CN102557121A - Method for synthesizing porous spherical lithium titanate - Google Patents

Method for synthesizing porous spherical lithium titanate Download PDF

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Publication number
CN102557121A
CN102557121A CN2010106099154A CN201010609915A CN102557121A CN 102557121 A CN102557121 A CN 102557121A CN 2010106099154 A CN2010106099154 A CN 2010106099154A CN 201010609915 A CN201010609915 A CN 201010609915A CN 102557121 A CN102557121 A CN 102557121A
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lithium
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source
gel
lithium titanate
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CN102557121B (en
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尹艳红
李少玉
曹朝霞
范志娟
丁现亮
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Henan Normal University
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Henan Normal University
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Abstract

The invention discloses a method for synthesizing porous spherical lithium titanate, and aims to provide a method for synthesizing porous spherical lithium titanate, which has high tap density, high specific capacity, high rate capability and simple process and is suitable for industrial production. Key points of the technical scheme of the invention are that: the processing steps include: (1) preparing slurry; (2) preparing gel; and (3) drying and sintering gel. Compared with the prior art, the synthesizing method has the remarkable advantages of high tap density, high rate capacity, high rate capability, simple process and suitability for industrial production.

Description

A kind of compound method of porous spherical lithium titanate
Technical field:
The present invention relates to a kind of preparation method of lithium ion battery negative material, particularly a kind of compound method of porous spherical lithium titanate.
Background technology:
Spinel lithium titanate (Li 4Ti 5O 12) have the security of good cycle performance and Geng Gao, be considered to one of the most promising lithium ion battery negative material always.But because Li 4Ti 5O 12The specific conductivity of material itself is lower, and (electronic conductivity is merely 10 -9S/cm), when high current charge-discharge, be easy to generate bigger polarization, cause the high rate performance of material relatively poor; In addition, the tap density of material is on the low side, has influence on volume of battery specific storage and energy density.These have all limited the application of lithium titanate anode material in power cell.
Effective regulation and control, modification through to the lithium titanate material pattern are the effective ways that improves its electroconductibility and even high rate performance; Like document Electrochemistry Communications; 2008; Among the 10:1513, the author adopts hydrothermal method to synthesize petal-like lithium titanate material, and the 8C specific discharge capacity reaches 165.8m Ah/g; Document Electrochimica Acta; 2007; 53:79 and Journal of Power Sources; 2007, the author adopts glue crystal template technology or sol-gel process to synthesize the lithium titanate material with mesoporous or hollow ball structure respectively among the 166:514, and its high rate performance all obtains improvement to a certain degree.In addition, can improve the tap density of material effectively through the synthesizing spherical material, like document Journal of Power Sources, 2007, the author adopts " outer gel " technology to synthesize spherical lithium titanate material among the 166:255, and tap density reaches 1.71g/cm 3Though the control technique to the lithium titanate pattern in sum is effective, synthesis technique is very complicated, the concentration of strict control solution, pH value, and temperature of reaction, stirring velocitys etc. perhaps need be used special reactor drum, and cost is higher, is not suitable for suitability for industrialized production.
Summary of the invention:
It is big to the purpose of this invention is to provide a kind of tap density, and specific storage is high, and good rate capability and technology simply are fit to the compound method of a kind of porous spherical lithium titanate of suitability for industrialized production.Technical scheme of the present invention is; A kind of compound method of porous spherical lithium titanate; It is characterized in that following steps are arranged: (1) places the ball grinder ball mill mixing to become uniform slurry lithium source, titanium source, organic monomer and dispersion agent, and the ball milling time is 12～48 hours, and said lithium source is any of Quilonum Retard, Lithium Hydroxide MonoHydrate, lithium nitrate, Lithium Acetate and lithium chloride; Said titanium source is titanium oxide or metatitanic acid; Said organic monomer is an acrylic amide, a kind of in USAF RH-1, DMAA, the vinylformic acid, and monomeric add-on is 2～20wt% of lithium source and titanium source total mass; Said dispersion agent is one or more in polyoxyethylene glycol, ethanol, water, ROHM, ammonium polymethacrylate, the Z 150PH, and the add-on of dispersion agent is 1～20wt% of lithium source and titanium source total mass; (2) in the formed slurry of step (1), add linking agent, initiator and catalyzer and process gel; Place vacuum drying oven 60-150 ℃ of drying gel then, process xerogel, described linking agent is N; A kind of in N ' methylene-bisacrylamide, the gelatin; Wherein the add-on of linking agent is 2%～10wt% of monomer mass, and said initiator is a kind of in ammonium persulphate, the hydrogen peroxide, and the add-on of initiator is 1%～10wt% of monomer mass; Said catalyzer is a tetraethylethylenediamine, and the add-on of catalyzer is 1%～5wt% of monomer mass; (3) gel with step (2) places loft drier after 60 ℃～150 ℃ oven dry, to obtain xerogel; Xerogel places retort furnace; Under nitrogen or argon gas atmosphere 500 ℃～800 ℃ the calcining 2～12 hours, promptly process have nanometer, the micron composite structure the porous spherical lithium titanate.The present invention and prior art have relatively that tap density is big, specific storage is high and good rate capability and technology simply are fit to the remarkable advantage of suitability for industrialized production.
Embodiment:
The embodiment of the compound method of porous spherical lithium titanate of the present invention:
(1) place lithium source, titanium source, organic monomer, dispersion agent the ball grinder ball mill mixing to become 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 retort furnace, under the protective atmosphere 500～800 ℃ of calcinings get final product product.
Lithium of the present invention source is Quilonum Retard, Lithium Hydroxide MonoHydrate, lithium nitrate, Lithium Acetate, lithium chloride; Said titanium source is titanium oxide, metatitanic acid.
Organic monomer of the present invention is a kind of in acrylic amide, USAF RH-1, DMAA, the vinylformic acid.Wherein monomeric add-on is 2～20wt% of lithium source and titanium source total mass.
Linking agent of the present invention is N, a kind of in N ' methylene-bisacrylamide, the gelatin.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, ROHM, ammonium polymethacrylate, the Z 150PH.The dispersion agent add-on is 1～20wt% of lithium source and titanium source total mass.
Initiator of the present invention is a kind of in ammonium persulphate, the hydrogen peroxide.The add-on of initiator is 1%～10wt% of monomer mass.
Catalyzer of the present invention is a tetraethylethylenediamine.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.
Compound method drying temperature of the present invention is 60 ℃～150 ℃, and sintering temperature is 500 ℃～800 ℃, and soaking time is 2～12 hours.
Atmosphere of the present invention is nitrogen, argon gas.
Usefulness of the present invention is:
(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 metals 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 nano-micrometre composite structure porous spherical lithium titanate anode material tool specific discharge capacity of gained high (100～165mAh/g), the high (1.5-1.8g/cm of tap density 3), advantages such as good rate capability;
(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 embodiment of the present invention:
Embodiment 1:
Take by weighing TiO according to stoichiometric ratio 2And LiCO 3Put into stainless steel jar mill (Stainless Steel Ball), add the vinylformic acid of lithium source and titanium source total mass 2wt%, Z 150PH 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 60 ℃ of loft drier after the oven dry, 600 ℃ of constant temperature 5 hours in the retort furnace under the nitrogen atmosphere; Cool to room temperature with the furnace, get Li 4Ti 5O 12Pale powder.Products therefrom is a spinel structure, has higher phase purity.Particle is that the porous class is spherical, and particle diameter is about 5 μ m, and tap density is 1.8g/cm 3
Take by weighing the lithium titanate that 0.85g prepares as stated above, add 0.1g acetylene black, 0.05g is dissolved in the PVDF 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 1.0V-2.5V voltage range, battery is carried out the charge and discharge cycles experiment.Battery is at 1C, 5C, and under the discharge-rate of 10C, specific storage is respectively 165mAh/g -1, 142mAh/g -1, 110mAh/g -1The capability retention of material is respectively 92%, 86% and 80% after the circulation of 100 weeks.
Embodiment 2:
According to stoichiometric ratio weighing LiOHH 2O and metatitanic acid are put into agate jar (agate ball), add the acrylic amide (AM) of lithium source and titanium 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, add the N-N-methylene diacrylamine (MBAM) of monomer mass 4wt% while stirring, the ammonium persulfate solution of 2wt%; 2wt% Tetramethyl Ethylene Diamine (TEMED); Continue to be stirred to and generate jelly shape gel, be put in 80 ℃ of loft drier after the oven dry, 700 ℃ of constant temperature 10 hours in the retort furnace under the argon gas atmosphere; Cool to room temperature with the furnace, get pale powder.Products therefrom is a spinel structure, has higher phase purity.Particle is that the porous class is spherical, and particle diameter is about 4 μ m, and tap density is 1.7g/cm 3Prepare battery by embodiment 1 method, test its charge-discharge performance.Battery is at 1C, 5C, and under the discharge-rate of 10C, specific storage is respectively 151mAh/g -1, 129mAh/g -1, 103mAh/g -1The capability retention of material is respectively 90%, 84% and 79% after the circulation of 100 weeks.
Embodiment 3:
According to stoichiometric ratio weighing CH 3COOLi2H 2O and TiO 2Put into urethane ball grinder (zirconia ball), add the USAF RH-1 of lithium source and titanium source total mass 15wt%, the ethanol of 10wt% again, mixing and ball milling 36 hours; Take out slurry, add the N-N-methylene diacrylamine (MBAM) of monomer mass 8wt% while stirring, the ammonium persulfate solution of 7wt%; The Tetramethyl Ethylene Diamine of 4wt% (TEMED); Continue to be stirred to and generate jelly shape gel, be put in 100 ℃ of loft drier after the oven dry, 500 ℃ of constant temperature 12 hours in the retort furnace under the nitrogen atmosphere; Cool to room temperature with the furnace, get pale powder.Products therefrom is a spinel structure, has higher phase purity.Particle is a porous spherical, and particle diameter is about 3 μ m, and tap density is 1.75g/cm 3Prepare battery by embodiment 1 method, test its charge-discharge performance.Battery is at 1C, 5C, and under the discharge-rate of 10C, specific storage is respectively 163mAh/g -1, 132mAh/g -1, 109mAh/g -1The capability retention of material is respectively 89%, 85% and 81% after the circulation of 100 weeks.
Embodiment 4:
According to stoichiometric ratio weighing LiNO 3Put into stainless steel jar mill (Stainless Steel Ball) with metatitanic acid, add the vinylformic acid of lithium source and titanium source total mass 20wt%, the ROHM of 15wt% again, mixing and ball milling 24 hours; Take out slurry, add the N-N-methylene diacrylamine (MBAM) of monomer mass 10wt% while stirring, the ammonium persulfate solution of 10wt%; The Tetramethyl Ethylene Diamine of 5wt% (TEMED); Continue to be stirred to and generate jelly shape gel, be put in 120 ℃ of loft drier after the oven dry, 800 ℃ of constant temperature 2 hours in the retort furnace under the nitrogen atmosphere; Cool to room temperature with the furnace, get pale powder.Products therefrom is a spinel structure, has higher phase purity.Particle is a porous spherical, and particle diameter is about 2 μ m, and tap density is 1.6g/cm3.Prepare battery by embodiment 1 method, test its charge-discharge performance.Battery is at 1C, 5C, and under the discharge-rate of 10C, specific storage is respectively 150mAh/g -1, 131mAh/g -1, 112mAh/g -1The capability retention of material is respectively 93%, 86% and 82% after the circulation of 100 weeks.
Embodiment 5:
According to stoichiometric ratio weighing LiCl and TiO 2Put into stainless steel jar mill (Stainless Steel Ball), add the acrylic amide (AM) of lithium source and titanium source total mass 20wt%, ammonium polymethacrylate and the appropriate amount of deionized water of 20wt% again, mixing and ball milling 24 hours; Take out slurry, add the N-N-methylene diacrylamine (MBAM) of monomer mass 10wt% while stirring, the ammonium persulfate solution of 10wt%; 5wt% Tetramethyl Ethylene Diamine (TEMED); Continue to be stirred to and generate jelly shape gel, be put in 150 ℃ of loft drier after the oven dry, 800 ℃ of constant temperature 4 hours in the retort furnace under the argon gas atmosphere; Cool to room temperature with the furnace, get pale powder.Products therefrom is a spinel structure, has higher phase purity.Particle is that the porous class is spherical, and particle diameter is about 2 μ m, and tap density is 1.5g/cm 3Prepare battery by embodiment 1 method, test its charge-discharge performance.Battery is at 1C, 5C, and under the discharge-rate of 10C, specific storage is respectively 159mAh/g -1, 140mAh/g -1, 104mAh/g -1The capability retention of material is respectively 91%, 84% and 81% after the circulation of 100 weeks.

Claims (1)

1. the compound method of a porous spherical lithium titanate; It is characterized in that following steps are arranged: (1) places the ball grinder ball mill mixing to become uniform slurry lithium source, titanium source, organic monomer and dispersion agent; The ball milling time is 12～48 hours; Said lithium source is any of Quilonum Retard, Lithium Hydroxide MonoHydrate, lithium nitrate, Lithium Acetate and lithium chloride, and said titanium source is titanium oxide or metatitanic acid, and said organic monomer is an acrylic amide; A kind of in USAF RH-1, DMAA, the vinylformic acid; Monomeric add-on is 2～20wt% of lithium source and titanium source total mass, and said dispersion agent is one or more in polyoxyethylene glycol, ethanol, water, ROHM, ammonium polymethacrylate, the Z 150PH, and the add-on of dispersion agent is 1～20wt% of lithium source and titanium source total mass; (2) in the formed slurry of step (1), add linking agent, initiator and catalyzer and process gel; Place vacuum drying oven 60-150 ℃ of drying gel then, process xerogel, described linking agent is N; A kind of in N ' methylene-bisacrylamide, the gelatin; Wherein the add-on of linking agent is 2%～10wt% of monomer mass, and said initiator is a kind of in ammonium persulphate, the hydrogen peroxide, and the add-on of initiator is 1%～10wt% of monomer mass; Said catalyzer is a tetraethylethylenediamine, and the add-on of catalyzer is 1%～5wt% of monomer mass; (3) gel with step (2) places loft drier after 60 ℃～150 ℃ oven dry, to obtain xerogel; Xerogel places retort furnace; Under nitrogen or argon gas atmosphere 500 ℃～800 ℃ the calcining 2～12 hours, promptly process have nanometer, the micron composite structure the porous spherical lithium titanate.
CN 201010609915 2010-12-29 2010-12-29 Method for synthesizing porous spherical lithium titanate Expired - Fee Related CN102557121B (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106972170A (en) * 2017-05-27 2017-07-21 河北省科学院能源研究所 A kind of lithium titanate electrode material with composite pore structural and preparation method thereof

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005239460A (en) * 2004-02-25 2005-09-08 Ishihara Sangyo Kaisha Ltd Method for manufacturing lithium titanate and lithium cell produced by using the lithium titanate
CN101219811A (en) * 2008-01-25 2008-07-16 南京大学 Anode material of lithium cell and solid-phase sintering production method at high temperature
CN101391806A (en) * 2007-09-20 2009-03-25 北京有色金属研究总院 Method for manufacturing spinelle lithium titanate for lithium ionic cell cathode material
CN101456582A (en) * 2009-01-05 2009-06-17 中信国安盟固利新能源科技有限公司 Synthetic method suitable for industrial production of lithium titanate
CN101510450A (en) * 2009-03-31 2009-08-19 北京科技大学 Method for preparing ceramic tritium proliferation agent in fusion stack cladding

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005239460A (en) * 2004-02-25 2005-09-08 Ishihara Sangyo Kaisha Ltd Method for manufacturing lithium titanate and lithium cell produced by using the lithium titanate
CN101391806A (en) * 2007-09-20 2009-03-25 北京有色金属研究总院 Method for manufacturing spinelle lithium titanate for lithium ionic cell cathode material
CN101219811A (en) * 2008-01-25 2008-07-16 南京大学 Anode material of lithium cell and solid-phase sintering production method at high temperature
CN101456582A (en) * 2009-01-05 2009-06-17 中信国安盟固利新能源科技有限公司 Synthetic method suitable for industrial production of lithium titanate
CN101510450A (en) * 2009-03-31 2009-08-19 北京科技大学 Method for preparing ceramic tritium proliferation agent in fusion stack cladding

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106972170A (en) * 2017-05-27 2017-07-21 河北省科学院能源研究所 A kind of lithium titanate electrode material with composite pore structural and preparation method thereof

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