CN1233554C - Intermeidiate phase carbon microball with graphited surface and its preparing method - Google Patents
Intermeidiate phase carbon microball with graphited surface and its preparing method Download PDFInfo
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- CN1233554C CN1233554C CNB2003101221554A CN200310122155A CN1233554C CN 1233554 C CN1233554 C CN 1233554C CN B2003101221554 A CNB2003101221554 A CN B2003101221554A CN 200310122155 A CN200310122155 A CN 200310122155A CN 1233554 C CN1233554 C CN 1233554C
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- mcmb
- microsphere
- graphited
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- catalyst
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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
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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
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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Abstract
The present invention discloses a mesophase carbon microsphere whose surface is graphitized and a preparation method thereof, and belongs to preparation techniques of cathode materials of lithium ion secondary cells. The surface of the microsphere is provided with a thin graphitized layer formed by catalytic graphitization at a temperature lower than 1600 DEG C, and the inner part of the mesophase carbon microsphere is provided with low temperature carbon. In the preparation method of the microsphere, the mesophase carbon microsphere is carbonized in inert atmosphere at 500 to 800 DEG C and is impregnated in a catalyst solution containing halides or nitrates of transition metal elements, and the microsphere obtained by evaporation and separation is catalytically graphitized at a constant temperature of 500 to 1600 DEG to obtain the microsphere whose surface is provided with the thin graphitized layer and inner part is provided with the low temperature carbon. The present invention has the advantages of energy saving and reduced production cost, avoids the high temperature graphitizing process which can not be overstepped when the mesophase carbon microsphere is used as the cathode active materials of the lithium ion secondary cells, and opens up a new path for the development of the cathode materials of the light lithium ion secondary cells with high capacity.
Description
Technical field
The present invention relates to graphited MCMB in a kind of surface and preparation method thereof, belong to the technology of preparing of ion secondary battery cathode material lithium.
Background technology
Lithium ion battery is a kind of brand-new high energy green battery of succeeding in developing for 20 end of the centurys, the negative pole main flow active material of commercial lithium-ion secondary cell is a carbonaceous material, wherein the lithium ion battery of making negative pole with graphited MCMB has advantages such as charging/discharging voltage is low, charge and discharge platform long, cycle life is good, has been used as the negative active core-shell material of high performance lithium ion battery.
At present, the balling-up method of MCMB generally includes copolycondensation method (CN1116386), catalysis polycondensation method (CN1278513, CN1272453, CN1382624) and emulsion process (Kodama M et al.Carbon, 1988,26 (4) 595-598.).When adopting this MCMB as ion secondary battery cathode material lithium, prior art must pass through charing, graphitization technique, wherein graphitization technique need be in the pyroprocessing more than 2800 ℃, the process energy consumption height causes production cost high, becomes the important factor that influences the lithium ion battery market price.In addition, although graphitized carbon material has above-mentioned plurality of advantages, its theoretical capacity maximum value only is 372mAh/g, and this becomes the new problem that must face of development lightweight high-capacity lithium ion cell.
Summary of the invention:
The object of the present invention is to provide graphited MCMB in a kind of surface and preparation method thereof.This technology has overcome existing with pyrographite metallization processes impassable in the preparation process of graphited MCMB as lithium ion battery negative material.
The present invention is realized that by following technical proposals the preparation method of the graphited MCMB in a kind of surface is characterized in that comprising following process:
1, will through the MCMB of copolycondensation method, catalysis polycondensation method or emulsion process balling-up in 650～800 ℃ in inert atmosphere charing handled 0.5～3 hour;
2, in the catalyst solution that the MCMB of the charing that step 1 obtains is preparing, flood, catalyst system therefor is halogen or the nitrate of transition metal Co, the mass ratio of catalyzer and MCMB is 10.1～50: 100, and become solution as solvent with catalyst preparation with ethanol, place this solution 20～100 ℃ of dippings 0.5～10 hour MCMB;
3, adopt MCMB and the separated from solvent of evaporation separation method with above-mentioned dipping;
4, the MCMB of impregnated catalyst is placed the charring furnace of protection of inert gas make secondary constant temperature and handle, be the catalyzed graphitization process, handled 3～20 hours in 700～1600 ℃;
5, through step 4 handle the MCMB obtain carry out pickling, carry out after being washed to the catalyst residue trace conventional drying promptly get surperficially have thin greying layer, inside is the MCMB of low temperature charcoal.
With the prepared surperficial graphited MCMB of above-mentioned method, it is characterized in that: the surface has the thin greying layer of 700～1600 ℃ of catalyzed graphitizations formation, the MCMB that inside becomes the low temperature charcoal, and the particle diameter of microballoon is 5～50 μ m.
The invention has the advantages that and avoided with MCMB when the negative electrode of lithium ionic secondary battery, impassable pyrographite metallization processes in its preparation process, thereby saved the energy, reduced production cost, outstanding its superiority in the carbonaceous negative active core-shell material is for a new path has been opened up in the exploitation of lightweight high-capacity lithium-ion secondary battery cathode material.
Embodiment:
[embodiment 1]
MCMB is put into charring furnace, and it is standby to rise to 650 ℃ and constant temperature 2 hours with the heat-up rate of 5 ℃/min under protection of nitrogen gas.
Take by weighing 12.12g CoCl
26H
2O also puts in the there-necked flask of 500mL, adds 300mL ethanol then in this flask, obtains the ethanolic soln of cobalt chloride after the stirring and dissolving.The MCMB that the above-mentioned charing of 60g is obtained joined in this solution normal temperature dipping 5 hours then, heats there-necked flask then ethanol evaporation and condensation are reclaimed, and the solid residue in the container is taken out promptly get the MCMB that is impregnated with catalyzer.
The MCMB that is impregnated with catalyzer places the charring furnace of nitrogen protection, rises to 1000 ℃ with the heat-up rate of 5 ℃/min and makes secondary constant temperature and handle, and constant temperature time is 10 hours.Treating that sample is cooled to after the room temperature is washed till colourlessly with 5% hydrochloric acid, and then be washed till pH=7 with deionized water, promptly gets the graphited MCMB of surface catalysis after the conventional drying.
Raman spectrum and XRD method are used in the degree of graphitization of sample surfaces degree of graphitization and MCMB integral body and the detection of interlamellar spacing respectively.At this moment because the degree of depth of raman spectrum test on the surperficial hundreds of Izod right side, all the raw material of wood-charcoal material except that the graphite monocrystalline are all at 1580cm
-1And 1360cm
-1Near present two Raman scattering peaks that originate from aromatic nucleus vibration.The former is a graphite peaks, belongs to the vibration of carbon one carbon bond on the fragrant configuration layer plane of graphite.The latter then is caused by the grain-size of graphite, disordered structure and defective.By the analysis of raman spectrum, can study the degree of graphitization or the ordering degree of charcoal material surface carbon structure, be widely used for studying the surface tissue of carbon material.And people I commonly used
1580/ I
1360The intensity at two peaks recently characterizes the graphite crystallization degree of charcoal solid material, and ratio is high more, and crystallization degree is high more.X ray can penetrate particulate, and the spectrogram of XRD can be described the crystalline structure with characterizing particles integral body.
[embodiment 2]
The carbonization process of the used MCMB of embodiment is identical with embodiment 1, the ethanolic soln step of preparation cobalt chloride is identical with embodiment 1, but the quality of used crystallization cobalt chloride is 6.06g, dipping time is also identical with embodiment, but the temperature that secondary constant temperature is handled is 700 ℃, constant temperature time is 10 hours, and other subsequent disposal is still identical with embodiment 1.
[comparative example 1]
Embodiment 1 used MCMB without any processing, is directly risen to 1000 ℃ and constant temperature by the heating curve of embodiment 1 and naturally cools to room temperature after 10 hours and obtain comparative sample.
[comparative example 2]
Embodiment 2 used MCMB without any processing, are directly risen to 700 ℃ and constant temperature by the heating curve of embodiment 1 and naturally cool to room temperature after 10 hours and obtain comparative sample.
Table 1 is the contrast table of the Raman data and the XRD data of the embodiment of the invention and comparative example
Table 1
| Raman data (I 1580/I 1360) | The d that the XRD diffraction records 002Interlamellar spacing | |
| Embodiment 1 | 1.18 | 3.4983 |
| Embodiment 2 | 1.00 | 3.5146 |
| Comparative example 1 | 0.80 | 3.5092 |
| Comparative example 2 | 0.82 | 3.5228 |
Claims (2)
1, the preparation method of the graphited MCMB in a kind of surface is characterized in that comprising following process:
(1) will through the MCMB of copolycondensation method, catalysis polycondensation method or emulsion process balling-up in 650～800 ℃ in inert atmosphere charing handled 0.5～3 hour;
(2) flood in the catalyst solution that the MCMB of the charing that step (1) obtains is preparing, catalyst system therefor is the CoCl of transition metal Co
26H
2O halogen, the mass ratio of catalyzer and MCMB are 10.1～50: 100, and become solution as solvent with catalyst preparation with ethanol, place this solution to flood 0.5～10 hour at 20～100 ℃ MCMB;
(3) adopt MCMB and the separated from solvent of evaporation separation method with above-mentioned dipping;
(4) MCMB of impregnated catalyst is placed the charring furnace of protection of inert gas make secondary constant temperature and handle, be the catalyzed graphitization process, handled 3～20 hours in 700～1600 ℃;
(5) through step (4) handle the MCMB obtain carry out pickling, carry out after being washed to the catalyst residue trace conventional drying promptly get surperficially have thin greying layer, inside is the MCMB of low temperature charcoal.
2, the graphited MCMB in a kind of surface, it is characterized in that: the surface has the thin greying layer of 700～1600 ℃ of catalyzed graphitizations formation, the MCMB that inside becomes the low temperature charcoal, the particle diameter of microballoon is 5～50 μ m, and the graphited MCMB in this surface is prepared from by the described method of claim 1.
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| CNB2003101221554A CN1233554C (en) | 2003-12-29 | 2003-12-29 | Intermeidiate phase carbon microball with graphited surface and its preparing method |
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| CNB2003101221554A CN1233554C (en) | 2003-12-29 | 2003-12-29 | Intermeidiate phase carbon microball with graphited surface and its preparing method |
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| CN1233554C true CN1233554C (en) | 2005-12-28 |
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Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20120094173A1 (en) * | 2009-06-25 | 2012-04-19 | Nagasaki University | Macro-porous graphite electrode material, process for production thereof, and lithium ion secondary battery |
| CN107623109A (en) * | 2016-07-15 | 2018-01-23 | 天津爱敏特电池材料有限公司 | A kind of preparation method of high power capacity long circulating stability lithium ion battery negative material |
| CN106898494B (en) * | 2017-03-15 | 2018-09-25 | 西安理工大学 | A kind of preparation method of carbonaceous mesophase spherules-carbon nano tube compound material |
| CN106952736B (en) * | 2017-05-16 | 2019-03-22 | 中南大学 | Lithium-ion capacitor and preparation method thereof |
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