CN102569750A - Cathode composite material of lithium ion battery and preparation method thereof - Google Patents
Cathode composite material of lithium ion battery and preparation method thereof Download PDFInfo
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Abstract
The invention provides a cathode composite material of a lithium ion battery. The cathode composite material comprises graphene and an electrode active material, wherein the electrode active material is one or more of intermediate-phase bituminous coal microspheres, silicon, lithium titanate, titanium dioxide, tin dioxide and graphite. According to the invention, the graphene and the electrode active material are mixed with water to obtain a mixed solution, which is dried to obtain the cathode composite material of the lithium ion battery. According to the invention, the graphene is adopted as an electroconductive additive, has favorable electroconductive performance, mechanical strength and huge specific surface area, can be favorably attached to the surface of the electrode active material, and is beneficial for shortening the diffusion path of lithium ions, so that the ionic conductivity of the cathode composite material of the lithium ion battery is increased; in addition, the addition of the graphene is beneficial to the enhancement of the full contact between the cathode material of the battery and a current collector, so that the cyclic performance and the multiplying power of the lithium ion battery can be improved in a better way; and the cathode composite material of the lithium ion battery, provided by the invention, has better electric properties.
Description
Technical field
The present invention relates to the electrode of lithium cell technical field, relate in particular to a kind of composite cathode material of lithium ion battery and preparation method thereof.
Background technology
In today that information technology is maked rapid progress and environmental protection comes into one's own day by day, the development of chemical power source is faced with bigger challenge.Lithium ion battery because have that energy density height, output voltage height, long service life, good cycle, self-discharge rate are low, advantage such as memory-less effect and good environmental performance and obtained bigger development; Its quantity and the output value are improved constantly; Application also enlarges rapidly; At electronic products such as mobile phone, notebook computer, video cameras; The vehicles such as electric automobile, electric bicycle, aerospace vehicles such as aircraft, satellite, airship, and all obtained a large amount of uses and had vast potential for future development in the military equipment such as warship, submarine.
The development in consumer electronics, electric automobile and energy storage field; Demands for higher performance such as energy density, power density, cycle-index and fail safe to lithium ion battery; Wherein the improvement of lithium ion battery negative material is to improve one of key of its performance, also is the focus and the difficult point of research.At present, in business-like production, MCMB has higher lithium storage content and good voltage platform as electrode active material, in lithium ion battery negative material, has obtained using widely.Yet, contact with point-to-point mode between the spherical particle of MCMB, cause its contact-making surface less; The contact poor effect causes conductance lower, and in the process of high current charge-discharge, also can influence lithium ion take off embedding fast; Therefore; This MCMB is not suitable for the use of high rate charge-discharge as lithium ion battery negative material, can not adapt to the demand for development of power lithium-ion battery far away.
In order to improve the high rate performance of lithium ion battery; Often in electrode active material, add conductive black in the prior art; Yet owing to also be a mode that contacts between traditional conductive black and active material; Can not form good conductive network equally, its specific capacity descends very soon under the situation of high current charge-discharge, can not adapt to the demand for development of power lithium-ion battery equally.Japanese expert's Iijima (Iijima) was found CNT (CNT) in 1991, and CNT has good axial one-dimensional electric ability, and people such as YZHANG discover; A CNT can play the conduction distance that hundreds of reaches to several thousand carbon black pellets; Its filamentary structure can be kept conductive network in cyclic process, improve the utilance of electrode active material and multiplying power discharging ability (Y ZHANG, the XG ZHANG that improves electrode; HL ZHANG; Et al.Composite anode material of silicon/graphite/carbon nanotubes for Li-ion batteries [J] .Electrochem Acta, 2006,51:4994～5000.).
Above-mentioned bibliographical information have the ability of better electrode multiplying power discharging than conductive black as the composite cathode material of lithium ion battery of conductive additive preparation as conductive additive with CNTs; But; The high rate performance of this composite cathode material of lithium ion battery is still lower; Still can not satisfy the development need of power lithium-ion battery, thereby limit the application of lithium ion battery.
Summary of the invention
The object of the present invention is to provide a kind of composite cathode material of lithium ion battery and preparation method thereof, composite cathode material of lithium ion battery provided by the invention has higher high rate performance, is beneficial to the application of lithium ion battery.
The present invention provides a kind of composite cathode material of lithium ion battery, comprises Graphene and electrode active material;
Said electrode active material is one or more in mesophase pitch carbon microspheres, silicon, lithium titanate, titanium dioxide, tin ash and the graphite.
Preferably, the particle diameter of said Graphene is 4 μ m～30 μ m.
Preferably, the mass ratio of said Graphene and said electrode active material is 1: (1～100).
Preferably, the mass ratio of said Graphene and said electrode active material is 1: (10～50).
Preferably, said electrode active material is one or more in mesophase pitch carbon microspheres, silicon, lithium titanate and the tin ash.
The present invention provides a kind of preparation method of composite cathode material of lithium ion battery, may further comprise the steps:
Graphene, electrode active material are mixed with water, obtain mixed solution;
Said mixed solution is carried out drying, obtain composite cathode material of lithium ion battery;
Said electrode active material is one or more in mesophase pitch carbon microspheres, silicon, lithium titanate, titanium dioxide, tin ash and the graphite.
Preferably, said Graphene, electrode active material are mixed with water, are specially:
Graphene and electrode active material are ground Graphene and electrode active material after obtaining grinding;
Under ultrasound condition, the Graphene after the said grinding is mixed with electrode active material and water.
Preferably, said drying is spray drying or freeze drying.
Preferably, said spray-dired temperature is 150 ℃～300 ℃.
Preferably, said cryodesiccated temperature is-20 ℃～60 ℃.
The present invention provides a kind of composite cathode material of lithium ion battery, comprises Graphene and electrode active material; Said electrode active material is one or more in middle asphalt carbon microballoon, silicon, lithium titanate, titanium dioxide, tin ash and the graphite.The present invention carries out drying with said Graphene, said electrode active material and after water mixes, and obtains composite cathode material of lithium ion battery.Comprise Graphene in the composite cathode material of lithium ion battery provided by the invention; It has excellent conducting performance, mechanical strength and huge specific area; And the combination between active material can improve the contact area of Graphene and electrode active material; Help to shorten the evolving path of lithium ion; Improve its ionic conductivity, the adding of Graphene simultaneously can also be strengthened fully contacting of cell negative electrode material and collector, thereby can improve the cycle performance and the high rate performance of lithium ion battery effectively; In addition, Graphene can be well attached to the surface of electrode active material, the separation of having avoided the electrode active material that electrode active material volumetric expansion or contraction in charge and discharge process cause with come off, increase its useful life.Experimental result shows that after charge and discharge cycles under the 0.1C multiplying power 50 times, the specific capacity of composite cathode material of lithium ion battery provided by the invention remains on about 90%; Along with the increase of charging and discharging currents, under the 0.5C multiplying power, the decay of the specific capacity of composite cathode material of lithium ion battery provided by the invention is slower, and high rate performance is good; Composite cathode material of lithium ion battery provided by the invention is after using 2 years, and its specific capacity still can remain on more than 60%.
In addition, the preparation method of the composite cathode material of lithium ion battery that this provides is simple, and raw material is easy to get, and has reduced production cost, is beneficial to the extensive use of lithium ion battery.
Description of drawings
Fig. 1 is the SEM image of the composite cathode material of lithium ion battery of the embodiment of the invention 1 preparation;
Fig. 2 is the discharge specific volume figure of the embodiment of the invention 1 and the composite cathode material of lithium ion battery of comparative example preparation,
Wherein, curve 1 is the discharge specific volume figure of the composite cathode material of lithium ion battery of the embodiment of the invention 1 preparation, and curve 2 is the discharge specific volume figure of the composite cathode material of lithium ion battery of comparative example preparation of the present invention;
Fig. 3 is the discharge-rate performance map of the embodiment of the invention 1 and the composite cathode material of lithium ion battery of comparative example preparation,
Wherein, curve 1 is the discharge-rate performance curve of the composite cathode material of lithium ion battery of the embodiment of the invention 1 preparation, and curve 2 is the discharge-rate performance curve of the composite cathode material of lithium ion battery of comparative example preparation of the present invention;
Fig. 4 is the SEM image of the composite cathode material of lithium ion battery of the embodiment of the invention 2 preparations.
Embodiment
The present invention provides a kind of composite cathode material of lithium ion battery, comprises Graphene and electrode active material;
Said electrode active material is one or more in mesophase pitch carbon microspheres, silicon, lithium titanate, titanium dioxide, tin ash and the graphite.
Lithium ion battery is meant with two kinds of different lithium intercalation compounds that can embed and deviate from lithium ion reversiblely respectively as the battery system of anode and negative pole.It is a kind of rechargeable battery, mainly relies on lithium ion between positive pole and negative pole, to move work.During charging, lithium ion takes off embedding from positive pole, through electrolyte and barrier film, is embedded in the negative pole; Then opposite during discharge, lithium ion takes off embedding from negative pole, through electrolyte and barrier film, is embedded in the positive pole.The negative material of battery is the chief component of lithium ion battery, and the quality of negative material performance directly has influence on the performance of lithium ion battery.
Composite cathode material of lithium ion battery provided by the invention comprises Graphene.Graphene is that the people such as physics professor Geim by Univ Manchester UK utilized the method for the high oriented graphite of tape stripping to obtain in 2004.Graphene has the thickness of atomic size, huge specific area, good thermal conductivity and electronic transmission performance, characteristics such as high mechanical strength and stability.Comprise Graphene in the composite cathode material of lithium ion battery provided by the invention; Because Graphene has perfect two-dimensional structure; Make its can with said electrode active material between organically combine; Make that the contact area between itself and the electrode active material is increased greatly, help to shorten the evolving path of lithium ion, improve its ionic conductivity; Strengthened simultaneously between the electrode active material and fully the contacting of said battery cathode composite material and collector, thereby improved the high rate performance and the cycle performance of composite cathode material of lithium ion battery; Graphene can be good at being attached to the surface of said electrode active material, the separation of avoided electrode active material volumetric expansion in charge and discharge process, shrinking the electrode active material that causes with come off, thereby prolonged useful life of lithium ion battery.
The present invention does not have special limitation to the technical parameter of said Graphene like particle diameter, specific area and conductivity etc., adopts Graphene well known to those skilled in the art to get final product.In the present invention, the particle diameter of said Graphene is preferably 4 μ m～30 μ m, more preferably 6 μ m～25 μ m; The specific area of said Graphene is preferably 120m
2/ g～200m
2/ g, more preferably 135m
2/ g～170m
2/ g; The conductivity of said Graphene is preferably 600S/cm～900S/cm, more preferably 680S/cm～800S/cm.
Composite cathode material of lithium ion battery provided by the invention comprises electrode active material, and the present invention does not have special limitation to said electrode active material, adopts the electrode active material as lithium ion battery negative material well known to those skilled in the art to get final product.In the present invention; Said electrode active material is one or more in mesophase pitch carbon microspheres, silicon, lithium titanate, titanium dioxide, tin ash and the graphite; Be preferably in mesophase pitch carbon microspheres, silicon, lithium titanate and the tin ash one or more; A kind of in mesophase pitch carbon microspheres, silicon, lithium titanate and the tin ash more preferably, said graphite is preferably one or both in Delanium and the native graphite.In composite cathode material of lithium ion battery provided by the invention, the mass ratio of said Graphene and said electrode active material is preferably 1: (1～100), more preferably 1: (10～50) most preferably are 1: (15～45).
The present invention provides a kind of composite cathode material of lithium ion battery, comprises Graphene and electrode active material; Said electrode active material is one or more in mesophase pitch carbon microspheres, silicon, lithium titanate, titanium dioxide, tin ash and the graphite.The present invention adopts Graphene as conductive additive; Excellent electric conductivity, huge specific area, the favorable mechanical performance of Graphene make its with said electrode active material between organically combine; Improved the contact area between said Graphene and the said electrode active material; Help to shorten the evolving path of lithium ion; Improve its ionic conductivity, strengthened fully contacting of battery cathode composite material and collector simultaneously, improved the cycle performance and the high rate performance of composite cathode material of lithium ion battery; Simultaneously; Graphene can be good at the surface attached to said electrode active material; The separation of avoided the volumetric expansion in charge and discharge process of said electrode active material, shrinking the said electrode active material cause with come off, prolonged the useful life of lithium ion battery.
Experimental result shows that after charge and discharge cycles under the 0.1C multiplying power 50 times, the specific capacity of composite cathode material of lithium ion battery provided by the invention remains on about 90%; Along with the increase of charging and discharging currents, under the 0.5C multiplying power, the capacity attenuation of composite cathode material of lithium ion battery provided by the invention is slower, and high rate performance is good; Composite cathode material of lithium ion battery provided by the invention is after using 2 years, and its specific capacity still can remain on more than 60%.
The present invention provides a kind of preparation method of composite cathode material of lithium ion battery, may further comprise the steps:
Graphene, electrode active material are mixed with water, obtain mixed solution;
Said mixed solution is carried out drying, obtain composite cathode material of lithium ion battery;
Said electrode active material is one or more in mesophase pitch carbon microspheres, silicon, lithium titanate, titanium dioxide, tin ash and the graphite.
The present invention at first mixes Graphene, electrode active material with water, obtain mixed solution.The present invention is with said Graphene, electrode active material and before water mixes; Preferably said Graphene and said electrode active material are ground; Graphene after obtaining grinding and electrode active material preferably under ultrasound condition, mix the Graphene after the said grinding with electrode active material and water.The present invention does not have particular restriction to the parameter of said grinding, adopts the technical scheme of grinding well known to those skilled in the art to get final product.In the present invention, the particle diameter of said Graphene is preferably 4 μ m～30 μ m, more preferably 6 μ m～25 μ m; The specific area of said Graphene is preferably 120m
2/ g～200m
2/ g, more preferably 135m
2/ g～170m
2/ g; The conductivity of said Graphene is preferably 600S/cm～900S/cm, more preferably 680S/cm～800S/cm; Said electrode active material is one or more in mesophase pitch carbon microspheres, silicon, lithium titanate, titanium dioxide, tin ash and the graphite; Be preferably in mesophase pitch carbon microspheres, silicon, lithium titanate and the tin ash one or more; A kind of in mesophase pitch carbon microspheres, silicon, lithium titanate and the tin ash more preferably, said graphite is preferably one or both in electrographite or the native graphite; The mass ratio of said Graphene and said electrode active material is preferably 1: (1～100), more preferably 1: (10～50) most preferably are 1: (15～45).
Obtain Graphene and electrode active material after the said grinding, the present invention preferably under ultrasound condition, mixes the Graphene after the said grinding with electrode active material and water, preferably obtain even mixed solution.The present invention does not have special limitation to said ultrasonic parameter like temperature, time etc., adopts ultrasonic technical scheme well known to those skilled in the art to get final product.In the present invention, said water is preferably deionized water, and the quality of said water is preferably 100 with the ratio of the gross mass of said Graphene and said electrode active material: (0.5～10), more preferably 100: (1～5) most preferably is 100: (2～3).
After obtaining mixed solution, the present invention carries out drying with said mixed solution, obtains composite cathode material of lithium ion battery.The present invention is to the parameter of said drying, and like temperature, the time etc. do not have specific (special) requirements, adopts the technical scheme of drying well known to those skilled in the art to get final product.In the present invention, said drying is preferably spray drying or freeze drying, more preferably spray drying; Said spray-dired temperature is preferably 150 ℃～300 ℃, and more preferably 160 ℃～290 ℃, more preferably 180 ℃～280 ℃; Said cryodesiccated temperature is preferably-20 ℃～60 ℃, more preferably-10 ℃～50 ℃; The time of said drying is preferably 10h～100h, more preferably 50h～80h.
The present invention is a raw material with Graphene, electrode active material, with its with obtain mixed solution after water mixes, with obtaining composite cathode material of lithium ion battery after the said mixed solution drying.Composite cathode material of lithium ion battery provided by the invention has higher high rate performance, cycle performance and useful life.Preparation method's step of composite cathode material of lithium ion battery provided by the invention is few, simple to operate, and raw material is easy to get, and has reduced production cost, is beneficial to the extensive use of lithium ion battery.
The present invention carries out ESEM (SEM) scanning analysis to the composite cathode material of lithium ion battery that obtains; Obtain the shape characteristic of composite cathode material of lithium ion battery; The result shows; In composite cathode material of lithium ion battery provided by the invention, Graphene is well attached to the surface of electrode active material, and the contact area between said Graphene and the said electrode active material obviously increases.
The present invention tests the electric property of the composite cathode material of lithium ion battery that obtains, and the result shows that composite cathode material of lithium ion battery provided by the invention is under the 0.1C multiplying power; Charge and discharge cycles 50 times; Its specific capacity still remains on the about 90% of initial specific capacity, along with the increase of charging and discharging currents, under the 0.5C multiplying power; The specific capacity decay of composite cathode material of lithium ion battery provided by the invention is slower, and high rate performance is good.
The present invention has tested the useful life of the composite cathode material of lithium ion battery that obtains, and the result shows that composite cathode material of lithium ion battery provided by the invention is after using 2 years, and its specific capacity still can remain on more than 60%.
The present invention provides a kind of composite cathode material of lithium ion battery, comprises Graphene and electrode active material; Said electrode active material is one or more in mesophase pitch carbon microspheres, silicon, lithium titanate, titanium dioxide, tin ash and the graphite.The present invention mixes said graphite with said electrode active material and water, the mixed solution that obtains is dry, obtains composite cathode material of lithium ion battery.Composite cathode material of lithium ion battery provided by the invention comprises Graphene; Its huge specific area has strengthened contacting between Graphene and the said electrode active material; Help the transmission of lithium ion, and it also has electric conductivity preferably, improved ionic conductivity; Strengthen contacting of cell negative electrode material and collector simultaneously, improved the cycle performance and the high rate performance of battery cathode composite material; Simultaneously Graphene can avoid electrode active material volumetric expansion in charge and discharge process effectively well attached on the said electrode active material, the separation of shrinking the electrode active material that causes with come off, thereby prolonged its useful life.In addition; Method provided by the invention is simple; Adopt ultrasonic mode that said Graphene is mixed with said electrode active material, make and mix more evenly between said Graphene and the said electrode active material, improved the performance of composite cathode material of lithium ion battery more.Preparation method's raw material provided by the invention is easy to get, and has reduced production cost, is beneficial to the extensive use of lithium ion battery.
In order to further specify the present invention, below in conjunction with embodiment composite cathode material of lithium ion battery provided by the invention and preparation method thereof is described in detail, but can not they be interpreted as the qualification to protection range of the present invention.
With the 0.1g particle diameter be about 10 μ m, specific area is 153m
2/ g, conductivity are that the Graphene of 712S/cm mixes with 10g mesophase pitch carbon microspheres, grind even back to wherein adding the 1010mL deionized water, the mixed solution that obtains mixing after the ultrasonic dispersion; Said mixed solution is joined in the spray dryer, and the flow velocity of control mixed solution is 3mL/min, and the charging aperture temperature is 150 ℃, and the discharging opening temperature is 50 ℃, obtains composite cathode material of lithium ion battery at discharging opening.
The present invention carries out ESEM (SEM) scanning analysis to the composite cathode material of lithium ion battery that obtains; The result is as shown in Figure 1; Fig. 1 is the SEM image of the composite cathode material of lithium ion battery of the embodiment of the invention 1 preparation, can be found out by Fig. 1, and Graphene is well attached to the surface of mesophase pitch carbon microspheres; Graphene is the face contact with contacting of mesophase pitch carbon microspheres, and its contact area has obtained increasing significantly.
The present invention tests the electric property of the composite cathode material of lithium ion battery that obtains; The result as shown in Figures 2 and 3; Fig. 2 is the discharge specific volume figure of composite cathode material of lithium ion battery under the 0.1C current density of the embodiment of the invention 1 and comparative example preparation; Can find out that by Fig. 2 the reversible capacity first of the composite cathode material of lithium ion battery of present embodiment preparation is up to 330mAh/g, after the following circulation of 0.1C multiplying power (1C=330mAh/g) 50 times; Its specific discharge capacity still can remain on 280mAh/g, is higher than the capacity of the composite cathode material of lithium ion battery of comparative example preparation from far away; Fig. 3 is the discharge-rate performance map of the embodiment of the invention 1 and the composite cathode material of lithium ion battery of comparative example preparation; Can find out by Fig. 3; Under the discharging condition of 0.1C～0.2C multiplying power; The composite cathode material of lithium ion battery of embodiment 1 preparation is close with the specific discharge capacity of the composite cathode material of lithium ion battery of comparative example preparation, and after the 0.5C multiplying power, it is original more than 85% that the specific discharge capacity of the composite cathode material of lithium ion battery that embodiment 1 prepares still can keep; The result shows that the lithium ion battery material that present embodiment obtains has higher electric conductivity.
The present invention is to testing the useful life of the composite cathode material of lithium ion battery that obtains; The result shows; The lithium ion battery negative material of present embodiment preparation is after discharging and recharging 200 times; Its specific capacity is about 65% of initial specific capacity, this explanation, and composite cathode material of lithium ion battery provided by the invention has higher useful life.
Comparative example
The 0.1g conductive black is mixed with 10g mesophase pitch carbon microspheres, grind even back to wherein adding the 40.2mL deionized water, the mixed solution that obtains mixing after the ultrasonic dispersion; Said mixed solution is joined in the spray dryer, and the flow velocity of control mixed solution is 3mL/min, and the charging aperture temperature is 150 ℃, and the discharging opening temperature is 50 ℃, obtains composite cathode material of lithium ion battery at discharging opening.
The present invention studies the electric property of the composite cathode material of lithium ion battery that comparative example obtains; The result as shown in Figures 2 and 3, Fig. 2 is the discharge specific volume figure of composite cathode material of lithium ion battery under the 0.1C current density of the embodiment of the invention 1 and comparative example preparation, can be found out by Fig. 2; The composite cathode material of lithium ion battery of comparative example preparation is after circulation 20 times; Its specific discharge capacity reduces, and after circulation 50 times, its discharge capacity ratio is less than 200mAh/g; Fig. 3 is the discharge-rate performance map of the embodiment of the invention 1 and the composite cathode material of lithium ion battery of comparative example preparation; Can go out by Fig. 3; Under the discharging condition of 0.1C～0.2C multiplying power; The specific discharge capacity of the composite cathode material of lithium ion battery of the composite cathode material of lithium ion battery of embodiment 1 preparation and comparative example preparation is close, and after the 0.5C multiplying power, the specific discharge capacity of the composite cathode material of lithium ion battery of comparative example preparation descends very fast; Be about 50% of its initial discharge specific capacity, be lower than the composite cathode material of lithium ion battery specific discharge capacity under the same conditions of embodiment 1 preparation from far away.
Embodiment 2
With the 1g particle diameter be about 30 μ m, specific area is 150m
2/ g, conductivity are that the Graphene of 715S/cm mixes with 50g mesophase pitch carbon microspheres, grind even back to wherein adding the 2550mL deionized water, the mixed solution that obtains mixing after the ultrasonic dispersion; Said mixed solution is joined in the spray dryer, and the flow velocity of control mixed solution is 6mL/min, and the temperature of charging aperture is 200 ℃, and the temperature of discharging opening is 80 ℃, and the place obtains composite cathode material of lithium ion battery at discharging opening.
The present invention carries out ESEM (SEM) scanning analysis to the composite cathode material of lithium ion battery that obtains; The result is as shown in Figure 4; Fig. 4 is the SEM image of the composite cathode material of lithium ion battery of the embodiment of the invention 2 preparation, can be found out by Fig. 4, and Graphene is well attached to the surface of mesophase pitch carbon microspheres; Graphene is the face contact with contacting of mesophase pitch carbon microspheres, and its contact area has obtained increasing significantly.
The present invention tests the electric property of the composite cathode material of lithium ion battery that obtains; The result shows; The reversible capacity first of the composite cathode material of lithium ion battery that present embodiment obtains is up to 340mAh/g, and after circulation under the 0.1C multiplying power 50 times, its capacity can remain 280mAh/g; When the 0.5C multiplying power, it is original more than 90% that the specific discharge capacity of the composite cathode material of lithium ion battery that present embodiment obtains still can keep.This explanation, composite cathode material of lithium ion battery provided by the invention has good high rate performance.
The present invention is to testing the useful life of the composite cathode material of lithium ion battery that obtains; The result shows; The lithium ion battery negative material of present embodiment preparation is after discharging and recharging 200 times; Its specific capacity is about 68% of initial specific capacity, this explanation, and composite cathode material of lithium ion battery provided by the invention has higher useful life.
Embodiment 3
With the 1g particle diameter be about 30 μ m, specific area is 150m
2/ g, conductivity are Graphene and the 50g lithium titanate powder of 715S/cm, grind even back to wherein adding the 2550mL deionized water, the mixed solution that obtains mixing after the ultrasonic dispersion; Said mixed solution is joined in the spray dryer, and the flow velocity of control mixed solution is 6mL/min, and the temperature of charging aperture is 200 ℃, and the temperature of discharging opening is 80 ℃, and the place obtains composite cathode material of lithium ion battery at discharging opening.
The present invention carries out ESEM (SEM) scanning analysis to the composite cathode material of lithium ion battery that obtains; The result shows; In the composite cathode material of lithium ion battery of present embodiment preparation; Attached to the surface of lithium titanate, Graphene is the face contact with contacting of lithium titanate to Graphene well, and its contact area has obtained increasing significantly.
The present invention tests the electric property of the composite cathode material of lithium ion battery that obtains; The result shows; The reversible capacity first of the composite cathode material of lithium ion battery that present embodiment obtains is up to 220mAh/g, and after circulation under the 0.1C multiplying power 50 times, its capacity can remain 200mAh/g; When 1C multiplying power circulation 100 times, the specific discharge capacity of the composite cathode material of lithium ion battery that present embodiment obtains still can keep 170mAh/g.This explanation, composite cathode material of lithium ion battery provided by the invention has good high rate performance.
The present invention is to testing the useful life of the composite cathode material of lithium ion battery that obtains; The result shows; The lithium ion battery negative material of present embodiment preparation is after discharging and recharging 200 times; Its specific capacity is about 62% of initial specific capacity, this explanation, and composite cathode material of lithium ion battery provided by the invention has higher useful life.
Embodiment 4
With the 1g particle diameter be about 5 μ m,, specific area is 160m
2/ g, conductivity are that the Graphene of 720S/cm mixes with 10g mesophase pitch carbon microspheres, grind even back to wherein adding the 550mL deionized water, the mixed solution that obtains mixing after the ultrasonic dispersion; Said mixed solution is joined in the spray dryer, and the flow velocity of control mixed solution is 10mL/min, and the temperature of charging aperture is 300 ℃, and the temperature of discharging opening is 100 ℃, and the place obtains composite cathode material of lithium ion battery at discharging opening.
The present invention carries out ESEM (SEM) scanning analysis to the composite cathode material of lithium ion battery that obtains; The result shows; In the composite cathode material of lithium ion battery of present embodiment preparation; Attached to the surface of mesophase pitch carbon microspheres, Graphene is the face contact with contacting of mesophase pitch carbon microspheres to Graphene well, and its contact area has obtained increasing significantly.
The present invention tests the electric property of the composite cathode material of lithium ion battery that obtains; The result shows; The reversible capacity first of the composite cathode material of lithium ion battery of present embodiment preparation is up to 350mAh/g, and after circulation under the 0.1C multiplying power 50 times, its capacity can remain 290mAh/g; When 0.5C, the specific discharge capacity of the composite cathode material of lithium ion battery of present embodiment preparation still can be kept original more than 90%, this explanation, and composite cathode material of lithium ion battery provided by the invention has higher conductivity.
The present invention is to testing the useful life of the composite cathode material of lithium ion battery that obtains; The result shows; The lithium ion battery negative material of present embodiment preparation is after discharging and recharging 200 times; Its specific capacity is about 60% of initial specific capacity, this explanation, and composite cathode material of lithium ion battery provided by the invention has higher useful life.
With the 1g particle diameter be about 5 μ m,, specific area is 160m
2/ g, conductivity are Graphene and the 10g nano silica fume of 720S/cm, grind even back to wherein adding the 550mL deionized water, the mixed solution that obtains mixing after the ultrasonic dispersion; Said mixed solution is joined in the spray dryer, and the flow velocity of control mixed solution is 10mL/min, and the temperature of charging aperture is 300 ℃, and the temperature of discharging opening is 100 ℃, and the place obtains composite cathode material of lithium ion battery at discharging opening.
The present invention carries out ESEM (SEM) scanning analysis to the composite cathode material of lithium ion battery that obtains; The result shows; In the composite cathode material of lithium ion battery of present embodiment preparation; Attached to the surface of nano-silicon, Graphene is the face contact with contacting of nano-silicon to Graphene well, and its contact area has obtained increasing significantly.
The present invention tests the electric property of the composite cathode material of lithium ion battery that obtains; The result shows; The reversible capacity first of the composite cathode material of lithium ion battery of present embodiment preparation is up to 1200mAh/g, and after circulation under the 0.1C multiplying power 50 times, its capacity can remain 900mAh/g; After 1C circulation 510 times, the specific discharge capacity of the composite cathode material of lithium ion battery of present embodiment preparation still can be up to 800mAh/g, this explanation, and composite cathode material of lithium ion battery provided by the invention has higher conductivity.
The present invention is to testing the useful life of the composite cathode material of lithium ion battery that obtains; The result shows; The lithium ion battery negative material of present embodiment preparation is after discharging and recharging 200 times; Its specific capacity is about 63% of initial specific capacity, this explanation, and composite cathode material of lithium ion battery provided by the invention has higher useful life.
Embodiment 6
With the 1g particle diameter be about 18 μ m,, specific area is 153m
2/ g, conductivity are that the Graphene of 712S/cm mixes with 5g mesophase pitch carbon microspheres, grind even back to wherein adding the 150mL deionized water, the mixed solution that obtains mixing after the ultrasonic dispersion; Said mixed solution is joined in the spray dryer, and the flow velocity of control mixed solution is 5mL/min, and the temperature of charging aperture is 250 ℃, and the temperature of discharging opening is 100 ℃, and the place obtains composite cathode material of lithium ion battery at discharging opening.
The present invention carries out ESEM (SEM) scanning analysis to the composite cathode material of lithium ion battery that obtains; The result shows; In the composite cathode material of lithium ion battery of present embodiment preparation; Attached to the surface of mesophase pitch carbon microspheres, Graphene is the face contact with contacting of mesophase pitch carbon microspheres to Graphene well, and its contact area has obtained increasing significantly.
The present invention tests the electric property of the composite cathode material of lithium ion battery that obtains; The result shows; The reversible capacity first of the composite cathode material of lithium ion battery of present embodiment preparation is up to 345mAh/g, and after circulation under the 0.1C multiplying power 50 times, its capacity can remain 285mAh/g; When 0.5C, the specific discharge capacity of the composite cathode material of lithium ion battery of present embodiment preparation still can be kept original more than 90%, this explanation, and composite cathode material of lithium ion battery provided by the invention has higher conductivity.
The present invention is to testing the useful life of the composite cathode material of lithium ion battery that obtains; The result shows; The lithium ion battery negative material of present embodiment preparation is after discharging and recharging 200 times; Its specific capacity is about 63% of initial specific capacity, this explanation, and composite cathode material of lithium ion battery provided by the invention has higher useful life.
Embodiment 7
With the 1g particle diameter be about 18 μ m,, specific area is 153m
2/ g, conductivity are Graphene and the 5g tin ash powder of 712S/cm, grind even back to wherein adding the 150mL deionized water, the mixed solution that obtains mixing after the ultrasonic dispersion; Said mixed solution is joined in the spray dryer, and the flow velocity of control mixed solution is 5mL/min, and the temperature of charging aperture is 250 ℃, and the temperature of discharging opening is 100 ℃, and the place obtains composite cathode material of lithium ion battery at discharging opening.
The present invention carries out ESEM (SEM) scanning analysis to the composite cathode material of lithium ion battery that obtains; The result shows; In the composite cathode material of lithium ion battery of present embodiment preparation; Attached to the surface of tin ash, Graphene is the face contact with contacting of tin ash to Graphene well, and its contact area has obtained increasing significantly.
The present invention tests the electric property of the composite cathode material of lithium ion battery that obtains; The result shows; The reversible capacity first of the composite cathode material of lithium ion battery of present embodiment preparation is up to 900mAh/g, and after circulation under the 0.1C multiplying power 50 times, its capacity can remain 850mAh/g; When 0.5C, the specific discharge capacity of the composite cathode material of lithium ion battery of present embodiment preparation still can be kept and maintain 750mAh/g, this explanation, and composite cathode material of lithium ion battery provided by the invention has higher conductivity.
The present invention is to testing the useful life of the composite cathode material of lithium ion battery that obtains; The result shows; The lithium ion battery negative material of present embodiment preparation is after discharging and recharging 200 times; Its specific capacity is about 60% of initial specific capacity, this explanation, and composite cathode material of lithium ion battery provided by the invention has higher useful life.
Embodiment 8
With the 1g particle diameter be about 5 μ m～10 μ m, specific area is 165m
2/ g, conductivity are that the Graphene of 750S/cm mixes with 10g mesophase pitch carbon microspheres, grind even back to wherein adding the 220mL deionized water, the mixed solution that obtains mixing after the ultrasonic dispersion; With liquid nitrogen said mixed solution is cooled to freezing state; Be placed on then in the freeze drier, the temperature in the control freeze drier is carried out freeze drying at-10 ℃ under vacuum condition; Treat the temperature recovery to 5 ℃ in the freeze drier, obtain composite cathode material of lithium ion battery.
The present invention carries out the SEM scanning analysis to the composite cathode material of lithium ion battery that obtains; The result shows; Graphene is well attached to the surface of mesophase pitch carbon microspheres, and contacting between Graphene and the mesophase pitch carbon microspheres is the face contact, and its contact area has obtained improving significantly.
The present invention tests the electric property of the composite cathode material of lithium ion battery that obtains; The result shows; But your capacity first of the composite cathode material of lithium ion battery that present embodiment obtains is up to 345mAh/g, and after circulation under the 0.1C multiplying power 50 times, its capacity still can remain 297mAh/g; When the 0.5C multiplying power, it is original more than 90% that the specific discharge capacity of the composite cathode material of lithium ion battery that present embodiment obtains still can keep.This explanation, composite cathode material of lithium ion battery provided by the invention has good high rate performance.
The present invention is to testing the useful life of the composite cathode material of lithium ion battery that obtains; The result shows; The lithium ion battery negative material of present embodiment preparation is after discharging and recharging 200 times; Its specific capacity is about 62% of initial specific capacity, this explanation, and composite cathode material of lithium ion battery provided by the invention has higher useful life.
Can know by above embodiment; Composite cathode material of lithium ion battery provided by the invention comprises Graphene and electrode active material, and said electrode active material is one or more in mesophase pitch carbon microspheres, silicon, lithium titanate, titanium dioxide, tin ash and the graphite.Said Graphene is with after electrode active material mixes, dry with the mixed solution that obtains then to wherein preferably adding deionized water, obtain composite cathode material of lithium ion battery.Composite cathode material of lithium ion battery provided by the invention adopts Graphene that electrode active material is carried out modification; The excellent electrochemical properties of Graphene has given composite cathode material of lithium ion battery superior electric property, makes it have higher specific discharge capacity and cycle period; And Graphene can be good at attached to the showing of electrode active material, the separation of having avoided the electrode electrode active material that electrode active material volumetric expansion or contraction in charge and discharge process cause with come off, increase its useful life.Further; The preparation method of composite cathode material of lithium ion battery provided by the invention is preferably under ultrasonic condition; With raw materials mix, make between Graphene and the electrode active material and mixed fully, improved the performance of composite cathode material of lithium ion battery more.Method provided by the invention is simple to operate, is beneficial to the application of lithium ion battery.
The above only is a preferred implementation of the present invention; Should be pointed out that for those skilled in the art, under the prerequisite that does not break away from the principle of the invention; Can also make some improvement and retouching, these improvement and retouching also should be regarded as protection scope of the present invention.
Claims (10)
1. a composite cathode material of lithium ion battery comprises Graphene and electrode active material;
Said electrode active material is one or more in mesophase pitch carbon microspheres, silicon, lithium titanate, titanium dioxide, tin ash and the graphite.
2. composite cathode material of lithium ion battery according to claim 1 is characterized in that, the particle diameter of said Graphene is 4 μ m～30 μ m.
3. according to claim 1 or 2 any described composite cathode material of lithium ion battery, it is characterized in that the mass ratio of said Graphene and said electrode active material is 1: (1～100).
4. composite cathode material of lithium ion battery according to claim 3 is characterized in that, the mass ratio of said Graphene and said electrode active material is 1: (10～50).
5. composite cathode material of lithium ion battery according to claim 1 is characterized in that, said electrode active material is one or more in mesophase pitch carbon microspheres, silicon, lithium titanate and the tin ash.
6. the preparation method of a composite cathode material of lithium ion battery may further comprise the steps:
Graphene, electrode active material are mixed with water, obtain mixed solution;
Said mixed solution is carried out drying, obtain composite cathode material of lithium ion battery;
Said electrode active material is one or more in mesophase pitch carbon microspheres, silicon, lithium titanate, titanium dioxide, tin ash and the graphite.
7. preparation method according to claim 6 is characterized in that, said Graphene, electrode active material is mixed with water, is specially:
Graphene and electrode active material are ground Graphene and electrode active material after obtaining grinding;
Under ultrasound condition, the Graphene after the said grinding is mixed with electrode active material and water.
8. according to claim 6 or 7 any described preparation methods, it is characterized in that said drying is spray drying or freeze drying.
9. preparation method according to claim 8 is characterized in that, said spray-dired temperature is 150 ℃～300 ℃.
10. preparation method according to claim 8 is characterized in that, said cryodesiccated temperature is-20 ℃～60 ℃.
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