CN109994733A - Graphene/carbon nanotube composite material and its preparation method and application - Google Patents
Graphene/carbon nanotube composite material and its preparation method and application Download PDFInfo
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- CN109994733A CN109994733A CN201711477862.3A CN201711477862A CN109994733A CN 109994733 A CN109994733 A CN 109994733A CN 201711477862 A CN201711477862 A CN 201711477862A CN 109994733 A CN109994733 A CN 109994733A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a kind of preparation methods of Graphene/carbon nanotube composite material, comprising: the preparation of graphite oxide/Carbon Nanotube system: being added carbon nanotube powder in the oxidation reaction process of graphite, obtains graphite oxide/Carbon Nanotube system;With reduction gained graphite oxide/Carbon Nanotube system, Graphene/carbon nanotube composite material is prepared.Application the invention also discloses Graphene/carbon nanotube composite material as electrode material conductive agent.Carbon nanotube is added in graphite oxide preparation process in method disclosed by the invention, then it is first passed through low temperature thermal expansion and carries out high temperature reduction again, composite material is prepared using one-step method, surfactant and reducing agent is not added, also without by difficult techniques of productionizations such as hydro-thermals, closest to graphene preparation process itself, simple process is easy to operate.
Description
Technical field
The present invention relates to a kind of composite materials, and in particular to a kind of graphene and carbon nano tube compound material and its preparation side
Method and application belong to electrochemical material application field.
Background technique
Lithium ion battery using more and more extensive, technology is also more and more mature, performance of the people to lithium ion battery
Propose requirements at the higher level.In order to guarantee the performance of lithium ion battery fast energy storage, electrode must simultaneously have good
Electronics and ionic conductivity.Main conductive agent to be applied is carbon material in lithium ion battery, respectively granular carbon black conductive
Agent, linear carbon nanotube, the graphene of carbon fiber and sheet, electrically conductive graphite etc..Most popular conductive agent is at present
Carbon black, it is cheap, but carbon black can just build conductive network separately as conductive agent additive amount needs are more, so that material
Energy density reduces, and carbon nanotube and graphene powder are as highly difficult, the stacking easy to reunite in battery pole piece of conductive agent dispersion
To together, good conductive network cannot be constructed.Therefore, it is slurried to play its electric conductivity for it by high-speed dispersion equipment preparation
Expect, dispersing agent influential on battery performance is added in slurry;And solid all very littles that contains are being transported containing a large amount of solvent
On be also required to very big cost.
CN103956498B is disclosed " a kind of preparation method of Graphene/carbon nanotube composite material ", the patent be by
Graphene oxide slurry, surfactant are added in single-glass reaction kettle and stir evenly, and adding carbon nano tube paste must mix
Close slurry;Mixed slurry is dried and crushed;The particle of crushing is added in Muffle furnace, extruding, reduction treatment in air.
CN103545115A discloses " graphene-carbon nano tube composite material and preparation method thereof and supercapacitor ",
It is to mix graphene oxide dispersion according to certain mass ratio with carbon nanotube in the patent, is then ultrasonically treated, connects
Addition potassium hydroxide, filtering, dry and reduction after stirring cohesion.
It is that a kind of graphene and carbon are received disclosed in patent CN104269556B, CN105932288A and CN104766645B
The composite mortar of mitron, component are graphene, carbon nanotube and dispersing agent.
The content of background technology part is only the technology that inventor is known, not the existing skill of natural representative this field
Art.
Summary of the invention
For the prior art there are one or more of problem, it is compound that the present invention provides a kind of graphene/carbon nano-tube
The preparation method of material;
The present invention also provides a kind of Graphene/carbon nanotube composite materials.
The purpose of the present invention implements by the following technical programs:
In one aspect of the invention, a kind of preparation method of Graphene/carbon nanotube composite material is provided, comprising:
The preparation of graphite oxide/Carbon Nanotube system;With
Reduction gained graphite oxide/Carbon Nanotube system.
According to an aspect of the present invention, the graphite oxide/Carbon Nanotube system the preparation method comprises the following steps:
Carbon nanotube powder is added in the oxidation reaction process of graphite, washs after reaction, be dried to obtain oxidation stone
Ink/Carbon Nanotube system.
According to an aspect of the present invention, the graphite oxide/Carbon Nanotube system the preparation method comprises the following steps:
S1: concentrated sulfuric acid graphite oxide is utilized;
S2: into the reaction system that S1 is obtained be added the further graphite oxide of potassium permanganate, in oxidation reaction process to
Carbon nanotube powder is added in reaction system;
S3: hydrogen peroxide being added into the reaction system that S2 is obtained, and it is compound to obtain graphite oxide/carbon nanotube after reaction
Solution;With
S4: gained graphite oxide/CNT composite solution is washed, is dried.
According to an aspect of the present invention, in the S1, the concentration of the concentrated sulfuric acid is 98%;The graphite and the concentrated sulfuric acid
Mass ratio be 1:(20-50), preferably 1:30.
According to an aspect of the present invention, the reaction condition of the S1 are as follows: in ice-water bath, 100-300rpm stirring condition
It is lower to mix the graphite and the concentrated sulfuric acid, react 10-30min;Preferably, hybrid reaction 20min under 150rpm stirring condition.
According to an aspect of the present invention, in the S2, the mass ratio of the graphite and potassium permanganate is 1:(2-4), it is excellent
Select 1:2.
According to an aspect of the present invention, in the S2, the mass ratio of the graphite and carbon nanotube powder is (1-15):
1, preferably 8:1.
According to an aspect of the present invention, the reaction condition of the S2 are as follows: under 100-300rpm stirring condition, obtained to S1
To reaction solution in be added potassium permanganate, the temperature that adition process controls reaction system is 10-20 DEG C, and potassium permanganate addition finishes
After be warming up at 25-35 DEG C and keep the temperature 1-2h;It keeps the temperature and carbon nanotube is added to reaction system after terminating, then make reaction system in 25-
Continue to keep the temperature 30min-2h at 35 DEG C.
According to an aspect of the present invention, in ice-water bath, under 200rpm stirring condition into the reaction system of the S1
The potassium permanganate is added.
According to an aspect of the present invention, then reaction system is made to continue to keep the temperature 60min at 30 DEG C.
According to an aspect of the present invention, the concrete operation method of the S3 are as follows:
Under stirring, water is first added into the reaction system that S2 is obtained, the temperature of control system is 10-80 DEG C, continues to keep
Stirring is lower to keep the temperature 40-80min;Hydrogen peroxide is added into reaction system again, keeps the temperature 20-40min, stops heating to get oxidation is arrived
Graphite/carbon nanotube composite solution;
Wherein the amount of the water is according to graphite: water=1g:(24-60) addition of the amount of mL, preferably graphite: water=1g:40mL;
With
Wherein the amount of the hydrogen peroxide is according to graphite: the addition of hydrogen peroxide=(1-5) g:1mL amount, preferably graphite: hydrogen peroxide
=2g:1mL.
According to an aspect of the present invention, described that gained graphite oxide/CNT composite solution is carried out in the S4
Washing, dry concrete operation method are as follows:
Gained graphite oxide/CNT composite solution is washed with hydrochloric acid solution, is then dried;
Wherein hydrochloric acid in the hydrochloric acid solution: the volume ratio of water is 1:(5-10), preferred hydrochloric acid: the volume ratio of water is 1:7.
According to an aspect of the present invention, the mode of washing is using one of centrifugation or suction filtration or combinations thereof;Wherein
The revolving speed of the centrifugation is 3000-6000rpm, centrifugation time 15-30min, preferably 5000rpm, time 20min;It is preferred that
Ground, the mode of washing use suction filtration mode, until to touch material non-sticky for hand;
Wherein the washing times are 3-5 times, use the hydrochloric acid solution 200-500ml every time, it is preferable that the washing
Number is 5 times, uses the hydrochloric acid solution 300ml every time.
Wherein the mode of the drying is using convection oven, and dry temperature is 60-80 DEG C, preferably 80 DEG C.
According to an aspect of the present invention, the reduction-oxidation graphite/carbon nanotube compound system is swollen using first Low Temperature Thermal
Swollen, high temperature reduction again method;
Wherein the temperature of the Low Temperature Thermal expansion is 180-250 DEG C, and the time of low temperature thermal expansion is 5-30min;Preferably,
The temperature of the low temperature thermal expansion is 200 DEG C, and the time of low temperature thermal expansion is 20min;With
Wherein the temperature of the high temperature reduction is 800-1000 DEG C, and the time of high temperature reduction is 1-2h;Preferably, the height
The temperature of temperature reduction is 1000 DEG C, and the high temperature reduction time is 2h.
According to an aspect of the present invention, the reduction-oxidation graphite/carbon nanotube compound system is swollen using first Low Temperature Thermal
Swollen, washing, dry, high temperature reduction again method;
Wherein the washing uses water washing 3-5 times, preferably 5 times, described dry dry using convection oven, drying temperature
It is 60-80 DEG C, preferably 80 DEG C;
And/or wherein the Low Temperature Thermal expansion carries out under vacuum condition or inert atmosphere;
And/or wherein the high temperature reduction carries out under vacuum condition or inert atmosphere.
In another aspect of this invention, a kind of Graphene/carbon nanotube composite material is provided, including graphene sheet layer,
And it is distributed in the carbon nanotube between graphene sheet layer, adjoining graphite alkene piece interlayer is separated by carbon nanotube.
According to an aspect of the present invention, carbon nanotube mass score is in the Graphene/carbon nanotube composite material
5-20%, preferably 10%.
According to an aspect of the present invention, the partial size D50 of the Graphene/carbon nanotube composite material is 3-15 μm.
According to an aspect of the present invention, the specific surface area of the Graphene/carbon nanotube composite material is 100-
300m2/g。
According to an aspect of the present invention, the tap density of the Graphene/carbon nanotube composite material is 0.1-0.5g/
cm3。
According to an aspect of the present invention, the oil factor of the Graphene/carbon nanotube composite material is 500-1000
(10-5m3/kg)。
According to an aspect of the present invention, Graphene/carbon nanotube composite material according to above-mentioned preparation method preparation and
At.In another aspect of this invention, a kind of Graphene/carbon nanotube composite material answering as electrode material conductive agent is also provided
With.
Detailed description of the invention
Attached drawing is used to provide further understanding of the present invention, and constitutes part of specification, with reality of the invention
It applies example to be used to explain the present invention together, not be construed as limiting the invention.In the accompanying drawings:
Fig. 1 is SEM photograph (amplification 20000 times) of the Graphene/carbon nanotube composite material of the present invention as conductive agent;
Fig. 2 is that Graphene/carbon nanotube composite material of the present invention (is put as SEM photograph of the conductive agent in anode pole piece
It is 10000 times big);
Fig. 3 is Graphene/carbon nanotube composite material of the present invention as conductive agent and market conductive agent in tertiary cathode
Pole piece resistance comparison diagram;
Fig. 4 is Graphene/carbon nanotube composite material of the present invention as conductive agent and market conductive agent in tertiary cathode
Battery high rate performance comparison diagram.
Specific embodiment
Hereinafter, certain exemplary embodiments are simply just described.As one skilled in the art will recognize that
Like that, without departing from the spirit or scope of the present invention, described embodiment can be modified by various different modes.
Therefore, attached drawing and description are considered essentially illustrative rather than restrictive.
In the first embodiment of the present invention, a kind of preparation method of Graphene/carbon nanotube composite material is provided,
Include:
The preparation of graphite oxide/Carbon Nanotube system;With
Reduction gained graphite oxide/Carbon Nanotube system.
According to a preferred embodiment of the present invention, the graphite oxide/Carbon Nanotube system the preparation method comprises the following steps:
Carbon nanotube powder is added in the oxidation reaction process of graphite, washs after reaction, be dried to obtain oxidation stone
Ink/Carbon Nanotube system.
According to a preferred embodiment of the present invention, the graphite oxide/Carbon Nanotube system the preparation method comprises the following steps:
S1: concentrated sulfuric acid graphite oxide is utilized;
S2: into the reaction system that S1 is obtained be added the further graphite oxide of potassium permanganate, in oxidation reaction process to
Carbon nanotube powder is added in reaction system;
S3: hydrogen peroxide being added into the reaction system that S2 is obtained, and it is compound to obtain graphite oxide/carbon nanotube after reaction
Solution;With
S4: gained graphite oxide/CNT composite solution is washed, is dried.
According to a preferred embodiment of the present invention, in the S1, the concentration of the concentrated sulfuric acid is 98%;The graphite with
The mass ratio of the concentrated sulfuric acid is 1:(20-50), such as: 1:20,1:30,1:40,1:50, etc.;It is preferred that 1:30.
According to a preferred embodiment of the present invention, the reaction condition of the S1 are as follows: in ice-water bath, 100-300rpm is stirred
Mix the graphite and the concentrated sulfuric acid under the conditions of mixing, react 10-30min, for example, revolving speed can for 100rpm, 150rpm, 200rpm,
250rpm, 300rpm, etc. the reaction time can be such as are as follows: 10min, 15min, 20min, 25min, 30min, etc.;Preferably,
Hybrid reaction 20min under 150rpm stirring condition.
According to a preferred embodiment of the present invention, in the S2, the mass ratio of the graphite and potassium permanganate is 1:(2-
4), such as: 1:2,1:3,1:4, etc.;It is preferred that 1:2.
According to a preferred embodiment of the present invention, in the S2, the mass ratio of the graphite and carbon nanotube powder is
(1-15): 1, such as: 1:1,2:1,3:1,4:1,5:1,6:1,7:1,8:1,9:1,10:1,11:1,12:1,13:1,14:1,
15:1, etc.;It is preferred that 8:1.
According to a preferred embodiment of the present invention, the reaction condition of the S2 are as follows: under 100-300rpm stirring condition,
Such as: 100rpm, 150rpm, 200rpm, 250rpm, 300rpm, etc.;Potassium permanganate is added into the reaction solution that S1 is obtained, adds
The temperature for entering process control reaction system is 10-20 DEG C, such as: 10 DEG C, 15 DEG C, 20 DEG C etc.;Potassium permanganate rises after being added
Temperature is to keeping the temperature 1-2h, such as be warming up to heat preservation 1h, the 2h such as 25 DEG C, 30 DEG C, 35 DEG C at 25-35 DEG C etc.;Heat preservation terminates rear Xiang Fanying
Carbon nanotube is added in system, then makes reaction system continue to keep the temperature 30min-2h at 25-35 DEG C, such as at 25 DEG C, 30 DEG C, 35 DEG C
Continue to keep the temperature 30min, 45min, 1h, 1.5h, 2h Deng under the conditions of, etc..
According to a preferred embodiment of the present invention, in ice-water bath, to the reaction of the S1 under 200rpm stirring condition
The potassium permanganate is added in system.
A key inventive point of the invention is that carbon nanotube is added during potassium permanganate oxidation graphite, in base, is added
The opportunity for entering carbon nanotube is the core technology inventive point of the most important thing.Inventor through this hair studies discovery: making reactant again
It ties up at 30 DEG C and continues to keep the temperature 60min, better effect.The present inventor is to when continuing heat preservation of reaction system after addition carbon nanotube
Between influence to the Graphene/carbon nanotube composite material being prepared as conductive agent battery high rate performance analyzed,
As shown in table 1 below.
Table 1: in step S2 be added carbon nanotube after reaction system continuation soaking time to the graphene/carbon being prepared
Influence of the nanometer tube composite materials as conductive agent battery high rate performance
Soaking time (min) | 30 | 45 | 60 | 90 | 120 |
0.1C(mAh/g) | 158.2 | 157.3 | 161.0 | 160.4 | 159.3 |
1C(mAh/g) | 141.3 | 140.6 | 143.8 | 139.8 | 138.6 |
2C(mAh/g) | 128.0 | 128.8 | 132.1 | 125.3 | 124.3 |
According to a preferred embodiment of the present invention, the concrete operation method of the S3 are as follows:
Under stirring, water is first added into the reaction system that S2 is obtained, the temperature of control system is 10-80 DEG C, such as: 10
DEG C, 20 DEG C, 30 DEG C, 40 DEG C, 50 DEG C, 60 DEG C, 70 DEG C, 80 DEG C, etc.;Continue to be kept stirring lower heat preservation 40-80min, such as:
40min, 50min, 60min, 70min, 80min, etc.;Hydrogen peroxide is added into reaction system again, keeps the temperature 20-40min, such as:
20min, 30min, 40min, etc.;Stop heating to get graphite oxide/CNT composite solution is arrived;
Wherein the amount of the water is according to graphite: water=1g:(24-60) addition of the amount of mL, such as: 1g:24mL, 1g:30mL,
1g:35mL, 1g:40mL, 1g:45mL, 1g:50mL, 1g:55mL, 1g:60mL, etc.;It is preferred that graphite: water=1g:40mL;With
Wherein the amount of the hydrogen peroxide is according to graphite: the addition of hydrogen peroxide=(1-5) g:1mL amount, such as: 1g:1mL, 2g:
1mL, 3g:1mL, 4g:1mL, 5g:1mL, etc.;It is preferred that graphite: hydrogen peroxide=2g:1mL.
According to a preferred embodiment of the present invention, described compound molten to gained graphite oxide/carbon nanotube in the S4
The concrete operation method that liquid is washed, dried are as follows:
Gained graphite oxide/CNT composite solution is washed with hydrochloric acid solution, is then dried;
Wherein hydrochloric acid in the hydrochloric acid solution: the volume ratio of water is 1:(5-10), such as: 1:5,1:6,1:7,1:8,1:9,
1:10, etc.;It is preferred that hydrochloric acid: the volume ratio of water is 1:7;
Wherein the mode of washing is using one of centrifugation or suction filtration or combinations thereof;Wherein the revolving speed of the centrifugation is
3000-6000rpm, such as: 3000rpm, 4000rpm, 5000rpm, 6000rpm, etc.;Centrifugation time is 15-30min, such as:
15min, 20min, 25min, 30min, etc.;It is preferred that 5000rpm, time 20min;Preferably, the mode of washing is using pumping
Filter mode, until to touch material non-sticky for hand;
Wherein the washing times are 3-5 times, such as: 3 times, 4 times, 5 times use the hydrochloric acid solution 200- every time
500ml, such as: 200ml, 300ml, 400ml, 500ml, etc., it is preferable that the washing times are 5 times, use the salt every time
Acid solution 300ml;With
Wherein the drying mode can be used convection oven, dry temperature be 60-80 DEG C, such as: 65 DEG C, 70 DEG C,
75 DEG C, 80 DEG C, etc.;It is preferred that 80 DEG C.
According to a preferred embodiment of the present invention, the reduction-oxidation graphite/carbon nanotube compound system is using first low
The method of warm expansion, again high temperature reduction;This restoring method does not need addition reducing agent, is directly restored by high temperature,
Not only can be with a large amount of functional groups on redox graphene surface, but also some impurity can be removed by high temperature, it is easy to industrial metaplasia
It produces.
According to a preferred embodiment of the present invention, the temperature of the low temperature thermal expansion is 180-250 DEG C, such as: 180
DEG C, 190 DEG C, 200 DEG C, 210 DEG C, 220 DEG C, 230 DEG C, 240 DEG C, 250 DEG C, etc.;The time of low temperature thermal expansion is 5-30min, example
Such as: 5min, 10min, 15min, 20min, 25min, 30min, etc.;Preferably, the temperature of the low temperature thermal expansion is 200 DEG C,
The time of low temperature thermal expansion is 20min.
According to a preferred embodiment of the present invention, the temperature of the high temperature reduction is 800-1000 DEG C, such as: 800 DEG C,
850 DEG C, 900 DEG C, 950 DEG C, 1000 DEG C, etc.;The time of high temperature reduction is 1-2h, such as 1h, 1.5h, 2h, etc.;Preferably, institute
The temperature for stating high temperature reduction is 1000 DEG C, and the high temperature reduction time is 2h.
According to a preferred embodiment of the present invention, the reduction-oxidation graphite/carbon nanotube compound system is using first low
Warm expansion, washing, dry, high temperature reduction again method;
Wherein the washing uses water washing 3-5 times, such as 3 times, 4 times, 5 times;It is preferred that 5 times, it is described dry using air blast
Oven drying, drying temperature are 60-80 DEG C, such as: 65 DEG C, 70 DEG C, 75 DEG C, 80 DEG C, etc.;It is preferred that 80 DEG C;
Wherein the Low Temperature Thermal expansion carries out under vacuum condition or inert atmosphere;
Wherein the high temperature reduction carries out under vacuum condition or inert atmosphere.
According to a preferred embodiment of the present invention, including graphene sheet layer and the carbon being distributed between graphene sheet layer
Nanotube, adjoining graphite alkene piece interlayer are separated by carbon nanotube.
According to a preferred embodiment of the present invention, carbon nanotube mass in the Graphene/carbon nanotube composite material
Score is 5-20%, such as: 5%, 10%, 15%, 20%, etc.;Preferably 10%.
According to a preferred embodiment of the present invention, the partial size D50 of the Graphene/carbon nanotube composite material is 3-15
μm, such as: 3 μm, 5 μm, 7 μm, 9 μm, 11 μm, 13 μm, 15 μm, etc..
According to a preferred embodiment of the present invention, the specific surface area of the Graphene/carbon nanotube composite material is
100-300m2/ g, such as: 100m2/g、150m2/g、200m2/g、250m2/g、300m2/ g, etc..
According to a preferred embodiment of the present invention, the tap density of the Graphene/carbon nanotube composite material is
0.1-0.5g/cm3, such as: 0.1g/cm3,0.2g/cm3,0.3g/cm3,0.4g/cm3,0.5g/cm3, etc..
According to a preferred embodiment of the present invention, the oil factor of the Graphene/carbon nanotube composite material is 500-
1000(10-5m3/ kg), such as: 500 (10-5m3/kg)、600(10-5m3/kg)、700(10-5m3/kg)、800(10-5m3/kg)、
900(10-5m3/kg)、1000(10-5m3/ kg), etc..
According to a preferred embodiment of the present invention, the Graphene/carbon nanotube composite material is according to above-mentioned system
Preparation Method is prepared.
In second embodiment of the present invention, a kind of Graphene/carbon nanotube composite material work of the invention is provided
For the application of electrode material conductive agent.The present invention is compound with carbon nanotube by graphene, is added in graphite oxide preparation process
Carbon nanotube, graphite oxide belongs to high oxidation exfoliated state at this time, and carbon nanotube, which is added, can be very good to be intercalation into oxidation stone
On the one hand the surface of ink and interlayer, the Graphene/carbon nanotube composite material being prepared hinder graphene overlapping, separately
Outer one side carbon nanotube itself also has good electric conductivity, and the two plays synergistic effect, can establish better conductive mesh
Network.And composite material is prepared using one-step method in the present invention, surfactant and reducing agent is not added, closest to graphite
Alkene preparation process itself, simple process are easy to operate.Graphene/carbon nanotube composite material of the invention is as ternary NCM battery
Graphene/carbon nanotube composite material is directly added into positive electrode system by the application of positive electrode.The graphene/carbon is received
Mitron composite material does not add any dispersing agent, is directly added into positive electrode system as powder without being fabricated to electrocondution slurry
In, constant more positive electrode pulping process.Conductive agent used in ternary is generally carbon black at present, and conductive agent is in a small number of ternarys
Carbon nano tube paste, carbon black additive amount in ternary at least want 2%, can just build conductive network, carbon nano tube paste due to
Its preparating mechanism, wherein it is more containing foreign metal, and required to reach dispersion, it is necessary to dispersing agent is added, otherwise carbon is received
The winding of mitron itself keeps its dispersibility excessively poor, and good conductive network cannot be established by being added directly into positive electrode.This
Invention composite material battery high rate performance under few additive is more preferable, that is, the present invention can add less in terms of additive amount
(1.0wt%) can reach other conductive agents level.
It is higher as excellent conductive agent conductivity needs first, the electron transfer rate of material could be improved in this way;Its
The secondary better Electolyte-absorptive of energy;Furthermore easily dispersion is needed, is easily dispersed during positive and negative pole material slurry to more preferable
Contacted with positive and negative pole material.The present invention is compound by carbon nanotube and graphene progress, and carbon nanotube is uniformly dispersed in graphite
The surface of alkene, hinders the overlapping of graphene, and evenly dispersed carbon nanotube itself also has good electric conductivity, is prepared
Graphene/carbon nanotube composite material contacts well with positive electrode, constructs good conductive network, as conductive agent,
Battery performance is also good in ternary NCM positive electrode.Referring to Fig. 1 and Fig. 2, Graphene/carbon nanotube composite material of the present invention
And its SEM photograph in pole piece, from Fig. 1 it is observed that carbon nanotube is uniformly dispersed in graphene surface, graphene layer
Interlayer is separated by carbon nanotube, and the overlapping that this structure one side carbon nanotube hinders graphene film interlayer is reunited, another
Well dispersed carbon nanotube of aspect itself also has good electric conductivity, and graphene/carbon nano-tube is compound as we can see from the figure
Material piece diameter size is 3-15 μm.From Fig. 2 it can be observed that part carbon nanotube with positive electrode is good contacts, play long-range
Conductive effect, is conducive to the transmission of electronics, and part carbon nanotube is dispersed in the surface of graphene, hinders the overlapping of graphene,
Be conducive to the dispersion of graphene, to establish better conductive network.The purpose of the present invention is prepare a kind of graphene/carbon nanometer
Pipe composite material, detailed process are that carbon nanotube is added in graphite oxide preparation process, and it is swollen then to be first passed through Low Temperature Thermal
It is swollen to carry out high temperature reduction again, material is prepared using one-step method, surfactant and reducing agent is not added, does not also pass through
The difficult technique of the productionizations such as hydro-thermal, it is simple to operation closest to graphene preparation process itself.
The present invention is a kind of process exploitation of Graphene/carbon nanotube composite material, compared with prior art, present invention tool
It has the following advantages:
From product macro-and micro-structure:
(1) compared with slurry type conductive agent, dispersing agent is free of, avoids dispersing agent from occurring under 4.2V or more high voltage secondary anti-
It answers.
(2) compared with slurry type conductive agent, solvent, the problems such as will not settling, subsidiary company angle and client angle are free of
Degree, can reduce very big cost.
(3) tap density of product is 0.1-0.5g/cm3, is conducive to technique application, existing highly conductive graphene powder its
Tap density all very littles.In ternary NCM positive electrode, under identical conduction agent additive amount, Graphene/carbon nanotube composite material
Conductive agent battery high rate performance is served as better than SP, CNT slurry in the market.Referring to Fig. 3,4, graphene/carbon nano-tube of the present invention is multiple
Process exploitation of the condensation material as conductive agent, its pole piece is electric in ternary NCM positive electrode system with existing conductive agent in the market
Resistance and the comparison of battery high rate performance are obtained from scheming to analyze in upper face data, and in ternary NCM positive electrode, identical conduction agent adds
Under dosage, Graphene/carbon nanotube composite material is as conductive agent battery high rate performance better than SP and CNT slurry in the market.
From product preparation process:
Carbon nanotube is added in graphite oxide preparation process, is then first passed through low temperature thermal expansion and carries out high temperature also again
Original is prepared material using one-step method, surfactant and reducing agent is not added, also without having by productions such as hydro-thermals
The technique of difficulty, it is simple to operation closest to graphene preparation process itself.
Hereinafter, preferred embodiments of the present invention will be described, it should be understood that preferred embodiment described herein is only used
In the description and interpretation present invention, it is not intended to limit the present invention.
Embodiment 1:
In ice-water bath, by graphite under 150rpm stirring condition: the concentrated sulfuric acid=1:30 mass ratio is added to reaction vessel
In, it is stirred to react 20min, then in ice-water bath, by graphite under 200rpm stirring condition: potassium permanganate=1:2 mass ratio
Potassium permanganate is slowly added into reaction solution, and control system temperature is 15 DEG C, and the entire process time that feeds is 30min ± 1min.
After potassium permanganate adds, entire reaction system is made to keep the temperature 2h at 30 DEG C, then by graphite: carbon nanotube powder=8:1 matter
The carbon nanotube powder of amount ratio directly adds reaction system, and entire reaction system is made to continue to keep the temperature 2h at 30 DEG C after adding.It protects
Temperature terminate after into reaction system slowly by graphite: water=1g:40mL water be added reaction system in, control reaction system medium temperature
Degree is 80 DEG C, mixing speed 200rpm.After adding water to keep the temperature 60min, into system by graphite: hydrogen peroxide=2g:1mL
Hydrogen peroxide is added, and keeps the temperature 30min minutes, closes heating.Configuration volume ratio is hydrochloric acid: the cleaning solution of water=1/7 is to above-mentioned anti-
Products therefrom is answered repeatedly to be washed, each wash volumes are 300mL, and washing times are 5 times, and the mode of washing used is pumping
Filter.The special mold briquetting of products therefrom filter cake will be filtered, the filter cake taking-up after pressure is put into culture dish and is placed in air blast baking
Dry in case, drying temperature is 80 DEG C, and drying time is to start timing at interval of two hours progress weighing materials since dry, up to
The two hours material weightlessness in interval is 0.5% as the dry standard completed.By the material after drying be placed in vacuum drying oven into
The thermal reduction of row low temperature, the temperature of vacuum drying oven are 200 DEG C, and the Low Temperature Thermal recovery time is 20min.Material after low temperature is heat-treated
Add water washing 5 times, be subsequently placed in drying in convection oven, drying temperature is 80 DEG C, and drying time is that timing is every since dry
Two hours progress weighing materials are spaced, until the two hours material weightlessness in interval is 0.5% as the dry standard completed.By water
Material after washing drying is placed in progress high temperature thermal reduction in tube furnace, and temperature is 1000 DEG C in tube furnace, when high temperature heat-treats
Between be 2h, finally obtain Graphene/carbon nanotube composite material.The Graphene/carbon nanotube composite material being prepared is made
It is added in tertiary cathode material system for conductive agent, additive amount 1.0%, is fabricated to positive plate after stirring slurry, film, drying,
Positive tablet quality is weighed, is put into glove box stand-by;The assembly of CR2032 button cell is carried out, assemble sequence is as follows: negative electrode casing court
On, it is sequentially placed into elastic slice, gasket, cathode lithium piece, diaphragm, positive plate (downward), appropriate electrolyte is added, finally buckles anode cover
(downward), directly battery is sealed with sealing machine, takes out set aside for use from glove box;Finally button cell is placed on newly
On prestige cell tester, test work step by Cycle: 0.1C fills/0.1C puts 3 circle of circulation, and 0.2C fills/and 0.2C puts 5 circle of circulation, 0.3C
Fill/1C puts 5 circle of circulation, and 0.3C fills/and 1C puts 5 circle of circulation, and it is tested, finally obtains its battery high rate performance as a result, being shown in Table 2
(data are respectively first circle discharge capacity under 0.1C, 1C, 2C multiplying power in table).
Embodiment 2:
In ice-water bath, by graphite under 150rpm stirring condition: the concentrated sulfuric acid=1:30 mass ratio is added to reaction vessel
In, it is stirred to react 20min, then in ice-water bath, by graphite under 200rpm stirring condition: potassium permanganate=1:2 mass ratio
Potassium permanganate is slowly added into reaction solution, and control system temperature is 15 DEG C, and the entire process time that feeds is about 30min.To
After potassium permanganate adds, entire reaction system is made to keep the temperature 2h at 30 DEG C, then by graphite: carbon nanotube powder=1:1 mass
The carbon nanotube powder of ratio directly adds reaction system, and entire reaction system is made to continue to keep the temperature 2h at 30 DEG C after adding.Heat preservation
Into reaction system slowly by graphite after end: water=1g:40mL water is added in reaction system, controls temperature in reaction system
It is 80 DEG C, mixing speed 200rpm.After adding water to keep the temperature 60min, into system by graphite: hydrogen peroxide=2g:1mL is double
Oxygen water is added, and keeps the temperature 30min minutes, closes heating.Configuration volume ratio is hydrochloric acid: the cleaning solution of water=1/7 is to above-mentioned reaction
Products therefrom is repeatedly washed, and each wash volumes are 300mL, and washing times are 5 times, and the mode of washing used is suction filtration.
The special mold briquetting of products therefrom filter cake will be filtered, the filter cake taking-up after pressure is put into culture dish and is placed in convection oven
Dry, drying temperature is 80 DEG C, and drying time is that timing was at interval of two hours progress weighing materials since dry, until interval
Two hours material weightlessness is 0.5% as the dry standard completed.It is low that material after drying is placed in vacuum drying oven progress
Warm reduction, the temperature of vacuum drying oven are 200 DEG C, and the Low Temperature Thermal recovery time is 20min.Material after low temperature is heat-treated adds water
Washing 5 times, is subsequently placed in convection oven dry, and drying temperature is 80 DEG C, drying time be since dry timing at interval of
Two hours progress weighing materials, until the two hours material weightlessness in interval is 0.5% as the dry standard completed.Washing is dry
Material after dry is placed in tube furnace progress high temperature thermal reduction, and temperature is 1000 DEG C in tube furnace, and the high temperature thermal reduction time is
2h finally obtains Graphene/carbon nanotube composite material.Using the Graphene/carbon nanotube composite material being prepared as leading
Electric agent is added in tertiary cathode material system, additive amount 1.0%, is fabricated to positive plate after stirring slurry, film, drying, weighs
Positive tablet quality is put into glove box stand-by;Carry out the assembly of CR2032 button cell, assemble sequence is as follows: negative electrode casing upward, according to
It is secondary to be put into elastic slice, gasket, cathode lithium piece, diaphragm, positive plate (downward), appropriate electrolyte is added, finally buckles anode cover (court
Under), directly battery is sealed with sealing machine, takes out set aside for use from glove box;Button cell is finally placed on new prestige
On cell tester, test work step by Cycle: 0.1C fills/0.1C puts 3 circle of circulation, and 0.2C fills/and 0.2C puts 5 circle of circulation, 0.3C
Fill/1C puts 5 circle of circulation, and 0.3C fills/and 1C puts 5 circle of circulation, and it is tested, finally obtains its battery high rate performance as a result, being shown in Table 2
(data are respectively first circle discharge capacity under 0.1C, 1C, 2C multiplying power in table).
Embodiment 3:
In ice-water bath, by graphite under 150rpm stirring condition: the concentrated sulfuric acid=1:30 mass ratio is added to reaction vessel
In, it is stirred to react 20min, then in ice-water bath, by graphite under 200rpm stirring condition: potassium permanganate=1:2 mass ratio
Potassium permanganate is slowly added into reaction solution, and control system temperature is 15 DEG C, and the entire process time that feeds is about 30min.To
After potassium permanganate adds, entire reaction system is made to keep the temperature 2h at 30 DEG C, then by graphite: carbon nanotube powder=15:1 mass
The carbon nanotube powder of ratio directly adds reaction system, and entire reaction system is made to continue to keep the temperature 2h at 30 DEG C after adding.Heat preservation
Into reaction system slowly by graphite after end: water=1g:40mL water is added in reaction system, controls temperature in reaction system
It is 80 DEG C, mixing speed 200rpm.After adding water to keep the temperature 60min, into system by graphite: hydrogen peroxide=2g:1mL is double
Oxygen water is added, and keeps the temperature 30min minutes, closes heating.Configuration volume ratio is hydrochloric acid: the cleaning solution of water=1/7 is to above-mentioned reaction
Products therefrom is repeatedly washed, and each wash volumes are 300mL, and washing times are 5 times, and the mode of washing used is suction filtration.
The special mold briquetting of products therefrom filter cake will be filtered, the filter cake taking-up after pressure is put into culture dish and is placed in convection oven
Dry, drying temperature is 80 DEG C, and drying time is that timing was at interval of two hours progress weighing materials since dry, until interval
Two hours material weightlessness is 0.5% as the dry standard completed.It is low that material after drying is placed in vacuum drying oven progress
Warm reduction, the temperature of vacuum drying oven are 200 DEG C, and the Low Temperature Thermal recovery time is 20min.Material after low temperature is heat-treated adds water
Washing 5 times, is subsequently placed in convection oven dry, and drying temperature is 80 DEG C, drying time be since dry timing at interval of
Two hours progress weighing materials, until the two hours material weightlessness in interval is 0.5% as the dry standard completed.Washing is dry
Material after dry is placed in tube furnace progress high temperature thermal reduction, and temperature is 1000 DEG C in tube furnace, and the high temperature thermal reduction time is
2h finally obtains Graphene/carbon nanotube composite material.Using the Graphene/carbon nanotube composite material being prepared as leading
Electric agent is added in tertiary cathode material system, additive amount 1.0%, is fabricated to positive plate after stirring slurry, film, drying, weighs
Positive tablet quality is put into glove box stand-by;Carry out the assembly of CR2032 button cell, assemble sequence is as follows: negative electrode casing upward, according to
It is secondary to be put into elastic slice, gasket, cathode lithium piece, diaphragm, positive plate (downward), appropriate electrolyte is added, finally buckles anode cover (court
Under), directly battery is sealed with sealing machine, takes out set aside for use from glove box;Button cell is finally placed on new prestige
On cell tester, test work step by Cycle: 0.1C fills/0.1C puts 3 circle of circulation, and 0.2C fills/and 0.2C puts 5 circle of circulation, 0.3C
Fill/1C puts 5 circle of circulation, and 0.3C fills/and 1C puts 5 circle of circulation, and it is tested, finally obtains its battery high rate performance as a result, being shown in Table 2
(data are respectively first circle discharge capacity under 0.1C, 1C, 2C multiplying power in table).
Embodiment 4:
In ice-water bath, by graphite under 150rpm stirring condition: the concentrated sulfuric acid=1:20 mass ratio is added to reaction vessel
In, it is stirred to react 20min, then in ice-water bath, by graphite under 200rpm stirring condition: potassium permanganate=1:2 mass ratio
Potassium permanganate is slowly added into reaction solution, and control system temperature is 15 DEG C, and the entire process time that feeds is about 30min.To
After potassium permanganate adds, entire reaction system is made to keep the temperature 2h at 30 DEG C, then by graphite: carbon nanotube powder=8:1 mass
The carbon nanotube powder of ratio directly adds reaction system, and entire reaction system is made to continue to keep the temperature 2h at 30 DEG C after adding.Heat preservation
Into reaction system slowly by graphite after end: water=1g:40mL water is added in reaction system, controls temperature in reaction system
It is 80 DEG C, mixing speed 200rpm.After adding water to keep the temperature 60min, into system by graphite: hydrogen peroxide=2g:1mL is double
Oxygen water is added, and keeps the temperature 30min minutes, closes heating.Configuration volume ratio is hydrochloric acid: the cleaning solution of water=1/7 is to above-mentioned reaction
Products therefrom is repeatedly washed, and each wash volumes are 300mL, and washing times are 5 times, and the mode of washing used is suction filtration.
The special mold briquetting of products therefrom filter cake will be filtered, the filter cake taking-up after pressure is put into culture dish and is placed in convection oven
Dry, drying temperature is 80 DEG C, and drying time is that timing was at interval of two hours progress weighing materials since dry, until interval
Two hours material weightlessness is 0.5% as the dry standard completed.It is low that material after drying is placed in vacuum drying oven progress
Warm reduction, the temperature of vacuum drying oven are 200 DEG C, and the Low Temperature Thermal recovery time is 20min.Material after low temperature is heat-treated adds water
Washing 5 times, is subsequently placed in convection oven dry, and drying temperature is 80 DEG C, drying time be since dry timing at interval of
Two hours progress weighing materials, until the two hours material weightlessness in interval is 0.5% as the dry standard completed.Washing is dry
Material after dry is placed in tube furnace progress high temperature thermal reduction, and temperature is 1000 DEG C in tube furnace, and the high temperature thermal reduction time is
2h finally obtains Graphene/carbon nanotube composite material.Using the Graphene/carbon nanotube composite material being prepared as leading
Electric agent is added in tertiary cathode material system, additive amount 1.0%, is fabricated to positive plate after stirring slurry, film, drying, weighs
Positive tablet quality is put into glove box stand-by;Carry out the assembly of CR2032 button cell, assemble sequence is as follows: negative electrode casing upward, according to
It is secondary to be put into elastic slice, gasket, cathode lithium piece, diaphragm, positive plate (downward), appropriate electrolyte is added, finally buckles anode cover (court
Under), directly battery is sealed with sealing machine, takes out set aside for use from glove box;Button cell is finally placed on new prestige
On cell tester, test work step by Cycle: 0.1C fills/0.1C puts 3 circle of circulation, and 0.2C fills/and 0.2C puts 5 circle of circulation, 0.3C
Fill/1C puts 5 circle of circulation, and 0.3C fills/and 1C puts 5 circle of circulation, and it is tested, finally obtains its battery high rate performance as a result, being shown in Table 2
(data are respectively first circle discharge capacity under 0.1C, 1C, 2C multiplying power in table).
Embodiment 5:
In ice-water bath, by graphite under 150rpm stirring condition: the concentrated sulfuric acid=1:50 mass ratio is added to reaction vessel
In, it is stirred to react 20min, then in ice-water bath, by graphite under 200rpm stirring condition: potassium permanganate=1:2 mass ratio
Potassium permanganate is slowly added into reaction solution, and control system temperature is 15 DEG C, and the entire process time that feeds is about 30min.To
After potassium permanganate adds, entire reaction system is made to keep the temperature 2h at 30 DEG C, then by graphite: carbon nanotube powder=8:1 mass
The carbon nanotube powder of ratio directly adds reaction system, and entire reaction system is made to continue to keep the temperature 2h at 30 DEG C after adding.Heat preservation
Into reaction system slowly by graphite after end: water=1g:40mL water is added in reaction system, controls temperature in reaction system
It is 80 DEG C, mixing speed 200rpm.After adding water to keep the temperature 60min, into system by graphite: hydrogen peroxide=2g:1mL is double
Oxygen water is added, and keeps the temperature 30min minutes, closes heating.Configuration volume ratio is hydrochloric acid: the cleaning solution of water=1/7 is to above-mentioned reaction
Products therefrom is repeatedly washed, and each wash volumes are 300mL, and washing times are 5 times, and the mode of washing used is suction filtration.
The special mold briquetting of products therefrom filter cake will be filtered, the filter cake taking-up after pressure is put into culture dish and is placed in convection oven
Dry, drying temperature is 80 DEG C, and drying time is that timing was at interval of two hours progress weighing materials since dry, until interval
Two hours material weightlessness is 0.5% as the dry standard completed.It is low that material after drying is placed in vacuum drying oven progress
Warm reduction, the temperature of vacuum drying oven are 200 DEG C, and the Low Temperature Thermal recovery time is 20min.Material after low temperature is heat-treated adds water
Washing 5 times, is subsequently placed in convection oven dry, and drying temperature is 80 DEG C, drying time be since dry timing at interval of
Two hours progress weighing materials, until the two hours material weightlessness in interval is 0.5% as the dry standard completed.Washing is dry
Material after dry is placed in tube furnace progress high temperature thermal reduction, and temperature is 1000 DEG C in tube furnace, and the high temperature thermal reduction time is
2h finally obtains Graphene/carbon nanotube composite material.Using the Graphene/carbon nanotube composite material being prepared as leading
Electric agent is added in tertiary cathode material system, additive amount 1.0%, is fabricated to positive plate after stirring slurry, film, drying, weighs
Positive tablet quality is put into glove box stand-by;Carry out the assembly of CR2032 button cell, assemble sequence is as follows: negative electrode casing upward, according to
It is secondary to be put into elastic slice, gasket, cathode lithium piece, diaphragm, positive plate (downward), appropriate electrolyte is added, finally buckles anode cover (court
Under), directly battery is sealed with sealing machine, takes out set aside for use from glove box;Button cell is finally placed on new prestige
On cell tester, test work step by Cycle: 0.1C fills/0.1C puts 3 circle of circulation, and 0.2C fills/and 0.2C puts 5 circle of circulation, 0.3C
Fill/1C puts 5 circle of circulation, and 0.3C fills/and 1C puts 5 circle of circulation, and it is tested, finally obtains its battery high rate performance as a result, being shown in Table 2
(data are respectively first circle discharge capacity under 0.1C, 1C, 2C multiplying power in table).
Embodiment 6:
In ice-water bath, by graphite under 150rpm stirring condition: the concentrated sulfuric acid=1:30 mass ratio is added to reaction vessel
In, it is stirred to react 20min, then in ice-water bath, by graphite under 200rpm stirring condition: potassium permanganate=1:4 mass ratio
Potassium permanganate is slowly added into reaction solution, and control system temperature is 15 DEG C, and the entire process time that feeds is about 30min.To
After potassium permanganate adds, entire reaction system is made to keep the temperature 2h at 30 DEG C, then by graphite: carbon nanotube powder=8:1 mass
The carbon nanotube powder of ratio directly adds reaction system, and entire reaction system is made to continue to keep the temperature 2h at 30 DEG C after adding.Heat preservation
Into reaction system slowly by graphite after end: water=1g:40mL water is added in reaction system, controls temperature in reaction system
It is 80 DEG C, mixing speed 200rpm.After adding water to keep the temperature 60min, into system by graphite: hydrogen peroxide=2g:1mL is double
Oxygen water is added, and keeps the temperature 30min minutes, closes heating.Configuration volume ratio is hydrochloric acid: the cleaning solution of water=1/7 is to above-mentioned reaction
Products therefrom is repeatedly washed, and each wash volumes are 300mL, and washing times are 5 times, and the mode of washing used is suction filtration.
The special mold briquetting of products therefrom filter cake will be filtered, the filter cake taking-up after pressure is put into culture dish and is placed in convection oven
Dry, drying temperature is 80 DEG C, and drying time is that timing was at interval of two hours progress weighing materials since dry, until interval
Two hours material weightlessness is 0.5% as the dry standard completed.It is low that material after drying is placed in vacuum drying oven progress
Warm reduction, the temperature of vacuum drying oven are 200 DEG C, and the Low Temperature Thermal recovery time is 20min.Material after low temperature is heat-treated adds water
Washing 5 times, is subsequently placed in convection oven dry, and drying temperature is 80 DEG C, drying time be since dry timing at interval of
Two hours progress weighing materials, until the two hours material weightlessness in interval is 0.5% as the dry standard completed.Washing is dry
Material after dry is placed in tube furnace progress high temperature thermal reduction, and temperature is 1000 DEG C in tube furnace, and the high temperature thermal reduction time is
2h finally obtains Graphene/carbon nanotube composite material.Using the Graphene/carbon nanotube composite material being prepared as leading
Electric agent is added in tertiary cathode material system, additive amount 1.0%, is fabricated to positive plate after stirring slurry, film, drying, weighs
Positive tablet quality is put into glove box stand-by;Carry out the assembly of CR2032 button cell, assemble sequence is as follows: negative electrode casing upward, according to
It is secondary to be put into elastic slice, gasket, cathode lithium piece, diaphragm, positive plate (downward), appropriate electrolyte is added, finally buckles anode cover (court
Under), directly battery is sealed with sealing machine, takes out set aside for use from glove box;Button cell is finally placed on new prestige
On cell tester, test work step by Cycle: 0.1C fills/0.1C puts 3 circle of circulation, and 0.2C fills/and 0.2C puts 5 circle of circulation, 0.3C
Fill/1C puts 5 circle of circulation, and 0.3C fills/and 1C puts 5 circle of circulation, and it is tested, finally obtains its battery high rate performance as a result, being shown in Table 2
(data are respectively first circle discharge capacity under 0.1C, 1C, 2C multiplying power in table).
Embodiment 7:
In ice-water bath, by graphite under 150rpm stirring condition: the concentrated sulfuric acid=1:30 mass ratio is added to reaction vessel
In, it is stirred to react 20min, then in ice-water bath, by graphite under 200rpm stirring condition: potassium permanganate=1:2 mass ratio
Potassium permanganate is slowly added into reaction solution, and control system temperature is 15 DEG C, and the entire process time that feeds is about 30min.To
After potassium permanganate adds, entire reaction system is made to keep the temperature 2h at 30 DEG C, then by graphite: carbon nanotube powder=8:1 mass
The carbon nanotube powder of ratio directly adds reaction system, and entire reaction system is made to continue to keep the temperature 2h at 30 DEG C after adding.Heat preservation
Into reaction system slowly by graphite after end: water=1g:24mL water is added in reaction system, controls temperature in reaction system
It is 80 DEG C, mixing speed 200rpm.After adding water to keep the temperature 60min, into system by graphite: hydrogen peroxide=2g:1mL is double
Oxygen water is added, and keeps the temperature 30min minutes, closes heating.Configuration volume ratio is hydrochloric acid: the cleaning solution of water=1/7 is to above-mentioned reaction
Products therefrom is repeatedly washed, and each wash volumes are 300mL, and washing times are 5 times, and the mode of washing used is suction filtration.
The special mold briquetting of products therefrom filter cake will be filtered, the filter cake taking-up after pressure is put into culture dish and is placed in convection oven
Dry, drying temperature is 80 DEG C, and drying time is that timing was at interval of two hours progress weighing materials since dry, until interval
Two hours material weightlessness is 0.5% as the dry standard completed.It is low that material after drying is placed in vacuum drying oven progress
Warm reduction, the temperature of vacuum drying oven are 200 DEG C, and the Low Temperature Thermal recovery time is 20min.Material after low temperature is heat-treated adds water
Washing 5 times, is subsequently placed in convection oven dry, and drying temperature is 80 DEG C, drying time be since dry timing at interval of
Two hours progress weighing materials, until the two hours material weightlessness in interval is 0.5% as the dry standard completed.Washing is dry
Material after dry is placed in tube furnace progress high temperature thermal reduction, and temperature is 1000 DEG C in tube furnace, and the high temperature thermal reduction time is
2h finally obtains Graphene/carbon nanotube composite material.Using the Graphene/carbon nanotube composite material being prepared as leading
Electric agent is added in tertiary cathode material system, additive amount 1.0%, is fabricated to positive plate after stirring slurry, film, drying, weighs
Positive tablet quality is put into glove box stand-by;Carry out the assembly of CR2032 button cell, assemble sequence is as follows: negative electrode casing upward, according to
It is secondary to be put into elastic slice, gasket, cathode lithium piece, diaphragm, positive plate (downward), appropriate electrolyte is added, finally buckles anode cover (court
Under), directly battery is sealed with sealing machine, takes out set aside for use from glove box;Button cell is finally placed on new prestige
On cell tester, test work step by Cycle: 0.1C fills/0.1C puts 3 circle of circulation, and 0.2C fills/and 0.2C puts 5 circle of circulation, 0.3C
Fill/1C puts 5 circle of circulation, and 0.3C fills/and 1C puts 5 circle of circulation, and it is tested, finally obtains its battery high rate performance as a result, being shown in Table 2
(data are respectively first circle discharge capacity under 0.1C, 1C, 2C multiplying power in table).
Embodiment 8:
In ice-water bath, by graphite under 150rpm stirring condition: the concentrated sulfuric acid=1:30 mass ratio is added to reaction vessel
In, it is stirred to react 20min, then in ice-water bath, by graphite under 200rpm stirring condition: potassium permanganate=1:2 mass ratio
Potassium permanganate is slowly added into reaction solution, and control system temperature is 15 DEG C, and the entire process time that feeds is about 30min.To
After potassium permanganate adds, entire reaction system is made to keep the temperature 2h at 30 DEG C, then by graphite: carbon nanotube powder=8:1 mass
The carbon nanotube powder of ratio directly adds reaction system, and entire reaction system is made to continue to keep the temperature 2h at 30 DEG C after adding.Heat preservation
Into reaction system slowly by graphite after end: water=1g:60mL water is added in reaction system, controls temperature in reaction system
It is 80 DEG C, mixing speed 200rpm.After adding water to keep the temperature 60min, into system by graphite: hydrogen peroxide=2g:1mL is double
Oxygen water is added, and keeps the temperature 30min minutes, closes heating.Configuration volume ratio is hydrochloric acid: the cleaning solution of water=1/7 is to above-mentioned reaction
Products therefrom is repeatedly washed, and each wash volumes are 300mL, and washing times are 5 times, and the mode of washing used is suction filtration.
The special mold briquetting of products therefrom filter cake will be filtered, the filter cake taking-up after pressure is put into culture dish and is placed in convection oven
Dry, drying temperature is 80 DEG C, and drying time is that timing was at interval of two hours progress weighing materials since dry, until interval
Two hours material weightlessness is 0.5% as the dry standard completed.It is low that material after drying is placed in vacuum drying oven progress
Warm reduction, the temperature of vacuum drying oven are 200 DEG C, and the Low Temperature Thermal recovery time is 20min.Material after low temperature is heat-treated adds water
Washing 5 times, is subsequently placed in convection oven dry, and drying temperature is 80 DEG C, drying time be since dry timing at interval of
Two hours progress weighing materials, until the two hours material weightlessness in interval is 0.5% as the dry standard completed.Washing is dry
Material after dry is placed in tube furnace progress high temperature thermal reduction, and temperature is 1000 DEG C in tube furnace, and the high temperature thermal reduction time is
2h finally obtains Graphene/carbon nanotube composite material.Using the Graphene/carbon nanotube composite material being prepared as leading
Electric agent is added in tertiary cathode material system, additive amount 1.0%, is fabricated to positive plate after stirring slurry, film, drying, weighs
Positive tablet quality is put into glove box stand-by;Carry out the assembly of CR2032 button cell, assemble sequence is as follows: negative electrode casing upward, according to
It is secondary to be put into elastic slice, gasket, cathode lithium piece, diaphragm, positive plate (downward), appropriate electrolyte is added, finally buckles anode cover (court
Under), directly battery is sealed with sealing machine, takes out set aside for use from glove box;Button cell is finally placed on new prestige
On cell tester, test work step by Cycle: 0.1C fills/0.1C puts 3 circle of circulation, and 0.2C fills/and 0.2C puts 5 circle of circulation, 0.3C
Fill/1C puts 5 circle of circulation, and 0.3C fills/and 1C puts 5 circle of circulation, and it is tested, finally obtains its battery high rate performance as a result, being shown in Table 2
(data are respectively first circle discharge capacity under 0.1C, 1C, 2C multiplying power in table).
Embodiment 9:
In ice-water bath, by graphite under 150rpm stirring condition: the concentrated sulfuric acid=1:30 mass ratio is added to reaction vessel
In, it is stirred to react 20min, then in ice-water bath, by graphite under 200rpm stirring condition: potassium permanganate=1:2 mass ratio
Potassium permanganate is slowly added into reaction solution, and control system temperature is 15 DEG C, and the entire process time that feeds is about 30min.To
After potassium permanganate adds, entire reaction system is made to keep the temperature 2h at 30 DEG C, then by graphite: carbon nanotube powder=8:1 mass
The carbon nanotube powder of ratio directly adds reaction system, and entire reaction system is made to continue to keep the temperature 2h at 30 DEG C after adding.Heat preservation
Into reaction system slowly by graphite after end: water=1g:40mL water is added in reaction system, controls temperature in reaction system
It is 80 DEG C, mixing speed 200rpm.After adding water to keep the temperature 60min, into system by graphite: hydrogen peroxide=1g:1mL is double
Oxygen water is added, and keeps the temperature 30min minutes, closes heating.Configuration volume ratio is hydrochloric acid: the cleaning solution of water=1/7 is to above-mentioned reaction
Products therefrom is repeatedly washed, and each wash volumes are 300mL, and washing times are 5 times, and the mode of washing used is suction filtration.
The special mold briquetting of products therefrom filter cake will be filtered, the filter cake taking-up after pressure is put into culture dish and is placed in convection oven
Dry, drying temperature is 80 DEG C, and drying time is that timing was at interval of two hours progress weighing materials since dry, until interval
Two hours material weightlessness is 0.5% as the dry standard completed.It is low that material after drying is placed in vacuum drying oven progress
Warm reduction, the temperature of vacuum drying oven are 200 DEG C, and the Low Temperature Thermal recovery time is 20min.Material after low temperature is heat-treated adds water
Washing 5 times, is subsequently placed in convection oven dry, and drying temperature is 80 DEG C, drying time be since dry timing at interval of
Two hours progress weighing materials, until the two hours material weightlessness in interval is 0.5% as the dry standard completed.Washing is dry
Material after dry is placed in tube furnace progress high temperature thermal reduction, and temperature is 1000 DEG C in tube furnace, and the high temperature thermal reduction time is
2h finally obtains Graphene/carbon nanotube composite material.Using the Graphene/carbon nanotube composite material being prepared as leading
Electric agent is added in tertiary cathode material system, additive amount 1.0%, is fabricated to positive plate after stirring slurry, film, drying, weighs
Positive tablet quality is put into glove box stand-by;Carry out the assembly of CR2032 button cell, assemble sequence is as follows: negative electrode casing upward, according to
It is secondary to be put into elastic slice, gasket, cathode lithium piece, diaphragm, positive plate (downward), appropriate electrolyte is added, finally buckles anode cover (court
Under), directly battery is sealed with sealing machine, takes out set aside for use from glove box;Button cell is finally placed on new prestige
On cell tester, test work step by Cycle: 0.1C fills/0.1C puts 3 circle of circulation, and 0.2C fills/and 0.2C puts 5 circle of circulation, 0.3C
Fill/1C puts 5 circle of circulation, and 0.3C fills/and 1C puts 5 circle of circulation, and it is tested, finally obtains its battery high rate performance as a result, being shown in Table 2
(data are respectively first circle discharge capacity under 0.1C, 1C, 2C multiplying power in table).
Embodiment 10:
In ice-water bath, by graphite under 150rpm stirring condition: the concentrated sulfuric acid=1:30 mass ratio is added to reaction vessel
In, it is stirred to react 20min, then in ice-water bath, by graphite under 200rpm stirring condition: potassium permanganate=1:2 mass ratio
Potassium permanganate is slowly added into reaction solution, and control system temperature is 15 DEG C, and the entire process time that feeds is about 30min.To
After potassium permanganate adds, entire reaction system is made to keep the temperature 2h at 30 DEG C, then by graphite: carbon nanotube powder=8:1 mass
The carbon nanotube powder of ratio directly adds reaction system, and entire reaction system is made to continue to keep the temperature 2h at 30 DEG C after adding.Heat preservation
Into reaction system slowly by graphite after end: water=1g:40mL water is added in reaction system, controls temperature in reaction system
It is 80 DEG C, mixing speed 200rpm.After adding water to keep the temperature 60min, into system by graphite: hydrogen peroxide=5g:1mL is double
Oxygen water is added, and keeps the temperature 30min minutes, closes heating.Configuration volume ratio is hydrochloric acid: the cleaning solution of water=1/7 is to above-mentioned reaction
Products therefrom is repeatedly washed, and each wash volumes are 300mL, and washing times are 5 times, and the mode of washing used is suction filtration.
The special mold briquetting of products therefrom filter cake will be filtered, the filter cake taking-up after pressure is put into culture dish and is placed in convection oven
Dry, drying temperature is 80 DEG C, and drying time is that timing was at interval of two hours progress weighing materials since dry, until interval
Two hours material weightlessness is 0.5% as the dry standard completed.It is low that material after drying is placed in vacuum drying oven progress
Warm reduction, the temperature of vacuum drying oven are 200 DEG C, and the Low Temperature Thermal recovery time is 20min.Material after low temperature is heat-treated adds water
Washing 5 times, is subsequently placed in convection oven dry, and drying temperature is 80 DEG C, drying time be since dry timing at interval of
Two hours progress weighing materials, until the two hours material weightlessness in interval is 0.5% as the dry standard completed.Washing is dry
Material after dry is placed in tube furnace progress high temperature thermal reduction, and temperature is 1000 DEG C in tube furnace, and the high temperature thermal reduction time is
2h finally obtains Graphene/carbon nanotube composite material agent.Using the Graphene/carbon nanotube composite material being prepared as
Conductive agent is added in tertiary cathode material system, additive amount 1.0%, is fabricated to positive plate after stirring slurry, film, drying, claims
Positive tablet quality is taken, is put into glove box stand-by;Carry out the assembly of CR2032 button cell, assemble sequence is as follows: negative electrode casing upward,
It is sequentially placed into elastic slice, gasket, cathode lithium piece, diaphragm, positive plate (downward), appropriate electrolyte is added, finally buckles anode cover (court
Under), directly battery is sealed with sealing machine, takes out set aside for use from glove box;Button cell is finally placed on new prestige
On cell tester, test work step by Cycle: 0.1C fills/0.1C puts 3 circle of circulation, and 0.2C fills/and 0.2C puts 5 circle of circulation, 0.3C
Fill/1C puts 5 circle of circulation, and 0.3C fills/and 1C puts 5 circle of circulation, and it is tested, finally obtains its battery high rate performance as a result, being shown in Table 2
(data are respectively first circle discharge capacity under 0.1C, 1C, 2C multiplying power in table).
Table 2: the battery high rate performance result of Graphene/carbon nanotube composite material of the invention as conductive agent
According to the first circle discharge capacity under the conditions of different multiplying (0.1C, 1C and 2C) in table 2, it can be seen that according to the present invention
The Graphene/carbon nanotube composite material that is prepared of method there is good gram volume and high rate performance as conductive agent.
Finally, it should be noted that the foregoing is only a preferred embodiment of the present invention, it is not intended to restrict the invention,
Although the present invention is described in detail referring to the foregoing embodiments, for those skilled in the art, still may be used
To modify the technical solutions described in the foregoing embodiments or equivalent replacement of some of the technical features.
All within the spirits and principles of the present invention, any modification, equivalent replacement, improvement and so on should be included in of the invention
Within protection scope.
Claims (11)
1. a kind of preparation method of Graphene/carbon nanotube composite material characterized by comprising
The preparation of graphite oxide/Carbon Nanotube system;With
Reduction gained graphite oxide/Carbon Nanotube system.
2. preparation method according to claim 1, which is characterized in that the graphite oxide/Carbon Nanotube system
The preparation method comprises the following steps:
Carbon nanotube powder is added in the oxidation reaction process of graphite, washs after reaction, be dried to obtain graphite oxide/carbon
Nanotube compound system.
3. preparation method according to claim 2, which is characterized in that the graphite oxide/Carbon Nanotube system
The preparation method comprises the following steps:
S1: concentrated sulfuric acid graphite oxide is utilized;
S2: the further graphite oxide of potassium permanganate, the Xiang Fanying in oxidation reaction process are added into the reaction system that S1 is obtained
Carbon nanotube powder is added in system;
S3: hydrogen peroxide being added into the reaction system that S2 is obtained, and it is compound molten to obtain graphite oxide/carbon nanotube after reaction
Liquid;With
S4: gained graphite oxide/CNT composite solution is washed, is dried.
4. preparation method according to claim 3, which is characterized in that
In the S1, the concentration of the concentrated sulfuric acid is 98%;The mass ratio of the graphite and the concentrated sulfuric acid is 1:(20-50), preferably
1:30;
And/or the reaction condition of the S1 are as follows: in ice-water bath, the graphite and dense is mixed under 100-300rpm stirring condition
Sulfuric acid reacts 10-30min;Preferably, hybrid reaction 20min under 150rpm stirring condition.
5. preparation method according to claim 3, which is characterized in that
In the S2, the mass ratio of the graphite and potassium permanganate is 1:(2-4), preferably 1:2;
And/or in the S2, the mass ratio of the graphite and carbon nanotube powder is (1-15): 1, preferably 8:1;
And/or the reaction condition of the S2 are as follows: under 100-300rpm stirring condition, be added into the reaction solution that S1 is obtained high
Potassium manganate, the temperature that adition process controls reaction system is 10-20 DEG C, and potassium permanganate is warming up at 25-35 DEG C after being added
Keep the temperature 1-2h;It keeps the temperature and carbon nanotube is added to reaction system after terminating, then reaction system is made to continue to keep the temperature at 25-35 DEG C
30min-2h;
Preferably, in ice-water bath, the potassium permanganate is added under 200rpm stirring condition into the reaction system of the S1;
And/or
Preferably, then reaction system is made to continue to keep the temperature 60min at 30 DEG C.
6. preparation method according to claim 3, which is characterized in that the concrete operation method of the S3 are as follows:
Under stirring, water is first added into the reaction system that S2 is obtained, the temperature of control system is 10-80 DEG C, continues to be kept stirring
Lower heat preservation 40-80min;Be added hydrogen peroxide into reaction system again, keep the temperature 20-40min, stop heating to get to graphite oxide/
CNT composite solution;
Wherein the amount of the water is according to graphite: water=1g:(24-60) addition of the amount of mL, preferably graphite: water=1g:40mL;With
Wherein the amount of the hydrogen peroxide is according to graphite: the addition of hydrogen peroxide=(1-5) g:1mL amount, preferably graphite: hydrogen peroxide=
2g:1mL.
7. preparation method according to claim 3, which is characterized in that
In the S4, the concrete operation method that gained graphite oxide/CNT composite solution is washed, dried
Are as follows:
Gained graphite oxide/CNT composite solution is washed with hydrochloric acid solution, is then dried;
Wherein hydrochloric acid in the hydrochloric acid solution: the volume ratio of water is 1:(5-10), preferred hydrochloric acid: the volume ratio of water is 1:7;
Wherein the mode of washing is using one of centrifugation or suction filtration or combinations thereof;Wherein the revolving speed of the centrifugation is 3000-
6000rpm, centrifugation time 15-30min, preferably 5000rpm, time 20min;Preferably, the mode of washing is using pumping
Filter mode, until to touch material non-sticky for hand;
Wherein the washing times are 3-5 times, use the hydrochloric acid solution 200-500ml every time, it is preferable that the washing times
It is 5 times, uses the hydrochloric acid solution 300ml every time;With
Wherein the mode of the drying is using convection oven, and dry temperature is 60-80 DEG C, preferably 80 DEG C.
8. preparation method according to claim 1, which is characterized in that the reduction-oxidation graphite/carbon nanometer tube complex
The method of the first low temperature thermal expansion of system's use, again high temperature reduction;
Wherein the temperature of the Low Temperature Thermal expansion is 180-250 DEG C, and the time of low temperature thermal expansion is 5-30min;Preferably, described
The temperature of low temperature thermal expansion is 200 DEG C, and the time of low temperature thermal expansion is 20min;With
Wherein the temperature of the high temperature reduction is 800-1000 DEG C, and the time of high temperature reduction is 1-2h;Preferably, the high temperature is also
Former temperature is 1000 DEG C, and the high temperature reduction time is 2h.
9. preparation method according to claim 8, which is characterized in that the reduction-oxidation graphite/carbon nanometer tube complex
System is using first low temperature thermal expansion, washing, dry, high temperature reduction again method;
Wherein the washing uses water washing 3-5 times, and preferably 5 times, described dry dry using convection oven, drying temperature is
60-80 DEG C, preferably 80 DEG C;
And/or wherein the Low Temperature Thermal expansion carries out under vacuum condition or inert atmosphere;
And/or wherein the high temperature reduction carries out under vacuum condition or inert atmosphere.
10. a kind of Graphene/carbon nanotube composite material, which is characterized in that including graphene sheet layer and be distributed in graphene film
Carbon nanotube between layer, adjoining graphite alkene piece interlayer are separated by carbon nanotube;
And/or in the Graphene/carbon nanotube composite material carbon nanotube mass score be 5-20%, preferably 10%;
And/or the partial size D50 of the Graphene/carbon nanotube composite material is 3-15 μm;
And/or the specific surface area of the Graphene/carbon nanotube composite material is 100-300m2/g;
And/or the tap density of the Graphene/carbon nanotube composite material is 0.1-0.5g/cm3;
And/or the oil factor of the Graphene/carbon nanotube composite material is 500-1000 (10-5m3/kg);
Preferably, Graphene/carbon nanotube composite material prepared according to preparation method of any of claims 1-9 and
At.
11. application of the Graphene/carbon nanotube composite material according to claim 10 as electrode material conductive agent.
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CN113428851A (en) * | 2021-06-11 | 2021-09-24 | 江苏天奈科技股份有限公司 | Graphene-carbon nanotube composite material, preparation method thereof and prepared graphene-carbon nanotube composite slurry |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103346022A (en) * | 2013-07-03 | 2013-10-09 | 中国科学院福建物质结构研究所 | Method for preparing graphene/ nanocarbon particle composite |
CN103956498A (en) * | 2014-04-18 | 2014-07-30 | 西南石油大学 | Preparation method of carbon nanotube/graphene composite material |
CN104852021A (en) * | 2015-03-24 | 2015-08-19 | 天津师范大学 | Preparation method of graphene/carbon nanotube composite material |
CN107516740A (en) * | 2017-07-12 | 2017-12-26 | 常州第六元素材料科技股份有限公司 | A kind of carbon ink, graphene powder combined conductive agent and preparation method thereof, application |
-
2017
- 2017-12-29 CN CN201711477862.3A patent/CN109994733A/en active Pending
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103346022A (en) * | 2013-07-03 | 2013-10-09 | 中国科学院福建物质结构研究所 | Method for preparing graphene/ nanocarbon particle composite |
CN103956498A (en) * | 2014-04-18 | 2014-07-30 | 西南石油大学 | Preparation method of carbon nanotube/graphene composite material |
CN104852021A (en) * | 2015-03-24 | 2015-08-19 | 天津师范大学 | Preparation method of graphene/carbon nanotube composite material |
CN107516740A (en) * | 2017-07-12 | 2017-12-26 | 常州第六元素材料科技股份有限公司 | A kind of carbon ink, graphene powder combined conductive agent and preparation method thereof, application |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN113428851A (en) * | 2021-06-11 | 2021-09-24 | 江苏天奈科技股份有限公司 | Graphene-carbon nanotube composite material, preparation method thereof and prepared graphene-carbon nanotube composite slurry |
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