CN111933949A - Graphene conductive agent with adjustable sheet diameter distribution ratio, preparation method thereof, negative electrode and lithium ion battery - Google Patents
Graphene conductive agent with adjustable sheet diameter distribution ratio, preparation method thereof, negative electrode and lithium ion battery Download PDFInfo
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Abstract
The invention provides a graphene conductive agent with adjustable sheet diameter distribution ratio, which comprises the following components in percentage by mass: graphene material: 0.1-20%; dispersing agent: 0.2-18%; other auxiliary agents: 0 to 12 percent; water: 80-99.8%; the graphene material comprises two or three of first graphene with D50 of 0.1-3 mu m, second graphene with D50 of 2-10 mu m and third graphene with D50 of 8-20 mu m. In the graphene conductive agent, the graphene with different sheet diameters can provide dimension-oriented conduction in a three-dimensional conductive network, has a very low steric hindrance effect, and can effectively improve the rate capability of a battery; the bridging effect of different sheet diameters in the active material greatly reduces the resistivity of the sheet, and effectively improves the specific capacity and the rate capability of the lithium battery. The invention also provides a preparation method of the graphene conductive agent with adjustable sheet diameter distribution ratio, a negative electrode and a lithium ion battery.
Description
Technical Field
The invention belongs to the technical field of lithium ion batteries, and particularly relates to a graphene conductive agent with adjustable sheet diameter distribution proportion, a preparation method thereof, a negative electrode and a lithium ion battery.
Background
The lithium ion battery has the characteristics of low cost, environmental friendliness, high specific energy, no memory effect, light weight and the like, and becomes an important component of a power supply (medical equipment, entertainment equipment, a computer, communication equipment, an electric automobile, an aerospace vehicle and the like). The positive electrode of the lithium ion battery usually adopts transition metal oxides as active materials, such as layered lithium cobaltate, lithium nickelate, lithium nickel cobaltate or lithium iron phosphate, and the negative electrode usually adopts graphite, silicon-based materials and the like as active materials.
Although active materials with good conductivity, such as hard carbon and graphite, are used as negative electrode materials, they expand and contract during many charge and discharge cycles, resulting in poor contact between the active materials, and therefore, it is urgently required to select a conductive agent with excellent conductivity, low density, and stable structure and chemical properties to be added to the active materials.
The conductive agent is generally classified into a metal-based conductive agent (silver powder, copper powder, nickel powder, etc.), a metal oxide-based conductive agent (tin oxide, iron oxide, zinc oxide, etc.), a carbon-based conductive agent (carbon black, graphite, etc.), a composite conductive agent (composite powder, composite fiber, etc.), and other conductive agents. The conductive agent added into the lithium ion battery can not participate in the redox reaction in the battery, and has high acid-base corrosion resistance, and the carbon conductive agent has the characteristics of low cost, light weight and the like besides meeting the conditions. The carbon-based conductive agent mainly comprises conductive graphite, conductive carbon black, a fibrous conductive agent and graphene. Since graphene is discovered, the application of graphene as a negative electrode conductive agent is always concerned, but the performance of the existing graphene conductive agent is still to be improved, and how to prepare a graphene conductive agent with good performance on a large scale is a problem to be solved at present.
Disclosure of Invention
The invention aims to provide a graphene conductive agent with adjustable sheet diameter distribution ratio, a preparation method thereof, a negative electrode and a lithium ion battery.
The invention provides a graphene conductive agent with adjustable sheet diameter distribution ratio, which comprises the following components in percentage by mass:
graphene material: 0.1-20%;
dispersing agent: 0.2-18%;
other auxiliary agents: 0 to 12 percent;
water: 80-99.8%;
the graphene material comprises two or three of first graphene with D50 of 0.1-3 mu m, second graphene with D50 of 2-10 mu m and third graphene with D50 of 8-20 mu m.
Preferably, in the graphene material, the mass fraction of the first graphene is 10-90%, the mass fraction of the second graphene is 10-90%, and the mass fraction of the third graphene is 0-40%.
Preferably, the other auxiliary agents comprise one or more of a stabilizing agent, a viscosity reducer, a bacteriostatic agent and an alkaline medium.
The preparation method of the graphene conductive agent with the adjustable sheet diameter distribution ratio comprises the following steps:
A) adding a dispersing agent and other additives into water, and uniformly stirring to obtain an additive solution;
B) adding a first graphite carbon material into the aid solution, and stirring and dispersing under an ultrasonic condition to obtain a first pre-dispersion liquid;
C) grinding the first pre-dispersion liquid, and then carrying out homogeneous stripping under the pressure of 100-200 MPa to obtain a graphene conductive agent containing first graphene and second graphene;
alternatively, the first and second electrodes may be,
D) adding a second graphite carbon material into the graphene conductive agent obtained in the step C), and stirring and dispersing under the ultrasonic condition to obtain a second pre-dispersion liquid;
E) grinding the second pre-dispersion liquid, and then carrying out homogeneous stripping under the pressure of 50-150 MPa to obtain a graphene conductive agent containing first graphene and second graphene;
in the graphene conductive agent in the step C) and the step E), the proportion of the first graphene to the second graphene is different;
alternatively, the first and second electrodes may be,
F) adding a third graphite carbon material into the graphene conductive agent obtained in the step E), and stirring and dispersing under the ultrasonic condition to obtain a third pre-dispersion liquid;
G) and grinding the third pre-dispersion liquid, and then carrying out homogeneous stripping under the pressure of 10-60 MPa to obtain the graphene conductive agent containing the first graphene, the second graphene and the third graphene.
Preferably, the power of the ultrasound in the step B) is 2-4 kW, and the linear speed of stirring is 5-12 m/s;
and C) grinding the zirconium beads with the particle size of 0.3-2.0 mm at the rotating speed of 200-1000 rpm, and then grinding the zirconium beads with the particle size of 0.1-1.0 mm at the rotating speed of 500-2000 rpm.
Preferably, the power of the ultrasound in the step D) is 2-4 kW, and the linear speed of stirring is 5-12 m/s;
and E) grinding the zirconium beads with the particle size of 0.3-2.0 mm at the rotating speed of 200-1000 rpm, and then grinding the zirconium beads with the particle size of 0.1-1.0 mm at the rotating speed of 500-2000 rpm.
Preferably, the power of the ultrasound in the step F) is 3-6 kW, and the linear speed of stirring is 10-15 m/s;
and G) grinding by using zirconium beads with the diameter of 0.3-2.0 mm at the rotating speed of 200-1000 rpm.
The invention provides a negative electrode which comprises the graphene conductive agent with the adjustable sheet diameter distribution ratio.
Preferably, the graphene conductive agent with adjustable sheet diameter distribution ratio is added to the negative electrode in a mass percentage of 0.1-5%.
The invention provides a lithium ion battery comprising the negative electrode.
The invention provides a graphene conductive agent with adjustable sheet diameter distribution ratio, which comprises the following components in percentage by mass: graphene material: 0.1-20%; dispersing agent: 0.2-18%; other auxiliary agents: 0 to 12 percent; water: 80-99.8%; the graphene material comprises two or three of first graphene with D50 of 0.1-3 mu m, second graphene with D50 of 2-10 mu m and third graphene with D50 of 8-20 mu m. In the graphene conductive agent, the graphene material is formed by compounding graphene with different sheet diameters, so that the dimension-oriented conduction in a three-dimensional conductive network can be provided, the steric effect is very low, and the rate capability of a battery can be effectively improved; the bridging effect of different sheet diameters in the active material greatly reduces the resistivity of the sheet, and effectively improves the specific capacity and the rate capability of the lithium battery.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the provided drawings without creative efforts.
Fig. 1 is an SEM image of graphene paste in a negative electrode active material in example 2 of the present invention;
fig. 2 is an SEM image of the graphene paste in the negative electrode active material in example 6 of the present invention.
Detailed Description
The invention provides a graphene conductive agent with adjustable sheet diameter distribution ratio, which comprises the following components in percentage by mass:
graphene material: 0.1-20%;
dispersing agent: 0.2-18%;
other auxiliary agents: 0 to 12 percent;
water: 80-99.8%;
the graphene material comprises two or three of first graphene with D50 of 0.1-3 mu m, second graphene with D50 of 2-10 mu m and third graphene with D50 of 8-20 mu m.
In the invention, the graphene material is prepared by compounding graphene materials with different particle sizes or sheet sizes, preferably two or three particle sizes, specifically, the graphene material can be prepared by compounding first graphene with D50 of 0.1-3 μm and second graphene with D50 of 2-10 μm, or can be prepared by compounding first graphene with D50 of 0.1-3 μm, second graphene with D50 of 2-10 μm and third graphene with D50 of 8-20 μm; the graphene material preferably accounts for 0.1-20% by mass, more preferably accounts for 1-18% by mass, and most preferably accounts for 5-15% by mass.
In the graphene material of the present invention, the mass fraction of the first graphene is preferably 10 to 90%, more preferably 20 to 80%, most preferably 30 to 70%, and most preferably 40 to 60%, and specifically, in one embodiment of the present invention, may be 20%, in another embodiment of the present invention, may be 30%, in another embodiment of the present invention, may be 40%, in another embodiment of the present invention, may be 50%, and in another embodiment of the present invention, may be 80%;
the mass fraction of the second graphene is preferably 10 to 90%, more preferably 20 to 80%, most preferably 30 to 70%, most preferably 40 to 60%, and particularly, in one embodiment of the present invention, 20%, in another embodiment of the present invention, 30%, in another embodiment of the present invention, 40%, in another embodiment of the present invention, 50%, in another embodiment of the present invention, 60%, and in another embodiment of the present invention, 80%;
the mass fraction of the third graphene is preferably 0 to 40%, more preferably 1 to 40%, and most preferably 10 to 30%, specifically, in one embodiment of the present invention, 0%, in another embodiment of the present invention, 10%, in another embodiment of the present invention, 20%, and in another embodiment of the present invention, 40%.
In the invention, the dispersing agent is preferably one or more of polyvinylpyrrolidone, polyethylene glycol, modified polyvinylpyrrolidone, sodium carboxymethyl cellulose, polyvinyl alcohol, modified polydimethylsiloxane and chitosan; more preferably polyvinylpyrrolidone, modified polyvinylpyrrolidone; the mass fraction of the dispersant is preferably 0.2-18%, more preferably 0.5-15%, and most preferably 1-10%.
The other auxiliary agents are preferably one or more of a stabilizer, a viscosity reducer, a bacteriostatic agent and an alkaline medium; the bacteriostatic agent is preferably one or more of isothiazolinone, benzisothiazolinone, piperazine triazine, quaternary ammonium salt, pyridinium, imidazolium salt and isoquinuclidine salt; the mass fraction of the bacteriostatic agent is preferably 0.01-0.4%, and more preferably 0.1-0.3%;
the stabilizer is preferably one or more of sodium carboxymethylcellulose, modified cellulose fiber, modified montmorillonite, modified urea and water-based polyamide; the mass fraction of the stabilizer is preferably 0.05-1%, more preferably 0.1-0.8%, and most preferably 0.3-0.6%;
the alkaline medium is preferably one or more of organic amine, ammonia water and sodium hydroxide; the mass fraction of the alkaline medium is preferably 0.01 to 0.5%, more preferably 0.05 to 0.4%, and most preferably 0.1 to 0.3%.
In the present invention, the water used as the solvent is preferably deionized water,
the invention also provides a preparation method of the graphene conductive agent with adjustable sheet diameter distribution ratio, which comprises the following steps:
A) adding a dispersing agent and other additives into water, and uniformly stirring to obtain an additive solution;
B) adding a first graphite carbon material into the aid solution, and stirring and dispersing under an ultrasonic condition to obtain a first pre-dispersion liquid;
C) grinding the first pre-dispersion liquid, and then carrying out homogeneous stripping under the pressure of 100-200 MPa to obtain a graphene conductive agent containing first graphene and second graphene;
in the graphene conductive agent in the step C) and the step E), the proportion of the first graphene to the second graphene is different;
alternatively, the first and second electrodes may be,
D) adding a second graphite carbon material into the graphene conductive agent obtained in the step C), and stirring and dispersing under the ultrasonic condition to obtain a second pre-dispersion liquid;
E) grinding the second pre-dispersion liquid, and then carrying out homogeneous stripping under the pressure of 50-150 MPa to obtain a graphene conductive agent containing first graphene and second graphene;
alternatively, the first and second electrodes may be,
F) adding a third graphite carbon material into the graphene conductive agent obtained in the step E), and stirring and dispersing under the ultrasonic condition to obtain a third pre-dispersion liquid;
G) and grinding the third pre-dispersion liquid, and then carrying out homogeneous stripping under the pressure of 10-60 MPa to obtain the graphene conductive agent containing the first graphene, the second graphene and the third graphene.
In the present invention, the kinds and the amounts of the raw materials are the same as those of the graphene conductive agent, and are not described herein again.
The invention preferably firstly adds the dispersant and the stabilizer into the water, stirs the mixture, then adds the alkaline medium and the viscosity reducer into the mixture, and stirs the mixture evenly to obtain the assistant solution.
In the invention, the stirring speed after the dispersant and the stabilizer are added is preferably 1-5 m/s, more preferably 2-4 m/s, and most preferably 2.5-3 m/s, and the stirring time is preferably 10-60 min, more preferably 20-50 min, and most preferably 30-40 min; the stirring speed after the alkaline medium and the viscosity reducer are added is preferably 1-5 m/s, more preferably 2-4 m/s, and most preferably 2-3 m/s, and the stirring time is preferably 1-20 min, more preferably 5-15 min, and most preferably 10 min.
After an auxiliary agent solution is obtained, adding a first graphite carbon material into the auxiliary agent solution, and stirring and dispersing under an ultrasonic condition to obtain a first pre-dispersion liquid;
in the invention, the first graphite-like carbon material is preferably one or more of graphite, expanded graphite, expandable graphite and graphene; the power of the ultrasonic wave is preferably 2-4 kW, more preferably 2.5-3 kW, the linear speed of stirring is preferably 5-12 m/s, more preferably 6-10 m/s, 7-9 m/s, and specifically, in the embodiment of the invention, the linear speed can be 7m/s, 8m/s, 9m/s or 10 m/s; the stirring time is preferably 1 to 5 hours, more preferably 2 to 4 hours, and most preferably 3 to 3.5 hours.
Grinding the obtained first pre-dispersion liquid to obtain grinding slurry;
in the invention, the grinding is preferably divided into two stages, wherein in the first stage, 0.3-2.0 mm zirconium beads are firstly used for grinding for 0.2-1 hour at the rotating speed of 200-1000 rpm, and in the second stage, 0.1-1.0 mm zirconium beads are used for grinding for 0.5-2 hours at the rotating speed of 500-2000 rpm. Preferably, the grinding speed of the first stage is preferably 200-1000 rpm, more preferably 500-1000 rpm, and the grinding time of the first stage is preferably 0.2-1 hour, more preferably 10-20 min, and most preferably 15 min; the rotation speed of the second stage of grinding is preferably 500 to 2000rpm, more preferably 1000 to 1500rpm, and most preferably 1200rpm, specifically, in the embodiment of the present invention, 1000rpm, 1200rpm, or 1500 rpm; the grinding time in the second stage is preferably 0.5 to 2 hours, and more preferably 1 to 1.5 hours.
The present invention preferably uses a horizontal sand mill for the above grinding.
After the grinding is finished, homogenizing and stripping the grinding slurry by using a homogenizer to obtain first graphene slurry containing first graphene and second graphene, namely a graphene conductive agent;
in the invention, the pressure of the homogeneous peeling is preferably 100-200 Mpa, more preferably 100-150 Mpa, and specifically, in the embodiment of the invention, the pressure may be 100Mpa, 120Mpa or 150 Mpa; the number of the homogeneous peeling is preferably 2 to 10, and more preferably 2 to 3.
After the first graphene slurry containing the first graphene and the second graphene is obtained, the second graphite carbon material is added into the first graphene slurry, and is stirred and dispersed under the ultrasonic condition to obtain a second pre-dispersion liquid.
In the invention, the second graphite-like carbon material is preferably one or more of graphite, expanded graphite, expandable graphite and graphene; the power of the ultrasonic wave is preferably 2-4 kW, more preferably 2.5-3 kW, the linear speed of stirring is preferably 5-12 m/s, more preferably 6-10 m/s, 7-9 m/s, and specifically, in the embodiment of the invention, the linear speed can be 7m/s, 8m/s, 9m/s or 10 m/s; the stirring time is preferably 1 to 5 hours, more preferably 2 to 4 hours, and most preferably 3 to 3.5 hours.
Grinding the obtained second pre-dispersion liquid to obtain grinding slurry;
in the invention, the grinding is preferably divided into two stages, wherein in the first stage, 0.3-2.0 mm zirconium beads are firstly used for grinding for 0.2-1 hour at the rotating speed of 200-1000 rpm, and in the second stage, 0.1-1.0 mm zirconium beads are used for grinding for 0.5-2 hours at the rotating speed of 500-2000 rpm. Preferably, the grinding speed of the first stage is preferably 200-1000 rpm, more preferably 500-1000 rpm, and the grinding time of the first stage is preferably 0.2-1 hour, more preferably 10-20 min, and most preferably 15 min; the rotation speed of the second stage of grinding is preferably 500 to 2000rpm, more preferably 1000 to 1500rpm, and most preferably 1200rpm, specifically, in the embodiment of the present invention, 1000rpm, 1200rpm, or 1500 rpm; the grinding time in the second stage is preferably 0.5 to 2 hours, and more preferably 1 to 1.5 hours.
The present invention preferably uses a horizontal sand mill for the above grinding.
After the grinding is finished, homogenizing and stripping the grinding slurry by using a homogenizer to obtain second graphene slurry containing the first graphene and the second graphene;
in the invention, the pressure of the homogeneous peeling is preferably 50-150 Mpa, more preferably 60-120 Mpa, most preferably 80-100 Mpa, and specifically, in the embodiment of the invention, the pressure may be 80Mpa, 90Mpa, 100Mpa or 150 Mpa; the number of the homogeneous peeling is preferably 2 to 10, and more preferably 2 to 3.
The graphene conductive agent containing the first graphene and the second graphene can be obtained by the method, and the research of the application finds that the rate performance of the graphene conductive agent containing the first graphene and the second graphene is obviously improved, but the gram capacity is slightly reduced compared with the performance of a negative electrode and a lithium ion battery which are made of graphene materials with undivided sheet diameters in the prior art; the third graphite-like carbon material is added into the graphene conductive agent, and the graphene conductive agent containing the first graphene, the second graphene and the third graphene can be further obtained by carrying out homogeneous stripping under low pressure (relative to high-pressure homogeneous stripping of the first graphite-like carbon material and medium-high-pressure homogeneous stripping of the second graphite-like carbon material), and the gram capacity and the rate capability of the composite slurry containing the three-sheet-diameter graphene are both improved more obviously.
Further, adding a third graphite carbon material into the slurry containing the first graphene and the second graphene, and stirring and dispersing under an ultrasonic condition to obtain a third pre-dispersion liquid;
the third graphite-like carbon material is preferably one or more of graphite, expanded graphite, expandable graphite and graphene; the power of the ultrasound is preferably 3-6 kW, more preferably 3-5 kW, and specifically, in the embodiment of the invention, the power can be 3kW, 3.5kW or 4 kW; the linear speed of the stirring is preferably 10-15 m/s, more preferably 11-14 m/s, most preferably 12-13 m/s, and specifically, in the embodiment of the invention, 12m/s and 14m/s can be adopted; the stirring time is preferably 1 to 5 hours, more preferably 2 to 4 hours, and most preferably 3 to 3.5 hours.
Grinding the obtained third pre-dispersion liquid to obtain grinding slurry;
in the present invention, the polishing is performed using 0.3 to 2.0mm zirconium beads at a rotation speed of 200 to 1000rpm for 0.2 to 1 hour. Preferably, the grinding speed is preferably 200 to 1000rpm, more preferably 500 to 1000rpm, and the grinding time is preferably 0.2 to 1 hour, more preferably 10 to 20min, and most preferably 15 min.
The present invention preferably uses a horizontal sand mill for the above grinding.
After the grinding is finished, homogenizing and stripping the grinding slurry by using a homogenizer to obtain a graphene conductive agent containing first graphene, second graphene and third graphene;
in the invention, the pressure of the homogeneous peeling is preferably 10-60 Mpa, more preferably 20-50 Mpa, most preferably 30-40 Mpa, and specifically, in the embodiment of the invention, the pressure may be 20Mpa, 30Mpa or 40 Mpa; the number of the homogeneous peeling is preferably 1 to 5, more preferably 1 to 2.
In the present invention, the mass ratio of the first, second and third graphitic carbon materials is preferably (10 to 100): (0-80): (0 to 50), more preferably (10 to 100): (30-60): (0 to 35), most preferably (30 to 70): (40-60): (15-30), specifically, in the embodiment of the present invention, after the embodiment proportion normalization (the sum of the ratios is 100), the ratio may be 100:0:0, 68:32:0, 63:37:0, 48:38:14, 30:50:20, 28:33:39, 29:50:21, or 13:69: 18.
The composite graphene slurry with different sheet diameter distributions and proportions can be prepared by the process; the distribution range and the proportion range can be realized by adjusting the formula proportion and equipment process parameters (such as sand mill parameters and homogenizer parameters).
The invention also provides a negative electrode, which comprises the graphene conductive agent with the adjustable sheet diameter distribution ratio, preferably, the addition amount of the graphene conductive agent in the negative electrode is preferably 0.1-5 wt%, more preferably 0.5-3 wt%, and most preferably 1-2 wt%.
The types and the use amounts of other components of the lithium ion battery negative electrode, such as negative electrode active materials, binders and other auxiliary agents, are conventional in the field, and the description of the invention is omitted.
The invention also provides a lithium ion battery, wherein the negative electrode in the lithium ion battery is the negative electrode, namely the negative electrode of the lithium ion battery containing the graphene conductive agent. Other components of the lithium ion battery, such as the anode and the electrolyte, can adopt related materials commonly used by those skilled in the art, and the description of the invention is omitted.
The invention provides a graphene conductive agent which comprises the following components in percentage by mass: graphene material: 0.1-20%; dispersing agent: 0.2-18%; other auxiliary agents: 0 to 12 percent; water: 80-99.8%; the graphene material comprises two or three of first graphene with D50 of 0.1-3 mu m, second graphene with D50 of 2-10 mu m and third graphene with D50 of 8-20 mu m. In the graphene conductive agent, the graphene material is formed by compounding graphene with different sheet diameters, so that the dimension-oriented conduction in a three-dimensional conductive network can be provided, the steric effect is very low, and the rate capability of a battery can be effectively improved; the bridging effect of different sheet diameters in the active material greatly reduces the resistivity of the sheet, and effectively improves the specific capacity and the rate capability of the lithium battery.
For further illustration of the present invention, the following describes in detail a graphene conductive agent with adjustable distribution ratio of sheet diameters, a preparation method thereof, a negative electrode, and a lithium ion battery provided by the present invention with reference to examples, but the present invention should not be construed as limiting the scope of the present invention.
In the following examples, "sheet diameter I" represents graphene having a D50 of 0.1 to 3 μm, "sheet diameter II" represents graphene having a D50 of 2 to 10 μm, and "sheet diameter III" represents graphene having a D50 of 8 to 20 μm.
Example 1
Firstly, respectively weighing 340g of polyvinylpyrrolidone and 40g of sodium carboxymethyl cellulose, adding into 18.8kg of deionized water, and stirring for 40min at a linear speed of 3 m/s; then, sequentially adding 10g of neutralizing amine and 8g of viscosity reducer, and stirring for 10min at the linear velocity of 2 m/s;
adding 800g of expanded graphite into the pre-solution obtained in the step, stirring and dispersing for 4 hours at a linear speed of 10m/s with an ultrasonic power of 3 kw;
thirdly, circularly grinding the pre-dispersion liquid obtained in the step (2) in a horizontal sand mill with 1mm of zirconium beads for 20 minutes (1000rpm), and then driving the pre-dispersion liquid into a horizontal sand mill with 0.5mm for grinding for 1 hour (1000 rpm);
step four, the sand grinding slurry obtained in the step 3 is subjected to homogeneous stripping and is stripped for 3 times under 100MPa to obtain graphene slurry (sheet diameter I: sheet diameter II: sheet diameter III: 2:8:0)
Example 2
Firstly, respectively weighing 320g of polyvinylpyrrolidone and 30g of sodium carboxymethyl cellulose, adding the polyvinylpyrrolidone and the sodium carboxymethyl cellulose into 18.4kg of deionized water, and stirring for 35min at a linear speed of 3 m/s; then, sequentially adding 12g of neutralizing amine and 9g of viscosity reducer, and stirring for 10min at a linear speed of 2 m/s;
adding 840g of expanded graphite into the pre-solution obtained in the step, stirring and dispersing for 3 hours at a linear speed of 8m/s with ultrasonic power of 2.5 kw;
thirdly, circularly grinding the pre-dispersion liquid obtained in the step (2) in a horizontal sand mill with 1mm of zirconium beads for 15 minutes (1000rpm), and then driving the pre-dispersion liquid into a horizontal sand mill with 0.3mm for grinding for 1 hour (1200 rpm);
step four, homogenizing and peeling the sand grinding slurry obtained in the step 3, and peeling for 2 times under 120MPa to obtain graphene slurry;
fifthly, adding 400g of expanded graphite into the pre-solution obtained in the fourth step, stirring and dispersing for 3 hours at a linear speed of 10m/s with ultrasonic power of 3 kw;
sixthly, circularly grinding the pre-dispersion liquid obtained in the step fifthly in a horizontal sand mill with zirconium beads of 1mm for 10 minutes (1000rpm), and then grinding the pre-dispersion liquid in a horizontal sand mill with zirconium beads of 0.3mm for 1 hour (1200 rpm);
performing homogeneous stripping on the sand grinding slurry obtained in the step VI, and stripping for 1 time at 100MPa to obtain graphene slurry (diameter I: diameter II: diameter III: 5:0)
Example 3
The method comprises the steps of respectively weighing 360g of polyvinylpyrrolidone and 30g of sodium carboxymethyl cellulose, adding the polyvinylpyrrolidone and the sodium carboxymethyl cellulose into 18kg of deionized water, and stirring for 30min at a linear speed of 3 m/s; then, sequentially adding 15g of neutralizing amine and 8g of viscosity reducer, and stirring for 10min at a linear speed of 2 m/s;
adding 1000g of expanded graphite into the pre-solution obtained in the step, stirring and dispersing for 3.5 hours at a linear speed of 10m/s with ultrasonic power of 3 kw;
thirdly, circularly grinding the pre-dispersion liquid obtained in the step (2) in a horizontal sand mill with 1mm of zirconium beads for 20 minutes (1000rpm), and then driving the pre-dispersion liquid into a horizontal sand mill with 0.3mm of zirconium beads for grinding for 1 hour (1500 rpm);
step four, homogenizing and peeling the sand grinding slurry obtained in the step 3, and peeling for 4 times under 150MPa to obtain graphene slurry;
fifthly, 600g of expanded graphite is added into the pre-solution obtained in the fourth step, the ultrasonic power is 3kw, and stirring and dispersing are carried out for 2.5 hours at a linear speed of 8 m/s;
sixthly, circularly grinding the pre-dispersion liquid obtained in the step fifthly in a horizontal sand mill with zirconium beads of 1mm for 15 minutes (1000rpm), and then grinding the pre-dispersion liquid in a horizontal sand mill with zirconium beads of 0.3mm for 1 hour (1500 rpm);
and sixthly, uniformly stripping the sand grinding slurry obtained in the step VI, and stripping the sand grinding slurry for 3 times at 150MPa to obtain graphene slurry (the sheet diameter I: the sheet diameter II: the sheet diameter III: 8:2: 0).
From examples 1 to 3, in example 1, the graphene slurry obtained through the first ultrasonic treatment, grinding and homogeneous peeling contains graphene with a sheet diameter I and a sheet diameter II; in the embodiments 2 to 3, the proportion of graphene with the sheet diameter I and the sheet diameter II in the obtained graphene slurry is adjusted by performing the ultrasonic treatment, the grinding and the homogeneous stripping twice, so that it can be shown that the composite graphene slurry with different sheet diameter distributions and proportions can be obtained by adjusting the process and the process parameters of each step.
Example 4
Firstly, respectively weighing 300g of polyvinylpyrrolidone and 20g of sodium carboxymethyl cellulose, adding the polyvinylpyrrolidone and the sodium carboxymethyl cellulose into 18.6kg of deionized water, and stirring for 30min at a linear speed of 2.5 m/s; then, sequentially adding 11g of neutralizing amine and 9g of viscosity reducer, and stirring for 10min at a linear speed of 2 m/s;
adding 500g of expanded graphite into the pre-solution obtained in the step, stirring and dispersing for 3 hours at a linear speed of 9m/s with ultrasonic power of 2 kw;
thirdly, circularly grinding the pre-dispersion liquid obtained in the step (2) in a horizontal sand mill with 1mm of zirconium beads for 10 minutes (1000rpm), and then driving the pre-dispersion liquid into a horizontal sand mill with 0.3mm of zirconium beads for grinding for 1 hour (1000 rpm);
step four, homogenizing and stripping the sand grinding slurry obtained in the step 3, and stripping for 2 times under 120MPa to obtain graphene slurry I;
fifthly, adding 400g of expanded graphite into the pre-solution obtained in the fourth step, stirring and dispersing for 3 hours at a linear speed of 10m/s with ultrasonic power of 2.5 kw;
sixthly, circularly grinding the pre-dispersion liquid obtained in the step fifthly in a horizontal sand mill with zirconium beads of 1mm for 10 minutes (1000rpm), and then grinding the pre-dispersion liquid in a horizontal sand mill with zirconium beads of 0.3mm for 1 hour (1000 rpm);
performing homogeneous stripping on the sand grinding slurry obtained in the step VI, and stripping for 1 time under 80MPa to obtain graphene slurry II;
adding 150g of expanded graphite into the pre-solution obtained in step-six, stirring and dispersing for 3 hours at a linear speed of 12m/s with the ultrasonic power of 3.5 kw;
the self-dyeing step is to grind the pre-dispersion liquid obtained in the step of the self-dyeing step in a horizontal sand mill with zirconium beads of 1mm for 10 minutes (1000rpm),
uniformly stripping the sand grinding slurry obtained in the step, and stripping for 2 times under 40MPa to obtain graphene slurry (sheet diameter I: sheet diameter II: sheet diameter III: 4:5:1)
Example 5
370g of polyvinylpyrrolidone and 20g of sodium carboxymethyl cellulose are respectively weighed and added into 18.6kg of deionized water, and stirring is carried out at a linear speed of 3m/s for 30 min; then sequentially adding 9g of neutralizing amine and 9g of viscosity reducer, and stirring for 10min at the linear velocity of 2 m/s;
adding 300g of expanded graphite into the pre-solution obtained in the step, stirring and dispersing for 3 hours at a linear speed of 8m/s with ultrasonic power of 2 kw;
thirdly, circularly grinding the pre-dispersion liquid obtained in the step (2) in a horizontal sand mill with 1mm of zirconium beads for 15 minutes (1000rpm), and then driving the pre-dispersion liquid into a horizontal sand mill with 0.3mm of zirconium beads for grinding for 1 hour (1000 rpm);
step four, homogenizing and stripping the sand grinding slurry obtained in the step 3, and stripping for 2 times under 120MPa to obtain graphene slurry I;
fifthly, adding 500g of expanded graphite into the pre-solution obtained in the fourth step, stirring and dispersing for 3 hours at a linear speed of 10m/s with ultrasonic power of 2.5 kw;
sixthly, circularly grinding the pre-dispersion liquid obtained in the step fifthly in a horizontal sand mill with zirconium beads of 1mm for 15 minutes (1000rpm), and then grinding the pre-dispersion liquid in a horizontal sand mill with zirconium beads of 0.3mm for 1 hour (1000 rpm);
performing homogeneous stripping on the sand grinding slurry obtained in the step VI, and stripping for 1 time under 100MPa to obtain graphene slurry II;
adding 200g of expanded graphite into the pre-solution obtained in step-six, stirring and dispersing for 3.5 hours at a linear speed of 12m/s with the ultrasonic power of 3 kw;
the self-dyeing step is to grind the pre-dispersion liquid obtained in the step of the self-dyeing step in a horizontal sand mill with zirconium beads of 1mm for 10 minutes (1000rpm),
uniformly stripping the sand grinding slurry obtained in the step, and stripping for 1 time under 30MPa to obtain graphene slurry (sheet diameter I: sheet diameter II: sheet diameter III: 4:2)
Example 6
Firstly, respectively weighing 264g of polyvinylpyrrolidone and 28g of sodium carboxymethyl cellulose, adding the weighed materials into 18.8kg of deionized water, and stirring for 40min at a linear speed of 3 m/s; then sequentially adding 8g of neutralizing amine and 8g of viscosity reducer, and stirring for 10min at a linear speed of 2 m/s;
adding 250g of expanded graphite into the pre-solution obtained in the step, stirring and dispersing for 3 hours at a linear speed of 7m/s with ultrasonic power of 2 kw;
thirdly, circularly grinding the pre-dispersion liquid obtained in the step (2) in a horizontal sand mill with 1mm of zirconium beads for 15 minutes (1000rpm), and then driving the pre-dispersion liquid into a horizontal sand mill with 0.5mm for grinding for 1.5 hours (1500 rpm);
step four, homogenizing and stripping the sand grinding slurry obtained in the step 3, and stripping for 3 times under 120MPa to obtain graphene slurry I;
fifthly, adding 300g of expanded graphite into the pre-solution obtained in the fourth step, stirring and dispersing for 3 hours at a linear speed of 9m/s with ultrasonic power of 3 kw;
sixthly, circularly grinding the pre-dispersion liquid obtained in the step fifthly in a horizontal sand mill with zirconium beads of 1mm for 15 minutes (1000rpm), and then grinding the pre-dispersion liquid in a horizontal sand mill with zirconium beads of 0.5mm for 1.5 hours (1500 rpm);
performing homogeneous stripping on the sand slurry obtained in the step VI, and stripping for 2 times under 80MPa to obtain graphene slurry II;
adding 350g of expanded graphite into the pre-solution obtained in step-six, stirring and dispersing for 4 hours at a linear speed of 14m/s with ultrasonic power of 4 kw;
the self-dyeing step is to grind the pre-dispersion liquid obtained in the step of the self-dyeing step in a horizontal sand mill with zirconium beads of 1mm for 15 minutes (1000rpm),
the obtained sand grinding slurry is homogenized and stripped at 20MPa for 1 time to obtain graphene slurry (the sheet diameter I: the sheet diameter II: the sheet diameter III: 3: 4).
Example 7
272g of polyvinyl pyrrolidone and 20g of sodium carboxymethyl cellulose are respectively weighed and added into 18.7kg of deionized water, and stirring is carried out for 30min at a linear speed of 3 m/s; then sequentially adding 8g of neutralizing amine and 8g of viscosity reducer, and stirring for 10min at a linear speed of 2 m/s;
adding 290g of expanded graphite into the pre-solution obtained in the step, stirring and dispersing for 3 hours at a linear speed of 8m/s with ultrasonic power of 2 kw;
thirdly, circularly grinding the pre-dispersion liquid obtained in the step (2) in a horizontal sand mill with 1mm of zirconium beads for 15 minutes (1000rpm), and then driving the pre-dispersion liquid into a horizontal sand mill with 0.5mm for grinding for 1.5 hours (1000 rpm);
step four, homogenizing and stripping the sand grinding slurry obtained in the step 3, and stripping for 3 times under 150MPa to obtain graphene slurry I;
fifthly, adding 500g of expanded graphite into the pre-solution obtained in the fourth step, stirring and dispersing for 3 hours at a linear speed of 10m/s with ultrasonic power of 3 kw;
sixthly, circularly grinding the pre-dispersion liquid obtained in the step fifthly in a horizontal sand mill with zirconium beads of 1mm for 15 minutes (1000rpm), and then grinding the pre-dispersion liquid in a horizontal sand mill with zirconium beads of 0.5mm for 1.5 hours (1000 rpm);
performing homogeneous stripping on the sand grinding slurry obtained in the step VI, and stripping for 1 time under 90MPa to obtain graphene slurry II;
adding 210g of expanded graphite into the pre-solution obtained in step-six, stirring and dispersing for 3 hours at a linear speed of 12m/s with ultrasonic power of 4 kw;
the self-dyeing step is to grind the pre-dispersion liquid obtained in the step of the self-dyeing step in a horizontal sand mill with zirconium beads of 1mm for 10 minutes (1000rpm),
the obtained sand grinding slurry is homogenized and stripped at 20MPa for 2 times to obtain graphene slurry (the sheet diameter I: the sheet diameter II: the sheet diameter III: 3:5: 2).
Example 8
272g of polyvinyl pyrrolidone and 22g of sodium carboxymethyl cellulose are respectively weighed and added into 18.9kg of deionized water, and stirring is carried out for 30min at a linear speed of 3 m/s; then, sequentially adding 6g of neutralizing amine and 9g of viscosity reducer, and stirring for 10min at a linear speed of 2 m/s;
adding 100g of expanded graphite into the pre-solution obtained in the step, stirring and dispersing for 3 hours at a linear speed of 7m/s with ultrasonic power of 2 kw;
thirdly, circularly grinding the pre-dispersion liquid obtained in the step (2) in a horizontal sand mill with 1mm of zirconium beads for 15 minutes (1000rpm), and then driving the pre-dispersion liquid into a horizontal sand mill with 0.5mm for grinding for 1 hour (1200 rpm);
step four, carrying out homogeneous stripping on the sand grinding slurry obtained in the step 3, and stripping for 2 times under 150MPa to obtain graphene slurry I;
fifthly, adding 550g of expanded graphite into the pre-solution obtained in the fourth step, stirring and dispersing for 3 hours at a linear speed of 9m/s with ultrasonic power of 2.5 kw;
sixthly, circularly grinding the pre-dispersion liquid obtained in the step fifthly in a horizontal sand mill with zirconium beads of 1mm for 15 minutes (1000rpm), and then grinding the pre-dispersion liquid in a horizontal sand mill with zirconium beads of 0.5mm for 1 hour (1200 rpm);
performing homogeneous stripping on the sand slurry obtained in the step VI, and stripping for 2 times under 80MPa to obtain graphene slurry II;
adding 150g of expanded graphite into the pre-solution obtained in step-six, stirring and dispersing for 3 hours at a linear speed of 12m/s with the ultrasonic power of 3.5 kw;
the self-dyeing step is to grind the pre-dispersion liquid obtained in the step of the self-dyeing step in a horizontal sand mill with zirconium beads of 1mm for 15 minutes (1000rpm),
the obtained sand grinding slurry is subjected to homogeneous stripping and is stripped for 1 time under 30MPa to obtain graphene slurry (sheet diameter I: sheet diameter II: sheet diameter III: 2:6: 2).
Example 9
Firstly, respectively weighing 178g of polyvinylpyrrolidone and 22g of sodium carboxymethyl cellulose, adding the weighed materials into 19kg of deionized water, and stirring for 40min at a linear speed of 3 m/s; then, sequentially adding 6g of neutralizing amine and 7g of viscosity reducer, and stirring for 10min at a linear speed of 2 m/s;
adding 800g of expanded graphite into the pre-solution obtained in the step, stirring and dispersing for 3 hours at a linear speed of 8m/s with ultrasonic power of 4 kw;
thirdly, circularly grinding the pre-dispersion liquid obtained in the step (2) in a horizontal sand mill with 1mm of zirconium beads for 20 minutes (1000rpm),
and (4) uniformly peeling the sand grinding slurry obtained in the step (3), and peeling the sand grinding slurry 2 times under 80MPa to obtain graphene slurry (sheet diameter I: sheet diameter II: sheet diameter III is 0:10: 0).
The conductive pastes and batteries prepared in examples 1 to 9 were tested, and the results are shown in Table 1,
TABLE 1 Performance data for conductive pastes of inventive examples 1-9
As can be seen from Table 1, compared with the control group, the gram capacity of the composite slurry with the sheet diameter I and the sheet diameter II is slightly reduced, but the multiplying power performance is obviously improved; the gram capacity and the rate capability of the composite slurry with the sheet diameter I, the sheet diameter II and the sheet diameter III are obviously improved.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. The graphene conductive agent with adjustable sheet diameter distribution ratio comprises the following components in percentage by mass:
graphene material: 0.1-20%;
dispersing agent: 0.2-18%;
other auxiliary agents: 0 to 12 percent;
water: 80-99.8%;
the graphene material comprises two or three of first graphene with D50 of 0.1-3 mu m, second graphene with D50 of 2-10 mu m and third graphene with D50 of 8-20 mu m.
2. The graphene conductive agent according to claim 1, wherein the graphene material contains 10 to 90% by mass of a first graphene, 10 to 90% by mass of a second graphene, and 0 to 40% by mass of a third graphene.
3. The graphene conductive agent according to claim 1, wherein the other auxiliary agents include one or more of a stabilizer, a viscosity reducer, a bacteriostatic agent and an alkaline medium.
4. The preparation method of the graphene conductive agent with the adjustable distribution ratio of the sheet diameter as claimed in any one of claims 1 to 3, comprising the following steps:
A) adding a dispersing agent and other additives into water, and uniformly stirring to obtain an additive solution;
B) adding a first graphite carbon material into the aid solution, and stirring and dispersing under an ultrasonic condition to obtain a first pre-dispersion liquid;
C) grinding the first pre-dispersion liquid, and then carrying out homogeneous stripping under the pressure of 100-200 MPa to obtain a graphene conductive agent containing first graphene and second graphene;
alternatively, the first and second electrodes may be,
D) adding a second graphite carbon material into the graphene conductive agent obtained in the step C), and stirring and dispersing under the ultrasonic condition to obtain a second pre-dispersion liquid;
E) grinding the second pre-dispersion liquid, and then carrying out homogeneous stripping under the pressure of 50-150 MPa to obtain a graphene conductive agent containing first graphene and second graphene;
in the graphene conductive agent in the step C) and the step E), the proportion of the first graphene to the second graphene is different;
alternatively, the first and second electrodes may be,
F) adding a third graphite carbon material into the graphene conductive agent obtained in the step E), and stirring and dispersing under the ultrasonic condition to obtain a third pre-dispersion liquid;
G) and grinding the third pre-dispersion liquid, and then carrying out homogeneous stripping under the pressure of 10-60 MPa to obtain the graphene conductive agent containing the first graphene, the second graphene and the third graphene.
5. The preparation method of claim 4, wherein the power of the ultrasound in the step B) is 2-4 kW, and the linear speed of stirring is 5-12 m/s;
and C) grinding the zirconium beads with the particle size of 0.3-2.0 mm at the rotating speed of 200-1000 rpm, and then grinding the zirconium beads with the particle size of 0.1-1.0 mm at the rotating speed of 500-2000 rpm.
6. The preparation method of claim 4, wherein the power of the ultrasound in the step D) is 2-4 kW, and the linear speed of stirring is 5-12 m/s;
and E) grinding the zirconium beads with the particle size of 0.3-2.0 mm at the rotating speed of 200-1000 rpm, and then grinding the zirconium beads with the particle size of 0.1-1.0 mm at the rotating speed of 500-2000 rpm.
7. The preparation method of claim 4, wherein the power of the ultrasound in the step F) is 3-6 kW, and the linear speed of stirring is 10-15 m/s;
and G) grinding by using zirconium beads with the diameter of 0.3-2.0 mm at the rotating speed of 200-1000 rpm.
8. A negative electrode comprises the graphene conductive agent with the adjustable sheet diameter distribution ratio of any one of claims 1 to 3 or the graphene conductive agent with the adjustable sheet diameter distribution ratio prepared by the preparation method of any one of claims 4 to 7.
9. The negative electrode according to claim 8, wherein the graphene conductive agent with the adjustable sheet diameter distribution ratio is added to the negative electrode in an amount of 0.1-5% by mass.
10. A lithium ion battery comprising the negative electrode of claim 8 or 9.
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