CN105070888A - Coupled carbon nano tube-graphene composite three-dimensional network structure-coated ternary material and preparation method thereof - Google Patents
Coupled carbon nano tube-graphene composite three-dimensional network structure-coated ternary material and preparation method thereof Download PDFInfo
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Abstract
The invention relates to the technical field of battery materials, in particular to a coupled carbon nano tube-graphene composite three-dimensional network structure-coated ternary material and a preparation method thereof. According to the coupled carbon nano tube-graphene composite three-dimensional network structure-coated ternary material, a nickel-cobalt-manganese ternary material, carbon nano tubes and graphene are taken as raw materials; and the ternary material is characterized by being prepared by the following steps: with polyvinyl pyrrolidone as a dispersing agent, through a liquid-phase self-assembling method, simultaneously connecting the graphene and the carbon nano tubes with a silane coupling agent to form a three-dimensional network structure; and evenly dispersing the coupled carbon nano tube-graphene composite material and the nickel-cobalt-manganese ternary material through a physical method, coating the surface of the nickel-cobalt-manganese ternary material, and sintering the nickel-cobalt-manganese ternary material in an inert atmosphere, so as to obtain the evenly coated product. The product provided by the invention has the advantages of high specific discharge capacity, long cycle life and simplicity in preparation process; and large-scale production is easy to realize.
Description
(1) technical field
The present invention relates to battery material technical field, ternary material that the carbon nano-tube-Graphene complex three-dimensional network configuration of particularly a kind of coupling is coated and preparation method thereof.
(2) background technology
Along with the progress of science and technology, the fields such as electronic product, electric automobile, Medical Devices and space flight and aviation are improved day by day to the requirement of energy storage device, and energy density is high, volume is little, the lithium ion battery that has extended cycle life is widely applied.Meeting after in safety, environmental protection, cost, life-span etc., crucial performance index are high-energy-density and repid discharge ability.Such as, beautiful, Deng state requires to reach 300Wh/kg to the energy density of lithium-ion-power cell of future generation, is the LiFePO developed at present
4more than 2 times of electrokinetic cell energy density.Therefore the approach of lithium ion battery energy density is improved mainly: the specific capacity one, improving positive electrode; Two, the electrode potential of positive electrode is improved thus the operating voltage of raising battery.Current business-like positive electrode LiCoO
2, LiMn
2o
4, LiFePO
4, its actual specific capacity is the highest only 145mAh/g, and there is the shortcomings such as cost is high, poor stability, consistency difference.And nickle cobalt lithium manganate composite material capacity is high, actual specific capacity can reach 200mAh/g and have that cost is lower, good stability, fail safe advantages of higher, in recent years, instead of part cobalt acid lithium gradually.Wherein, Co can reduce cation mixing effectively, the layer structure of stabilizing material, and Ni can improve the capacity of material, and Mn not only can reduce the cost of material, and can improve the safety and stability of material.Therefore the excellent cycle performance of this materials show, obtains the accreditation in market.
Cobalt nickel lithium manganate ternary material is since calendar year 2001 begins one's study, and with its stable specific capacity, fail safe preferably and structural stability and moderate cost, rapidly by industrialization, particularly when cobalt price is higher, its cost advantage is more obvious.Current ternary material is mainly used in the cylindrical with rectangular lithium ion battery of box hat or aluminum hull.With regard to application, cobalt nickel lithium manganate ternary material is applied to portable power source, feature phone and electric bicycle etc. mostly to the less demanding field of energy density.In the field such as smart mobile phone and panel computer, mainly cobalt acid lithium at present, mainly because ternary material exist compacted density low, be easy to the shortcomings such as inflatable, its application in power-type lithium ion battery, high voltage system lithium battery is also in development at present.And the coming five years nickel-cobalt lithium manganate material is the main flow of research and development and industrialization, being also that most is potential becomes power-type lithium ion battery of future generation and use for electronic products high-energy-density small-scale lithium ion cell positive electrode.And the cobalt nickel lithium manganate ternary material of densification and Towards Higher Voltage to environment and equipment requirement lower, prepare difficulty of processing less, consistency and reliability high, and the target of high-energy-density can be reached.
Through studying for a long period of time, though this material has good chemical property, with regard to practicality, problem is still had to need solution badly.Ternary material, after first week takes off lithium, easily causes oxygen loss and phase transformation, causes larger head week irreversible loss.In addition, this materials conductive rate is low, and large high rate performance is not good.And ternary material easily cation mixing occurs in lithium layer, in wide discharge voltage range, easily make organic electrolyte and electrode material that strong side reaction occurs, increase the impedance of battery in charge and discharge process, reduce the chemical property of material.
In order to improve the performance of ternary material, no matter scientific research personnel is from the preparation method of material, or a large amount of sturdy research work is all done in the doping vario-property of material or coating modification.The preparation method of material comprises high temperature solid-state method, coprecipitation, sol-gal process, hydro thermal method, spray drying process, the crystallization control precipitation method etc., in addition, the structure of ternary material can be made more stable by suitable doping, reduce ion mixing effect, and effectively can improve the cycle performance of material.The element of doping is wanted to enter the position of wanting substitution ion, radius and the ion that will replace of Doped ions will have close radius to ensure the stable of material structure, the ion of doping itself will have good stability, and discord electrolyte reacts, and redox reaction can not occur.Doping is divided into anion doped and cation doping.Cationic doped chemical has Ti, Mg, Al, Cr, Zr and rare earth element etc., mostly anion dopedly is halogen, and adulterating more is F
-ion.Secondly, the large focus that Surface coating is also research is at present carried out to ternary material, it refers to the Surface coating thin film material at material, film substrate does not generally change the structure of material itself, by the coated conductance that can improve material, reduce electrolyte to the erosion of material, thus improve cycle performance and the high rate performance of material.Surface coated means comprise that oxide is coated, Phosphate coating, fluoride are coated, anode material for lithium-ion batteries is coated and carbon is coated.Here emphasis carbon is coated, the people such as GuoR adopt the PVA with low cracking temperature to successfully synthesize the coated nickel-cobalt-manganese ternary material of carbon, and its carbon content is optimized, when carbon content is 1.0wt%, the cycle performance of material and high rate performance improve a lot than not coated material.SinhaN.N etc. adopt one-step method and are that carbon source has synthesized the coated submicron order nickel-cobalt-manganese ternary material precursor of carbon with glucose, and obtain nickle cobalt lithium manganate crystal in 900 DEG C of synthesis 6h.Its carbon coating layer of research surface has excellent cycle performance, and capacity attenuation when greatly inhibit high-multiplying power discharge.Rao etc. prepare LiCo by microemulsion method
1/3ni
1/3mn
1/3o
2, then prepared LiCo by ball milling
1/3ni
1/3mn
1/3o
2graphene complex.Be respectively 172mAh/g and 153mAh/g with the first all specific discharge capacities of 1C, 5C discharge and recharge, the performance of material is improved.Chinese Academy of Sciences's process by the method for ball milling, Graphene and ternary material are carried out compound, during 3C discharge and recharge, the capability retention after 20 weeks that circulates is 82%.
Above carbon covered effect is not clearly, the graphene coated chemical property that better improve material more coated than traditional carbon.And the exploitation of the coated ternary material of graphene/carbon nano-tube contributes to obtaining important breakthrough at battery energy storage and power electric car field.
(3) summary of the invention
The present invention in order to make up the deficiencies in the prior art, provide a kind of improve material lithium ion diffusion coefficient and electronic conductivity, suppression material is at coated ternary material of the carbon nano-tube-Graphene complex three-dimensional network configuration of the coupling of the capacity attenuation of high-multiplying power discharge and preparation method thereof.
The present invention is achieved through the following technical solutions:
The ternary material that a kind of carbon nano-tube-Graphene complex three-dimensional network configuration of coupling is coated, with nickel-cobalt-manganese ternary material, carbon nano-tube and Graphene are raw material, it is characterized in that: take polyvinylpyrrolidone as dispersant, adopt silane coupler to connect Graphene and carbon nano-tube by liquid phase from the mode of combination simultaneously, it is made to form three-dimensional net structure, then after the carbon nanometer tube-graphene composite material of coupling and nickel-cobalt-manganese ternary material being uniformly dispersed by physical method, be coated on the surface of nickel-cobalt-manganese ternary material, be placed in inert atmosphere sintering and obtain evenly coated product.
In order to overcome, conductivity in existing nickel-cobalt-manganese ternary material is low and lithium ion diffusion coefficient is little in the present invention, the problem of battery rate charge-discharge poor performance, the technical scheme of employing is, the electron conduction that Graphene is strong, decrease the interface resistance between electrode active material and electrolyte, be conducive to Li
+conduction; The graphene sheet layer of two-dimensional structure is coated on electrode material surface, inhibits dissolving and the phase transformation of metal oxide, maintains the Stability Analysis of Structures of electrode material in charge and discharge process.The carbon nano-tube of one-dimentional structure is that the conduction of lithium ion and electronics provides excellent transmission channel, and conductivity is higher.In order to make full use of the performance of Graphene and carbon nano-tube uniqueness, the tridimensional network that this project utilizes silane coupler to be combined into by these two kinds of carbon carrys out coated ternary material, utilize the distinctive small-size effect of this composite carbon and skin effect, and the model ylid bloom action power of self controls ternary material particle in nanoscale, and the contact that can increase between active material, improve the conductance of overall electrode, be conducive 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 steps:
(1) under normal temperature, by weight ratio be the graphene dispersion of 0.1-1% in organic solvent, ultrasonic disperse 40min obtains graphene dispersing solution, then think to add in solution carbon nano-tube and a small amount of silane coupler that weight ratio is 0.2-0.8%, stir the graphene-carbon nano tube dispersion liquid that 30min obtains coupling;
(2) under normal temperature, be that the polyvinylpyrrolidone of 2% is dissolved in deionized water by weight ratio, after physical mixed is uniformly dispersed, add nickel-cobalt-manganese ternary material, stir 40min and obtain ternary material dispersion liquid;
(3) the graphene-carbon nano tube dispersion liquid of above-mentioned coupling is imported in ternary material dispersion liquid, after dispersion 10min, be placed in thermostatic mixer, at 60-80 DEG C, stir solvent evaporated;
(4) by after the product grinding after evaporating solvent, 400 orders sieve, and be then placed in protective atmosphere and sinter 3-6h at 250-500 DEG C, and grinding obtains product after sieving.
Its preferred technical scheme is:
The specific area of described Graphene is 500-1000m
2/ g, its nanometer sheet number of plies is 2-6 layer, and its conductivity is better; The specific area of carbon nano-tube is 40-70m
2/ g, its particle diameter is 60-100nm, and its conductance is higher; The mass ratio of Graphene and carbon nano-tube is 1:1-5.
In described step (1), the weight ratio of Graphene is 0.1-0.5%, and the weight ratio of carbon nano-tube is 0.2-0.5%.
In step (1), organic solvent is one or both in ethanol, isopropyl alcohol, n-butanol, glycerol, methyl alcohol, 1-METHYLPYRROLIDONE and acetone.
In step (2), physical admixture be stir, one or more in ultrasonic and high speed shear emulsification.
In step (4), protective atmosphere is nitrogen atmosphere or argon gas atmosphere.
Compared with prior art, the present invention adopts the method for liquid phase self assembly to obtain to have the graphene-carbon nano tube complex carbon material of tridimensional network, and is coated on the surface of nickel-cobalt-manganese ternary material.On the one hand, the interpolation of conductive agent graphene-carbon nano tube composite material, reduces the interface resistance between electrode active material and electrolyte, is conducive to Li
+conduction, improve conductivity and the lithium ion diffusion coefficient of material; On the other hand, the surface of the graphene-carbon nano tube of tridimensional network coated ternary material equably, certainly reuniting of material can be suppressed, and the contact that can increase between active material, ensure that in cyclic process, electronic and ionic binary channels is unimpeded, improve the conductance of overall electrode, reduce the polarization process in battery charge and discharge process, improve the cycle performance of battery.
The graphene-carbon nano tube complex carbon material of compound 0.4%, under 0.2C multiplying power, first all discharge capacities reach 172.5mAh/g, under 1C multiplying power, first all discharge capacities are 158.2mAh/g, than raw material height about 15mAh/g, after circulating 110 weeks, capability retention reaches 87.2%, and under 8C circulation, capacity, still up to 129.5mAh/g, improves cyclical stability and the high rate performance of material.
In addition, the interpolation of carbon nano-tube, reduces production cost, makes this new material have great theory directive significance and engineer applied value at the expansive approach in battery energy storage and power electric car field.The method technique is simple, easy to operate, is easy to large-scale production.
The invention belongs to field of electrochemical batteries, described product has high specific discharge capacity captain cycle life, and its preparation process is simple, is easy to large-scale production.
(4) accompanying drawing explanation
Below in conjunction with accompanying drawing, the present invention is further illustrated.
Fig. 1 is the high rate performance figure of complex ternary material prepared after the graphene-carbon nano tube of the different covering amount of compound;
Fig. 2 is the high rate performance figure of complex ternary material prepared after the graphene-carbon nano tube of compound different proportion;
Fig. 3 is the material of compound different proportion graphene-carbon nano tube and pure Graphene and raw-material multiplying power discharging comparison diagram;
Fig. 4 is material and the cycle life figure of raw material under 1C multiplying power of compound different proportion graphene-carbon nano tube and pure Graphene;
Fig. 5 is after composite graphite alkene-carbon nano-tube, the scanning electron microscope (SEM) photograph of material;
Fig. 6 is that graphene-carbon nano tube complex ternary material and raw-material XRD scheme.
(5) embodiment
Below in conjunction with embodiment, the invention will be further described.Following examples for illustration of the present invention, but are not used for limiting the scope of the invention.
Embodiment 1:
(1) by the graphene dispersion of 0.1g in organic solvent, ultrasonic disperse 40min obtains graphene dispersing solution, then in solution, adds the carbon nano-tube that weight ratio is 0.1g, and a small amount of silane coupler, stir 30min, obtain the graphene-carbon nano tube dispersion liquid of coupling; Under normal temperature, 1.0g polyvinylpyrrolidone is dissolved in 50.0g deionized water, after physical mixed is uniformly dispersed, adds 50.0g nickel-cobalt-manganese ternary material, stir 40min, obtain ternary material dispersion liquid;
(2) pour in ternary material dispersion liquid by the graphene-carbon nano tube dispersion liquid of coupling, after dispersion 10min, be placed in thermostatic mixer, 80 DEG C are stirred solvent evaporated;
(3) by after above-mentioned product grinding, 400 orders sieve, and are placed in nitrogen atmosphere and sinter, and are warming up to 300 DEG C with 2 DEG C/min, and are incubated 5 hours.Naturally, after cooling, after grinding, 400 orders sieve the coated ternary material of carbon nano-tube-Graphene complex three-dimensional network configuration of obtaining coupling.
The blue electric CT2001A discharge and recharge instrument in Wuhan is adopted to carry out the chemical property of constant current charge-discharge test anode material of lithium battery.Experimental cell carries out in the glove box being full of argon gas, and the electrolyte of use is LiPF
6/ EC+DMC+EMC(volume ratio 1:1:1), barrier film is Celgard2400 type barrier film; Be metal lithium sheet to electrode.The chemical property of material adopts CR2032 type button cell to investigate.
Be dissolved in by PVDF in NMP, preparation quality mark is the PVDF solution of 4%, stirs and for subsequent use after being placed in baking oven 80 DEG C of dry 12h.Respectively the product of rear gained coated in embodiment 1 and nickel cobalt manganese raw material used, conductive carbon black SuperP, conductive carbon black KS and above-mentioned PVDF solution are mixed according to mass ratio 88:3:3:6, after abundant stirring, slurries are uniformly coated on aluminium foil, roll with two roller tablet press after 120 DEG C of vacuumize 12h.Make with sheet-punching machine the electrode slice that diameter is 10mm, then weighed by electrode slice, 120 DEG C of vacuumize 5h, are positioned in glove box, are assembled into CR2032 type button cell, carry out charge-discharge test after button cell being placed 8h.
Cycle performance curve: at 25 ± 1 DEG C, voltage range is 3.0-4.3V (VsLi
+/ Li) under constant current charge-discharge test is carried out to battery.Gs-CNTs(11 in Fig. 4)LNCM curve is cycle life figure after embodiment 1 composite graphite alkene-carbon nano-tube material under 1C multiplying power, the last fortnight carries out activation processing to material under 0.2C constant current charge-discharge.When 0.2C rate charge-discharge, the first discharge specific capacity of embodiment 1 product is 172.5mAh/g, and raw-material first discharge specific capacity is 168.5mAh/g.Therefore under 0.2C discharge and recharge, first discharge specific capacity only differs 4mAh/g, DeGrain.But under 1C rate charge-discharge, it is 158.2mAh/g that embodiment 1 product obtains first discharge specific capacity, and circulation is after 100 weeks, and capability retention is 87.2%.And raw-material first discharge specific capacity is 142mAh/g, after circulating 100 weeks, capability retention is 81.5%.Namely, when 1C discharge and recharge, after circulating 100 weeks, the specific discharge capacity of the material prepared by embodiment 1 is than raw-material specific discharge capacity height 22mAh/g.Illustrate coated after, the lithium ion activity that embodiment 1 product obtains anode portion is higher, and for raw material, it is easier that the embedding of lithium ion is deviate from.As can be seen here, after using graphene-carbon nano tube to modify nickel cobalt manganese anode material, reduce the polarization process of inside battery, improve the cyclical stability of material.
High rate performance curve: at 3.0-4.3V(VsLi+/Li) in voltage range, constant current charge-discharge test is carried out to battery.Gs-CNTs(11 in Fig. 3)LNCM curve is after embodiment 1 composite graphite alkene-carbon nano-tube, the high rate performance figure of material.Under 0.5C and 1C multiplying power discharging electric current, two Battery pack specific discharge capacities all relatively, be respectively 165.5 and 161.2mAh/g, when obvious with the gap of two groups during 2C and 5C current discharge, the specific discharge capacity of the material after compound is respectively 149.9 and 129.5mAh/g, and during 8C current discharge, the specific discharge capacity of material still can reach 99.4mAh/g.And there is no the material of composite graphite alkene-carbon nano-tube, during with 5C and 8C current discharge, the specific discharge capacity of material only has 96.3mAh/g and 52.1mAh/g respectively, and after showing composite graphite alkene, the high-rate discharge ability of material significantly improves, and enhances the antidamping ability of nickel-cobalt-manganese ternary material.
After composite graphite alkene-carbon nano-tube, the scanning electron microscope (SEM) photograph of material as shown in Figure 5, after compound, can find out clearly, Graphene and carbon nano-tube define a tridimensional network, be wrapped in the centre of nickel-cobalt-manganese ternary material granule, inhibit certainly reuniting of material, and add the contact between active material.
After composite graphite alkene-carbon nano-tube, the XRD figure of material as shown in Figure 6.After coated, the structure of material is not had much affect, the intensity ratio at (003) peak and (104) peak
i (003)/
i (104)be respectively 1.199,1.241, this ratio is often used to the lithium nickel mixing degree weighing nickel-cobalt-manganese ternary material, when
i (003)/
i (104)when being greater than 1.2, material has lower lithium nickel mixing degree, can find out, after coated, is more conducive to the reversible deintercalation of lithium ion.
Embodiment 2:
The ratio of the graphene-carbon nano tube composite material that present embodiment is selected in step one as different from Example 1.Concrete preparation method is as follows:
By the graphene dispersion of 0.067g in organic solvent, ultrasonic disperse 40min obtains graphene dispersing solution and then in solution, adds the carbon nano-tube that weight ratio is 0.133g, and a small amount of silane coupler, stir 30min, obtain the graphene-carbon nano tube dispersion liquid of coupling; Under normal temperature, 1.0g polyvinylpyrrolidone is dissolved in 50.0g deionized water, after physical mixed is uniformly dispersed, adds 50.0g nickel-cobalt-manganese ternary material, stir 40min, obtain ternary material dispersion liquid;
Other steps are identical with embodiment 1, obtain the positive electrode in the present invention, i.e. Gs-CNTs(12)LNCM.
Embodiment 3:
The ratio of the graphene-carbon nano tube composite material that present embodiment is selected in step one as different from Example 1.Concrete preparation method is as follows:
By the graphene dispersion of 0.05g in organic solvent, sound dispersion 40min obtains graphene dispersing solution and then in solution, adds the carbon nano-tube that weight ratio is 0.15g, and a small amount of silane coupler, stir 30min, obtain the graphene-carbon nano tube dispersion liquid of coupling; Under normal temperature, 1.0g polyvinylpyrrolidone is dissolved in 50.0g deionized water, after physical mixed is uniformly dispersed, adds 50.0g nickel-cobalt-manganese ternary material, stir 40min, obtain ternary material dispersion liquid;
Other steps are identical with embodiment 1, obtain the positive electrode in the present invention, i.e. Gs-CNTs(13)LNCM.
Embodiment 4:
The ratio of the graphene-carbon nano tube composite material that present embodiment is selected in step one as different from Example 1.Concrete preparation method is as follows:
By the graphene dispersion of 0.04g in organic solvent, sound dispersion 40min obtains graphene dispersing solution and then in solution, adds the carbon nano-tube that weight ratio is 0.16g, and a small amount of silane coupler, stir 30min, obtain the graphene-carbon nano tube dispersion liquid of coupling; Under normal temperature, 1.0g polyvinylpyrrolidone is dissolved in 50.0g deionized water, after physical mixed is uniformly dispersed, adds 50.0g nickel-cobalt-manganese ternary material, stir 40min, obtain ternary material dispersion liquid;
Other steps are identical with embodiment 1, obtain the positive electrode in the present invention, i.e. Gs-CNTs(14)LNCM.
Embodiment 5:
The ratio of the graphene-carbon nano tube composite material that present embodiment is selected in step one as different from Example 1.Concrete preparation method is as follows:
By the graphene dispersion of 0.033g in organic solvent, sound dispersion 40min obtains graphene dispersing solution and then in solution, adds the carbon nano-tube that weight ratio is 0.166g, and a small amount of silane coupler, stir 30min, obtain the graphene-carbon nano tube dispersion liquid of coupling; Under normal temperature, 1.0g polyvinylpyrrolidone is dissolved in 50.0g deionized water, after physical mixed is uniformly dispersed, adds 50.0g nickel-cobalt-manganese ternary material, stir 40min, obtain ternary material dispersion liquid;
Other steps are identical with embodiment 1, obtain the positive electrode in the present invention, i.e. Gs-CNTs(15)LNCM.
The high rate performance figure of the material that the graphene-carbon nano tube compound nickel-cobalt-manganese ternary material of the coupling prepared by embodiment 2, embodiment 3, embodiment 4, embodiment 5 is measured during discharge and recharge under 0.2C-2C multiplying power as shown in Figure 2.
Embodiment 6:
(1) by the graphene dispersion of 0.067g in organic solvent, ultrasonic disperse 40min obtains graphene dispersing solution, then in solution, adds the carbon nano-tube that weight ratio is 0.133g, and a small amount of silane coupler, stir 30min, obtain the graphene-carbon nano tube dispersion liquid of coupling; Under normal temperature, 1.0g polyvinylpyrrolidone is dissolved in 50.0g deionized water, after physical mixed is uniformly dispersed, adds 50.0g nickel-cobalt-manganese ternary material, stir 40min, obtain ternary material dispersion liquid;
(2) pour in ternary material dispersion liquid by the graphene-carbon nano tube dispersion liquid of coupling, after dispersion 10min, be placed in thermostatic mixer, 60 DEG C of low temperature stir solvent evaporated;
(3) by after above-mentioned product grinding, 400 orders sieve, and are placed in nitrogen atmosphere and sinter, and are warming up to 300 DEG C with 2 DEG C/min, and are incubated 5 hours.Naturally, after cooling, after grinding, 400 orders sieve the coated ternary material of carbon nano-tube-Graphene complex three-dimensional network configuration of obtaining coupling.
Embodiment 7:
The temperature of the evaporating solvent that present embodiment is selected in step 2 as different from Example 6.Concrete preparation method is as follows:
By the sample of gained in step one, the graphene-carbon nano tube dispersion liquid by coupling is poured in ternary material dispersion liquid, after dispersion 10min, is placed in thermostatic mixer, and 70 DEG C of low temperature stir solvent evaporated;
Other steps are identical with embodiment 6, obtain the positive electrode in the present invention, i.e. Gs-CNTs(12)LNCM.
Embodiment 8:
(1) by the graphene dispersion of 0.067g in organic solvent, ultrasonic disperse 40min obtains graphene dispersing solution, then in solution, adds the carbon nano-tube that weight ratio is 0.133g, and a small amount of silane coupler, stir 30min, obtain the graphene-carbon nano tube dispersion liquid of coupling; Under normal temperature, 1.0g polyvinylpyrrolidone is dissolved in 50.0g deionized water, after physical mixed is uniformly dispersed, adds 50.0g nickel-cobalt-manganese ternary material, stir 40min, obtain ternary material dispersion liquid;
(2) pour in ternary material dispersion liquid by the graphene-carbon nano tube dispersion liquid of coupling, after dispersion 10min, be placed in thermostatic mixer, 80 DEG C of low temperature stir solvent evaporated;
(3) by after above-mentioned product grinding, 400 orders sieve, and are placed in nitrogen atmosphere and sinter, and are warming up to 250 DEG C with 2 DEG C/min, and are incubated 5 hours.Naturally, after cooling, after grinding, 400 orders sieve the coated ternary material of carbon nano-tube-Graphene complex three-dimensional network configuration of obtaining coupling.
Embodiment 9:
The calcining heat of present embodiment step 3 kind material as different from Example 8.Concrete preparation method is as follows:
After being ground by the product of gained in step 2,400 orders sieve, and are placed in nitrogen atmosphere and sinter, and are warming up to 400 DEG C with 2 DEG C/min, and are incubated 5 hours.Naturally, after cooling, after grinding, 400 orders sieve the coated ternary material of carbon nano-tube-Graphene complex three-dimensional network configuration of obtaining coupling.
Other are identical with embodiment 8, obtain the positive electrode in the present invention.
Embodiment 10:
Present embodiment is the calcining heat of material in step 3 as different from Example 8.Concrete preparation method is as follows:
After being ground by the product of gained in step 2,400 orders sieve, and are placed in nitrogen atmosphere and sinter, and are warming up to 500 DEG C with 2 DEG C/min, and are incubated 5 hours.Naturally, after cooling, after grinding, 400 orders sieve the coated ternary material of carbon nano-tube-Graphene complex three-dimensional network configuration of obtaining coupling.
Other are identical with embodiment 8, obtain the positive electrode in the present invention.
Embodiment 11:
(1) by the graphene dispersion of 0.067g in organic solvent, ultrasonic disperse 40min obtains graphene dispersing solution, then in solution, adds the carbon nano-tube that weight ratio is 0.133g, and a small amount of silane coupler, stir 30min, obtain the graphene-carbon nano tube dispersion liquid of coupling; Under normal temperature, 1.0g polyvinylpyrrolidone is dissolved in 50.0g deionized water, after physical mixed is uniformly dispersed, adds 50.0g nickel-cobalt-manganese ternary material, stir 40min, obtain ternary material dispersion liquid;
(2) pour in ternary material dispersion liquid by the graphene-carbon nano tube dispersion liquid of coupling, after dispersion 10min, be placed in thermostatic mixer, 80 DEG C of low temperature stir solvent evaporated;
(3) by after above-mentioned product grinding, 400 orders sieve, and are placed in nitrogen atmosphere and sinter, and are warming up to 300 DEG C with 2 DEG C/min, and are incubated 3 hours.Naturally, after cooling, after grinding, 400 orders sieve the coated ternary material of carbon nano-tube-Graphene complex three-dimensional network configuration of obtaining coupling.
Embodiment 12:
Present embodiment is the calcination time of material in step 3 as different from Example 11.Concrete preparation method is as follows:
After the product of gained in step 2 is ground, after 400 orders sieve, be placed in nitrogen atmosphere and sinter, be warming up to 300 DEG C with 2 DEG C/min, and be incubated 4 hours.Naturally, after cooling, after grinding, 400 orders sieve the coated ternary material of carbon nano-tube-Graphene complex three-dimensional network configuration of obtaining coupling.
Other steps are identical with embodiment 11, obtain the positive electrode in the present invention.
Embodiment 13:
Present embodiment is the calcination time of material in step 3 as different from Example 11.Concrete preparation method is as follows:
After the product of gained in step 2 is ground, after 400 orders sieve, be placed in nitrogen atmosphere and sinter, be warming up to 300 DEG C with 2 DEG C/min, and be incubated 6 hours.Naturally, after cooling, after grinding, 400 orders sieve the coated ternary material of carbon nano-tube-Graphene complex three-dimensional network configuration of obtaining coupling.
Other steps are identical with embodiment 11, obtain the positive electrode in the present invention.
Embodiment 14:
Present embodiment is the covering amount of graphene-carbon nano tube in step one as different from Example 1.In embodiment 1, the covering amount of graphene-carbon nano tube is 0.4%.
By the graphene dispersion of 0.05g in organic solvent, ultrasonic disperse 40min obtains graphene dispersing solution, then in solution, adds the carbon nano-tube that weight ratio is 0.05g, and a small amount of silane coupler, stir 30min, obtain the graphene-carbon nano tube dispersion liquid of coupling; Under normal temperature, 1.0g polyvinylpyrrolidone is dissolved in 50.0g deionized water, after physical mixed is uniformly dispersed, adds 50.0g nickel-cobalt-manganese ternary material, stir 40min, obtain ternary material dispersion liquid;
Other steps are identical with embodiment 1, obtain the positive electrode in the present invention.The covering amount of graphene-carbon nano tube is 0.2%.
Embodiment 15:
Present embodiment is the covering amount of graphene-carbon nano tube in step one as different from Example 1.In embodiment 1, the covering amount of graphene-carbon nano tube is 0.4%.
By the graphene dispersion of 0.075g in organic solvent, ultrasonic disperse 40min obtains graphene dispersing solution, then in solution, adds the carbon nano-tube that weight ratio is 0.075g, and a small amount of silane coupler, stir 30min, obtain the graphene-carbon nano tube dispersion liquid of coupling; Under normal temperature, 1.0g polyvinylpyrrolidone is dissolved in 50.0g deionized water, after physical mixed is uniformly dispersed, adds 50.0g nickel-cobalt-manganese ternary material, stir 40min, obtain ternary material dispersion liquid;
Other steps are identical with embodiment 1, obtain the positive electrode in the present invention.The covering amount of graphene-carbon nano tube is 0.3%.
Embodiment 16:
Present embodiment is the covering amount of graphene-carbon nano tube in step one as different from Example 1.In embodiment 1, the covering amount of graphene-carbon nano tube is 0.4%.
By the graphene dispersion of 0.25g in organic solvent, ultrasonic disperse 40min obtains graphene dispersing solution, then in solution, adds the carbon nano-tube that weight ratio is 0.25g, and a small amount of silane coupler, stir 30min, obtain the graphene-carbon nano tube dispersion liquid of coupling; Under normal temperature, 1.0g polyvinylpyrrolidone is dissolved in 50.0g deionized water, after physical mixed is uniformly dispersed, adds 50.0g nickel-cobalt-manganese ternary material, stir 40min, obtain ternary material dispersion liquid;
Other steps are identical with embodiment 1, obtain the positive electrode in the present invention.The covering amount of graphene-carbon nano tube is 1.0%.
The high rate performance figure of the graphene-carbon nano tube compound nickel-cobalt-manganese ternary material of the coupling prepared by embodiment 1, embodiment 13, embodiment 14, embodiment 15 as shown in Figure 1.
Although invention has been described for composition graphs above; but the present invention is not limited to above-mentioned embodiment; above-mentioned embodiment is only schematic; instead of it is restrictive; those of ordinary skill in the art is under enlightenment of the present invention; when not departing from present inventive concept, can also change above-mentioned execution mode and revise, these all belong within protection of the present invention.
Claims (7)
1. the ternary material that the carbon nano-tube-Graphene complex three-dimensional network configuration of a coupling is coated, with nickel-cobalt-manganese ternary material, carbon nano-tube and Graphene are raw material, it is characterized in that: take polyvinylpyrrolidone as dispersant, adopt silane coupler to connect Graphene and carbon nano-tube by liquid phase from the mode of combination simultaneously, it is made to form three-dimensional net structure, then after the carbon nanometer tube-graphene composite material of coupling and nickel-cobalt-manganese ternary material being uniformly dispersed by physical method, be coated on the surface of nickel-cobalt-manganese ternary material, be placed in inert atmosphere sintering and obtain evenly coated product.
2. the preparation method of ternary material according to claim 1, it is characterized by, under comprising the steps: (1) normal temperature, by weight ratio be the graphene dispersion of 0.1-1% in organic solvent, ultrasonic disperse 40min obtains graphene dispersing solution, then think to add in solution carbon nano-tube and a small amount of silane coupler that weight ratio is 0.2-0.8%, stir the graphene-carbon nano tube dispersion liquid that 30min obtains coupling; (2) under normal temperature, be that the polyvinylpyrrolidone of 2% is dissolved in deionized water by weight ratio, after physical mixed is uniformly dispersed, add nickel-cobalt-manganese ternary material, stir 40min and obtain ternary material dispersion liquid; (3) the graphene-carbon nano tube dispersion liquid of above-mentioned coupling is imported in ternary material dispersion liquid, after dispersion 10min, be placed in thermostatic mixer, at 60-80 DEG C, stir solvent evaporated; (4) by after the product grinding after evaporating solvent, 400 orders sieve, and be then placed in protective atmosphere and sinter 3-6h at 250-500 DEG C, and grinding obtains product after sieving.
3. the preparation method of ternary material according to claim 2, is characterized in that: the specific area of described Graphene is 500-1000m
2/ g, its nanometer sheet number of plies is 2-6 layer; The specific area of carbon nano-tube is 40-70m
2/ g, its particle diameter is 60-100nm; The mass ratio of Graphene and carbon nano-tube is 1:1-5.
4. the preparation method of ternary material according to claim 2, is characterized in that: in described step (1), and the weight ratio of Graphene is 0.1-0.5%, and the weight ratio of carbon nano-tube is 0.2-0.5%.
5. revive according to claim 2 preparation method of ternary material of Sohu, it is characterized in that: in step (1), and organic solvent is one or both in ethanol, isopropyl alcohol, n-butanol, glycerol, methyl alcohol, 1-METHYLPYRROLIDONE and acetone.
6. the preparation method of ternary material according to claim 2, is characterized in that: in step (2), physical admixture be stir, one or more in ultrasonic and high speed shear emulsification.
7. the preparation method of ternary material according to claim 1, is characterized in that: in step (4), and protective atmosphere is nitrogen atmosphere or argon gas atmosphere.
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| CN114512662A (en) * | 2022-03-02 | 2022-05-17 | 芜湖天弋能源科技有限公司 | Lithium ion battery anode material and preparation method thereof, and lithium ion battery |
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| CN105070888B (en) | 2017-11-14 |
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