CN104934574A - Preparation method of ultra-high density cobaltosic oxide/porous graphene nano-composite anode material for lithium ion battery - Google Patents
Preparation method of ultra-high density cobaltosic oxide/porous graphene nano-composite anode material for lithium ion battery Download PDFInfo
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Abstract
The invention relates to a preparation method of an ultra-high density cobaltosic oxide/porous graphene nano-composite anode material for a lithium ion battery and brings forward a novel low-cost in-situ growth method. According to the method, evenly distributed in plane defect sites are manufactured on the surface of oxidized graphene by means of strong oxidization of a chemical reagent; and then through a low-temperature hydrothermal reaction, in-situ growth of ultra-high density cobaltosic oxide nano-particles happens on porous graphene with the defect active sites. Cobaltosic oxide accounts for more than 92% of the compound, and adverse effects such as the drop in first coulombic efficiency and tilt of a charging/discharging platform due to addition of overmuch graphene can remarkably be improved. In the cobaltosic oxide/porous graphene nano-composite material, graphene can effectively improve conductivity insufficiency of cobaltosic oxide; and volume effect of cobaltosic oxide during the cyclic process can be well overcome due to the particle size of 5-10 nm. Thus, the material has ultra-high electrochemical performance. According to the invention, the principle is simple, and the material is easy to produce.
Description
Technical field
The invention belongs to new energy materials and electrochemical energy source research field, be specifically related to the brand-new preparation method of a kind of super-high density for lithium ion battery cobaltosic oxide/porous graphene nano composite anode material.
Background technology
Lithium ion battery, because of the high advantage of its energy density, obtains development at a high speed, and is widely used as the power supply of the portable type electronic products such as mobile phone, camera, notebook computer in the past 20 years.In recent years, hybrid-electric car, the development of plug-in hybrid-electric car and large-scale energy storage device, has higher requirement in energy density, high rate performance and cycle life to lithium ion battery of future generation.The theoretical capacity of graphite cathode material general at present only has 372 mAh g
-1, therefore improve negative material capacity and be considered to develop one of advanced battery system approach the most effective and important.Up to the present, various types of materials comprises lithium alloy (Si, Sn, Ge, Sb), transition metal oxide (SnO
2, TiO
2, MnO
2, Co
3o
4, Fe
2o
3), transition metal nitride, high molecular polymer and corresponding composite material, be obtained for detailed research.Wherein, cobaltosic oxide material is because of its stable chemical state and higher theoretical capacity (890 mAh g
-1), be considered to one of negative material of most application potential.
But the commercial applications of cobaltic-cobaltous oxide negative pole material, still face two main bottleneck problems: i.e. own electronic poorly conductive and there is violent bulk effect in embedding/de-lithium process of circulation.Because theoretical capacity is higher, de-/embedding along with a large amount of lithium ion in cyclic process, material volume is expansion/contraction repeatedly, causes the mechanization of material to be pulverized, and departs from gradually to lose to conduct electricity with collector substrate and be connected, and finally causes the quick decline of capacity.In addition, the change repeatedly of material volume, the solid electrolyte diaphragm that material surface also can be caused to be formed constantly destroys-lives again, and causes the lasting consumption of lithium ion, also can accelerate the attenuation process of capacity.
In order to solve the problem, improve the chemical property of cobaltosic oxide material, the improvement in this design on material structure and preparation technology is just extremely important.These improve and mainly comprise preparation all kinds of nanostructure, such as nanotube, nano wire, nano particle, and nanometer sheet and hollow square body and hollow ball etc. and development carbon composite, to reach the object improved electron conduction He overcome volume effectiveness.But from actual effect, the chemical property of cobaltosic oxide especially cycle performance does not improve significantly.Current research shows, only have when the particle diameter of cobaltosic oxide particle is at 10 below nm, the impact of its bulk effect just can drop to lower level.Therefore, if can synthesize the cobaltosic oxide nano particle of particle diameter between 5-10nm, and it be evenly anchored on carbonaceous conductive network material, its chemical property will be greatly improved.
Graphene is a kind of high-graphitized Two-dimensional Carbon nano material, there is surface area large, good conductivity, the feature such as the high and pliability of mechanical strength is excellent, be widely used in lithium electricity electrode material, himself not only can as negative material, and is mostly conductive carriers as active material.On Graphene, growth in situ cobaltosic oxide nano particle can improve the chemical property of cobaltosic oxide preferably, but due to the restriction of synthetic method, in the cobalt oxide/graphene composite material obtained at present, the quality proportion of active material is all very low, the highlyest can only reach about 30-50%.Because Graphene specific area is large, the coulombic efficiency of first charge-discharge generally only has about 50-60%, and Graphene does not have smooth charge and discharge platform, therefore in composite material, the ratio of Graphene is too high, can significantly reduce its first charge-discharge efficiency, and shorten the plateau potential width of the discharge and recharge of cobaltosic oxide.Therefore can well as under the prerequisite of conductive carrier at guarantee Graphene, synthesis high-density cobaltosic oxide/graphene nanocomposite material, improve the mass fraction of active material as far as possible, to improving coulombic efficiency first, reduce lithium ion consumption, make full use of the width of cobaltosic oxide charge/discharge platform, have very important significance.But be respectively 201210152479.1 at application number, 201010158087.7 and in the application for patent of 201310074309.0, although inventor uses hydro-thermal reaction respectively, the methods such as spraying heating have prepared cobalt oxide/graphene nano composite material, but the preparation method of all not mentioned high-density cobaltosic oxide composite material and correlated results, this shows that development high-density cobaltosic oxide composite material still has suitable difficulty and challenge.
Therefore, develop a kind of novel preparation method, can at the cobaltosic oxide nano particle of graphenic surface growth in situ high density or super-high density, and the particle diameter of accurate these nano particles of control is between 5-10 nm, ensureing to strengthen on the basis of cobaltosic oxide electric conductivity, at utmost reduce too much Graphene consumption to the impact of composite material chemical property, and effectively can overcome the violent bulk effect of cobaltosic oxide, thus obtain the cobalt oxide/graphene composite nano material with excellent electrochemical performance, important meaning is had to its application in hybrid-electric car and large-scale energy storage device.
Summary of the invention
The object of the invention is to provide the novel processing step of a kind of super-high density cobaltosic oxide/porous graphene nano composite material.Mainly by using the chemical reagent with strong oxidizing property to being that Graphene processes before modified, a large amount of equally distributed in-plane defects site is produced at graphenic surface, adopt hydrothermal synthesis method subsequently, growth in situ high-density cobaltosic oxide nano particle on the porous graphene that these have defect avtive spot.Wherein the average grain diameter of cobaltosic oxide particle is between 5-10 nm, and in the orderly dense arrangement of the rare apparent height of graphite.In composite material, the mass fraction of cobaltosic oxide can reach more than 92%.The method not only can significantly improve add too much Graphene after cause coulombic efficiency first to decline and the adverse effect such as charge/discharge platform inclination.Super-high density cobaltosic oxide/porous graphene nano composite material can overcome cobaltosic oxide material electronics poorly conductive well and there is the main technical bottleneck problem of violent bulk effect these two in embedding/de-lithium process of circulation, thus there is higher reversible capacity, excellent multiplying power and cycle performance.
In order to achieve the above object, the technical solution used in the present invention is: the graphene oxide first by preparing chemical method carries out the ultrasonic process of further Strong oxdiative, poroid defective bit in a large amount of uniform nanoscale face is manufactured on its surface, utilize low-temperature hydrothermal synthetic reaction subsequently, at porous graphene surface in situ growth cobaltosic oxide nano particle, the cobalt oxide/graphene composite material prepared heats a period of time in atmosphere, ensure cobaltosic oxide complete oxidation, finally under argon gas condition, graphene oxide is reduced, final acquisition high-density cobaltosic oxide/porous graphene nano composite material.
Concrete preparation method is as follows:
(1) first graphene oxide is prepared by the conventional chemical method (Hummers method) preparing graphene oxide, main process is: the reaction bulb assembling 250 mL in ice-water bath, add the appropriate concentrated sulfuric acid, the solid mixture of 2 g graphite powders and 1 g sodium nitrate is added under magnetic agitation, slowly add 6 g potassium permanganate again, control reaction temperature and be no more than 10 DEG C, take out stir 2 h under condition of ice bath after, at room temperature stirring reaction 5 days.Then sample is used 5%(mass fraction) H
2sO
4solution dilutes, and after stirring 2 h, adds 6 mL H
2o
2, solution becomes glassy yellow, and h is centrifugal for stirring reaction 2.Then with the H that concentration is suitable
2sO
4, H
2o
2mixed solution and HCl cyclic washing, finally with distilled water washing for several times, make its pH ~ 7, the tan precipitate obtained is graphite oxide (GO).Finally that sample is fully dry in the vacuum drying chamber of 40 DEG C.Enter in deionized water by the graphite oxide of acquisition, 60 W power ultrasonic about 3 h, precipitates overnight, puts into baking oven 40 DEG C of dryings, obtains the graphene oxide that lamella is thinner after getting upper liquid eccentric cleaning.
(2) weigh the graphene oxide that certain mass (0.2 ~ 100g) prepares, be dissolved in 10 ~ 1000 mL, tri-water, ultrasonic disperse, to evenly, adds 100-5000mL strong oxidizer reagent solution, high-power ultrasonic 4 hours ~ 1 day subsequently.After centrifugal, the solid product obtained is taken out, 60 DEG C of oven dry, namely obtain the Graphene that surface has the poroid defect of even.
(3) select suitable cobalt salt, with urea, porous graphene, water is ultrasonic mixing by a certain percentage, proceeds to water heating kettle, hydro-thermal reaction 8-16 hour at 55 DEG C ~ 95 DEG C, centrifugal taking-up solid product, after three water washings for several times, and 60 DEG C of oven dry.
(4) above-mentioned solid product is heated 6-10 hour under 250-400 DEG C of air conditions, under tube furnace inert gas conditions, at 400-600 DEG C, finally reduce 1-5 hour, just can prepare high-density cobaltosic oxide/porous graphene nano composite material.
Described strong oxidizer reagent solution comprises red fuming nitric acid (RFNA), the concentrated sulfuric acid, the combining form of hydrogen peroxide, ammonium nitrate, potassium nitrate, perchloric acid and salt thereof, dichromic acid and salt, permanganic acid and salt thereof, perbenzoic acid, peroxophosphoric acid, phosphorus pentoxide and wherein any agent.
Described cobalt salt comprises cobalt chloride, cobaltous sulfate, cobalt nitrate, the salt that all cobalt cations such as cobalt acetate and anion are formed and combining form.
The mass ratio of described graphene oxide and strong oxidizer reagent is between 0.01 ~ 0.5.
In described manufacture face, the mode of poroid defective bit is high-power ultrasonic pattern, comprises ultrasonic cleaning instrument and cell pulverization instrument etc.
Described low-temperature hydrothermal reaction temperature controls between 55 DEG C ~ 95 DEG C, and the time is 8-16 hour.
Described air heat temperature range is 250-400 DEG C, 6-10 hour, and under inert gas, reduction temperature scope is 400-600 DEG C, 1-5 hour.
outstanding advantages of the present invention and effect show
(1) by Strong oxdiative reagent and high-power ultrasonic effect, can at the poroid in-plane defects of a large amount of equally distributed nanometers of surface of graphene oxide manufacture, these defects are as reactivity site, reacted by low-temperature hydrothermal, can at porous graphene surface in situ growing high density cobaltosic oxide nano particle, wherein the average grain diameter of cobaltosic oxide particle is between 5-10 nm, and in the orderly dense arrangement of the rare apparent height of graphite.In composite material, the mass fraction of cobaltosic oxide can reach more than 92%, solves technical bottleneck Graphene being difficult to growing high density cobaltosic oxide nano particle.
(2) super-high density cobaltosic oxide/porous graphene nano composite material of preparing of the present invention, Graphene, as carrier material, only plays the effect of reinforced composite electronic conductivity.The adverse effects such as coulombic efficiency decline first and charge/discharge platform inclination can not be caused after adding too much Graphene, make cobaltosic oxide material can give play to best performance advantage.
(3) electrochemical performance of product.This composite material can overcome cobaltosic oxide material electronics poorly conductive well and there is the main technical bottleneck problem of violent bulk effect these two in embedding/de-lithium process of circulation, thus there is higher reversible capacity, excellent multiplying power and cycle performance.Reversible capacity can reach 900-1000 mAh g
-1left and right, under 2C multiplying power, can keep more than 80% of initial capacity, under 30C multiplying power, still can keep more than 20% of initial capacity.Through 100 circulations, capacity can not be decayed substantially, has application prospect.
(4) lot stability of product is good, and synthesis technique is simple, and reappearance is splendid.
(5) preparation method's cost of the present invention is very low, and agents useful for same is cheap, is beneficial to enforcement, is very suitable for commercialization and applies.
Accompanying drawing explanation
There is in accompanying drawing 1 embodiment one ESEM (SEM) image of the porous oxidation Graphene of the poroid in-plane defects of nanometer.
Transmission electron microscope (TEM) image of super-high density cobaltosic oxide/porous graphene nano composite material in accompanying drawing 2 embodiment one.
The thermogravimetric curve of super-high density cobaltosic oxide/porous graphene nano composite material in accompanying drawing 3 embodiment one.
The high rate performance curve of super-high density cobaltosic oxide/porous graphene nano composite material in accompanying drawing 4 embodiment two.
The long-term cycle performance of super-high density cobaltosic oxide/porous graphene nano composite material in accompanying drawing 5 embodiment four.
Embodiment
Below in conjunction with enforcement example, the invention will be further described; what be necessary to herein means out is that following examples can only be used for further illustrating for of the present invention; can not be interpreted as content of the present invention, nonessential improvement on this basis and adjustment still belong to protection scope of the present invention.
Embodiment one
(1) first graphene oxide is prepared by the conventional chemical method (Hummers method) preparing graphene oxide.(2) (1 graphene oxide g) prepared, is dissolved in 100 mL, tri-water, and ultrasonic disperse, to evenly, adds 1000 mL concentrated nitric acid solutions, high-power ultrasonic 4 hours subsequently to weigh certain mass.After centrifugal, the solid product obtained is taken out, 60 DEG C of oven dry, namely obtain the Graphene that surface has the poroid defect of even;
(3) suitable CoCl is selected
2, with urea, porous graphene, water is ultrasonic mixing by a certain percentage, proceeds to water heating kettle, hydro-thermal reaction 8 hours at 55 DEG C, centrifugal taking-up solid product, after three water washings for several times, and 60 DEG C of oven dry;
(4) above-mentioned solid product is heated 6 hours under 250 DEG C of air conditionses, finally under tube furnace inert gas conditions at 400 DEG C reductase 12 hour, just can prepare high-density cobaltosic oxide/porous graphene nano composite material.
Embodiment two
(1) first graphene oxide is prepared by the conventional chemical method (Hummers method) preparing graphene oxide;
(2) (5 graphene oxides g) prepared, are dissolved in 500 mL, tri-water, and ultrasonic disperse, to evenly, adds 4000 mL potassium bichromate solutions, high-power ultrasonic 10 hours subsequently to weigh certain mass.After centrifugal, the solid product obtained is taken out, 60 DEG C of oven dry, namely obtain the Graphene that surface has the poroid defect of even;
(3) suitable CoSO is selected
4, with urea, porous graphene, water is ultrasonic mixing by a certain percentage, proceeds to water heating kettle, hydro-thermal reaction 10 hours at 75 DEG C, centrifugal taking-up solid product, after three water washings for several times, and 60 DEG C of oven dry;
(4) above-mentioned solid product is heated 10 hours under 300 DEG C of air conditionses, finally reduce 4 hours at 600 DEG C under tube furnace inert gas conditions, just can prepare high-density cobaltosic oxide/porous graphene nano composite material.
Embodiment three
(1) first graphene oxide is prepared by the conventional chemical method (Hummers method) preparing graphene oxide;
(2) weigh the graphene oxide that certain mass (50g) prepares, be dissolved in 1000 mL, tri-water, ultrasonic disperse, to evenly, adds 5000mL perchloric acid solution, high-power ultrasonic 1 day subsequently.After centrifugal, the solid product obtained is taken out, 60 DEG C of oven dry, namely obtain the Graphene that surface has the poroid defect of even;
(3) select suitable cobalt nitrate, with urea, porous graphene, water is ultrasonic mixing by a certain percentage, proceeds to water heating kettle, hydro-thermal reaction 12 hours at 80 DEG C, centrifugal taking-up solid product, after three water washings for several times, and 60 DEG C of oven dry;
(4) above-mentioned solid product is heated 8 hours under 350 DEG C of air conditionses, finally reduce 3 hours at 500 DEG C under tube furnace inert gas conditions, just can prepare high-density cobaltosic oxide/porous graphene nano composite material.
Embodiment four
(1) first graphene oxide is prepared by the conventional chemical method (Hummers method) preparing graphene oxide;
(2) weigh the graphene oxide that certain mass (100g) prepares, be dissolved in 1000 mL, tri-water, ultrasonic disperse, to evenly, adds the 5000mL concentrated sulfuric acid+hydrogen peroxide (v:v=1:1) solution, high-power ultrasonic 1 day subsequently.After centrifugal, the solid product obtained is taken out, 60 DEG C of oven dry, namely obtain the Graphene that surface has the poroid defect of even;
(3) select suitable cobalt acetate, with urea, porous graphene, water is ultrasonic mixing by a certain percentage, proceeds to water heating kettle, hydro-thermal reaction 16 hours at 95 DEG C, centrifugal taking-up solid product, after three water washings for several times, and 60 DEG C of oven dry;
(4) above-mentioned solid product is heated 9 hours under 400 DEG C of air conditionses, finally reduce 4 hours at 550 DEG C under tube furnace inert gas conditions, just can prepare high-density cobaltosic oxide/porous graphene nano composite material.
It is below the characterizing method of super-high density cobaltosic oxide in the present invention/porous graphene nano composite material chemical property.
(1) manufacture of pole piece
1.2g composite material and 0.15g super conductive agent (Super P) and Kynoar (PVDF) binding agent are dispersed in a certain amount of 1-METHYLPYRROLIDONE (NMP) solvent, half an hour is stirred with the rotating speed of 10000 turns per minute, after slurry fully mixes, on coating machine, coating is dry; The dry thickness of electrode slice controls between 40 ~ 60 μm, then uses roll squeezer to be pressed between 20 ~ 30 μm by obtained electrode slice.
(2) manufacture of button cell
Above-mentioned electrode slice and metal lithium sheet, respectively as the positive pole of battery and negative pole, use Celgard 2500 barrier film, 1mol/LiPF
6/ EC+DEC (volume ratio 1:1) solution is electrolyte, in glove box, assemble button cell.According to the conventional process that button cell manufactures, after cutting, drying sheet, assembling, fluid injection and sealing compacting, the battery of gained changes into.
(3) material electric performance test
Changing into of battery: use 0.05C (1C=1000 mAhg
-1) current density constant current charge and discharge cycle 3 times, charge cutoff current potential is 0.01V, and electric discharge stopping potential is carry out high rate performance test to it after 3.0V completes.
Battery high rate performance is tested: after having changed into, battery charges with the multiplying power of 0.1C, circulate 4 times with 0.1C, 0.2C, 0.5C, 1C, 2C, 5C, 10C, 15C, 20C and 30C multiplying power discharging respectively, third time, discharge capacity was as the stable discharging capacity under this discharge-rate, charge cutoff current potential is 0.01 V, and electric discharge stopping potential is 3.0V.
Cycle performance of battery is tested:
After multiplying power has been tested, battery carries out charge and discharge cycles 100 times with the multiplying power of 0.1 C, and charge cutoff current potential is 0.01 V, and electric discharge stopping potential is 3.0V.
Claims (7)
1., for a preparation method for the super-high density cobaltosic oxide/porous graphene nano composite anode material of lithium ion battery, the method comprises following step:
A graphene oxide mixes with strong oxidizer by () according to a certain ratio, by Strong oxdiative reagent and high-power ultrasonic effect, at the poroid in-plane defects of a large amount of equally distributed nanometers of surface of graphene oxide manufacture;
B (), to have the porous graphene of the poroid in-plane defects of nanometer for carrier, is added cobalt salt and urea in proportion, is reacted by low-temperature hydrothermal, at porous graphene surface in situ growing high density cobaltosic oxide nano particle;
C solid product that () hydro-thermal reaction obtains heats under air conditions, reduces by under tube furnace inert gas conditions, prepares high-density cobaltosic oxide/porous graphene nano composite material.
2. as claimed in claim 1 for the super-high density cobaltosic oxide/porous graphene nano composite anode material preparation method of lithium ion battery, strong oxidizer reagent solution used comprises red fuming nitric acid (RFNA), the concentrated sulfuric acid, any combination of hydrogen peroxide, ammonium nitrate, potassium nitrate, perchloric acid and salt thereof, dichromic acid and salt, permanganic acid and salt thereof, perbenzoic acid, peroxophosphoric acid, phosphorus pentoxide and mentioned reagent.
3. as claimed in claim 1 for the super-high density cobaltosic oxide/porous graphene nano composite anode material preparation method of lithium ion battery, cobalt salt used comprises cobalt chloride, cobaltous sulfate, cobalt nitrate, the salt that all cobalt cations such as cobalt acetate and anion are formed and any combination thereof.
4., as claimed in claim 1 for the super-high density cobaltosic oxide/porous graphene nano composite anode material preparation method of lithium ion battery, the mass ratio of graphene oxide used and Strong oxdiative reagent is between 0.01 ~ 0.5.
5., as claimed in claim 1 for the super-high density cobaltosic oxide/porous graphene nano composite anode material preparation method of lithium ion battery, in manufacture face, the mode of poroid defective bit is high-power ultrasonic pattern.
6., as claimed in claim 1 for the super-high density cobaltosic oxide/porous graphene nano composite anode material preparation method of lithium ion battery, low-temperature hydrothermal reaction temperature controls between 55 DEG C ~ 95 DEG C, and the time is 8-16 hour; Under air conditions, heating temperature range is 250-400 DEG C, and the time is 6-10 hour; Under inert gas, reduction temperature scope is 400-600 DEG C, and the time is 1-5 hour.
7. cobaltosic oxide/porous graphene the nano composite anode material utilizing the cobaltosic oxide of the super-high density for lithium ion battery any one of claim 1-6 described in claim/porous graphene nano composite anode material preparation method to obtain, it is characterized in that the average grain diameter of cobaltosic oxide particle is between 5-10 nm, and in the orderly dense arrangement of the rare apparent height of graphite, in composite material, the mass fraction of cobaltosic oxide reaches more than 92%.
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| CN106099081A (en) * | 2016-08-30 | 2016-11-09 | 安徽师范大学 | A kind of cobalt oxide/graphene nano composite material and preparation method thereof, lithium ion battery negative, lithium ion battery |
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