CN105070888B - Ternary material of CNT graphene complex three-dimensional network structure cladding of coupling and preparation method thereof - Google Patents
Ternary material of CNT graphene complex three-dimensional network structure cladding of coupling and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to battery material technical field, particularly discloses ternary material of CNT graphene complex three-dimensional network structure cladding of a kind of coupling and preparation method thereof.The ternary material of the CNT graphene complex three-dimensional network structure cladding of the coupling, using nickel-cobalt-manganese ternary material, CNT and graphene as raw material, it is characterised in that：Using polyvinylpyrrolidone as dispersant, graphene and CNT are connected using silane coupler from by way of combining liquid phase simultaneously, form it into three-dimensional net structure, then after the CNT graphene composite material of coupling and nickel-cobalt-manganese ternary material being uniformly dispersed by physical method, the surface of nickel-cobalt-manganese ternary material is coated on, is placed in the product that sintering is uniformly coated in inert atmosphere.The product of the present invention has high specific discharge capacity captain's cycle life, and its preparation process is simple, is easy to large-scale production.
Description
（One）Technical field
The present invention relates to battery material technical field, CNT-graphene complex three-dimensional of more particularly to a kind of coupling
Ternary material of network structure cladding and preparation method thereof.
（Two）Background technology
With the development of science and technology the field such as electronic product, electric automobile, Medical Devices and space flight and aviation is to energy storage device
It is required that increasingly improve, energy density height, small volume, the lithium ion battery that has extended cycle life are widely applied.Meeting to pacify
Entirely, after environmental protection, cost, life-span etc., crucial performance indications are high-energy-density and repid discharge ability.For example, beautiful, day
Reach 300Wh/kg Deng energy density requirement of the state to lithium-ion-power cell of future generation, be the LiFePO currently developed4
More than 2 times of electrokinetic cell energy density.Therefore the approach of raising lithium ion battery energy density is mainly：First, positive pole is improved
The specific capacity of material；2nd, the electrode potential of positive electrode is improved so as to improving the operating voltage of battery.It is commercialized at present
Positive electrode LiCoO2、LiMn2O4、LiFePO4, its actual specific capacity highest only has 145mAh/g, and it is high, safe cost to be present
The shortcomings of property is poor, uniformity difference.And nickle cobalt lithium manganate composite capacity is high, actual specific capacity up to 200mAh/g and with into
The advantages that this is relatively low, stability is good, safe, in recent years, gradually instead of part cobalt acid lithium.Wherein, Co can be effectively
Reduce cation mixing, the layer structure of stabilizing material, Ni can improve the capacity of material, Mn can not only reduce material into
This, and the safety and stability of material can be improved.Therefore the excellent cycle performance of the materials show, obtains market
Accreditation.
Cobalt nickel lithium manganate ternary material is since 2001 begin one's study, with its stable specific capacity, preferable security
With structural stability and moderate cost, rapidly by industrialization, particularly when cobalt price is higher, its cost advantage is more bright
It is aobvious.Ternary material is mainly used in the cylinder and rectangular lithium ion battery of box hat or aluminum hull at present.For application, nickel
It is less demanding to energy density that cobalt manganic acid lithium ternary material is applied to portable power source, feature phone and electric bicycle etc. mostly
Field.In the field such as smart mobile phone and tablet personal computer, presently mainly cobalt acid lithium, it is primarily due to ternary material and compacting is present
Density is low, is easy to the shortcomings of inflatable, its application in power-type lithium ion battery, high voltage system lithium battery at present also in
Development.And the coming five years nickel-cobalt lithium manganate material is the main flow of research and development and industrialization, and it is most potential as next
For power-type lithium ion battery and use for electronic products high-energy-density small-scale lithium ion cell positive electrode.And densification and height
The cobalt nickel lithium manganate ternary material of voltage is relatively low to environment and equipment requirement, and it is smaller to prepare difficulty of processing, uniformity and reliable
Property it is high, and the target of high-energy-density can be reached.
Through studying for a long period of time, though the material is with good chemical property, and it is still problematic to need solution badly for practicality
Certainly.Ternary material easily causes oxygen loss and phase transformation, causes larger first all irreversible losses after first week takes off lithium.In addition, the material
Conductance is low, and big high rate performance is bad.And cation mixing easily occurs in lithium layer for ternary material, in wide discharge voltage model
The interior side reaction for easily making organic electrolyte strong with electrode material generation is enclosed, increases impedance of the battery in charge and discharge process,
Reduce the chemical property of material.
In order to improve the performance of ternary material, though scientific research personnel from the preparation method of material, or the doping of material
A large amount of sturdy research work have all been done in modified or coating modification.The preparation method of material includes high temperature solid-state method, coprecipitated
Shallow lake method, sol-gal process, hydro-thermal method, spray drying process, control crystalline deposit method etc., in addition, can be made by appropriate doping
The structure of ternary material is more stable, reduces ion mixing effect, and can effectively improve the cycle performance of material.The member of doping
Element will can enter the position for wanting substitution ion, and the radius of Doped ions and the ion to be substituted will have similar radius to ensure
The stabilization of material structure, the ion of doping will have good stability in itself, and discord electrolyte reacts, and oxygen will not occur
Change reduction reaction.Doping is divided into anion doped and cation doping.The doped chemical of cation have Ti, Mg, Al, Cr, Zr and
Rare earth element etc., anion doped is mostly halogen, and it is F to adulterate more-Ion.Secondly, surface is carried out to ternary material
Cladding and the big focus studied at present, it refers to the Surface coating thin film material in material, and film substrate is typically not
Change the structure of material in itself, the conductance of material can be improved by cladding, erosion of the electrolyte to material is reduced, so as to change
The cycle performance and high rate performance of kind material.Surface coated means include oxide cladding, Phosphate coating, fluoride bag
Cover, anode material for lithium-ion batteries coats and carbon coating.Here emphasis carbon coating, Guo R et al. is using with low cracking temperature
The PVA of degree successfully synthesizes the nickel-cobalt-manganese ternary material of carbon coating, and its carbon content is optimized, when carbon content is
During 1.0wt%, the material that cycle performance and the high rate performance ratio of material are uncoated improves a lot.Sinha N.N etc. use one
Footwork and the submicron order nickel-cobalt-manganese ternary material precursor that carbon coating has been synthesized using glucose as carbon source, and in 900 DEG C of synthesis
6h has obtained nickle cobalt lithium manganate crystal.Research its carbon coating layer of surface has excellent cycle performance, and greatly suppresses height
Capacity attenuation during multiplying power discharging.Rao etc. prepares LiCo by microemulsion method1/3Ni1/3Mn1/3O2, then be prepared for by ball milling
LiCo1/3Ni1/3Mn1/3O2Graphene complex.With the first all specific discharge capacities of 1C, 5C discharge and recharge be respectively 172mAh/g and
153mAh/g, the performance of material are improved.Chinese Academy of Sciences's process graphene and ternary material are carried out by the method for ball milling
Compound, during 3C discharge and recharges, capability retention is 82% after circulation 20 weeks.
Carbon coating effect above is not it is obvious that graphene coated preferably improves material than traditional carbon coating
Chemical property.And the exploitation of the ternary material of graphene/carbon nano-tube cladding contributes in battery energy storage and power electric car neck
Domain obtains important breakthrough.
（Three）The content of the invention
The present invention is in order to make up the deficiencies in the prior art, there is provided a kind of lithium ion diffusion coefficient and electronics for improving material
Electrical conductivity, suppress CNT-graphene complex three-dimensional network structure of the material in the coupling of the capacity attenuation of high-multiplying power discharge
Ternary material of cladding and preparation method thereof.
The present invention is achieved through the following technical solutions：
The ternary material of the CNT of a kind of coupling-graphene complex three-dimensional network structure cladding, with nickel-cobalt-manganese ternary
Material, CNT and graphene are raw material, it is characterised in that：Using polyvinylpyrrolidone as dispersant, while pass through liquid phase
Graphene and CNT are connected using silane coupler from the mode of combination, form it into three-dimensional net structure, then will
After the carbon nanometer tube-graphene composite material and nickel-cobalt-manganese ternary material of coupling are uniformly dispersed by physical method, nickel is coated on
The surface of cobalt-manganese ternary material, it is placed in the product that sintering is uniformly coated in inert atmosphere.
Electrical conductivity is low small with lithium ion diffusion coefficient in existing nickel-cobalt-manganese ternary material in order to overcome by the present invention, and battery is again
The problem of rate charge-discharge performance difference, the technical scheme used is the strong electron conduction of graphene, reduces electrode active material
Interface resistance between electrolyte, is advantageous to Li+Conduction；The graphene sheet layer of two-dimensional structure is coated on electrode material table
Face, it is suppressed that the dissolving and phase transformation of metal oxide, maintain the Stability Analysis of Structures of electrode material in charge and discharge process.One-dimentional structure
CNT provide excellent transmission channel for the conduction of lithium ion and electronics, and electrical conductivity is higher.In order to make full use of
The performance of graphene and CNT uniqueness, the tridimensional network that both carbon are combined into by this project using silane coupler
To coat ternary material, using the distinctive small-size effect of the composite carbon and skin effect, and the model ylid bloom action power of itself
To control ternary material particle in nanoscale, and the contact between active material can be increased, improve the conductance of overall electrode,
Be advantageous to lithium ion and electronics fast storage in the material and transmission, reduce polarization process, improve cycle performance.
The preparation method of ternary material of the present invention, comprises the following steps：
（1）Under normal temperature, by weight than the graphene dispersion for 0.1-1% in organic solvent, ultrasonic disperse 40min is obtained
Graphene dispersing solution, then think to add weight in solution than the CNT for 0.2-0.8% and a small amount of silane coupler,
The graphene-carbon nano tube dispersion liquid that stirring 30min is coupled；
（2）Under normal temperature, by weight than being dissolved in for 2% polyvinylpyrrolidone in deionized water, physical mixed is uniformly dispersed
Afterwards, nickel-cobalt-manganese ternary material is added, stirring 40min obtains ternary material dispersion liquid；
（3）The graphene-carbon nano tube dispersion liquid of above-mentioned coupling is imported in ternary material dispersion liquid, after disperseing 10min,
It is placed in thermostatic mixer, is stirred at 60-80 DEG C and evaporate solvent；
（4）After the product grinding after evaporation solvent, the sieving of 400 mesh, it is subsequently placed in protective atmosphere at 250-500 DEG C
3-6h is sintered, product is obtained after grinding sieving.
Its preferable technical scheme is：
The specific surface area of the graphene is 500-1000 m2/ g, its nanometer sheet number of plies are 2-6 layers, and its electric conductivity is preferable；
The specific surface area of CNT is 40-70 m2/ g, its particle diameter are 60-100nm, and its conductance is higher；Graphene and CNT
Mass ratio be 1:1-5.
The step（1）In, the weight ratio of graphene is 0.1-0.5%, and the weight ratio of CNT is 0.2-0.5%.
Step（1）In, organic solvent is ethanol, isopropanol, n-butanol, glycerine, methanol, 1-METHYLPYRROLIDONE and third
One or both of ketone.
Step（2）In, physical admixture is stirring, the one or more in ultrasonic and high speed shearing emulsification.
Step（4）In, protective atmosphere is nitrogen atmosphere or argon gas atmosphere.
Compared with prior art, the present invention obtains the graphite with tridimensional network using the method for liquid phase self assembly
Alkene-carbon nano tube composite carbon material, and it is coated on the surface of nickel-cobalt-manganese ternary material.On the one hand, conductive agent graphene-carbon
The addition of nanometer tube composite materials, the interface resistance between electrode active material and electrolyte is reduced, is advantageous to Li+Biography
Lead, improve the electric conductivity and lithium ion diffusion coefficient of material；On the other hand, the graphene-carbon nano tube of tridimensional network
The surface of ternary material is equably coated, reuniting certainly for material can be suppressed, and the contact between active material can be increased, is ensured
Electronic and ionic binary channels is unimpeded in cyclic process, improves the conductance of overall electrode, reduces the polarization in battery charge and discharge process
Journey, improve the cycle performance of battery.
Compound 0.4% graphene-carbon nano tube complex carbon material, first all discharge capacities reach 172.5mAh/ under 0.2C multiplying powers
First all discharge capacities are 158.2mAh/g, 15mAh/g higher than raw material or so under g, 1C multiplying power, and after circulating 110 weeks, capacity is kept
Rate is up to 87.2%, and under 8C circulations, capacity is still up to 129.5mAh/g, improves the cyclical stability of material and forthright again
Energy.
In addition, the addition of CNT, reduces production cost, make the new material in battery energy storage and power electric car field
Expansion application there is great theory directive significance and engineering application value.This method technique is simple and convenient to operate, and is easy to advise
Modelling produces.
The invention belongs to field of electrochemical batteries, described product has high specific discharge capacity captain's cycle life, its
Preparation process is simple, is easy to large-scale production.
（Four）Brief description of the drawings
The present invention is further illustrated below in conjunction with the accompanying drawings.
Fig. 1 be compound different covering amounts graphene-carbon nano tube after prepared complex ternary material high rate performance
Figure；
Fig. 2 be compound different proportion graphene-carbon nano tube after prepared complex ternary material high rate performance figure；
Fig. 3 is compound different proportion graphene-carbon nano tube and the material of pure graphene and the multiplying power discharging of raw material
Comparison diagram；
Fig. 4 is the material and raw material of compound different proportion graphene-carbon nano tube and pure graphene under 1C multiplying powers
Cycle life figure；
Fig. 5 is the scanning electron microscope (SEM) photograph of material after composite graphite alkene-CNT；
Fig. 6 is the XRD of graphene-carbon nano tube complex ternary material and raw material.
（Five）Embodiment
With reference to embodiment, the invention will be further described.Following examples are used to illustrate the present invention, but are not used to
Limit the scope of the present invention.
Embodiment 1：
（1）By 0.1g graphene dispersion in organic solvent, ultrasonic disperse 40min obtains graphene dispersing solution, then
Weight is added into solution than the CNT for 0.1g, and a small amount of silane coupler, 30min is stirred, is coupled
Graphene-carbon nano tube dispersion liquid；Under normal temperature, 1.0g polyvinylpyrrolidones are dissolved in 50.0g deionized waters, physical mixed
After being uniformly dispersed, 50.0g nickel-cobalt-manganese ternary materials are added, 40min is stirred, obtains ternary material dispersion liquid；
（2）The graphene-carbon nano tube dispersion liquid of coupling is poured into ternary material dispersion liquid, after disperseing 10min, is placed in
In thermostatic mixer, 80 DEG C of stirrings evaporate solvent；
（3）After above-mentioned product is ground, the sieving of 400 mesh, after be placed in nitrogen atmosphere and sinter, be warming up to 300 with 2 DEG C/min
DEG C, and it is incubated 5 hours.After natural cooling, 400 mesh sieve the CNT-graphene complex three-dimensional net being coupled after grinding
The ternary material of network structure cladding.
The electrochemistry of constant current charge-discharge test anode material of lithium battery is carried out using the blue electric CT2001A discharge and recharges instrument in Wuhan
Energy.Experimental cell is carried out in the glove box full of argon gas, and the electrolyte used is LiPF6/EC+DMC+EMC（Volume ratio 1：
1：1）, barrier film is the type barrier films of Celgard 2400；It is metal lithium sheet to electrode.The chemical property of material uses CR2032 type knobs
Button battery is investigated.
PVDF is dissolved in NMP, prepares the PVDF solution that mass fraction is 4%, stir be placed in baking oven 80 DEG C it is dry
It is standby after dry 12h.The product and nickel cobalt manganese raw material used, conductive carbon black Super of gained after being coated respectively in embodiment 1
P, conductive carbon black KS and above-mentioned PVDF solution are according to mass ratio 88:3:3:6 mixing, after being sufficiently stirred, slurries are uniformly coated on
On aluminium foil, rolled after 120 DEG C of vacuum drying 12h with double roller tablet press machine.A diameter of 10mm electrode slice is made of sheet-punching machine, then
Electrode slice is weighed, 120 DEG C of vacuum drying 5h, is positioned in glove box, CR2032 type button cells is assembled into, by button cell
Charge-discharge test is carried out after placing 8h.
Cycle performance curve：At 25 ± 1 DEG C, voltage range is 3.0-4.3 V (Vs Li+/ Li) under to battery carry out
Constant current charge-discharge test.Gs-CNTs in Fig. 4（11）@LNCM curves is after the composite graphite alkene of embodiment 1-carbon nano-tube materials
Cycle life figure under 1C multiplying powers, the last fortnight are to carry out activation process to material under 0.2C constant current charge-discharges.At 0.2C times
During rate discharge and recharge, the first discharge specific capacity of the product of embodiment 1 is 172.5mAh/g, and the first discharge specific capacity of raw material is
168.5mAh/g.Therefore under 0.2C discharge and recharges, first discharge specific capacity differs only by 4mAh/g, DeGrain.But in 1C multiplying powers
Under discharge and recharge, it is 158.2mAh/g that the product of embodiment 1, which obtains first discharge specific capacity, and circulate 100 weeks after, capability retention is
87.2%.And the first discharge specific capacity of raw material is 142mAh/g, after circulating 100 weeks, capability retention 81.5%.I.e. in 1C
During discharge and recharge, after circulating 100 weeks, the specific discharge capacity of the material prepared by embodiment 1 is higher than the specific discharge capacity of raw material
22mAh/g.After illustrating cladding, the lithium ion activity that the product of embodiment 1 obtains anode portion is higher, for raw material,
The insertion abjection of lithium ion is easier.As can be seen here, nickel cobalt manganese anode material is modified using graphene-carbon nano tube
Afterwards, the polarization process of inside battery is reduced, improves the cyclical stability of material.
High rate performance curve：In 3.0-4.3V（Vs Li+/Li）In voltage range, constant current charge-discharge survey is carried out to battery
Examination.Gs-CNTs in Fig. 3（11）@LNCM curves are the high rate performance figure of material after the composite graphite alkene of embodiment 1-CNT.
Under 0.5C and 1C multiplying power discharging electric currents, two Battery pack specific discharge capacities all relatively, respectively 165.5 and 161.2mAh/
G, two groups of gap is obvious when with 2C and 5C current discharges, it is compound after the specific discharge capacity of material be respectively
149.9 and 129.5mAh/g, and during 8C current discharges, the specific discharge capacity of material remains to reach 99.4mAh/g.Without compound
The material of graphene-carbon nano tube, during with 5C and 8C current discharges, the specific discharge capacity of material only have respectively 96.3mAh/g and
52.1mAh/g, show that the high-rate discharge ability of material after composite graphite alkene significantly improves, enhance nickel-cobalt-manganese ternary material
Antidamping ability.
After composite graphite alkene-CNT, the scanning electron microscope (SEM) photograph of material can clearly be seen as shown in figure 5, after compound
Go out, graphene and CNT form a tridimensional network, are wrapped in the centre of nickel-cobalt-manganese ternary material granule, suppress
Material from reuniting, and add the contact between active material.
After composite graphite alkene-CNT, the XRD of material is as shown in Figure 6.After cladding, do not have to the structure of material
Too big influence,（003）Peak and（104）The intensity ratio at peakI (003)/I (104)Respectively 1.199,1.241, the frequent quilt of this ratio
For weighing the lithium nickel mixing degree of nickel-cobalt-manganese ternary material, whenI (003)/I (104)During more than 1.2, material has relatively low lithium nickel
Mixing degree, it can be seen that after cladding, be more beneficial for the reversible deintercalation of lithium ion.
Embodiment 2：
Present embodiment graphene-carbon nano tube composite material selected in step 1 as different from Example 1
Ratio.Specific preparation method is as follows：
By 0.067g graphene dispersion in organic solvent, ultrasonic disperse 40min obtain graphene dispersing solution then to
Weight is added in solution than the CNT for 0.133g, and a small amount of silane coupler, 30min is stirred, is coupled
Graphene-carbon nano tube dispersion liquid；Under normal temperature, 1.0g polyvinylpyrrolidones are dissolved in 50.0g deionized waters, physical mixed
After being uniformly dispersed, 50.0g nickel-cobalt-manganese ternary materials are added, 40min is stirred, obtains ternary material dispersion liquid；
Other steps are same as Example 1, obtain the positive electrode in the present invention, i.e. Gs-CNTs（12）@LNCM.
Embodiment 3：
Present embodiment graphene-carbon nano tube composite material selected in step 1 as different from Example 1
Ratio.Specific preparation method is as follows：
By 0.05g graphene dispersion in organic solvent, then the scattered 40min of sound obtains graphene dispersing solution to solution
Middle addition weight stirs 30min, the graphite being coupled than the CNT for 0.15g, and a small amount of silane coupler
Alkene-carbon nano tube dispersion liquid；Under normal temperature, 1.0g polyvinylpyrrolidones are dissolved in 50.0g deionized waters, physical mixed is disperseed
After uniformly, 50.0g nickel-cobalt-manganese ternary materials are added, 40min is stirred, obtains ternary material dispersion liquid；
Other steps are same as Example 1, obtain the positive electrode in the present invention, i.e. Gs-CNTs（13）@LNCM.
Embodiment 4：
Present embodiment graphene-carbon nano tube composite material selected in step 1 as different from Example 1
Ratio.Specific preparation method is as follows：
By 0.04g graphene dispersion in organic solvent, then the scattered 40min of sound obtains graphene dispersing solution to solution
Middle addition weight stirs 30min, the graphite being coupled than the CNT for 0.16g, and a small amount of silane coupler
Alkene-carbon nano tube dispersion liquid；Under normal temperature, 1.0g polyvinylpyrrolidones are dissolved in 50.0g deionized waters, physical mixed is disperseed
After uniformly, 50.0g nickel-cobalt-manganese ternary materials are added, 40min is stirred, obtains ternary material dispersion liquid；
Other steps are same as Example 1, obtain the positive electrode in the present invention, i.e. Gs-CNTs（14）@LNCM.
Embodiment 5：
Present embodiment graphene-carbon nano tube composite material selected in step 1 as different from Example 1
Ratio.Specific preparation method is as follows：
By 0.033g graphene dispersion in organic solvent, then the scattered 40min of sound obtains graphene dispersing solution to molten
Weight is added in liquid than the CNT for 0.166g, and a small amount of silane coupler, stirs 30min, the stone being coupled
Black alkene-carbon nano tube dispersion liquid；Under normal temperature, 1.0g polyvinylpyrrolidones are dissolved in 50.0g deionized waters, physical mixed point
After dissipating uniformly, 50.0g nickel-cobalt-manganese ternary materials are added, 40min is stirred, obtains ternary material dispersion liquid；
Other steps are same as Example 1, obtain the positive electrode in the present invention, i.e. Gs-CNTs（15）@LNCM.
As the compound nickel of graphene-carbon nano tube of the coupling prepared by embodiment 2, embodiment 3, embodiment 4, embodiment 5
The high rate performance figure of cobalt-manganese ternary material material measured during discharge and recharge under 0.2C-2C multiplying powers is as shown in Figure 2.
Embodiment 6：
（1）By 0.067 g graphene dispersion in organic solvent, ultrasonic disperse 40min obtains graphene dispersing solution, so
Weight is added in backward solution than the CNT for 0.133 g, and a small amount of silane coupler, 30min is stirred, obtains
The graphene-carbon nano tube dispersion liquid of coupling；Under normal temperature, 1.0g polyvinylpyrrolidones are dissolved in 50.0g deionized waters, thing
After reason mixing is uniformly dispersed, 50.0g nickel-cobalt-manganese ternary materials are added, 40min is stirred, obtains ternary material dispersion liquid；
（2）The graphene-carbon nano tube dispersion liquid of coupling is poured into ternary material dispersion liquid, after disperseing 10min, is placed in
In thermostatic mixer, 60 DEG C of low temperature stirrings evaporate solvent；
（3）After above-mentioned product is ground, the sieving of 400 mesh, after be placed in nitrogen atmosphere and sinter, be warming up to 300 with 2 DEG C/min
DEG C, and it is incubated 5 hours.After natural cooling, 400 mesh sieve the CNT-graphene complex three-dimensional net being coupled after grinding
The ternary material of network structure cladding.
Embodiment 7：
The temperature of present embodiment evaporation solvent selected in step 2 as different from Example 6.Specific preparation side
Method is as follows：
By the sample of gained in step 1, the graphene-carbon nano tube dispersion liquid that will be coupled, which pours into ternary material, to be disperseed
In liquid, after disperseing 10min, it is placed in thermostatic mixer, 70 DEG C of low temperature stirrings evaporate solvent；
Other steps are same as Example 6, obtain the positive electrode in the present invention, i.e. Gs-CNTs（12）@LNCM.
Embodiment 8：
（1）By 0.067 g graphene dispersion in organic solvent, ultrasonic disperse 40min obtains graphene dispersing solution, so
Weight is added in backward solution than the CNT for 0.133 g, and a small amount of silane coupler, 30min is stirred, obtains
The graphene-carbon nano tube dispersion liquid of coupling；Under normal temperature, 1.0g polyvinylpyrrolidones are dissolved in 50.0g deionized waters, thing
After reason mixing is uniformly dispersed, 50.0g nickel-cobalt-manganese ternary materials are added, 40min is stirred, obtains ternary material dispersion liquid；
（2）The graphene-carbon nano tube dispersion liquid of coupling is poured into ternary material dispersion liquid, after disperseing 10min, is placed in
In thermostatic mixer, 80 DEG C of low temperature stirrings evaporate solvent；
（3）After above-mentioned product is ground, the sieving of 400 mesh, after be placed in nitrogen atmosphere and sinter, be warming up to 250 with 2 DEG C/min
DEG C, and it is incubated 5 hours.After natural cooling, 400 mesh sieve the CNT-graphene complex three-dimensional net being coupled after grinding
The ternary material of network structure cladding.
Embodiment 9：
The calcining heat of present embodiment step 3 kind material as different from Example 8.Specific preparation method is as follows：
After the product grinding of gained in step 2, the sieving of 400 mesh, after be placed in nitrogen atmosphere and sinter, with 2 DEG C/min liters
Temperature is incubated 5 hours to 400 DEG C.After natural cooling, the 400 mesh CNT-graphene being coupled that sieves is compound after grinding
The ternary material of three-dimensional net structure cladding.
Other are same as Example 8, obtain the positive electrode in the present invention.
Embodiment 10：
Present embodiment as different from Example 8 in step 3 material calcining heat.Specific preparation method is as follows：
After the product grinding of gained in step 2, the sieving of 400 mesh, after be placed in nitrogen atmosphere and sinter, with 2 DEG C/min liters
Temperature is incubated 5 hours to 500 DEG C.After natural cooling, the 400 mesh CNT-graphene being coupled that sieves is compound after grinding
The ternary material of three-dimensional net structure cladding.
Other are same as Example 8, obtain the positive electrode in the present invention.
Embodiment 11：
（1）By 0.067 g graphene dispersion in organic solvent, ultrasonic disperse 40min obtains graphene dispersing solution, so
Weight is added in backward solution than the CNT for 0.133 g, and a small amount of silane coupler, 30min is stirred, obtains
The graphene-carbon nano tube dispersion liquid of coupling；Under normal temperature, 1.0g polyvinylpyrrolidones are dissolved in 50.0g deionized waters, thing
After reason mixing is uniformly dispersed, 50.0g nickel-cobalt-manganese ternary materials are added, 40min is stirred, obtains ternary material dispersion liquid；
（2）The graphene-carbon nano tube dispersion liquid of coupling is poured into ternary material dispersion liquid, after disperseing 10min, is placed in
In thermostatic mixer, 80 DEG C of low temperature stirrings evaporate solvent；
（3）After above-mentioned product is ground, the sieving of 400 mesh, after be placed in nitrogen atmosphere and sinter, be warming up to 300 with 2 DEG C/min
DEG C, and it is incubated 3 hours.After natural cooling, 400 mesh sieve the CNT-graphene complex three-dimensional net being coupled after grinding
The ternary material of network structure cladding.
Embodiment 12：
Present embodiment as different from Example 11 in step 3 material calcination time.Specific preparation method is as follows：
After the product grinding of gained in step 2, after the sieving of 400 mesh, it is placed in nitrogen atmosphere and sinters, with 2 DEG C/min
300 DEG C are warming up to, and is incubated 4 hours.After natural cooling, the 400 mesh CNT-graphene being coupled that sieves is multiple after grinding
Close the ternary material of three-dimensional net structure cladding.
Other steps are identical with embodiment 11, obtain the positive electrode in the present invention.
Embodiment 13：
Present embodiment as different from Example 11 in step 3 material calcination time.Specific preparation method is as follows：
After the product grinding of gained in step 2, after the sieving of 400 mesh, it is placed in nitrogen atmosphere and sinters, with 2 DEG C/min
300 DEG C are warming up to, and is incubated 6 hours.After natural cooling, the 400 mesh CNT-graphene being coupled that sieves is multiple after grinding
Close the ternary material of three-dimensional net structure cladding.
Other steps are identical with embodiment 11, obtain the positive electrode in the present invention.
Embodiment 14：
Present embodiment as different from Example 1 in step 1 graphene-carbon nano tube covering amount.In embodiment 1
The covering amount of graphene-carbon nano tube is 0.4%.
By 0.05g graphene dispersion in organic solvent, ultrasonic disperse 40min obtains graphene dispersing solution, Ran Houxiang
Weight is added in solution than the CNT for 0.05g, and a small amount of silane coupler, 30min is stirred, is coupled
Graphene-carbon nano tube dispersion liquid；Under normal temperature, 1.0g polyvinylpyrrolidones are dissolved in 50.0g deionized waters, physical mixed
After being uniformly dispersed, 50.0g nickel-cobalt-manganese ternary materials are added, 40min is stirred, obtains ternary material dispersion liquid；
Other steps are same as Example 1, obtain the positive electrode in the present invention.The covering amount of graphene-carbon nano tube
For 0.2%.
Embodiment 15：
Present embodiment as different from Example 1 in step 1 graphene-carbon nano tube covering amount.In embodiment 1
The covering amount of graphene-carbon nano tube is 0.4%.
By 0.075g graphene dispersion in organic solvent, ultrasonic disperse 40min obtains graphene dispersing solution, Ran Houxiang
Weight is added in solution than the CNT for 0.075g, and a small amount of silane coupler, 30min is stirred, is coupled
Graphene-carbon nano tube dispersion liquid；Under normal temperature, 1.0g polyvinylpyrrolidones are dissolved in 50.0g deionized waters, physical mixed
After being uniformly dispersed, 50.0g nickel-cobalt-manganese ternary materials are added, 40min is stirred, obtains ternary material dispersion liquid；
Other steps are same as Example 1, obtain the positive electrode in the present invention.The covering amount of graphene-carbon nano tube
For 0.3%.
Embodiment 16：
Present embodiment as different from Example 1 in step 1 graphene-carbon nano tube covering amount.In embodiment 1
The covering amount of graphene-carbon nano tube is 0.4%.
By 0.25g graphene dispersion in organic solvent, ultrasonic disperse 40min obtains graphene dispersing solution, Ran Houxiang
Weight is added in solution than the CNT for 0.25g, and a small amount of silane coupler, 30min is stirred, is coupled
Graphene-carbon nano tube dispersion liquid；Under normal temperature, 1.0g polyvinylpyrrolidones are dissolved in 50.0g deionized waters, physical mixed
After being uniformly dispersed, 50.0g nickel-cobalt-manganese ternary materials are added, 40min is stirred, obtains ternary material dispersion liquid；
Other steps are same as Example 1, obtain the positive electrode in the present invention.The covering amount of graphene-carbon nano tube
For 1.0%.
It is compound as the graphene-carbon nano tube of the coupling prepared by embodiment 1, embodiment 13, embodiment 14, embodiment 15
The high rate performance figure of nickel-cobalt-manganese ternary material is as shown in Figure 1.
Although above in conjunction with figure, invention has been described, and the invention is not limited in above-mentioned specific embodiment party
Formula, above-mentioned embodiment is only schematical, rather than restricted, and one of ordinary skill in the art is in this hair
Under bright enlightenment, without deviating from the spirit of the invention, above-mentioned embodiment can also be changed and changed, these
Belong within the protection of the present invention.
Claims (7)
- A kind of 1. ternary material of the CNT of coupling-graphene complex three-dimensional network structure cladding, with nickel-cobalt-manganese ternary material Material, CNT and graphene are raw material, it is characterised in that：Using polyvinylpyrrolidone as dispersant, while by liquid phase certainly The mode of combination connects graphene and CNT using silane coupler, forms it into three-dimensional net structure, then will be even After the carbon nanometer tube-graphene composite material and nickel-cobalt-manganese ternary material of connection are uniformly dispersed by physical method, nickel cobalt is coated on The surface of manganese ternary material, it is placed in the product that sintering is uniformly coated in inert atmosphere；The preparation method of the product is specifically： （1）Under normal temperature, by weight than the graphene dispersion for 0.1-1% in organic solvent, ultrasonic disperse 40min obtains graphene point Dispersion liquid, weight is then added into solution than the CNT for 0.2-0.8% and a small amount of silane coupler, stirs 30min The graphene-carbon nano tube dispersion liquid being coupled；（2）Under normal temperature, by weight than being dissolved in for 2% polyvinylpyrrolidone In ionized water, after physical mixed is uniformly dispersed, nickel-cobalt-manganese ternary material is added, stirring 40min obtains ternary material dispersion liquid； （3）The graphene-carbon nano tube dispersion liquid of above-mentioned coupling is imported in ternary material dispersion liquid, after disperseing 10min, is placed in constant temperature Stirred in agitator, at 60-80 DEG C and evaporate solvent；（4）After the product grinding after evaporation solvent, the sieving of 400 mesh, then put 3-6h is sintered at 250-500 DEG C in protective atmosphere, product is obtained after grinding sieving.
- A kind of 2. ternary material of the CNT of the coupling described in claim 1-graphene complex three-dimensional network structure cladding Preparation method, it is characterized in that, comprise the following steps：（1）Under normal temperature, by weight than the graphene dispersion for 0.1-1% organic In solvent, ultrasonic disperse 40min obtains graphene dispersing solution, and weight is then added into solution than the carbon nanometer for 0.2-0.8% Pipe and a small amount of silane coupler, the graphene-carbon nano tube dispersion liquid that stirring 30min is coupled；（2）, will under normal temperature Weight for 2% polyvinylpyrrolidone than being dissolved in deionized water, after physical mixed is uniformly dispersed, adds nickel-cobalt-manganese ternary material Material, stirring 40min obtain ternary material dispersion liquid；（3）The graphene-carbon nano tube dispersion liquid of above-mentioned coupling is imported into ternary material Expect in dispersion liquid, after disperseing 10min, be placed in thermostatic mixer, stirred at 60-80 DEG C and evaporate solvent；（4）By evaporation solvent After product grinding afterwards, the sieving of 400 mesh, it is subsequently placed in protective atmosphere at 250-500 DEG C and sinters 3-6h, after grinding sieving To product.
- 3. preparation method according to claim 2, it is characterised in that：The specific surface area of the graphene is 500-1000 m2/ g, its nanometer sheet number of plies are 2-6 layers；The specific surface area of CNT is 40-70 m2/ g, its particle diameter are 60-100nm；Graphite The mass ratio of alkene and CNT is 1:1-5.
- 4. preparation method according to claim 2, it is characterised in that：Step（1）In, the weight ratio of graphene is 0.1- 0.5%, the weight ratio of CNT is 0.2-0.5%.
- 5. preparation method according to claim 2, it is characterised in that：Step（1）In, organic solvent be ethanol, isopropanol, One or both of n-butanol, glycerine, methanol, 1-METHYLPYRROLIDONE and acetone.
- 6. preparation method according to claim 2, it is characterised in that：Step（2）In, physical admixture is stirring, surpassed One or more in sound and high speed shearing emulsification.
- 7. preparation method according to claim 2, it is characterised in that：Step（4）In, protective atmosphere is nitrogen atmosphere or argon Gas atmosphere.
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| PCT/CN2016/085323 WO2017005078A1 (en) | 2015-07-09 | 2016-06-08 | Ternary material coated with three-dimensional network structure of coupled carbon nanotube-graphene composite and manufacturing method thereof |
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