CN103730638B - A kind of preparation method of nitrogen-doped carbon material - Google Patents

A kind of preparation method of nitrogen-doped carbon material Download PDF

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Publication number
CN103730638B
CN103730638B CN201310478193.7A CN201310478193A CN103730638B CN 103730638 B CN103730638 B CN 103730638B CN 201310478193 A CN201310478193 A CN 201310478193A CN 103730638 B CN103730638 B CN 103730638B
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nitrogen
carbon
composite
doped
egg
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CN103730638A (en
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杨治政
王慧远
王邦勇
戚文
王栋
卢轮
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Jilin University
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Jilin University
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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
    • H01M4/58—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
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • 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
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • 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 discloses the preparation method of a kind of nitrogen-doped carbon material, described material with carbon element has meso-hole structure, doped with nitrogen element in material with carbon element, and can control nitrogen-doping content in material with carbon element, and its composite is the composite modified through this kind of material with carbon element；Preparation method selects the high-temperature calcination carbonization under an inert atmosphere of egg raw material to form nitrogen-doped carbon material, comprises the following steps: (1) carries out the compound of material with egg solution for solvent；(2) egg is cooked by boiling water, forms the jelly of similar sponge cake tin ash；(3) calcining obtains nitrogen-doped carbon composite under an inert atmosphere.This method can prepare the structural composite material with nitrogen-doped carbon cladding, and in material with carbon element, nitrogen element content is controlled；The nitrogen-doped carbon composite prepared is suitable as li-ion electrode materials, is simultaneously applicable to the fields such as anticorrosive and gas absorption.

Description

A kind of preparation method of nitrogen-doped carbon material
Technical field
The present invention relates to the preparation method of a kind of inorganic functional material, particularly relate to high-temperature calcination system under a kind of employing inert atmosphere The method of standby nitrogenous material with carbon element, belongs to inorganic advanced technical field of nano-composite material preparation technology.
Background technology
It is high that lithium ion battery has voltage, and specific capacity is big, discharging voltage balance and the plurality of advantages such as security is high, it has also become novel One of the focus of research and development in secondary chemical sources of electric energy field, the improvement of its performance depends on anode and cathode active materials. At present, the negative material of commercial applications is mainly graphitized carbon material, but the theoretical capacity of material with carbon element is only 372mAh/g, Along with the progress of society, traditional graphitized carbon material has been difficult to meet people to cathode material for high capacity lithium ion battery Demand.
With graphite-phase ratio, the interlamellar spacing of amorphous carbon is relatively big, can accelerate lithium ion diffusion, the isotropic knot of amorphous carbon simultaneously Structure feature also makes the lithium ion wherein can be with free diffusing, and the amorphous carbon on graphite granule top layer can quickly guide lithium ion to enter The interlayer of graphite, this high rate during charging-discharging being all conducive to improving electrode.Amorphous carbon can be changed by multiple method Property, to reach different effect.Doping is a kind of conventional method, by doping nitrogen or boron element, thus it is possible to vary semiconductor The electronic property of material.Graphitic carbon material band structure after doping changes, and electrical conductivity improves, therefore the graphite after doping Material with carbon element has bigger development space than original graphitic carbon material.Containing carbon and nitrogen element in protein, therefore pass through high temperature inert Calcine protein under atmosphere and can bring it about carburizing reagent, the amorphous carbon of the most remaining N doping.
Summary of the invention
It is an object of the invention to provide the preparation method of a kind of nitrogenous material with carbon element, this preparation method technique is simple, low cost, preparation Material with carbon element there is meso-hole structure, doped with nitrogen element in material with carbon element, and nitrogen element content in material with carbon element can be controlled, its composite wood Material is the composite modified through this kind of material with carbon element, is suitable as lithium ion battery negative material.
The above-mentioned purpose of the present invention is achieved through the following technical solutions: forge with egg solution for raw material high temperature under anaerobic condition Burning carbonization and form nitrogen-doped carbon material, concrete preparation process includes:
(1) take to filter after fresh-laid egg clear liquid stirs homogeneous process in 1-48 hour and go the removal of impurity, be proportionally added into deionized water and stir Mixing, the content controlling water is 0-500%；
(2) in egg white solution, powder tin ash is added, ultrasonic to being uniformly dispersed after stirring 0.1-12 hour；
(3) egg molecule degeneration shrink pack is made to be layed onto tin ash surface with steam heating；
(4) centrifugal, washing, the most under an inert atmosphere 300-700 DEG C are calcined 1-6 hour, it is thus achieved that nitrogen-doped carbon and titanium dioxide Tin composite material；
Egg described in step (1) can also use the aqueous solution of other oroteins or peptide matters to replace, product material with carbon element Still rich in nitrogen, and the preparation method of its composite still has applicability；
Egg white solution described in step (1), by adding glucose and can regulate and control mass ratio between egg white and glucose, reach The content of nitrogen element in material with carbon element in regulation and control product；
Nitrogenous material with carbon element described in step (4) has meso-hole structure, and when being not added with tin ash, this material with carbon element may be used for Composite sulfur simple substance, elementary silicon are as li-ion electrode materials；
Nitrogenous carbon composite described in step (4) can remove metal oxide by subsequent corrosion means, and residue has sky The nitrogenous material with carbon element of core structure.
Technique scheme of the present invention has the advantage that
1) reaction mechanism of the present invention is to utilize the nitrogen element of self in protein molecule, is formed by inert atmosphere high-temperature calcination The amorphous carbon of N doping.
2) the albumen water soluble used of the present invention, it is simple to the synthesis of composite；And receive during protein generation sex change Compound phase can be wrapped up the composite forming clad structure in protein by contracting, is conducive to alleviating the volume of compound phase Expand.
3) present invention is by mixing albumen in proportion with glucose, can realize the doping content of nitrogen element in amorphous carbon Regulation and control.
4) present invention need not special process equipment, and available rotten egg and other protein etc., waste material recycles Can reduce production cost, Technology for Heating Processing is simple.
Accompanying drawing explanation
Fig. 1 is the Flied emission low power morphology observation of N doping amorphous carbon prepared by the present invention
Fig. 2 is N doping amorphous carbon cladding Fe prepared by the present invention3O4The Flied emission morphology observation of composite
Detailed description of the invention
The particular content of the present invention is further illustrated below in conjunction with example.
The invention discloses the preparation method of a kind of nitrogen-doped carbon material, described material with carbon element has meso-hole structure, mixes in material with carbon element Miscellaneous have nitrogen element, and can control nitrogen-doping content in material with carbon element, and its composite is through being combined that this kind of material with carbon element is modified Material；Preparation method selects the high-temperature calcination carbonization under an inert atmosphere of egg raw material to form nitrogen-doped carbon material, including following Step: (1) carries out the compound of material with egg solution for solvent；(2) egg is cooked by boiling water, forms similar sponge cake The jelly of tin ash；(3) calcining obtains nitrogen-doped carbon composite under an inert atmosphere.This method can prepare to be had nitrogen and mixes The structural composite material of miscellaneous carbon cladding, and in material with carbon element, nitrogen element content is controlled；The nitrogen-doped carbon composite prepared is suitable as For li-ion electrode materials, it is simultaneously applicable to the fields such as anticorrosive and gas absorption.
Embodiment one
(1) taking egg white solution stirring and carry out homogeneous process in 24 hours, then go the removal of impurity by filtration, 40 grams of egg white solutions add Enter and be uniformly mixed in 30 ml deionized water；
(2) egg white solution is heated in the steam of boiling water, make egg molecule generation sex change shrink, formed and be similar to chicken The colloid of cake；
(3) 500 DEG C of calcinings can obtain the amorphous carbon of N doping for 3 hours under nitrogen protection；
Embodiment two
(1) taking egg white solution stirring and carry out homogeneous process in 12 hours, then go the removal of impurity by filtration, 20 grams of egg white solutions add It is uniformly mixed in 20 ml deionized water；
(2) in egg white solution, 0.5 gram of tin ash is added, ultrasonic to being uniformly dispersed after stirring 1 hour；
(3) suspension is heated in the steam of boiling water, make egg molecule generation sex change shrink, formed and be similar to egg The colloid of cake；
(4) centrifugal, washing, the most under an inert atmosphere 500 DEG C of calcinings can obtain the two of nitrogen-doped carbon cladding for 6 hours Tin oxide composite；
Embodiment three
(1) taking egg white solution stirring and carry out homogeneous process in 48 hours, then go the removal of impurity by filtration, 30 grams of egg white solutions are molten Enter and be uniformly mixed in 30 ml deionized water；
(2) in egg white solution, 1 gram of glucose is added, 0.5 gram of tin ash, ultrasonic equal to dispersion after stirring 1 hour Even；
(3) suspension is heated in the steam of boiling water, make egg molecule generation sex change shrink, formed and be similar to egg The colloid of cake；
(4) tin ash that dried 600 DEG C of calcinings the most under an inert atmosphere can obtain nitrogen-doped carbon cladding for 6 hours is combined Material；
Embodiment four
(1) taking egg white solution stirring and carry out homogeneous process in 48 hours, then go the removal of impurity by filtration, 20 grams of egg white solutions are molten Enter and be uniformly mixed in 20 ml deionized water；
(2) in egg white with glucose mixed solution, add 2.16 grams of iron chloride, after ultrasonic 30 minutes, stir 2 hours； Add 20 milliliters of hydrazine hydrates；
(3) by insulation 20 hours under suspension in a kettle. 140 degree, Fe is prepared3O4Composite wood with protein Material；
(4) dried 500 DEG C of calcinings under an inert atmosphere can obtain the Fe that nitrogen-doped carbon is coated with for 3 hours3O4Composite wood Material；
Embodiment five
(1) take egg white solution stirring and carry out homogeneous process in 10 hours, then go the removal of impurity by filtration, 30 grams of egg white solutions and Glucose 50:1 in mass ratio is mixed to join in 80 ml deionized water and is uniformly mixed；
(2) in egg white with glucose mixed solution, add iron chloride, stir 1 hour and extremely dissolve, add NaOH molten Liquid generates FeOOH suspension；
(3) egg molecule degeneration shrink pack is made to overlay on FeOOH surface 100 DEG C of heating of suspension；
(4) centrifugal, washing, the most under an inert atmosphere 500 DEG C of calcinings can obtain nitrogen-doped carbon and Fe in 6 hours3O4 Composite；
(5) in composite, hydrochloric acid is added, by the Fe in composite3O4Erosion removal, it is thus achieved that hollow N doping without Setting carbon, in amorphous carbon material, high temperature injects sulphur simple substance, can be used for the electrode of lithium-sulfur cell.
Embodiment six
(1) take egg white solution stirring and carry out homogeneous process in 20 hours, then go the removal of impurity by filtration, 30 grams of egg white solutions and Deionized water is uniformly mixed；
(2) egg molecule degeneration is made to shrink 100 DEG C of heating of suspension；
(3) dried 500 DEG C of calcinings under an inert atmosphere can obtain N doping amorphous carbon in 6 hours；
(4) in N doping amorphous carbon, high temperature injects sulphur simple substance, can be used for the electrode of lithium-sulfur cell.

Claims (4)

1. the preparation method of a nitrogen-doped carbon material, it is characterised in that:
Described material with carbon element is meso-hole structure, doped with nitrogen element in material with carbon element, and can control nitrogen-doping content in material with carbon element, Its composite is the composite of this kind of material with carbon element cladding；With egg solution for raw material high-temperature calcination carbon under anaerobic condition Changing and form nitrogen-doped carbon material, concrete preparation process includes:
(1) taking fresh-laid egg clear liquid to stir 1-48 hour, homogeneous filters after processing and goes the removal of impurity, is proportionally added into deionized water also Being uniformly mixed, the content controlling water is 0-500%；
(2) in egg white solution, powder tin ash is added, ultrasonic to being uniformly dispersed after stirring 0.1-12 hour；
(3) egg molecule degeneration shrink pack is made to be layed onto tin ash surface with steam heating；
(4) centrifugal, washing, the most under an inert atmosphere 300-700 DEG C are calcined 1-6 hour, it is thus achieved that nitrogen-doped carbon and dioxy Change tin composite material.
The preparation method of a kind of nitrogen-doped carbon material the most according to claim 1, it is characterised in that:
Egg white solution described in step (1), by adding glucose and regulating and controlling mass ratio between egg white and glucose, reaches regulation and control The content of nitrogen element in material with carbon element in product.
The preparation method of a kind of nitrogen-doped carbon material the most according to claim 1, it is characterised in that:
Nitrogenous material with carbon element described in step (4) has meso-hole structure, and when being not added with tin ash, this material with carbon element is for multiple Close sulphur simple substance, elementary silicon as li-ion electrode materials.
The preparation method of a kind of nitrogen-doped carbon material the most according to claim 1, it is characterised in that:
Nitrogenous carbon composite described in step (4), removes metal oxide by subsequent corrosion means, and residue has sky The nitrogenous material with carbon element of core structure.
CN201310478193.7A 2013-10-12 2013-10-12 A kind of preparation method of nitrogen-doped carbon material Expired - Fee Related CN103730638B (en)

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CN103992144B (en) * 2014-05-20 2016-03-30 中国科学技术大学 A kind of method being prepared nitrogenous carbon material by biomass pyrolytic carbonization
CN103979530A (en) * 2014-06-11 2014-08-13 安徽工业大学 Method for preparing porous carbon for electrochemical capacitor from egg white used as raw material
CN105655154B (en) * 2016-01-11 2018-05-01 河南师范大学 A kind of preparation method of graphene-activity Carbon composites electrode material for super capacitor
CN105977491A (en) * 2016-06-08 2016-09-28 北京化工大学 Nitrogen-doped hierarchical porous carbon electrode material and application thereof
CN106410215A (en) * 2016-09-20 2017-02-15 福建农林大学 Preparation method of N-doped hematite electrode material
CN106996946B (en) * 2017-03-31 2020-03-31 温州大学 Nitrogen-doped circular carbon sheet and tin oxide composite material as well as preparation method and application thereof
CN108063254A (en) * 2017-11-14 2018-05-22 合肥国轩高科动力能源有限公司 A kind of preparation method of nitrogen carbon coating niobium pentaoxide material
CN108400300B (en) * 2018-02-11 2019-08-02 长沙理工大学 A kind of titanium dioxide/nitrogen-doped carbon cladding SnO2Combination electrode material and preparation method thereof
CN108598411B (en) * 2018-04-20 2020-10-27 湖北工程学院 Nitrogen-doped carbon-coated tin oxide/iron oxide composite material, preparation method thereof and lithium battery material
CN108690677A (en) * 2018-06-20 2018-10-23 深圳烯创美科技有限公司 A kind of modified graphene lubricating oil and preparation method
CN108987719B (en) * 2018-07-27 2020-11-03 盐城市新能源化学储能与动力电源研究中心 Three-dimensional sulfur-doped porous carbon/tin dioxide composite electrode material and preparation method thereof
CN110600719B (en) * 2019-09-12 2021-10-22 河南电池研究院有限公司 Porous silicon-carbon lithium ion battery cathode material with high rate performance and preparation method thereof
CN115050945B (en) * 2022-07-15 2023-09-22 湖北工业大学 Preparation method of biomass nitrogen-doped carbon-coated lithium-rich lithium iron phosphate positive electrode material

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