum Retard, lithium hydroxide, lithium nitrate, Lithium Acetate, lithium chloride; Described manganese source is manganous carbonate, manganese acetate, Manganse Dioxide, manganous nitrate, Manganous chloride tetrahydrate or manganous hydroxide.
Organic monomer of the present invention is a kind of in acrylamide, Methacrylamide, DMAA, the vinylformic acid, and wherein monomeric add-on is 2～20wt% of lithium source and manganese source total mass.
Linking agent of the present invention is N, a kind of in N ' methylene-bisacrylamide, the gelatin, and wherein the add-on of linking agent is 2%～10wt% of monomer mass.
Dispersion agent of the present invention is one or more in polyoxyethylene glycol, ethanol, water, polyacrylic acid, ammonium polymethacrylate, the polyvinyl alcohol, the dispersion agent add-on is that 1～20wt% initiator of the present invention of lithium source and manganese source total mass is a kind of in ammonium persulphate, the hydrogen peroxide, and the add-on of initiator is 1%～10wt% of monomer mass.
Catalyzer of the present invention is a tetraethylethylenediamine, and the add-on of catalyzer is 1%～5wt% of monomer mass.
Ball mill container of the present invention is a kind of in agate jar, urethane ball grinder, stainless steel jar mill, the corundum ball grinder, be situated between a kind of in alumina balls, zirconia ball, agate ball, the Stainless Steel Ball of mill.The ball milling time is 12～48 hours.
Synthetic method Drying of gels temperature of the present invention is 60 ℃～150 ℃, and the microwave treatment conditions of xerogel is low fire, moderate heat or high fiery 1～60 minute, and the sintering temperature in the retort furnace is 600 ℃～800 ℃, and soaking time is 4～10 hours.
Atmosphere of the present invention is air.
Beneficial effect of the present invention
(1) utilizes the complexing anchorage effect of the template of in-situ polymerization formation, can make the mixing of raw material reach the molecular level level metal ion;
(2) material forms micron particles by the nanoparticle reunion, has both had the good electrical property of nanoparticle, has possessed the good electrode processing characteristics of micron particles again; Maintain a large amount of pore structures between the primary particle, be more conducive to the infiltration of electrolytic solution, can fundamentally improve the electrical property of material;
(3) the Conglobation type spherical lithium manganate material of gained have the specific discharge capacity height (110～135mAh/g), tap density height (2.2-2.5g/cm
3), the cycle performance excellence (25 ℃, 50 times the circulation volume conservation rate is 97%; 50 ℃, 50 times the circulation volume conservation rate is 93%) etc. advantage;
(4) the initial pattern of raw material, solvability etc. are not had particular requirement, the range of choice of raw material is wide, and technology is simple, and production cost is low, is fit to suitability for industrialized production.
Specific embodiments of the invention are:
Embodiment 1
Take by weighing LiCl and MnCO according to stoichiometric ratio
3Put into stainless steel jar mill (Stainless Steel Ball), add the vinylformic acid of lithium source and manganese source total mass 2wt%, polyvinyl alcohol and the appropriate amount of deionized water of 1wt% again, mixing and ball milling 12 hours, take out slurry, add the N-N-methylene diacrylamine (MBAM) of monomer mass 2wt% while stirring, the aqueous hydrogen peroxide solution of 1wt%, 1wt% Tetramethyl Ethylene Diamine (TEMED), continue to be stirred to and generate jelly shape gel, be put in 100 ℃ of loft drier after the oven dry, the low fire of microwave was handled 60 minutes.Under the air atmosphere in the retort furnace 800 ℃ the calcining 4 hours, cool to room temperature with the furnace, make product.Product is a spinel structure, is agglomerated into micron-size spherical by the nano level primary particle, and particle diameter is about 3 μ m, and tap density is 2.50g/ml.
Take by weighing the lithium titanate that 0.85g prepares as stated above, add 0.1g acetylene black, 0.05g be dissolved in the poly(vinylidene fluoride) tackiness agent of N-N ' dimethyl pyrrolidone, mix the formation slurry, being evenly coated on the Copper Foil, in the argon gas atmosphere glove box, is counter electrode with the metal lithium sheet, celgard2400 is a barrier film, the LiPF of 1mol/L
6-EC+DEC (1: 1) is an electrolytic solution, is assembled into CR2016 type button cell, and testing tool is a LAND CT2001 type battery test system.In the 3.0V-4.5V voltage range, battery is carried out the charge and discharge cycles experiment.The first discharge specific capacity of product under the 1C multiplying power is 135mAh/g; The capacity attenuation of circulation after 50 times is respectively 3% and 6% when normal temperature and high temperature.
Embodiment 2
According to stoichiometric ratio weighing Li
2CO
3And Mn (OH)
2Put into agate jar (agate ball), add the acrylamide (AM) of lithium source and manganese source total mass 8wt%, polyoxyethylene glycol (PEG) and the appropriate amount of deionized water of 5wt% again, mixing and ball milling 48 hours, take out slurry, the N-N-methylene diacrylamine (MBAM) that adds monomer mass 4wt% while stirring, the ammonium persulfate solution of 2wt%, 2wt% Tetramethyl Ethylene Diamine (TEMED), continue to be stirred to generation jelly shape gel, after being put in 120 ℃ of loft drier oven dry, the high fire of microwave was handled 20 minutes, and 750 ℃ of constant temperature of retort furnace are 6 hours under the air atmosphere, make product.Product is a spinel structure, is agglomerated into micron-size spherical by the nano level primary particle, and particle diameter is about 5 μ m, and tap density is 2.25g/ml.According to the method among the embodiment 1 product is carried out electric performance test, the first discharge specific capacity of product under the 1C multiplying power is 132mAh/g; The capacity attenuation of circulation after 50 times is respectively 3.6% and 5.8% when normal temperature and high temperature.
Embodiment 3
According to stoichiometric ratio weighing LiNO
3And Mn (NO
3)
2Put into urethane ball grinder (zirconia ball), add lithium source and the Methacrylamide of manganese source total mass 15wt%, the ethanol of 10wt% again, mixing and ball milling 36 hours, take out slurry, the N-N-methylene diacrylamine (MBAM) that adds monomer mass 8wt% while stirring, the ammonium persulfate solution of 7wt%, the Tetramethyl Ethylene Diamine of 4wt% (TEMED), continue to be stirred to generation jelly shape gel, after being put in 150 ℃ of loft drier oven dry, the microwave moderate heat was handled 40 minutes, and 700 ℃ of constant temperature 8 hours in the retort furnace makes product under the air atmosphere.Product is a spinel structure, is agglomerated into micron-size spherical by the nano level primary particle, and particle diameter is about 2 μ m, and tap density is 2.39g/ml.Product is carried out electric performance test, and 1C discharges and recharges, and its first discharge specific capacity the best is 130mAh/g; The capacity attenuation of circulation after 50 times is respectively 2.2% and 5% when normal temperature and high temperature.
Embodiment 4
According to stoichiometric ratio weighing Li
2CO
3Put into stainless steel jar mill (Stainless Steel Ball) with electrolytic manganese dioxide, add lithium source and the vinylformic acid of manganese source total mass 20wt%, the polyacrylic acid of 15wt% again, mixing and ball milling 24 hours, take out slurry, the N-N-methylene diacrylamine (MBAM) that adds monomer mass 10wt% while stirring, the ammonium persulfate solution of 10wt%, the Tetramethyl Ethylene Diamine of 5wt% (TEMED), continue to be stirred to generation jelly shape gel, after being put in 80 ℃ of loft drier oven dry, the low fire of microwave was handled 50 minutes, and 650 ℃ of constant temperature 10 hours in the retort furnace makes product under the air atmosphere.Product is a spinel structure, is agglomerated into micron-size spherical by the nano level primary particle, and particle diameter is about 4 μ m, and tap density is 2.36g/ml.Product is carried out electric performance test, and 1C discharges and recharges, and its first discharge specific capacity the best is 128mAh/g; The capacity attenuation of circulation after 50 times is respectively 2% and 4% when normal temperature and high temperature.
Embodiment 5
According to stoichiometric ratio weighing LiAc and Mn (Ac)
2Put into stainless steel jar mill (Stainless Steel Ball), the acrylamide (AM) that adds lithium source and manganese source total mass 10wt% again, the ammonium polymethacrylate of 20wt% and appropriate amount of deionized water, mixing and ball milling 24 hours, take out slurry, the N-N-methylene diacrylamine (MBAM) that adds monomer mass 6wt% while stirring, the ammonium persulfate solution of 5wt%, 3wt% Tetramethyl Ethylene Diamine (TEMED), continue to be stirred to generation jelly shape gel, after being put in 60 ℃ of loft drier oven dry, the microwave moderate heat was handled 30 minutes, and 800 ℃ of constant temperature 4 hours in the retort furnace makes product under the air atmosphere.Product is a spinel structure, is agglomerated into micron-size spherical by the nano level primary particle, and particle diameter is about 4 μ m, and tap density is 2.28g/ml.Product is carried out electric performance test, and 1C discharges and recharges, and its first discharge specific capacity the best is 127mAh/g; The capacity attenuation of circulation after 50 times is respectively 2.5% and 4.8% when normal temperature and high temperature.
Embodiment 6
According to stoichiometric ratio weighing LiOH and MnCl
2Put into stainless steel jar mill (Stainless Steel Ball), the acrylamide (AM) that adds lithium source and manganese source total mass 5wt% again, the ammonium polymethacrylate of 10wt% and appropriate amount of deionized water, mixing and ball milling 24 hours, take out slurry, the N-N-methylene diacrylamine (MBAM) that adds monomer mass 3wt% while stirring, the ammonium persulfate solution of 2wt%, 1wt% Tetramethyl Ethylene Diamine (TEMED), continue to be stirred to generation jelly shape gel, after being put in 100 ℃ of loft drier oven dry, the high fire of microwave was handled 1 minute, and 600 ℃ of constant temperature 10 hours in the retort furnace makes product under the air atmosphere.Product is a spinel structure, is agglomerated into micron-size spherical by the nano level primary particle, and particle diameter is about 6 μ m, and tap density is 2.50g/ml.Product is carried out electric performance test 50 ℃ the time, and 1C discharges and recharges, and sample first discharge specific capacity the best is 125mAh/g; The capacity attenuation of circulation after 50 times is respectively 4% and 6.5% when normal temperature and high temperature.
Claims (1)
1. the preparation method of a conglobation lithium manganate is characterized in that following steps are arranged:
(1) the lithium source, the manganese source, organic monomer, dispersion agent places the ball grinder ball milling to be mixed into uniform slurry, the ball milling time is 12～48 hours, described lithium source is a Quilonum Retard, lithium hydroxide, lithium nitrate, Lithium Acetate, lithium chloride, described manganese source is a manganous carbonate, manganese acetate, Manganse Dioxide, manganous nitrate, Manganous chloride tetrahydrate, or manganous hydroxide, described organic monomer is an acrylamide, Methacrylamide, DMAA, a kind of in the vinylformic acid, wherein monomeric add-on is 2～20wt% of lithium source and manganese source total mass, described dispersion agent is a polyoxyethylene glycol, ethanol, water, polyacrylic acid, ammonium polymethacrylate, in the polyvinyl alcohol one or more, dispersion agent add-on are 1～20wt% of lithium source and manganese source total mass;
(2) in the formed slurry of step (1), add linking agent, initiator, catalyzer, the preparation gel, described linking agent is N, a kind of in N ' methylene-bisacrylamide, the gelatin, the add-on of linking agent is 2%～10wt% of monomer mass; Initiator is a kind of in ammonium persulphate, the hydrogen peroxide, and the add-on of initiator is 1%～10wt% of monomer mass; Catalyzer is a tetraethylethylenediamine, and the add-on of catalyzer is 1%～5wt% of monomer mass;
(3) gel with step (2) places loft drier to obtain xerogel after 60 ℃～150 ℃ oven dry, xerogel places microwave oven, low fire, moderate heat or high fire were handled 1～60 minute, place retort furnace again, the conglobation lithium manganate was made in insulation in 4-10 hour after 600 ℃～800 ℃ calcinings in air atmosphere.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106410180A (en) * | 2016-11-11 | 2017-02-15 | 河南师范大学 | Lithium ion battery positive pole material, and preparation method and application thereof |
| CN111484041A (en) * | 2020-04-17 | 2020-08-04 | 中南大学 | Method for preparing lithium hydroxide by using low-concentration lithium-containing solution |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0816292A1 (en) * | 1996-06-27 | 1998-01-07 | The Honjo Chemical Corporation | Process for producing lithium manganese oxide with spinel structure |
| US6558843B1 (en) * | 2000-02-02 | 2003-05-06 | Korea Advanced Institute Of Science And Technology | Method for manufacturing lithium-manganese oxide powders for use in lithium secondary battery |
| CN101381108A (en) * | 2008-09-28 | 2009-03-11 | 江苏双登电源有限公司 | Method for synthesizing spherical lithium manganate |
| CN101913655A (en) * | 2010-09-10 | 2010-12-15 | 河南联合新能源有限公司 | Method for preparing lithium manganate cathode material by microwave sintering |
-
2010
- 2010-12-29 CN CN 201010609865 patent/CN102173456B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0816292A1 (en) * | 1996-06-27 | 1998-01-07 | The Honjo Chemical Corporation | Process for producing lithium manganese oxide with spinel structure |
| US6558843B1 (en) * | 2000-02-02 | 2003-05-06 | Korea Advanced Institute Of Science And Technology | Method for manufacturing lithium-manganese oxide powders for use in lithium secondary battery |
| CN101381108A (en) * | 2008-09-28 | 2009-03-11 | 江苏双登电源有限公司 | Method for synthesizing spherical lithium manganate |
| CN101913655A (en) * | 2010-09-10 | 2010-12-15 | 河南联合新能源有限公司 | Method for preparing lithium manganate cathode material by microwave sintering |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106410180A (en) * | 2016-11-11 | 2017-02-15 | 河南师范大学 | Lithium ion battery positive pole material, and preparation method and application thereof |
| CN111484041A (en) * | 2020-04-17 | 2020-08-04 | 中南大学 | Method for preparing lithium hydroxide by using low-concentration lithium-containing solution |
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| CN102173456B (en) | 2012-12-05 |
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