CN108183218A - A kind of graphene-titanium dioxide composite negative pole slurry for lithium ion battery and preparation method thereof - Google Patents
A kind of graphene-titanium dioxide composite negative pole slurry for lithium ion battery and preparation method thereof Download PDFInfo
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- CN108183218A CN108183218A CN201711459373.5A CN201711459373A CN108183218A CN 108183218 A CN108183218 A CN 108183218A CN 201711459373 A CN201711459373 A CN 201711459373A CN 108183218 A CN108183218 A CN 108183218A
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- H01M4/00—Electrodes
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- H—ELECTRICITY
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- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
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- H—ELECTRICITY
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- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
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Abstract
Field of lithium of the present invention, provides a kind of for graphene titanium dioxide composite negative pole slurry of lithium ion battery and preparation method thereof, and negative electrode slurry includes the component of following parts by weight：94 96 parts of graphene titanium dioxide composite aerogel powder, 03 parts of conductive agent, 02 parts of dispersant, 13 parts of adhesive, 01 parts of thickener, 140 160 parts of water.Contain graphene titanium dioxide aerogel composite in the negative electrode slurry of the present invention, its not only large specific surface area, it is and flexible higher, after negative plate surface cure, gained negative plate surface is more smooth, and harsh feeling is weak, therefore diaphragm can be effectively prevent to be pierced, it is higher with the adhesive force of negative current collector after negative electrode slurry curing simultaneously, it is not easily to fall off, battery can be extended.
Description
Technical field
The present invention relates to field of lithium, particularly, it is multiple to be related to a kind of graphene-titanium dioxide for lithium ion battery
Close negative electrode slurry and preparation method thereof.
Background technology
With the development of new energy, lithium ion battery has obtained significant progress in every field.And lithium ion battery
Positive and negative pole material for promoted lithium ion battery performance play key effect.For ion cathode material lithium, earliest all
It is using carbon material, silicon, titanium and composite material etc. then occurs.On the other hand, graphene has individual layer two-dimensional sheet knot
Structure, specific surface area is larger, has outstanding electric conductivity, thermal conductivity, low-resistivity etc., is highly suitable as negative material, existing
All there is application in the negative plate of many lithium ion batteries of technology.With graphene or its composite wood with other negative materials
Material can significantly reduce the internal resistance of cell, improve cycle performance of battery as cathode.
Although graphene has many merits, by research, the inventors discovered that there is also some to lack for graphene
Point：Although graphene has individual layer two-dimensional sheet structure, in actual use the piece interlayer between adjoining graphite alkene
Away from can be gradually reduced so that the extent of exfoliation of graphene reduces, and is reduced so as to cause its flexibility, hardness increases.When by graphene
After being coated on negative current collector (be usually copper foil) surface cure as negative material and by it, hard graphene and other
Cathode granular materials can cause negative plate surface to become very coarse, after lithium ion battery works long hours, due to battery every
Film is influenced with the long-term extruding contact of negative plate and high temperature, and diaphragm is easily pierced through by negative plate, and micro-short circuit easily occurs even
Faulty membrane situation.
Under normal conditions, in the prior art in order to improve diaphragm punctured resistance, one layer of ceramics can be coated in membrane surface
Coating, but this can bring new problem again：Due to the setting of ceramic coating, lead to the gas permeability of diaphragm and the leaching to electrolyte
Lubricant nature is all greatly reduced, so as to influence battery performance.
Patent 201210533334.6 discloses a kind of graphene composite lithium ion battery cathode material and preparation method thereof,
Negative material includes multi-layer graphene lamella, and hollow Nano cathode stratum granulosum, graphene are equipped between adjacent graphene sheet layer
By hollow Nano cathode particle, semi-surrounding is spaced apart lamella one by one, and there are gaps between adjacent graphene sheet layer；Hollow Nano
Cathode particle is made of carbon outer layer, hollow metal negative electrode material inner layer.Preparation method includes：By organic preceding body of silica
Body, cationic surfactant, tin-salt solution, organic carbon source hybrid reaction；Add in the dispersion liquid of graphene oxide or graphene
Reaction, dry intermediate product；Treated liquid handles to obtain head product；Head product is heat-treated to obtain product.The cathode material of the present invention
Expect that good conductivity, electrochemical lithium storage content is big, energy density is high, good cycle.Prepare industrialization easy to implement, low cost.
Although above-mentioned patent employs graphene-supported cathode particle (carbon, silicon materials), on the surface with skill of the present invention
Art scheme is similar, but it is only easily to be expanded to solve traditional negative material to cause with graphene coated negative material
The technical issues of negative material fails, and can not solve graphene and other negative materials that negative plate rear surface is made is more thick
The technical issues of rough.
In addition, relatively low with the adhesive force of negative current collector copper foil after negative electrode slurry coating, curing in the prior art, the later stage holds
It is easy to fall off, so as to influence battery life.
Invention content
In order to solve the above technical problem, the present invention provides a kind of graphene-titanium dioxide for lithium ion battery
Composite negative pole slurry and preparation method thereof, containing graphene-titanium dioxide aerogel composite in negative electrode slurry of the invention,
Its not only large specific surface area, but also flexible higher, after negative plate surface cure, gained negative plate surface is more smooth,
Harsh feeling is weak, therefore diaphragm can be effectively prevent to be pierced, while the adhesive force after negative electrode slurry curing with negative current collector
It is higher, it is not easily to fall off, battery can be extended.
The technical scheme is that：A kind of graphene-titanium dioxide composite negative pole slurry for lithium ion battery,
It is characterized in that, includes the component of following parts by weight：
Graphene -94-96 parts of titanium dioxide composite aerogel powder,
0-3 parts of conductive agent,
0-2 parts of dispersant,
1-3 parts of adhesive,
0-1 parts of thickener,
140-160 parts of water.
Contain graphene-titanium dioxide aerogel composite in the negative electrode slurry of the present invention, not only large specific surface area,
And it is flexible higher, after negative plate surface cure, gained negative plate surface is more smooth, and harsh feeling is weak, therefore can
Diaphragm is effectively prevent to be pierced, extends battery.
As a further preference, the preparation method of the graphene-titanium dioxide composite aerogel particle is as follows：
A) ultrasonic washing is carried out to graphene oxide, and dry under condition of negative pressure.
B) by graphene oxide in mass ratio 1:1-2 is added in butyl titanate, is sufficiently stirred, and adds graphene oxide
The absolute ethyl alcohol of 10-30 times of quality, then add saturation solubility sodium bicarbonate, be uniformly mixed, with liquid A；By 1-
The glacial acetic acid of 2mol/L and absolute ethyl alcohol, water 3-5 in mass ratio:15-25:3-7 is uniformly mixed, and liquid B is made.
C) liquid B is added drop-wise in the liquid A of its 2-3 times of quality under agitation；Obtain complex sol.
D) by complex sol aging 1-2 days at room temperature, plural gel is obtained after washing.
E) water and ethyl alcohol being sufficiently displaced from n-hexane in plural gel take out gel, use Co 2 supercritical fluid
It is dry, obtain graphene oxide-titanium dioxide composite aerogel.
F) graphene oxide-titanium dioxide composite aerogel is placed under reduction atmosphere and is heated to 200-300 DEG C, reduction is anti-
2-4h is answered, graphene-titanium dioxide composite aerogel powder is made after milled processed.
The present invention prepares graphene-titanium dioxide composite aerogel powder using special process, specially：
In step a), ultrasonic washing is first carried out to graphene oxide before the reaction, and dry under condition of negative pressure.Its
The effect of middle ultrasonic washing is to make to release the impurity being originally adsorbed between graphene oxide layer；The effect of negative pressure
It is to be removed using draught head by the air between graphene oxide layer.Above-mentioned processing can utmostly discharge the suction of graphene
Attached capacity improves its adsorptivity, conducive to subsequent operation.
In step b) and step c), graphene oxide will be first added in butyl titanate, and make its butyl titanate abundant
It penetrates between the lamellar structure of graphene oxide.Then addition ethyl alcohol is made into liquid A, and liquid B is added drop-wise in liquid A,
Hydrolyze butyl titanate.In the process, due to being adsorbed with a large amount of butyl titanates between graphene oxide layer structure, because
The hydrolysis of this butyl titanate is happened between the lamellar structure of graphene oxide.Hydrolysis is exothermic reaction, more acute
It is strong, and colloidal tio 2 is generated between lamellar structure, the presence of heat and colloidal tio 2 can be by graphene
Lamellar structure struts, and from the extent of exfoliation of graphene is caused to improve, the deformation space with bigger, flexibility increases.On the other hand,
Since titanium dioxide is coated by flexible single-layer graphene, harsh feeling can also reduce.When graphene-titanium dioxide is compound
After aeroge is used as negative material and it is coated on negative current collector surface cure, the smooth of negative plate surface can be improved
Property, diaphragm is not easy to be pierced.And although the technical solution of patent 201210533334.6 that background of invention refers to is from table
See similar to technical solution of the present invention on face, but it is only to solve carbon, silicium cathode material with graphene coated negative material
Material easily expands the technical issues of negative material is caused to fail, addition graphene be after hydrolysis, it is therefore straight
The silicon dioxide colloid negligible amounts of graphene sheet layer structural generation are connected on, graphene sheet layer structure spacing can not be strutted enough.
It is mainly the physical adsorbability by graphene that it, which coats negative material,；On the other hand, patent 201210533334.6
Also and the technical problems to be solved by the invention are unaware that, therefore it can not solve graphene and other negative materials are made
The technical issues of negative plate rear surface is more coarse.
In addition, the present invention specially adjusts the mass ratio of graphene oxide and butyl titanate in step c), increase metatitanic acid fourth
The dosage of ester makes its saturation be carried between graphene oxide layer structure, to increase piece interlamellar spacing.
When liquid B is added dropwise, due to containing sodium bicarbonate in liquid A, reacts after being combined with glacial acetic acid, discharge two
Carbonoxide in colloidal sol generating process, can increase the porosity of colloidal sol, so as to improve negative material specific surface area, promote electricity
Pond performance.
As a further preference, in step a), the graphene oxide is modified by hydroxylating：Graphene oxide is added
It adds in water and is configured to the graphene oxide dispersion of a concentration of 3-7wt%, graphene oxide quality 0.2- is added into solution
0.4 times of potassium hydroxide is heated to 85-95 DEG C, reacts 6-8h, and hydroxylating graphite oxide is made after being filtered, washed, drying
Alkene.
It is actually with the shape of titanium hydroxide between titanium dioxide by TiO 2 sol made from sol-gel method
Formula forms colloid by hydroxyl, and the present invention is exactly using this point, and hydroxylating modification has been carried out to graphene oxide, is aoxidized
Hydroxyl on graphene can form hydrogen bond or the combination of other chemical bonds between titanium hydroxide, and graphene oxide is enable to join
It is reacted with the formation of colloidal sol.As a result, in the ageing process of colloidal sol, graphene oxide and titanium dioxide are fully bonded, by dioxy
Change titanium " locking " between the lamellar structure of graphene oxide, improve its stability.
In addition, graphene oxide carry out hydroxylating modification another advantage is that, the modified graphene oxide of hydroxylating
It is more prone to combine in negative current collector copper foil, improves adhesive force of the negative electrode slurry in copper foil surface.But hydroxylating is modified journey
It is that the higher the better that degree, which is not, yet, and team of the present invention finds, graphene oxide is modified by hydroxylating, and electric conductivity can be by one
Fixed influence, it is therefore desirable to its modification degree is strictly controlled according to actual conditions.
As a further preference, in step c), the rate of addition of liquid B is 1-2mL/s.
As a further preference, in step e), supercritical fluid drying condition be pressure 6-8MPa, 40-50 DEG C of temperature,
Time 8-12h.
As a further preference, described adhesive is polytetrafluoroethylene (PTFE) or butadiene-styrene rubber.
As a further preference, the conductive agent is carbon nanotube or Super P.
As a further preference, the dispersant is polyvinylpyrrolidone.
As a further preference, the thickener is sodium carboxymethylcellulose.
The preparation method of a kind of graphene-titanium dioxide composite negative pole slurry for lithium ion battery, including following step
Suddenly：
1) each component is weighed by proportioning.
2) first thickener is added in the water of half formula ratio, then adds adhesive successively under agitation, divides
Powder, conductive agent and graphene-titanium dioxide composite aerogel powder add the water of surplus after being uniformly dispersed.
3) gained slurry is ground, negative electrode slurry is made.
The invention has the advantages that：
1st, contain graphene-titanium dioxide aerogel composite in negative electrode slurry of the invention, not only specific surface area
Greatly, and flexible higher, after negative plate surface cure, gained negative plate surface is more smooth, and harsh feeling is weak, therefore energy
Enough diaphragm is effectively prevent to be pierced, extend battery.
2nd, it is higher with the adhesive force of negative current collector after negative electrode slurry curing of the present invention, it is not easily to fall off, battery can be extended
Service life.
Specific embodiment
The embodiment of the present invention is described in detail below, but the present invention can be limited and be covered according to claim
Multitude of different ways implement.
Embodiment 1
A kind of graphene-titanium dioxide composite negative pole slurry for lithium ion battery includes the component of following parts by weight：
Graphene -95 parts of titanium dioxide composite aerogel powder, 1.5 parts of Super P, 1 part of polyvinylpyrrolidone gather
2 parts of tetrafluoroethene, 0.5 part of sodium carboxymethylcellulose, 150 parts of water.
The preparation method of graphene-titanium dioxide composite negative pole slurry, includes the following steps：
1) each component is weighed by proportioning.
2) first thickener is added in the water of half formula ratio, then adds adhesive successively under agitation, divides
Powder, conductive agent and graphene-titanium dioxide composite aerogel powder add the water of surplus after being uniformly dispersed.
3) gained slurry is ground, negative electrode slurry is made.
Wherein, the preparation method of the graphene-titanium dioxide composite aerogel particle is as follows：
A) ultrasonic washing is carried out to graphene oxide, and dry under condition of negative pressure.
B) by graphene oxide in mass ratio 1:1.5 are added in butyl titanate, are sufficiently stirred, and add graphene oxide 20
Then the absolute ethyl alcohol of times quality adds the sodium bicarbonate of saturation solubility, be uniformly mixed, with liquid A.By 1.5mol/L's
Glacial acetic acid and absolute ethyl alcohol, water in mass ratio 4:20:5 are uniformly mixed, and liquid B is made.
C) liquid B is added drop-wise to the rate of addition of 1.5mL/s in the liquid A of its 2.5 times of quality under agitation；
To complex sol.
D) by complex sol aging 1.5 days at room temperature, plural gel is obtained after washing.
E) water and ethyl alcohol being sufficiently displaced from n-hexane in plural gel take out gel, use Co 2 supercritical fluid
Dry (pressure 7MPa, temperature 45 C, time 10h), obtains graphene oxide-titanium dioxide composite aerogel.
F) graphene oxide-titanium dioxide composite aerogel is placed under reduction atmosphere and is heated to 250 DEG C, reduction reaction
Graphene-titanium dioxide composite aerogel powder is made after milled processed by 3h.
Embodiment 2
A kind of graphene-titanium dioxide composite negative pole slurry for lithium ion battery includes the component of following parts by weight：
Graphene -95 parts of titanium dioxide composite aerogel powder, 1.5 parts of Super P, 1 part of polyvinylpyrrolidone gather
2 parts of tetrafluoroethene, 0.5 part of sodium carboxymethylcellulose, 150 parts of water.
The preparation method of graphene-titanium dioxide composite negative pole slurry, includes the following steps：
1) each component is weighed by proportioning.
2) first thickener is added in the water of half formula ratio, then adds adhesive successively under agitation, divides
Powder, conductive agent and graphene-titanium dioxide composite aerogel powder add the water of surplus after being uniformly dispersed.
3) gained slurry is ground, negative electrode slurry is made.
Wherein, the preparation method of the graphene-titanium dioxide composite aerogel particle is as follows：
The hydroxylating of graphene oxide is modified：Graphene oxide is added in water to the oxidation for being configured to a concentration of 5wt%
Graphene dispersing solution adds the potassium hydroxide of 0.3 times of graphene oxide quality into solution, is heated to 90 DEG C, reacts 7h, passes through
Be filtered, washed, dry after hydroxylating graphene oxide is made.
A) ultrasonic washing is carried out to hydroxylating graphene oxide, and dry under condition of negative pressure.
B) by graphene oxide in mass ratio 1:1.5 are added in butyl titanate, are sufficiently stirred, and add graphene oxide 20
Then the absolute ethyl alcohol of times quality adds the sodium bicarbonate of saturation solubility, be uniformly mixed, with liquid A.By 1.5mol/L's
Glacial acetic acid and absolute ethyl alcohol, water in mass ratio 4:20:5 are uniformly mixed, and liquid B is made.
C) liquid B is added drop-wise to the rate of addition of 1.5mL/s in the liquid A of its 2.5 times of quality under agitation；
To complex sol.
D) by complex sol aging 1.5 days at room temperature, plural gel is obtained after washing.
E) water and ethyl alcohol being sufficiently displaced from n-hexane in plural gel take out gel, use Co 2 supercritical fluid
Dry (pressure 7MPa, temperature 45 C, time 10h), obtains graphene oxide-titanium dioxide composite aerogel.
F) graphene oxide-titanium dioxide composite aerogel is placed under reduction atmosphere and is heated to 250 DEG C, reduction reaction
Graphene-titanium dioxide composite aerogel powder is made after milled processed by 3h.
Embodiment 3
A kind of graphene-titanium dioxide composite negative pole slurry for lithium ion battery includes the component of following parts by weight：
Graphene -94 parts of titanium dioxide composite aerogel powder, 3 parts of carbon nanotube, 0.5 part of polyvinylpyrrolidone, fourth
1.5 parts of benzene rubber, 1 part of sodium carboxymethylcellulose, 140 parts of water.
The preparation method of graphene-titanium dioxide composite negative pole slurry, includes the following steps：
1) each component is weighed by proportioning.
2) first thickener is added in the water of half formula ratio, then adds adhesive successively under agitation, divides
Powder, conductive agent and graphene-titanium dioxide composite aerogel powder add the water of surplus after being uniformly dispersed.
3) gained slurry is ground, negative electrode slurry is made.
Wherein, the preparation method of the graphene-titanium dioxide composite aerogel particle is as follows：
The hydroxylating of graphene oxide is modified：
Graphene oxide is added in water to the graphene oxide dispersion for being configured to a concentration of 3wt%, is added into solution
Add the potassium hydroxide of 0.2 times of graphene oxide quality, be heated to 85 DEG C, react 8h, hydroxyl is made after being filtered, washed, drying
Base graphene oxide.
A) ultrasonic washing is carried out to hydroxylated graphene oxide, and dry under condition of negative pressure.
B) by graphene oxide in mass ratio 1:1 is added in butyl titanate, is sufficiently stirred, and adds 10 times of graphene oxide
The absolute ethyl alcohol of quality, then add saturation solubility sodium bicarbonate, be uniformly mixed, with liquid A.By the ice vinegar of 1mol/L
Acid and absolute ethyl alcohol, water in mass ratio 3:15:3 are uniformly mixed, and liquid B is made.
C) liquid B is added drop-wise to the rate of addition of 1mL/s in the liquid A of its 2 times of quality under agitation；It is answered
Close colloidal sol.
D) by complex sol aging 1 day at room temperature, plural gel is obtained after washing.
E) water and ethyl alcohol being sufficiently displaced from n-hexane in plural gel take out gel, use Co 2 supercritical fluid
Dry (pressure 6MPa, 40 DEG C of temperature, time 12h), obtains graphene oxide-titanium dioxide composite aerogel.
F) graphene oxide-titanium dioxide composite aerogel is placed under reduction atmosphere and is heated to 200- DEG C, reduction reaction
Graphene-titanium dioxide composite aerogel powder is made after milled processed by 4h.
Embodiment 4
A kind of graphene-titanium dioxide composite negative pole slurry for lithium ion battery includes the component of following parts by weight：
Graphene -96 parts of titanium dioxide composite aerogel powder, 0.5 part of carbon nanotube, 2 parts of polyvinylpyrrolidone, fourth
1 part of benzene rubber, 0.5 part of sodium carboxymethylcellulose, 160 parts of water.
The preparation method of graphene-titanium dioxide composite negative pole slurry, includes the following steps：
1) each component is weighed by proportioning.
2) first thickener is added in the water of half formula ratio, then adds adhesive successively under agitation, divides
Powder, conductive agent and graphene-titanium dioxide composite aerogel powder add the water of surplus after being uniformly dispersed.
3) gained slurry is ground, negative electrode slurry is made.
Wherein, the preparation method of the graphene-titanium dioxide composite aerogel particle is as follows：
Graphene oxide is added in water the oxidation stone for being configured to a concentration of 7wt% by the hydroxylating modification of graphene oxide
Black alkene dispersion liquid adds the potassium hydroxide of 0.4 times of graphene oxide quality into solution, is heated to 95 DEG C, reacts 6h, passed through
Hydroxylating graphene oxide is made after filter, washing, drying.
A) ultrasonic washing is carried out to hydroxylated graphene oxide, and dry under condition of negative pressure.
B) by graphene oxide in mass ratio 1:2 are added in butyl titanate, are sufficiently stirred, and add 30 times of graphene oxide
The absolute ethyl alcohol of quality, then add saturation solubility sodium bicarbonate, be uniformly mixed, with liquid A.By the ice vinegar of 2mol/L
Acid and absolute ethyl alcohol, water in mass ratio 5:25:7 are uniformly mixed, and liquid B is made.
C) liquid B is added drop-wise to the rate of addition of 2mL/s in the liquid A of its 3 times of quality under agitation；It is answered
Close colloidal sol.
D) by complex sol aging 2 days at room temperature, plural gel is obtained after washing.
E) water and ethyl alcohol being sufficiently displaced from n-hexane in plural gel take out gel, use Co 2 supercritical fluid
Dry (pressure 8MPa, temperature 50 C, time 8h), obtains graphene oxide-titanium dioxide composite aerogel.
F) graphene oxide-titanium dioxide composite aerogel is placed under reduction atmosphere and is heated to 300 DEG C, reduction reaction
Graphene-titanium dioxide composite aerogel powder is made after milled processed by 2h.
Embodiment 5
A kind of graphene-titanium dioxide composite negative pole slurry for lithium ion battery includes the component of following parts by weight：
Graphene -94.5 parts of titanium dioxide composite aerogel powder, 1.5 parts of Super P, polyvinylpyrrolidone 1.5
Part, 2 parts of polytetrafluoroethylene (PTFE), 0.5 part of sodium carboxymethylcellulose, 150 parts of water.
The preparation method of graphene-titanium dioxide composite negative pole slurry, includes the following steps：
1) each component is weighed by proportioning.
2) first thickener is added in the water of half formula ratio, then adds adhesive successively under agitation, divides
Powder, conductive agent and graphene-titanium dioxide composite aerogel powder add the water of surplus after being uniformly dispersed.
3) gained slurry is ground, negative electrode slurry is made.
Wherein, the preparation method of the graphene-titanium dioxide composite aerogel particle is as follows：
The hydroxylating of graphene oxide is modified：Graphene oxide is added in water to the oxidation for being configured to a concentration of 6wt%
Graphene dispersing solution adds the potassium hydroxide of 0.3 times of graphene oxide quality into solution, is heated to 90 DEG C, reacts 8h, passes through
Be filtered, washed, dry after hydroxylating graphene oxide is made.
A) ultrasonic washing is carried out to hydroxylated graphene oxide, and dry under condition of negative pressure.
B) by graphene oxide in mass ratio 1:1.5 are added in butyl titanate, are sufficiently stirred, and add graphene oxide 25
Then the absolute ethyl alcohol of times quality adds the sodium bicarbonate of saturation solubility, be uniformly mixed, with liquid A.By 1.5mol/L's
Glacial acetic acid and absolute ethyl alcohol, water in mass ratio 4:20:6 are uniformly mixed, and liquid B is made.
C) liquid B is added drop-wise to the rate of addition of 1.2mL/s in the liquid A of its 2-3 times of quality under agitation；
To complex sol.
D) by complex sol aging 2 days at room temperature, plural gel is obtained after washing.
E) water and ethyl alcohol being sufficiently displaced from n-hexane in plural gel take out gel, use Co 2 supercritical fluid
Dry (pressure 7MPa, temperature 50 C, time 9h), obtains graphene oxide-titanium dioxide composite aerogel.
F) graphene oxide-titanium dioxide composite aerogel is placed under reduction atmosphere and is heated to 260 DEG C, reduction reaction
Graphene-titanium dioxide composite aerogel powder is made after milled processed by 3h.
Comparative example 1
A kind of lithium ion battery anode slurry includes the component of following parts by weight：
55 parts of titanium dioxide, 40 parts of graphene, 1.5 parts of Super P, 1 part of polyvinylpyrrolidone, polytetrafluoroethylene (PTFE) 2
Part, 0.5 part of sodium carboxymethylcellulose, 150 parts of water.
Comparative example 2
A kind of lithium ion battery anode slurry includes the component of following parts by weight：
Graphene -95 parts of titanium dioxide composite aerogel powder, 1.5 parts of Super P, 1 part of polyvinylpyrrolidone gather
2 parts of tetrafluoroethene, 0.5 part of sodium carboxymethylcellulose, 150 parts of water.
Wherein, the preparation method of the graphene-titanium dioxide composite aerogel particle is as follows：
A) butyl titanate with the ethyl alcohol of its 15 times of quality is mixed, obtains liquid A；By the glacial acetic acid of 1.5mol/L with it is anhydrous
Ethyl alcohol, water in mass ratio 4:20:5 are uniformly mixed, and liquid B is made.
B) liquid B is added drop-wise to the rate of addition of 1.5mL/s in the liquid A of its 2.5 times of quality under agitation；
To colloidal sol.
C) graphene oxide of butyl titanate quality 2/3 is added in colloidal sol, be uniformly dispersed.
D) by complex sol aging 1.5 days at room temperature, plural gel is obtained after washing.
E) water and ethyl alcohol being sufficiently displaced from n-hexane in plural gel take out gel, use Co 2 supercritical fluid
Dry (pressure 7MPa, temperature 45 C, time 10h), obtains graphene oxide-titanium dioxide composite aerogel.
F) graphene oxide-titanium dioxide composite aerogel is placed under reduction atmosphere and is heated to 250 DEG C, reduction reaction
Graphene-titanium dioxide composite aerogel powder is made after milled processed by 3h.
Comparative example 1 is directly using titanium dioxide and the physical mixed material of graphene, graphene-titanium dioxide of comparative example 2
Titanium composite aerogel powder is that graphene oxide is added after hydrolysis in preparation process.
Negative electrode slurry made from 1-2 of the embodiment of the present invention and comparative example 1-2 is under equal conditions coated on cathode copper
Foil surface, is made negative plate, and the adhesive force of negative plate face coat is tested and surface sense organ is evaluated.
Wherein adhesion test method is：Applying pulling force to negative plate both ends makes its parallel drawing, is applied by testing cathode
The peel strength of layer represents the adhesive force situation of cathode coating,
| Group number | Coating adhesion | Average coating thickness | Coating surface sense organ |
| Embodiment 1 | 16.2N/m | 25.0μm | Feel is more smooth, and harsh feeling is weak |
| Embodiment 2 | 17.8N/m | 25.3μm | Feel is more smooth, and harsh feeling is weak |
| Comparative example 1 | 15.9N/m | 24.6μm | Feel is coarse, hairiness spicule |
| Comparative example 2 | 16.3N/m | 25.2μm | Feel is coarse, hairiness spicule |
The foregoing is only a preferred embodiment of the present invention, is not intended to restrict the invention, for the skill of this field
For art personnel, the invention may be variously modified and varied.All within the spirits and principles of the present invention, that is made any repaiies
Change, equivalent replacement, improvement etc., should all be included in the protection scope of the present invention.
Claims (10)
1. a kind of graphene-titanium dioxide composite negative pole slurry for lithium ion battery, which is characterized in that including following weight
The component of part：
Graphene -94-96 parts of titanium dioxide composite aerogel powder,
0-3 parts of conductive agent,
0-2 parts of dispersant,
1-3 parts of adhesive,
0-1 parts of thickener,
140-160 parts of water.
2. a kind of graphene-titanium dioxide composite negative pole slurry for lithium ion battery according to claim 1, special
Sign is that the preparation method of the graphene-titanium dioxide composite aerogel particle is as follows：
A) ultrasonic washing is carried out to graphene oxide, and dry under condition of negative pressure；
B) by graphene oxide in mass ratio 1:1-2 is added in butyl titanate, is sufficiently stirred, addition graphene oxide 10-30
Then the absolute ethyl alcohol of times quality adds the sodium bicarbonate of saturation solubility, be uniformly mixed, with liquid A；By 1-2mol/L's
Glacial acetic acid and absolute ethyl alcohol, water 3-5 in mass ratio:15-25:3-7 is uniformly mixed, and liquid B is made；
C) liquid B is added drop-wise in the liquid A of its 2-3 times of quality under agitation；Obtain complex sol；
D) by complex sol aging 1-2 days at room temperature, plural gel is obtained after washing；
E) water and ethyl alcohol being sufficiently displaced from n-hexane in plural gel take out gel, are dried with Co 2 supercritical fluid,
Obtain graphene oxide-titanium dioxide composite aerogel；
F) graphene oxide-titanium dioxide composite aerogel is placed under reduction atmosphere and is heated to 200-300 DEG C, reduction reaction 2-
Graphene-titanium dioxide composite aerogel powder is made after milled processed by 4h.
3. a kind of graphene-titanium dioxide composite negative pole slurry for lithium ion battery according to claim 2, special
Sign is, in step a), the graphene oxide is modified by hydroxylating：
Graphene oxide is added in water to the graphene oxide dispersion for being configured to a concentration of 3-7wt%, is added into solution
The potassium hydroxide of 0.2-0.4 times of graphene oxide quality is heated to 85-95 DEG C, 6-8h is reacted, after being filtered, washed, drying
Hydroxylating graphene oxide is made.
4. a kind of graphene-titanium dioxide composite negative pole slurry for lithium ion battery according to claim 2, special
Sign is, in step c), the rate of addition of liquid B is 1-2mL/s.
5. a kind of graphene-titanium dioxide composite negative pole slurry for lithium ion battery according to claim 2, special
Sign is, in step e), supercritical fluid drying condition be pressure 6-8MPa, 40-50 DEG C of temperature, time 8-12h.
6. a kind of graphene-titanium dioxide composite negative pole slurry for lithium ion battery according to claim 1, special
Sign is that described adhesive is polytetrafluoroethylene (PTFE) or butadiene-styrene rubber.
7. a kind of graphene-titanium dioxide composite negative pole slurry for lithium ion battery according to claim 1, special
Sign is that the conductive agent is carbon nanotube or SuperP.
8. a kind of graphene-titanium dioxide composite negative pole slurry for lithium ion battery according to claim 1, special
Sign is that the dispersant is polyvinylpyrrolidone.
9. a kind of graphene-titanium dioxide composite negative pole slurry for lithium ion battery according to claim 1, special
Sign is that the thickener is sodium carboxymethylcellulose.
10. a kind of starch according to the arbitrary graphene for the lithium ion battery-titanium dioxide composite negative poles of claim 1-9
The preparation method of material, it is characterised in that include the following steps：
1) each component is weighed by proportioning；
2) first by thickener be added to half formula ratio water in, then under agitation successively add adhesive, dispersant,
Conductive agent and graphene-titanium dioxide composite aerogel powder add the water of surplus after being uniformly dispersed；
3) gained slurry is ground, negative electrode slurry is made.
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Denomination of invention: Graphene titanium dioxide composite negative electrode slurry for lithium ion battery and preparation method thereof Effective date of registration: 20210918 Granted publication date: 20201103 Pledgee: Bank of Beijing Limited by Share Ltd. Changsha branch Pledgor: Hunan Jinyang New Carbon Material Co.,Ltd. Registration number: Y2021430000053 |