CN109626355A - The production method and its application of situ Nitrogen Doping hollow carbon sphere and preparation method thereof and electrode material - Google Patents
The production method and its application of situ Nitrogen Doping hollow carbon sphere and preparation method thereof and electrode material Download PDFInfo
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Abstract
The present invention provides the production methods and its application of a kind of situ Nitrogen Doping hollow carbon sphere and preparation method thereof and electrode material；It is related to electrochemical energy field of material technology.The present invention is with SiO2Ball is as dura mater plate, using formaldehyde as carbon source, using one or more substances in acamol and adjacent acetyl amino phenyl, para-aminophenol, m-aminophenol as nitrogen source；Dura mater plate, carbon source, nitrogen source are placed in the reaction system of ethyl alcohol, water and ammonium hydroxide；By sol-gel process, phenolic resin prepared by aldol reaction is wrapped in SiO2Ball prepares the SiO with core-shell structure2/ phenolic resin ball, by being carbonized, going silicon to obtain the hollow carbon sphere of N doping.The hollow carbon sphere of obtained N doping has many advantages, such as that nanoscale is small, pattern is uniform, large specific surface area, energy storage, catalysis and in terms of have broad application prospects.
Description
Technical field
The present invention relates to electrochemical energy field of material technology more particularly to a kind of situ Nitrogen Doping hollow carbon sphere and its systems
The production method and its application of Preparation Method and electrode material.
Background technique
The storage and conversion of the energy have become the major issue for restricting world economy sustainable development.Secondary alkali metal ion
(Li+,Na+,K+Deng) battery has specific energy high, it has extended cycle life, memory-less effect, operating voltage is high, and self discharge is small and right
Environmental-friendly advantage；It is widely used in portable electronic piece, the every field such as aerospace and electric car.However rechargeable
Metal ion battery because of low power density, be insufficient for people's demand growing to lithium ion battery.With section
The development of skill, requirement of the every field to metal ion battery performance is also higher and higher, and negative electrode material is to influence battery performance
One of principal element, therefore a kind of have both high power density and the electrode anode material of high capacity is urgently studied.
Carbon material has a wide range of applications in secondary alkali metal-ion battery.Due to hollow carbosphere appearance with higher
The advantages that amount, excellent high rate performance, electrochemical stability, a large amount of research has been obtained recently.It is typical in hollow carbosphere
Micropore and it is mesoporous more ion storage active site can be not only provided, but also can provide be easy to ion transmission channel,
To greatly improve its capacity and high rate performance.In addition, Heteroatom doping is also proved to be a kind of increase carbon material electronics
The effective ways of electric conductivity and capacity.Such as Mu etc. (Nanoscale, 2017,9,13257-13263) is by sacrificing template simultaneously
It is prepared for a kind of carbon hollow ball of N doping using ammonia as nitrogen source, has shown good catalytic as oxygen reduction catalyst
Energy.Wang etc. (Nano Energy, 2017,41) by forming SiO with tetraethyl orthosilicate under alkaline condition2Ball and as mould
Plate is prepared for a kind of hollow carbosphere of N doping by formaldehyde and meta position Phenol Polymerization using ethylenediamine as nitrogen source.The nitrogen is mixed
Miscellaneous carbosphere has shown excellent chemical property in all-solid sodium ion capacitor.The above method all uses additional nitrogen
The method in source introduces nitrogen-atoms in carbon ball, this has resulted in doping and the not high enough disadvantage of the uniformity.Bin etc.
(J.Am.Chem.Soc.2107,139,13492-13498) then pass through using meta position amino-phenol and formaldehyde as carbon source and nitrogen source
Polymerization reaction is prepared for a kind of microballoon of situ Nitrogen Doping, and is become hollow structure by acetone soak.But the party
Method technics comparing is complicated, and can waste a large amount of solvent and carbon source, increases cost greatly, to hinder its industry rule
Modelling significantly limits its practical application.However, for the situ Nitrogen Doping hollow Nano carbon of tetraethyl orthosilicate self-contained template
The research of ball is but rarely reported, and solves the problems, such as that this is still a challenge at present.
Summary of the invention
In consideration of it, the present invention provides the systems of a kind of situ Nitrogen Doping hollow carbon sphere and preparation method thereof and electrode material
Make method and its application；Be intended to using carbon source formaldehyde etc., nitrogen source acetaminophenol, adjacent acetyl amino phenyl, para-aminophenol,
Amino-phenol etc., with tetraethyl orthosilicate self-contained SiO2Template is prepared for the SiO of phenolic resin package by aldol reaction2
Ball, and SiO is etched away using diluted hydrofluoric acid or sodium hydroxide solution after 500-1500 DEG C of calcining under argon atmosphere2Ball to
It is prepared for a kind of situ Nitrogen Doping hollow carbon sphere.It is provided as sodium cell negative pole material, heteroatomic introducing for porous carbon sky ball
Many defects and vacancy, improve the conductivity of material, accelerate electrode reaction dynamic process, to improve the specific volume of material
Amount and high rate performance.Distinguishing feature of the invention is directly to have synthesized the hollow carbon sphere of situ Nitrogen Doping using nitrogenous precursor
Electrode material, and required raw material sources are extensive, cheap, equipment is simple, it is reproducible, be easily achieved the extensive work of low cost
Industry metaplasia produces.The hollow carbon sphere of obtained N doping has many advantages, such as that nanoscale is small, pattern is uniform, large specific surface area,
Energy storage, catalysis and absorption etc. have broad application prospects.
In order to achieve the above-mentioned object of the invention, the present invention is the following technical schemes are provided: a kind of situ Nitrogen Doping hollow carbon sphere
Preparation method, which is characterized in that it is with SiO2Ball is as dura mater plate, using formaldehyde as carbon source, with acamol and adjacent second
Acylamino- benzene, para-aminophenol, in m-aminophenol one or more substances as nitrogen source；Dura mater plate, carbon source, nitrogen source are placed in
In the reaction system of ethyl alcohol, water and ammonium hydroxide；By sol-gel process, the phenolic resin of aldol reaction preparation is wrapped up
In SiO2Ball prepares the SiO with core-shell structure2/ phenolic resin ball, by being carbonized, going silicon to obtain the hollow carbon of N doping
Ball.
A further technical solution lies in the SiO2Ball silicon source is orthosilicic acid orthocarbonate or tetraethyl orthosilicate.
A further technical solution lies in ethyl alcohol, water and ammonium hydroxide press quality in the reaction system of the ethyl alcohol, water and ammonium hydroxide
It is configured than 0.1:0.5:100-100:10:1.
A further technical solution lies in the carbonisation is by SiO2/ phenolic resin ball is put into tube furnace in argon gas
500-1500 DEG C of heating under atmosphere.
A further technical solution lies in described to go silicon process to be impregnated using diluted hydrofluoric acid or sodium hydroxide solution
Processing.
A further technical solution lies in comprising following steps:
(1) it takes 0.05-50g ammonium hydroxide to be added in the mixed liquor of second alcohol and water, carries out ultrasonic degasification；
(2) carbon source and nitrogen source are added into step (1), SiO is then added2Ball silicon source: orthosilicic acid orthocarbonate or silicic acid four
Ethyl ester；It is heated to 80-100 DEG C and keeps the temperature 0.1-100h；Filtering washes, is obtained by drying to the SiO with core-shell structure2/ phenolic aldehyde
Resin balls；Wherein, SiO2The mass ratio R of ball silicon source and carbon source1For 0.2-200, SiO2The mass ratio R of ball silicon source and nitrogen source2For
0.1-100；
(3) by SiO in step (2)2/ phenolic resin ball is put into tube furnace 500-1500 DEG C of heating 0.1- under an argon atmosphere
100h does carbonization treatment；Then it goes silicon to handle using diluted hydrofluoric acid or sodium hydroxide solution immersion, filters, washes, dries i.e.
Obtain situ Nitrogen Doping hollow carbon sphere.
A further technical solution lies in the carbon source dosage is 0.05-55g, and the nitrogen source dosage is 0.033-33g；
SiO2Ball silicon source dosage is 0.01-100g.
In technical solution provided by the present invention, the situ Nitrogen Doping hollow carbon sphere prepared using method described above,
Average diameter is 450-500nm, and wall thickness is in 8-20nm.
In technical solution provided by the present invention, electrode material is prepared using situ Nitrogen Doping hollow carbon sphere described above
Method, which is characterized in that it includes the following steps:
A, according to situ Nitrogen Doping hollow carbon sphere powder: acetylene black: the mass ratio of PVDF is that 80:10:10 prepares material, is placed in
In mortar and NMP is added, is ground to uniform paste；
B, paste in step (A) is coated on copper foil of affluxion body, coating thickness is 150 microns；
C, the copper foil for coating completion in step B is dried, then is dried in vacuo 12h at a temperature of 120 DEG C, according to predetermined dimension
It is cut into electrode slice.
In technical solution provided by the present invention, using method described above preparation electrode material secondary alkali metal from
Application in sub- cell negative electrode material.
The invention has the following advantages over the prior art:
1, the hollow carbon sphere electrode material of situ Nitrogen Doping has directly been synthesized using nitrogenous precursor.
2 and required raw material sources are extensive, cheap, equipment is simple, it is reproducible, be easily achieved it is inexpensive extensive
Industrialized production.
3, the hollow carbon sphere of obtained N doping has many advantages, such as that nanoscale is small, pattern is uniform, large specific surface area,
Energy storage, catalysis and absorption etc. have broad application prospects.
Detailed description of the invention
Fig. 1 is carbon coating SiO before etching prepared by the embodiment of the present invention 12Scanning electron microscope (SEM) photograph.
Fig. 2 is the scanning electron microscope (SEM) photograph of N doping hollow sphere prepared by the embodiment of the present invention 3.
Fig. 3 is the x-ray diffraction pattern of N doping hollow sphere prepared by the embodiment of the present invention 3.
Fig. 4 is cyclic voltammetry of the N doping hollow sphere of the preparation of the embodiment of the present invention 4 as sodium cell negative pole material
It can figure.
The present invention will be further described in detail below with reference to the accompanying drawings and specific embodiments.
Specific embodiment
The present invention is described in detail with specific embodiment below in conjunction with the accompanying drawings.The present embodiment is being with the technology of the present invention
Under the premise of implemented, give detailed embodiment and specific operation process, but protection scope of the present invention is not limited to down
Belong to embodiment.
Disclosure sets forth a kind of preparation methods of situ Nitrogen Doping hollow carbon sphere, which is characterized in that it is with SiO2Ball is made
For dura mater plate, using formaldehyde as carbon source, in acamol and adjacent acetyl amino phenyl, para-aminophenol, m-aminophenol
One or more substances are as nitrogen source；Dura mater plate, carbon source, nitrogen source are placed in the reaction system of ethyl alcohol, water and ammonium hydroxide；By molten
Phenolic resin prepared by aldol reaction is wrapped in SiO by glue-gel process2Ball prepares the SiO with core-shell structure2/
Phenolic resin ball, by being carbonized, going silicon to obtain the hollow carbon sphere of N doping.
In the preferred embodiment of the present invention, the SiO2Ball silicon source is orthosilicic acid orthocarbonate or tetraethyl orthosilicate.
In the preferred embodiment of the present invention, ethyl alcohol, water and ammonium hydroxide in mass ratio 0.1 in the reaction system of ethyl alcohol, water and ammonium hydroxide:
0.5:100-100:10:1 configuration.
In the preferred embodiment of the present invention, the carbonisation is by SiO2/ phenolic resin ball is put into tube furnace in argon gas gas
500-1500 DEG C of heating under atmosphere.
It is described to go silicon process to carry out at immersion using diluted hydrofluoric acid or sodium hydroxide solution in the preferred embodiment of the present invention
Reason.
In the preferred embodiment of the present invention, specifically comprise the following steps:
(1) it takes 0.05-50g ammonium hydroxide to be added in the mixed liquor of second alcohol and water, carries out ultrasonic degasification；
(2) carbon source and nitrogen source are added into step (1), SiO is then added2Ball silicon source: orthosilicic acid orthocarbonate or silicic acid four
Ethyl ester；It is heated to 80-100 DEG C and keeps the temperature 0.1-100h；Filtering washes, is obtained by drying to the SiO with core-shell structure2/ phenolic aldehyde
Resin balls；Wherein, SiO2The mass ratio R of ball silicon source and carbon source1For 0.2-200, SiO2The mass ratio R of ball silicon source and nitrogen source2For
0.1-100；
(3) by SiO in step (2)2/ phenolic resin ball is put into tube furnace 500-1500 DEG C of heating 0.1- under an argon atmosphere
100h does carbonization treatment；Then it goes silicon to handle using diluted hydrofluoric acid or sodium hydroxide solution immersion, filters, washes, dries i.e.
Obtain situ Nitrogen Doping hollow carbon sphere.
In the preferred embodiment of the present invention, the carbon source dosage is 0.05-55g, and the nitrogen source dosage is 0.033-33g；
SiO2Ball silicon source dosage is 0.01-100g.
Disclosure sets forth the situ Nitrogen Doping hollow carbon spheres prepared using method described above, which is characterized in that its
Average diameter is 450-500nm, and wall thickness is in 8-20nm.
Disclosure sets forth the method for preparing electrode material using situ Nitrogen Doping hollow carbon sphere described above, feature exists
In comprising following steps:
A, according to situ Nitrogen Doping hollow carbon sphere powder: acetylene black: the mass ratio of PVDF is that 80:10:10 prepares material, is placed in
In mortar and NMP is added, is ground to uniform paste；
B, paste in step (A) is coated on copper foil of affluxion body, coating thickness is 150 microns；
C, the copper foil for coating completion in step B is dried, then is dried in vacuo 12h at a temperature of 120 DEG C, according to predetermined dimension
It is cut into electrode slice.
Disclosure sets forth the electrode materials using above method preparation in secondary alkali metal-ion battery negative electrode material
Application.
Embodiment 1
It weighs 0.05g ammonium hydroxide and ultrasound 10 minutes in the mixed liquor of 0.5g ethyl alcohol and 5g water is added；It is then respectively adding 5g first
Aldehyde solution and 0.033g acamol (or adjacent acetyl amino phenyl, para-aminophenol and m-aminophenol etc.)；
It states then up and 0.01g orthosilicic acid orthocarbonate (TPOS) or tetraethyl orthosilicate (TEOS) is added in solution, and will be molten
Liquid is heated to 80 DEG C and keeps the temperature 100h.It filters, wash while hot, the SiO obtained by drying to phenolic resin package2Microballoon, and by sample
Product are put into tube furnace 500 DEG C of heating 100h under an argon atmosphere.Gained sample is finally impregnated into 1h using diluted sodium hydroxide solution,
Filtering washes, is obtained by drying to situ Nitrogen Doping hollow carbon sphere.
Gained situ Nitrogen Doping hollow carbon sphere is pulverized, according to situ Nitrogen Doping hollow carbon sphere powder: acetylene black: PVDF
Mass ratio be 80:10:10 prepare material, be placed in mortar and be added NMP, be ground to uniform paste；And control with a thickness of
150 microns it is uniformly coated in preparing device dried on copper foil after be put into 120 DEG C of vacuum drying 12h of vacuum oven, finally
Using slitter by the copper foil for being coated with electrode material being baked uniform electrode slice.
Using sodium piece as to electrode, 1M NaClO4(ethylene carbonate (EC): diethyl carbonate (DC) volume ratio is 1:1)
The diaphragm, (O in casing are used as sodium electricity electrolyte, 25 μm of porous monolayer films (PP, Celgard 2400)2And H2O content is all
High-purity argon gas atmosphere less than 0.1ppm) 2032 type button cells of assembling.Test indicate that in sodium ion half-cell, 0.05A/
The specific discharge capacity of the current density lower electrode material of g has reached 299mAh/g, and tests sodium capacitor by 100 circle long circulatings
Measuring conservation rate is 95%.Show good energy-storage property and cyclical stability.
Embodiment 2
It weighs 5g ammonium hydroxide and ultrasound 10 minutes in the mixed liquor of 5g ethyl alcohol and 5g water is added；It is molten to be then respectively adding 8.2g formaldehyde
Liquid and 4.5g para-aminophenol.Addition 88g tetraethyl orthosilicate (TEOS) in solution is stated then up, and solution is heated to 80 DEG C
And keep the temperature 6h.It filters, wash while hot, the SiO obtained by drying to phenolic resin package2Microballoon, and sample is put into tube furnace and is existed
The lower 1100 DEG C of heating 3h of argon atmospher.Gained sample is finally impregnated into 48h using diluted sodium hydroxide solution, filtering, washing, drying are
Obtain situ Nitrogen Doping hollow carbon sphere.
Gained situ Nitrogen Doping hollow carbon sphere is pulverized, according to situ Nitrogen Doping hollow carbon sphere powder: acetylene black: PVDF
Mass ratio be 80:10:10 prepare material, be placed in mortar and be added NMP, be ground to uniform paste；And control with a thickness of
150 microns it is uniformly coated in preparing device dried on copper foil after be put into 120 DEG C of vacuum drying 12h of vacuum oven, finally
Using slitter by the copper foil for being coated with electrode material being baked uniform electrode slice.
Using sodium piece as to electrode, 1M NaClO4(ethylene carbonate (EC): diethyl carbonate (DC) volume ratio is 1:1)
The diaphragm, (O in casing are used as sodium electricity electrolyte, 25 μm of porous monolayer films (PP, Celgard 2400)2And H2O content is all
High-purity argon gas atmosphere less than 0.1ppm) 2032 type button cells of assembling.Test indicate that in sodium ion half-cell, 0.05A/
The specific discharge capacity of the current density lower electrode material of g has reached 306mAh/g, and tests sodium capacitor by 100 circle long circulatings
Measuring conservation rate is 89%.Show good energy-storage property and cyclical stability.
Embodiment 3
It weighs 32g ammonium hydroxide and ultrasound 10 minutes in the mixed liquor of 1.6g ethyl alcohol and 0.32g water is added；It is then respectively adding 5g first
Aldehyde solution and 19g neighbour's acetyl amino phenyl.Addition 12g orthosilicic acid orthocarbonate (TPOS) in solution is stated then up, and solution is added
Heat is to 80 DEG C and keeps the temperature 17h.It filters, wash while hot, the SiO obtained by drying to phenolic resin package2Microballoon, and sample is put into
Tube furnace 900 DEG C of heating 6h under an argon.Gained sample is finally impregnated into filtering, water for 24 hours using diluted sodium hydroxide solution
It washes, is obtained by drying to situ Nitrogen Doping hollow carbon sphere.
Gained situ Nitrogen Doping hollow carbon sphere is pulverized, according to situ Nitrogen Doping hollow carbon sphere powder: acetylene black: PVDF
Mass ratio be 80:10:10 prepare material, be placed in mortar and be added NMP, be ground to uniform paste；And control with a thickness of
150 microns it is uniformly coated in preparing device dried on copper foil after be put into 120 DEG C of vacuum drying 12h of vacuum oven, finally
Using slitter by the copper foil for being coated with electrode material being baked uniform electrode slice.
Using sodium piece as to electrode, 1M NaClO4(ethylene carbonate (EC): diethyl carbonate (DC) volume ratio is 1:1)
The diaphragm, (O in casing are used as sodium electricity electrolyte, 25 μm of porous monolayer films (PP, Celgard 2400)2And H2O content is all
High-purity argon gas atmosphere less than 0.1ppm) 2032 type button cells of assembling.Test indicate that in sodium ion half-cell, 0.05A/
The specific discharge capacity of the current density lower electrode material of g has reached 339mAh/g, and tests sodium capacitor by 100 circle long circulatings
Measuring conservation rate is 92%.Show good energy-storage property and cyclical stability.
Embodiment 4
It weighs 50g ammonium hydroxide and ultrasound 10 minutes in the mixed liquor of 26g ethyl alcohol and 38g water is added；It is then respectively adding 55g formaldehyde
Solution and 3.45g m-aminophenol.Addition 100g tetraethyl orthosilicate (TEOS) in solution is stated then up, and solution is heated to
80 DEG C and keep the temperature 0.01h.It filters, wash while hot, the SiO obtained by drying to phenolic resin package2Microballoon, and sample is put into pipe
Formula furnace 1200 DEG C of heating 0.1h under an argon.Gained sample is finally impregnated into 48h, filtering, water using diluted sodium hydroxide solution
It washes, is obtained by drying to situ Nitrogen Doping hollow carbon sphere.
Gained situ Nitrogen Doping hollow carbon sphere is pulverized, according to situ Nitrogen Doping hollow carbon sphere powder: acetylene black: PVDF
Mass ratio be 80:10:10 prepare material, be placed in mortar and be added NMP, be ground to uniform paste；And control with a thickness of
150 microns it is uniformly coated in preparing device dried on copper foil after be put into 120 DEG C of vacuum drying 12h of vacuum oven, finally
Using slitter by the copper foil for being coated with electrode material being baked uniform electrode slice.
Using sodium piece as to electrode, 1M NaClO4(ethylene carbonate (EC): diethyl carbonate (DC) volume ratio is 1:1)
The diaphragm, (O in casing are used as sodium electricity electrolyte, 25 μm of porous monolayer films (PP, Celgard 2400)2And H2O content is all
High-purity argon gas atmosphere less than 0.1ppm) 2032 type button cells of assembling.Test indicate that in sodium ion half-cell, 0.05A/
The specific discharge capacity of the current density lower electrode material of g has reached 279mAh/g, and tests sodium capacitor by 100 circle long circulatings
Measuring conservation rate is 86%.Show good energy-storage property and cyclical stability.
Embodiment 5
It weighs 2g ammonium hydroxide and ultrasound 10 minutes in the mixed liquor of 100g ethyl alcohol and 10g water is added；It is then respectively adding 15g formaldehyde
Solution and 9g neighbour's acetyl amino phenyl.Addition 1g orthosilicic acid orthocarbonate (TPOS) in solution is stated then up, and solution is heated to
90 DEG C and keep the temperature 17h.It filters, wash while hot, the SiO obtained by drying to phenolic resin package2Microballoon, and sample is put into tubular type
Furnace 1000 DEG C of heating 2h under an argon.Finally gained sample is impregnated for 24 hours using diluted sodium hydroxide solution, filtering, is dried at washing
It is dry to obtain situ Nitrogen Doping hollow carbon sphere.
Gained situ Nitrogen Doping hollow carbon sphere is pulverized, according to situ Nitrogen Doping hollow carbon sphere powder: acetylene black: PVDF
Mass ratio be 80:10:10 prepare material, be placed in mortar and be added NMP, be ground to uniform paste；And control with a thickness of
150 microns it is uniformly coated in preparing device dried on copper foil after be put into 120 DEG C of vacuum drying 12h of vacuum oven, finally
Using slitter by the copper foil for being coated with electrode material being baked uniform electrode slice.
Using sodium piece as to electrode, 1M NaClO4(ethylene carbonate (EC): diethyl carbonate (DC) volume ratio is 1:1)
The diaphragm, (O in casing are used as sodium electricity electrolyte, 25 μm of porous monolayer films (PP, Celgard 2400)2And H2O content is all
High-purity argon gas atmosphere less than 0.1ppm) 2032 type button cells of assembling.Test indicate that in sodium ion half-cell, 0.05A/
The specific discharge capacity of the current density lower electrode material of g has reached 316mAh/g, and tests sodium capacitor by 100 circle long circulatings
Measuring conservation rate is 94%.Show good energy-storage property and cyclical stability.
Embodiment 6
It weighs 34g ammonium hydroxide and ultrasound 10 minutes in the mixed liquor of 12g ethyl alcohol and 100g water is added；It is then respectively adding 7g formaldehyde
Solution and 33g neighbour's acetyl amino phenyl.Addition 3.67g tetraethyl orthosilicate (TEOS) in solution is stated then up, and solution is heated
To 100 DEG C and keep the temperature 100h.It filters, wash while hot, the SiO obtained by drying to phenolic resin package2Microballoon, and sample is put into
Tube furnace 1500 DEG C of heating 42h under an argon.Gained sample is finally impregnated into 9h, filtering, water using diluted sodium hydroxide solution
It washes, is obtained by drying to situ Nitrogen Doping hollow carbon sphere.
Gained situ Nitrogen Doping hollow carbon sphere is pulverized, according to situ Nitrogen Doping hollow carbon sphere powder: acetylene black: PVDF
Mass ratio be 80:10:10 prepare material, be placed in mortar and be added NMP, be ground to uniform paste；And control with a thickness of
150 microns it is uniformly coated in preparing device dried on copper foil after be put into 120 DEG C of vacuum drying 12h of vacuum oven, finally
Using slitter by the copper foil for being coated with electrode material being baked uniform electrode slice.
Using sodium piece as to electrode, 1M NaClO4(ethylene carbonate (EC): diethyl carbonate (DC) volume ratio is 1:1)
The diaphragm, (O in casing are used as sodium electricity electrolyte, 25 μm of porous monolayer films (PP, Celgard 2400)2And H2O content is all
High-purity argon gas atmosphere less than 0.1ppm) 2032 type button cells of assembling.Test indicate that in sodium ion half-cell, 0.05A/
The specific discharge capacity of the current density lower electrode material of g has reached 287mAh/g, and tests sodium capacitor by 100 circle long circulatings
Measuring conservation rate is 89%.Show good energy-storage property and cyclical stability.
Embodiment 7
It weighs 1g ammonium hydroxide and ultrasound 10 minutes in the mixed liquor of 16g ethyl alcohol and 27g water is added；It is then respectively adding 6.8g formaldehyde
Solution and 8.2g neighbour's acetyl amino phenyl.Addition 19g tetraethyl orthosilicate (TEOS) in solution is stated then up, and solution is heated to
95 DEG C and keep the temperature 26h.It filters, wash while hot, the SiO obtained by drying to phenolic resin package2Microballoon, and sample is put into tubular type
Furnace 1200 DEG C of heating 1h under an argon.Gained sample is finally impregnated into 8h using diluted sodium hydroxide solution, filtering, is dried at washing
It is dry to obtain situ Nitrogen Doping hollow carbon sphere.
Gained situ Nitrogen Doping hollow carbon sphere is pulverized, according to situ Nitrogen Doping hollow carbon sphere powder: acetylene black: PVDF
Mass ratio be 80:10:10 prepare material, be placed in mortar and be added NMP, be ground to uniform paste；And control with a thickness of
150 microns it is uniformly coated in preparing device dried on copper foil after be put into 120 DEG C of vacuum drying 12h of vacuum oven, finally
Using slitter by the copper foil for being coated with electrode material being baked uniform electrode slice.
Using sodium piece as to electrode, 1M NaClO4(ethylene carbonate (EC): diethyl carbonate (DC) volume ratio is 1:1)
The diaphragm, (O in casing are used as sodium electricity electrolyte, 25 μm of porous monolayer films (PP, Celgard 2400)2And H2O content is all
High-purity argon gas atmosphere less than 0.1ppm) 2032 type button cells of assembling.Test indicate that in sodium ion half-cell, 0.05A/
The specific discharge capacity of the current density lower electrode material of g has reached 308mAh/g, and tests sodium capacitor by 100 circle long circulatings
Measuring conservation rate is 96%.Show good energy-storage property and cyclical stability.
Carbon coating SiO before the etching prepared in embodiment 12The SEM of microballoon schemes as shown in Figure 1, Fig. 1 shows: preparation
Microsphere diameter is in 450-500nm, and pattern is uniform.
The SEM of the N doping hollow sphere prepared in embodiment 3 schemes as shown in Fig. 2, Fig. 2 shows: the N doping of preparation is hollow
Bulb diameter is in 150-500nm, and hollow structure is obvious and pattern is uniform.
The XRD diagram of the N doping hollow sphere prepared in embodiment 3 is as shown in figure 3, Fig. 3 shows: the N doping of preparation is hollow
Ball is the uniform amorphous carbon material of comparison of ingredients.
The N doping hollow sphere prepared in embodiment 4 as sodium cell negative pole material cyclic voltammetric performance map as shown in figure 4,
Fig. 4 shows: N doping hollow sphere is as sodium cell negative pole material first effect with higher and good invertibity.
The average diameter of situ Nitrogen Doping hollow carbon sphere electrode material provided by the invention is 450-500nm, and wall thickness is in 8-
20nm.Ion transmission channel is greatly shortened, electrode reaction dynamic process is improved.Embodiment statistics indicate that, this hair
As anode material of lithium-ion battery under the current density of 50mA/g, reversible capacity is the N doping hollow carbon sphere of bright offer
334mAh/g, capacity retention ratio is 84.7% after circulation 100 is enclosed, and has excellent cyclical stability；Under 5A/g current density
When specific capacity be 60mAh/g, show good high rate performance.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (10)
1. a kind of preparation method of situ Nitrogen Doping hollow carbon sphere, which is characterized in that it is with SiO2Ball is as dura mater plate, with formaldehyde
For carbon source, made with acamol and one or more substances in adjacent acetyl amino phenyl, para-aminophenol, m-aminophenol
For nitrogen source；Dura mater plate, carbon source, nitrogen source are placed in the reaction system of ethyl alcohol, water and ammonium hydroxide；By sol-gel process, by hydroxyl
The phenolic resin of aldehyde condensation reaction preparation is wrapped in SiO2Ball prepares the SiO with core-shell structure2/ phenolic resin ball passes through
The hollow carbon sphere for being carbonized, silicon being gone to obtain N doping.
2. a kind of preparation method of situ Nitrogen Doping hollow carbon sphere according to claim 1, which is characterized in that the SiO2Ball
Silicon source is orthosilicic acid orthocarbonate or tetraethyl orthosilicate.
3. a kind of preparation method of situ Nitrogen Doping hollow carbon sphere according to claim 1, which is characterized in that the ethyl alcohol,
Ethyl alcohol, water and ammonium hydroxide 0.1:0.5:100-100:10:1 in mass ratio configuration in the reaction system of water and ammonium hydroxide.
4. a kind of preparation method of situ Nitrogen Doping hollow carbon sphere according to claim 1, which is characterized in that described to be carbonized
Journey is by SiO2/ phenolic resin ball is put into tube furnace 500-1500 DEG C of heating under an argon atmosphere.
5. a kind of preparation method of situ Nitrogen Doping hollow carbon sphere according to claim 1, which is characterized in that described to go silicon mistake
Journey is to carry out immersion treatment using diluted hydrofluoric acid or sodium hydroxide solution.
6. a kind of preparation method of situ Nitrogen Doping hollow carbon sphere described in any one of -5 claims according to claim 1,
It is characterized in that comprising following steps:
(1) it takes 0.05-50g ammonium hydroxide to be added in the mixed liquor of second alcohol and water, carries out ultrasonic degasification；
(2) carbon source and nitrogen source are added into step (1), SiO is then added2Ball silicon source: orthosilicic acid orthocarbonate or tetraethyl orthosilicate；
It is heated to 80-100 DEG C and keeps the temperature 0.1-100h；Filtering washes, is obtained by drying to the SiO with core-shell structure2/ phenolic resin
Ball；Wherein, SiO2The mass ratio R of ball silicon source and carbon source1For 0.2-200, SiO2The mass ratio R of ball silicon source and nitrogen source2For 0.1-
100；
(3) by SiO in step (2)2/ phenolic resin ball is put into tube furnace 500-1500 DEG C of heating 0.1-100h under an argon atmosphere
Do carbonization treatment；Then it goes silicon to handle using diluted hydrofluoric acid or sodium hydroxide solution immersion, filters, washes, obtained by drying arriving
Situ Nitrogen Doping hollow carbon sphere.
7. a kind of preparation method of situ Nitrogen Doping hollow carbon sphere according to claim 6, which is characterized in that the carbon source is used
Amount is 0.05-55g, and the nitrogen source dosage is 0.033-33g；SiO2Ball silicon source dosage is 0.01-100g.
8. utilizing the situ Nitrogen Doping hollow carbon sphere of the preparation of method described in claim 1-7, which is characterized in that its average diameter
For 450-500nm, wall thickness is in 8-20nm.
9. utilizing the method that situ Nitrogen Doping hollow carbon sphere prepares electrode material described in claim 8, which is characterized in that it includes
Following steps:
A, according to situ Nitrogen Doping hollow carbon sphere powder: acetylene black: the mass ratio of PVDF is that 80:10:10 prepares material, is placed in mortar
In and NMP is added, be ground to uniform paste；
B, paste in step (A) is coated on copper foil of affluxion body, coating thickness is 150 microns；
C, the copper foil for coating completion in step B is dried, then is dried in vacuo 12h at a temperature of 120 DEG C, be cut into according to predetermined dimension
Electrode slice.
10. electrode material the answering in secondary alkali metal-ion battery negative electrode material prepared using claim 9 the method
With.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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| CN111591985A (en) * | 2020-05-07 | 2020-08-28 | 武汉理工大学 | Macro preparation method of microporous nitrogen-rich egg yolk @ eggshell structure carbon microspheres |
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Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102643513A (en) * | 2012-05-14 | 2012-08-22 | 中国科学院长春应用化学研究所 | Preparation method of meta-aminophenol-formaldehyde resin spheres and preparation method of carbon spheres |
| CN104961121A (en) * | 2015-06-24 | 2015-10-07 | 上海大学 | Preparation method for nitrogen-doped nuclear shell hollow carbon |
| CN106167255A (en) * | 2016-07-05 | 2016-11-30 | 北京理工大学 | A kind of microwave preparation of single dispersing size adjustable hollow porous carbon ball |
| CN106409522A (en) * | 2016-10-10 | 2017-02-15 | 华南师范大学 | Manganese dioxide-coated hollow carbon spheres and preparation method and application thereof |
| CN106898762A (en) * | 2017-05-05 | 2017-06-27 | 天津师范大学 | A kind of preparation method of lithium ion battery high-capacity cathode material |
| CN107572509A (en) * | 2017-10-13 | 2018-01-12 | 上海应用技术大学 | A kind of hollow carbon graphite ball nano material of N doping and preparation method thereof |
| CN108246338A (en) * | 2018-02-13 | 2018-07-06 | 福州大学 | A kind of N doping ordered mesopore carbon catalysis material and its preparation method and application |
| CN108417803A (en) * | 2018-03-12 | 2018-08-17 | 华南理工大学 | A kind of N doping hollow carbon sphere composite material and preparation method and application |
| CN108569697A (en) * | 2018-06-21 | 2018-09-25 | 夏辉 | A kind of nitrogen doped micropore carbon ball and preparation method thereof for electrode material for super capacitor |
| CN108822302A (en) * | 2018-06-20 | 2018-11-16 | 同济大学 | A kind of Janus nano particle and the preparation method and application thereof |
-
2019
- 2019-01-14 CN CN201910029770.1A patent/CN109626355A/en active Pending
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102643513A (en) * | 2012-05-14 | 2012-08-22 | 中国科学院长春应用化学研究所 | Preparation method of meta-aminophenol-formaldehyde resin spheres and preparation method of carbon spheres |
| CN104961121A (en) * | 2015-06-24 | 2015-10-07 | 上海大学 | Preparation method for nitrogen-doped nuclear shell hollow carbon |
| CN106167255A (en) * | 2016-07-05 | 2016-11-30 | 北京理工大学 | A kind of microwave preparation of single dispersing size adjustable hollow porous carbon ball |
| CN106409522A (en) * | 2016-10-10 | 2017-02-15 | 华南师范大学 | Manganese dioxide-coated hollow carbon spheres and preparation method and application thereof |
| CN106898762A (en) * | 2017-05-05 | 2017-06-27 | 天津师范大学 | A kind of preparation method of lithium ion battery high-capacity cathode material |
| CN107572509A (en) * | 2017-10-13 | 2018-01-12 | 上海应用技术大学 | A kind of hollow carbon graphite ball nano material of N doping and preparation method thereof |
| CN108246338A (en) * | 2018-02-13 | 2018-07-06 | 福州大学 | A kind of N doping ordered mesopore carbon catalysis material and its preparation method and application |
| CN108417803A (en) * | 2018-03-12 | 2018-08-17 | 华南理工大学 | A kind of N doping hollow carbon sphere composite material and preparation method and application |
| CN108822302A (en) * | 2018-06-20 | 2018-11-16 | 同济大学 | A kind of Janus nano particle and the preparation method and application thereof |
| CN108569697A (en) * | 2018-06-21 | 2018-09-25 | 夏辉 | A kind of nitrogen doped micropore carbon ball and preparation method thereof for electrode material for super capacitor |
Non-Patent Citations (1)
| Title |
|---|
| 李云倩: ""功能化多孔碳材料的制备及其应用研究"", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》 * |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110416520A (en) * | 2019-07-31 | 2019-11-05 | 安徽相源新能源有限公司 | A kind of preparation process of high discharge capacity stable type lithium cell |
| CN110416520B (en) * | 2019-07-31 | 2020-11-06 | 安徽相源新能源有限公司 | Preparation process of high-discharge-capacity stable lithium battery cell |
| CN111591985A (en) * | 2020-05-07 | 2020-08-28 | 武汉理工大学 | Macro preparation method of microporous nitrogen-rich egg yolk @ eggshell structure carbon microspheres |
| CN111591985B (en) * | 2020-05-07 | 2023-07-18 | 武汉理工大学 | Macroscopic quantity preparation method of microporous nitrogen-doped yolk@eggshell structure carbon microsphere |
| CN112090395A (en) * | 2020-08-07 | 2020-12-18 | 华南农业大学 | Method for preparing carbon cage with ultrahigh dye adsorption performance by using different activating agents |
| CN112090395B (en) * | 2020-08-07 | 2021-12-14 | 华南农业大学 | Method for preparing carbon cage with ultrahigh dye adsorption performance by using different activating agents |
| CN112079344A (en) * | 2020-08-19 | 2020-12-15 | 广东工业大学 | Hollow carbon sphere with fluorescent pink as precursor and preparation method and application thereof |
| CN112209358A (en) * | 2020-09-16 | 2021-01-12 | 中山大学 | In-situ nitrogen-doped hollow carbon sphere, and preparation method and application thereof |
| CN112563500A (en) * | 2020-12-04 | 2021-03-26 | 广东工业大学 | Preparation method of hollow bowl-shaped carbon-based metal/selenium/oxygen co-doped composite material and lithium ion battery |
| CN113666360A (en) * | 2021-08-17 | 2021-11-19 | 太原理工大学 | Method for preparing nano carbon spheres based on mixed phenol and nano carbon spheres |
| CN114368738A (en) * | 2021-12-28 | 2022-04-19 | 江苏众钠能源科技有限公司 | Preparation method of hollow carbon sphere with through mesopores and composite sodium metal cathode thereof |
| CN114368738B (en) * | 2021-12-28 | 2024-03-22 | 江苏众钠能源科技有限公司 | Preparation method of hollow carbon sphere with through mesoporous and composite sodium metal anode thereof |
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