CN105206839B - A kind of modified carbon nano-tube and preparation method thereof, lithium ion cell positive and preparation method thereof and lithium ion battery - Google Patents
A kind of modified carbon nano-tube and preparation method thereof, lithium ion cell positive and preparation method thereof and lithium ion battery Download PDFInfo
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Abstract
The present invention provides a kind of modified carbon nano-tube and preparation method thereof, lithium ion cell positive and preparation method thereof and lithium ion batteries.A kind of modified carbon nano-tube, the polar group including carbon nanotube and carbon nano tube surface, the polar group are-COOLi.The characteristics of modified carbon nano-tube of the invention has easily dispersion, and dispersion is at low cost, good conductivity.Lithium ion battery of the dispersion liquid of the carbon nanotube used as conductive agent, compared to unmodified carbon nano tube dispersion liquid conductive agent, which has lower DC impedance and AC impedance, and battery high-rate charge-discharge capability is significantly promoted.
Description
Technical field
The invention belongs to field of lithium ion battery more particularly to a kind of modified carbon nano-tube and preparation method thereof, lithium ion
Anode and preparation method thereof and lithium ion battery.
Background technique
Carbon nanotube in a certain temperature conditions, is used using organic alkane class, olefines or alkynes micromolecular
The method of vapor deposition so that small organic molecule is on specific metal or metal oxide nanoparticles surface, catalytic growth and
It obtains.Carbon nanotube presses sp2The C-C key of hybrid form bonding has extremely excellent electric conductivity, thermal conductivity and mechanical strength.
Based on the above feature, carbon nanotube, which is used as lithium ion battery conductive agent, will make battery pole piece have excellent electric conductivity,
The biggish one-dimensional caliber ratio of carbon nanotube can make it form reticular structure within the scope of long-range simultaneously, firmly by active material
Grab and tie up, not only enhance the bonding stability between active material, while also enhancing the flexibility of pole piece.Commercial synthesis at present
The method that carbon nanotube mostly uses greatly CVD to be vapor-deposited, carbon nano tube growth will will form the poly- of similar ball of yarn after completing
Unity structure, along with the active force between carbon nanotube molecule, so that carbon nanotube directly application has biggish difficulty.The knot of agglomerate
Fruit can not play enough effects but also carbon nanotube active part is less.Traditional method is using PVP, dodecyl
The substances such as benzene sulfonic acid sodium salt, cetyl benzenesulfonic acid sodium are equal by carbon nanotube using modes such as mechanical ball mill, high speed shear, ultrasonic waves
It is even be dispersed in certain solvent such as N-Methyl pyrrolidone, DMAC N,N' dimethyl acetamide, N,N-dimethylformamide, water, in alcohols.
It is hanged obtained from will obtaining that carbon nanotube agglomerate is completely open as suitable dispersing method and being dispersed as single-root carbon nano-tube
Supernatant liquid.This suspension is widely used in the conductive layer of metal surface and the conductive unit in heat-conducting layer, electronic component, modeling
The conductive additive etc. in conductive and thermally conductive additive, carbon nanotube reinforcing fiber, battery in material.
There is no surface treated carbon nanotube, there is very strong attraction between molecule, scatter needs
Long time and very high energy consumption, this significantly increases production cost.Meanwhile though carbon nanotube as electron conduction pole
Good additive application increases the motion path of lithium ion in lithium ion battery to a certain extent, to active material
The surface cladding of material part also weakens the ionic conductivity of pole piece, so that battery is under high power charging-discharging, efficiency for charge-discharge
With energy efficiency decrease to some degree.
Summary of the invention
The present invention is lithium ion battery ionic conductivity when solving existing carbon nanotube to be applied to lithium ion cell positive
The technical problem of difference, when providing one kind applied to lithium ion cell positive, the good carbon modified of lithium ion battery ionic conductivity is received
Mitron and preparation method thereof, lithium ion cell positive and preparation method thereof and lithium ion battery.
The present invention provides a kind of modified carbon nano-tube, the modified carbon nano-tube includes carbon nanotube and carbon nanotube table
The polar group in face, the polar group are-COOLi.
Modified carbon nano-tube of the invention, is formed with-COOLi on the carbon nanotubes, in-COOLi group ,-COO-'s
It introduces so that the repulsive force of carbon nanotube increases, so that carbon nanotube is easier to scatter, carbon nanotube dispersion degree more fills
Point, available active carbon number of nanotubes increases in slurries, is applied to lithium ion battery, it will greatly promote electronic conductance；
It is applied to the carbon nanotube with-COOLi group as conductive agent in electrodes of lithium-ion batteries ,-COOLi group ionizes out
Li+It can be with the Li in electrolyte+It interacts, lithium ion transport channel is formed, to be greatly improved the ion of pole piece
Conductance.The modified carbon nano-tube is applied in lithium ion battery, not only improves electronic conductance, while improving ion-conductance
It leads, to be greatly improved the high-rate charge-discharge capability of battery.
The present invention also provides the preparation methods of the modified carbon nano-tube, the described method comprises the following steps:
S1, by carbon nanotube and nitric acid haptoreaction, obtain the first mixed liquor；
S2, the first mixed liquor is cooled down, removes extra nitric acid, is dried to obtain solid matter；
S3, step S2 obtained solid substance is dispersed in water, adds LiX and obtains the second mixed liquor, then filtered, dry
Dry modified carbon nano-tube to obtain the final product；
Wherein, X CO3 2-、O2-、OH-。
The preparation method of modified carbon nano-tube of the invention, using above-mentioned method of modifying, it will in nonpolar carbon originally
Nanotube surface, the groups such as oxidation formation-COOH, reuses LiX and reacts with it, general-COOH group becomes-COOLi.It generates
- COOLi group in ,-COO-Introducing so that the repulsive force of carbon nanotube increases so that carbon nanotube is easier point
It scattering, carbon nanotube dispersion degree is more abundant, and available active carbon number of nanotubes increases in slurries, it is applied to lithium ion battery,
Electronic conductance will greatly be promoted；It is applied to lithium ion cell electrode for the carbon nanotube with-COOLi group as conductive agent
In piece, Li that-COOLi group ionizes out+It can be with the Li in electrolyte+It interacts, forms lithium ion transport channel, from
And it is greatly improved the ionic conductance of pole piece.The modified carbon nano-tube is applied in lithium ion battery, electricity is not only improved
Sub- conductance, while ionic conductance is improved, to be greatly improved the high-rate charge-discharge capability of battery.
Third object of the present invention is to provide a kind of lithium ion cell positive, the anode includes positive-active material
Material, conductive agent and binder；The conductive agent is modified carbon nano-tube of the present invention.
Lithium ion cell positive of the invention contains the carbon nanotube with-COOLi group as conductive agent ,-COOLi
The Li that group ionizes out+It can be with the Li in electrolyte+It interacts, lithium ion transport channel is formed, to greatly be promoted
The ionic conductance of pole piece.
The present invention also provides the preparation methods of lithium ion cell positive described above, and the method includes following steps
It is rapid:
S1, conductive agent is dispersed to obtain conductive agent dispersion liquid；
S2, binder is dissolved in the first solvent, the conductive agent dispersant that step S1 is obtained then is added and is mixed
Close solution；
Positive electrode active materials are added in S3, Xiang Suoshu mixed solution, anode sizing agent is prepared；
S4, the anode sizing agent is coated on plus plate current-collecting body, be dried to obtain lithium ion cell positive；
Wherein, the conductive agent is modified carbon nano-tube of the present invention.
The preparation method of lithium ion cell positive of the invention ,-COO-Introducing so that the repulsive force of carbon nanotube increases,
So that carbon nanotube is easier to scatter, carbon nanotube dispersion degree is more abundant, available activity carbon nanotube number in slurries
Amount increases, and is applied to lithium ion battery, it will greatly promote electronic conductance；Make containing the carbon nanotube with-COOLi group
The Li for ionizing out for conductive agent ,-COOLi group+It can be with the Li in electrolyte+It interacts, it is logical to form lithium ion transport
Road, to be greatly improved the ionic conductance of pole piece.
Fifth object of the present invention is to provide a kind of lithium ion battery, the lithium ion battery includes shell, electrode
Group and electrolyte；The electrode group and the electrolyte are sealingly received in the shell, and the electrode group includes anode, cathode
And between positive electrode and negative electrode and by it is described anode and the separated diaphragm of the cathode；The lithium just extremely of the present invention
Ion battery anode.
The modified carbon nano-tube is applied in lithium ion battery by lithium ion battery of the invention, overcome dispersion at present it is difficult,
It is bad and the active incomplete problem of carbon nanotube can be used in lithium ion battery intermediate ion electric conductivity, so that carbon nano tube dispersion liquid
Active carbon nanotube number increase, the production time shorten, production cost reduce, by this dispersion liquid be applied to lithium ion battery with
Afterwards, there is lower direct current and AC impedance, to show excellent high-rate charge-discharge capability.
Detailed description of the invention
Fig. 1 is the infrared spectrogram of the carbon nanotube of embodiment 1-3 and comparative example 1；
Fig. 2 is the SEM figure that the modified carbon nano-tube of embodiment 1 amplifies 10000 times；
Fig. 3 is the SEM figure that the modified carbon nano-tube of embodiment 1 amplifies 20000 times；
Fig. 4 is the SEM figure that the modified carbon nano-tube of embodiment 1 amplifies 50000 times；
Fig. 5 is the SEM figure that the unmodified carbon nanotube of comparative example 1 amplifies 10000 times；
Fig. 6 is the SEM figure that the unmodified carbon nanotube of comparative example 1 amplifies 20000 times；
Fig. 7 is the SEM figure that the unmodified carbon nanotube of comparative example 1 amplifies 50000 times；
Fig. 8 be embodiment 1, embodiment 3 with regard to the carbon nanotube of comparative example 1 ultraviolet spectrogram；
Fig. 9 is the AC impedance figure of the lithium ion battery of embodiment 1-3 and comparative example 1.
Specific embodiment
In order to which the technical problems, technical solutions and beneficial effects solved by the present invention is more clearly understood, below in conjunction with
Embodiment, the present invention will be described in further detail.It should be appreciated that specific embodiment described herein is only used to explain
The present invention is not intended to limit the present invention.
The present invention provides a kind of modified carbon nano-tube, the modified carbon nano-tube includes carbon nanotube and carbon nanotube table
The polar group in face, the polar group are-COOLi.
Provided modified carbon nano-tube according to the present invention, it is preferable that the surface of the carbon nanotube includes the first vacancy
Defect and the second vacancy defect, the polar group are located at first vacancy defect position.
Provided modified carbon nano-tube according to the present invention, it is preferable that the carbon nanotube is prepared into for chemical deposition
The carbon nanotube arrived.
The present invention also provides the preparation methods of modified carbon nano-tube described above, the described method comprises the following steps:
S1, by carbon nanotube and nitric acid haptoreaction, obtain the first mixed liquor；
S2, the first mixed liquor is cooled down, removes extra nitric acid, is dried to obtain solid matter；
S3, step S2 obtained solid substance is dispersed in water, adds LiX and obtains the second mixed liquor, then filtered, dry
Dry modified carbon nano-tube to obtain the final product；
Wherein, X CO3 2-、O2-、OH-。
The preparation method of provided modified carbon nano-tube according to the present invention, it is preferable that the mass concentration of the nitric acid is
15%-40%.Nitric acid in this concentration range can prepare a part of vacancy defect and be oxidized, and a part of vacancy defect is not by oxygen
The carbon nanotube of change could prepare the carbon nanotube of more dominance energy of the invention.In carbon nanotube growth process, end group will form
Defect and two kinds of wall defects, end group position reactivity is big, easy to oxidize；Wall defects reactivity is small, not oxidizable.Pipe
The oxidation of wall defect can destroy entire carbon nanotube conducting plane, and then reduce electronic conductance.The oxidation of end group defect not only may be used
To guarantee the electronic conductance of carbon nanotube, while space repulsion can be brought to carbon nanotube, so that it is easier to disperse.This hair
It is bright only to aoxidize end group defect, it does not aoxidize or small amounts wall defects increases carbon and receive in defective locations introducing-COOLi
The electronic conductance and ionic conductance of mitron.The nitric acid can buy the nitric acid of the mass concentration, can also be bigger with concentration
Nitric acid is diluted with water to obtain, and in the present invention, the nitric acid nitric acid uses mass concentration to add water to be diluted for 65% concentrated nitric acid
It arrives.
The preparation method of provided modified carbon nano-tube according to the present invention, it is preferable that the carbon nanotube and the nitre
The mass ratio of acid is 1:5-20.Since the specific surface area of carbon nanotube is larger, guarantee processability more preferably modified carbon nano-tube,
The mass ratio of the carbon nanotube and the nitric acid is 1:5-20.
The preparation method of provided modified carbon nano-tube according to the present invention, in order to guarantee the progress and reaction of oxidation reaction
More sufficiently, it is preferable that
Catalytic condition is that reflux is boiled in the step S1, and the temperature boiled that flows back is 100-150 DEG C, when
Between be 30-120min.
The preparation method of provided modified carbon nano-tube according to the present invention, in order to guarantee reaction can it is easier into
Row, it is preferable that in step S3, the mass ratio of the carbon nanotube and the water is 1:3-5.
The preparation method of provided modified carbon nano-tube according to the present invention, guarantee all react away-COOH, preferably
Ground, in step S3, the additional amount of the LiX is the pH 7.0-8.0 for making the second mixed liquor.
The preparation method of provided modified carbon nano-tube according to the present invention, in order to guarantee LiX more fully with-COOH it is anti-
It answers, it is preferable that in step S3, the temperature of the reaction is 100-150 DEG C, time 10-20min.
The preparation method of provided modified carbon nano-tube according to the present invention removes the method for extra nitric acid in step S2
It is 5-6.5 to be washed with water to the pH of supernatant liquor.
The present invention also provides a kind of lithium ion cell positive, the anode includes positive electrode active materials, conductive agent and glues
Tie agent；The conductive agent is modified carbon nano-tube of the present invention.
Provided lithium ion cell positive according to the present invention, it is preferable that the positive electrode active materials are LiCoO2、
LiMn2O4、LiNiO2、LiVPO4、LiCoAlO2、LiMnCoO2、LiFeaM1-aPO4、LiCoxNiyMnzO2One of or it is a variety of,
Wherein M is one of Co, Ni and Mn or a variety of, 0.5≤a≤1, x+y+z=1,0≤x≤1,0≤y≤1,0≤z≤1.
Provided lithium ion cell positive according to the present invention, it is preferable that living with the anode for being equivalent to 100 parts by weight
Property substance, the content of the conductive agent is 0.5-10 parts by weight, and the content of the binder is 0.5-20 parts by weight.
Provided lithium ion cell positive according to the present invention, the binder are various binders commonly used in the art,
Such as Kynoar, polytetrafluoroethylene (PTFE), polyacrylate, polyurethane, epoxy resin, butadiene-styrene rubber, poly- methylcellulose, poly- first
At least one of base sodium cellulosate, hydroxypropyl methyl cellulose and POLYPROPYLENE GLYCOL.
The present invention also provides a kind of preparation methods of lithium ion cell positive, the described method comprises the following steps:
S1, conductive agent is dispersed to obtain conductive agent dispersion liquid；
S2, binder is dissolved in the first solvent, the conductive agent dispersant that step S1 is obtained then is added and is mixed
Close solution；
Positive electrode active materials are added in S3, Xiang Suoshu mixed solution, anode sizing agent is prepared；
S4, the anode sizing agent is coated on plus plate current-collecting body, be dried to obtain lithium ion cell positive；
Wherein, the conductive agent is modified carbon nano-tube of the present invention.
The preparation method of provided lithium ion cell positive according to the present invention, it is preferable that step S1 includes by dispersing agent
It is added in the second solvent, adds modified carbon nano-tube mixing, zirconium ball progress ball milling is then added and obtains conductive agent dispersion liquid.
The preparation method of provided lithium ion cell positive according to the present invention, it is preferable that with the conductive agent dispersion liquid
Total weight on the basis of, the content of the modified carbon nano-tube is 2-20wt%, and the content of the dispersing agent is 0.2-40wt%, institute
The content for stating solvent is 40-97.8wt%.
The preparation method of provided lithium ion cell positive according to the present invention, it is preferable that the average diameter of the zirconium ball
For 0.1-1mm, the weight of the zirconium ball is 1-20 times of the modified carbon nano-tube weight.
The preparation method of provided lithium ion cell positive according to the present invention, it is preferable that the binder, described first
Solvent, the conductive dispersions weight ratio be and the weight ratio of positive electrode active materials is 1-20:100:1-60.
The preparation method of provided lithium ion cell positive according to the present invention, first solvent and second solvent
Respectively stand alone as N-Methyl pyrrolidone, n,N-dimethylacetamide, n,N-Dimethylformamide, water, in organic alcohols extremely
Few one kind.
The dispersing agent be polyvinylpyrrolidone, neopelex, cetyl benzenesulfonic acid sodium, stearic acid,
At least one of organic quaternary ammonium salt, polyoxyethylene.
The present invention also provides a kind of lithium ion battery, the lithium ion battery includes shell, electrode group and electrolyte；Institute
State electrode group and the electrolyte be sealingly received in the shell, the electrode group include anode, cathode and be located at anode with
Between cathode and by it is described anode and the separated diaphragm of the cathode；The lithium ion battery just extremely of the present invention is just
Pole.
Below by specific embodiment, the present invention is further described in detail.
Embodiment 1
1, modified carbon nano-tube is prepared
(1) 120 are flowed back by carbon nanotube and dust technology (mass concentration 15%) after proportionally 1:5 is mixed, at 100 DEG C
Minute obtains mixed liquor；
(2) it by above-mentioned mixed liquor cooled and filtered, is repeatedly washed with deionized until supernatant liquor pH is 6.0；
(3) it by after the drying of obtained carbon nanotube solid, is mixed evenly with deionized water according to 1:5, addition is certain
The LiOH solid of amount adjusts the pH to 7.5 of mixed liquor；
(4) above-mentioned mixed liquor is boiled 20 minutes in 100 DEG C of reflux, mixed liquor cooled and filtered, deionized water is washed 3 times
After, solid is obtained by drying to modified carbon nano-tube A1.
2, lithium ion cell positive is prepared
(1) dispersing agent is added in solvent, stirring is completely dissolved for 10 minutes；Then carbon nanotube is added, stirs 10 minutes；
Zirconium ball is added in mixed liquor, carbon nano tube dispersion liquid can be obtained within ball milling 90 minutes；
The quality of modified carbon nano-tube solid is 5%；The quality of dispersing agent PVP is 1%；The matter of solvent N-methyl pyrilidone
Amount is 94%；The average diameter of zirconium ball is 0.1mm, and quality is 3 times of carbon nanotube actual mass；
(2) 5gPVDF binder is added in 60gN- methyl pyrrolidone (NMP), after all dissolutions, is added above-mentioned
The modified carbon nano-tube dispersion liquid 40g of preparation, after mixing by the carbon-coated LiFePO of 100g4(purchased from Canada
Phostech) powder is slowly added in above-mentioned mixed solution, and high-speed stirred 2 hours, anode sizing agent is made.At 16 microns of thickness
Double spread on aluminium foil is dried under the conditions of 130 DEG C, and rolling to volume density is 2.3g/cm3, pole piece is then cut into 470cm
(length) × 45cm(wide) × 0.0140cm think gauge, obtain positive B1.
3, negative electrode of lithium ion battery is prepared
By natural graphite (being purchased from Bei Terui new material Co., Ltd), carbon black Super P(purchased from the general industrial chemistry of Shanghai remittance
Product Co., Ltd), binder SBR(be purchased from Suzhou Rui Hong Co., Ltd) and sodium carboxymethylcellulose (CMC) (purchased from the long light in Shanghai
Enterprise development Co., Ltd) it is uniformly mixed in deionized water according to weight ratio 100:1.6:5:2.In the copper with a thickness of 10 microns
Double spread on foil, and dried under the conditions of 100 DEG C, rolling to volume density is 1.4g/cm3, pole piece is then cut into size
It is thick for 495cm(long) × 46cm(wide) × 0.0090cm() cathode C1.
4, lithium ion battery is prepared
(1), the assembly of battery
Above-mentioned anode, cathode and polypropylene isolation film (being purchased from U.S. Celgard Co., Ltd) are wound into a side
The battery core of shape, is inserted in after battery case, by LiPF6The in the mixed solvent of EC:EMC=3:7 is dissolved in by the concentration of 1mol/L, so
Afterwards by resulting electrolyte injection 3.6g~4.5g into battery.
(2), it is melted into
Battery placed to 48 hours at 50 °C, then at normal temperature by battery, with 11mA constant-current charge to 3.6V,
The lithium ion battery D1 that nominal capacity is 600mAh is made.
Embodiment 2
1, modified carbon nano-tube is prepared
(1) carbon nanotube and dust technology (mass concentration 30) after proportionally 1:10 is mixed, are flowed back 30 points at 150 DEG C
Clock obtains mixed liquor；
(2) it by above-mentioned mixed liquor cooled and filtered, is repeatedly washed with deionized until supernatant liquor pH is 6.5；
(3) it by after the drying of obtained carbon nanotube solid, is mixed evenly with deionized water according to 1:3, addition is certain
The Li of amount2CO3Solid adjusts the pH to 8.0 of mixed liquor；
(4) above-mentioned mixed liquor is boiled 10 minutes in 150 DEG C of reflux, mixed liquor cooled and filtered, deionized water is washed 3 times
After, solid is obtained by drying to modified carbon nano-tube A2.
2, lithium ion cell positive is prepared
(1) dispersing agent is added in solvent, stirring 30 minutes to being completely dissolved；Then carbon nanotube is added, stirs 30 points
Clock；Zirconium ball is added in mixed liquor, carbon nano tube dispersion liquid can be obtained within ball milling 180 minutes；
The quality of modified carbon nano-tube solid is 2%；The quality of dispersing agent PVP is 0.2%；Solvent N-methyl pyrilidone
Quality is 97.8%；The average diameter of zirconium ball is 1mm, and quality is 20 times of carbon nanotube actual mass；
(2) 5gPVDF binder is added in 60gN- methyl pyrrolidone (NMP), after all dissolutions, is added above-mentioned
The modified carbon nano-tube dispersion liquid 100g of preparation, after mixing by the carbon-coated LiFePO of 100g4(purchased from Canada
Phostech) powder is slowly added in above-mentioned mixed solution, and high-speed stirred 2 hours, anode sizing agent is made.At 16 microns of thickness
Double spread on aluminium foil is dried under the conditions of 130 DEG C, and rolling to volume density is 2.3g/cm3, pole piece is then cut into 470cm
(length) × 45cm(wide) × 0.0140cm think gauge, obtain positive B1.
Cathode and lithium ion battery D2 are prepared according to the method for embodiment 1.
Embodiment 3
1, modified carbon nano-tube is prepared
(1) 100 are flowed back by carbon nanotube and dust technology (mass concentration 40%) after proportionally 1:20 is mixed, at 120 DEG C
Minute obtains mixed liquor；
(2) it by above-mentioned mixed liquor cooled and filtered, is repeatedly washed with deionized until supernatant liquor pH is 5.0；
(3) it by after the drying of obtained carbon nanotube solid, is mixed evenly with deionized water according to 1:4, addition is certain
The Li of amount2O solid adjusts the pH to 7.0 of mixed liquor；
(4) above-mentioned mixed liquor is boiled 15 minutes in 120 DEG C of reflux, mixed liquor cooled and filtered, deionized water is washed 3 times
After, solid is obtained by drying to modified carbon nano-tube A3.
2, lithium ion cell positive is prepared
(1) dispersing agent is added in solvent, stirring 20 minutes to being completely dissolved；Then carbon nanotube is added, stirs 20 points
Clock；Zirconium ball is added in mixed liquor, carbon nano tube dispersion liquid can be obtained within ball milling 150 minutes；
The quality of modified carbon nano-tube solid is 20%；The quality of dispersing agent PVP is 40%；Solvent N-methyl pyrilidone
Quality is 40%；The average diameter of zirconium ball is 0.5mm, and quality is 10 times of carbon nanotube actual mass；
(2) 5gPVDF binder is added in 60gN- methyl pyrrolidone (NMP), after all dissolutions, is added above-mentioned
The modified carbon nano-tube dispersion liquid 10g of preparation, after mixing by the carbon-coated LiFePO of 100g4(purchased from Canada
Phostech) powder is slowly added in above-mentioned mixed solution, and high-speed stirred 2 hours, anode sizing agent is made.At 16 microns of thickness
Double spread on aluminium foil is dried under the conditions of 130 DEG C, and rolling to volume density is 2.3g/cm3, pole piece is then cut into 470cm
(length) × 45cm(wide) × 0.0140cm think gauge, obtain positive B1.
Cathode and lithium ion battery D3 are prepared according to the method for embodiment 1.
Comparative example 1
Anode, cathode and lithium ion battery CD1 are prepared according to the method for embodiment 1.Difference is: the carbon in anode is received
Mitron slurries change unmodified carbon nanotube CA1 into.
Performance test
1, FTIR infrared test
Modified carbon nano-tube A1-A3 that example 1-3 is obtained and unmodified carbon nanotube CA1 powder solid are mixed with KBr
After closing grinding drying, using Brooker-FTIR spectrum tester, carried out from 500cm-1 to 4000cm-1 to sample
Scanning, records the light transmittance of sample and draws curve, as shown in Figure 1, the corresponding absorption peak in the first hole position and the second hole position
It is identified in figure.
2, SEM is tested
The unmodified carbon nanotube that the carbon nanotube for the modification that embodiment 1 obtains and comparative example 1 are applied is done respectively and is amplified
10000 times, 20000 times, 50000 times of SEM experiment.As a result as illustrated in figs. 2-7.
3, ultraviolet spectra
The carbon nanotube CA1 of modified carbon nano-tube A1 and A3 and comparative example 1 that embodiment 1 and 3 is obtained are respectively according to carbon
Nanotube: three kinds of Carbon nano-tube dispersants are made in the ratio of PVP:NMP=5:1:94.Take above-mentioned four kinds of dispersing agents dilute on a small quantity respectively
After releasing 300 times, using ultraviolet spectra tester, is scanned from 200nm to 800nm, measure absorption value.In visible light region, carbon is received
Mitron degree of scatter is higher, and the active carbon number of nanotubes in solution is more, also bigger to the absorption of visible light.Therefore, ultraviolet
Visible light region absorption value is higher in map, shows that carbon nanotube degree of scatter is also higher.As a result as shown in Figure 8.
4, battery performance test
(1) measurement of anode pole piece resistivity
Example 1-3 and anode pole piece in comparative example 1 respectively remove wherein one side with adhesive tape, and it is 16mm that diameter, which is made,
Disk, using Suzhou lattice four-point probe, test pole sheet resistivity, the results are shown in Table 1.
(2) measurement of DCIR DC impedance performance
Lithium ion battery D1-D3 and CD1 are charged to 3.8V respectively with the electric current of 0.1C, respectively with 0.1C, 1C, 3C, 5C,
The discharge rate of 10C is by battery discharge 30s, on the basis of 0.1C electric current and corresponding average voltage, using formula DCIR=
(U0.1C-U)/(I-I0.1C), wherein U and I is the voltage and current under corresponding test condition, as shown in table 2.
(3) measurement of AC impedance
Lithium ion battery D1-D3 and CD1 are charged 5 hours with the electric current of 0.1C, adjustment battery charge state to 50%SOC,
After battery is shelved 4 hours in -20 DEG C, lead to ac impedance measurement equipment using Switzerland ten thousand, with 5mV constant pressure test method, from
40000Hz is scanned to 0.01Hz, and the size of semicircle is Rct in resolution chart, is a major criterion for measuring ionic conductance.
Rct is smaller, shows that ionic conductivity is higher.As shown in Figure 9.Horizontal axis represents the real part (Z ', unit Ω) of AC impedance in figure, indulges
Axis represents the imaginary part (Z ", unit Ω) of AC impedance.
(4) measurement of multiplying power charging performance
Lithium ion battery D1-D3 and CD1 are put to 2.0V respectively with the electric current of 0.1C, after shelving 10min, with the electricity of 0.5C
Stream is charged to 3.8V；Using same method, charging current is changed to 1C, 5C, 10C, 15C, 20C respectively, records each fill
Capacitance.Data are as shown in table 3.
(5) measurement of multiplying power discharging property
Lithium ion battery D1-D3 and CD1 are charged to 3.8V respectively with the electric current of 0.1C, after shelving 10min, with the electricity of 0.5C
It banishes to 2.0V；Using same method, discharge current is changed to 1C, 5C, 10C, 15C, 20C respectively, records each put
Capacitance.Data are as shown in table 4.
Table 1
。
Table 2
。
Table 3
。
Table 4
。
From table 1 it follows that the resistivity of the anode pole piece prepared with modified carbon nano-tube of the invention is significantly lower than
With the resistivity of anode pole piece prepared by the unmodified carbon nanotube of comparative example 1, illustrate the carbon nanometer with modification of the invention
The resistance value of the standby anode pole piece of control is smaller.
From Table 2, it can be seen that obvious with the DC impedance of the lithium ion battery of modified carbon nano-tube preparation of the invention
Lower than the DC impedance of the lithium ion battery prepared with the unmodified carbon nanotube of comparative example 1, illustrate with modification of the invention
Carbon nanotube preparation lithium ion battery DC impedance value it is smaller.
As can be seen that the big multiplying power charge and discharge of the lithium ion battery prepared with modified carbon nano-tube of the invention from table 3-4
Capacitance conservation rate is apparently higher than the high rate charge-discharge of the lithium ion battery prepared with the unmodified carbon nanotube of comparative example 1
Conservation rate illustrates that the rate charge-discharge performance of the lithium ion battery prepared with the carbon nanotube of modification of the invention is more preferable.
From figure 1 it appears that modified A1 carbon nanotube is in 3500cm-1There is-COOLi stretching vibration peak above,
1000cm-1Also there is stronger fingerprint vibration peak, it was demonstrated that it is aerobic in the first weaker vacancy relative to unmodified carbon nanotube
Change；Modified carbon nano-tube A2 is in 1000cm-1To 2000cm-1Between have apparent-COOLi bending vibration and 3000cm-1Have above
Significantly-COOLi stretching vibration, it was demonstrated that it aoxidizes position and has been not limited to the first weaker vacancy；Modified carbon nano-tube A3
Show extremely strong absorption peak, it was demonstrated that it also has very thorough oxidation in the second vacancy, so that-COOLi absorption peak becomes non-
Chang Mingxian.
As can be seen that the structure of modified carbon nano-tube of the invention is looser, mutually from the comparison of Fig. 2-4 and Fig. 5-7
Between repulsion it is bigger, be easy dispersion.
As can be seen from Figure 8, the degree of scatter of modified carbon nano-tube of the invention is higher than the unmodified carbon of comparative example
The degree of scatter of nanotube.
It can be seen in figure 9 that the ionic conductivity of lithium ion battery of the invention is apparently higher than the lithium ion of comparative example
The ionic conductivity of battery.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all in essence of the invention
Made any modifications, equivalent replacements, and improvements etc., should all be included in the protection scope of the present invention within mind and principle.
Claims (17)
1. a kind of modified carbon nano-tube, which is characterized in that the modified carbon nano-tube includes carbon nanotube and carbon nano tube surface
Polar group, the polar group be-COOLi；The surface of the carbon nanotube includes the first vacancy defect and the second vacancy
Defect, first vacancy defect are end group defect, and second vacancy defect is wall defects；The polar group is located at institute
State the first vacancy defect position.
2. modified carbon nano-tube according to claim 1, which is characterized in that the carbon nanotube is chemical deposition preparation
Obtained carbon nanotube.
3. a kind of preparation method of modified carbon nano-tube described in claim 1, which is characterized in that the method includes following steps
It is rapid:
S1, by carbon nanotube and nitric acid haptoreaction, obtain the first mixed liquor；
S2, the first mixed liquor is cooled down, removes extra nitric acid, is dried to obtain solid matter；
S3, step S2 obtained solid substance is dispersed in water, adds LiX and obtains the second mixed liquor, then filtered, drying is
Obtain the modified carbon nano-tube；
Wherein, X CO3 2-、O2-、OH-；The mass concentration of the nitric acid is 15%-40%.
4. the preparation method of modified carbon nano-tube according to claim 3, which is characterized in that the carbon nanotube with it is described
The mass ratio of nitric acid is 1:5-20.
5. the preparation method of modified carbon nano-tube according to claim 3, which is characterized in that contacted in the step S1 anti-
The condition answered is that reflux is boiled, and the temperature boiled that flows back is 100-150 DEG C, time 30-120min.
6. the preparation method of modified carbon nano-tube according to claim 3, which is characterized in that in step S3, the carbon is received
The mass ratio of mitron solid and the water is 1:3-5.
7. the preparation method of modified carbon nano-tube according to claim 3, which is characterized in that in step S3, the LiX's
Additional amount is the pH 7.0-8.0 for making the second mixed liquor.
8. the preparation method of modified carbon nano-tube according to claim 3, which is characterized in that in step S3, the reaction
Temperature be 100-150 DEG C, time 10-20min.
9. a kind of lithium ion cell positive, which is characterized in that the anode includes positive electrode active materials, conductive agent and binder；
The conductive agent is the described in any item modified carbon nano-tubes of claim 1-2.
10. lithium ion cell positive according to claim 9, which is characterized in that the positive electrode active materials are LiCoO2、
LiMn2O4、LiNiO2、LiVPO4、LiCoAlO2、LiMnCoO2、LiFeaM1-aPO4、LiCoxNiyMnzO2One of or it is a variety of,
Wherein M is one of Co, Ni and Mn or a variety of, 0.5≤a≤1, x+y+z=1,0≤x≤1,0≤y≤1,0≤z≤1.
11. lithium ion cell positive according to claim 9, which is characterized in that be equivalent to the anode of 100 parts by weight
Active material, the content of the conductive agent are 0.5-10 parts by weight, and the content of the binder is 0.5-20 parts by weight.
12. a kind of preparation method of lithium ion cell positive, which is characterized in that the described method comprises the following steps:
S1, conductive agent is dispersed to obtain conductive agent dispersion liquid；
S2, binder is dissolved in the first solvent, it is molten that the conductive agent dispersion liquid that then addition step S1 is obtained is mixed to get mixing
Liquid；
Positive electrode active materials are added in S3, Xiang Suoshu mixed solution, anode sizing agent is prepared；
S4, the anode sizing agent is coated on plus plate current-collecting body, be dried to obtain lithium ion cell positive；
Wherein, the conductive agent is the described in any item modified carbon nano-tubes of claim 1-2.
13. the preparation method of lithium ion cell positive according to claim 12, which is characterized in that step S1 includes that will divide
Powder is added in the second solvent, adds modified carbon nano-tube mixing, and zirconium ball progress ball milling is then added and obtains conductive agent point
Dispersion liquid.
14. the preparation method of lithium ion cell positive according to claim 13, which is characterized in that with the conductive agent point
On the basis of the total weight of dispersion liquid, the content of the modified carbon nano-tube is 2-20wt%, and the content of the dispersing agent is 0.2-
40wt%, the content of second solvent are 40-97.8wt%.
15. the preparation method of lithium ion cell positive according to claim 13, which is characterized in that the zirconium ball is averaged
Diameter is 0.1-1mm, and the weight of the zirconium ball is 1-20 times of the modified carbon nano-tube weight.
16. the preparation method of lithium ion cell positive according to claim 12, which is characterized in that the binder, institute
The weight ratio for stating the first solvent and the conductive agent dispersion liquid is 1-20:100:1-60.
17. a kind of lithium ion battery, which is characterized in that the lithium ion battery includes shell, electrode group and electrolyte；The electricity
Pole group and the electrolyte are sealingly received in the shell, and the electrode group is including anode, cathode and is located at positive electrode and negative electrode
Between and by it is described anode and the separated diaphragm of the cathode；It is described just extremely lithium described in claim 9-11 any one from
Sub- anode.
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| CN108511692A (en) * | 2017-12-21 | 2018-09-07 | 中国石油大学(北京) | A kind of lithium ion cell electrode and preparation method thereof |
| CN110342493B (en) * | 2018-04-03 | 2021-07-30 | 清华大学 | Transition metal oxide/carbon nanotube composite material and preparation method thereof |
| CN110634591B (en) * | 2019-09-29 | 2021-04-16 | 新奥石墨烯技术有限公司 | Conductive paste, preparation method and application thereof, and battery |
| CN110828792A (en) * | 2019-10-24 | 2020-02-21 | 王世扬 | Organic-inorganic hybrid lithium ion battery cathode material and preparation method thereof |
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