(19)
(11)EP 3 653 576 A2

(12)EUROPEAN PATENT APPLICATION

(43)Date of publication:
20.05.2020 Bulletin 2020/21

(21)Application number: 19185627.7

(22)Date of filing:  11.07.2019
(51)Int. Cl.: 
C01B 32/194  (2017.01)
C01B 33/113  (2006.01)
H01M 4/38  (2006.01)
B82Y 30/00  (2011.01)
H01M 4/36  (2006.01)
(84)Designated Contracting States:
AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR
Designated Extension States:
BA ME
Designated Validation States:
KH MA MD TN

(30)Priority: 16.11.2018 TW 107141138

(71)Applicant: National Chung-Shan Institute of Science and Technology
325 Taoyuan City (TW)

(72)Inventors:
  • Lee, Po-Han
    104 Taipei City (TW)
  • Weng, Biing-Jyh
    244 New Taipei City (TW)
  • Gee, Chuen-Ming
    325 Taoyuan City (TW)
  • Chen, Bo-Wen
    320 Taoyuan City (TW)

(74)Representative: Straus, Alexander et al
2K Patent- und Rechtsanwälte Dr. Alexander Straus Keltenring 9
82041 München / Oberhaching
82041 München / Oberhaching (DE)

  


(54)ANODE MATERIAL OF NANO-SILICON HAVING MULTILAYER-GRAPHENE AS CARRIER AND COATED WITH SILICON SUBOXIDE AND WITH AMORPHOUS CARBON LAYER AND METHOD FOR FABRICATING THE SAME


(57) An anode material of nano-silicon (12) is provided. The anode material has multilayer-graphene (11) as a carrier and is coated with silicon suboxide and with an amorphous carbon layer (13). The anode material has multilayer-graphene (11) to serve as a carrier, nano-silicon (12) which is adsorbed on the multilayer-graphene (11) and both the multilayer-graphene (11) and the nano-silicon (12) serve as a core, silicon suboxide and the amorphous carbon layer (13) to cover the multilayer-graphene (11) and the nano-silicon (12), and a plurality of buffering holes (14) which are disposed on the anode material to provide buffering space (14). An anode material of high quality is realized by coating multilayer-graphene (11) which serves as a carrier of nano-silicon (12) with silicon suboxide and with the amorphous carbon layer (13).




Description

Field of the Invention



[0001] This invention generally relates to a method for producing an anode material by using nano-silicon and silicon suboxide and to an anode material of nano-silicon which has multilayer-graphene as a carrier and is coated with silicon suboxide and with an amorphous carbon layer according to the pre-characterizing clauses of claims 1 and 5.

Background of the Invention



[0002] With the rapid development of the modern technology and of the quality of life, all kinds of 3C high-tech electronic products tend to become light, thin, short, small and multi-functional while high-performance lithium batteries become available when the requirements, such as safe to use, low cost, high quality and friendly to the environment, of a battery are taken into consideration. Among them, an anode material of a lithium ion secondary battery may be made of materials such as mesocarbon microbeads, natural graphite, and artificial graphite.

[0003] At present, the application of an anode active material, a conductive agent and a mesophase carbon microbead-based carbon material is getting more and more useful, and the carbon material has excellent charging and discharging capacity, cycle performance and thermal stability, in particular, for use as a power source in a portable device of a lithium-ion batteries, a super-capacitor, and a solar cell.

[0004] In most of the lithium ion batteries, graphite serves as the anode material, and it has the advantages of long cycle life, stable voltage, fast charging and discharging ... etc. However, due to lower theoretical capacitance of carbon, it limits the increase of the energy density of a lithium ion battery. Nowadays, it is still urgent to find an alternative material to increase the capacity of the batteries. When silicon serves as an anode material of a lithium ion battery, it would have higher theoretical capacity than that of the graphite-based carbon material. When a small amount of silicon is added to be mixed with a carbon material, the unit capacity of the anode may be greatly increased to be used in a lithium battery system of the next generation in the future. As an early approach for silicon/carbon material, SiH4 is used by means of chemical vapor deposition so that nano-silicon is uniformly deposited on the porous carbon material, and the capacity can be increased from 330 mAh/g ∼ 360 mAh/g to approximately 1000 mAh/g ∼ 2000 mAh/g. This study confirms the practicability of the silicon/carbon material for use in the anode.

[0005] However, because the volume of silicon expands up to 4 times in the charging and discharging cycles, it causes irreversible defects on the surface of silicon and results in drawbacks, such as decreased battery capacity and lower Coulombic efficiency. Therefore, it is still needed in the industry to develop silicon suboxide or silicon/carbon anode material to suppress the volume expansion of silicon in the charging and discharging cycles by means of an oxide or a carbon layer. In such a way, the trade-off between the cost and efficiency can be simultaneously balanced so as to prepare an anode electrode of a high quality lithium ion battery.

Summary of the Invention



[0006] The present invention aims at providing an anode material of nano-silicon with multilayer-graphene as a carrier. The nano-silicon and the multilayer-graphene are coated with silicon suboxide (i.e. SiOx) and with an amorphous carbon layer to integrate the multilayer-graphene, the nano-silicon, the amorphous carbon layer and a plurality of buffering holes ... etc. to prepare an anode electrode of a high quality lithium battery.

[0007] This is achieved by an anode material of nano-silicon with multilayer-graphene as a carrier and a method for producing an anode material by using nano-silicon and silicon suboxide according to the pre-characterizing clauses of claims 1 and 5. The dependent claims pertain to corresponding further developments and improvements.

[0008] As will be seen more clearly from the detailed description following below, the claimed method for fabricating an anode material having multilayer-graphene as a carrier and coated with silicon suboxide and with an amorphous carbon layer includes the following steps. Firstly, an etchant and a silicon-containing starting material are provided to obtain a mixture solution after a mixing process, and a terminator is added to the mixture solution to make the mixture solution become a neutral solution. Then multilayer-graphene is added to the mixture solution for mixing before adding an organic carbon source. The resultant mixture solution is subjected to a calcination process to obtain a core shell material, and the core shell material is subjected to a pulverizing and sieving process to obtain an anode material which has a plurality of buffering holes. The multilayer-graphene serves as a carrier and is coated with silicon suboxide and with an amorphous carbon layer, before the core shell material is washed with a solvent.

[0009] As will be seen more clearly from the detailed description following below, the claimed anode material of nano-silicon having multilayer-graphene as a carrier and coated with silicon suboxide and with an amorphous carbon layer includes multilayer graphene, nano-silicon, silicon suboxide, and a plurality of buffering holes. The multilayer graphene serves as a carrier. The nano-silicon is adsorbed on the multilayer-graphene and both the multilayer-graphene and the nano-silicon serve as a core. The silicon suboxide and an amorphous carbon layer are coated on the multilayer-graphene and on the nano-silicon. The buffering holes are disposed on the anode material to provide buffering space.

[0010] These and other objectives of the present invention will no doubt become clear to those of ordinary skill in the art after reading the following detailed description of the preferred embodiment that is illustrated in the various figures and drawings.

Brief Description of the Drawings



[0011] The invention is further illustrated by way of example, taking reference to the accompanying drawings. Thereof

FIG. 1 is a perspective view of a schematic drawing illustrating an anode material of nano-silicon which has multilayer-graphene as a carrier and is coated with silicon suboxide and with an amorphous carbon layer of the present invention,

FIG. 2 is a flow chart of a method for fabricating an anode material of nano-silicon which has multilayer-graphene as a carrier and is coated with silicon suboxide and with an amorphous carbon layer of the present invention,

FIG. 3 is a perspective view of a schematic drawing illustrating a synchrotron X-ray diffraction (SXRD) pattern of Si/SiOx/MLG/C, SiOx (commercial), Si and SiO2 of the present invention,

FIG. 4 is a perspective view of a schematic drawing illustrating a partial enlarged view of FIG. 3 of the present invention,

FIG. 5 is a perspective view of a schematic drawing illustrating an SEM image of the Si/SiOx/MLG/C sample of the invention and an EDS mapping image of (Si, C, O) of the present invention,

FIG. 6 is a perspective view of a schematic drawing illustrating an SEM image of the SiOx (commercial) sample and an EDS mapping image of (Si, C, O) of the present invention,

FIG. 7 is a perspective view of a schematic drawing illustrating an SEM image of the Si/SiOx/C sample (Example 2) of the present invention,

FIG. 8 is a perspective view of a schematic drawing illustrating an SEM image of the Si/SiOx/MLG/C sample (Example 3) of the present invention,

FIG. 9 is a perspective view of a schematic drawing illustrating a spectrum analysis of the XPS Si2p of the Si/SiOx/MLG/C of the present invention,

FIG. 10 is a perspective view of a schematic drawing illustrating the spectrum analysis of the XPS Si2p of SiOx (commercial) of the present invention,

FIG. 11 is a perspective view of a schematic drawing illustrating a charging and discharging curve of a half-cell of the Si/SiOx/MLG/C material according to Example 3 of the present invention,

FIG. 12 is a perspective view of a schematic drawing illustrating a charging and discharging curve of a half-cell of the comparative example 1 of the SiOx (commercial) material of the present invention,

FIG. 13 is a schematic diagram illustrating a half-cell test of the 15 wt% Si/SiOx/MLG/C + 85 wt% MCMB material according to Example 5 of the present invention,

FIG. 14 is a schematic diagram illustrating a half-cell test of 15 wt% SiOx (commercial) + 85 wt% MCMB material of the present invention,

FIG. 15 is a schematic diagram illustrating a half-cell test chart of long charging and discharging cycle test of the material of Example 5 (15 wt% Si/SiOx/MLG/C + 85wt% MCMB) and the material of Comparative Example 3 (15 wt% SiOx (commercial) + 85 wt% MCMB) of the present invention.


Detailed Description



[0012] Specific embodiments are provided to elaborate the practice of the invention. The advantages and efficacy thereof would be readily appreciated by persons of ordinary skill in the art from the disclosure of the invention.

[0013] The theoretical capacity of silicon as an anode material is approximately 3500 mAh/g, and partial amount of addition is capable of greatly increasing the overall energy density of the anode of a battery. However, due to the volume expansion of Si as many as 4 times in the charging and discharging cycles, irreversible defects occur on the surface of silicon and result in drawbacks, such as a decrease in battery capacity, or lower Coulombic efficiency ... etc. One objective of the invention is to solve the above problems by using a structure containing Si/SiOx/MLG/C, whose outermost structure is SiOx along with amorphous carbon which is obtained from a thermal pyrolysis process of an organic carbon source to wrap Si/graphene inside the structure to form a core-shell structure. Such core-shell structure is capable of restricting the drastic volume expansion of silicon during the charging and discharging cycles, so that the silicon powder may not form major defects so as to maintain its conductive paths. The capacity of the anode material may be accordingly maintained within a given range. By changing the oxygen content on Si and controlling the graphene and the carbon layer, the capacity of the composite anode material which has nano-silicon wrapped inside of silicon suboxide and an amorphous carbon layer may be kept in a range of approximately 1600 mAh g-1 ∼ 1800 mAh g-1 which is comparable with that of a commercial product.

[0014] Please refer to FIG. 1. FIG. 1 is a perspective view of a schematic drawing illustrating an anode material of nano-silicon which has multilayer-graphene as a carrier and is coated with silicon suboxide and with an amorphous carbon layer. As shown in FIG. 1, the invention provides an anode material of nano-silicon with multilayer-graphene to serve as a carrier. Both the nano-silicon and the multilayer-graphene are coated with silicon suboxide and with an amorphous carbon layer. The anode material of nano-silicon includes: multilayer-graphene 11 to serve as a carrier, nano-silicon 12 adsorbed on the multilayer-graphene 11 and both the multilayer-graphene 11 and the nano-silicon 12 serving as a core, a silicon suboxide and an amorphous carbon layer 13 to wrap the multilayer-graphene 11 and the nano-silicon 12, and a plurality of buffering holes 14 disposed on the anode material in order to provide sufficient buffering space.

[0015] Please refer to FIG. 2. FIG. 2 illustrates a flow chart of a method for fabricating an anode material of nano-silicon which has multilayer-graphene as a carrier and is coated with silicon suboxide and with an amorphous carbon layer. As shown in FIG. 2, the invention provides a method for fabricating an anode material of nano-silicon which has multilayer-graphene as a carrier and is coated with silicon suboxide and with an amorphous carbon layer. The method includes the steps of:
  1. (A) providing an etchant and a silicon-containing starting material to obtain a mixture solution after a mixing process, and adding a terminator to the mixture solution to make the mixture solution become a neutral solution S201;
  2. (B) adding multilayer-graphene to the mixture solution for mixing before adding an organic carbon source S202;
  3. (C) subjecting the mixture solution in the step (B) to a calcination process to obtain a core shell material S203; and
  4. (D) subjecting the core shell material to a pulverizing and sieving process to obtain an anode material which has a plurality of buffering holes and multilayer-graphene as a carrier and is coated with silicon suboxide and with an amorphous carbon layer, before the core shell material is washed with a solvent S204.


[0016] The [nano-silicon or SiOx or (nano-silicon and SiOx)] / multilayer-graphene / (silicon suboxide + amorphous carbon) anode material of the invention is mixed with a binder and with a conductive agent in a certain ratio to form a slurry then it is applied on a 10 µm copper foil. First, the solvent was dried at 80 °C and then it is baked in a vacuum oven at 110 °C for 24 hours to remove the solvent to obtain a finished electrode. The finished electrode is cut to form circular chips of 12 mm in diameter (12ϕ) for making CR2032 button-type lithium ion secondary batteries. The batteries are subjected to a capacity test of a half-cell (lithium metal as the counter electrode (15 mm diameter, 15ϕ)) which uses 1.0 M LiPF6 in an EC (ethylene carbonate) : FEC (fluoroethylene carbonate) : DMC (dimethyl carbonate) : EMC (ethylene methyl carbonate) = 28 : 7 : 10 : 55 composite solvent with additional additives of 1% VC (vinylene carbonate) and 1.5% PS (1,3-propane sultone). The machine model for measuring the capacity is BAT-750B.

Example 1



[0017] 500 mL of 0.25 mM NaOH solution is prepared and continuously stirred at 200 rpm. 25 g of 200 nm silicon powder is added to the above NaOH solution to undergo a reaction for 0.5 hour, and then citric acid is added and stirred as a terminator. The terminator is added to adjust the pH value to be 7 so that silicon stops reacting with NaOH. High temperature calcination is performed at 900 °C to carry out a carbonization treatment (calcination process). The obtained nano-silicon-based anode material (a structure of nano-silicon / (silicon suboxide + amorphous carbon)) is pulverized, grinded and sieved to mix the active materials: conductive agent: PAA: SBR: CMC at a proportion of 73:12:2.5:5.6:6.9 to form a slurry. In mixing, CMC is first mixed with PAA then the active materials and conductive agents are premixed by means of dry blending before they are added to the solution of CMC and PAA. At last, SBR is added and uniformly mixed. The obtained slurry is applied to a copper foil by doctor blade coating. This sample is called Si/SiOx/C-0.5h.

Example 2



[0018] 500 mL of 0.25 mM NaOH solution is prepared and continuously stirred at 200 rpm. 25 g of 200 nm silicon powder is added to the above NaOH solution to undergo a reaction for 4 hour, and then citric acid is added and stirred as a terminator. The terminator is added to adjust the pH value to be 7 so that silicon stops reacting with NaOH. High temperature calcination is performed at 900 °C to carry out a carbonization treatment (calcination process). The obtained nano-silicon-based anode material (a structure of nano-silicon / (silicon suboxide + amorphous carbon)) is pulverized, grinded and sieved to mix the active materials: conductive agent: PAA: SBR: CMC at a proportion of 73:12:2.5:5.6:6.9 to form a slurry. In mixing, CMC is first mixed with PAA then the active materials and conductive agents are premixed by means of dry blending before they are added to the solution of CMC and PAA. At last, SBR is added and uniformly mixed. The obtained slurry is applied to a copper foil by doctor blade coating. This sample is called Si/SiOx/C.

Example 3



[0019] 500 mL of 0.25 mM NaOH solution is prepared and continuously stirred at 200 rpm. 25 g of 200 nm silicon powder is added to the above NaOH solution to undergo a reaction for 4 hour, and then citric acid is added and stirred as a terminator. The terminator is added to adjust the pH value to be 7 so that silicon stops reacting with NaOH. Later 2.5 g of multi-layer graphene (MLG) is added and stirred for 12 hours to allow the nano-silicon powder effectively dispersed on MLG. High temperature calcination is performed at 900 °C to carry out a carbonization treatment (calcination process). The by-products, for example water-soluble salts such as Na2CO3, of the terminator and NaOH after calcination is washed off with deionized water after the obtained nano-silicon-based anode material (a structure of nano-silicon / (silicon suboxide + amorphous carbon)) is pulverized, grinded and sieved. The active materials: conductive agent: PAA: SBR: CMC are mixed at a proportion of 73:12:2.5:5.6:6.9 to form a slurry. In mixing, CMC is first mixed with PAA then the active materials and conductive agents are premixed by means of dry blending before they are added to the solution of CMC and PAA. At last, SBR is added and uniformly mixed. The obtained slurry is applied to a copper foil by doctor blade coating. This sample is called Si/SiOx/MLG/C.

Example 4



[0020] The anode material Si/SiOx/MLG/C of Example 3 (5%) is mixed with a commercial graphite material, mesocarbon microbeads (MCMB, 95%) to form a slurry (active materials: conductive agent: PAA: SBR: CMC are mixed at a proportion of 93:3:0.67:1.5:1.83), and then subjected to an electrode plate preparation and to a battery assembly process. This sample is called 5 wt% Si/SiOx/MLG/C + 95 wt% mesocarbon microbead (MCMB).

Example 5



[0021] The anode material Si/SiOx/MLG/C of Example 3 (15%) is mixed with a commercial graphite material, mesocarbon microbeads (MCMB, 85%) at a proportion shown in Example 4 to form a slurry, and then subjected to an electrode plate preparation and to a battery assembly process. This sample is called 15 wt% Si/SiOx/MLG/C + 85 wt% mesocarbon microbead (MCMB).

Comparative Example 1



[0022] Commercially available carbon-coated SiOx powder (0.8 < x < 0.95) is purchased to prepare electrode plates and a half-cell is assembled and subjected to tests in the same mixing process and proportion of Example 1. The results are compared with these of Example 3. This sample is called SiOx (commercial).

Comparative Example 2



[0023] The SiOx anode material of Comparative Example 1 is mixed with 95% of commercially available graphite material mesocarbon microbeads (the same proportion as in Example 4) to form a slurry, and then subjected to an electrode plate preparation and to a battery assembly process. Compared with Example 4, this sample is called 5 wt% SiOx (commercial) + 95 wt% MCMB.

Comparative Example 3



[0024] The SiOx anode material of Comparative Example 1 is mixed with 85% of commercially available graphite material mesocarbon microbeads (the same proportion as in Example 4) to form a slurry, and then subjected to an electrode plate preparation and to a battery assembly process. Compared with Example 5, this sample is called 15 wt% SiOx (commercial) + 85 wt% MCMB.

[0025] Please refer to FIG. 3. FIG. 3 is a perspective view of a schematic drawing illustrating a synchrotron X-ray diffraction (SXRD) pattern of Si/SiOx/MLG/C, SiOx (commercial), Si and SiO2 of the invention. Please refer to FIG. 4. FIG. 4 is a perspective view of a schematic drawing illustrating a partial enlarged view of FIG. 3 of the invention. As shown in the drawings, the position at Si peak and intensity of Si/SiOx/MLG/C are very close to those of a standard Si with the difference that ∼120 is the diffraction peak of the amorphous phase of SiOx. The enlarged view of FIG. 4 clearly shows that a standard Si still has some minor peaks of SiO2 here, which is confirmed by the comparison with a standard SiO2. The reason why there are still some observed signals of SiO2 on the standard Si is because nano-silicon tends to form a thin layer of native silicon oxide easily by oxidation in the atmosphere, and it is observed in the sample of Si/SiOx/MLG/C that the signal of SiO2 is much stronger than that of the Si standard, so it can be confirmed that this synthesis method can indeed turn a nano-silicon into a Si/SiOx composite sample. However, since X-ray is less sensitive to oxygen, the photoelectron spectroscopy (XPS) is instead needed to determine if it is SiO2 or SiOx. For the commercially available SiOx, it is an amorphous phase material composed of Si and SiO2. The current study of the structure of the material suggests that it is a two-phase material in which one Si atom may be simultaneously bonded to four neighbor Si atoms (Si phase) or to four neighbor O atoms (SiO2 phase). But some studies have also pointed out that SiOx is a mono-phase material in which Si-Si bonding and Si-O bonding are randomly distributed throughout the whole structure. It is known from the results of SXRD that the material Si/SiOx/MLG/C is indeed a material composed of amorphous phase SiOx and crystal phase of Si.

[0026] Please refer to FIG. 5. FIG. 5 is a perspective view of a schematic drawing illustrating an SEM image of the Si/SiOx/MLG/C sample of the invention and an EDS mapping image of (Si, C, O) of the invention. Please refer to FIG. 6. FIG. 6 is a perspective view of a schematic drawing illustrating an SEM image of the SiOx (commercial) sample and an EDS mapping image of (Si, C, O). As shown in the drawing, FIG. 5 shows the SEM (scan electron microscope) image of the Si/SiOx/MLG/C and its EDS mapping results which contains the three elements of Si, C and O. With respect to the silicon element, it can be observed that it is evenly distributed on the particles, and further it can be observed that the oxygen element and the carbon element have a higher concentration at the outer periphery of the particles and in the core part the concentration of oxygen element and the carbon element is lower. Hence, it may be inferred along with the results of SXRD that the major material composition of the outer shell is C and SiOx while the major material composition in the inner core is Si, which verifies the concept of the core-shell material which is proposed by the invention. To be compared with the SiOx (commercial) sample in FIG. 6, the EDS mapping results shows that C, Si, O are uniformly distributed on the particles with a relatively lower content of C because the commercial product is prepared by a high-temperature gas phase method and the composition of the entire material is uniform with the pulverization is finally carried out before the carbon coating is carried out.

[0027] Please refer to FIG. 7. FIG. 7 is a perspective view of a schematic drawing illustrating an SEM image of the Si/SiOx/C sample (Example 2) of the invention. Please refer to FIG. 8. FIG. 8 illustrates an SEM image of the Si/SiOx/MLG/C sample (Example 3) of the invention. As shown in drawing, it can be clearly observed that the addition of MLG as a carrier of Si/SiOx in the process reduces the formation of finer powders, makes the slurry mixing process easier and makes the dispersion more uniform. Once peeling occurs, the electrode's capacity would be drastically reduced and the electrical impedance is increased. It can be observed from the comparison between Example 2 and Example 3 that the Coulombic efficiency in the first circle is improved because of the improvement of the dispersion so that Si/SiOx is less likely to crack or to peel during the charging and discharging process to improve the resultant Coulombic efficiency although the addition of MLG makes the reversible capacity of the Si/SiOx/MLG/C composite material decrease and the capacitance of the MLG itself is lower than that of Si/SiOx.

[0028] Please refer to FIG. 9. FIG. 9 is a perspective view of a schematic drawing illustrating a spectrum analysis of the XPS Si2p of the Si/SiOx/MLG/C of the invention. Please refer to FIG. 10. FIG. 10 is a perspective view of a schematic drawing illustrating the spectrum analysis of the XPS Si2p of SiOx (commercial) of the invention. As shown in the drawing, the valences of Si on the surface of the sample of Si/SiOx/MLG/C are from Si0 to Si4+. The semi-quantitative analysis results of C, O, Si by XPS full spectrum scan of Table 2 show that the percentages in the Si/SiOx/MLG/C sample are 31%, 39%, 30%, but the percentages in the SiOx (commercial) sample are 87%, 10%, 3%. The large difference mainly resides in the XPS analysis mainly on the surface analysis (depth ∼10 nm). Because the SiOx (commercial) sample is prepared by a high-temperature gas phase method before the chemical vapor deposition carbon coating is carried out, more signals of carbon is detected by the analysis of the SiOx (commercial) sample. For the Si/SiOx/MLG/C sample, the contents of the surface composition of C, O, Si are close to one another because the material composition of the shell is SiOx/C. Further to analyze the valence distribution of Si2p individual peaks (Table 3), it is known from the calculated results of the analysis of different Si valences that the parameter x would be 1.56 if the material is averagely represented by an general formula SiOx. However, when reviewing the prior art references, it is estimated that the unit capacity per gram would be lower than 800 mAh g-1 for SiOx with x = 1.56 but the reversible capacity of the Si/SiOx/MLG/C sample from Table 1 is shown to be 1814 mAh g-1 so it is confirmed again that the sample is a composite material with an outer shell of SiOx/C and with an inner core of Si/MLG. On the contrary, for the SiOx (commercial) sample the main valence of Si is 2+ and x is 0.94 from the calculation of the valence analysis, which is pretty close to the oxygen content disclosed in the patent of the supplier.
TABLE 1 Semi-quantitative analysis results of C, O, Si by XPS full spectrum scan
Atomic %COSi
Si/SiOx/MLG/C 31% 39% 30%
SiOx (commercial) 87% 10% 3%
TABLE 2 Analysis of individual peaks of the valence distribution of XPS Si2p spectrum
Si valence (Area %)Si0Si1+Si2+Si3+Si4+SiOx
Si/SiOx/MLG/C 7% 3% 9% 33% 48% SiO1.56
SiOx (commercial) 5% 0% 85% 9% 0% SiO0.94


[0029] Please refer to FIG. 11. FIG. 11 is a perspective view of a schematic drawing illustrating a test chart of a half-cell of the Si/SiOx/MLG/C material according to Example 3 of the invention. Please refer to FIG. 12. FIG. 12 is a perspective view of a schematic drawing illustrating a test chart of a half-cell of the comparative example 1 of the SiOx (commercial) material. As shown in FIG. 11, FIG. 11 consists of the 0.4 V redox characteristic platform of Si and the oblique rising line of SiOx, while FIG. 10 shows the characteristic charging and discharging curve of SiOx (commercial), but the two materials have problems of low Coulombic efficiency and of poor battery life when used individually so only the first cycle Coulombic efficiency and the reversible capacitance are measured in the tests. A comparison of the two shows that the sample of Si/SiOx/MLG/C has a high reversible capacity (1814 mAh g-1) while the SiOx (commercial) sample has a commercially average capacity up to ∼1600 mAh g-1. The Coulombic efficiency of the Si/SiOx/MLG/C sample is slightly 2% lower. However, it is observed from the graphite-mixed test results in Table 1 that the first cycle Coulombic efficiency of the two samples is close to each other in spite of 5% mixing or of 15% mixing. Accordingly it is inferred that the Coulombic efficiency of the Si/SiOx/MLG/C sample is slightly lower than that of the SiOx (commercial) sample when Si/SiOx/MLG/C is used alone because there is no other graphite material to help suppress its volume expansion. The SiOx (commercial) has slightly higher Coulombic efficiency because there is a large amount of Li2O and Li4SiO4 to be helpful in suppressing its volume expansion when it is activated after the first circle. In accordance with these, from Table 3 it is known that each of the two materials has its own problem of lower first cycle Coulombic efficiency due to respective different reasons. For the SiOx (commercial), it needs addition lithium to form Li2O and Li4SiO4 at its first cycle. But for Si/SiOx/MLG/C, the first cycle Coulombic efficiency is lower owing to the volume expansion of its core Si to result in breaking or cracking. Surely, its outer shell of SiOx still consumes some of the lithium to form Li2O and Li4SiO4 to help suppress the volume expansion. By absorbing its volume expansion along with the mixed graphite, the first cycle Coulombic efficiency of Examples 4 and 5 and Comparative Examples 2 and 3 are similar. Further, the unit gram capacity of the anode material formed by mixing graphite of the same proportion is higher than that of the SiOx (commercial) sample because the Si/SiOx/MLG/C sample has a higher reversible capacity.
Table 3 Tests of half-cells of the Si/SiOx/MLG/C materials in examples and of SiOx (commercial) sample.
 Composition of anode materialCharging capacity of the first cycle (mAh g-1)Discharging capacity of the first cycle (mAh g-1)First cycle Coulombic efficiency (%)Residual capacity rate after 100 cycles (%)
Example 1 Si/SiOx/C-0.5h 2986 1986 66.5 -*
Example 2 Si/SiOx/C 2643 1914 72.4 -*
Example 3 Si/SiOx/MLG/C 2329 1814 77.9 -*
Example 4 5wt% Si/SiOx/MLG/C + 95 wt. % MCMB 470 427 90.9 93.1
Example 5 15wt% Si/SiOx/MLG/C + 85 wt % MCMB 644 570 88.5 80.3
Comparative Example 1 SiOx (commercial) 1983 1594 80.4 -*
Comparative Example 2 5wt% SiOx (commercial) + 95wt% MCMB 450 411 91.3 88.4
Comparative Example 3 15wt% SiOx (commercial) + 85wt% MCMB 605 537 88.7 62.0


[0030] Please refer to FIG. 13. FIG. 13 is a perspective view of a schematic drawing illustrating a half-cell test chart of the 15 wt% Si/SiOx/MLG/C + 85 wt% MCMB material according to Example 5 of the invention. Please refer to FIG. 14. FIG. 14 is a perspective view of a schematic drawing illustrating a half-cell test chart of 15 wt% SiOx (commercial) + 85 wt% MCMB material of the invention. Please refer to FIG. 15. FIG. 15 is a perspective view of a schematic drawing illustrating a half-cell test chart of long charging and discharging cycle of the material of Example 5 (15 wt% Si/SiOx/MLG/C + 85wt% MCMB) and the material of Comparative Example 3 (15 wt% SiOx (commercial) + 85 wt% MCMB). As shown in drawing, as far as the capacity is concerned, silicon still has higher capacity contribution although only 15% of Si/SiOx/MLG/C or of SiOx (commercial) is mixed so the silicon-oxygen-based materials still dominate the charging-discharging curves. Due to the 85% graphite anode, it shows a better first cycle Coulombic efficiency and cycle life. FIG. 15 illustrates a half-cell test of long charging and discharging cycle of the material of Example 5 (15 wt% Si/SiOx/MLG/C + 85wt% MCMB) and the material of Comparative Example 3 (15 wt% SiOx (commercial) + 85 wt% MCMB) with 0.5 C current (1C = 550 mA g-1). Example 5 has better stability. After 5 cycles of 0.1 C charging and discharging cycles and 100 cycles of a long cycle test of 0.5 C, the capacity retention is still kept over 80%. However, for Comparative Example 3, under the same conditions, the capacity decreases more after 80 cycles at 0.5 C, and the capacity retention drops to only 62% after 100 cycles.

[0031] The anode material of the invention uses nano-Si as a raw material to undergo alkali etching and Si/SiOx are dispersed on the surface of the MLG by a wet dispersion method in the presence of a solvent, and finally it is coated with an organic pyrolysis carbon layer so that nano-Si can be uniformly distributed in the composite material. MLG along with SiOx slows down the volume expansion effect and cracking of Si which are caused by the charging and discharging cycles. 15% of the anode material with a commercial graphite anode material is physically mixed to form a slurry, to form an electrode and finally fabricated to be a CR2032 battery. The measured reversible capacity is about ∼570 mAh g-1 after testing, which is ∼1.6 time higher than that of a pure graphite anode material (∼350 mAh g-1) with the first circle Coulombic efficiency up to ∼ 89%, and its capacity retention is 80% after 100 cycles. Compared with commercial SiOx material, it has better capacity retention and advantages of process cost so it is suitable to serve as an anode material for the lithium ion batteries of high energy density.


Claims

1. An anode material of nano-silicon (12) having multilayer-graphene (11) as a carrier and coated with silicon suboxide and with an amorphous carbon layer (13), characterized by:

multilayer-graphene (11) serving as a carrier;

nano-silicon (12) adsorbed on the multilayer-graphene (11), both the multilayer-graphene (11) and the nano-silicon (12) serving as a core;

silicon suboxide and an amorphous carbon layer (13) coated on the multilayer-graphene (11) and on the nano-silicon (12); and

a plurality of buffering holes (14) disposed on the anode material to provide buffering space.


 
2. The anode material of nano-silicon (12) having multilayer-graphene (11) as a carrier and coated with silicon suboxide and with an amorphous carbon layer (13) of Claim 1, characterized in that the nano-silicon (12) has a particle size in a range of 50 nm ∼ 300 nm.
 
3. The anode material of nano-silicon (12) having multilayer-graphene (11) as a carrier and coated with silicon suboxide and with an amorphous carbon layer (13) of Claim 1, characterized in that the nano-silicon (12) is attached to the multilayer-graphene (11) by means of hydroxyl groups.
 
4. The anode material of nano-silicon (12) having multilayer-graphene (11) as a carrier and coated with silicon suboxide and with an amorphous carbon layer (13) of Claim 1, characterized in that the amorphous carbon layer (13) is obtained from an organic carbon source through an organic pyrolysis process, and the organic carbon source is selected from a group consisting of glucose, sucrose, citric acid, polyvinyl alcohol, polyethylene glycol, polyacrylonitrile, asphalt, a phenolic resin, polyaniline, an epoxy resin, polyvinylpyrrolidone, and an unsaturated hydrocarbon gas.
 
5. A method for fabricating an anode material having multilayer-graphene (11) as a carrier and coated with silicon suboxide and with an amorphous carbon layer (13), characterized by:

providing an etchant and a silicon-containing starting material to obtain a mixture solution after a mixing process, and adding a terminator to the mixture solution to make the mixture solution become a neutral solution;

adding multilayer-graphene (11) to the mixture solution for mixing before adding an organic carbon source;

subjecting the mixture solution with the added multilayer-graphene (11) to a calcination process to obtain a core shell material; and

subjecting the core shell material to a pulverizing and sieving process to obtain an anode material which has a plurality of buffering holes (14) and multilayer-graphene (11) as a carrier and is coated with silicon suboxide and with an amorphous carbon layer (13), before the core shell material is washed with a solvent.


 
6. The method for fabricating an anode material having multilayer-graphene (11) as a carrier and coated with silicon suboxide and with an amorphous carbon layer (13) of Claim 5, characterized in that the etchant is selected from a group consisting of a NaOH solution and a KOH solution.
 
7. The method for fabricating an anode material having multilayer-graphene (11) as a carrier and coated with silicon suboxide and with an amorphous carbon layer (13) of Claim 5, characterized in that the silicon-containing starting material is selected from a group consisting of silicon powder and silicon suboxide powder.
 
8. A method for fabricating an anode material having multilayer-graphene (11) as a carrier and coated with silicon suboxide and with an amorphous carbon layer (13) of Claim 5, characterized in that the solvent is selected from the group consisting of deionized water, glycerol, and ethanol.
 
9. The method for fabricating an anode material having multilayer-graphene (11) as a carrier and coated with silicon suboxide and with an amorphous carbon layer (13) of Claim 5, characterized in that the terminator is selected from a group consisting of hydrochloric acid (HCl), nitric acid (HNO3), sulfuric acid (H2SO4), citric acid and acetic acid.
 
10. The method for fabricating an anode material having multilayer-graphene (11) as a carrier and coated with silicon suboxide and with an amorphous carbon layer (13) of Claim 5, characterized in that the organic carbon source is selected from a group consisting of glucose, sucrose, citric acid, polyvinyl alcohol, polyethylene glycol, polyacrylonitrile, asphalt, a phenolic resin, polyaniline, an epoxy resin, polyvinylpyrrolidone, and an unsaturated hydrocarbon gas.
 
11. The method for fabricating an anode material having multilayer-graphene (11) as a carrier and coated with silicon suboxide and with an amorphous carbon layer (13) of Claim 5, characterized in that a temperature range of the calcination process is 600 °C ∼ 1000 °C.
 
12. The method for fabricating an anode material having multilayer-graphene (11) as a carrier and coated with silicon suboxide and with an amorphous carbon layer (13) of Claim 5, characterized in that a pulverizing procedure in the pulverizing and sieving process is selected from a group consisting of machining, ball milling and grinding.
 
13. The method for fabricating an anode material having multilayer-graphene (11) as a carrier and coated with silicon suboxide and with an amorphous carbon layer (13) of Claim 5, characterized in that a sieve which is used in the pulverizing and sieving process has a mesh number between 80 mesh and 600 mesh.
 
14. A method for fabricating an anode material having multilayer-graphene (11) as a carrier and coated with silicon suboxide and with an amorphous carbon layer (13) of Claim 5, characterized in that a binder, a conductive agent, a solvent and the anode material which has multilayer-graphene (11) as a carrier and is coated with silicon suboxide and with an amorphous carbon layer (13) are applied on a metal foil to prepare an anode electrode after mixed together.
 
15. The method for fabricating an anode material having multilayer-graphene (11) as a carrier and coated with silicon suboxide and with an amorphous carbon layer (13) of Claim 5, characterized in that the binder is selected from a group consisting of PVDF, CMC, SBR, Alginate, Chitosan and LA132.
 




Drawing