CN102931386A - Method for preparing carbon nano tube doped lithium titanate composite electrode material - Google Patents
Method for preparing carbon nano tube doped lithium titanate composite electrode material Download PDFInfo
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- CN102931386A CN102931386A CN201210383844XA CN201210383844A CN102931386A CN 102931386 A CN102931386 A CN 102931386A CN 201210383844X A CN201210383844X A CN 201210383844XA CN 201210383844 A CN201210383844 A CN 201210383844A CN 102931386 A CN102931386 A CN 102931386A
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- 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 discloses a method for preparing a carbon nano tube doped lithium titanate composite electrode material. The composite electrode material consists of lithium titanate and a carbon nano tube; and the mass ratio of lithium titanate to carbon nano tube is (88-95):(5-12). The method comprises the following steps of: doping the multi-wall carbon nano tube into lithium carbonate or lithium acetate and titanium dioxide which serve as reactants; and preparing the carbon nano tube doped lithium titanate composite electrode material by a ball grinding process and a microwave method. According to the method, the process is simple, the materials are uniform, the particle size is small, the specific capacity is high, and the multiplying power is high.
Description
Technical field
The present invention relates to a kind of preparation method of doped carbon nanometer pipe lithium titanate composite electrode material, belong to new energy field.
Background technology
As a kind of novel energy storage material, the performance of lithium titanate uniqueness, and easy synthetic method, so that it is at new energy field, especially energy storage aspect becomes one of desirable negative material.This material is " zero strain " material, and in the charge and discharge process, the Infix and desfix of lithium ion can't affect crystal structure and change, and has good cycle performance.Current driving force and energy-storage battery are expensive, and multiplying power and cycle life is the difficult problem of lithium ion battery always, how lithium titanate preparation technology are simplified, and improve the focus that its multiplying power property becomes society research.Mainly by the high temperature solid-state method preparation, this technique is synthetic under hot conditions, for up to nearly 20 hours, consumes a large amount of energy and fund at present.Simultaneously also there is the people to prepare lithium titanate by sol method, obtained very good chemical property, but technique is very complicated, be not suitable for plant layout production.Carbon nano-tube has larger draw ratio as a kind of good conductive agent, can form good netted conductive structure, and the electric conductivity that can improve lithium titanate improves its multiplying power property.Compare with other method, microwave method preparation technology is very simple, economizes on resources.Its mode of heating is material internal and outside homogeneous heating, is conducive to improve the uniformity of material, has very huge application prospect and researching value.
Summary of the invention
The present invention utilizes method for preparing lithium titanate by microwave, and purpose is to overcome the shortcoming that the reaction time is long, consumption of natural resource is many of high temperature solid-state method.Improve the uniformity of material by the characteristics of homogeneous heating inside and outside the microwave method material, by the particle diameter of carbon nano-tube isolation and the Heat Treatment Control material of short time.Improve its conduction and multiplying power property by doped carbon nanometer pipe, obtain the lithium titanate composite electrode material of high magnification characteristic.
The present invention realizes by following principle, the interpolation of carbon nano-tube can help the distribution of dispersed titanium dioxide and lithium carbonate particle, lithium titanate crystal grain grows up when making it to suppress pyroreaction, carbon nano-tube has good electric conductivity simultaneously, the draw ratio that it is larger so that carbon nano-tube is woven into each other is netted, can be to form good netted conductive path between the lithium titanate particle, improve the electric conductivity of lithium titanate, improve its multiplying power property.Utilize simultaneously method for preparing lithium titanate by microwave, the reaction time is short, consumption of natural resource is few, is fit to factory's large-scale production.The simultaneously inhibition of the shorter very big degree of annealing time the crystallization time of lithium titanate under high-temperature condition, have little time to crystallize into larger grain (caning be controlled in about 200nm).Because temperature heats from the inside to surface simultaneously, be heated evenly the uniformity that can improve material during the microwave method sintering.Can control the granularity of material, improve the specific area of material, increase the conductive path of ion.
The preparation method of a kind of doped carbon nanometer pipe lithium titanate composite electrode material provided by the invention may further comprise the steps:
1) utilize lithium carbonate or lithium acetate and titanium dioxide as reactant, doping multi-walled carbon nano-tubes (MWCNTs) is as presoma;
2) take by weighing in proportion lithium carbonate or lithium acetate, titanium dioxide, doping multi-walled carbon nano-tubes (MWCNTs), being that the ratio of 5:4 takes by weighing lithium titanate or lithium acetate and titanium dioxide in lithium and titanium mol ratio wherein, is that 88 ~ 95: 5 ~ 12 ratio takes by weighing carbon nano-tube in lithium titanate and doping multi-walled carbon nano-tubes (MWCNTs) mass ratio; The above-mentioned material mixing and ball milling that takes by weighing was both got presoma in 8 hours;
3) presoma with preparation is pressed into sheet under the pressure of 30MP, then puts into the ceramic crucible of filling carbon black, covers ceramic cap, places microwave oven; Microwave frequency is 2455MHz, and power is 160 ~ 800W, and the microwave time is 6 ~ 12 minutes, cools off rapidly after taking out to make the doped carbon nanometer pipe lithium titanate composite electrode material.
Above-mentioned doping multi-walled carbon nano-tubes (MWCNTs) caliber is 20nm.
Above-mentioned steps 2) the preferred mass ratio of lithium titanate and multi-walled carbon nano-tubes (MWCNTs) is 90:10 in.
Above-mentioned steps 3) the microwave time is preferably 9 minutes in.
Beneficial effect of the present invention:
1, compares with traditional solid phase method, have that technique is simple, the reaction time is short, consumption of natural resource is few;
2, material homogeneity is good, material particle size is little (about 200 nanometers).
3, doped carbon nanometer pipe has improved the electric conductivity of lithium titanate, has greatly improved the multiplying power property of material.
Embodiment
Below in conjunction with the present invention is further described:
Example 1
Be that the molar ratio of 4:5 takes by weighing with titanium dioxide and lithium carbonate by Ti:Li, carbon nano-tube is that the ratio of 95:5 takes by weighing (wherein lithium titanate is lithium carbonate and titanium dioxide quality and 84%) in the mass ratio of lithium titanate and MWCNTs.Then add a small amount of alcohol, the ratio ball milling take ratio of grinding media to material as 50:1 obtained precursor in 8 hours.Until air-dry afterwards compressed tablets shape under 30MP pressure, then the sheet precursor is placed in the ceramic crucible that carbon black is housed, carbon black is covered precursor prevent the carbon nano-tube oxidation.Microwave frequency is 2455MHz, and power is 800W, and sintering time is 6 minutes.After the composite material of preparation fully ground, 5% PVDF was as binding agent, and NPM makes electrode slice (3.8g.cm as dispersant in the aluminium foil coating
-1), be packaged into battery take metal lithium sheet as negative pole.Under charge-discharge test 0.1C, 1C, the 10C condition first discharge capacity be respectively 220,165,90 mAh.g
-1
Example 2
Be that the molar ratio of 4:5 takes by weighing with titanium dioxide and lithium carbonate by Ti:Li, carbon nano-tube is that the ratio of 91:9 takes by weighing (wherein lithium titanate is lithium carbonate and titanium dioxide quality and 84%) in the mass ratio of lithium titanate and MWCNTs.Then add a small amount of alcohol, the ratio ball milling take ratio of grinding media to material as 50:1 obtained precursor in 8 hours.Until air-dry afterwards compressed tablets shape under 30MP pressure, then the sheet precursor is placed in the ceramic crucible that carbon black is housed, carbon black is covered precursor prevent the carbon nano-tube oxidation.Microwave frequency is that 2455MHz power is 700W, and sintering time is 8 minutes.After the composite material of preparation fully ground, 5% PVDF was as binding agent, and NPM makes electrode (3.8g.cm as dispersant in the aluminium foil coating
-1), be packaged into battery take metal lithium sheet as negative pole.Under charge-discharge test 0.1C, 1C, the 10C condition first discharge capacity be respectively 225,173,120 mAh.g
-1
Example 3
Be that the molar ratio of 4:5 takes by weighing with titanium dioxide and lithium carbonate by Ti:Li, carbon nano-tube is that the ratio of 90:10 takes by weighing (wherein lithium titanate is lithium carbonate and titanium dioxide quality and 84%) in the mass ratio of lithium titanate and MWCNTs.Then add a small amount of alcohol, the ratio ball milling take ratio of grinding media to material as 50:1 obtained precursor in 8 hours.Until air-dry afterwards compressed tablets shape under 30MP pressure, then the sheet precursor is placed in the ceramic crucible that carbon black is housed, carbon black is covered precursor prevent the carbon nano-tube oxidation, microwave frequency is that 2455MHz power is 640W, sintering time is 9 minutes.After the composite material of preparation fully ground, 5% PVDF was as binding agent, and NPM makes electrode (3.8g.cm as dispersant in the aluminium foil coating
-1), be packaged into battery take metal lithium sheet as negative pole.0.1C, under the 1C, 10C condition first discharge capacity be respectively 222,175,126 mAh.g
-1
Example 4
Be that the molar ratio of 4:5 takes by weighing with titanium dioxide and lithium carbonate by Ti:Li, carbon nano-tube is that the ratio of 89:11 takes by weighing (wherein lithium titanate is lithium carbonate and titanium dioxide quality and 84%) in the mass ratio of lithium titanate and MWCNTs.Then add a small amount of alcohol, the ratio ball milling take ratio of grinding media to material as 50:1 obtained precursor in 8 hours.Until air-dry afterwards compressed tablets shape under 30MP pressure, then the sheet precursor is placed in the ceramic crucible that carbon black is housed, carbon black is covered precursor prevent the carbon nano-tube oxidation.Microwave frequency is that 2455MHz power is 400W, and sintering time is 11 minutes.After the composite material of preparation fully ground, 5% PVDF was as binding agent, and NPM makes electrode (3.8g.cm as dispersant in the aluminium foil coating
-1), be packaged into battery take metal lithium sheet as negative pole.0.1C, under the 1C, 10C condition first discharge capacity be respectively 219,170,122 mAh.g
-1
Example 5
Be that the molar ratio of 4:5 takes by weighing with titanium dioxide and lithium carbonate by Ti:Li, carbon nano-tube is that the ratio of 88:12 takes by weighing (wherein lithium titanate is lithium carbonate and titanium dioxide quality and 84%) in the mass ratio of lithium titanate and MWCNTs.Then add a small amount of alcohol, the ratio ball milling take ratio of grinding media to material as 50:1 obtained precursor in 8 hours.Until air-dry afterwards compressed tablets shape under 30MP pressure, then the sheet precursor is placed in the ceramic crucible that carbon black is housed, carbon black is covered precursor prevent the carbon nano-tube oxidation.Microwave frequency is that 2455MHz power is 300W, and sintering time is 12 minutes.After the composite material of preparation fully ground, 5% PVDF was as binding agent, and NPM makes electrode (3.8g.cm as dispersant in the aluminium foil coating
-1), be packaged into battery take metal lithium sheet as negative pole.0.1C, under the 1C, 10C condition first discharge capacity be respectively 209,166,120mAh.g
-1
Example 6
Be that the molar ratio of 4:5 takes by weighing with titanium dioxide and lithium acetate by Ti:Li, MWCNTs is that the ratio of 90:10 takes by weighing (wherein lithium titanate is lithium acetate and titanium dioxide quality and 47.5%) in the mass ratio of lithium titanate and MWCNTs.Then add a small amount of alcohol, the ratio ball milling take ratio of grinding media to material as 50:1 obtained precursor in 8 hours.Until air-dry afterwards compressed tablets shape under 30MP pressure, then the sheet precursor is placed in the ceramic crucible that carbon black is housed, carbon black is covered precursor prevent the carbon nano-tube oxidation.Microwave frequency is that 2455MHz power is 160W, and sintering time is 9 minutes.After the composite material of preparation fully ground, 5% PVDF was as binding agent, and NPM makes electrode (3.8g.cm as dispersant in the aluminium foil coating
-1), be packaged into battery take metal lithium sheet as negative pole.0.1C, under the 1C, 10C condition first discharge capacity be respectively 225,168,130 mAh.g
-1
Comparative example 1
Except the microwave time be 6,7,8,9 minutes different from example 1, other conditions are all consistent with example 1.Find through the XRD test, sintering time is lower than 9 minutes generation product, and there is the characteristic peak of titanium dioxide in the thing diffraction maximum, and the time is more short more obvious, and is then consistent with standard card in the time of 9 minutes.After the composite material of microwave 8 minutes preparation fully ground, 5% PVDF was as binding agent, and NPM makes electrode (3.8g.cm as dispersant in the aluminium foil coating
-1), be packaged into button cell take metal lithium sheet as negative pole, under 0.1C, 1C, the 10C condition first discharge capacity be respectively 180,135,80 mAh.g
-1
Claims (4)
1. the preparation method of a doped carbon nanometer pipe lithium titanate composite electrode material, its feature may further comprise the steps:
As reactant, the doping multi-walled carbon nano-tubes is as presoma with lithium carbonate or lithium acetate and titanium dioxide;
Be that 5: 4 ratio takes by weighing lithium carbonate or lithium acetate and titanium dioxide in lithium and titanium mol ratio, lithium titanate and doping multi-walled carbon nano-tubes mass ratio are that 88 ~ 95: 5 ~ 12 ratio takes by weighing carbon nano-tube; The above-mentioned material mixing and ball milling that takes by weighing was namely got precursor in 8 hours;
Under the pressure of 30MP, be pressed into the precursor of preparation on chip, then put into the ceramic crucible of filling carbon black, cover ceramic cap, place microwave oven; Microwave frequency is 2455MHz, and power is 160 ~ 800W, and the microwave time is 6 ~ 12 minutes, cools off rapidly after taking out to make the doped carbon nanometer pipe lithium titanate composite electrode material.
2. preparation method according to claim 1, it is characterized in that: the caliber of above-mentioned doping multi-walled carbon nano-tubes is 20nm.
3. preparation method according to claim 1 is characterized in that: the mass ratio of lithium titanate and doping multi-walled carbon nano-tubes is 90:10 above-mentioned steps 2).
4. preparation method according to claim 1 is characterized in that: the microwave time is 9 minutes above-mentioned steps 3).
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Application publication date: 20130213 |