CN102280635A - Co3O4-C composite material and preparation method thereof and lithium battery and cathode thereof - Google Patents
Co3O4-C composite material and preparation method thereof and lithium battery and cathode thereof Download PDFInfo
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- CN102280635A CN102280635A CN2011101833964A CN201110183396A CN102280635A CN 102280635 A CN102280635 A CN 102280635A CN 2011101833964 A CN2011101833964 A CN 2011101833964A CN 201110183396 A CN201110183396 A CN 201110183396A CN 102280635 A CN102280635 A CN 102280635A
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- ion battery
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Abstract
The invention relates to a Co3O4-C composite material which comprises spinel-type Co3O4 and amorphous carbon, is granular, and each granule comprises a plurality of layered unfolded hemispherical layers. The invention also relates to a preparation method of the Co3O4-C composite material, and the method comprises the following steps: adding an alkali liquid into an oil-in-water emulsion, then allowing the solution to stand, and performing centrifugation processing, wherein the oil-in-water emulsion comprises a water-soluble cobalt salt, a surfactant, a cosurfactant, an organic solvent, and water; coating the precipitate obtained after the centrifugation processing on a substrate material; performing first roasting of the precipitate coated on the substrate material in inert atmosphere, then performing second roasting in oxygen-containing atmosphere. The invention also relates to a lithium ion battery cathode including the Co3O4-C composite material, and a lithium ion battery. The lithium ion battery prepared by using the Co3O4-C composite material of the invention as a cathode material has high specific capacity and rate capability.
Description
Technical field
The present invention relates to a kind of Co
3O
4-C composite, this Co
3O
4-C composite manufacture method is by the Co of described method preparation
3O
4-C composite comprises the lithium ion battery negative of this composite, and the lithium ion battery that comprises this lithium ion battery negative.
Background technology
Lithium ion battery receives much concern because of it has advantages such as operating voltage height, specific energy height, self-discharge rate are low, asepsis environment-protecting, becomes the main power supply of present electronic product and electric equipment.Yet, along with the renewal of electronic product in recent years and people to the extensive concern of energy source and power, lithium ion battery is had higher requirement, need it to have higher energy density, higher power density and longer useful life.
Review the development process of lithium ion battery negative material,, once be considered to comparatively ideal negative material because lithium metal has premium properties such as high power capacity, electronegative potential.But, in the cyclic process, produce easily on the one hand Li dendrite on lithium anode surface and cause piercing through barrier film and cause short circuit, form easily on the other hand passivation layer and hindered the embedding of lithium ion and deviate from, cause the decay of battery capacity and the reduction in service life.
Subsequently, after the carbon back negative material occurs, because that it has a cost is low, higher cycle efficieny and good electrochemistry stable circulation performance, thus be widely used.But its lithium storage content is lower, and theoretical specific capacity is about 372mAh/g, and when high magnification charges potential safety hazard is arranged, so the development of new negative material becomes the key that improves the lithium ion battery performance.
P.Poizot etc.
[1]Proposed transition metal oxide first and can be used as lithium ion battery negative material, and confirmed that by experiment its specific discharge capacity is 2～3 times of graphite cathode.Yet the transition metal oxide negative material also exists following problem: irreversible capacity height first; The cubical expansivity height causes cycle life low in the cyclic process; Because it is a semi-conducting material, the relatively poor high rate performance that causes of its conductivity is poor.At the shortcoming of cycle performance difference, one of effective way that the researcher is considered as hollow ball structure to address this problem.S.Y.Zeng etc.
[2]The Fe that has prepared the hollow ball structure by hydro-thermal method
2O
3B.X.Li etc.
[3]Made the MnO of cavity structure
2, and explained the control action of Ostwald maturing process to pattern.Xi Wang etc.
[4]The Co that has prepared the polytrope structure by hydro-thermal method
3O
4
By above-mentioned document as can be known, hollow ball structure can provide surge volume for the volumetric expansion that produces in the material cyclic process, thereby improves the cyclical stability of transition metal oxide negative pole.But also there are some inevitable defectives in this class hollow ball structure, as: big cavity volume has caused the volume and capacity ratio of system to descend.In the polytrope structure, though improved the utilance of cavity volume slightly, the internal layer spherical shell can not contact with the conductive agent outside the spherical shell, makes that the high rate performance of this class formation negative material is not good.Therefore, for cycle performance and the high rate performance that improves simultaneously the transition metal oxide negative material, be still waiting to develop the more rational electrode material of a kind of appearance structure.
List of references
[1]P.Poizot，S.Laruelle，S.Grugeon，L.Dupont，J.-M.Tarascon，Nature2000，407，496.
[2]S.Y.Zeng，K.B.Tang，T.W.Li，Z.H.Liang，D.Wang，Y.K.Wang，W.W.Zhou，J.Phys.Chem.C?2007，111，10217.
[3]B.X.Li，G.X.Rong，Y.Xie，L.F.Huang，C.Q.Feng，Inorg.Chem.2006，45，6404.
[4]Xi?Wang，Xing-Long?Wu，Yu-Guo?Guo，Yeteng?Zhong，Xinqiang?Cao，Ying?Ma，Jiannian?Yao，Adv.Funct.Mater.2010，20，1680.
Summary of the invention
The objective of the invention is provides a kind of Co in order to overcome the defects of existing lithium ion battery negative material
3O
4-C composite and preparation method thereof, and the lithium ion battery negative and the lithium ion battery that comprise this composite.
The invention provides a kind of Co
3O
4-C composite, described composite contains spinel-type Co
3O
4And amorphous carbon, wherein, described composite is graininess, and each particle comprises the hemisphere layer of a plurality of stacked expansion.
The present invention also provides a kind of Co
3O
4-C composite manufacture method, this method comprises:
(1) add alkali lye in emulsion oil-in-water, leave standstill successively then and centrifugal treating, described emulsion oil-in-water contains water soluble cobaltous salt, surfactant, cosurfactant, organic solvent and water;
(2) sediment that obtains after the centrifugal treating is coated on the base material;
(3) under inert atmosphere, make the sediment that is coated on the base material under first temperature, carry out the roasting first time;
(4) containing under the atmosphere of oxygen, making the sediment through the roasting first time under second temperature, carry out the roasting second time, obtaining covering the Co on the substrate material surface
3O
4-C composite;
Described first temperature can make described surfactant charing, and described second temperature can make the hydroxide of cobalt be oxidized to Co
3O
4And can not make the carbonizing production oxidation of described surfactant.
The present invention also provides the Co by the said method preparation
3O
4-C composite.
The present invention also provides a kind of lithium ion battery negative, and this lithium ion battery negative comprises collector and the negative material that covers on this collection liquid surface, and wherein, described negative material is described Co provided by the invention
3O
4-C composite.
The present invention also provides a kind of lithium ion battery, this lithium ion battery comprises battery container, electrode group and electrolyte, and electrode group and electrolyte are sealed in the battery container, and the electrode group comprises positive pole, barrier film and negative pole, wherein, described negative pole is a described lithium ion battery negative provided by the invention.
According to Co of the present invention
3O
4-C composite is graininess, each particle comprises the hemisphere layer of a plurality of stacked expansion, so that this composite can provide surge volume for the volumetric expansion of material, improves the specific area of material, shorten the diffusion distance of lithium ion in material, make material that more storage lithium points position can be provided.Therefore, this Co
3O
4-C composite has cyclical stability height, good rate capability and specific capacity advantages of higher as lithium ion battery negative material.
Description of drawings
Fig. 1 is described Co provided by the invention
3O
4The formation mechanism schematic diagram of-C composite;
Fig. 2 is the sedimentary stereoscan photograph that is coated among the embodiment 1 on the Copper Foil, and multiplication factor is 2000 times;
Fig. 3 is the sedimentary stereoscan photograph that is coated among the embodiment 1 on the Copper Foil, and multiplication factor is 7000 times;
Fig. 4 is the Co of embodiment 1 preparation
3O
4The stereoscan photograph of-C composite, multiplication factor are 1000 times;
Fig. 5 is the Co of embodiment 1 preparation
3O
4The stereoscan photograph of-C composite, multiplication factor are 2000 times;
Fig. 6 is the Co of embodiment 1 preparation
3O
4The stereoscan photograph of-C composite, multiplication factor are 15000 times;
Fig. 7 is the Co of embodiment 1-4 preparation
3O
4The XRD spectra of-C composite, abscissa are angle 2 θ, and unit is: degree (°), ordinate is diffracted intensity, unit is: absolute unit (a.u.);
Fig. 8 is that the simulated battery of embodiment 7-10 preparation is that 3.0-0.02V (with respect to the voltage of lithium sheet), current density are 0.1mA/cm discharging and recharging the blanking voltage scope
2Under test the Co that obtains
3O
4The charge-discharge performance figure of-C composite, abscissa are cycle-index, and unit is: inferior; Ordinate is specific discharge capacity, and unit is: MAh/g (mAh/g);
Fig. 9 is that the simulated battery of embodiment 7 preparations is to test the Co that obtains under 3.0-0.02V (with respect to the voltage of lithium sheet), the different current density discharging and recharging the blanking voltage scope
3O
4The charge-discharge performance figure of-C composite, abscissa are cycle-index, and unit is: inferior; Ordinate is specific discharge capacity, and unit is: MAh/g (mAh/g);
Figure 10 is that the lithium ion battery of embodiment 13 preparations is that 4.5-1.7V, current density are 0.1mA/cm discharging and recharging the blanking voltage scope
2Under test the Co that obtains
3O
4The charge-discharge performance figure of-C composite, abscissa are cycle-index, and unit is: inferior; Ordinate is specific discharge capacity, and unit is: MAh/g (mAh/g).
Embodiment
According to a first aspect of the invention, the invention provides a kind of Co
3O
4-C composite, described composite contains spinel-type Co
3O
4And amorphous carbon, wherein, described composite is graininess, and each particle comprises the hemisphere layer of a plurality of stacked expansion.
In the present invention, term " hemisphere layer " be meant near or the planar layer of approximate hemisphere, to have geometric hemisphere planar and not should be understood to this layer.
In the present invention, term " the hemisphere layer of expansion " is meant the layer that forms along the radial development of the opening of hemisphere layer.The opening size of the layer that forms after launching is greater than the opening size without the hemisphere layer that launches.
According to described Co provided by the invention
3O
4-C composite, wherein, at each described Co
3O
4In-C the composite material granular, there is part to separate between the hemisphere layer of adjacent two described expansion, makes to have between layers the gap.In the preferred case, the part of 20-95% is separated between the hemisphere layer of two adjacent described expansion, and more preferably the part of 50-80% is separated.As each described Co
3O
4When-C composite material granular had said structure, described particle had a plurality of layer, and the gap of interlayer can provide surge volume for volumetric expansion, therefore, and with described Co
3O
4When-C composite was used as lithium ion battery negative material, this composite can improve cycle performance.And, with existing hollow ball structure Particle Phase ratio as lithium ion battery negative material, described Co of the present invention
3O
4-C composite material granular has not only overcome the shortcoming that the internal layer spherical shell can not contact with the conductive agent outside the spherical shell, and has relatively bigger specific area, has shortened the insertion of lithium distance, thereby has been conducive to improve the high rate performance of material; In addition, described Co of the present invention
3O
4Between layers gap in the-C composite material granular can provide more storage lithium point position, thereby have higher specific capacity.
According to described Co provided by the invention
3O
4-C composite, wherein, the number of plies of the hemisphere layer that launches in each described particle is 3-20, is preferably 10-15.
According to described Co provided by the invention
3O
4-C composite, wherein, the radial dimension of each described particle can be the 3-15 micron, is preferably the 5-8 micron.Described radial dimension is meant the opening size of hemisphere layer of the outermost expansion of described particle.
According to described Co provided by the invention
3O
4-C composite, wherein, take described composite gross mass as benchmark, Co
3O
4Content be 95.1-98.2 quality %, be preferably 96.5-97 quality %; The content of amorphous carbon is 1.8-4.9 quality %, is preferably 3-3.5 quality %.
According to described Co provided by the invention
3O
4-C composite, wherein, the specific area of described composite is 77.5-100m
2/ g is preferably 85-100m
2/ g.
According to a second aspect of the invention, the present invention also provides a kind of Co
3O
4-C composite manufacture method, this method may further comprise the steps:
(1) add alkali lye in emulsion oil-in-water, leave standstill successively then and centrifugal treating, described emulsion oil-in-water contains water soluble cobaltous salt, surfactant, cosurfactant, organic solvent and water;
(2) sediment that obtains after the centrifugal treating is coated on the base material;
(3) under inert atmosphere, make the sediment that is coated on the base material under first temperature, carry out the roasting first time;
(4) containing under the atmosphere of oxygen, making the sediment through the roasting first time under second temperature, carry out the roasting second time, obtaining covering the Co on the substrate material surface
3O
4-C composite;
Described first temperature can make described surfactant charing, and described second temperature can make the hydroxide of cobalt be oxidized to Co
3O
4And can not make the carbonizing production oxidation of described surfactant.
According to described method provided by the invention, as shown in Figure 1, described Co
3O
4The formation mechanism of-C composite may be: airborne oxygen makes the part divalence cobalt oxidation of the water soluble cobaltous salt in the emulsion oil-in-water become the trivalent cobalt; By add alkali lye in described emulsion oil-in-water, divalence cobalt and trivalent cobalt are precipitated formation hydroxide simultaneously by alkali lye, obtain cobalt (II) cobalt (III) hydrotalcite nano piece (referred to as Co (II)-Co (III)-LDHs); Examine (being organic solvent) as template with the oil that is dispersed in aqueous phase, utilize oil-water interfaces upper surface activating agent with oxy radical (such as hydroxyl) and the hydrogen bond action between the hydrotalcite nano piece, induce hydrotalcite nano piece to examine surperficial ordered arrangement at oil, make the plane of hydrotalcite nano piece be self-assembled into sphere structure perpendicular to oily nuclear radius; Because the density variation of oil nuclear and hydrotalcite shell under the effect of centrifugal force, makes the hydrotalcite outer casing rupture, by in the separated hydrotalcite that forms the similar hemisphere structure of launching, reach simultaneously the purpose of removing oil nuclear; Then, be coated in equably on the surface of base material by the hydrotalcite with similar hemisphere structure, and successively respectively at inert atmosphere with contain in the atmosphere of oxygen and carry out roasting, thereby described Co provided by the invention formed
3O
4-C composite.
According to described method provided by the invention, in step (1), described emulsion oil-in-water can make by cobalt saline solution, surfactant, cosurfactant and organic solvent are mixed.The speed that stirs can be 100-1000 rev/min, and the time of stirring can be 15-30 minute.
According to described method provided by the invention, in step (1), described alkali lye joins in the described emulsion oil-in-water gradually, and the pH value of the emulsion oil-in-water behind the feasible adding of the adding speed of the described alkali lye alkali lye is maintained 9-11.With respect to the described emulsion oil-in-water of 100 mass parts, the addition of described alkali lye is the 10-40 mass parts, is preferably the 20-30 mass parts; Joining day is more than 15 minutes, is preferably 15-40 minute.
According to described method provided by the invention, in step (1), the described time of leaving standstill can be 4-10 hour.
According to described method provided by the invention, in step (1), the condition of described centrifugal treating can comprise: rotating speed is 2000-9000 rev/min, and the processing time is 1-10 minute.
According to described method provided by the invention, in the described emulsion oil-in-water of step (1), the volume ratio of described surfactant and described cosurfactant can be 2-4: 1, the concentration of described water soluble cobaltous salt can be 0.04-0.5mol/L, described surfactant can be 2-4 with described volume of organic solvent ratio: 1, and water can be 20-60 with described volume of organic solvent ratio: 1.
In the present invention, described surfactant can be various surfactants with oxy radical, and described oxy radical for example can be hydroxyl, carboxyl, sulfonic group etc.In the preferred case, described surfactant is one or more in TritonX, dodecyl sodium sulfate, polyethylene glycol and the polyacrylic acid, most preferably is TritonX.
In the present invention, described cosurfactant can for example can be C for examining the small-molecule substance of size with the oil that the surfactant acting in conjunction is formed by organic solvent with control
1-C
5Organic alcohol.Under the preferable case, described cosurfactant is one or more in n-butanol, isobutanol, isopropyl alcohol and the normal propyl alcohol, most preferably is n-butanol.
In the present invention, described organic solvent is one or more in cyclohexane, benzene, styrene and the toluene, is preferably cyclohexane.
In the present invention, described water soluble cobaltous salt is one or more in cobalt nitrate, cobalt chloride, cobalt acetate, cobalt oxalate and the cobaltous sulfate, is preferably cobalt nitrate.
In the present invention, the purpose that adds described alkali lye is in order to control the pH value of mixed liquor.Therefore, the aqueous solution of the conventional various alkaline agents that use in this area all can be used as described alkali lye of the present invention, and what described alkali lye for example can be in ammonia spirit, potassium hydroxide aqueous solution, sodium hydrate aqueous solution and the aqueous solution of urea is at least a.Yet, on the surface for the oil nuclear that impels hydrotalcite nano piece to be arranged in an orderly manner to be formed by organic solvent, with the final formation Co that comprises the hemisphere layer of a plurality of stacked expansion of the present invention
3O
4-C composite material granular, described alkali lye is preferably ammonia spirit.The concentration of described ammonia spirit can be 3-10 quality %.
According to described method provided by the invention, in step (2), described base material can for example can be Copper Foil, aluminium foil, stainless steel substrates or silicon chip etc. for the conductive solids material of the surfacing of various routines.
According to described method provided by the invention, in step (2), there is no particular limitation for the described sedimentary amount that applies on the described base material.Yet, for the ease of forming Co of the present invention
3O
4-C composite, the described sedimentary amount that applies on the described base material is preferably 15-60mg/cm
2
According to described method provided by the invention, in step (3), the condition optimization of the described roasting first time comprises: described first temperature is 350-450 ℃, and roasting time is 0.5-3 hour.
According to described method provided by the invention, the inert atmosphere in the step (3) can be at least a in nitrogen, helium, neon and the argon gas.
According to described method provided by the invention, in step (4), the condition optimization of the described roasting second time comprises: described second temperature is 200-300 ℃, and roasting time is 0.5-3 hour.
According to described method provided by the invention, in step (4), the described atmosphere that contains oxygen can be air etc.
According to a third aspect of the present invention, the present invention also provides the Co by the said method preparation
3O
4-C composite.
According to a fourth aspect of the present invention, the present invention also provides a kind of lithium ion battery negative, and this lithium ion battery negative comprises collector and the negative material that covers on this collection liquid surface, and described negative material is described Co provided by the invention
3O
4The Co of-C composite and/or method according to the present invention preparation
3O
4-C composite.
Lithium ion battery negative according to the present invention, the amount of the described negative material that covers on the described collection liquid surface can be 0.1-5mg/cm
2, be preferably 0.3-2mg/cm
2
Lithium ion battery negative according to the present invention, described collector can for example can be Copper Foil, aluminium foil, stainless steel substrates or silicon chip etc. for the conductive solids material of the surfacing of various routines.
The preparation method of described lithium ion battery negative can may further comprise the steps:
(1) add alkali lye in emulsion oil-in-water, leave standstill successively then and centrifugal treating, described emulsion oil-in-water contains water soluble cobaltous salt, surfactant, cosurfactant, organic solvent and water;
(2) sediment that obtains after the centrifugal treating is coated on the collection liquid surface;
(3) under inert atmosphere, make the sediment that is coated on the collection liquid surface under first temperature, carry out the roasting first time;
(4) containing under the atmosphere of oxygen, making the sediment through the roasting first time under second temperature, carry out the roasting second time, obtaining being coated with on the collection liquid surface Co
3O
4The lithium ion battery negative of-C composite;
Described first temperature can make described surfactant charing, and described second temperature can make the hydroxide of cobalt be oxidized to Co
3O
4And can not make the carbonizing production oxidation of described surfactant.
The described Co that above-mentioned steps (the 1)-concrete operation method of (4) and the selection of reagent and preamble are described
3O
4-C composite manufacture method is identical.
According to a fifth aspect of the present invention, the present invention also provides a kind of lithium ion battery, this lithium ion battery comprises battery container, electrode group and electrolyte, electrode group and electrolyte are sealed in the battery container, the electrode group comprises positive pole, barrier film and negative pole, wherein, described negative pole is a described lithium ion battery negative provided by the invention.
The structure of described electrode group is conventionally known to one of skill in the art, and in general, described electrode group comprises positive pole, barrier film and negative pole, and barrier film is between positive pole and negative pole.
Described positive pole comprises plus plate current-collecting body and the positive electrode active materials that is coated on the plus plate current-collecting body.
Described positive electrode active materials is not particularly limited, and can be the positive electrode active materials of the embedding of this area routine/removal lithium embedded, is preferably at least a in LiMn2O4, cobalt acid lithium, lithium nickelate and the LiFePO 4.
Described plus plate current-collecting body is conventionally known to one of skill in the art, for example can be selected from aluminium foil, Copper Foil or various Punching steel strip.
Described barrier film is arranged between positive pole and the negative pole, has electrical insulation capability and liquid retainability energy.Described barrier film can be selected from and well known to a person skilled in the art various barrier films used in the lithium ion battery, for example polyolefin micro porous polyolefin membrane, polyethylene felt, glass mat or ultra-fine fibre glass paper.
Described electrolyte can be the electrolyte of various routines, for example nonaqueous electrolytic solution.Described nonaqueous electrolytic solution is the solution that electrolyte lithium salt forms in nonaqueous solvents, can use the nonaqueous electrolytic solution of routine well known by persons skilled in the art.Can be selected from lithium hexafluoro phosphate (LiPF such as electrolyte lithium salt
6), lithium perchlorate (LiClO
4), LiBF4 (LiBF
4), hexafluoroarsenate lithium (LiAsF
6), hexafluorosilicic acid lithium (LiSiF
6), tetraphenyl lithium borate (LiB (C
6H
5)
4), lithium chloride (LiCl), lithium bromide (LiBr), chlorine lithium aluminate (LiAlCl
4) and fluorocarbon based Sulfonic Lithium (LiC (SO
2CF
3)
3), LiCH
3SO
3, LiN (SO
2CF
3)
2In one or more.Nonaqueous solvents can be selected from chain acid esters and ring-type acid esters mixed solution, wherein the chain acid esters can be fluorine-containing for dimethyl carbonate (DMC), diethyl carbonate (DEC), methyl ethyl carbonate (EMC), carbonic acid first propyl ester (MPC), dipropyl carbonate (DPC) and other, sulfur-bearing or contain in the chain organosilane ester of unsaturated bond one or more.The ring-type acid esters can (γ-BL), sultone and other be fluorine-containing, sulfur-bearing or contain in the ring-type organosilane ester of unsaturated bond one or more for ethylene carbonate (EC), propene carbonate (PC), vinylene carbonate (VC), gamma-butyrolacton.
According to lithium ion battery provided by the invention, the preparation method of this battery is as well known to those skilled in the art, and in general, the preparation method of this battery comprises the electrode group is inserted in the battery case, adds electrolyte, and sealing obtains lithium ion battery then.Wherein, the method for sealing, the consumption of electrolyte is conventionally known to one of skill in the art.
The invention will be further described by the following examples, but protection scope of the present invention is not limited in this.
Present embodiment is used for illustrating described Co provided by the invention
3O
4-C composite and preparation method thereof and lithium ion battery negative.
Get 7.5mmol cobalt nitrate (Co (NO
3)
26H
2O) be dissolved in the 150mL deionized water, again successively to wherein adding the 10mL triton x-100 (available from Xilong Chemical Co., Ltd, TX-100), 5mL n-butanol and 2.5mL cyclohexane, under high-speed stirred, fully mixed 30 minutes, obtain the emulsion oil-in-water of pink colour clear.Under agitation, slowly to wherein dripping the ammonia spirit that concentration is 5 quality %, the dripping quantity of ammonia spirit is 35mL, and dripping process control is 30 minutes, is controlled to be 10 with the pH value with emulsion oil-in-water.Left standstill after dropwising 8 hours, and carried out then centrifugation, and lower sediment thing Direct Uniform is coated on the surface of Copper Foil, the amount of the described lower sediment thing that applies on the Copper Foil is 42mg/cm
2, adopt ESEM that the sediment that is coated on the Copper Foil is characterized, obtain the stereoscan photograph shown in Fig. 2 (amplifying 2000 times) and Fig. 3 (amplifying 7000 times).
Then, will be coated in sediment on the Copper Foil under nitrogen atmosphere, 400 ℃ of lower calcinings 1 hour, afterwards again under air, 250 ℃ of lower calcinings 1 hour, make the sediment that is coated on the Copper Foil form Co of the present invention
3O
4-C composite A 1 obtains being coated with on the Copper Foil described Co
3O
4The lithium ion battery negative B1 of-C composite, described Co
3O
4The overlay capacity of-C composite on Copper Foil is 3.5mg/cm
2
Adopt ESEM to this Co
3O
4-C composite A 1 characterizes, obtain the stereoscan photograph shown in Fig. 4 (amplifying 1000 times), Fig. 5 (amplifying 2000 times) and Fig. 6 (amplifying 15000 times), can find out in (particularly Fig. 6) from figure between the hemisphere layer of adjacent two expansion of particle of this composite that about 70% part separates, the particle size that can observe this composite simultaneously is about 6-7 micron.
Present embodiment is used for illustrating described Co provided by the invention
3O
4-C composite and preparation method thereof and lithium ion battery negative.
Get 20mmol cobalt chloride (CoCl
26H
2O) be dissolved in the 100mL deionized water, again successively to wherein adding the 15mL triton x-100 (available from Xilong Chemical Co., Ltd, TX-100), 5mL n-butanol and 5mL cyclohexane, under high-speed stirred, fully mixed 30 minutes, obtain the emulsion oil-in-water of pink colour clear.Under agitation, slowly to wherein dripping the ammonia spirit that concentration is 5 quality %, the dripping quantity of ammonia spirit is 40mL, and dripping process control is 25 minutes, is controlled to be 11 with the pH value with emulsion oil-in-water.Left standstill after dropwising 4 hours, and carried out then centrifugation, and lower sediment thing Direct Uniform is coated on the surface of Copper Foil, the amount of the described lower sediment thing that applies on the Copper Foil is 55mg/cm
2
Then, will be coated in sediment on the Copper Foil under nitrogen atmosphere, 450 ℃ of lower calcinings 1 hour, afterwards again under air, 200 ℃ of lower calcinings 1 hour, make the sediment that is coated on the Copper Foil form Co of the present invention
3O
4-C composite A 2 obtains being coated with on the Copper Foil described Co
3O
4The lithium ion battery negative B2 of-C composite, described Co
3O
4The overlay capacity of-C composite on Copper Foil is 4.8mg/cm
2
Can observe this Co by ESEM
3O
4About 65% part is separated between the hemisphere layer of adjacent two expansion of the particle of-C composite, and the particle size of this composite is about 7-8 micron.
Embodiment 3
Present embodiment is used for illustrating described Co provided by the invention
3O
4-C composite and preparation method thereof and lithium ion battery negative.
Get 60mmol cobalt acetate (Co (CH
3COO)
22H
2O) be dissolved in the 200mL deionized water, again successively to wherein adding the 10mL triton x-100 (available from Xilong Chemical Co., Ltd, TX-100), 2.5mL n-butanol and 5mL cyclohexane, under high-speed stirred, fully mixed 30 minutes, obtain the emulsion oil-in-water of pink colour clear.Under agitation, slowly to wherein dripping the ammonia spirit that concentration is 5 quality %, the dripping quantity of ammonia spirit is 50mL, and dripping process control is 35 minutes, is controlled to be 9 with the pH value with emulsion oil-in-water.Left standstill after dropwising 10 hours, and carried out then centrifugation, and lower sediment thing Direct Uniform is coated on the surface of Copper Foil, the amount of the described lower sediment thing that applies on the Copper Foil is 25mg/cm
2
Then, will be coated in sediment on the Copper Foil under nitrogen atmosphere, 350 ℃ of lower calcinings 1 hour, afterwards again under air, 300 ℃ of lower calcinings 1 hour, make the sediment that is coated on the Copper Foil form Co of the present invention
3O
4-C composite A 3 obtains being coated with on the Copper Foil described Co
3O
4The lithium ion battery negative B3 of-C composite, described Co
3O
4The overlay capacity of-C composite on Copper Foil is 1.8mg/cm
2
Can observe this Co by ESEM
3O
4About 73% part is separated between the hemisphere layer of adjacent two expansion of the particle of-C composite, and the particle size of this composite is about 12-15 micron.
Present embodiment is used for illustrating described Co provided by the invention
3O
4-C composite and preparation method thereof and lithium ion battery negative.
Get 60mmol cobalt oxalate (CoC
2O
44H
2O) be dissolved in the 150mL deionized water, again successively to wherein adding the 10mL triton x-100 (available from Xilong Chemical Co., Ltd, TX-100), 4mL n-butanol and 4mL cyclohexane, under high-speed stirred, fully mixed 30 minutes, obtain the emulsion oil-in-water of pink colour clear.Under agitation, slowly to wherein dripping the ammonia spirit that concentration is 5 quality %, the dripping quantity of ammonia spirit is 45mL, and dripping process control is 30 minutes, is controlled to be 9 with the pH value with emulsion oil-in-water.Left standstill after dropwising 6 hours, and carried out then centrifugation, and lower sediment thing Direct Uniform is coated on the surface of Copper Foil, the amount of the described lower sediment thing that applies on the Copper Foil is 18mg/cm
2
Then, will be coated in sediment on the Copper Foil under nitrogen atmosphere, 400 ℃ of lower calcinings 1 hour, afterwards again under air, 250 ℃ of lower calcinings 1 hour, make the sediment that is coated on the Copper Foil form Co of the present invention
3O
4-C composite A 4 obtains being coated with on the Copper Foil described Co
3O
4The lithium ion battery negative B4 of-C composite, described Co
3O
4The overlay capacity of-C composite on Copper Foil is 0.4mg/cm
2
Can observe this Co by ESEM
3O
4About 70% part is separated between the hemisphere layer of adjacent two expansion of the particle of-C composite, and the particle size of this composite is about 3-6 micron.
Embodiment 5
Present embodiment is used for illustrating described Co provided by the invention
3O
4-C composite and preparation method thereof and lithium ion battery negative.
Method according to embodiment 1 prepares Co
3O
4-C composite, difference be, be coated on the Copper Foil sediment earlier under nitrogen atmosphere, 500 ℃ of lower calcinings 1 hour, afterwards again under air, 200 ℃ of lower calcinings 1 hour, thereby make Co
3O
4-C composite A 5 and lithium ion battery negative B5.
Embodiment 6
Present embodiment is used for illustrating described Co provided by the invention
3O
4-C composite and preparation method thereof and lithium ion battery negative.
Method according to embodiment 1 prepares Co
3O
4-C composite, difference are to replace triton x-100 with isopyknic dodecyl sodium sulfate (available from Chemical Reagent Co., Ltd., Sinopharm Group), thereby make Co
3O
4-C composite A 6 and lithium ion battery negative B6.
Embodiment 7-12
In the lithium ion battery negative performance test,, can adopt metal lithium sheet usually as electrode is made up simulated battery for eliminating anodal influence.Adopt the lithium ion battery negative B1-B6 for preparing among the embodiment 1-6 as negative pole respectively, adopt the metal lithium sheet conduct to electrode, adopt barrier film Celgard 2400 as barrier film, adopt ethylene carbonate (EC)+dimethyl carbonate (DMC)+methyl ethyl carbonate (EMC) (solvent volume was than 1: 1: 1)+1mol/L LiPF
6As electrolyte, at the German Braun UNlab of company type inert atmosphere glove box (O
2And H
2The content of O is all less than 1ppm) in be assembled into simulated battery C1-C6.
Embodiment 13
The lithium ion battery negative B1 that adopts preparation among the embodiment 1 is as negative pole, adopt lithium cobaltate cathode (with aluminium foil as collector, cobalt acid lithium is as positive electrode) as anodal, adopt barrier film Celgard2400 as barrier film, adopt ethylene carbonate (EC)+dimethyl carbonate (DMC)+methyl ethyl carbonate (EMC) (solvent volume was than 1: 1: 1)+1mol/L LiPF
6As electrolyte, at the German Braun UNlab of company type inert atmosphere glove box (O
2And H
2The content of O is all less than 1ppm) in be assembled into lithium ion battery D1.
The Co that embodiment 1-4 is prepared
3O
4-C composite A 1-A4 carries out respectively X-ray diffraction and characterizes, and corresponding XRD spectra as shown in Figure 7.36.9 °, 65.2 ° and 31.2 ° respectively corresponding 311,440 and 220 crystal faces of three main peaks wherein are all with spinel-type Co
3O
4(JCPDS card No.78-1970) is consistent for the standard spectrogram, and 26 ° of small peaks of locating correspond to the diffraction maximum of the amorphous carbon that forms after the surfactant carbonization.Co is described thus
3O
4-C composite mainly contains spinel-type Co
3O
4And amorphous carbon.
Adopt the blue electric CT 2001A type battery test system in Wuhan respectively simulated battery C1-C4 to be carried out electrochemical property test, discharging and recharging the cut-ff voltage scope is 3.0-0.02V, and charging and discharging currents density is 0.1mA/cm
2, test result as shown in Figure 8.
Under different current densities, simulated battery C1 is carried out the high rate performance test, test result is as shown in Figure 9.
The result shows, by described Co provided by the invention
3O
4-C composite has the specific capacity height, the characteristics of good cycling stability and good rate capability.
Test case 3
Adopt the respectively Co to preparing among the embodiment 1-6 of specific surface-pore size distribution determining instrument (AS-1C-VP, U.S. Kang Ta company)
3O
4-C composite A 1-A6 carries out the experiment of nitrogen adsorption/desorption, and is concrete, makes described Co
3O
4The preliminary treatment 10 hours under 200 ℃, vacuum condition of-C composite records specific area by BET specific area method of testing then.Test result is as shown in table 1 below.
Table 1
| Co 3O 4-C composite | A1 | A2 | A3 | A4 | A5 | A6 |
| Specific area (m 2/ g) | 89.38 | 96.26 | 98.12 | 93.68 | 79.54 | 77.68 |
Data by table 1 can be found out, Co of the present invention
3O
4-C composite has bigger specific area.
Adopt the blue electric CT 2001A type battery test system in Wuhan respectively simulated battery C1-C6 to be carried out electrochemical property test, concrete, the blanking voltage scope is 3.0-0.02V, (charging and discharging currents density is about 0.1mA/cm in the 0.2C multiplying power discharging and recharging
2) under, detect described Co
3O
4The specific discharge capacity of-C composite A 1-A6; The blanking voltage scope is 3.0-0.02V, (charging and discharging currents density is about 2.5mA/cm in the 5C multiplying power discharging and recharging
2) under, detect described Co
3O
4The high-rate discharge ability of-C composite A 1-A6.Test result is as shown in table 2 below.
Table 2
Data by table 2 can be found out, Co according to the present invention
3O
4-C composite has high specific discharge capacity and high rate performance.
Test case 5
Adopt the blue electric CT 2001A type battery test system in Wuhan that lithium ion battery D1 is carried out electrochemical property test, discharging and recharging the cut-ff voltage scope is 4.5～1.7V, and charging and discharging currents density is 0.1mA/cm
2, test result as shown in figure 10.
Shown by Figure 10 test result, by described Co provided by the invention
3O
4The lithium ion battery that-C composite is made has height ratio capacity and high cyclical stability, test data and simulated battery data consistent.
Above embodiment only is used to describe preferred implementation of the present invention; but; the present invention is not limited to the detail in the above-mentioned execution mode; in technical conceive scope of the present invention; can carry out multiple simple variant to technical scheme of the present invention, these simple variant all belong to protection scope of the present invention.
Claims (17)
1. Co
3O
4-C composite, described composite contains spinel-type Co
3O
4And amorphous carbon, it is characterized in that described composite is graininess, and each particle comprises the hemisphere layer of a plurality of stacked expansion.
2. composite according to claim 1 wherein, in each described particle, has part to separate between the hemisphere layer of adjacent two described expansion, and the part of preferred 20-95% is separated, and more preferably the part of 50-80% is separated.
3. composite material according to claim 1 and 2, wherein, the number of plies of the hemisphere layer that launches in each described particle is 3-20, is preferably 10-15; The radial dimension of each described particle is the 3-15 micron, is preferably the 5-8 micron.
4. composite according to claim 1 and 2, wherein, take the gross mass of described composite as benchmark, spinel-type Co
3O
4Content be 95.1-98.2 quality %, be preferably 96.5-97 quality %; The content of amorphous carbon is 1.8-4.9 quality %, is preferably 3-3.5 quality %.
5. composite material according to claim 1 and 2, wherein, the specific area of described composite material is 77.5-100m
2/ g is preferably 85-100m
2/ g.
6. Co
3O
4-C composite manufacture method, this method may further comprise the steps:
(1) add alkali lye in emulsion oil-in-water, leave standstill successively then and centrifugal treating, described emulsion oil-in-water contains water soluble cobaltous salt, surfactant, cosurfactant, organic solvent and water;
(2) sediment that obtains after the centrifugal treating is coated on the base material;
(3) under inert atmosphere, make the sediment that is coated on the base material under first temperature, carry out the roasting first time;
(4) containing under the atmosphere of oxygen, making the sediment through the roasting first time under second temperature, carry out the roasting second time, obtaining covering the Co on the substrate material surface
3O
4-C composite;
Described first temperature can make described surfactant charing, and described second temperature can make the hydroxide of cobalt be oxidized to Co
3O
4And can not make the carbonizing production oxidation of described surfactant.
7. method according to claim 6, wherein, in step (1), described emulsion oil-in-water makes by cobalt saline solution, surfactant, cosurfactant and organic solvent are mixed, the speed that stirs is 100-1000 rev/min, and the time of stirring is 15-30 minute.
8. method according to claim 6, wherein, in step (1), described alkali lye joins in the described emulsion oil-in-water gradually, and the pH value of the emulsion oil-in-water behind the feasible adding of the adding speed of the described alkali lye alkali lye is maintained 9-11.
9. method according to claim 6, wherein, in step (1), the described time of leaving standstill is 4-10 hour; The condition of described centrifugal treating comprises: rotating speed is 2000-9000 rev/min, and the processing time is 1-10 minute.
10. method according to claim 6, wherein, in described emulsion oil-in-water, the volume ratio of described surfactant and described cosurfactant is 2-4: 1, the concentration of described water soluble cobaltous salt is 0.04-0.5mol/L, described surfactant is 2-4 with described volume of organic solvent ratio: 1, and water is 20-60 with described volume of organic solvent ratio: 1.
11. according to any described method among the claim 6-10, wherein, described surfactant is one or more in TritonX, dodecyl sodium sulfate, polyethylene glycol and the polyacrylic acid, is preferably TritonX; Described cosurfactant is one or more in n-butanol, isobutanol, isopropyl alcohol and the normal propyl alcohol, is preferably n-butanol; Described organic solvent is one or more in cyclohexane, benzene, styrene and the toluene, is preferably cyclohexane; Described water soluble cobaltous salt is one or more in cobalt nitrate, cobalt chloride, cobalt acetate, cobalt oxalate and the cobaltous sulfate, is preferably cobalt nitrate; Described alkali lye is one or more in ammonia spirit, potassium hydroxide aqueous solution, sodium hydrate aqueous solution and the aqueous solution of urea, is preferably ammoniacal liquor.
12. method according to claim 6, wherein, in step (2), described base material is Copper Foil, aluminium foil, stainless steel substrates or silicon chip.
13. method according to claim 6, wherein, in step (2), the described sedimentary amount that applies on the described base material is 15-60mg/cm
2
14. method according to claim 6, wherein, in step (3), the condition of the described roasting first time comprises: described first temperature is 350-450 ℃, and roasting time is 0.5-3 hour; In step (4), the condition of the described roasting second time comprises: described second temperature is 200-300 ℃, and roasting time is 0.5-3 hour.
15. the Co by the described method preparation of any one among the claim 6-14
3O
4-C composite.
16. a lithium ion battery negative, this lithium ion battery negative comprise collector and the negative material that covers on this collection liquid surface, it is characterized in that described negative material is the described Co of any one in claim 1-5 and 15
3O
4-C composite.
17. lithium ion battery, this lithium ion battery comprises battery container, electrode group and electrolyte, and electrode group and electrolyte are sealed in the battery container, and the electrode group comprises positive pole, barrier film and negative pole, it is characterized in that described negative pole is the described lithium ion battery negative of claim 16.
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| CN111359625A (en) * | 2020-04-23 | 2020-07-03 | 中国科学院地球环境研究所 | Carbon composite nano cobaltosic oxide-based formaldehyde normal-temperature catalyst and preparation method thereof |
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