CN101492576A - Carbon nano-complex particle, preparation and uses thereof - Google Patents

Carbon nano-complex particle, preparation and uses thereof Download PDF

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Publication number
CN101492576A
CN101492576A CNA2008100565815A CN200810056581A CN101492576A CN 101492576 A CN101492576 A CN 101492576A CN A2008100565815 A CNA2008100565815 A CN A2008100565815A CN 200810056581 A CN200810056581 A CN 200810056581A CN 101492576 A CN101492576 A CN 101492576A
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carbon
metal oxide
carbon nano
particle
liquid
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CN101492576B (en
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万立骏
张伟明
郭玉国
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Institute of Chemistry CAS
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    • 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 carbon nano composite particle, the preparation method and the application thereof. The carbon nano composite particle consists of a nuclear layer and a shell layer, wherein, the nuclear layer is provided with metal oxide nano particles, and the shell layer is a carbon film. The carbon nano composite particle is prepared by the method with the following steps: (a) the metal oxide nano particles are dispersed in the liquid; (b) soluble carbon source is dispersed in the liquid; (c) the liquid obtained in the step (a) and the step (b) can be mixed together and then heated to lead the soluble carbon source to be decomposed, so that a carbon precursor film can be generated on the surface of the metal oxide nano particle; (d) the particles which are obtained in the step (c) and are coated with the carbon precursor films are insulated from oxygen and processed by heat treatment; the carbon precursor films can be carbonized to obtain the carbon nano composite particle. The carbon nano composite particle can be used for negative pole material of a lithium ion battery.

Description

A kind of carbon nano-complex particle and preparation method thereof and application
Technical field
The present invention relates to a kind of carbon nano-complex particle and preparation method thereof and application in the nano composite material technical field.
Background technology
Many transition metal oxides all can be used as the negative material of high performance lithium ion battery, have very high theoretical capacity.Wherein the oxide of iron is very promising high-performance negative material, and it has low cost, higher electron conduction and very high theoretical specific capacity (Fe 3O 4: 925mAh/g, Fe 2O 3: 1007mAh/g, the theoretical specific capacity of now widely used carbon negative pole material only is 372mAh/g) etc. advantage.But in the practical application of lithium ion battery negative material, the problem of transition metal oxide ubiquity cycle performance difference, through after the discharging and recharging for several times, its capacity sharply reduces, and does not reach actual needs far away.Its reason mainly is the following aspects: at first, these negative material electron conductions are generally relatively poor, and embed and deviate from the very big volume change of existence in the process at lithium ion, thereby the easy efflorescence of electrode materials, cause electrode materials and collector to disengage, cause capacitance loss.The second, the generation and the decomposition of transition metal oxide meeting catalytic solid electrolyte interface (SEI) film in charge and discharge process, this also is the capacity major reason of decay fast.Therefore, develop a kind of good cycle, capacity height, economy and be suitable for the Novel anode material of large-scale production industry has very important significance to lithium ion battery.
Summary of the invention
The purpose of this invention is to provide a kind of carbon nano-complex particle and preparation method thereof.
Carbon nano-complex particle provided by the present invention is made up of stratum nucleare and shell, and described stratum nucleare is a metal oxide nanoparticles, and described shell is a carbon film; The median size of described metal oxide nanoparticles is 10nm-1000nm; The thickness of described carbon film is 1nm-100nm.
Wherein, described metal oxide can be as lithium ion battery negative material, and concrete metal oxide can be Fe 2O 3And/or Fe 3O 4
The method for preparing carbon nano-complex particle provided by the present invention may further comprise the steps:
(a) metal oxide nanoparticles is dispersed in the liquid;
(b) the solubility carbon source is dispersed in the liquid;
(c) will heat after step (a) and the liquid mixing that (b) obtains, described solubility carbon source is decomposed, generate the carbon matrix precursor film on described metal oxide nanoparticles surface;
(d) with the particle starvation thermal treatment that is coated with the carbon matrix precursor film that obtains in the step (c), make the carbonization of described carbon matrix precursor film, obtain carbon nano-complex particle.
Wherein, the liquid in the described step (a) is a kind of or its arbitrary combination in water, ethanol and the ethylene glycol; Solubility carbon source in the described step (b) is a kind of or its arbitrary combination in glucose, sucrose and the Zulkovsky starch.
Wherein, the liquid in the described step (b) is water or alcohol-water mixed solution; In the described alcohol-water mixed solution, the alcoholic acid volumn concentration is 1%-100%.
Wherein, described metal oxide can as lithium ion battery negative material, be preferably Fe 2O 3And/or Fe 3O 4
Wherein, the mol ratio of described metal oxide nanoparticles and solubility carbon source is 0.1-100.
Though have very high theoretical capacity, there is the shortcoming of electroconductibility and cycle performance difference as the negative material of high performance lithium ion battery in transition metal oxide; And the carbon negative pole material that generally uses in the lithium ion battery, though theoretical capacity is lower, its electron conduction is good, volume change is little in the charge and discharge process, and carbon material surface SEI film is more stable, so carbon material has good cycle performance.The present invention is dexterously with transition metal oxide and carbon material combination, at transition metal oxide coated with uniform one deck carbon film, improve its electron conduction greatly, prevent the reunion of adjacent active particle, therefore the SEI film of stabilizing active particle surface has simultaneously greatly improved the cycle performance and the high rate performance of these active substances.
Carbon nano-complex particle provided by the present invention can be used as lithium ion battery negative material and uses.Wherein metal oxide is as main active substances, and outer carbon film has greatly improved cycle performance and the high rate performance of metal oxide as protective layer.
Compare with other prior art, the present invention has following characteristics:
1, technology of the present invention does not have particular requirement for the pattern of the metal oxide of needs coating;
2, the carbon-coating that coats in the technology of the present invention is evenly continuous, and thickness can be by the ratio of metal oxide and carbon source, and the reaction time is regulated;
If 3 metal oxides are Fe 2O 3, the carbonization of carbon matrix precursor and Fe among the present invention 2O 3To Fe 3O 4Conversion be spontaneous finishing simultaneously, saved cost.
4, pass through at the even carbon film of metal oxide nanoparticles surface deposition, improve its electron conduction, prevent the reunion of adjacent active particle, the SEI film of stabilizing active particle surface has simultaneously greatly improved their cycle performance and high rate performances as lithium ion battery negative material.
The method for preparing carbon nano-complex particle among the present invention is simple, economical, be suitable for large-scale production, will be widely used in lithium ion battery industry.
Description of drawings
Fig. 1 is the α-Fe among the embodiment 1 2O 3The ESEM of nano particle (SEM) photo.
Fig. 2 is for characterizing the Fe among the embodiment 1 2O 3/ Fe 3O 4-C composite, a is SEM photo on a large scale, and b is high-resolution transmission electron microscope (TEM) photo, and wherein 1 is carbon-coating, and 2 is stratum nucleare Fe 2O 3/ Fe 3O 4
Fig. 3 is for characterizing the α-Fe among the embodiment 1 2O 3Nano particle and Fe 2O 3/ Fe 3O 4The X-ray diffraction of-C composite (XRD) collection of illustrative plates wherein, is α-Fe on Fig. 3 2O 3The XRD collection of illustrative plates of nano particle, the peak that marks are α-Fe 2O 3Diffraction maximum (Fe 2O 3, JCPDS No.89-8103), be Fe under Fig. 3 2O 3/ Fe 3O 4The XRD collection of illustrative plates of-C composite, the peak of asterisk indication are α-Fe 2O 3Diffraction maximum (Fe 2O 3, JCPDS No.89-8103), other peaks that mark are Fe 3O 4Diffraction maximum (Fe 3O 4, JCPDS No.65-3107).
Fig. 4 is the α-Fe among the embodiment 1 2O 3Nano particle and Fe 2O 3/ Fe 3O 4-C composite is as the comparison of lithium ion battery negative material chemical property.Wherein a is the cycle performance result, and preceding 5 charge and discharge cycles are carried out under the C/5 charge-discharge magnification, and back 80 circulations are carried out under the C/2 charge-discharge magnification; B is the high rate performance result.
Embodiment
Below with α-Fe 2O 3Nano particle is example, illustrates preparation and the performance thereof of carbon nano-complex particle of the present invention.
The following examples are by the thermal decomposition under hydrothermal condition of the carbon sources such as glucose, at ferriferous oxide (Fe 2O 3Or Fe 3O 4) precursor film of nano grain surface uniform deposition one deck carbon, the heat treatment by starvation makes the carbon matrix precursor carbonization then, simultaneously Fe 2O 3Can be Fe by outer carbon film partial reduction also 3O 4, obtain at last ferriferous oxide-carbon composite.Concrete step is as follows:
A) with Fe 2O 3Or Fe 3O 4Nanoparticulate dispersed is in water or other liquid;
B) with glucose, sucrose, Zulkovsky starch or other solubility carbon source are water-soluble, the alcohol-water mixed solution, or in other liquid;
C) place autoclave to heat above-mentioned two liquid mixing, make the carbon source decomposes, at Fe 2O 3Or Fe 3O 4Nano grain surface generates even carbon matrix precursor film;
D) with c) in the oxide particle starvation heat treatment that is coated with carbon matrix precursor that obtains, carbon matrix precursor carbonization this moment, simultaneously Fe 2O 3Can be Fe by the carbon film partial reduction 3O 4, obtain final ferriferous oxide-carbon composite.
Wherein, this method is utilized glucose, sucrose, and the thermal decomposition in soluble starch and other soluble carbon source is at ferriferous oxide (Fe 2O 3Or Fe 3O 4) the coated with carbon precursor film.
In the said method, if initial reactant is Fe 2O 3, in last heat treatment process, have simultaneously the carbonization of carbon matrix precursor film and Fe 2O 3Partial reduction is Fe 3O 4Two processes; If initial reactant is Fe 3O 4Then only there is carbonisation.Therefore two kinds of reactants all can obtain ferriferous oxide-carbon composite.
Embodiment 1, preparation carbon nano-complex particle
α-Fe 2O 3Nano particle is by the FeCl with 19mM 3The NaH of (Beijing chemical reagents corporation) and 0.3mM 2PO 4The solution of (Beijing chemical reagents corporation) obtained 100 ℃ of lower ageings in 48 hours.
Detect the α-Fe that obtains under the above-mentioned condition with NEC's ESEM (JEOL-6700F) 2O 3The particle diameter of nano particle and size distribution.The result shows this α-Fe 2O 3Nano particle is uniform spindle, and length is 400nm-500nm, and draw ratio is 4 (Fig. 1).
At first, with 0.3g α-Fe 2O 3Nano particle (as shown in Figure 1) is dispersed in the 5mL deionized water by ultrasonic (ultrasonic power is 250W, and the time is 2 minutes).Secondly, 0.6g glucose is dissolved in the 15mL deionized water, and adds 10mL ethanol; Under stirring condition, above-mentioned glucose solution is joined α-Fe 2O 3In the suspension of nano particle.Again, above-mentioned mixed liquor is transferred in the autoclave of a 40mL, be heated to 190 ℃ and kept 12-15 hour, cool to room temperature, centrifugal sediment is also used distilled water flushing, and obtain being coated with the α-Fe of carbon matrix precursor film 100 ℃ of lower dryings 2O 3Nano particle.At last, the nano particle that obtains is placed tube furnace, logical nitrogen protection is heated to 600 ℃ and kept 12 hours, namely obtains Fe after the cooling 2O 3/ Fe 3O 4-C composite particles.
Fe 2O 3/ Fe 3O 4-C composite particles characterizes:
Analyze Fe with NEC's ESEM (JEOL-6700F) and NEC's transmission electron microscope (JEOL-2010) 2O 3/ Fe 3O 4-C composite particles.The result is as shown in Figure 2: (a) be 33000 scanning electron microscope (SEM) photo for enlargement ratio; (b) for enlargement ratio be 300000 transmission electron microscope (TEM) photo.
As seen from the figure, can clearly observe very thin carbon coating layer through the sample particle surface that coating is processed, the carbon-coating of coating is evenly continuous, and thickness is 10nm, and Fig. 2 (b) is the gained transmission electron microscope photo.Fe 2O 3/ Fe 3O 4Particle (stratum nucleare) is spindle, and length is 400nm-500nm, and draw ratio is 4.
Coat carbon-coating front and back particulate crystalline structure with powder x-ray diffraction (Rigaku DmaxrB, CuK alpha-ray) analysis.The result as shown in Figure 3.Wherein (a) is for coating the front α-Fe of carbon-coating 2O 3The XRD spectra of nano particle.Its result and α-Fe 2O 3The standard spectrogram conforms to, and illustrates that the particle before the bag carbon is α-Fe 2O 3(b) be the Fe after process coating and the heat treatment 2O 3/ Fe 3O 4The XRD spectra of-C composite particles.Its result had both comprised Fe 3O 4The standard diffraction maximum, comprise again faint α-Fe 2O 3Standard diffraction maximum (shown in asterisk among the figure), most of Fe in heat treatment is described 2O 3Change Fe into 3O 4
The application of embodiment 2, carbon nano-complex particle
Fe 2O 3/ Fe 3O 4The Electrochemical Characterization of-C composite particles: its Electrochemical Characterization is to adopt Swagelok type battery, and working electrode is the Fe among the embodiment 1 2O 3/ Fe 3O 4-C composite particles, binding agent and carbon black are made into slurry with 75: 15: 15 (mass ratio) mixing, are coated to then on the electric conductor Copper Foil.Use glass fibre membrane (Britain Whatman company) as barrier film, 1M LiPF 6(solvent is 1: 1 diethyl carbonate of volume ratio and methylcarbonate mixed solution) as electrolytic solution, the lithium sheet metal is as counter electrode.Assembling obtains battery.
Simultaneously with the α-Fe among the embodiment 1 2O 3Nano particle, binding agent and carbon black are made into slurry with 75: 15: 15 (mass ratio) mixing, are coated to then the working electrode that obtains on the electric conductor Copper Foil, and barrier film, electrolyte and the same to electrode are assembled into battery, in contrast according to the method described above.
Above-mentioned two kinds of batteries are measured on the charge-discharge test instrument, and the interval that discharges and recharges of test is 5mV-3V, at room temperature carries out the cycle performance test with C/5 (charge-discharge magnification) and C/2 (charge-discharge magnification); At room temperature carry out the high rate performance test with C/5 (charge-discharge magnification), C/2 (charge-discharge magnification), 1C (charge-discharge magnification), 2C (charge-discharge magnification), 5C (charge-discharge magnification).
The result (a) is the cycle performance result of battery as shown in Figure 4, (b) is the high rate performance result.On scheming, can find out the Fe that carbon obtains after coating 2O 3/ Fe 3O 4The cycle performance of-C composite and high rate performance and α-Fe 2O 3Nano particle is compared, and very big lifting is all arranged.

Claims (10)

1, a kind of carbon nano-complex particle is made up of stratum nucleare and shell, and described stratum nucleare is a metal oxide nanoparticles, and described shell is a carbon film; The median size of described stratum nucleare is 10nm-1000nm; The thickness of described shell is 1nm-100nm.
2, carbon nano-complex particle according to claim 1 is characterized in that: described metal oxide can be as lithium ion battery negative material; Described metal oxide is preferably Fe 2O 3And/or Fe 3O 4
3, carbon nano-complex particle according to claim 1 is characterized in that: described metal oxide is Fe 2O 3And/or Fe 3O 4Described stratum nucleare is spindle, and length is 400nm-500nm, and draw ratio is 4; The thickness of described shell is 1nm-100nm.
4, a kind of method for preparing the described carbon nano-complex particle of claim 1 may further comprise the steps:
(a) metal oxide nanoparticles is dispersed in the liquid;
(b) the solubility carbon source is dispersed in the liquid;
(c) will heat after step (a) and the liquid mixing that (b) obtains, described solubility carbon source is decomposed, generate the carbon matrix precursor film on described metal oxide nanoparticles surface;
(d) with the particle starvation thermal treatment that is coated with the carbon matrix precursor film that obtains in the step (c), make the carbonization of described carbon matrix precursor film, obtain carbon nano-complex particle.
5, method according to claim 4 is characterized in that: the liquid in the described step (a) is a kind of or its arbitrary combination in water, ethanol and the ethylene glycol; Solubility carbon source in the described step (b) is a kind of or its arbitrary combination in glucose, sucrose and the Zulkovsky starch; Liquid in the described step (b) is water or alcohol-water mixed solution.
6, method according to claim 5 is characterized in that: in the described alcohol-water mixed solution, the alcoholic acid volumn concentration is 1%-100%.
7, according to arbitrary described method in the claim 4 to 6, it is characterized in that: described metal oxide can as lithium ion battery negative material, be preferably Fe 2O 3And/or Fe 3O 4
8, method according to claim 7 is characterized in that: described stratum nucleare is a fusiform, and length is 400nm-500nm, and length-to-diameter ratio is 4; The thickness of described shell is 1nm-100nm.
9, according to arbitrary described method in the claim 4 to 8, it is characterized in that: the mol ratio of described metal oxide nanoparticles and solubility carbon source is 0.1-100.
10, in the claims 1 to 3 arbitrary described carbon nano-complex particle as the application in the lithium ion battery negative material.
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