CN104253267A - Carbon-clad spinel lithium titanate material, production method and application thereof - Google Patents

Carbon-clad spinel lithium titanate material, production method and application thereof Download PDF

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Publication number
CN104253267A
CN104253267A CN201310264622.0A CN201310264622A CN104253267A CN 104253267 A CN104253267 A CN 104253267A CN 201310264622 A CN201310264622 A CN 201310264622A CN 104253267 A CN104253267 A CN 104253267A
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lithium titanate
lithium
titanate
carbon
few
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曾乐才
廖文俊
蒿豪
杨霖霖
刘佳丽
余爱水
黄桃
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Fudan University
Shanghai Electric Group Corp
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Fudan University
Shanghai Electric Group Corp
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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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • 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
    • 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
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • 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

The invention relates to a carbon-clad spinel lithium titanate Li4MxTiyO12 material used as a lithium ion battery cathode material, a production method and an application thereof. The cathode material is spinel type Li4MxTiyO12 or a mono or multiple other metallic element-doped compound Li4MxTiyO12. A synthetic method comprises the following steps: mixing an organic titanium solution and lithium salt liquid to prepare sol; aging the sol to obtain a lithium titanate gel predecessor; calcining the gel predecessor, and being conversed to the spinel lithium titanate material with nano size; or comprises the following steps: dispersing the prepared lithium titanate in a carbon source organic solution, removing the solution, and calcining to obtain the spinel lithium titanate/carbon composite material with nano size. Compared with lithium titanate Li4Ti5O12 prepared by a conventional method, the spinel lithium titanate material has better multiplying power characteristic, when the spinel lithium titanate material is used as a lithium ion battery cathode, the power performance of the cell can be obviously increased.

Description

Carbon coating spinelle lithium titanate material and production method thereof and application
Technical field
The present invention relates to a kind of lithium ion battery negative material and production method thereof, particularly relate to a kind of production method of the carbon coating spinelle lithium titanate for lithium ion battery negative material, and the carbon coating spinelle lithium titanate that described method is produced, the invention still further relates to a kind of lithium ion battery negative and the lithium ion battery that comprise described spinel lithium titanate.
Background technology
Along with the exhaustion increasingly of petroleum resources and increasingly sharpening of environmental pollution; the development of countries in the world to electric automobile and large-scale environmental protection energy-storage battery all gives shows great attention to; and formulated corresponding development plan, expect to alleviate more and more serious energy crisis and air environmental pollution problem with this.At present, large-scale lithium ion battery is considered to the potential automobile power cell of most and environmental protection energy-storage battery, as KR10-2012-0023021(A) disclosed lithium carbonate electrode active material and battery, and US2013063867(A1) the disclosed oxygen defect portion lithium carbonate nano particle that carries out N doping and obtain and battery.Domestic and international many automobile production producers are getting down to the research of vehicle lithium ion battery, and have achieved part commercialization.The intermediate energy storage battery adopting large-scale lithium ion battery to network as wind power generation and solar power generation, has become the new highlight of large-scale environmental protection energy-storage battery research.
Spinel type lithium titanate Li 4ti 5o 12it is the representative of novel lithium battery cathode material, there is Heat stability is good, overcharging resisting electricity, high rate during charging-discharging superior, good cycle, high security and the advantage such as environmentally friendly, therefore it become the desirable negative material of large-scale lithium ion battery, its electrochemical potential, up to 1.5V, is safest negative material.Its cycle life can reach 20000 times, and 65 ° of C high temperature circulation reach 8000 times.It will be further appreciated that, Li 4ti 5o 12generally can not generate solid electrolyte interface film, extremely be conducive to heavy-current discharge, battery cycle life and high temperature performance can be improved.The energy of 20% can only be released under conventional batteries-20 ° of C, and spinel type lithium titanate Li 4ti 5o 12material still can release the energy of 40% when-40 ° of C, and heavy-current discharge effect is fine.
Along with the progressively development of electric automobile, to spinel type lithium titanate Li 4ti 5o 12performance requirement also progressively improve.In order to meet the automobile high power required when starting, accelerating and climbing, need to improve spinel type lithium titanate Li further 4ti 5o 12multiplying power property.But due to spinel type lithium titanate Li 4ti 5o 12itself be an electron-like insulating material, electron conduction difference (<10-13S/cm), limits the multiplying power performance of this material to a certain extent, also limit its application in high power lithium ion cell field.
Nanoscale can shorten lithium ion and the evolving path of electronics in electric discharge or charging process effectively, and therefore nanometer technology improves spinel type lithium titanate Li 4ti 5o 12one of important channel of multiplying power property.In addition, by Li 4ti 5o 12external sheath one deck carbon increases Li 4ti 5o 12electric conductivity, improving multiplying power problem with this is then be conducive to most realizing industrialized approach.But, the spinel type lithium titanate Li with nanoscale and nanostructure is synthesized by the method for routine 4ti 5o 12more difficult.
Existing lithium titanate Li 4ti 5o 12the preparation method of negative material mainly contains following two classes.First kind high temperature solid-phase sintering method.The method synthesis technique is simple, after only the lithium source of chemical formula proportioning and titanium source material fully need being mixed, product is calcined 12-48 hour to obtain within the scope of 700-1000 ° of C, but the material that this legal system is standby, particle size generally at tens microns, and does not possess non-uniform topographical, though can be used as the negative material of lithium ion battery, but due to the impact of its particle diameter and pattern, its multiplying power property can not meet high power lithium ion cell, especially the requirement of electrokinetic cell; Equations of The Second Kind is hydrothermal synthesis method, and this method can prepare less particle size (generally in hundreds of nanometers), but due to the limitation of synthetic method itself, make material not have good crystal formation, the cycle performance of material is affected.In sum, to be difficult to prepare yardstick homogeneous or have the nanometer spinel type lithium titanate Li of ad hoc structure for existing synthetic method 4ti 5o 12.
Summary of the invention
For solving the problem, the invention provides a kind of synthesis of nano spinel type lithium titanate Li 4ti xm yo 12new method, and synthesis nanometer spinel type Li 4ti xm yo 12surface is coated one deck carbon again, the method for taking this is prepared (the spinel lithium titanate Li of nano-scale 4ti xm yo 12/ carbon composite).This method can synthesize the homogeneous nanometer spinel type lithium titanate Li of yardstick 4ti xm yo 12/ carbon composite.
The present invention first aspect is to provide another kind of production spinel type lithium titanate Li 4ti xm yo 12method, wherein, x is selected from 4.9-5.0, and be preferably 4.95-5.0, be more preferably 4.97-5.0; Y>=0; X+y=4.9-5.1, and be preferably 4.95-5.05, most preferably be 5.
Described in the present invention first aspect, method comprises the steps:
Step 1, joins in organic titanic compound solution by lithium salts and doping metals M solion, forms colloid;
Step 2, by described colloid ageing, obtains the lithium titanate precursor adulterated;
Step 3, calcines described lithium titanate precursor, obtains the nano lithium titanate adulterated;
Step 4, is scattered in nano lithium titanate in the solvent dissolving carbon source, calcines, obtain the spinel lithium titanate Li of carbon-coated nano size after sloughing solvent 4ti 5o 12; Wherein, described carbon source is to calcine the material of carbonization.
Those skilled in the art are it is understood that in first aspect of the present invention, and in reinforced process, Li, M and Ti molar ratio should be at or about molecular formula Li 4ti xm yo 12in ratio, and preferably, the molal quantity sum of lithium and M and the mol ratio of titanium elements preferably control 4: (5 ± 0.3), are more preferably and control 4: (5 ± 0.2).
In first aspect of the present invention, described " doping metals " or M be selected from mendeleev periodic table of elements first main group, the second main group, the 3rd main group, transition metal or rare earth metal any one or a few.As the combination of any one or a few in the metallic elements such as Na, K, Li, Zn, Mg, Mn, Ru, Pd, Mo, Zr, Y, Nb, Ba, Al, Cu, Co, Cr, Fe, In, Ga, Ni, V, La, Nd, Sm, Ce.
In first aspect of the present invention, described organic titanium is preferably any one or a few the mixture in titanate esters or organic acid titanium salt, titanium organic complex.Preferably be selected from any one or a few the mixture in titanate esters, beta diketone titanium, organic acid titanium salt.Concrete example is as the mixture of one or more in diisostearoyl ethylene titanate, hydroxyl lactyl-lactic acid conjunction titanium, isopropyl tri(dioctylpyrophosphato)titanate, butyl titanate, isopropyl triisostearoyltitanate, tetraisopropyl titanate, titanium acetylacetone.
In first aspect of the present invention, described lithium salts can be any one or a few the mixing in inorganic salts or organic salt, as any one or a few the mixture in lithium acetate, lithium formate, butyric acid lithium, propionic acid lithium, lithium carbonate, lithium nitrate, lithium sulfate, lithium hydroxide and above-mentioned lithium salts water and thing.
In first aspect of the present invention, described organic titanic compound or lithium salts are dissolved in organic solvent respectively, to form described organic titanic compound solution or lithium salt solution.
Wherein, described organic solvent can be any one or a few the compound in ketone, alcohol, ether, ester, acetonitrile.Particularly, the citing of described ketone is selected from any one or a few the mixture in acetone, butanone, cyclohexanone; The citing of described alcohol is selected from any one or a few the mixture in methyl alcohol, ethanol, normal propyl alcohol, isopropyl alcohol, n-butanol, ethylene glycol; Described ether is selected from any one or a few the mixture in ether, butyl ether, ethyl methyl ether, benzinum.
In first aspect of the present invention, can also comprise stabilizer in lithium salt solution, described stabilizer is preferably organic carboxyl acid.Described organic carboxyl acid can be monoacid or polyacid, as any one or a few the mixture in formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, sad, malonic acid, ethanedioic acid, succinic acid, citric acid, tartaric acid, malic acid, salicylic acid, ascorbic acid, citric acid, benzoic acid, be more preferably any one or a few the mixture in acetic acid, citric acid, tartaric acid.
In first aspect of the present invention, in step 2, can also comprise drying steps after described ageing, described drying is preferably carried out at the temperature of≤100 ° of C, and preferred temperature is 40-100 ° of C, is more preferably 50-80 ° of C, is more preferably 60-80 ° of C.
In first aspect of the present invention, in step 3, in described calcination process, calcining heat is preferably 500-1000 ° of C, is more preferably 500-900 ° of C, is more preferably 600-850 ° of C.
In first aspect of the present invention, in step 3, in described calcination process, calcination time is preferably 0.5-5h, is more preferably 1-4h, is more preferably 1.5-3h, as 2-2.5h.
Wherein, in a kind of preferred embodiment in the present invention first, described calcination process is divided into two stages to carry out, first stage is pre-sintered state, and calcining heat is preferably 500-700 ° of C, is more preferably 550-680 ° of C, be more preferably 580-670 ° of C, be more preferably 600-650 ° of C, as 620 ° of C, 640 ° of C etc., most preferably be 650 ° of C; Second stage is the sintering stage, and sintering temperature is preferably 700-900 ° of C, is more preferably 730-880 ° of C, is more preferably 750-850 ° of C, as 780 ° of C, and 800 ° of C, 830 ° of C.
Wherein, described presintering time first stage is preferably 10min-60min, is more preferably 15-50min, is more preferably 20-40min, as 30-40min.
Wherein, described second stage sintering time is preferably 0.5-4h, is more preferably 1-3.5h, is more preferably 1.5-3h, as 2-2.5h.
In first aspect of the present invention, in step 3, after calcination process, ball milling step can also be comprised.Wherein, described Ball-milling Time is preferably 0.5-3h, is more preferably 1-2h.
Second aspect of the present invention is to provide a kind of production spinel type lithium titanate Li 4ti 5o 12method, i.e. x=5, y=0 in method described in first aspect.
Described in the present invention second aspect, method comprises the steps:
Step 1, joins in organic titanic compound solution by lithium salt solution, form colloid;
Step 2, by described colloid ageing, obtains lithium titanate precursor;
Step 3, calcines described lithium titanate precursor, obtains nano lithium titanate.
Step 4, is scattered in nano lithium titanate in the solvent dissolving carbon source, calcines, obtain the spinel lithium titanate Li of carbon-coated nano size after sloughing solvent 4ti 5o 12; Wherein, described carbon source is to calcine the material of carbonization.
In second aspect of the present invention, described organic titanium is preferably any one or a few the mixture in titanate esters or organic acid titanium salt, titanium organic complex.Preferably be selected from any one or a few the mixture in titanate esters, beta diketone titanium, organic acid titanium salt.Concrete example is as the mixture of one or more in diisostearoyl ethylene titanate, hydroxyl lactyl-lactic acid conjunction titanium, isopropyl tri(dioctylpyrophosphato)titanate, butyl titanate, isopropyl triisostearoyltitanate, tetraisopropyl titanate, titanium acetylacetone.
In second aspect of the present invention, described lithium salts can be any one or a few the mixing in inorganic salts or organic salt, as any one or a few the mixture in lithium acetate, lithium formate, butyric acid lithium, propionic acid lithium, lithium carbonate, lithium nitrate, lithium sulfate, lithium hydroxide and above-mentioned lithium salts water and thing.
In second aspect of the present invention, described organic titanic compound or lithium salts are dissolved in organic solvent respectively, to form described organic titanic compound solution or lithium salt solution.
In second aspect of the present invention, in reinforced process, the mol ratio of lithium and titanium elements preferably controls 4: (5 ± 0.2), are more preferably and control 4: 5.
Wherein, described organic solvent can be any one or a few the compound in ketone, alcohol, ether, ester, acetonitrile.Particularly, the citing of described ketone is selected from any one or a few the mixture in acetone, butanone, cyclohexanone; The citing of described alcohol is selected from any one or a few the mixture in methyl alcohol, ethanol, normal propyl alcohol, isopropyl alcohol, n-butanol, ethylene glycol; Described ether is selected from any one or a few the mixture in ether, butyl ether, ethyl methyl ether, benzinum.
In second aspect of the present invention, can also comprise stabilizer in lithium salt solution, described stabilizer is preferably organic carboxyl acid.Described organic carboxyl acid can be monoacid or polyacid, as any one or a few the mixture in formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, sad, malonic acid, ethanedioic acid, succinic acid, citric acid, tartaric acid, malic acid, salicylic acid, ascorbic acid, citric acid, benzoic acid, be more preferably any one or a few the mixture in acetic acid, citric acid, tartaric acid.
In second aspect of the present invention, in reinforced process, the molal quantity sum of lithium and M and the mol ratio of titanium elements preferably control 4: (5 ± 0.3), are more preferably and control 4: (5 ± 0.2).
In second aspect of the present invention, in step 2, can also comprise drying steps after described ageing, described drying is preferably carried out at the temperature of≤100 ° of C, and preferred temperature is 40-100 ° of C, is more preferably 50-80 ° of C, is more preferably 60-80 ° of C.
In second aspect of the present invention, in step 3, in described calcination process, temperature is preferably 500-1000 ° of C, is more preferably 500-900 ° of C, is more preferably 600-850 ° of C.
Wherein, in a kind of preferred embodiment in the present invention second, described calcination process is divided into two stages to carry out, first stage is pre-sintered state, and calcining heat is preferably 500-700 ° of C, is more preferably 550-680 ° of C, be more preferably 580-670 ° of C, be more preferably 600-650 ° of C, as 620 ° of C, 640 ° of C etc., most preferably be 650 ° of C; Second stage is the sintering stage, and sintering temperature is preferably 700-900 ° of C, is more preferably 730-880 ° of C, is more preferably 750-850 ° of C, as 780 ° of C, and 800 ° of C, 830 ° of C.
Wherein, described presintering time first stage is preferably 10min-60min, is more preferably 15-50min, is more preferably 20-40min, as 30-40min.
Wherein, described second stage sintering time is preferably 0.5-4h, is more preferably 1-3.5h, is more preferably 1.5-3h, as 2-2.5h.
In second aspect of the present invention, in step 3, after calcination process, ball milling step can also be comprised.Wherein, described Ball-milling Time is preferably 0.5-3h, is more preferably 1-2h.
During the one of the method described in above-mentioned first or second aspect of the present invention is preferably implemented: described carbon source is preferably any one or a few the mixture in polymeric material, pitch; As the mixture of any one or a few in polyacrylonitrile, polyolefin, phenolic resins, Lauxite, furfuryl alcohol resin, epoxy resin, polyaniline, polyamide, polyurethane, polyester, glucose, pitch.
Wherein, described carbon source is more preferably any one or a few the mixture in furfuryl alcohol resin, epoxy resin, phenolic resins, polyacrylonitrile, pitch, and described mixture is as the mixture of phenolic resins and pitch.
In described a kind of preferred embodiment, solvent described in step 4 can be any one or a few the mixture that can dissolve arbitrarily in the solvent of carbon source, and concrete example is selected from any one or a few the mixture in ethanol, chloroform, carrene, carbon tetrachloride, acetone, benzene, toluene, chlorobenzene, dimethylbenzene, oxolane, ethyl acetate.Should be understood that, the selection that above-mentioned solvent is answered can dissolve described carbon source, and such as, select ethanol for dissolving phenolic resins, carbon tetrachloride or chloroform are used for dissolved bitumen etc.
In described a kind of preferred embodiment, calcining described in step 4 is preferably carried out under anaerobic, is more preferably and carries out in inert gas or reducibility gas environment.
Described inert gas or reducibility gas are preferably selected from any one or a few the gaseous mixture in the gases such as hydrogen, nitrogen, argon gas, carbon dioxide.
In described a kind of preferred embodiment, in calcination process described in step 4, calcining heat is preferably 600-1000 ° of C, is more preferably 650-900 ° of C, is more preferably 700-800 ° of C, as 730 ° of C, and 750 ° of C, 770 ° of C etc.
In described a kind of preferred embodiment, in calcination process described in step 4, calcination time is preferably 0.5-5h, is more preferably 1-4h, is more preferably 1.5-3h, as 2-2.5h.
Third aspect of the present invention is to provide the carbon coating spinelle lithium titanate Li that a kind of any one method above-mentioned is produced 4ti xm yo 12material (spinel type nano lithium titanate Li 4ti xm yo 12/ carbon composite); Wherein, x is selected from 4.9-5.0, and is preferably 4.95-5.0, is more preferably 4.97-5.0; Y>=0; X+y=4.9-5.1, and be preferably 4.95-5.05, most preferably be 5.
Wherein, described material comprises spinel lithium titanate Li 4ti xm yo 12as nuclear material, and coated by the carbon coating layer institute as shell material.
Carbon coating spinelle lithium titanate Li described in third aspect of the present invention 4ti xm yo 12in material, M be selected from mendeleev periodic table of elements first main group, the second main group, the 3rd main group, transition metal or rare earth metal any one or a few.As the mixture of any one or a few in the metallic elements such as Na, K, Li, Zn, Mg, Mn, Ru, Pd, Mo, Zr, Y, Nb, Ba, Al, Cu, Co, Cr, Fe, In, Ga, Ni, V, La, Nd, Sm, Ce.
In 3rd aspect of the present invention, described carbon coating spinelle lithium titanate Li 4ti xm yo 12material particle size≤500nm, is preferably 10-500nm, is more preferably 50-500nm, is more preferably 100-500nm, be more preferably 200-500nm, be more preferably 300-500nm, be more preferably 400-500nm.
In 3rd aspect of the present invention, described carbon coating spinelle lithium titanate Li 4ti xm yo 12material is when 1/3C charge and discharge, and capacity>=150mAh/g, is preferably>=160mAh/g, is more preferably 150-170mAh/g, is more preferably 160-165mAh/g; When 1C charge and discharge, capacity>=140mAh/g, is preferably>=145mAh/g, is more preferably 140-160mAh/g, is more preferably 145-155mAh/g; When 20C charge and discharge, capacity>=95mAh/g, is preferably>=100mAh/g, is more preferably 100-120mAh/g, is more preferably 100-115mAh/g.
In 3rd aspect of the present invention, described carbon coating spinelle lithium titanate Li 4ti xm yo 12material, charge and discharge circulation 100 weeks under 1C condition, capacity dimension holdup>=97%, be more preferably>=97.5%, be more preferably 97.5-99.8%, be more preferably 98-99.5%, as 98.5%, 99%.
The present invention the 4th aspect is to provide a kind of above-mentioned any carbon coating spinelle lithium titanate Li 4ti xm yo 12the application of material in lithium ion battery negative material.
The present invention the 5th aspect is to provide a kind of lithium ion battery negative material, and described lithium ion battery negative material contains above-mentioned any carbon coating spinelle lithium titanate Li 4ti xm yo 12material.
In 5th aspect of the present invention, described lithium ion battery negative material is also containing conductive agent, binding agent, collector.
Wherein, carbon coating spinelle lithium titanate Li 4ti xm yo 12material, between conductive agent and binding agent weight ratio be preferably (75-90): (5-20): (1-10), be more preferably (80-85): (10-15): (3-8), most preferably is 85: 10: 5.
The present invention the 6th aspect is to provide a kind of lithium ion battery, and it contains the negative pole of the present invention the 5th described in aspect, and electrolyte.
In lithium ion battery described in the present invention the 6th aspect, diaphragm can also be comprised, as polypropylene diaphragm.
In lithium ion battery described in the present invention the 6th aspect, described electrolyte can be the electrolyte that can be used for arbitrarily lithium ion battery, as LiPF 6, any one or its any mixture in DEC, DMC, EC, as LiPF 6the mixture of/EC, DEC, DMC.
More preferably, described electrolyte concentration is preferably 0.1-2mol/L, is more preferably 0.5-1.5mol/L, as 1.0mol/L.
The invention provides a kind of negative material carbon coating spinelle lithium titanate Li of high performance lithium ion 4ti xm yo 12material (spinel type nano lithium titanate Li 4ti xm yo 12/ carbon composite) preparation method, this negative material is the coated spinel-type Li of carbon 4ti 5o 12or the coated unitary of carbon or polynary other doped with metal elements compound Ls i 4ti xm yo 12, and specify that its pattern should be nano particle.The lithium titanate Li prepared with conventional method 4ti 5o 12compare, lithium titanate Li prepared by the method 4ti xm yo 12there is better multiplying power property.When being employed lithium ion battery negative, the power-performance of battery can be improved significantly.
Accompanying drawing explanation
Fig. 1 is the spinel type nano lithium titanate Li prepared in the embodiment of the present invention 4ti xm yo 12/ carbon composite electromicroscopic photograph, wherein:
Fig. 1 a is stereoscan photograph;
Fig. 1 b is transmission electron microscope photo.
Embodiment
Under by embodiment, the present invention is further illustrated:
Embodiment 1:
Adopt the method synthesis of nano Li in claims 4ti 5o 12/ carbon composite.Concrete steps are as follows: in 1000mL three-neck flask, add two acetate hydrate lithium (CH 3cOOLi2H 2o, 29.48g, 0.289mol), inject 200mL absolute ethyl alcohol, rapid stirring under 20 ° of C; Butyl titanate ((C is dripped in flask 4h 9o) 4ti, 120mL, 0.3526mol) (Li: Ti=0.82, mol ratio), drip in five minutes.Add 24mL deionized water, 20mL glacial acetic acid in 160mL absolute ethyl alcohol, glass bar stirs.Solution is transferred in dropping funel, be injected under rapid stirring (20s injects complete) in flask.
20 ° of C constant temperature stir 3h, form vitreosol, obtain white gels after ageing 24h.By ageing gained gel vacuumize 12h under 80 ° of C, obtain white slightly buff powder, after ball milling 1h, present white fine-powder shape, obtained precursor.By gained precursor powder in atmosphere after 600 ° of C presintering, then be warmed up to 750-850 ° of C sintering, with ball milling 1h after stove cooling, obtain white lithium titanate powder LTO.
Select phenolic resins and low melting point pitch as the carbon source material of LTO chemical method carbon coated.Preparation method is as follows: LTO and phenolic resins and pitch, as solvent, dissolve, fully dissolve after disperseing, form homogeneous suspension-turbid liquid by absolute ethyl alcohol (coated phenolic resins with) and carbon tetrachloride (coated pitch with).By suspension-turbid liquid agitating heating under 70 ° of C of preparation, boil off solvent, in time becoming pasty state, be placed in air dry oven 60 ° of C degree dry.Move on in porcelain boat by the LTO of dried coated phenolic resins, put into tube furnace, under logical condition of nitrogen gas, 5 ° of C/min are warming up to 700-800 ° of C respectively, are incubated 2 hours, obtain nanometer Li 4ti 5o 12/ carbon composite.
The nanometer Li obtained 4ti 5o 12/ carbon composite, at 400-500nm(, granular size is shown in that Fig. 1 a) and have typical carbon coating layer (in see Fig. 1 b grain edges).
Be assembled into button cell as follows and carry out electro-chemical test:
Button cell assembling method: by composite material prepared in above-described embodiment and comparative example and conductive agent, binding agent according to: the ratio mixed slurry of 85: 10: 5, then controls certain thickness and coats in aluminum foil current collector.With 1.0mol/L LiPF 6/ EC+DEC+DMC(volume ratio 1: 1: 1) be electrolyte, Li sheet is negative pole, and it is barrier film that the U.S. produces Cellgard-2400 type polypropylene screen, in the glove box being full of argon gas, be assembled into button cell.Then on the LandCT2001A type battery test system of Wuhan Jin Nuo Electronics Co., Ltd. production, multiplying power test and cycle life test are carried out to synthetic material.
Test result shows, when 1/3C charge and discharge, the capacity of this material is 160mAh/g; During 1C charge and discharge, its capacity is 145mAh/g; When 20C charge and discharge, the capacity of this material is 100mAh/g.Under 1C condition, charge and discharge circulation 100 weeks, capacity dimension holdup is that 99%(refers to table 1).
Comparative example 1:
Conventional solid synthetic method is adopted to prepare Li 4ti 5o 12material: after 0.5moL titanium dioxide and the grinding evenly of 0.2moL lithium carbonate, calcine 24 hours under 800 ° of C, product.Obtain Li 4ti 5o 12the granular size of material is at about 2 μm.Assemble button as follows and carry out electro-chemical test.Test result shows, when 1/3C charge and discharge, the capacity of this material is 155mAh/g; During 1C charge and discharge, its capacity is 120mAh/g; When 20C charge and discharge, the capacity of this material is 70mAh/g.Under 1C condition, charge and discharge circulation 100 weeks, capacity dimension holdup is that 98%(refers to table 1).
Embodiment 2:
Adopt the method synthesis of nano Li in claims 4zn 0.1ti 4.95o 12/ carbon composite particle.Two acetate hydrate lithium (CH are added in 1000mL three-neck flask 3cOOLi2H 2o, 29.48g, 0.289mol) and two water zinc acetate ((CH 3cOO) 2zn2H 2o, 2.195g, 0.01moL), inject 200mL absolute ethyl alcohol, rapid stirring under 20 ° of C; Butyl titanate ((C is dripped in flask 4h 9o) 4ti, 118.8mL, 0.03491mol) (Li: Zn: Ti=4.1: 0.1: 4.95), drip in five minutes.Add 24mL deionized water, 20mL glacial acetic acid in 160mL absolute ethyl alcohol, glass bar stirs.
Remaining step is with embodiment 1.
Obtain product, its granular size is at 400-500nm.Assemble button by method described in embodiment 1 and carry out electro-chemical test.Test result shows, when 1/3C charge and discharge, the capacity of this material is 160mAh/g; During 1C charge and discharge, its capacity is 150mAh/g; When 20C charge and discharge, the capacity of this material is 110mAh/g.Under 1C condition, charge and discharge circulation 100 weeks, capacity dimension holdup is that 99%(refers to table 1).
Embodiment 3:
Adopt the method synthesis of nano Li in claims 4mg 0.05ti 4.975o 12/ C composite material nanometer particle.Two acetate hydrate lithium (CH are added in 1000mL three-neck flask 3cOOLi2H 2o, 29.48g, 0.289mol) and four acetate hydrate magnesium (Mg (CH 3cOO) 24H 2o, 1.072g, 0.005moL), inject 200mL absolute ethyl alcohol, rapid stirring under 20 ° of C; Butyl titanate ((C is dripped in flask 4h 9o) 4ti, 119.4mL, 0.3508mol) (Li: Zn: Ti=4.1: 0.05: 4.975), drip in five minutes.Add 24mL deionized water, 20mL glacial acetic acid in 160mL absolute ethyl alcohol, glass bar stirs.Remaining step is with embodiment 1.Obtain nanometer Li 4mg 0.05ti 4.975o 12/ C composite material nanometer particle.
Remaining step is with embodiment 1.
Assemble button by method described in embodiment 1 and carry out electro-chemical test.Test result shows, when 1/3C charge and discharge, the capacity of this material is 165mAh/g; During 1C charge and discharge, capacity is 155mAh/g; When 20C charge and discharge, the capacity of this material is 115mAh/g.Under 1C condition, charge and discharge circulation 100 weeks, capacity dimension holdup is that 99%(refers to table 1).
Table 1 the present invention and the lithium ion battery negative material the performance test results prepared by prior art
As can be seen from above-described embodiment, spinel type nano lithium titanate Li provided by the present invention 4m xti yo 12the power-performance that/carbon composite can promote battery improves the cycle life of battery, because its nanoscale shortens the evolving path of lithium ion in charge and discharge process, thus promotes the power of battery; And the carbon of external sheath can improve lithium titanate conductivity while reduce lithium titanate contact with electrolytical, thus suppress both side reaction generation, improve the cycle life of battery from two aspects.
Be described in detail specific embodiments of the invention above, but it is just as example, the present invention is not restricted to specific embodiment described above.To those skilled in the art, any equivalent modifications that the present invention is carried out and substituting also all among category of the present invention.Therefore, equalization conversion done without departing from the spirit and scope of the invention and amendment, all should contain within the scope of the invention.

Claims (15)

1. produce spinel type lithium titanate Li for one kind 4ti xm yo 12method, it is characterized in that, x is selected from 4.9-5.0, y>=0, x+y=4.9-5.1; Described method comprises the steps:
Step 1, joins in organic titanic compound solution by lithium salts and doping metals M solion, forms colloid;
Step 2, by described colloid ageing, obtains the lithium titanate precursor adulterated;
Step 3, calcines described lithium titanate precursor, obtains the nano lithium titanate adulterated;
Step 4, is scattered in nano lithium titanate in the solvent dissolving carbon source, calcines, obtain the spinel lithium titanate Li of carbon-coated nano size after sloughing solvent 4ti 5o 12; Wherein, described carbon source is to calcine the material of carbonization.
2. method according to claim 1, is characterized in that, in calcination process described in step 3, temperature is 500-1000 ° of C.
3. method according to claim 2, is characterized in that, calcination process described in step 3 is divided into two stages to carry out, and the first stage is pre-sintered state, and calcining heat is 500-700 ° of C; Second stage is the sintering stage, and sintering temperature is 700-900 ° of C.
4. method according to claim 1, is characterized in that, described organic titanium is any one or a few the mixture in titanate esters or organic acid titanium salt, titanium organic complex.
5. method according to claim 1, is characterized in that, described lithium salts is selected from any one or a few the mixing in inorganic salts or organic salt.
6. method according to claim 1, is characterized in that, described " doping metals " or M be selected from mendeleev periodic table of elements first main group, the second main group, the 3rd main group, transition metal or rare earth metal any one or a few.
7. method according to claim 6, it is characterized in that, described " doping metals " or M are selected from any one or a few the combination in Na, K, Li, Zn, Mg, Mn, Ru, Pd, Mo, Zr, Y, Nb, Ba, Al, Cu, Co, Cr, Fe, In, Ga, Ni, V, La, Nd, Sm, Ce metallic element.
8. method according to claim 1, is characterized in that, x=5, y=0.
9. method according to claim 1, it is characterized in that, described carbon source is selected from any one or a few the mixture in polyacrylonitrile, polyolefin, phenolic resins, Lauxite, furfuryl alcohol resin, epoxy resin, polyaniline, polyamide, polyurethane, polyester, glucose, pitch.
10. method according to claim 1, is characterized in that, in calcination process described in step 4, calcining heat is 600-1000 ° of C.
The carbon coating spinelle lithium titanate Li that method described in 11. 1 kinds of above-mentioned any one claims is produced 4ti xm yo 12material; Wherein, x is selected from 4.9-5.0; Y>=0; X+y=4.9-5.1, described carbon coating spinelle lithium titanate Li 4ti xm yo 12material comprises spinel lithium titanate Li 4ti xm yo 12as nuclear material, and coated by the carbon coating layer institute as shell material; Described carbon coating spinelle lithium titanate Li 4ti xm yo 12material particle size≤500nm.
12. carbon coating spinelle lithium titanate Li according to claim 11 4ti xm yo 12material, is characterized in that, described carbon coating spinelle lithium titanate Li 4ti xm yo 12material when 1/3C charge and discharge, capacity>=150mAh/g; When 1C charge and discharge, capacity>=140mAh/g; When 20C charge and discharge, capacity>=95mAh/g.
Carbon coating spinelle lithium titanate Li described in 13. 1 kinds of above-mentioned any one claims 4ti xm yo 12the application of material in lithium ion battery negative material.
14. 1 kinds of lithium ion battery negative materials, is characterized in that, described lithium ion battery negative material contains carbon coating spinelle lithium titanate Li described in above-mentioned any one claim 4ti xm yo 12material.
15. 1 kinds of lithium ion batteries, is characterized in that, containing the negative pole described in the claims in the present invention 14, and electrolyte.
CN201310264622.0A 2013-06-27 2013-06-27 Carbon-clad spinel lithium titanate material, production method and application thereof Pending CN104253267A (en)

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