CN102169980A - Preparation method of anode active material - Google Patents
Preparation method of anode active material Download PDFInfo
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- CN102169980A CN102169980A CN2010101170800A CN201010117080A CN102169980A CN 102169980 A CN102169980 A CN 102169980A CN 2010101170800 A CN2010101170800 A CN 2010101170800A CN 201010117080 A CN201010117080 A CN 201010117080A CN 102169980 A CN102169980 A CN 102169980A
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Abstract
The invention provides a preparation method of an anode active material, which comprises the steps of: a, adding a titanium source and an organic carbon source in an organic solution with the pH value of 0-6 to prepare a mixture solution; b, adding an oxidizing agent in the mixture solution, reacting for 1-24h at a temperature of 20-80 DEG C, then separating and settling, washing with water, drying to obtain a titanium-containing precursor; and c, carrying out mixing and ball-milling on the titanium-containing precursor obtained in the step b and a lithium source, and then roasting in an inert gas. A lithium titanate composite material prepared by adopting the method disclosed by the invention has less impurity phases; the prepared nanometer lithium titanate particles are attractive in appearance; and the preparation method has the advantages of short time, low energy consumption, low cost, high yield, uniform particles of the prepared material, stable performance of the prepared material, simple and controllable process, and capability of realizing massive industrialized clean production.
Description
Technical field
The present invention relates to a kind of preparation method of negative active core-shell material.
Background technology
Lithium ion battery has energy density height (150-200Wh/kg), the high and low self discharge of operating voltage, long-life, memory-less effect and advantage such as environmentally friendly has been widely used in fields such as mobile communication, notebook computer, video camera, camera, portable instrument, also be the electric automobile studied energetically of various countries, the first-selected supporting power supply of space power system, become the first-selection of the alternative energy.
And advanced electrode material becomes the core technology that present lithium ion battery updates.Existing commercial negative active core-shell material is generally material with carbon element, and material with carbon element can not satisfy the demand of now big multiplying power power power consumption equipment, for example power vehicle is in braking procedure, braking time is of short duration, generally be no more than 10s ground, the immediate current that the motor demand is bigger, with effective braking and recuperated energy, automobile has 50～60% braking energy recyclable in theory, and the braking energy of actual recovered＜20%, charge-discharge magnification, the especially rate of charge of existing material with carbon element is difficult to reach the basic demand of electric automobile fast charging and discharging.Simultaneously since behind the embedding lithium current potential of carbon electrode approaching with the current potential of lithium metal, when over-charging of battery, the easy precipitating metal lithium of carbon electrodes, it and electrolyte reaction generation combustible gas mixture, thus to battery particularly electrokinetic cell cause very big potential safety hazard.And also there is the common imbedding problem of electrolyte in graphite electrode, and this also will influence the cyclical stability of electrode.
The Li of spinel structure
4Ti
5O
12Current potential with respect to lithium electrode is 1.55V, and theoretical specific capacity is 175mAh/g, actual specific capacity 150～160mAh/g; Simultaneously embed or deviate from the process at Li+, crystal formation does not change, and change in volume is less than 1%, and the repeated charge crystal structure is not easy to change, the cycle life excellence (＞1500Cycles); And Li
4Ti
5O
12Do not form the SEI film with the electrolyte reaction, the internal resistance of cell is anti-can not to rise, safe, is fit to advantages such as big electric current quick charge, becomes the focus and the difficult point of existing research.
Prepare Li at present
4Ti
5O
12Method mainly contain two kinds of solid reaction process and liquid phase methods, solid reaction process is usually with TiO
2With LiOHH
2O or Li
2CO
3Mix, handled 12～24 hours down at high temperature (800 ℃～1000 ℃) then, obtain product Li
4Ti
5O
12Ball milling can be adopted, also a certain amount of carbon or organic carbon source and then heat treatment under inert atmosphere can be in raw material, added.Solid-phase synthesis is simple to operate, is easy to industrialization; But product characters is difficult to meticulous control, is difficult to prepare fine granular, and material conductivity is relatively poor; And also difficulty of reaction control, exist reaction not exclusively, heterogeneity, generally can remaining TiO in the product
2Or monoclinic crystal Li
2TiO
3, capacity attenuation is fast in actual use, and is unfavorable for commercial the application.The synthetic superfines that can synthesis nano of liquid phase method, general employing organic precursor is a raw material, hydrolysis or alcoholysis by raw material form colloidal sol, colloidal sol solvent flashing, aging losing flowability under certain condition obtains gel, gets product to the end again through Overheating Treatment, this method complex process, cost is higher, output is lower, and is unfavorable for high volume process production, and also than the purer lithium titanate of difficult preparation.
Prior art also has open with TiCl
4Or titanyl sulfate under acid condition with graphite mix the back with kerosene be decentralized medium with ammoniacal liquor one-tenth preparation precursor after with lithium source sintering, prepare spherical carbon dope lithium titanate, but the impurity of the product that this method obtains is many mutually, impurity level is big, contains rutile TiO easily
2And the amount of each preparation can be restricted, unsuitable large-scale production is promoted, Zhi Bei particle can be reunited simultaneously, the deposit seed size should not be controlled, synthetic presoma particle diameter is still bigger, and the particle diameter heterogeneity, and particle diameter distribution width is bigger, not only the electric conductivity of material is still undesirable, and influences performances such as the consistency of final material and stability; Thereby cause the lithium ion the evolving path long, chemical property is not ideal enough, and the specific capacity decay is serious.
Summary of the invention
The lithium titanate impurity that the objective of the invention is to overcome prior art for preparing is many mutually, impurity level is big and multiplying power discharging property is undesirable, provides a kind of and can prepare multiplying power discharging property height, free from admixture, nanoscale metatitanic acid cathode of lithium active material and the easy method of technology.
This method step comprises:
A, titanium source and organic carbon source are joined the pH value be configured to mixed solution in the organic solution of 0-6;
Wherein, the titanium source is selected from one or more in isopropyl titanate, metatitanic acid four fourth fat, metatitanic acid, titanium tetrachloride or the titanyl sulfate;
B, in above-mentioned mixed solution, add oxidant, in 20-80 ℃ of reaction 1-24h down, back precipitation separation, washing, dry must the titaniferous precursor;
C, with step b gained titaniferous precursor and lithium source mixing and ball milling, the back roasting under inert atmosphere.
The present inventor is unexpected to be found, adopts the dephasign of the lithium titanate composite material that method of the present invention makes few, TiO
2And Li
2TiO
3Amount be set on 100 the basis TiO for the main peak intensity of measuring the spinel-type Li-Ti oxide determine by X-ray diffraction
2Main peak intensity can reach 2.6%, Li
2TiO
3Main peak intensity can reach 1.8%.The titaniferous precursor that reason is speculated as the present invention's preparation may be deposited in this under inert gas for coating organic metatitanic acid precipitation, finds to generate the TiO of the rutile structure that contains partially crystallizable through carrying out analysis of components behind 400 degrees centigrade of sintering 4h
2, the unexpected titaniferous precursor of this kind structure of finding can better react with the lithium source, prepares more pure phase, free from admixture almost, the lithium titanate that performance is more excellent; The particle diameter of the titaniferous precursor of method preparation simultaneously of the present invention is less, can reach 40 nanometers, and uniform particle diameter, mixes more evenly when helping sintering with the lithium source, and forming well equal dispersion is to make reaction more even, more complete, more thorough.
Be added with organic carbon source when particularly preparing the titaniferous precursor, organic carbon source can be attached to particle surface as carrier, can effectively stop the continued growth of particle, and intercepted the short grained reunion of nanometer, the homogeneity and the consistency of product of particle diameter have effectively been controlled, and well modified particle surface, make the product particle pattern perfection of final preparation; Organic carbon source plays certain flocculating effect as carrier simultaneously, makes particle be easy to separate, and has helped guaranteeing the uniformity and the stability of system.And when sintering, can further stop the contact and the reunion of nano particle, the effectively product cut size and the pattern of the material of the final preparation of control; Organic carbon source can remain one deck carbon at particle surface when sintering simultaneously, coated particle, when strengthening conductivity, further stop particle agglomeration, and carbon coats more even, more perfect, complete, the carbon encapsulated material that overcomes existing preparation exists shortcomings such as coating blind area, coating uneven thickness, the perfect nano particle negative active core-shell material of processability.
The lithium titanate particle of preparation is a nanoscale, average particulate diameter can reach nanoscale, particle diameter is distributed in the scope of 50-300 nanometer, the particle size distribution homogeneous, improved the conductivity of material, the battery of preparation is in the charging and discharging cyclic process, and the electrode polarization degree is low, is not easy to occur local overcharging and overdischarge; This nano particle pattern perfection simultaneously has short lithium ion and takes off the embedding stroke, makes battery the electrode polarization degree is little when high power charging-discharging, reversible capacity is high, has extended cycle life; And the nano particle of the present invention preparation has bigger specific area, and particle voids rate height can provide a large amount of spaces for the migration of taking off embedding and organic solvent molecule of lithium ion, helps improving the big current ratio flash-over characteristic of battery.
The preparation method of lithium titanate composite material provided by the invention weak point consuming time, energy consumption is low, cost is low, productive rate is high, the material granule of preparation evenly, stable, the technological process simple controllable of material property of preparation, can realize that large-scale industry cleans production.
Description of drawings
Fig. 1 is ESEM (SEM) picture behind 400 ℃ of sintering 4h of titaniferous precursor of the embodiment of the invention 1 preparation;
Fig. 2 is X ray crystal diffraction (XRD) picture behind 400 ℃ of sintering 4h of titaniferous precursor of the embodiment of the invention 1 preparation;
Fig. 3 is the Li of the embodiment of the invention 1 preparation
4Ti
5O
12ESEM (SEM) picture;
Fig. 4 is the Li of the embodiment of the invention 1 preparation
4Ti
5O
12X ray crystal diffraction (XRD) picture;
Fig. 5 is the charge-discharge magnification curve chart of the simulated battery of the embodiment of the invention 1 preparation.
Embodiment
In order to make technical problem solved by the invention, technical scheme and beneficial effect clearer,, the present invention is further elaborated below in conjunction with drawings and Examples.Should be appreciated that specific embodiment described herein only in order to explanation the present invention, and be not used in qualification the present invention.
The invention provides a kind of preparation method of pure phase nanometer lithium titanate anode active material.This method step comprises: a, titanium source and organic carbon source are joined the pH value be configured to mixed solution in the organic solution of 0-6;
Wherein, the titanium source is selected from one or more in isopropyl titanate, metatitanic acid four fourth fat, metatitanic acid, titanium tetrachloride or the titanyl sulfate;
B, in above-mentioned mixed solution, add oxidant, in 20-80 ℃ of reaction 1-24h down, back precipitation separation, washing, dry must the titaniferous precursor;
C, with step b gained titaniferous precursor and lithium source mixing and ball milling, the back roasting under inert atmosphere.Adopt the dephasign of the lithium titanate composite material that method of the present invention makes few, the lithium titanate particle of preparation is a nanoscale, the granule-morphology perfection, simultaneously preparation method's weak point consuming time, energy consumption is low, cost is low, productive rate is high, the material granule of preparation evenly, stable, the technological process simple controllable of material property of preparation, can realize that large-scale industry cleans production.
The present invention further preferably before with titaniferous precursor and lithium source mixing and ball milling, with the titaniferous precursor under inert atmosphere in 400-600 ℃ of sintering 2-6h.The titaniferous precursor is prepared into the titanium dioxide of carbon coated, form the tight and compact grain of coating layer, to further help and the mixing of lithium source, the organic carbon source of avoiding particle absorption simultaneously coming off or damage when mixing and ball milling, help further preparing the perfect carbon of pattern and coat the lithium titanate particle, further optimize the performance of lithium titanate.
Organic carbon source of the present invention can be selected from and well known to a person skilled in the art various carbon sources, the present invention is preferably selected from one or more in aniline, pyrroles, thiophene or the furans, these materials can be in polymerization under the oxidizing condition, form the more uniform more fully deposit seed surface that is coated on of network configuration, further controlled grain diameter.
Precipitation separation of the present invention, washing, dry post-processing step for preparation titaniferous precursor, operation is adopted and be well known to a person skilled in the art various methods of operation, for example wash suction filtration repeatedly, also can adopt and well known to a person skilled in the art various customary means, for example adopt the washing repeatedly that is equal to centrifugal, isolate titaniferous precursor solid, flush away impurity, acid etc.The dry employing well known to a person skilled in the art various drying means, for example 80 ℃ of vacuum drying chamber oven dry.The present invention can also comprise and well known to a person skilled in the art other various post-processing steps, for example grinds etc., obtains the titaniferous presoma.
Preferred oxidant of the present invention is selected from one or more in ammonium persulfate, hydrogen peroxide or the iron chloride.Can make reaction more complete, and more effective polymerization organic carbon source, be easy to simultaneously remove.The mol ratio of preferred oxidant of the present invention and organic carbon source is 0.5-4, more preferably 1-3.
The preferred organic solution of the present invention is selected from one or more the acid-containing solution in ethanol, methyl alcohol, the acetone.It is more even that organic solution can make titanate and organic carbon source disperse, and acid condition can stop the hydrolysis of titanate simultaneously, helps controlling the granular size of titaniferous precursor.Acid in the further preferred acid-containing solution of the present invention is selected from one or more in hydrochloric acid, sulfuric acid, phosphoric acid or the acetic acid, reduces cost.
Preferred lithium of the present invention source is selected from one or more in lithium hydroxide, lithium acetate, lithium chloride, lithium chromate, four water citric acid lithiums, tetrachloro-lithium aluminate, lithium bromide, LiBF4 or the lithium oxalate.
The Ti in the further preferred titanium source of the present invention and the mol ratio of organic carbon source are 10-2, more preferably 3-6.Make more complete, the more uniform coating titaniferous of organic carbon source precursor particle, modify more perfectly, guarantee that simultaneously reaction can be more complete; And the lithium titanate composite material of preparation contains the phosphorus content of 2-5%, and carbon can evenly be coated on the lithium titanate particle surface, coats perfectly, helps improving conductivity, improves cycle performance.
Ti in the further preferred titaniferous precursor of the present invention and the mol ratio of the Li in the lithium source are 1-1.67.Further optimal control reaction prevents the generation of impurity.
Ball milling of the present invention can adopt and well known to a person skilled in the art ball milling, with the absolute ethyl alcohol medium ball milling in high speed ball mill for example with titaniferous presoma and lithium source, high speed ball mill the present invention be not particularly limited, can be and select the capable ball mill of star, agitating ball mill, high energy vibration ball mill etc. for use, the volume ratio of ball, material can be 5-10: 1, and the volume of ball, material can account for the 60-75% of mill tank volume.Also comprise reprocessing behind the ball milling, for example dry, can 80 ℃ of oven dry in vacuum drying chamber.
Roasting of the present invention is not particularly limited, and can be one section roasting, also can be the multistage roasting, and the temperature of the preferred roasting of the present invention is 600-900 ℃; Time is 8-28h.Heating rate is 10 ℃/min.Cooling can also can be adopted annealing in process for the stove cooling, optimizes grain diameter, and the rate of temperature fall of annealing in process is 5 ℃/min.The preferred inert gas of the present invention is gases such as Ar, nitrogen.Can also adopt after the roasting of the present invention and well known to a person skilled in the art various post-processing steps.
Below in conjunction with specific embodiment the present invention is further described.
(1) preparation of negative active core-shell material
HCl145ml with 37% is dissolved in the ethanol of 1800ml (pH=1), stirs, and adds the aniline of 30ml, after the isopropyl titanate of 265ml slowly is added dropwise in the solution, fully stir 1h, the back slowly drips 10mlH
2O
2Be warmed up to 80 ℃ of insulation 5h, filter, with distilled water, ethanol cyclic washing dry the titaniferous precursor, under the Ar atmosphere protection, 400 ℃ of roasting 4h, cooling, grinding.
Observe the pattern of the material of above-mentioned preparation with JSM-5610LV type scanning electron microscopy (SEM), as shown in Figure 1, find out that obviously the particle average grain diameter is approximately 40 nanometers, grain diameter is little, and size is even, big or small basically identical, there is not obvious agglomeration, the pattern perfection.
Adopt Japanese D/MAX-PC2200X x ray diffractometer x of science (Cu target, λ=0.15405nm) product is carried out the crystal structure analysis of thing phase.As shown in Figure 2, the material of obviously finding out preparation among the figure is the indefiniteness TiO that contains rutile structure
2
With the above-mentioned material that makes is the titanium source, is the lithium source with the LITHIUM BATTERY lithium acetate, and both mol ratios are 4: 5, is medium ball milling 2h with the absolute ethyl alcohol in high speed ball mill.The sample that ball milling is good places 80 ℃ of oven dry of vacuum drying chamber, and in box atmosphere furnace, carry out roasting heat at last and handle, under the Ar Buchholz protection, 400 ℃ of insulation 6h, 700 ℃ of insulation 12h, heating rate is 5 ℃/min, can get black Li with the stove cooling
4Ti
5O
12Negative active core-shell material.
Adopt JSM-5610LV type scanning electron microscopy (SEM) to observe the Li of above-mentioned preparation
4Ti
5O
12Pattern, as shown in Figure 3, the particle average grain diameter is approximately 200 nanometers as can be seen, substantially all is distributed in the 100-300 nanometer range, and grain diameter is little, and size is even, and big or small basically identical does not have obvious agglomeration, the pattern perfection, specific area is big.
(the Cu target, λ=0.15405nm) is to the Li of above-mentioned preparation to adopt Japanese D/MAX-PC2200X x ray diffractometer x of science
4Ti
5O
12Carry out thing phase crystal structure analysis (XRD).As shown in Figure 4, as can be seen on the main peak intensity of the spinel-type Li-Ti oxide of determining is set to 100 basis, TiO
2Main peak intensity be 2.6%, Li
2TiO
3Main peak intensity be 1.8%.The lithium titanate of preparation is purer, is pure phase substantially, free from admixture.And peak shape is narrow and sharp, and crystalline form is better.
The carbon and sulfur analytical instrument of the HCS-800A of employing Dekai Instrument Co., Ltd., Shanghai is to the Li of above-mentioned preparation
4Ti
5O
12Carry out the carbon content test, the result is 4.4%.
(2) preparation of simulated battery:
Press mass ratio Li
4Ti
5O
12: acetylene black: PVDF=80: 10: 10 mixed evenly back compressing tablet is made, and pole piece is more than 120 ℃ of vacuumize 24h.Simulated battery is that negative pole, celgard2400 polypropylene porous film are barrier film with the metal lithium sheet, 1mol/L LiPF
6Ethylene carbonate (EC) and the mixed solution of dimethyl carbonate (DMC) (volume ratio is=1: 1) be electrolyte.The assembling process of all batteries is all carried out in being full of the glove box of argon gas.
The preparation of titaniferous precursor:
H with 98%
2SO
450ml is dissolved in the methyl alcohol of 2000ml (pH=2), stirs, and adds the aniline of 35ml, and 340ml titanyl sulfate (greater than 98%) is added dropwise in the solution gradually, fully stirs 1h.With 80g (NH
4)
2S
2O
8Be dissolved in the 1500ml deionized water, after slowly be added drop-wise in the above-mentioned solution, be warmed up to 70 ℃ of insulation 8h, filter, with deionized water, the oven dry of methyl alcohol cyclic washing.
Adopt the method identical with embodiment 1 to observe the pattern of material behind the titaniferous precursor sintering of above-mentioned preparation, average grain diameter is approximately 60 nanometers as can be seen, and grain diameter is little, and size is even, and big or small basically identical does not have obvious agglomeration, the pattern perfection.
Adopt the method identical to prepare negative active core-shell material and simulated battery with embodiment 1.
Adopt the particle average grain diameter of the lithium titanate composite material that the method test identical with embodiment 1 prepare to be approximately 200 nanometers, substantially all be distributed in the 100-400 nanometer range, grain diameter is little, size is even, and big or small basically identical does not have obvious agglomeration, the pattern perfection, specific area is big.XRD shows that the lithium titanate of preparation is purer, is set on 100 the basis TiO when the main peak intensity of the spinel-type Li-Ti oxide of determining
2Main peak intensity be 3.2%, Li
2TiO
3Main peak intensity 1.7%.The lithium titanate of preparation is purer, is pure phase substantially, free from admixture.And peak shape is narrow and sharp, and crystalline form is better.Carbon content is 2.7%.
Embodiment 3
Adopt the method identical with embodiment 1 to prepare negative active core-shell material and simulated battery, different is that the organic carbon source that adds is the pyrroles.
Adopt the particle average grain diameter of the lithium titanate composite material that the method test identical with embodiment 1 prepare to be approximately 250 nanometers, substantially all be distributed in the 100-400 nanometer range, grain diameter is little, size is even, and big or small basically identical does not have obvious agglomeration, the pattern perfection, specific area is big.XRD shows that the lithium titanate of preparation is purer, is set on 100 the basis TiO when the main peak intensity of the spinel-type Li-Ti oxide of determining
2Main peak intensity be 2.8%, Li
2TiO
3Main peak intensity be 1.5%.The lithium titanate of preparation is purer, is pure phase substantially, free from admixture.And peak shape is narrow and sharp, and crystalline form is better.Carbon content is 3.2%.
Embodiment 4
Adopt the method identical with embodiment 1 to prepare negative active core-shell material and simulated battery, that different is H
2O
2Addition be 5ml.
Adopt the particle average grain diameter of the lithium titanate composite material that the method test identical with embodiment 1 prepare to be approximately 250 nanometers, it is little substantially all to be distributed in 200-500 nanometer range endoparticle particle diameter, and size is even, the size basically identical, there is not obvious agglomeration, the pattern perfection, specific area is big.XRD shows that the lithium titanate of preparation is purer, is set on 100 the basis TiO when the main peak intensity of the spinel-type Li-Ti oxide of determining
2Main peak intensity be 3.0%, Li
2TiO
3Main peak intensity be 2.1%.The lithium titanate of preparation is purer, is pure phase substantially, free from admixture.And peak shape is narrow and sharp, and crystalline form is better.Carbon content is 4.2%.
Embodiment 5
Adopt the method identical with embodiment 1 to prepare negative active core-shell material and simulated battery, that different is H
2O
2Addition be 40ml.
Adopt the particle average grain diameter of the lithium titanate composite material that the method test identical with embodiment 1 prepare to be approximately 230 nanometers, substantially all be distributed in the 100-300 nanometer range, grain diameter is little, size is even, the size basically identical does not have obvious agglomeration, and specific area is big.XRD shows that the lithium titanate of preparation is purer, is set on 100 the basis TiO when the main peak intensity of the spinel-type Li-Ti oxide of determining
2Main peak intensity be 3.0%, Li
2TiO
3Main peak intensity be 2.3%.The lithium titanate of preparation is purer, is pure phase substantially, free from admixture.And peak shape is narrow and sharp, and crystalline form is better.Carbon content is 4.6%.
Embodiment 6
Adopt the method identical with embodiment 1 to prepare negative active core-shell material and simulated battery, that different is H
2O
2Addition be 2.5ml.
Adopt the particle average grain diameter of the lithium titanate composite material that the method test identical with embodiment 1 prepare to be approximately 480 nanometers, substantially all be distributed in the 50-600 nanometer range, grain diameter is little, size is even, and big or small basically identical does not have obvious agglomeration, the pattern perfection, specific area is big.XRD shows that the lithium titanate of preparation is purer, is set on 100 the basis TiO when the main peak intensity of the spinel-type Li-Ti oxide of determining
2Main peak intensity be 5.8%, Li
2TiO
3Main peak intensity be 4.3%.The lithium titanate of preparation is purer, is pure phase substantially, free from admixture.And peak shape is narrow and sharp, and crystalline form is better.Carbon content is 3.5%.
Embodiment 7
Adopt the method identical with embodiment 1 to prepare negative active core-shell material and simulated battery, different is titaniferous precursor directly mixes with the lithium source as the titanium source without sintering.
Adopt the particle average grain diameter of the lithium titanate composite material that the method test identical with embodiment 1 prepare to be approximately 470 nanometers, substantially all be distributed in the 80-540 nanometer range, grain diameter is little, size is even, and big or small basically identical does not have obvious agglomeration, the pattern perfection, specific area is big.XRD shows that the lithium titanate of preparation is purer, is set on 100 the basis TiO when the main peak intensity of the spinel-type Li-Ti oxide of determining
2Main peak intensity be 4.5%, Li
2TiO
3Main peak intensity be 3.7%.The lithium titanate of preparation is purer, is pure phase substantially, free from admixture.And peak shape is narrow and sharp, and crystalline form is better.Carbon content is 3.5%.
Comparative Examples 1
With 24gTiOSO
4Stir the 4h dissolving in the solution of adding 60ml 5mol/LHCl, make TiOCl solution.To account for Li
4Ti
5O
12Mass percent is that 4.4% carbon black 0.6g adds in the above-mentioned solution, and ball milling mixes.Under stirring condition, be added dropwise to 2ml and contain in the kerosene decentralized medium that mass percent is 3% class of department 80 surfactants, and continue to feed ammonia, whenever contain 1 mole Ti in the solution
4+Need to feed the ammonia of 100L, stop to stir, gel precipitation is come out.With the gel centrifugation, the ammoniacal liquor of using 30ml spends the deionized water washing again with the ageing of gained gel, detects less than Cl to washings
-, centrifugal, the oven dry in back obtains the carbon dope gel micro-ball.
In lithium titanium mol ratio is that 4: 5 ratio takes by weighing Li
2CO
3With the carbon dope gel micro-ball presoma of above-mentioned gained in high speed ball mill, be medium ball milling 2h with the absolute ethyl alcohol.The sample that ball milling is good places 80 ℃ of oven dry of vacuum drying chamber, and in box atmosphere furnace, carry out roasting heat at last and handle, under the Ar Buchholz protection, 400 ℃ of insulation 6h, 700 ℃ of insulation 12h, heating rate is 5 ℃/min, can get black Li with the stove cooling
4Ti
5O
12Negative active core-shell material.
The lithium titanate SEM that adopts the method identical with embodiment 1 to observe preparation schemes, and the particle average grain diameter is approximately 1 micron, particle size distribution in the scope of 500-3500 nanometer, the particle size distribution broad, the size heterogeneity can be seen obvious reunion, the particle crystalline form is imperfect.XRD (as shown in Figure 8) shows the lithium titanate of preparation, is set on 100 the basis TiO when the main peak intensity of the spinel-type Li-Ti oxide of determining
2Main peak intensity be 8.8%, Li
2TiO
3Main peak intensity be 6.3%, non-pure phase, impurity level is big.And peak shape broad.
Performance test
First discharge specific capacity test: the battery of embodiment 1-7 and Comparative Examples 1 preparation placed carry out the charge-discharge performance test on the charge-discharge test instrument, the discharge voltage interval is 1.0～2.5V, and discharging current is 0.1C.Test result such as table 1.
Cycle performance test: the battery of embodiment 1-7 and Comparative Examples 1 preparation placed carry out the charge-discharge performance test on the charge-discharge test instrument, the discharge voltage interval is 1.0～2.5V, and discharging current is 0.5C.Test result such as table 1.
High rate performance test: the battery of embodiment 1-7 and Comparative Examples 1 preparation placed carry out the charge-discharge performance test on the charge-discharge test instrument, the discharge voltage interval is 1.0～2.5V, and discharging current is respectively 0.1C, 0.5C, 1C, 2C, 5C, test result such as table 2.
Table 1
| First discharge specific capacity (mAh/g) | The 20th discharge capacity (mAh/g) | The 100th discharge capacity (mAh/g) | |
| |
171 | 151 | 149 |
| |
169 | 147 | 142 |
| Embodiment 3 | 163 | 145 | 139 |
| Embodiment 4 | 158 | 144 | 137 |
| Embodiment 5 | 155 | 145 | 135 |
| Embodiment 6 | 148 | 134 | 126 |
| Embodiment 7 | 152 | 140 | 128 |
| Comparative Examples 1 | 140 | 128 | 119 |
Table 2
| 0.1C specific discharge capacity (mAh/g) | 1C specific discharge capacity (mAh/g) | 10C specific discharge capacity (mAh/g) | 20C specific discharge capacity (mAh/g) | 30C specific discharge capacity (mAh/g) | |
| |
171 | 147 | 91 | 72 | 55 |
| |
169 | 139 | 86 | 69 | 51 |
| Embodiment 3 | 163 | 137 | 86 | 68 | 49 |
| Embodiment 4 | 158 | 137 | 85 | 66 | 50 |
| Embodiment 5 | 155 | 136 | 84 | 60 | 45 |
| Embodiment 6 | 148 | 123 | 58 | 20 | 8 |
| Embodiment 7 | 152 | 132 | 78 | 47 | 36 |
| Comparative Examples 1 | 140 | 115 | 55 | 13 |
Adopt the dephasign of the lithium titanate composite material that method of the present invention makes few as can be seen, TiO
2And Li
2TiO
3Amount be set on 100 the basis TiO for the main peak intensity of measuring the spinel-type Li-Ti oxide determine by X-ray diffraction
2Main peak intensity can reach 2.6%, Li
2TiO
3Main peak intensity can arrive 1.8%.The particle diameter of the lithium titanate composite material of the preparation of the present invention simultaneously is little, be nano particle, uniform particle diameter, the stability and the consistency of product are better, and the material of preparation contains evenly, perfect carbon coating layer, the electric conductivity excellence, specific area is big, big current ratio flash-over characteristic excellence is laid a good foundation for the development of battery, helps development of technology.
Simultaneously preparation method of the present invention weak point consuming time, energy consumption is low, cost is low, productive rate is high, the material granule of preparation evenly, stable, the technological process simple controllable of material property of preparation, can realize that large-scale industry cleans production, help commercial the application.
The above only is preferred embodiment of the present invention, not in order to restriction the present invention, all any modifications of being done within the spirit and principles in the present invention, is equal to and replaces and improvement etc., all should be included within protection scope of the present invention.
Claims (10)
1. the preparation method of a negative active core-shell material is characterized in that, step comprises:
A, titanium source and organic carbon source are joined the pH value be configured to mixed solution in the organic solution of 0-6;
Described titanium source is selected from one or more in isopropyl titanate, metatitanic acid four fourth fat, metatitanic acid, titanium tetrachloride or the titanyl sulfate;
B, in above-mentioned mixed solution, add oxidant, in 20-80 ℃ of reaction 1-24h down, back precipitation separation, washing, dry must the titaniferous precursor;
C, with step b gained titaniferous precursor and lithium source mixing and ball milling, the back roasting under inert atmosphere.
2. the preparation method of negative active core-shell material according to claim 1 is characterized in that, among the described step c before titaniferous precursor and the lithium source mixing and ball milling, also comprise with the titaniferous precursor under inert atmosphere in 400-600 ℃ of sintering 2-6h.
3. the preparation method of negative active core-shell material according to claim 1 is characterized in that, described organic carbon source is selected from one or more in aniline, pyrroles, thiophene or the furans.
4. the preparation method of negative active core-shell material according to claim 1 is characterized in that, described oxidant is selected from one or more in ammonium persulfate, hydrogen peroxide or the iron chloride.
5. the preparation method of negative active core-shell material according to claim 1 is characterized in that, described organic solution is selected from one or more the acid-containing solution in ethanol, methyl alcohol or the acetone.
6. the preparation method of negative active core-shell material according to claim 5 is characterized in that, the acid in the described acid-containing solution is selected from one or more in hydrochloric acid, sulfuric acid, phosphoric acid or the acetic acid.
7. the preparation method of negative active core-shell material according to claim 1, it is characterized in that described lithium source is selected from one or more in lithium hydroxide, lithium acetate, lithium chloride, lithium chromate, four water citric acid lithiums, tetrachloro-lithium aluminate, lithium bromide, LiBF4 or the lithium oxalate.
8. the preparation method of negative active core-shell material according to claim 1 is characterized in that, the mol ratio of described oxidant and organic carbon source is 0.5-4.
9. the preparation method of negative active core-shell material according to claim 1 is characterized in that, the Ti in the described titanium source and the mol ratio of organic carbon source are 10-2;
The mol ratio of Li is 1-1.67 in Ti in the described titaniferous precursor and the lithium source.
10. the preparation method of negative active core-shell material according to claim 1 is characterized in that, the temperature of described roasting is 600 ℃-900 ℃; Time is 8h-28h.
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| CN102569767A (en) * | 2012-01-19 | 2012-07-11 | 中国科学院过程工程研究所 | Polymer composite lithium titanate electrode material and preparation method thereof |
| CN102832383A (en) * | 2012-09-17 | 2012-12-19 | 广东电网公司电力科学研究院 | Method for preparing spherical lithium titanate material with high tap density |
| CN103311506A (en) * | 2013-06-25 | 2013-09-18 | 蒋涛 | Preparation method of silicon graphene-coated lithium titanate composite negative electrode material |
| CN103456939A (en) * | 2013-07-24 | 2013-12-18 | 湖南大学 | Method for preparing cathode material carbon-coated lithium titanate for lithium ion battery from metatitanic acid |
| CN106684343A (en) * | 2015-11-11 | 2017-05-17 | 深圳市沃特玛电池有限公司 | Lithium titanate/carbon composite material and preparation method therefor, and lithium ion battery |
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| CN102569767B (en) * | 2012-01-19 | 2015-02-18 | 中国科学院过程工程研究所 | Polymer composite lithium titanate electrode material and preparation method thereof |
| CN102832383A (en) * | 2012-09-17 | 2012-12-19 | 广东电网公司电力科学研究院 | Method for preparing spherical lithium titanate material with high tap density |
| CN103311506A (en) * | 2013-06-25 | 2013-09-18 | 蒋涛 | Preparation method of silicon graphene-coated lithium titanate composite negative electrode material |
| CN103311506B (en) * | 2013-06-25 | 2015-09-23 | 深圳宏泰电池科技有限公司 | The preparation method of the coated lithium titanate composite anode material of a kind of 3 SiC 2/graphite alkene |
| CN103456939A (en) * | 2013-07-24 | 2013-12-18 | 湖南大学 | Method for preparing cathode material carbon-coated lithium titanate for lithium ion battery from metatitanic acid |
| CN103456939B (en) * | 2013-07-24 | 2015-12-23 | 湖南大学 | Metatitanic acid is utilized to prepare the method for the coated lithium titanate of lithium ion battery negative material carbon |
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| CN106920958A (en) * | 2015-12-27 | 2017-07-04 | 深圳市沃特玛电池有限公司 | A kind of lithium titanate preparation method |
| CN107275612A (en) * | 2017-06-19 | 2017-10-20 | 上海纳米技术及应用国家工程研究中心有限公司 | The carambola shape lithium titanate titanium dioxide electrodes material and preparation method and application of a kind of multilevel hierarchy |
| CN108451522A (en) * | 2018-03-28 | 2018-08-28 | 北京华灿康国际医药研究有限公司 | A kind of Medical Devices |
| CN108451522B (en) * | 2018-03-28 | 2023-05-30 | 广州源康健信息科技有限公司 | Medical equipment |
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