CN107393622B - Graphene-titanium suboxide composite conductive agent and preparation method thereof - Google Patents

Graphene-titanium suboxide composite conductive agent and preparation method thereof Download PDF

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CN107393622B
CN107393622B CN201710501278.0A CN201710501278A CN107393622B CN 107393622 B CN107393622 B CN 107393622B CN 201710501278 A CN201710501278 A CN 201710501278A CN 107393622 B CN107393622 B CN 107393622B
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graphene
titanium dioxide
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conductive agent
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CN107393622A (en
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秦志鸿
刘鹏
赵永胜
周旭峰
刘兆平
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NINGBO MORSH TECHNOLOGY Co Ltd
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01BCABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/04Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of carbon-silicon compounds, carbon or silicon
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01BCABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/06Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
    • H01B1/08Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances oxides
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01BCABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B13/00Apparatus or processes specially adapted for manufacturing conductors or cables

Abstract

The invention relates to a graphene-titanium dioxide composite conductive agent, which comprises a graphene material and a modified titanium dioxide material, wherein the modified titanium dioxide material is obtained by modifying a titanium dioxide material through polymer alcohol or polyhydric alcohol, the surface of the modified titanium dioxide material is provided with hydroxyl groups, and the graphene material is tightly compounded with the modified titanium dioxide material through the hydroxyl groups on the surface of the modified titanium dioxide material. The invention also provides a preparation method of the graphene-titanium dioxide composite conductive agent.

Description

Graphene-titanium suboxide composite conductive agent and preparation method thereof
Technical Field
The invention relates to a graphene material, in particular to a graphene-titanium dioxide composite conductive agent and a preparation method thereof.
Background
The graphene is sp2The two-dimensional crystal material of the hybrid monoatomic layer has unique electrical, mechanical and thermal properties. The electron mobility of graphene at normal temperature exceeds 15000cm2Higher than carbon nanotubes and silicon crystals, and has a resistivity of only 10-6Ω · m is a material known to have the smallest resistivity. Since the discovery of graphene, a series of research works have been carried out on the excellent characteristics of graphene, such as using graphene for manufacturing touch screens and optical panels by utilizing the good light transmission and thermal conductivity of graphene; the graphene is used as a conductive additive of a battery energy storage device and the like by utilizing the high electron transfer rate of the graphene, so that the graphene has a wide application prospect.
The titanium dioxide material has good conductivity and higher chemical and electrochemical stability at room temperature, is in the same order of magnitude as the high-conductivity carbon material, and the conductivity of the titanium dioxide material changes along with the n valueIn which Ti is changed4O7The conductivity is best, and the conductivity is as high as 1500S cm-1. In addition, the density of the titanium dioxide material is low, so that the light weight of the product is facilitated, and the specific energy of the electrochemical energy storage device is improved. The honeycomb structure and the high specific surface area of the titanium dioxide material can be beneficial to improving the utilization rate of active substances; the titanium dioxide material has excellent chemical stability and corrosion resistance, and can stably exist in strong acid and strong alkali environments, so that the titanium dioxide material is a novel material which can be applied to various chemical energy storage devices.
Chinese patent application No. 201010593157.1 discloses a method for preparing graphene composite conductive powder, which is prepared by oxidizing graphene. Although the dispersibility of the composite conductive powder obtained by the method is improved, the composite conductive powder has relatively low conductivity, the powder is easy to agglomerate in a solvent and is not easy to disperse, and the preparation process has multiple steps and long time consumption, so that the method is not beneficial to large-scale industrial production and application.
Disclosure of Invention
In view of this, the invention provides a graphene-titanium oxide composite conductive agent with high conductivity and a preparation method thereof, so as to solve the problems in the prior art.
The invention provides a graphene-titanium dioxide composite conductive agent which comprises a graphene material and a modified titanium dioxide material, wherein the modified titanium dioxide material is obtained by modifying a titanium dioxide material through polymer alcohol or polyhydric alcohol, the surface of the modified titanium dioxide material is provided with hydroxyl groups, and the graphene material is tightly compounded with the modified titanium dioxide material through the hydroxyl groups on the surface of the modified titanium dioxide material.
The invention also provides a preparation method of the graphene-titanium dioxide composite conductive agent, which comprises the following steps:
(1) mixing a titanium dioxide material, a modifier and water to prepare modified titanium dioxide slurry, wherein the modifier is polymer alcohol or polyalcohol;
(2) dispersing a graphene material in water to obtain graphene slurry, mixing the graphene slurry with the modified titanium dioxide slurry, and performing self-assembly to obtain composite slurry; and
(3) and drying the composite slurry to obtain the graphene-titanium oxide composite conductive agent.
Compared with the prior art, the graphene-titanium suboxide composite conductive agent has the following advantages:
firstly, the surface of the modified titanium dioxide material is provided with hydroxyl groups. The graphene material can be self-assembled on the surface of the modified titanium oxide through the hydroxyl group, so that the graphene material can be tightly compounded with the modified titanium oxide material through the hydroxyl group carried on the surface of the modified titanium oxide material.
Secondly, the graphene materials are blocked by the modified titanium dioxide material, so that stacking and agglomeration of graphene sheet layers are effectively avoided, and the dispersion effect and the utilization rate of the graphene materials are improved.
Thirdly, the modified titanium dioxide material has good stability and conductivity, so that the obtained graphene-titanium dioxide composite conductive agent has excellent stability and conductivity.
The preparation method of the graphene-titanium dioxide composite conductive agent has the advantages of simple process, easiness in operation and suitability for industrial application.
Drawings
Fig. 1 is a scanning electron micrograph of the graphene-titanium suboxide composite conductive agent prepared in example 1.
Detailed Description
The graphene-titanium dioxide composite conductive agent and the preparation method thereof provided by the present invention will be further described below.
The invention provides a graphene-titanium dioxide composite conductive agent. The graphene-titanium dioxide composite conductive agent comprises a graphene material and a modified titanium dioxide material. The modified titanium dioxide material is obtained by modifying a titanium dioxide material with polymer alcohol or polyalcohol. The surface of the modified titanium dioxide material is provided with hydroxyl groups. The graphene material is tightly compounded with the modified titanium oxide material through hydroxyl groups carried on the surface of the modified titanium oxide material.
The structure of the graphene material is not particularly limited, and it may include graphene nanoplatelets, graphene nanoribbons, few-layer graphene (2-5 layers), multi-layer graphene (2-9 layers), graphene quantum dots, chemically modified graphene (graphene oxide, reduced graphene oxide), and derivatives of these graphene-based materials). The graphene materials are defined in the literature "Allinthegraphenefamily-Arecommendendrenchedtwo-dimensional carbon materials". The graphene material may also be selected from materials having a thickness of 20nm or less, more preferably 10nm or less. In the embodiment, the thickness of the graphene material is preferably less than or equal to 3nm, and the thinner the graphene material is, the better the flexibility is, and the easier the processing is. The preparation method of the graphene material is not limited, and the graphene material can be prepared by a graphene product or a conventional preparation method which is well known to those skilled in the art. The graphene material of the invention is preferably a graphene product provided by Ningbo ink science and technology Co. The graphene material may be selected from graphene materials prepared by thermal expansion of graphene oxide prepared by any one of chemical oxidation methods such as a Brodie method, a Hummers method or a staudenmier method, or may be prepared by mechanical exfoliation, liquid phase exfoliation or electrochemical exfoliation, and also graphene oxide or other chemically modified graphene materials may be used in the present invention.
The titanium suboxide material is Ti4O7、Ti3O5、Ti5O9One kind of (1). The titanium dioxide material has a microscopic shape which is not limited, and can be at least one of powder, rod, ceramic sheet and porous.
The polyalcohol is at least one of pentaerythritol, ethylene glycol, propylene glycol, butanediol, hexanediol, neopentyl glycol, diethylene glycol, dipropylene glycol, trimethylolpropane and glycerol, and the polymer alcohol is at least one of polyethylene glycol and polyvinyl alcohol.
The mass ratio of the graphene material to the titanium dioxide material is 1: (0.1-10). Preferably, the mass ratio of the graphene material to the modified titanium dioxide material is 1: (0.5-5).
The invention provides a preparation method of a graphene-titanium dioxide composite conductive agent, which comprises the following steps:
s1, mixing a titanium dioxide material, a modifier and water to prepare modified titanium dioxide slurry, wherein the modifier is polymer alcohol or polyol;
s2, dispersing the graphene material in water to obtain graphene slurry, mixing the graphene slurry with the modified titanium dioxide slurry, and carrying out self-assembly to obtain composite slurry; and
and S3, drying the composite slurry to obtain the graphene-titanium dioxide composite conductive agent.
In step S1, the titanium dioxide material is Ti4O7、Ti3O5、Ti5O9One kind of (1). The titanium dioxide material has a microscopic shape which is not limited, and can be at least one of powder, rod, ceramic sheet and porous. The polyalcohol is at least one of pentaerythritol, ethylene glycol, propylene glycol, butanediol, hexanediol, neopentyl glycol, diethylene glycol, dipropylene glycol, trimethylolpropane and glycerol, and the polymer alcohol is at least one of polyethylene glycol and polyvinyl alcohol. The mass ratio of the titanium dioxide material to the modifier is 1: (0.01-1).
The mass fraction of the titanium dioxide material in the modified titanium dioxide slurry is 1-5%.
In step S2, the source and preparation method of the graphene treatment are not limited, and the graphene product known to those skilled in the art may be used or prepared by a conventional preparation method. The graphene treatment of the present invention is preferably a graphene slurry or a graphene powder product provided by Ningbo ink science and technology Co. The graphene material may be selected from graphene prepared by liquid phase reduction or thermal expansion of graphene oxide prepared by any one of chemical oxidation methods such as a Brodie method, Hummers method or Staudenmaier method. Graphene prepared by mechanical exfoliation, liquid phase exfoliation or electrochemical exfoliation may also be selected.
The graphene material can be prepared from a graphite intercalation compound, and the specific preparation method is as follows (the graphite intercalation compound is prepared according to a known synthesis method): the prepared graphite intercalation compound is subjected to microwave and high-temperature expansion stripping to obtain expanded graphite worms, and the expanded graphite worms are dispersed in water to prepare graphene through dispersion stripping technologies such as ultrasonic stripping and shearing dispersion.
The preparation method of the graphene stripped by the electrochemical method comprises the following steps: and electrochemically stripping graphene to obtain a graphene mixture dispersed in an electrolyte according to a known electrochemical stripping technology, washing and purifying the graphene mixture, and performing ultrasonic dispersion to obtain the graphene.
The mass ratio of the graphene material to the titanium dioxide material in the step (1) is 1: (0.1-10). Preferably, the mass ratio of the graphene material to the titanium dioxide material in the step (1) is 1: (0.5-5).
In step S3, the drying method is not limited, and is preferably a drying process, a hot-pressing drying process, a freeze-drying process, a spray-drying process, or a granulation drying process. In an embodiment, the drying is more preferably spray drying, freeze drying, hot press drying or oven drying. Different drying temperatures are set according to different drying modes.
Compared with the prior art, the graphene-titanium suboxide composite conductive agent has the following advantages:
firstly, the surface of the modified titanium dioxide material is provided with hydroxyl groups. The graphene material can be self-assembled on the surface of the modified titanium oxide through the hydroxyl group, so that the graphene material can be tightly compounded with the modified titanium oxide material through the hydroxyl group carried on the surface of the modified titanium oxide material.
Secondly, the graphene materials are blocked by the modified titanium dioxide material, so that stacking and agglomeration of graphene sheet layers are effectively avoided, and the dispersion effect and the utilization rate of the graphene materials are improved.
Thirdly, the modified titanium dioxide material has good stability and conductivity, so that the obtained graphene-titanium dioxide composite conductive agent has excellent stability and conductivity.
The preparation method of the graphene-titanium dioxide composite conductive agent has the advantages of simple process, easiness in operation and suitability for industrial application.
The graphene-titanium dioxide composite conductive agent and the preparation method thereof according to the present invention will be further described with reference to specific examples.
Example 1
Respectively preparing 2% graphene aqueous slurry and 4% Ti4O7Modified aqueous slurry:
a) preparing graphene material aqueous slurry with the mass concentration of 2%: weighing 40Kg of graphene aqueous slurry with the mass concentration of 5%, adding water to dilute the slurry until the graphene content is 2%, and uniformly stirring the slurry;
b) ti with a mass concentration of 4%4O7Preparing modified water-based slurry: weighing 2kg of Ti4O7Material according to Ti4O7Weighing polyethylene glycol according to the mass ratio of 1:0.05, adding a certain amount of water to dilute to Ti4O7The mass concentration of the material is 4 percent, and the material is uniformly stirred and dispersed;
mixing the prepared graphene material aqueous slurry and Ti4O7Uniformly mixing the aqueous slurry to obtain graphene/Ti4O7Compound slurry, and spray drying the intermediate slurry to obtain graphene/Ti4O7And compounding the conductive agent.
For the obtained graphene/Ti4O7The composite conductive agent is subjected to a microscopic morphology test, and the result is shown in figure 1. As can be seen from FIG. 1, the graphene/Ti4O7In the composite conductive agent, the surface of graphene is uniformly covered with high-conductivity Ti4O7A material.
Example 2
Respectively preparing 0.1 mass percent graphene material aqueous slurry and 5 mass percent Ti4O7Water for modifying materialSlurry preparation:
a) preparing 0.1% graphene material aqueous slurry by mass: weighing 40Kg of graphene aqueous slurry with the mass concentration of 5%, and adding water to dilute until the graphene content is 0.1%;
b) 5% by mass of Ti4O7Preparing material modified water-based slurry: 0.2kg of Ti was weighed4O7According to Ti4O7Weighing 0.2kg of ethylene glycol at the mass ratio of 1:1, adding a certain amount of water to dilute the ethylene glycol to Ti4O7The mass concentration is 5 percent, and the mixture is stirred and dispersed evenly;
mixing the prepared graphene material aqueous slurry and Ti4O7Uniformly mixing the aqueous slurry to obtain graphene/Ti4O7Compound slurry, and spray drying the intermediate slurry to obtain graphene/Ti4O7And compounding the conductive agent.
Example 3
Respectively preparing 3% graphene material aqueous slurry and 1% Ti4O7Material modified aqueous slurry:
a) preparing 3% graphene material aqueous slurry by mass: weighing 40Kg of graphene aqueous slurry with the mass concentration of 5%, adding water to dilute until the content of graphene is 3%, and uniformly stirring;
b) 1% by mass of Ti4O7Preparing material modified water-based slurry: weighing 20kg of Ti for lithium battery4O7Material according to Ti4O7Weighing 0.2kg of pentaerythritol according to the mass ratio of the material to the pentaerythritol of 1:0.01, and adding a certain amount of water to dilute until the Ti content is reduced4O7The mass concentration of the material is 1 percent, and the material is uniformly stirred and dispersed;
mixing the prepared graphene material aqueous slurry and Ti4O7Uniformly mixing the aqueous slurry to obtain graphene/Ti4O7Compound slurry, and spray drying the intermediate slurry to obtain graphene/Ti4O7And compounding the conductive agent.
Example 4
Respectively preparing graphene material aqueous slurry with the mass concentration of 1% and Ti with the mass concentration of 2%3O5Material modified aqueous slurry:
a) preparing graphene material aqueous slurry with the mass concentration of 1%: weighing 40Kg of graphene aqueous slurry with the mass concentration of 5%, adding water to dilute until the graphene content is 1%, and uniformly stirring;
b) 2% by mass of Ti3O5Preparing material modified water-based slurry: weighing 4kgTi3O5Material according to Ti3O5Weighing 0.4kg of 2-propylene glycol according to the mass ratio of the material to the 2-propylene glycol of 1:0.1, adding a certain amount of water to dilute the material to Ti3O5Stirring and dispersing the mixture uniformly with the mass concentration of 2%;
mixing the prepared graphene material aqueous slurry and Ti3O5Uniformly mixing the aqueous slurry to obtain graphene/Ti3O5Compound slurry, and spray drying the intermediate slurry to obtain graphene/Ti3O5And compounding the conductive agent.
Example 5
Respectively preparing 2% graphene material aqueous slurry and 4% Ti3O5Material modified aqueous slurry:
a) preparing graphene material aqueous slurry with the mass concentration of 2%: weighing 40Kg of graphene aqueous slurry with the mass concentration of 5%, adding water to dilute the slurry until the graphene content is 2%, and uniformly stirring the slurry; b) ti with a mass concentration of 4%3O5Preparing material modified water-based slurry: weighing 2kgTi3O5Material according to Ti3O5Weighing 2kg of neopentyl glycol according to the mass ratio of 1:1 of the material to the neopentyl glycol, and adding a certain amount of water to dilute until Ti is obtained3O5The mass concentration is 4 percent, and the mixture is stirred and dispersed evenly;
mixing the prepared graphene material aqueous slurry and Ti3O5Uniformly mixing the aqueous slurry to obtain graphene/Ti3O5Composite slurry, filter-pressing the intermediate slurry, and drying in a drying oven to obtain graphene/Ti3O5And compounding the conductive agent.
Example 6
Respectively preparing 3% graphene material aqueous slurry and 5% Ti5O9Material modified aqueous slurry:
a) preparing graphene material aqueous slurry with the mass concentration of 2%: weighing 40Kg of graphene aqueous slurry with the mass concentration of 5%, adding water to dilute the slurry until the graphene content is 2%, and uniformly stirring the slurry;
b) 5% by mass of Ti5O9Preparing material modified water-based slurry: weighing 20kg of Ti for lithium battery5O9Material according to Ti5O9Weighing 20kg of sorbitol at a mass ratio of the material to the sorbitol of 1:1, adding a certain amount of water to dilute until Ti is formed5O9The mass concentration of the material is 5 percent, and the material is uniformly stirred and dispersed;
mixing the prepared graphene material aqueous slurry and Ti5O9Uniformly mixing the aqueous slurry to obtain graphene/Ti5O9Composite slurry, filter-pressing the intermediate slurry, and drying in a drying oven to obtain graphene/Ti3O5And compounding the conductive agent.
Example 7
Respectively preparing 2% graphene material aqueous slurry and 4% Ti5O9Material modified aqueous slurry:
a) preparing graphene material aqueous slurry with the mass concentration of 2%: weighing 40Kg of graphene aqueous slurry with the mass concentration of 5%, adding water to dilute the slurry until the graphene content is 2%, and uniformly stirring the slurry;
b) ti with a mass concentration of 4%5O9Preparing material modified water-based slurry: weighing 4kgTi5O9Material according to Ti5O9Weighing 0.4kg of polyglycerol according to the mass ratio of the materials to the polyglycerol of 1:0.1, adding a certain amount of water to dilute the polyglycerol to Ti5O9The mass concentration of the material is 4 percent, and the material is uniformly stirred and dispersed;
the prepared graphene material aqueous slurryMaterial and Ti5O9Uniformly mixing the aqueous slurry to obtain graphene/Ti5O9Composite slurry, and spray drying the intermediate slurry to obtain graphene/Ti5O9And compounding the conductive agent.
Example 8
Respectively preparing 3% graphene material aqueous slurry and 5% Ti4O7Material modified aqueous slurry:
a) preparing 3% graphene material aqueous slurry by mass: weighing 40Kg of graphene aqueous slurry with the mass concentration of 5%, adding water to dilute until the content of graphene is 3%, and uniformly stirring; b) 5% by mass of Ti4O7Preparing material modified water-based slurry: weighing 10kgTi4O7Material according to Ti4O7Weighing 10kg of dimeric glycerol according to the mass ratio of the material to the dimeric glycerol of 1:1, and adding a certain amount of water to dilute until the Ti content is reduced4O7The mass concentration is 5%.
Mixing the prepared graphene material aqueous slurry and Ti4O7Uniformly mixing the aqueous slurry to obtain graphene/Ti4O7Composite slurry, and spray drying the intermediate slurry to obtain graphene/Ti4O7And compounding the conductive agent.
Example 9
Respectively preparing 0.1 mass percent graphene material aqueous slurry and 5 mass percent Ti3O5Material modified aqueous slurry:
a) preparing 0.1% graphene material aqueous slurry by mass: weighing 40Kg of graphene aqueous slurry with the mass concentration of 5%, adding water to dilute the slurry until the graphene content is 0.1%, and uniformly stirring the slurry;
b) 5% by mass of Ti3O5Preparing material modified water-based slurry: weighing 0.2kgTi3O5Material according to Ti3O5Weighing 0.2kg of diethylene glycol according to the mass ratio of the material to the diethylene glycol of 1:1, and adding a certain amount of water to dilute until Ti is formed3O5The mass concentration is 5 percent, and the mixture is stirredDispersing uniformly;
mixing the prepared graphene material aqueous slurry and Ti3O5Uniformly mixing the material modified aqueous slurry to obtain graphene/Ti3O5Compounding intermediate material, and hot-pressing and drying the intermediate slurry at 100 ℃ to obtain graphene/Ti3O5And (3) compounding conductive powder.
The above description of the embodiments is only intended to facilitate the understanding of the method of the invention and its core idea. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.

Claims (3)

1. The graphene-titanium dioxide composite conductive agent is characterized by comprising a graphene material and a modified titanium dioxide material, wherein the mass ratio of the graphene material to the modified titanium dioxide material is 1: (0.5-5), the modified titanium dioxide material is obtained by modifying a titanium dioxide material through polymer alcohol or polyhydric alcohol, and the mass ratio of the titanium dioxide material to the polymer alcohol or polyhydric alcohol is 1: (0.01-1), the surface of the modified titanium oxide material is provided with hydroxyl groups, the graphene material is tightly compounded with the modified titanium oxide material through the hydroxyl groups on the surface of the modified titanium oxide material, wherein the titanium oxide in the modified titanium oxide material is Ti4O7Said Ti4O7Covering the surface of the graphene;
the preparation method of the graphene-titanium dioxide composite conductive agent comprises the following steps:
(1) mixing a titanium dioxide material, a modifier and water to prepare modified titanium dioxide slurry, wherein the modifier is polymer alcohol or polyalcohol;
(2) dispersing a graphene material in water to obtain graphene slurry, mixing the graphene slurry with the modified titanium dioxide slurry, and performing self-assembly to obtain composite slurry; and
(3) and drying the composite slurry to obtain the graphene-titanium oxide composite conductive agent.
2. The graphene-titanium monoxide composite conductive agent according to claim 1, wherein the polyol is at least one of pentaerythritol, ethylene glycol, propylene glycol, butylene glycol, hexylene glycol, neopentyl glycol, diethylene glycol, dipropylene glycol, trimethylolpropane, and glycerin, and the polymer alcohol is at least one of polyethylene glycol and polyvinyl alcohol.
3. The graphene-titanium monoxide composite conductive agent according to claim 1, wherein the modified titanium monoxide slurry in the step (1) contains 1 to 5% by mass of a titanium monoxide material.
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CN111525133A (en) * 2020-03-25 2020-08-11 眉山顺应动力电池材料有限公司 Composite conductive agent, lithium ion positive electrode material prepared from composite conductive agent and lithium ion battery
WO2022034852A1 (en) * 2020-08-13 2022-02-17 株式会社村田製作所 Film manufacturing method and conductive film
CN113233553B (en) * 2021-05-28 2022-06-24 东莞理工学院 Ti loaded with graphene nanoparticles4O7Method for preparing anode
CN113461049A (en) * 2021-08-11 2021-10-01 贵阳精一科技有限公司 Preparation method of ultrahigh-purity titanium dioxide
CN115849860B (en) * 2022-11-14 2023-10-24 北京科技大学 Graphene/magneli phase TinO 2n-1 Nanoparticle composite high-heat-conductivity film and preparation method thereof

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2687483A1 (en) * 2012-07-16 2014-01-22 Basf Se Graphene containing nitrogen and optionally iron and/or cobalt
CN104388923A (en) * 2014-10-17 2015-03-04 山东科技大学 Making method of graphene modified titanium oxide metal anticorrosion coating
CN104805323A (en) * 2015-03-23 2015-07-29 武汉理工大学 Graphene/titanium composite material and preparation method thereof
CN105098176A (en) * 2014-06-30 2015-11-25 浙江天能电池(江苏)有限公司 Positive lead plaster of lead-acid storage battery
CN105148894A (en) * 2015-09-23 2015-12-16 长沙理工大学 Preparation method of hydroxylation titanium oxide/graphene visible light catalysis material
CN105355320A (en) * 2015-10-23 2016-02-24 河北麦森钛白粉有限公司 Production technology of nanoscale conductive titanium dioxide

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2687483A1 (en) * 2012-07-16 2014-01-22 Basf Se Graphene containing nitrogen and optionally iron and/or cobalt
CN105098176A (en) * 2014-06-30 2015-11-25 浙江天能电池(江苏)有限公司 Positive lead plaster of lead-acid storage battery
CN104388923A (en) * 2014-10-17 2015-03-04 山东科技大学 Making method of graphene modified titanium oxide metal anticorrosion coating
CN104805323A (en) * 2015-03-23 2015-07-29 武汉理工大学 Graphene/titanium composite material and preparation method thereof
CN105148894A (en) * 2015-09-23 2015-12-16 长沙理工大学 Preparation method of hydroxylation titanium oxide/graphene visible light catalysis material
CN105355320A (en) * 2015-10-23 2016-02-24 河北麦森钛白粉有限公司 Production technology of nanoscale conductive titanium dioxide

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