CN108735994A - A kind of preparation method of N doping hollow carbon sphere - Google Patents

A kind of preparation method of N doping hollow carbon sphere Download PDF

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Publication number
CN108735994A
CN108735994A CN201810504569.XA CN201810504569A CN108735994A CN 108735994 A CN108735994 A CN 108735994A CN 201810504569 A CN201810504569 A CN 201810504569A CN 108735994 A CN108735994 A CN 108735994A
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China
Prior art keywords
hollow carbon
doping
preparation
carbon sphere
hours
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Pending
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CN201810504569.XA
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Chinese (zh)
Inventor
魏明灯
张伟峰
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Fuzhou University
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Fuzhou University
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Priority to CN201810504569.XA priority Critical patent/CN108735994A/en
Publication of CN108735994A publication Critical patent/CN108735994A/en
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • 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
    • H01M4/625—Carbon or graphite
    • 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 belongs to lithium ion battery material technical fields, and in particular to a kind of preparation method of N doping hollow carbon sphere.The present invention is at high temperature to be graphitized carbon-coating using carbon-coated titanium dioxide mesomorphic as template, is further dissolved internal titanium dioxide by hydrofluoric acid, you can obtain the hollow carbon sphere of N doping.Preparation process of the present invention is simple, and prepared N doping hollow carbon sphere has fine cyclical stability and high rate performance.

Description

A kind of preparation method of N doping hollow carbon sphere
Technical field
The invention belongs to lithium ion battery material technical fields, and in particular to a kind of preparation side of N doping hollow carbon sphere Method.
Background technology
The most common cathode of lithium ion battery is graphite at present.The theoretical specific capacity of graphite is relatively low, is 372 mAh/g.Companion With the fast development of electric vehicle, portable electronic product, the capacity of graphite is difficult to meet actual use need.Therefore it develops high The lithium cell cathode material of capacity is particularly important.Nitrogen-doped carbon ball has unique structural advantage, in cathode of lithium battery Relevant research has received widespread attention in terms of material.Due to large specific surface area, nitrogen-doped carbon material can be filled with electrolyte Tap is touched, and can combine more Li than same amount of graphite+Ion.The pore structure of N doping carbon ball prosperity can provide Li+From The path that son quickly transmits.Defective locations in material, such as vacancy, hetero atom etc. can be used as storage lithium site.Therefore, It is good that N doping carbon ball makees the specific capacity shown when lithium cell cathode material height, fast charging and discharging performance.
Invention content
The purpose of the present invention is to provide a kind of preparation methods of N doping hollow carbon sphere.The present invention provides a kind of nitrogen to mix The preparation method of miscellaneous hollow carbon sphere, this method is simple for process, and inexpensive, low energy consumption, and favorable reproducibility is had excellent performance.
To achieve the above object, the present invention adopts the following technical scheme that：
A kind of preparation method of N doping hollow carbon sphere is using carbon-coated titanium dioxide mesomorphic as template, at high temperature by carbon Layer graphitization further dissolves internal titanium dioxide by hydrofluoric acid, you can obtain the hollow carbon sphere of N doping.
Specifically preparation process is：0.1-2 grams of titanium sulfate is scattered in respectively in the sulfuric acid solution of 1-10 mol/Ls, then It is added dropwise in the reaction kettle containing 1-10 milliliters of butyl oleates and 1-10 milliliters of oleyl amines, at 100-200 DEG C after stirring 30 minutes Baking oven in, react 5-20 hour, after natural cooling gained white depositions through deionized water washing several times after centrifuge out Come, then 70 DEG C of dryings 12 hours in air, is further calcined 2-10 hours at 400-800 DEG C of argon atmospher, you can obtain Carbon coating anatase phase titanium dioxide mesomorphic（TiO2@C）Composite nano materials.Further with TiO2@C are presoma, are dissolved in HF acid TiO is removed in solution2Template.After centrifuge washing, 70 DEG C of dryings in air obtain N-GC hollow carbon spheres in 12 hours.
The remarkable advantage of the present invention is：Preparation process of the present invention is simple, and prepared N doping hollow carbon sphere has very Good cyclical stability and high rate performance.
Description of the drawings
Fig. 1 TiO2The scanning electron microscope (SEM) photograph of@C；
The transmission electron microscope picture of Fig. 2 N-GC hollow carbon spheres；
The chemical property figure of Fig. 3 N-GC hollow carbon spheres.
Specific implementation mode
Further to disclose rather than the present invention is limited, the present invention is described in further detail below in conjunction with example.
Embodiment 1
A kind of preparation method of N doping hollow carbon sphere, the sulfuric acid that 0.1-2 grams of titanium sulfate is scattered in 1-10 mol/Ls respectively are molten In liquid, be then added dropwise in the reaction kettle containing 1-10 milliliters of butyl oleates and 1-10 milliliters of oleyl amines, stirring 30 minutes after In 100-200 DEG C of baking oven, react 5-20 hour, after natural cooling gained white depositions through deionized water washing several times after from The heart is separated, then 70 DEG C of dryings 12 hours in air, is further calcined 2-10 hours at 400-800 DEG C of argon atmospher, It can be obtained carbon coating anatase phase titanium dioxide mesomorphic（TiO2@C）Composite nano materials.Further with TiO2@C are presoma, It is dissolved in HF acid solutions and removes TiO2Template.After centrifuge washing, 70 DEG C of dryings in air obtain N-GC hollow carbon spheres in 12 hours.
N doping hollow carbon sphere prepared by the present invention has fine cyclical stability and high rate performance, electrochemical research knot Fruit shows that capacity can reach when current density is 0.5 A/g and stablizes in 774.5 mAh/g, even if in the high current of 2 A/g Under density, capacity can still reach 721.1 mAh/g after 500 circle of cycle.Good chemical property has benefited from the big ratio of material Surface area increases the contact area of electrode material and electrolyte, and nitrogen atom structure is introduced in the carbon grid of graphite carbon surface, Increase the active sites of graphitic carbon adsorption lithium ion.
Lithium ion battery assembles：N-GC hollow sub-microspheres in mass ratio：Kynoar：Acetylene black=70：20：10 mixing It is equably coated on copper foil after grinding and does cathode, reference electrode and be lithium metal to electrode, electrolyte is by 1.0 M LiPF6's PC+EC+5%FEC (v/v of PC/EC=1/1) solution.All assemblings carry out in glove box.
The foregoing is merely presently preferred embodiments of the present invention, all equivalent changes done according to scope of the present invention patent with Modification should all belong to the covering scope of the present invention.

Claims (3)

1. a kind of preparation method of N doping hollow carbon sphere, it is characterised in that：Using carbon-coated titanium dioxide mesomorphic as template, Carbon-coating is graphitized under high temperature, further internal titanium dioxide is dissolved by hydrofluoric acid, obtains the hollow carbon sphere of N doping.
2. a kind of preparation method of N doping hollow carbon sphere according to claim 1, it is characterised in that：Specific preparation process Including：
（1）0.1-2 grams of titanium sulfate is scattered in respectively in the sulfuric acid solution of 1-10 mol/Ls, is then added dropwise containing 1-10 In the reaction kettle of milliliter butyl oleate and 1-10 milliliters of oleyl amines, stirring is reacted in an oven after 30 minutes, gained after natural cooling White depositions are centrifuged after deionized water is washed several times and are come out；
（2）Then 70 DEG C of dryings 12 hours in air are further calcined 2-10 hours at 400-800 DEG C under an argon atmosphere, Obtain carbon coating anatase phase titanium dioxide mesomorphic TiO2@C composite nano materials；
（3）With TiO2@C are presoma, are dissolved in HF acid solutions and remove TiO2Template；After centrifuge washing, 70 DEG C of dryings in air Obtain within 12 hours N-GC N doping hollow carbon spheres.
3. a kind of preparation method of N doping hollow carbon sphere according to claim 2, it is characterised in that：Step（1）Middle baking The reaction condition of case is 100-200 DEG C and reacts 5-20 hours.
CN201810504569.XA 2018-05-24 2018-05-24 A kind of preparation method of N doping hollow carbon sphere Pending CN108735994A (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110148754A (en) * 2019-05-31 2019-08-20 厦门大学 N doping porous hollow carbon ball and its preparation method and application and lithium metal battery
CN110252335A (en) * 2019-05-31 2019-09-20 苏州大学 A kind of carbon-coating nickel ruthenium nano material and its preparation method and application
CN112694121A (en) * 2020-12-30 2021-04-23 程承 Porous carbon microsphere in-situ composite nano TiO2Preparation method and application of
CN115172757A (en) * 2021-04-01 2022-10-11 宁德时代新能源科技股份有限公司 Current collector and preparation method thereof, and secondary battery and device

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103855366A (en) * 2012-11-28 2014-06-11 中国科学院大连化学物理研究所 Nitrogen-doped porous carbon material for lithium-air battery positive electrode
CN107170978A (en) * 2017-06-09 2017-09-15 福州大学 A kind of carbon coating titanium dioxide mesomorphic nano composite material and its application

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103855366A (en) * 2012-11-28 2014-06-11 中国科学院大连化学物理研究所 Nitrogen-doped porous carbon material for lithium-air battery positive electrode
CN107170978A (en) * 2017-06-09 2017-09-15 福州大学 A kind of carbon coating titanium dioxide mesomorphic nano composite material and its application

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110148754A (en) * 2019-05-31 2019-08-20 厦门大学 N doping porous hollow carbon ball and its preparation method and application and lithium metal battery
CN110252335A (en) * 2019-05-31 2019-09-20 苏州大学 A kind of carbon-coating nickel ruthenium nano material and its preparation method and application
CN110148754B (en) * 2019-05-31 2021-01-15 厦门大学 Nitrogen-doped porous hollow carbon sphere, preparation method and application thereof, and lithium metal battery
CN110252335B (en) * 2019-05-31 2022-03-29 苏州大学 Carbon-coated nickel-ruthenium nano material and preparation method and application thereof
CN112694121A (en) * 2020-12-30 2021-04-23 程承 Porous carbon microsphere in-situ composite nano TiO2Preparation method and application of
CN115172757A (en) * 2021-04-01 2022-10-11 宁德时代新能源科技股份有限公司 Current collector and preparation method thereof, and secondary battery and device
CN115172757B (en) * 2021-04-01 2024-01-26 宁德时代新能源科技股份有限公司 Current collector, preparation method thereof, secondary battery and device

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Application publication date: 20181102

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