CN111244406A - Fluorinated graphene modified titanium dioxide material, and preparation and application thereof - Google Patents

Fluorinated graphene modified titanium dioxide material, and preparation and application thereof Download PDF

Info

Publication number
CN111244406A
CN111244406A CN201811443917.3A CN201811443917A CN111244406A CN 111244406 A CN111244406 A CN 111244406A CN 201811443917 A CN201811443917 A CN 201811443917A CN 111244406 A CN111244406 A CN 111244406A
Authority
CN
China
Prior art keywords
titanium dioxide
fluorinated graphene
percent
mass fraction
hours
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN201811443917.3A
Other languages
Chinese (zh)
Inventor
曲超
张洪章
李先锋
张华民
刘翠连
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Dalian Institute of Chemical Physics of CAS
Original Assignee
Dalian Institute of Chemical Physics of CAS
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Dalian Institute of Chemical Physics of CAS filed Critical Dalian Institute of Chemical Physics of CAS
Priority to CN201811443917.3A priority Critical patent/CN111244406A/en
Publication of CN111244406A publication Critical patent/CN111244406A/en
Pending legal-status Critical Current

Links

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/364—Composites as mixtures
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention provides a preparation method of fluorinated graphene modified titanium dioxide. The method can form a C-F-Ti bond on the surface of the titanium dioxide, and the titanium dioxide and the fluorinated graphene are compounded in the atomic scale, so that the electron conduction resistance is greatly reduced, and the rate capability of the titanium dioxide material is improved. Meanwhile, fluorine atoms are fully doped into the crystal lattice of the titanium dioxide, so that the lithium ion diffusivity is further improved. According to the specific technical scheme, the fluorinated graphene modified titanium dioxide material comprises a C-F-Ti bond on the surface of titanium dioxide, the fluorinated graphene and the titanium dioxide are fully compounded, and partial fluorine elements are embedded in titanium dioxide lattices. In the fluorinated graphene modified titanium dioxide material, the mass fraction of titanium dioxide in the whole material is 50-99%, preferably 60-98%, and most preferably 70-95%. The carbon element accounts for 1 to 25 percent of the mass fraction of the whole material, preferably 2 to 20 percent, and most preferably 5 to 18 percent, and the fluorine element accounts for 0.2 to 20 percent, preferably 0.5 to 18 percent, and most preferably 0.8 to 15 percent of the mass fraction of the whole material.

Description

Fluorinated graphene modified titanium dioxide material, and preparation and application thereof
Technical Field
The invention belongs to the field of lithium ion batteries and lithium ion super capacitors, and particularly relates to a lithium battery cathode and a preparation method thereof.
Background
Titanium dioxide is a cathode material with great potential, has little volume change (4%) in the charge-discharge process, good cycle stability, a higher voltage platform (1.7V vs. Li +/Li), can effectively avoid lithium dendrites, has proper theoretical capacity (335mAh/g), and has the advantages of environmental protection, stable structure, low cost, abundant resources and the like.
However, titanium dioxide itself had poor conductivity (. about.10-13 Scm-1) and ion diffusibility (10)-1110-13cm2s-1) is not as desirable, especially under conditions requiring high rate cycling, the above problem is more severe, severely increasing electrode reaction polarization.
In response to the above problems, two strategies have been mainly adopted for improvement. 1. Modification treatment of nano-level or nano-structure design shortens electron conduction path and ion diffusion path, and provides more abundant reaction sites. However, the method greatly increases the material cost, and in addition, the agglomeration of the nano material and the like increases the difficulty of electrode preparation; 2. titanium dioxide and a material with good conductivity are compounded or heteroatom doping is changed, but simple compounding is increased along with charge-discharge circulation, so that the conductive material and the titanium dioxide fall off and are separated, and the performance of the battery is reduced.
Disclosure of Invention
The invention provides a preparation method of fluorinated graphene modified titanium dioxide. The method can form a C-F-Ti bond on the surface of the titanium dioxide, and the titanium dioxide and the fluorinated graphene are compounded in the atomic scale, so that the electron conduction resistance is greatly reduced, and the rate capability of the titanium dioxide material is improved. Meanwhile, fluorine atoms are fully doped into the crystal lattice of the titanium dioxide, so that the lithium ion diffusivity is further improved.
According to the specific technical scheme, the fluorinated graphene modified titanium dioxide material comprises a C-F-Ti bond on the surface of titanium dioxide, the fluorinated graphene and the titanium dioxide are fully compounded, and partial fluorine elements are embedded in titanium dioxide lattices.
In the fluorinated graphene modified titanium dioxide material, the mass fraction of titanium dioxide in the whole material is 50-99%, preferably 60-98%, and most preferably 70-95%. The carbon element accounts for 1 to 25 percent of the mass fraction of the whole material, preferably 2 to 20 percent, and most preferably 5 to 18 percent, and the fluorine element accounts for 0.2 to 20 percent, preferably 0.5 to 18 percent, and most preferably 0.8 to 15 percent of the mass fraction of the whole material.
The crystalline phase of the titanium dioxide can be anatase, rutile, brookite and Ti02One or two or more of-B.
The fluorinated graphene modified titanium dioxide provided by the invention can be prepared according to the following method but not limited to the following method: mixing organic alcohol, acetic acid, deionized water and fluorinated graphene into uniform liquid; adding an organic titanium compound with the mass fraction of 1.0-20 of the liquid, stirring for 0.5-10 hours, wherein the preferable mass fraction of the organic titanium compound is 2.0-15, the optimal mass fraction is 4.0-10, the optimal stirring time is 1-8 hours, and the optimal stirring time is 1.5-6 hours, then stopping stirring, filtering, centrifuging or evaporating the liquid to obtain a mesophase, calcining the mesophase at the high temperature of 300-;
the above mentioned homogeneous liquid consists of: 40-90 mass percent of organic alcohol, 1.0-3.0 mass percent of acetic acid, 0.1-6 mass percent of deionized water and 0.1-5 mass percent of fluorinated graphene. The organic alcohol comprises one or more than two of methanol, ethanol, propanol, isopropanol and butanol.
The inert gas is one or more than two of nitrogen, argon and helium.
The F/C ratio in the fluorinated graphene is 0.1-1.5, preferably 0.3-1.3, and most preferably 0.5-1.2, the number of layers of the fluorinated graphene is 1-15, preferably 1-10, and most preferably 1-5.
The invention has the beneficial effects that a C-F-Ti bond is formed on the surface of the titanium dioxide, the titanium dioxide and the fluorinated graphene are compounded on the atomic scale, the electron conduction resistance is greatly reduced, the rate capability of the titanium dioxide material is improved, and the power performance of the lithium ion battery using the titanium dioxide as the cathode is improved.
Detailed Description
Dissolving 9g of the prepared modified titanium dioxide material, 0.4g of polyvinylidene fluoride and 0.6g of conductive agent into 25g N-methyl pyrrolidone, uniformly dispersing, and blade-coating on an aluminum foil with the electrode supporting amount of 3mg/cm2. The prepared electrode is subjected to a tapping test, the working electrode is modified titanium dioxide, the counter electrode is a lithium sheet, and the electrolyte is 1mol/L lithium hexafluorophosphate (the solvent is ethylene carbonate: dimethyl carbonate: diethyl carbonate: 1: 1: 1 (volume ratio)). The charge and discharge multiplying power of the battery is 1C/20C/100C, and the charge and discharge cutoff voltage is 1V-2.5V.
Examples
Example 1
After 50g of ethanol, 2g of acetic acid, 2g of fluorinated graphene (F/C ratio of 1.1, 5 layers) and 0.5g of water are mixed uniformly, 60g of tetrabutyl titanate is slowly added, and after stirring for 5 hours, the liquid is evaporated to dryness to obtain an intermediate phase. Then calcining for 8 hours at 600 ℃ in the argon atmosphere, and cooling to prepare the powder material.
The material is subjected to element analysis, wherein the mass fraction of carbon elements accounts for 10%, the mass fraction of fluorine elements accounts for 5%, and the balance is titanium dioxide.
The XPS test and peak separation are carried out on the material, wherein 684.8e V belongs to a Ti-F bond 686.6e V belongs to a C-F bond, and 685.7e V belongs to a C-F-Ti bond, so that the fluorinated graphene modified titanium dioxide material is proved to contain the C-F-Ti bond, the Ti-F bond and the C-F bond, and the bonds are beneficial to greatly reducing the electronic conduction resistance of the composite titanium dioxide and the fluorinated graphene on the atomic scale.
The materials are subjected to electrode preparation and battery test, and the conditions of the electrode preparation and the battery test are shown in a table.
Comparative examples 1,
After 50g of ethanol, 2g of acetic acid and 0.5g of water are mixed uniformly, 60g of tetrabutyl titanate is slowly added, the mixture is stirred for 5 hours, and then the liquid is evaporated to dryness to obtain an intermediate phase. Then calcining for 8 hours at 600 ℃ in the argon atmosphere, and cooling to prepare the powder material.
The material is subjected to elemental analysis to obtain titanium dioxide.
The material was XPS tested and peak fractionated with no 684.8e V, 686.6e V, 685.7e V present.
The materials are subjected to electrode preparation and battery test, and the conditions of the electrode preparation and the battery test are shown in a table.
Comparative example 2
After 50g of ethanol, 2g of acetic acid, 2g of graphene (5 layers) and 0.5g of water are uniformly mixed, 60g of tetrabutyl titanate is slowly added, the mixture is stirred for 5 hours, and then the liquid is evaporated to dryness to obtain an intermediate phase. Then calcining for 8 hours at 600 ℃ in the argon atmosphere, and cooling to prepare the powder material.
The material is subjected to element analysis, wherein the mass fraction of carbon elements accounts for 10.5%, and the balance is titanium dioxide.
The material was XPS tested and peak fractionated with no 684.8e V, 686.6e V, 685.7e V present.
The materials are subjected to electrode preparation and battery test, and the conditions of the electrode preparation and the battery test are shown in a table.
Example 2
Uniformly mixing 60g of methanol, 3g of acetic acid, 3g of fluorinated graphene (F/C ratio of 1.2, 4 layers) and 0.3g of water, slowly adding 70g of tetrapropyl titanate, stirring for 4.5 hours, and evaporating the liquid to obtain an intermediate phase. Then calcining the mixture for 68 hours at 800 ℃ in a nitrogen atmosphere, and cooling the mixture to prepare the powder material.
The materials are subjected to electrode preparation and battery test, and the conditions of the electrode preparation and the battery test are shown in a table.
Example 3
After 80g of isopropanol, 2.7g of acetic acid, 3g of fluorinated graphene (F/C ratio of 1.1, 5 layers) and 0.3g of water are mixed uniformly, 90g of tetrabutyl titanate is slowly added, stirring is carried out for 3 hours, and then liquid is evaporated to dryness to obtain an intermediate phase. Then calcining the mixture for 10 hours at 500 ℃ in an argon atmosphere, and cooling the mixture to prepare a powder material.
The above materials were subjected to electrode preparation and battery testing, the electrode preparation and battery testing conditions being illustrated in the figure.
Example 4
After 50g of ethanol, 2g of acetic acid, 2g of fluorinated graphene (F/C ratio of 1.1, 5 layers) and 4g of water are mixed uniformly, 60g of tetramethyl titanate is slowly added, and after stirring for 7 hours, the liquid is evaporated to dryness to obtain an intermediate phase. Then calcining for 8 hours at 700 ℃ under the argon atmosphere, and cooling to prepare the powder material.
The materials are subjected to electrode preparation and battery test, and the conditions of the electrode preparation and the battery test are shown in a table.
Example 5
After 50g of butanol, 2g of acetic acid, 1.6g of fluorinated graphene (F/C ratio of 1.2, 3 layers) and 6g of water are uniformly mixed, 65g of tetrabutyl titanate is slowly added, and after stirring for 5 hours, the liquid is evaporated to dryness to obtain an intermediate phase. Then calcining for 8 hours at 600 ℃ under the atmosphere of argon, and cooling to prepare the powder material.
The materials are subjected to electrode preparation and battery test, and the conditions of the electrode preparation and the battery test are shown in a table.
Example 6
After 50g of ethanol, 2g of acetic acid, 2g of fluorinated graphene (F/C ratio of 0.28, 12 layers) and 7g of water are mixed uniformly, 70g of tetrabutyl titanate is slowly added, and after stirring for 5 hours, the liquid is evaporated to dryness to obtain an intermediate phase. Then calcining for 8 hours at 550 ℃ under the argon atmosphere, and cooling to prepare the powder material.
The materials are subjected to electrode preparation and battery test, and the conditions of the electrode preparation and the battery test are shown in a table.
Example 7
After 50g of methanol, 2g of acetic acid and 3g of fluorinated graphene (F/C ratio of 1.4, 12 layers) are uniformly mixed, 80g of tetrabutyl titanate is slowly added, the mixture is stirred for 6 hours, and then the liquid is evaporated to dryness to obtain an intermediate phase. Then calcining for 7.5 hours at 700 ℃ under the argon atmosphere, and cooling to prepare the powder material.
The materials are subjected to electrode preparation and battery test, and the conditions of the electrode preparation and the battery test are shown in a table.
Example 8
After 40g of propanol, 2g of acetic acid and 2g of fluorinated graphene (F/C ratio of 1.1, 5 layers) are mixed uniformly, 80g of tetrabutyl titanate is slowly added, the mixture is stirred for 5 hours, and then the liquid is evaporated to dryness to obtain an intermediate phase. Then calcining for 8 hours at 600 ℃ under the atmosphere of argon, and cooling to prepare the powder material.
The materials are subjected to electrode preparation and battery test, and the conditions of the electrode preparation and the battery test are shown in a table.
Example 9
Mixing 37g of ethanol, 2g of acetic acid and 2g of fluorinated graphene (F/C ratio is 1.1, 5 layers) uniformly, slowly adding 75g of tetrabutyl titanate, stirring for 5 hours, and evaporating the liquid to obtain an intermediate phase. Then calcining for 8 hours at 600 ℃ under the atmosphere of argon, and cooling to prepare the powder material.
The materials are subjected to electrode preparation and battery test, and the conditions of the electrode preparation and the battery test are shown in a table.
Example 10
After 50g of ethanol, 2g of acetic acid and 2g of fluorinated graphene (F/C ratio of 1.1, 5 layers) are mixed uniformly, 75g of tetrabutyl titanate is slowly added, the mixture is stirred for 7 hours, and then the liquid is evaporated to dryness to obtain an intermediate phase. Then calcining for 12 hours at 800 ℃ under the argon atmosphere, and cooling to prepare the powder material.
The materials are subjected to electrode preparation and battery test, and the conditions of the electrode preparation and the battery test are shown in a table.
Figure BDA0001885332980000051
The data results in the table show that the electrode material prepared by the invention is applied to a lithium ion battery as a negative electrode, and the electrode material forms a C-F-Ti bond on the surface of titanium dioxide, so that the titanium dioxide and the fluorinated graphene are compounded in the atomic scale, the electron conduction resistance is greatly reduced, and the rate capability of the titanium dioxide material is improved. Meanwhile, fluorine atoms are fully doped into the crystal lattice of the titanium dioxide, so that the lithium ion diffusivity is further improved. Greatly improves the battery performance of the battery under high multiplying power.

Claims (7)

1. A fluorinated graphene modified titanium dioxide material is prepared by compounding fluorinated graphene and titanium dioxide; the titanium dioxide accounts for 55 to 98 percent of the mass fraction of the whole material, wherein the mass fraction is preferably 62 to 97 percent, and the most preferably 70 to 94 percent.
2. The fluorinated graphene-modified titanium dioxide material according to claim 1, wherein: the surface of the material contains C-F-Ti bonds, and part of fluorine elements are embedded in titanium dioxide lattices; the titanium dioxide accounts for 55 to 98 percent of the mass fraction of the whole material, the carbon element accounts for 1 to 25 percent of the mass fraction of the whole material, and the fluorine element accounts for 0.2 to 20 percent of the mass fraction of the whole material;
preferably, the titanium dioxide accounts for 62 to 97 percent of the mass of the whole material, the carbon element accounts for 2 to 20 percent of the mass of the whole material, and the fluorine element accounts for 0.5 to 18 percent of the mass of the whole material;
more preferably, the mass fraction of titanium dioxide in the bulk material is 70-94%, the mass fraction of carbon element in the bulk material is 5-18%, and the mass fraction of fluorine element in the bulk material is 0.8-15%.
3. The fluorinated graphene-modified titanium dioxide material according to claim 1 or 2, wherein: the crystalline phase of the titanium dioxide can be anatase, rutile, brookite and Ti02One or two or more of-B.
4. A method for preparing a fluorinated graphene-modified titanium dioxide material according to any one of claims 1 to 3, wherein:
1) mixing organic alcohol, acetic acid, deionized water and fluorinated graphene into uniform liquid;
2) adding the organic titanium compound with the mass 1.0-20 times (preferably 2.0-15 times, most preferably 4.0-10 times) of the mass of the liquid into the liquid, stirring for 0.5-10 hours (preferably stirring time is 1-8 hours, most preferably stirring time is 1.5-6 hours), stopping stirring, filtering, centrifuging or evaporating the liquid to obtain a mesophase, calcining the mesophase at 300-1000 ℃ (preferably 350-900 ℃), most preferably 400-850 ℃) for 1-24 hours (preferably 2-20 hours, most preferably 3-12 hours) under inert atmosphere gas, and cooling to obtain a powder material;
the above mentioned homogeneous liquid consists of: the weight portion of the material is as follows: 40-90 parts of organic alcohol, 1.0-3.0 parts of acetic acid, 0.1-6 parts of deionized water and 0.1-5 parts of fluorinated graphene.
5. The method of claim 4, wherein:
the organic alcohol comprises one or more than two of methanol, ethanol, propanol, isopropanol and butanol;
the inert atmosphere gas is one or more than two of nitrogen, argon and helium;
the F/C ratio in the fluorinated graphene is 0.1-1.5, preferably 0.3-1.3, and most preferably 0.5-1.2; the number of graphene layers of the fluorinated graphene is 1-15, preferably 1-10, and most preferably 1-5.
6. The method of claim 4, wherein: the organic titanium compound is one or more than two of tetrabutyl titanate, tetramethyl titanate, tetraethyl titanate and tetrapropyl titanate.
7. Use of the fluorinated graphene-modified titanium dioxide material according to any one of claims 1 to 3 as an electrode active material in a negative electrode of a lithium ion battery.
CN201811443917.3A 2018-11-29 2018-11-29 Fluorinated graphene modified titanium dioxide material, and preparation and application thereof Pending CN111244406A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201811443917.3A CN111244406A (en) 2018-11-29 2018-11-29 Fluorinated graphene modified titanium dioxide material, and preparation and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201811443917.3A CN111244406A (en) 2018-11-29 2018-11-29 Fluorinated graphene modified titanium dioxide material, and preparation and application thereof

Publications (1)

Publication Number Publication Date
CN111244406A true CN111244406A (en) 2020-06-05

Family

ID=70877425

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201811443917.3A Pending CN111244406A (en) 2018-11-29 2018-11-29 Fluorinated graphene modified titanium dioxide material, and preparation and application thereof

Country Status (1)

Country Link
CN (1) CN111244406A (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115368766A (en) * 2022-08-19 2022-11-22 佛山科学技术学院 Fluorinated graphene/titanium dioxide composite anti-corrosion filler and preparation method thereof

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102683657A (en) * 2012-05-11 2012-09-19 常州第六元素材料科技股份有限公司 Graphene composite material for cathode of lithium ion battery and preparation method of graphene composite material
CN104624220A (en) * 2015-02-10 2015-05-20 济南大学 Preparation method of TiO2/rGO composite
CN108807923A (en) * 2018-06-21 2018-11-13 清远佳致新材料研究院有限公司 The preparation method of sodium-ion battery modifying titanium dioxide-graphene negative material

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102683657A (en) * 2012-05-11 2012-09-19 常州第六元素材料科技股份有限公司 Graphene composite material for cathode of lithium ion battery and preparation method of graphene composite material
CN104624220A (en) * 2015-02-10 2015-05-20 济南大学 Preparation method of TiO2/rGO composite
CN108807923A (en) * 2018-06-21 2018-11-13 清远佳致新材料研究院有限公司 The preparation method of sodium-ion battery modifying titanium dioxide-graphene negative material

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
BO TANG等: "Graphene Modified TiO2 Composite Photocatalysts:Mechanism, Progress and Perspective", 《NANOMATERIALS》 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115368766A (en) * 2022-08-19 2022-11-22 佛山科学技术学院 Fluorinated graphene/titanium dioxide composite anti-corrosion filler and preparation method thereof
CN115368766B (en) * 2022-08-19 2023-11-07 佛山科学技术学院 Fluorinated graphene/titanium dioxide composite anti-corrosion filler and preparation method thereof

Similar Documents

Publication Publication Date Title
Yao et al. 5, 7, 12, 14-Pentacenetetrone as a high-capacity organic positive-electrode material for use in rechargeable lithium batteries
CN102903930B (en) A kind of lithium rechargeable battery and preparation method thereof
US11551878B2 (en) Electricity storage device
JP5897971B2 (en) Electrode active material, electrode for non-aqueous secondary battery, non-aqueous secondary battery and method for producing electrode for non-aqueous secondary battery
JP2012221754A (en) Negative electrode for lithium secondary battery, and lithium secondary battery
US10854877B2 (en) All-solid-state secondary battery
WO2023108946A1 (en) Positive pole piece modified by polymer film, and manufacturing method
CN114883559A (en) Naphthoquinone-quinoxaline organic electrode material and application thereof in aqueous zinc ion battery
US9786949B2 (en) Composite metal oxide, method for producing composite metal oxide, and sodium secondary battery
WO2019096012A1 (en) Lithium titanate composite material and preparation method therefor, negative electrode plate, and lithium ion battery
CN112053860A (en) Two-dimensional Ni-MOF/Ti applied to super capacitor3C2Preparation method of (1)
CN102456866A (en) Organic free radical polymer electrode as well as preparation and application for same
Wang et al. Engineering the interplanar spacing of K-birnessite for ultra-long cycle Zn-ion battery through “hydrothermal potassium insertion” strategy
Hao et al. In situ deposition method preparation of Li4Ti5O12–SnO2 composite materials for lithium ion batteries
CN108695509B (en) Composite lithium battery positive electrode with high energy storage efficiency, preparation method thereof and lithium battery
CN104795538B (en) A kind of oxygen-containing fluorination bismuth anode material for lithium-ion batteries of synthesis in solid state and preparation method thereof
CN107369565B (en) Magnesium ion hybrid supercapacitor and preparation method thereof
CN111244406A (en) Fluorinated graphene modified titanium dioxide material, and preparation and application thereof
CN111244402B (en) Fluorinated graphene modified lithium titanate material, preparation and application
WO2007009363A1 (en) An electrochemical supercapacitor using organic polymer free radical /carbon composite material as positive electrode
CN115710352A (en) Binder for lithium ion battery silicon cathode and lithium ion battery silicon cathode
CN111293359A (en) Additive for low-temperature lithium ion battery, electrolyte using additive and lithium ion battery
Zhao et al. Lithium storage properties of Li2MoO3 and its effect as a cathode additive in full cells
JP2000113885A (en) Negative electrode for lithium secondary battery
CN111244403B (en) Fluorinated graphene modified niobium pentoxide material and preparation and application thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
RJ01 Rejection of invention patent application after publication
RJ01 Rejection of invention patent application after publication

Application publication date: 20200605