CN103560233A - Carbon coated silicon graphite cathode material of lithium ion battery and preparation method thereof - Google Patents
Carbon coated silicon graphite cathode material of lithium ion battery and preparation method thereof Download PDFInfo
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- CN103560233A CN103560233A CN201310548457.1A CN201310548457A CN103560233A CN 103560233 A CN103560233 A CN 103560233A CN 201310548457 A CN201310548457 A CN 201310548457A CN 103560233 A CN103560233 A CN 103560233A
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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
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/386—Silicon or alloys based on silicon
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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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
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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 relates to a carbon coated silicon graphite cathode material of a lithium ion battery and a preparation method thereof, belonging to the field of electrochemical power supply. The cathode material comprises silicon, graphite and amorphous carbon, wherein carbon particles are adhered to the surfaces of graphite particles, and an amorphous carbon layer is coated on the surface of silicon and graphite. The preparation method comprises steps of fully mixing the silicon, graphite and carbon source, drying, then putting in a high temperature reaction furnace, and sintering for certain time at high temperature under the protection of inert gas, thereby obtaining the carbon coated silicon graphite cathode material. The cathode material has good cycling stability, high first cycle coulombic efficiency, good multiplying power cycle performance, and comprehensive electrochemical property. The preparation method is simple, is suitable for industrial volume production, does not pollute the environment, and is environment-friendly.
Description
Technical field
The present invention relates to a kind of lithium ion battery cathode material and its preparation method, particularly coated 3 SiC 2/graphite powder body material of negative active core-shell material carbon and preparation method thereof, the invention belongs to field of electrochemical power source.
Background technology
In recent years, along with the fast development of mobile phone, notebook computer, digital camera, electric tool etc.Especially along with the Quick Extended in hybrid vehicle and pure electric automobile market, people have proposed than in the past higher requirement the capacity of the lithium ion battery as power supply, cycle life and fail safe.At present, the negative active core-shell material of commercial Li-ion battery is to adopt various graphite carbon materials, and its theoretical specific capacity only has 372 mAh/g, is difficult to meet the requirement of energy-density lithium ion battery.Compare with graphite negative electrodes material, silicon up to approximately 4200 mAh/g, is the more than ten times of commercialization graphite cathode material as the theoretical specific capacity of lithium ion battery negative material, is suitable for very much high-octane lithium ion battery.Yet the change in volume of silicon in charge and discharge process surpasses 300%, this causes the cycle performance of silicium cathode very low, and the coulombic efficiency of circulation is very low first, thereby cannot meet the requirement of practical application.
For improving the charge and discharge cycles stability of silicon materials, people have proposed a variety of improved methods, as adopt the silicon grain of nano-scale, and at coated with carbon (Angewandte Chemie International Edition 47 (2008) 1645-1649 of nano-silicon, Journal of Power Sources 189 (2009) 761-765), prepare cavernous silicon powder (Angewandte Chemie International Edition 47 (2008) 10151-10154) etc., above method can significantly improve the charge and discharge cycles stability of silicon materials.
Yet silicon materials also exist a significant deficiency as lithium ion battery negative material, that is exactly that the coulombic efficiency circulating is first too low, generally only has 80% even lower.In other words, in circulation first, have the capacity over 20% irreversibly to lose, this can not meet the requirement of practical application.The coulombic efficiency that circulates first of silicon is low is difficult to find the positive electrode that can mate, and has therefore seriously hindered the practical application of silicon materials in lithium ion battery.According to research in the past, except form solid electrolyte film can cause the coulombic efficiency of circulation first of silicon materials low, the compound L i that silicon forms in charging process
12si
7formation can be higher, therefore also can reduce the coulombic efficiency (Rare Metal Materials and Engineering 39 (2010) 2079-2083) of circulation first.At present, the coulombic efficiency that circulates first that how to improve silicon materials is still a huge challenge to meet the requirement of practical application.
At present, the coulombic efficiency of circulation first of the negative material graphite carbon material that commercial Li-ion battery is used can reach more than 90%, therefore silicon being mixed as negative material with graphite is the effective ways that improve its coulombic efficiency that circulates first, simultaneously, utilize carbon to be coated to hold the volumetric expansion of silicon materials in charge and discharge cycles process, therefore, cyclical stability and the coulombic efficiency that circulates first of the coated 3 SiC 2/graphite negative material of carbon will be expected to be improved simultaneously.But so far, to the research of the coated 3 SiC 2/graphite powder body material of carbon seldom.A patent of invention < < lithium ion battery silicon/carbon/composite cathode material of silicon/carbon/graphite and preparation method thereof > > (patent publication No.: the preparation method who CN1761089N) discloses a kind of silicon/carbon/graphite mixed powder material, it is characterized in that the silica flour after ball milling and graphite to add in carbohydrate saturated solution, after oven dry, add the concentrated sulfuric acid, utilize the dehydration carbonization of the concentrated sulfuric acid to prepare the electrode material that silicon, graphite, amorphous carbon mix.The cycle performance of this silicon/carbon/graphite material is better, but the coulombic efficiency that circulates first only has 70% left and right, is difficult to meet practical requirement.
Summary of the invention
The present invention aims to provide the coated 3 SiC 2/graphite lithium ion battery cathode material and its preparation method of a kind of carbon.In the coated 3 SiC 2/graphite powder body material of this carbon, silicon nanoparticle sticks to micron order graphite granule surface, and then the surface of silicon and graphite has all been wrapped by the amorphous carbon of one deck.Meanwhile, prepare the coated 3 SiC 2/graphite powder body material of this carbon and adopt solid-phase synthesis, by the even mixing of raw material silica flour, graphite powder and carbon source and high temperature sintering carbonization subsequently, obtain the coated 3 SiC 2/graphite powder body material of this carbon.The coated 3 SiC 2/graphite powder body material of this carbon possesses good cyclical stability and the high coulombic efficiency of circulation first simultaneously.
The present invention realizes by following scheme:
Silicon, graphite and carbon source mix according to certain mass ratio, and its additional proportion is: 1:1≤silicon: graphite mass ratio≤1:15,1:0.5≤silicon: carbon source mass ratio≤1:5; Then under inert gas shielding, temperature is elevated to 700
0c ~ 1100
0c constant temperature 1 ~ 5 hour, last cool to room temperature; Carbon source generally adopts pitch, phenolic resins, starch.
Compared with prior art, the present invention possesses following advantage:
1. in the resulting carbon coated Si of the present invention graphite composite powder material, silicon nanoparticle sticks to the surface of micron order graphite granule, and meanwhile, amorphous carbon-coating is coated on the surface of 3 SiC 2/graphite.Utilize amorphous carbon coating layer and graphite to hold volumetric expansion and the contraction of silicon grain in charge and discharge cycles.Meanwhile, utilize the splendid graphite of conductivity to improve the conductivity of the coated 3 SiC 2/graphite powder body material of this carbon, and then improve the comprehensive electrochemical of this negative material.
2. adopt the prepared coated 3 SiC 2/graphite negative material of carbon of the present invention to possess good charge-discharge performance and rate charge-discharge performance simultaneously, and the high coulombic efficiency of circulation first.
3. preparation method's condition of the present invention is moderate, and technological process is simple, is very easy to suitability for industrialized production.Meanwhile, there is not environmental pollution, environmental protection.
accompanying drawing explanation
Fig. 1 (a) and (b) be respectively the stereoscan photograph of raw silicon and graphite.
Fig. 2 silicon, graphite and asphalt quality ratio are for 1:1:5 and through 700
o(a) X-ray diffraction spectrum of the 3 SiC 2/graphite powder body material that the carbon of 5 hours gained of C insulation is coated, (b) stereoscan photograph, (c) transmission electron microscope photo and (d) the high-resolution-ration transmission electric-lens photo of boxed area in figure (c).
Fig. 3 silicon, graphite and asphalt quality ratio are for 1:1:5 and through 700
o(a) charge-discharge performance curve (current density 0.2 mA/cm of the 3 SiC 2/graphite powder body material that the carbon of 5 hours gained of C insulation is coated
2) and (b) the high rate performance curve under different current density conditions.
Fig. 4 silicon, graphite and phenolic resins mass ratio are 1:4:2 and through 850
o(a) X-ray diffraction spectrum of the 3 SiC 2/graphite powder body material that the carbon of 3 hours gained of C insulation is coated, (b) stereoscan photograph and (c) transmission electron microscope photo.
Fig. 5 silicon, graphite and phenolic resins mass ratio are 1:4:2 and through 850
o(a) charge-discharge performance curve (current density 0.2 mA/cm of the 3 SiC 2/graphite powder body material that the carbon of 3 hours gained of C insulation is coated
2) and (b) the high rate performance curve under different current density conditions.
Fig. 6 silicon, graphite and starch quality ratio are for 1:15:0.5 and through 1100
o(a) X-ray diffraction spectrum of the 3 SiC 2/graphite powder body material that the carbon of 1 hour gained of C insulation is coated, (b) stereoscan photograph and (c) transmission electron microscope photo.
Fig. 7 silicon, graphite and starch quality ratio are for 1:15:0.5 and through 1100
o(a) charge-discharge performance curve (current density 0.2 mA/cm of the 3 SiC 2/graphite powder body material that the carbon of 1 hour gained of C insulation is coated
2) and (b) the high rate performance curve under different current density conditions.
Embodiment
Fig. 1 (a) and (b) be respectively the stereoscan photograph of raw silicon and graphite.Silicon grain presents subsphaeroidal, and size is between 50 ~ 150 nm.And graphite granule is elliposoidal, its size is much larger than silicon grain, on average in 10 μ m left and right.Silicon, graphite and pitch are mixed according to mass ratio 1:1:5, after abundant grinding, put into tube furnace, under argon shield condition, temperature is increased to 700
oc is also incubated 5 hours, last cool to room temperature.
Fig. 2 (a) is the X-ray diffraction spectrum of the material for preparing, through demarcating, finds, contains silicon, graphite and amorphous carbon in material, does not in addition contain other dephasign.Fig. 2 (b) is the stereoscan photograph of material, from photo, can find out, silicon grain sticks to the surface of micron order graphite granule.Fig. 2 (c) is the transmission electron microscope photo of material, and Fig. 2 (d) is the high-resolution-ration transmission electric-lens photo of boxed area in Fig. 2 (c), and high-resolution photo shows that boxed area is graphite, and the surface of graphite has been coated the amorphous carbon of one deck.Silicon grain surface in Fig. 2 (c) has also been coated the amorphous carbon-coating of one deck, its thickness approximately 10 nm.Above result shows, in the material preparing, silicon grain sticks to the surface of micron order graphite granule, and silicon grain and graphite granule surface have all been wrapped by one deck amorphous carbon layer, and what obtain is the coated 3 SiC 2/graphite powder body material of carbon.
Through said method, prepare the coated 3 SiC 2/graphite powder body material of carbon, the negative active core-shell material using it as lithium ion battery is prepared into lithium ion experimental button cell, tests its performance.Fig. 3 (a) is that the coated 3 SiC 2/graphite powder body material of carbon is at current density 0.2 mA/cm
2the charge-discharge performance curve obtaining under condition.Its first embedding lithium/de-lithium specific capacity be respectively 1003/834 mAh/g, the coulombic efficiency of circulation is 83% first.After 40 charge and discharge cycles, its reversible capacity still reaches 400 mAh/g.Fig. 3 (b) is the rate charge-discharge performance curve of material.Although under different current densities, this powder body material all exists certain capacity attenuation, high rate performance is better on the whole.
embodiment 2
Silicon, graphite and phenolic resins are mixed according to mass ratio 1:4:2, after abundant grinding, put into tube furnace, under nitrogen protection condition, temperature is increased to 850
oc is also incubated 3 hours, last cool to room temperature.
Fig. 4 (a) is the X-ray diffraction spectrum of preparing resulting materials, therefrom can calibrate, and contains silicon, graphite and amorphous carbon in material.Fig. 4 (b) is the stereoscan photograph of material, from photo, can obviously find out, silicon grain has sticked to the surface of graphite granule, and its smooth surface shows, on the surface of silicon and graphite, has been wrapped by one deck amorphous carbon layer.Fig. 4 (c) is the transmission electron microscope photo of material, can obviously find out, silicon grain has sticked on the surface of graphite granule.
Negative active core-shell material using the coated 3 SiC 2/graphite powder body material of this carbon as lithium ion battery is prepared into lithium ion experimental button cell, at 0.2 mA/cm
2charge-discharge performance under current condition is as shown in Fig. 5 (a).The embedding lithium of circulation/de-lithium specific capacity is respectively 925/796 mAh/g first, and the coulombic efficiency of circulation reaches 86% first.After 40 charge and discharge cycles, reversible capacity still reaches 653 mAh/g, and capability retention reaches 82%.Fig. 5 (b) is the rate charge-discharge performance of material under different current density conditions, and the coated 3 SiC 2/graphite powder body material of this carbon demonstrates excellent high rate performance.At first 0.3 mA/cm
2under current density condition, its first discharge specific capacity is 664 mAh/g, through 40 charge and discharge cycles under different current densities, when current density returns to 0.3 mA/cm
2time, its reversible capacity still can return to 660 mAh/g, and capacity restorability reaches 99%.
embodiment 3
Silicon, graphite and starch are mixed according to mass ratio 1:15:0.5, after abundant grinding, put into tube furnace, under argon shield condition, temperature is increased to 1100
oc is also incubated 1 hour, last cool to room temperature.
Fig. 6 (a) is the X-ray diffraction spectrum of preparing resulting materials, therefrom can calibrate, and obviously contains silicon and graphite in material, and the reflection peak of dispersing of amorphous carbon is not remarkable, illustrates that the relative amount of amorphous carbon reduces.Fig. 6 (b) is the stereoscan photograph of material, and silicon grain has sticked to the surface of graphite granule, and the surface of silicon and graphite has been wrapped by one deck amorphous carbon layer.Fig. 6 (c) is the transmission electron microscope photo of material, further proves that silicon grain has sticked on the surface of graphite granule.
Negative active core-shell material using the coated 3 SiC 2/graphite powder body material of this carbon as lithium ion battery is prepared into lithium ion experimental button cell, at 0.2 mA/cm
2under current condition, test its charge-discharge performance, as shown in Fig. 7 (a).The embedding lithium that it circulates first/de-lithium specific capacity is respectively 912/825 mAh/g, and the coulombic efficiency of circulation reaches 90% first.After 40 charge and discharge cycles, reversible capacity still reaches 505 mAh/g.Fig. 7 (b) is the rate charge-discharge performance of material under different current density conditions, the coated 3 SiC 2/graphite powder body material of this carbon demonstrates more excellent rate charge-discharge performance equally, after 40 charge and discharge cycles under different current densities, its capacity restorability reaches 91%.
Claims (6)
1. the coated 3 SiC 2/graphite powder body material of lithium ion battery anode active material-carbon, is characterized in that this powder body material is comprised of silicon, graphite and amorphous carbon, and wherein silicon grain sticks to graphite granule surface, and silicon and graphite are coated by amorphous carbon layer.
2. the coated 3 SiC 2/graphite negative material of the carbon in lithium ion battery as described in right 1, the mass ratio that it is characterized in that silicon and graphite is 1:1 ~ 1:15.
3. the preparation method of the coated 3 SiC 2/graphite powder body material of a lithium ion battery anode active material carbon; it is characterized in that silicon, graphite and carbon source to mix than even according to certain mass; then by mixed powder at high temperature sintering certain hour, subsequently cool to room temperature under inert gas shielding condition.
4. the preparation method of the coated 3 SiC 2/graphite powder body material of a kind of lithium ion battery anode active material carbon as described in right 3, is characterized in that in raw material, the mass ratio of silicon and graphite is 1:1 ~ 1:15; The mass ratio of silicon and carbon source is 1:0.5 ~ 1:5; Sintering temperature is 700
oc ~ 1100
oc; Sintering time is 1 ~ 5 hour; Carbon source is pitch, phenolic resins and starch.
5. the preparation method of the coated 3 SiC 2/graphite powder body material of a kind of lithium ion battery anode active material carbon as described in right 3 or 4, is characterized in that the preferred 1:3 ~ 1:15 of mass ratio of silicon and graphite in raw material.
6. the preparation method of the coated 3 SiC 2/graphite powder body material of a kind of lithium ion battery anode active material carbon as described in right 3 or 4, is characterized in that the preferred pitch of carbon source.
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| CN105261733A (en) * | 2015-09-08 | 2016-01-20 | 湖南星城石墨科技股份有限公司 | Preparation method of nano silicon-based/carbon composite material |
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| US11641013B2 (en) | 2020-03-03 | 2023-05-02 | Samsung Sdi Co., Ltd. | Negative active material for rechargeable lithium battery and rechargeable lithium battery including same |
| CN112028067A (en) * | 2020-09-02 | 2020-12-04 | 南京同宁新材料研究院有限公司 | Silicon-carbon negative electrode material and preparation method thereof |
| WO2022140952A1 (en) * | 2020-12-28 | 2022-07-07 | 宁德新能源科技有限公司 | Silicon-carbon composite particle, negative electrode active material and negative electrode containing same, electrochemical device, and electronic device |
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