CN107317011A - A kind of preparation method of the ordered porous carbon coating silicon nano composite material of N doping - Google Patents

A kind of preparation method of the ordered porous carbon coating silicon nano composite material of N doping Download PDF

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Publication number
CN107317011A
CN107317011A CN201710505128.7A CN201710505128A CN107317011A CN 107317011 A CN107317011 A CN 107317011A CN 201710505128 A CN201710505128 A CN 201710505128A CN 107317011 A CN107317011 A CN 107317011A
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preparation
doping
silicon
composite material
porous carbon
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CN201710505128.7A
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张朝峰
邱立峰
许润涛
饶娟
李春晓
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Hefei University of Technology
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Hefei University of Technology
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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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • 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
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/386—Silicon or alloys based on silicon
    • 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
    • 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 discloses a kind of preparation method of the ordered porous carbon coating silicon nano composite material of N doping, it is to coat nano silicon particles using Dopamine hydrochloride first, and cobalt acetate catalytic treatment is then used again, most target product is obtained through high-temperature calcination afterwards.The composite material and preparation method thereof of the present invention is simple, and the cyclical stability and circulation specific capacity of products therefrom are good, can be used as a kind of excellent lithium ion battery negative material.

Description

A kind of preparation method of the ordered porous carbon coating silicon nano composite material of N doping
Technical field
The present invention relates to ordered porous carbon coating silicon nano composite material of a kind of N doping and preparation method thereof, belong to many Hole field of nanometer material technology.
Background technology
Capacity of lithium ion battery is big, operating voltage is high, self discharge is low, it is safe, have extended cycle life, memory-less effect, Small volume, lightweight, specific energy are high, and without the heavy metal harmful substance of cadmium, lead, mercury etc, therefore such ring will not be produced Pollute in border.In recent years, the high speed development of portable electric appts, electric tool and electric vehicle engineering is to lithium ion battery Performance proposes higher requirement, so as to excite the lithium ion battery negative material of height ratio capacity of new generation, long circulation life Research.The lithium ion battery negative material that scale in the market is used mainly graphite material, the theoretical specific volume of graphite About 372mAh/g is measured, cycle performance is poor, short life, it is impossible to meet requirement of the current people for battery performance, develop Fabrication of High Specific Capacitance Amount, good cycle lithium ion battery it is very urgent.Silicon is the element largely existed on the earth, and pure silicon material is with very High theoretical specific capacity, about 4200mAh/g, the current potential of silicon materials are conducive to the insertion and abjection of lithium ion, and silicon materials possess The above advantage, makes silicon materials turn into most promising novel cathode material for lithium ion battery.But silicon is in the process of lithiumation Middle volume is changed into 3 times of original volume, and volume, which becomes the expansive force produced greatly, can destroy the physical arrangement of electrode, cause electrode breakages, Decline material activity, so as to cause the specific capacity of silicon electrode to be greatly reduced.Due to the bulk effect that silicon electrode has, cause Silicon materials surface is difficult to form stable solid electrolyte film (SEI).The physical arrangement of electrode is destroyed, and is newly occurred in electrode Silicon face can constantly form new SEI films, therefore the charge/discharge efficiency of battery can all be reduced, the decay speed of battery capacity Degree is accelerated.By arduous exploration for many years, researcher is found as silicon particle, silicon nanowires, porous silicon, silicon/graphene are multiple Condensation material, silicon/carbon fiber and carbon nano tube compound material, silicon/conducting polymer composite material etc. can effectively solve the problem that the body of silicon Product expansion issues, a new direction is provided for the research of lithium ion battery of future generation.
The content of the invention
The invention provides a kind of preparation method of the ordered porous carbon coating silicon nano composite material of N doping, it is intended to carries The cyclical stability and circulation specific capacity of high material.
The present invention solves technical problem, adopts the following technical scheme that：
The preparation method of the ordered porous carbon coating silicon nano composite material of N doping of the present invention, its feature is, including Following steps：
(1) nano silicon particles are added to the water and ultrasonic disperse is uniform, adjusted pH to 8.25~8.75, then add hydrochloric acid Dopamine, 10~14h of stirring reaction, is centrifuged at room temperature, obtains Si@PDA composite constructions；
(2) the Si@PDA composite constructions are added to the catalyst acetic acid that temperature is 50 DEG C, concentration is 350~380g/L In the aqueous solution of cobalt, 48h is soaked, then takes out and dries；
(3) dried product exhibited obtained by step (2) is calcined into 4h for 700 DEG C under argon atmosphere, products therefrom is again in dust technology In 100 DEG C of backflow 4h to remove the compound of cobalt, be then centrifuged for, dry, that is, obtain the ordered porous carbon of target product N doping Coated Si nano composite material.
By cobalt acetate to PDA processing in step (2), it is ordered porous carbon structure that can make final product.
It is preferred that, the mass ratio of nano silicon particles and Dopamine hydrochloride is 1 in step (1):6.
It is preferred that, the temperature dried described in step (2) is 50 DEG C, the time is 12h.
It is preferred that, the concentration of dust technology described in step (3) is 8mol/L.
It is preferred that, the temperature dried described in step (3) is 60 DEG C, the time is 12h.
Compared with the prior art, beneficial effects of the present invention are embodied in：
The composite of the present invention is prepared using conventional medication, and method is simple, and products therefrom is ordered porous for N doping Composite construction, one layer of dopamine of outer surface just forms a kind of orderly carbon structure after catalysis and calcining, this N doping Carbon is conducive to the raising of electric conductivity；Volumetric expansion of the loose structure to silicon in charge and discharge process between carbon provides effective Space, improves the capacity and cycle performance of its battery；Therefore, composite of the invention can be used as a kind of excellent lithium-ion electric Pond negative material.
Brief description of the drawings
Fig. 1 is the gained Si@PDA of the embodiment of the present invention 1 SEM photograph；
Fig. 2 is the gained Si@PDA of the embodiment of the present invention 1 TEM photos；
Fig. 3 is the SEM photograph of the gained control sample of comparative example 1 of the present invention；
Fig. 4 (a), (b) are TEM photo of the gained control sample of comparative example 1 of the present invention under different amplification；
Fig. 5 is the SEM photograph of the gained composite of the embodiment of the present invention 1；
Fig. 6 (a), (b) are TEM photo of the gained composite of the embodiment of the present invention 1 under different amplification；
Fig. 7 is the EDS images of the gained composite of the embodiment of the present invention 1；
Fig. 8 is the embodiment of the present invention 1 and the gained composite XRD of comparative example 1；
Fig. 9 is the Raman spectrogram of the embodiment of the present invention 1 and the gained composite of comparative example 1；
Figure 10 is the TGA images of the embodiment of the present invention 1 and the gained composite of comparative example 1；
Figure 11 is the chemical property figure of the gained control sample of comparative example 1 of the present invention；
Figure 12 is the chemical property figure of the gained composite of the embodiment of the present invention 1；
Figure 13 is the electrochemistry circulation figure of the gained composite of the embodiment of the present invention 1.
Embodiment
Below by embodiment, the present invention is described in detail, and following embodiments are under premised on technical solution of the present invention Implemented, give detailed embodiment and specific operating process, but protection scope of the present invention be not limited to it is following Embodiment.
Experimental method is conventional method unless otherwise specified used in following embodiments.
Agents useful for same, material etc. unless otherwise specified, are commercially obtained in the following example.
Battery performance test is using blue electric battery test system in following embodiments, by gained negative pole in following embodiments Composite, Ketjen black and PVDF are 70 according to mass ratio:20:Slurries are made in 10 well mixed are dissolved in nmp solution, then Equably be applied in copper foil current collector and working electrode be made, glass fibre membrane is barrier film, electrolyte is binary electrolyte, full of 2032 button cells are assembled into argon gas glove box, test voltage scope is 0.01V-3V vs Li+/Li。
Embodiment 1
The present embodiment prepares the ordered porous carbon coating silicon nano composite material of N doping as follows：
(1) 25mg nano silicon particles are added in 300mL water and ultrasonic disperse is uniform, adjusted pH to 8.5, then add 150mg Dopamine hydrochlorides (PDA), stirring reaction 12h, is centrifuged at room temperature, obtains Si@PDA composite constructions；
(2) Si@PDA composite constructions are added to the water-soluble of the catalyst acetic acid cobalt that temperature is 50 DEG C, concentration is 380g/L In liquid, 48h is soaked, then takes out and 12h is dried in 50 DEG C of freeze-day with constant temperature baking ovens；
(3) dried product exhibited obtained by step (2) is calcined into 4h for 700 DEG C under argon atmosphere, products therefrom is again in concentration 100 DEG C of backflow 4h to be to remove the compound of cobalt in 8mol/L dust technology, are then centrifuged for, dry in 60 DEG C of freeze-day with constant temperature baking ovens 12h, that is, obtain the ordered porous carbon coating silicon nano composite material of N doping.
Comparative example 1
The present embodiment is prepared the carbon coating silicon nano composite material of N doping by the identical method of embodiment 1, and difference only exists It is specific as follows in without using catalyst：Si@PDA composite constructions are calcined into 4h for 700 DEG C under argon atmosphere, that is, obtain N doping Carbon coating silicon nano composite material, be designated as control sample.
Fig. 1 and Fig. 2 is SEM the and TEM photos of Si@PDA composite constructions obtained by above-described embodiment, it can be seen that material diameter Between 80~100nm.
Fig. 3 and Fig. 4 be in comparative example 1 plus SEM the and TEM photos of control sample obtained by catalyst (Fig. 4 (a), (b) is not With the TEM photos under multiplication factor), it can be seen that outer surface carbon is disordered carbon, and without loose structure.
Fig. 5 and Fig. 6 is that embodiment 1 adds SEM and TEM photos (Fig. 6 that cobalt acetate carries out composite obtained by catalytic treatment (a), (b) is the TEM photos under different amplification), compared with control sample, material is in nano silicon particles Surface coating after catalysis The porous carbon being ordered into, porous carbon can effectively improve the electric conductivity of composite, and hole can be buffered effectively Volumetric expansion problem of the silicon during lithiumation.
Fig. 7 is the EDS images of the gained sample of embodiment 1, it can be seen that one layer of outer surface PDA after calcining, except Formed beyond carbon, the also doping containing nitrogen, nitrogen doped with the raising beneficial to carbon material electric conductivity, to improving battery performance Have contributed much.
Fig. 8 is to add cobalt acetate in embodiment 1 to carry out in composite (Si@NC-Co) and comparative example 1 obtained by catalytic treatment The XRD of gained control sample (Si@NC) is not handled with cobalt acetate, by the contrast at two groups of peaks in figure, two groups of peaks are all accorded with Close Si spectrogram crest, and the substantially crest of a graphene more after being handled with cobalt acetate.This has been turned out through cobalt acetate Composite after catalytic treatment is after calcining, and the PDA of silicon face is converted into the orderly carbon of graphite alkylene, is conducive to improving silicon The electric conductivity of material.
Fig. 9 is to add cobalt acetate in embodiment 1 to carry out in composite (Si@NC-Co) and comparative example obtained by catalytic treatment Not with cobalt acetate handle composite (Si@NC) Raman spectrogram, as can be seen from the figure in 1350 and 1585cm-1 Two Characteristic Raman peaks it is corresponding be D bands and G bands, this is the characteristic peak of carbon.With the relative G bands of D bands after cobalt acetate catalytic treatment Reduction, shows after being handled with cobalt acetate, the degree of order increase of carbon.Died down with cobalt acetate processing postpeak, show to use at cobalt acetate Reason does not produce influence to nano-silicon.So as to also demonstrate nano silicon material height after cobalt acetate catalytic treatment is coated with PDA The obtained Si@C composites of temperature calcining, are a kind of composites of ordered porous carbon coating silicon, can improve leading for silicon materials Electrically, overcome silicon materials volumetric expansion problem during lithiumation, the superior function that silicon has in itself is not destroyed yet.
Figure 10 is the thermogravimetric analysis figure of embodiment 1 and the gained composite of comparative example 1, can from the thermogravimetric curve of silicon Go out, become to 700 DEG C of contents for 105%, be because generating SiO2, the composite (Si@NC) not handled with cobalt acetate Now the content of silicon is 70%, and the content of composite (Si@NC-Co) after being handled with cobalt acetate now silicon is 45%, explanation The content reduction of silicon after being handled with cobalt acetate, the amount of nitrogenous porous carbon then increases.
Figure 11 and Figure 12 are respectively the chemical property figure of comparative example 1 and the gained composite of embodiment 1.It can be seen that with The nitrogenous porous carbon formed after cobalt acetate processing effectively raises the chemical property of composite.It is former in 1C multiplying powers All charge/discharge capacities have been decayed, but the specific capacity of battery is still maintained at 1000mAh g after circulating 100 weeks-1Left and right.Figure 13 be the circulation figure of the gained composite of embodiment 1, it can be seen that by different current density circulations in 70 weeks, is returned again Battery still keeps 1300mAh g after to 0.5A/g current density-1Height ratio capacity, therefore battery is functional.And do not have During useful cobalt acetate processing, simply one layer of common carbon on silicon nanoparticle surface, at present chemical property and business are coated on Changing the graphite material used does not have big gap, and after being circulated 100 weeks in 1C multiplying powers, the specific capacity of battery is only 400mAh g-1Left and right, it is impossible to meet requirement of the people for high-performance novel lithium ion battery.Therefore, the present invention uses cobalt acetate catalytic treatment The ordered porous carbon coating silicon nano composite material of the N doping of formation is a kind of excellent lithium ion battery negative material.

Claims (5)

1. the preparation method of the ordered porous carbon coating silicon nano composite material of a kind of N doping, it is characterised in that including as follows Step：
(1) nano silicon particles are added to the water and ultrasonic disperse is uniform, adjust pH to 8.25~8.75, then add hydrochloric acid DOPA Amine, 10~14h of stirring reaction, is centrifuged at room temperature, obtains Si@PDA composite constructions；
(2) the Si@PDA composite constructions are added to the catalyst acetic acid cobalt that temperature is 50 DEG C, concentration is 350~380g/L In the aqueous solution, 48h is soaked, then takes out and dries；
(3) dried product exhibited obtained by step (2) is calcined into 4h for 700 DEG C under argon atmosphere, products therefrom is again 100 in dust technology DEG C backflow 4h is then centrifuged for, dried, that is, obtain the ordered porous carbon coating silicon of target product N doping to remove the compound of cobalt Nano composite material.
2. preparation method according to claim 1, it is characterised in that：Nano silicon particles and Dopamine hydrochloride in step (1) Mass ratio be 1:6.
3. preparation method according to claim 1, it is characterised in that：Described in step (2) dry temperature for 50 DEG C, when Between be 12h.
4. preparation method according to claim 1, it is characterised in that：The concentration of dust technology described in step (3) is 8mol/ L。
5. preparation method according to claim 1, it is characterised in that：Described in step (3) dry temperature for 60 DEG C, when Between be 12h.
CN201710505128.7A 2017-06-28 2017-06-28 A kind of preparation method of the ordered porous carbon coating silicon nano composite material of N doping Pending CN107317011A (en)

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Cited By (7)

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Publication number Priority date Publication date Assignee Title
CN108149343A (en) * 2017-12-12 2018-06-12 东华大学 The composite nano fiber of N doping porous carbon cladding nano silicon particles and preparation
CN109301182A (en) * 2018-09-05 2019-02-01 东华大学 Static Spinning cobalt/N doping porous carbon nano-composite fiber and its preparation and application
CN109786666A (en) * 2019-03-21 2019-05-21 福建蓝海黑石新材料科技有限公司 A kind of nitrogen-doped carbon coated Si nano particle composite material, preparation method and application
CN110280290A (en) * 2019-07-08 2019-09-27 华南理工大学 One kind having flower-shaped type nitrogen-doped carbon-spinel-type microspherical catalyst of high-specific surface area and the preparation method and application thereof
CN111146434A (en) * 2019-12-26 2020-05-12 宁德新能源科技有限公司 Negative electrode material, and electrochemical device and electronic device comprising same
CN111446440A (en) * 2020-05-22 2020-07-24 扬州大学 Nitrogen-doped carbon-coated hollow mesoporous silica/cobalt nano composite material and lithium ion battery cathode material thereof
CN114639828A (en) * 2020-12-16 2022-06-17 南京大学 Multi-lamellar flower-shaped network structure silicon-carbon composite material and preparation method and application thereof

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CN103318871A (en) * 2013-07-03 2013-09-25 黑龙江大学 Preparation method for synthesizing graphite porous carbon material with activated carbon serving as raw material
CN104538598A (en) * 2015-01-06 2015-04-22 山东大学 Simple preparation method of graphite and/or silicon negative electrode material with surface coated with carbon
CN106477561A (en) * 2016-09-22 2017-03-08 广西大学 A kind of preparation method of boron nitrogen double base auto-dope three-dimensional drape Graphene electrodes material

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103318871A (en) * 2013-07-03 2013-09-25 黑龙江大学 Preparation method for synthesizing graphite porous carbon material with activated carbon serving as raw material
CN104538598A (en) * 2015-01-06 2015-04-22 山东大学 Simple preparation method of graphite and/or silicon negative electrode material with surface coated with carbon
CN106477561A (en) * 2016-09-22 2017-03-08 广西大学 A kind of preparation method of boron nitrogen double base auto-dope three-dimensional drape Graphene electrodes material

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108149343A (en) * 2017-12-12 2018-06-12 东华大学 The composite nano fiber of N doping porous carbon cladding nano silicon particles and preparation
CN108149343B (en) * 2017-12-12 2019-12-10 东华大学 Composite nanofiber with silicon nanoparticles coated with nitrogen-doped porous carbon and preparation method thereof
CN109301182A (en) * 2018-09-05 2019-02-01 东华大学 Static Spinning cobalt/N doping porous carbon nano-composite fiber and its preparation and application
CN109786666A (en) * 2019-03-21 2019-05-21 福建蓝海黑石新材料科技有限公司 A kind of nitrogen-doped carbon coated Si nano particle composite material, preparation method and application
CN110280290A (en) * 2019-07-08 2019-09-27 华南理工大学 One kind having flower-shaped type nitrogen-doped carbon-spinel-type microspherical catalyst of high-specific surface area and the preparation method and application thereof
CN110280290B (en) * 2019-07-08 2021-10-26 华南理工大学 Flower-shaped nitrogen-doped carbon-spinel microsphere catalyst with high specific surface area and preparation method and application thereof
CN111146434A (en) * 2019-12-26 2020-05-12 宁德新能源科技有限公司 Negative electrode material, and electrochemical device and electronic device comprising same
CN111446440A (en) * 2020-05-22 2020-07-24 扬州大学 Nitrogen-doped carbon-coated hollow mesoporous silica/cobalt nano composite material and lithium ion battery cathode material thereof
CN111446440B (en) * 2020-05-22 2022-07-05 扬州大学 Nitrogen-doped carbon-coated hollow mesoporous silica/cobalt nano composite material and lithium ion battery cathode material thereof
CN114639828A (en) * 2020-12-16 2022-06-17 南京大学 Multi-lamellar flower-shaped network structure silicon-carbon composite material and preparation method and application thereof

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Application publication date: 20171103