# Patent

## Title
Negative active material, method of preparing the same, and lithium battery including the same

## Abstract

Provided are a negative active material, a method of preparing the same, and a lithium battery including the negative active material, wherein the negative active material includes a carbonaceous material that has a peak with respect to a surface (002) at a Bragg angle 2θ of 26.4°±0.1° in an X-ray diffraction spectrum, has a full width at half maximum of the peak with respect to the surface (002) of about 0.2° to about 0.6°, has an interlayer spacing (d002) of the surface (002) measured by X-ray diffraction of about 3.36 Å to about 3.37 Å, and has a crystallite size measured from the full width at half maximum of the peak with respect to the surface (002) of about 10 nm to about 45 nm, wherein the carbonaceous material includes a core; and an amorphous carbon layer disposed on a non-cracked surface portion of the core.

## Background
CROSS-REFERENCE TO RELATED APPLICATIONS
This application claims the benefit of Korean Patent Application No. 10-2011-0044075, filed on May 11, 2011, in the Korean Intellectual Property Office, the disclosure of which is incorporated herein in its entirety by reference.
BACKGROUND
1. Field
One or more embodiments relate to a negative active material, a method of preparing the same, and a lithium battery including the negative active material, and more particularly, to a negative active material with improved input and output characteristics and high rate characteristics, a method of preparing the same, and a lithium battery including the negative active material.
2. Description of the Related Technology
Secondary lithium batteries used in portable electronic devices for information communication, such as personal digital assistances (PDAs), mobile phones, or notebook computers, electric bicycles, electronic vehicles, etc. have a discharge voltage that is at least two times greater than those of conventional batteries and thus exhibit high energy density.
A secondary lithium battery includes a positive electrode, a negative electrode, and either an organic electrolytic solution or a polymer electrolytic solution filling a space between the positive and negative electrodes, wherein the positive and negative electrodes each include an active material that allows lithium ions to be intercalated and deintercalated. In this structure, when lithium ions are intercalated and deintercalated between the positive and negative electrodes, oxidation and reduction reactions occur, and thus, electrical energy is generated.
An example of a positive active material for a secondary lithium battery is an oxide that includes lithium and transition metal and has a structure enabling intercalation of lithium ions. Examples of the oxide are lithium cobalt oxide (LiCoO2), lithium nickel oxide (LiNiO2), and lithium nickel cobalt manganese oxide (Li[NiCoMn]O2, Li[Ni1-x-yCoxMy]O2).
For use as a negative active material, research into various carbonaceous materials, including artificial and natural graphites, hard carbon, and non-carbonaceous material such as silicon (Si), which allow lithium ions to be intercalated and deintercalated, is being performed.
The carbonaceous materials are porous, and thus, stable due to their small volumetric change. However, typically, carbonaceous materials have low battery capacity due to their porous structures. Also, even when the battery capacity is high, because pores clog, input and output characteristics and high rate characteristics of a battery decrease.
Accordingly, there is a need to develop high performance negative active materials having improved input and output characteristics and high rate characteristics.
SUMMARY
One or more embodiments include a negative active material that has a plate structure with high crystallinity and has improved input and output characteristics and high rate characteristics.
One or more embodiments include a method of preparing a negative active material that has improved input and output characteristics and high rate characteristics.
One or more embodiments include a lithium battery that has improved input and output characteristics and high rate characteristics.
Additional aspects will be set forth in part in the description which follows and, in part, will be apparent from the description, or may be learned by practice of the presented embodiments.
According to one or more embodiments, a negative active material includes a carbonaceous material that has a peak with respect to a surface (002) at a Bragg angle 2θ of 26.4°±0.1° in an X-ray diffraction spectrum, has a full width at half maximum of the peak with respect to the surface (002) of about 0.2° to about 0.6°, has an interlayer spacing (d002) of the surface (002) measured by X-ray diffraction of about 3.36 Å to about 3.37 Å, and has a crystallite size measured from the full width at half maximum of the peak with respect to the surface (002) of about 10 nm to about 45 nm.
The carbonaceous material may have a crystalloid plate structure.
The negative active material may include: a core including a carbonaceous material; and an amorphous carbon layer disposed on a non-cracked portion of a surface of the core.
The amorphous carbon layer may be spherical or oval, and a longer direction particle size thereof d50 is from about 1 μm to about 40 μm.
The core may have voids therein.
The core may have cracks at a surface thereof extending from the voids present inside the core.
At least a portion of the voids may include amorphous carbon.
A sulfur content of the core may be from about 1000 ppm to about 2000 ppm.
A BET specific surface area of the negative active material may be from about 10 m2/g to about 60 m2/g.
The negative active material may additionally include metal nanoparticles.
The metal nanoparticles may be selected from the group consisting of silicon (Si), tin (Sn), nickel (Ni), and a mixture thereof.
A size of the metal nanoparticles may be from about 1 nm to about 500 nm.
According to one or more embodiments, a method of preparing a negative active material, includes: preparing a carbonaceous core; forming cracks at a portion of a surface of the carbonaceous core; and forming an amorphous carbon layer on the carbonaceous core having the cracked surface portion, wherein the carbonaceous core has a peak with respect to a surface (002) at a Bragg angle 2θ of 26.4°±0.1° in an X-ray diffraction spectrum, has a full width at half maximum of the peak with respect to the surface (002) of about 0.2° to about 0.6°, has an interlayer spacing (d002) of the surface (002) measured by X-ray diffraction of about 3.36 Å to about 3.37 Å, and has a crystallite size measured from the full width at half maximum of the peak with respect to the surface (002) of about 10 nm to about 45 nm.
The preparing of the carbonaceous core may include: preparing a carbonaceous material having a crystalloid plate structure; and forming the carbonaceous material in a spherical shape.
The preparing of the carbonaceous core having the crystalloid plate structure may include: expanding graphite by using an expanding agent; and heat treating the graphite.
The expanding agent may include at least one selected from the group consisting of a sulfuric acid, a nitric acid, a hydrochloric acid, an acetic acid, and a perchloric acid.
An amount of the expanding agent may be from about 1 to about 80 parts by weight based on 100 parts by weight of the graphite.
The heat treatment is performed at a temperature of about 200° C. to about 400° C.
The forming of cracks at a portion of a surface of the carbonaceous core may include heat treating at a temperature of 800° C. to 1000° C.
According to one or more embodiments, a lithium battery includes: a positive electrode including a positive active material; a negative electrode comprising the negative active material described above; and an electrolytic solution interposed between the positive and negative electrodes.



BRIEF DESCRIPTION OF THE DRAWINGS
These and/or other aspects will become apparent and more readily appreciated from the following description of the embodiments, taken in conjunction with the accompanying drawings in which:
FIG. 1A shows a scanning electron microscopy (SEM) image of a carbonaceous core prepared according to Preparation Example 1;
FIG. 1B shows a transmission electron microscope (TEM) image of the carbonaceous core prepared according to Preparation Example 1;
FIG. 2 shows a SEM image of a negative active material prepared according to Example 1;
FIG. 3 shows an enlarged SEM image at 3.5× magnification of a negative active material prepared according to Example 1;
FIG. 4 shows a SEM image of a negative active material prepared according to Example 3;
FIG. 5 shows an enlarged SEM image at 10× magnification of a negative active material prepared according to Example 3;
FIG. 6 shows a TEM image of a cross-section of a negative active material particle according to an embodiment;
FIG. 7 shows size distribution results of a negative active material according to an embodiment;
FIG. 8A shows X-ray diffraction analysis results of carbonaceous cores prepared according to Preparation Examples 1 and 2 and Comparative Preparation Example 1;
FIG. 8B shows X-ray diffraction analysis results of a carbonaceous core prepared according to Comparative Preparation Example 3;
FIG. 9 is an exploded perspective view of a lithium battery according to an embodiment; and
FIG. 10 shows a graph showing high rate characteristics of lithium batteries prepared according to Examples 4 and 6 and Comparative Examples 4 and 5.



DETAILED DESCRIPTION
A negative active material, a method of preparing the same, and a lithium battery including the negative active material will now be described in detail with reference to embodiments, examples of which are illustrated in the accompanying drawings. In this regard, the embodiments may have different forms and should not be construed as being limited to the descriptions set forth herein. Accordingly, the embodiments are merely described below, by referring to the figures, to explain aspects of the present description.
As an aspect of the present embodiments, a negative active material according to an embodiment includes a carbonaceous material that has a peak with respect to a surface (002) at a Bragg angle 2θ of 26.4°±0.1° in an X-ray diffraction spectrum, has a full width at half maximum of the peak with respect to the surface (002) of about 0.2° to about 0.6°, has an interlayer spacing (d002) of the surface (002) measured by X-ray diffraction of about 3.36 Å to about 3.37 Å, and has a crystallite size measured from the full width at half maximum of the peak with respect to the surface (002) of about 10 nm to about 45 nm.
The crystal structure of the negative active material may also be confirmed by referring to FIG. 8A that shows X-ray diffraction analysis results obtained using a CuK-alpha characteristic X-ray wavelength of 1.541 Å.
A peak of the negative active material with respect to the surface (002) may be present at a Bragg angle 2θ of about 26.4°±about 0.1°, for example, about 26.4° to about 26.5°, in an X-ray diffraction spectrum.
A full width at half maximum of the peak of the negative active material with respect to the surface (002) may be about 0.2° to about 0.6°, for example, about 0.3° to about 0.5°.
An interlayer spacing (d002) of the surface (002) of the negative active material measured by X-ray diffraction may be from about 3.36 Å to about 3.37 Å, for example, about 3.36 Å to about 3.37 Å. The interlayer spacing (d002) of the surface (002) of the negative active material may be calculated by substituting a value of a Bragg angle 2θ at which a peak of the surface (002) is present in the X-ray diffraction spectrum obtained by X-ray diffraction analysis into a Bragg equation.
A crystallite size measured from the full width at half maximum of the peak with respect to the surface (002) may be from about 10 nm to about 45 nm, for example, from about 13 nm to about 40 nm. The crystallite size of the negative active material may be calculated by substituting a value of the full width at half maximum of the peak with respect to the surface (002) in the X-ray diffraction spectrum into Scherrer's equation.




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From the results described above, it is confirmed that unlike typical hard carbon, the negative active material is a carbonaceous material with high crystallinity.
The carbonaceous material may have a crystalloid plate structure. The crystalloid plate structure may include a deformed plate structure, such as a bent plate structure, a plate structure with a curved end, a plate structure with a partially defect plate, etc. The “plate structure” of the carbonaceous material may be easily understood by referring to the carbonaceous material shown in FIG. 1A.
The carbonaceous material may include a polycyclic nano-sheet including fused carbon atom rings that are aligned on a plane, and n polycyclic nano-sheets may be stacked in a direction perpendicular to the plane, where n may be an integer of 2 to 50, or an integer of 2 to 40, or an integer of 2 to 30.
Each carbon atom ring may refer to, for example, a ring that consists of 6 carbon atoms connected in a hexagonal shape.
The term “cycle that consists of 6 carbon atoms connected in a hexagonal shape” used herein refers to a hexagonal ring in which carbon is located at each vertex. Hereinafter, this term will also be referred to as “6-membered carbon cycle.” The polycyclic nano-sheet has a plurality of 6-membered carbon rings, which are fused to form a beehive shape, aligning on a plane. In this case, the wording “aligning on a plane” refers to aligning and extending of a plurality of laterally fused 6-membered carbon rings. For example, the wording “aligning on a plane” does not include aligning and extending of vertically fused 6-membered carbon rings.
Among carbons of the polycyclic nano-sheet, adjacent carbons may be bonded to each other via a sp2 bond. By doing so, a resonance structure may be formed in the 6-membered carbon ring and thus, electrons migrate easily.
Because the polycyclic nano-sheet consists of a plurality of 6-membered carbon rings that are fused and aligned on a plane, a thickness of the polycyclic nano-sheet may be, for example, carbon atom particle size±0.1 nm. In this regard, the thickness of the polycyclic nano-sheet, for example, carbon atom particle size±0.1 nm, is determined in consideration of the presence of a bent polycyclic nano-sheet, a polycyclic nano-sheet with a curved end, or a polycyclic nano-sheet with a partially defect plate.
The carbonaceous material may have the stack of n polycyclic nano-sheets as described above. In this case, the n polycyclic nano-sheets may be stacked in a direction perpendicular to the plane on which a plurality of 6-membered carbon rings of the polycyclic nano-sheet are fused and aligned, where n may be an integer of 2 to 50, or an integer of 2 to 40, or an integer of 2 to 30, or an integer of 2 to 20.
Regarding the carbonaceous material, from among carbons of the n polycyclic nano-sheets, a first carbon and a second carbon, which satisfy an inequality L1≧L2 (where L1 refers to a distance between the first carbon and the second carbon, and L2 refers to a distance between a third carbon and a fourth carbon, wherein the third carbon is selected from carbons of the n polycyclic nano-sheets other than the first carbon and the second carbon, and the fourth carbon is selected from carbons of the n polycyclic nano-sheets other than the first carbon, the second carbon, and the third carbon), are selected. When the first carbon is positioned at the origin A (0, 0, 0) of a three-dimensional coordinate system having an x-axis, a y-axis, and a z-axis, the second carbon may have a coordinate B (a, b, c), where a and b are each independently 10 μm or less and c may be 100 nm or less. In this regard, L1 refers to a distance between the first carbon and the second carbon, and L2 refers to a distance between the third carbon and the fourth carbon, wherein the third carbon is selected from carbons of the n polycyclic nano-sheets other than the first carbon and the second carbon, and the fourth carbon is selected from carbons of the n polycyclic nano-sheets other than the first carbon, the second carbon, and the third carbon. For example, the first carbon and the second carbon may refer to two carbons that are spaced apart from each other the most among any two carbons selected from carbons of the n polycyclic nano-sheets.
a and b may be each independently 10 μm or less, or about 0.1 μm to about 10 μm. For example, a and b may each be about 1 μm to about 10 μm. a and b may respectively indicate a width and a length in a perpendicular direction to a thickness direction of the carbonaceous material.
c may be 100 nm or less, or about 0.5 nm to about 100 nm, or about 0.5 nm to about 90 nm, or about 0.5 nm to about 50 nm. For example, c may be about 0.5 nm to about 20 nm, but is not limited thereto. c may indicate a length of the thickness direction of the carbonaceous material.
Accordingly, the carbonaceous material may be, for example, nanoparticle powder having the plate structure.
If the carbonaceous material has such ranges of a, b, and c, although not wishing to be limited to a particular theory, electrons may migrate easily and thus the carbonaceous material has excellent conductivity
The negative active material may include: a core including the carbonaceous material; and an amorphous carbon layer that are continuously or discontinuously formed on a surface of the core.
A lithium battery including the negative active material including the carbonaceous material may have improved input and output characteristics and high rate characteristics.
For example, the negative active material may include a core including the carbonaceous material; and an amorphous carbon layer formed on a non-cracked portion of the surface of the core.
Because the negative active material easily allows lithium ions to be intercalated and deintercalated and has an increased specific surface due to the inclusion of the amorphous carbon layer on the non-cracked portion of the surface of the core, a lithium battery including the negative active material may have improved input and output characteristics and high rate characteristics.
The amorphous carbon layer formed on the surface of the core may be a pitch coating.
A pitch source available for use herein may be, for example, a petroleum-based material or a coal-based material, and examples thereof are a coal-tar pitch, a petroleum pitch, an organic synthesis pitch prepared by polymerization-fusing of a fused polycyclic aromatic hydrocarbon compound, and an organic synthesis pitch obtained by polymerization-fusing of a hetero atom-containing fused polycyclic aromatic hydrocarbon compound. For example, the pitch source may be a coal-tar pitch, but is not limited thereto, and any one of various pitch sources available in the art may be used herein.
The pitch coating may be formed by, for example, carbonating the pitch source through heat treatment. Due to the heat treatment, conductivity of the negative active material may be improved.
The amorphous carbon layer may be formed as a pitch coating having a thickness of about 1 nm to about 50 nm, for example, about 5 nm to about 20 nm. If the thickness of the pitch coating is within the ranges described above, a negative active material having improved conductivity may be formed.
The negative active material may be, for example, spherical or oval, and a longer direction particle size of the negative active material, that is, d50, may be from about 1 μm to about 40 μm, for example about 5 μm to about 20 μm. Examples of the surface and shape of the negative active material may be seen by referring to FIGS. 2 and 3, which are described below. The definition of d50 may be easily understood by one of ordinary skill in the art, and may be seen by referring to FIG. 7, which is described below.
When the negative active material is spherical or oval, the negative active material may provide flexibility when slurry and an electrode plate are prepared. A negative active material having the d50 range described above may be suitable for the preparation of slurry, and may allow a negative electrode to be surface-coated uniformly when the negative electrode is manufactured.
The core of the negative active material may have voids. The voids may be amorphous and may be at least two voids. The presence and shape of the voids in the core are confirmed by referring to FIG. 6.
The voids are not present in hard carbon or conventional graphite used as a negative active material. Due to the voids, a contact area between the negative active material and lithium ions may be widened. Thus, the negative active material included in a battery has excellent input and output characteristics and high rate characteristics.
A porosity of the negative active material may be from about 1% to about 40%, or about 2% to about 10%. The porosity may refer to a percent of a total volume of voids based on a total volume of the negative active material.
The negative active material may have cracks at its surface extending from the voids present inside the core. The cracks of the negative active material are easily infiltrated with an electrolytic solution, and thus, high rate characteristics of the negative active material may be improved.
In the negative active material, at least a portion of the voids may be occupied with amorphous carbon. If at least a portion of the voids is occupied with amorphous carbon, input and output characteristics and high rate characteristics of the negative active material may be further improved.
A sulfur content in the core of the negative active material may be from about 1000 ppm to about 2000 ppm, for example, about 1200 ppm to about 1800 ppm.
The sulfur content refers to a residual amount of a sulfuric acid which is used as an expanding agent when the core is prepared, and may be quantified by using an inductively coupled plasma (ICP) emission spectrometer.
If the core has the sulfur content range described above, an amorphous carbon layer at the surface of the core may form easily cracks due to side reactions, such as generation of SO2 gas. Accordingly, a negative active material including a carbonaceous material that includes the cracked amorphous carbon layer at its surface may have increased specific surface area, and thus, a lithium battery including the negative active material may have improved input and output characteristics.
A BET specific surface area of the negative active material may be from about 10 m2/g to about 60 m2/g, or about 10 m2/g to about 50 m2/g, or about 10 m2/g to about 40 m2/g. The BET specific surface area of the negative active material is measured by a ‘nitrogen adsorption BET specific surface area measurement device (ASAP2400’) manufactured by Micro Meritex Co. Ltd (Sayama City, Japan).
A negative active material having the BET specific surface area range described above may have excellent input and output characteristics and high rate characteristics.
The negative active material may further include metal nanoparticles.
A negative active material including metal nanoparticles may have, in addition to, improved input and output characteristics and high rate characteristics, improved conductivity.
The metal nanoparticles may be selected from the group consisting of silicon (Si), tin (Sn), nickel (Ni), and a mixture thereof. A size of the metal nanoparticles may be from about 1 nm to about 500 nm.
If the size of the metal nanoparticles is within the range described above, the destruction of the negative active material due to volumetric expansion of the metal nanoparticles, such as Si particles, during charging and discharging may be effectively reduced.
An average particle size of the negative active material that additionally includes metal nanoparticles may be from about 3 μm to about 60 μm, for example, about 3 μm to about 50 μm.
The average particle size ranges of the negative active material described above are appropriate for slurry preparation and handling. If the average particle size of the negative active material is within the ranges described above, a final BET specific surface area is from about 3 m2/g to about 20 m2/g, and thus, formation of a solid electrolyte interface (SEI) on a surface of a negative electrode may be appropriately controlled.
As another aspect of the present embodiments, a method of preparing a negative active material, according to an embodiment, includes preparing a carbonaceous core; forming cracks at a portion of a surface of the carbonaceous core; and forming an amorphous carbon layer on the carbonaceous core having the cracked surface portion, wherein the carbonaceous core has a peak with respect to a surface (002) at a Bragg angle 2θ of 26.4°±0.1° in an X-ray diffraction spectrum, has a full width at half maximum of the peak with respect to the surface (002) of about 0.2° to about 0.6°, has an interlayer spacing (d002) of the surface (002) measured by X-ray diffraction of about 3.36 Å to about 3.37 Å, and has a crystallite size measured from the full width at half maximum of the peak with respect to the surface (002) of about 10 nm to about 45 nm.
The preparing of a carbonaceous core may include preparing a carbonaceous material having a crystalloid plate structure; and forming the carbonaceous material in a spherical shape.
The preparing of a carbonaceous material having a crystalloid plate structure may include expanding graphite by using an expanding agent; and heat treating the expanded graphite.
The expanding of graphite by using an expanding agent may include immersing graphite in a solution including an expanding agent for about 1 to about 24 hours. However, the expanding method is not limited thereto, and any one of various methods for preparing expanded graphite may be used herein.
The expanding agent may include at least one selected from the group consisting of a sulfuric acid, a nitric acid, a hydrochloric acid, an acetic acid, and a perchloric acid. For example, the expanding agent may include at least one selected from the group consisting of a sulfuric acid, a nitric acid, and an acetic acid. For example, the expanding agent may be a sulfuric acid.
An amount of the expanding agent may be from about 1 to about 80 parts by weight, or about 1 to about 70 parts by weight, based on 100 parts by weight of graphite.
If graphite is expanded by using an expanding agent having the amount ranges described above, the carbonaceous core of the negative active material may have a sulfur content of about 1000 ppm to about 2000 ppm. Thus, the surface of the carbonaceous core may be cracked by side reactions, such as generation of SO2 gas.
Accordingly, lithium are easily intercalated and deintercalated, which leads to production of a lithium battery including the carbonaceous material with improved initial efficiency.
A heat treatment temperature may be from about 200° C. to about 400° C., for example, about 200° C. to about 350° C. A heat treatment time may be from about 1 second to about 5 hours, for example, 10 seconds to 1 hour.
Because the expanding of graphite includes immersing of graphite in a great amount of the solution including the expanding agent, the heat treatment should be performed at a low temperature.
If the heat treatment temperature and time are within the ranges described above, graphite may expand at such a level that particles satisfying the “c” range described above are sufficiently obtainable without substantial damage to carbon-carbon bonds.
Furthermore, a solvent may be added to the expanded graphite, and the expanded graphite in the solvent is pulverized.
As the solvent, a material that does not substantially react with the expanded graphite and provides fluidity may be used. Non-limiting examples of the solvent are alcohols (for example, ethanol).
Subsequently, the expanded graphite included in the solvent is pulverized. As a pulverizing method, a method using a homogenizer, a method using a micro fluidizer, etc. may be used. The pulverizing method may be repeatedly performed a few times. Alternatively, different pulverizing methods may each be used at least twice. Before the expanded graphite is pulverized, the expanded graphite may be mixed with an acid.
Thereafter, the solvent used is removed from the pulverized product and the resultant graphite particles are aggregated to form a spherical carbonaceous core.
The removal of the solvent may be performed by using various methods in consideration of, for example, a boiling point of the solvent. For example, the pulverized product is filtered and washed, and then heat treated at a temperature of 80° C.
In the forming of cracks at a portion of the surface of the carbonaceous core, cracks are artificially formed at a portion of the surface of the graphite-based core material through heat treatment.
The forming of cracks at a portion of the surface of the carbonaceous core may include heat treating at a temperature of about 800° C. to about 1000° C., for example, about 850° C. to about 1000° C. A heat treatment time may be from about 0.1 hours to about 5 hours, for example, about 0.5 hours to about 1 hour.
When the heat treatment temperature and time are within the ranges described above, the portion of the surface of the carbonaceous core may be cracked due to SO2 gas present in the carbonaceous core. Accordingly, lithium ions are easily intercalated and deintercalated, and thus, a lithium battery including the carbonaceous core material may have improved input and output characteristics and high rate characteristics.
In the forming of an amorphous carbon layer on the carbonaceous core having the cracked surface portion, an amorphous carbon, for example, a pitch is provided to the surface of the carbonaceous core and then heat treated to form an amorphous carbon layer.
Examples of the pitch are a coal-tar pitch, a petroleum pitch, an organic synthesis pitch prepared by polymerization-fusing of a fused polycyclic aromatic hydrocarbon compound, and an organic synthesis pitch obtained by polymerization-fusing of a hetero atom-containing fused polycyclic aromatic hydrocarbon compound. For example, the pitch may be a coal-tar pitch. For example, a pitch may be provided to the surface of the carbonaceous core by chemically depositing carbon. However, the pitch formation method is not limited thereto, and may be any one of various methods available in the art.
The forming of the amorphous carbon layer may include heat treating at a temperature of about 700° C. to about 2000° C., for example, 800° C. to 2000° C., for 30 minutes to 72 hours. However, the heat treatment temperature and time are not limited thereto. The heat treatment process may be performed to carbonate the pitch provided to the surface of the graphite-based core in an inert gas atmosphere or a non-acidic atmosphere.
If the heat treatment temperature and time are within the ranges described above, crystallinity of the negative active material may be improved. A lithium battery including the negative active material may have improved high rate characteristics.
As another aspect of the present embodiments, a lithium battery according to an embodiment includes a positive electrode including a positive active material; a negative electrode including a negative active material as described above; and an electrolytic solution interposed between the positive and negative electrodes. In this regard, the negative active material may include a carbonaceous material that has a peak with respect to a surface (002) at a Bragg angle 2θ of 26.4°±0.1° in an X-ray diffraction spectrum, has a full width at half maximum of the peak with respect to the surface (002) of about 0.2° to about 0.6°, has an interlayer spacing (d002) of the surface (002) measured by X-ray diffraction of about 3.36 Å to about 3.37 Å, and has a crystallite size measured from the full width at half maximum of the peak with respect to the surface (002) of about 10 nm to about 45 nm. Such a negative active material may enable easy intercalation and deintercalation of lithium ions, and accordingly, a lithium battery including the negative active material may have improved input and output characteristics and high rate characteristics.
The positive electrode includes a current collector and a positive active material layer disposed on the current collector. An example of a positive active material that is used to form the positive active material layer is a compound that allows lithium to be reversibly intercalated and deintercalated, that is, a lithiumated intercalation compound. Examples of the positive active material are: LiaA1-bXbD2 (where 0.95≦a≦1.1, and 0≦b≦0.5); LiaE1-bXbO2-cDc (where 0.95≦a≦1.1, 0≦b≦0.5, and 0≦c≦0.05); LiE2-bXbO4-cDc (where 0≦b≦0.5 and 0≦c≦0.05); LiaNi1-b-cCobBcDα (where 0.95≦a≦1.1, 0≦b≦0.5, 0≦c≦0.05, and 0<α≦2); LiaNi1-b-cCobXcO2-αMα (where 0.95≦a≦1.1, 0≦b≦0.5, 0≦c≦0.05, and 0<α<2); LiaNi1-b-cCobXcO2-αM2 (where 0.95≦a≦1.1, 0≦b≦0.5, 0≦c≦0.05, and 0<α<2); LiaNi1-b-cMnbXcDα (where 0.95≦a≦1.1, 0≦b≦0.5, 0≦c≦0.05, and 0<α≦2); LiaNi1-b-cMnbXcO2-αMα (where 0.95≦a≦1.1, 0≦b≦0.5, 0≦c≦0.05, and 0<α<2); LiaNi1-b-cMnbXcO2-αM2 (where 0.95≦a≦1.1, 0≦b≦0.5, 0≦c≦0.05, and 0<α<2); LiaNibEcGdO2 (where 0.90≦a≦1.1, 0≦b≦0.9, 0≦c≦0.5, and 0.001≦d≦0.1); LiaNibCocMndGeO2 (where 0.90≦a≦1.1, 0≦b≦0.9, 0≦c≦0.5, and 0≦d≦0.5, and 0≦e≦0.1); LiaNiGbO2 (where 0.90≦a≦1.1 and 0.001≦b≦0.1); LiaCoGbO2 (where 0.90≦a≦1.1 and 0.001≦b≦0.1); LiaMnGbO2 (where 0.90≦a≦1.1 and 0.001≦b≦0.1); LiaMn2GbO4 (where 0.90≦a≦1.1 and 0≦b≦0.1); QO2; QS2; LiQS2; V2O5; LiV2O5; LiZO2; LiNiVO4; Li(3-f)J2(PO4)3(0≦f≦2); Li(3-f)Fe2(PO4)3(0≦f≦2); LiFePO4; and lithium titanate.
In these chemical formulae, A is selected from the group consisting of Ni, Co, Mn, and a combination thereof, but is not limited thereto; X is selected from the group consisting of Al, Ni, Co, Mn, Cr, Fe, Mg, Sr, V, rare earth elements, and a combination thereof, but is not limited thereto; D is selected from the group consisting of O, F, S, P, and a combination thereof, but is not limited thereto; E is selected from the group consisting of Co, Mn, and a combination thereof, but is not limited thereto; M is selected from the group consisting of F, S, P, and a combination thereof, but is not limited thereto; G is selected from the group consisting of Al, Cr, Mn, Fe, Mg, La, Ce, Sr, V, and a combination thereof, but is not limited thereto; Q is selected from the group consisting of Ti, Mo, Mn, and a combination thereof, but is not limited thereto; Z is selected from the group consisting of Cr, V, Fe, Sc, Y, and a combination thereof, but is not limited thereto; and J is selected from the group consisting of V, Cr, Mn, Co, Ni, Cu, and a combination thereof, but is not limited thereto. For example, the positive active material may be lithium titanate.
The lithium titanate may include, according to a crystal structure, a spinel type lithium titanate, an anatase type lithium titanate, a ramsdellite type lithium titanate, etc.
In detail, the positive active material may be represented by Li4-xTi5O12 (0≦x≦3). For example, the positive active material may be Li4Ti5O12, but is not limited thereto.
A detailed example of the positive active material may be LiaNibCocMndGeO2 (where 0.90≦a≦1.1, 0≦b≦0.9, 0≦c≦0.5, 0≦d≦0.5, and e=0, for example, a=1, b=0.5, c=0.2, d=0.3, and e=0), LiMn2O4, etc., but is not limited thereto.
A lithium electrode may be used as the positive electrode.
A coating layer may be additionally formed on a surface of these compounds as the positive active material. Alternatively, these compounds may be mixed with a compound including a coating layer. The coating layer may include at least one coating element compound selected from the group consisting of oxide of a coating atom, hydroxide of a coating atom, oxycarbonate of a coating atom, and hydroxycarbonate of a coating atom. The coating atom compound of the coating layer may be amorphous or crystalline. The coating atom in the coating layer may be Mg, Al, Co, K, Na, Ca, Si, Ti, V, Sn, Ge, Ga, B, As, Zr or a mixture thereof.
In a method of forming the coating layer, these compounds may be coated with the coating elements described above by using any method that does not affect the properties of the positive active material. Such a method may be, for example, a spray coating method or an immersion method. These coating methods may be obvious to one of ordinary skill in the art and thus are not described herein in detail.
The positive active material layer may also include a binder.
The binder allows positive active material particles to be attached to each other, and also, attaches the positive active material to the current collector. Examples of the binder are polyvinyl alcohol, carboxymethyl cellulose, hydroxypropyl cellulose, diacetylcellulose, polyvinylchloride, carboxylated poly(vinyl chloride), polyvinyl fluoride, a polymer including ethylene oxide, polyvinylpyrrolidone, polyurethane, polytetrafluoroethylene, polyvinylidene fluoride, polyethylene, polypropylene, styrene-butadiene rubber, acrylated styrene-butadiene rubber, epoxy resin, and nylon. However, the binder is not limited to these materials.
The current collector may include Al, but is not limited thereto.
To prepare the positive electrode, a positive active material and a binder (selectively, including a conductive material) are mixed in a solvent to prepare a composition for forming the positive active material layer, and the composition is applied to a current collector. Because the method of manufacturing the positive electrode is well known in the art, the method will not be described in detail in the present specification. The solvent may be, but is not limited to, N-methylpyrrolidone.
The positive active material layer may also include a conductive material. The conductive material may include at least one selected from the group consisting of carbon black, ketjen black, acetylene black, artificial graphite, natural graphite, copper powder, nickel powder, aluminum powder, silver powder, and polyphenylene, but is not limited thereto.
As described above, the negative electrode may include a negative active material including a carbonaceous material that has a peak with respect to a surface (002) at a Bragg angle 2θ of 26.4°±0.1° in an X-ray diffraction spectrum, has a full width at half maximum of the peak with respect to the surface (002) of about 0.2° to about 0.6°, has an interlayer spacing (d002) of the surface (002) measured by X-ray diffraction of about 3.36 Å to about 3.37 Å, and has a crystallite size measured from the full width at half maximum of the peak with respect to the surface (002) of about 10 nm to about 45 nm. Also, according to a performance of the lithium battery, the negative active material may be used in combination of at least one selected from the group consisting of natural graphite, silicon/carbon composite (SiOx), silicon metal, silicon film, lithium metal, lithium alloy, carbonaceous materials, and graphite. An example of the lithium alloy is lithium titanate. The lithium titanate, according to a crystal structure, may include a spinel-shaped lithium titanate, an anatase-shaped lithium titanate, ramsdellite-shaped lithium titanate, etc.
In a composition for forming a negative active material layer, a binder and a solvent may be the same as described with respect to the positive electrode. A conductive material which is selectively included in the composition for forming a negative active material layer may be understood by referring to the description above. In some cases, the composition for forming the positive active material layer and the composition for forming the negative active material layer may further include a plasticizer to form pores in an electrode plate.
The electrolytic solution includes a non-aqueous organic solvent and a lithium salt.
The non-aqueous organic solvent may act as a medium through which ions involved in an electrochemical reaction of the lithium battery may be transported.
The non-aqueous organic solvent may be a carbonate-based solvent, an ester-based solvent, an ether-based solvent, a ketone-based solvent, an alcohol-based solvent, or an aprotic solvent. Examples of the carbonate-based solvent are dimethyl carbonate (DMC), diethyl carbonate (DEC), dipropyl carbonate (DPC), methylpropyl carbonate (MPC), ethyl propyl carbonate (EPC), ethyl methyl carbonate (EMC), ethylene carbonate (EC), propylene carbonate (PC), and butylene carbonate (BC). Examples of the ester-based solvent are methyl acetate, ethyl acetate, n-propyl acetate, dimethylacetate, methyl propionate, ethyl propionate, γ-butyrolactone, decanolide, valerolactone, mevalonolactone, and caprolactone. Examples of the ether-based solvent are dibutyl ether, tetraglyme, diglyme, dimethoxyethane, 2-methyltetrahydrofuran, and tetrahydrofuran. An example of the ketone-based solvent is cyclohexanone. Examples of the alcohol-based solvent include ethyl alcohol and isopropyl alcohol. Examples of the aprotic solvent are: nitriles such as R—CN, where R is a linear, branched, or cyclic C2 to C20 hydrocarbon group and has a double-bond aromatic ring or ether bond; amides such as dimethylformamide; and dioxolane-based sulfolanes such as a 1,3-dioxolane sulfolane.
These non-aqueous organic solvents may be used alone or in combination thereof. If these non-aqueous organic solvents are used in combination, the mixture ratio may be appropriately controlled according to a desired battery performance and may be obvious to one of ordinary skill in the art.
The lithium salt is dissolved in an organic solvent, acts as a lithium ion supplier in the lithium battery to operate the lithium battery, and promotes movement of lithium ions between the positive and negative electrodes. The lithium salt may include at least one supporting electrolytic salt selected from the group consisting of LiPF6, LiBF4, LiSbF6, LiAsF6, LiN(SO2C2F5)2, Li(CF3SO2)2N, LiC4F9SO3, LiClO4, LiAlO2, LiAlCl4, LiN(CxF2x-1SO2)(CyF2y+1SO2) where x and y are natural numbers, LiCl, LiI, and LiB(C2O4)2[lithium bis(oxalato)borate; LiBOB]. The concentration of the lithium salt may be in a range of about 0.1 to about 2.0 M. If the concentration of the lithium salt is within this range, an electrolyte has appropriate levels of conductivity and viscosity and thus exhibits excellent electrolytic performance, and lithium ions may migrate effectively.
According to the type of the lithium battery, a separator may be further disposed between the positive and negative electrodes. Examples of the separator include a polyethylene single layer, a polypropylene single layer, a polyvinylidene fluoride single layer, a combination thereof, a polyethylene/polypropylene double-layered structure, a polyethylene/polypropylene/polyethylene triple-layered structure, and a polypropylene/polyethylene/polypropylene triple-layered structure.
The lithium battery may be a lithium ion battery, a lithium ion polymer battery, or a lithium polymer battery, according to the separator used and the electrolyte used. Also, the lithium battery may be a cylindrical lithium battery, a rectangular lithium battery, a coin-like lithium battery, or a pouch-like lithium battery, according to the battery shape. Also, the lithium battery may be a bulky lithium battery, or a thin lithium battery according to the battery size. Also, the lithium battery according to the present embodiment may be a primary battery or a secondary battery. Methods of manufacturing the batteries described above are obvious to one of ordinary skill in the art and thus detailed description thereof will not be described herein.
FIG. 9 is an exploded perspective view of a lithium battery 100 according to an embodiment. Referring to FIG. 9, the lithium battery 100 includes a positive electrode 114, a negative electrode 112, a separator 113 interposed between the positive electrode 114 and the negative electrode 112, an electrolyte (not shown) with which the positive electrode 114, the negative electrode 112, and the separator 113 are immersed, a battery case 120, and a sealing member 140 for sealing the battery case 120. The lithium battery 100 of FIG. 9 is formed by sequentially stacking the positive electrode 114, the negative electrode 112, and the separator 113 and then rolling the resultant structure and placing the rolled structure in the battery case 120.
The present embodiments will be described in further detail with reference to the following examples. These examples are for illustrative purposes only and are not intended to limit the scope of the present embodiments.
EXAMPLES
Preparation of Carbonaceous Core
Preparation Example 1
100 parts by weight of graphite (sp270, Japan graphite) was immersed in an expansion solution of 30 parts by weight of sulfuric acid and stirred for 120 minutes, and then expanded graphite and acidic powder were washed and separated by filtering under reduced pressure, thereby isolating the expanded graphite.
The expanded graphite was heated at a temperature of 400° C. for 1 hour, gas generated therefrom was discharged through an exhaust pipe, and the result was dispersed in ethanol and pulverized by using a homogenizer at a rate of 12,000 rpm for 10 minutes. The resultant mixture was additionally pulverized by using a micro fluidizer, filtered by using a filtering device, washed using ethanol, and then, dried in an oven at a temperature of 120° C., thereby preparing carbonaceous core powder.
FIG. 1A shows a scanning electron microscopy (SEM) image of the carbonaceous core powder prepared according to Preparation Example 1. Referring to FIG. 1A, individual carbonaceous core nanoparticles contained in the carbonaceous core powder have commonly a crystalloid plate structure.
FIG. 1B shows a transmission electron microscope (TEM) image of the carbonaceous core prepared according to Preparation Example 1. In FIG. 1B, a portion indicated by a dashed circle indicates, for example, sides of the carbonaceous core nanoparticles of the crystalloid plate structure of FIG. 1A, and confirms that a thickness of the carbonaceous core nanoparticles of the crystalloid plate structure was about 10 nm. Accordingly, from FIG. 1B, it was confirmed that c (“c” is already defined above) of the carbonaceous core nanoparticles prepared as described above is about 10 nm.
A size distribution of the carbonaceous core nanoparticles was evaluated by using Melvern, Hydro2000. Regarding a or b (“a” and “b” are already defined above) of the carbonaceous core nanoparticles, it was confirmed that d10 is 2.1 micrometers, d50 is 4.11 micrometers, and d90 is 7.16 micrometers.
The carbonaceous core powder was loaded into a device for forming a round shape (product of Nara Machine Co., Ltd, model name: NHS), and then the device was driven at a rate of 13,500 rpm for 10 minutes to prepare a carbonaceous core.
The carbonaceous core was heat treated at a temperature of 1000° C. for 1 hour, thereby preparing a carbonaceous core having a surface with a cracked portion.
Preparation Example 2
A carbonaceous core was prepared in the same manner as in Preparation Example 1, except that Si particle powder having a particle size of 300 nm was added to the carbonaceous core powder.
Preparation Example 3
100 parts by weight of graphite (sp270, Japan graphite) was immersed in 30 parts by weight of a mixed solution including a sulfuric acid and acetic acid (a mole ratio of sulfuric acid:acetic acid=1:2) and stirred for 120 minutes, and expanded graphite and acidic powder were washed and separated by filtering under reduced pressure, thereby isolating the expanded graphite
The expanded graphite was expanded by heat treating at a temperature of 400° C. for 1 hour, gas generated therefrom was exhausted through an exhaust pipe, and the result was dispersed in ethanol and pulverized by using a homogenizer at a rate of 12,000 rpm for 10 minutes. The resultant mixture was additionally pulverized by using a micro fluidizer, filtered by using a filtering device, washed using ethanol, and then, dried in an oven at a temperature of 120° C., thereby preparing a carbonaceous core powder.
The carbonaceous core powder was loaded into a device for forming a round form (product of Nara Machine Co., Ltd, model name: NHS), and then the device was driven at a rate of 13,500 rpm for 10 minutes to prepare a carbonaceous core.
Comparative Preparation Example 1
A carbonaceous core was prepared in the same manner as in Preparation Example 1, except that graphite (MSG product) was used instead of carbonaceous core powder.
Comparative Preparation Example 2
A carbonaceous core was prepared in the same manner as in Preparation Example 1, except that instead of the carbonaceous core powder, 100 parts by weight of graphite (MSG product) was immersed in 30 parts by weight of a sulfuric acid and dried.
Comparative Preparation Example 3
A carbonaceous core was prepared in the same manner as in Preparation Example 1, except that instead of the carbonaceous core powder, needle cork (Nippon Steel Corporation, 25 μm) was heat treated in an inert gas atmosphere at a temperature of 1100° C. to remove impurities. 5 g of the needle cork source was placed in a reactor containing an aqueous solution including 37.5 g of sodium chlorate (NaClO3) and 150 mL of nitric acid (70%) and stirred at a temperature of 25° C. for 24 hours, followed by washing with distilled water to prepare oxidized graphite powder.
Preparation of Negative Active Material
Example 1
100 parts by weight of the carbonaceous core prepared according to Preparation Example 1 was treated with 20 parts by weight of a coal-tar pitch. The carbonaceous core having a surface on which the coal-tar pitch was formed was heat treated in an N2 atmosphere at a temperature of 1000° C. for 1 hour, thereby preparing a negative active material in which the coal-tar pitch having cracks was formed on a portion of the surface of the carbonaceous core.
FIGS. 2 and 3 show SEM images of the negative active material prepared according to Example 1. Referring to FIGS. 2 and 3, the negative active material is spherical or oval, and a portion of a surface of the negative active material has cracks.
FIG. 6 shows a transmission electron microscope (TEM) image of the negative active material. Referring to FIG. 6, it shows that the negative active material had voids.
FIG. 7 is a graph of a longer direction particle size dispersion of the negative active material measured by using Melvern, Hydro2000. Referring to FIG. 7, it was confirmed that the longer direction particle size of the negative active material, that is, d50, was 12 micrometers.
Example 2
A negative active material was prepared in the same manner as in Example 1, except that instead of the carbonaceous core prepared according to Preparation Example 1, the carbonaceous core prepared according to Preparation Example 2 was used.
Example 3
A negative active material was prepared in the same manner as in Example 1, except that instead of the carbonaceous core prepared according to Preparation Example 1, the carbonaceous core prepared according to Preparation Example 3 was used.
FIGS. 4 and 5 show SEM images of the negative active material. Referring to FIGS. 4 and 5, unlike those shown in the images of FIGS. 2 and 3, the negative active material has a smooth surface.
Comparative Example 1
A negative active material was prepared in the same manner as in Example 1, except that instead of the carbonaceous core prepared according to Preparation Example 1, the carbonaceous core prepared according to Comparative Preparation Example 1 was used.
Comparative Example 2
A negative active material was prepared in the same manner as in Example 1, except that instead of the carbonaceous core prepared according to Preparation Example 1, the carbonaceous core prepared according to Comparative Preparation Example 2 was used.
Comparative Example 3
A negative active material was prepared in the same manner as in Example 1, except that instead of the carbonaceous core prepared according to Preparation Example 1, the carbonaceous core prepared according to Comparative Preparation Example 3 was used.
Manufacture of Lithium Battery
Example 4
The negative active material prepared according to Example 1 as a negative active material was mixed with polyvinylidene fluoride as a binder at a weight ratio of 94:6 in an N-methylpyrrolidone solvent, thereby preparing a negative electrode slurry. The negative electrode slurry was coated to a thickness of 90 μm on a lithium foil, thereby forming a thin electrode plate, and then, the thin electrode plate was dried at a temperature of 135° C. for 3 hours or more, and then pressed to reduce the thickness of the thin electrode plate to 70 μm. The resultant electrode plate was punched to form a 13φ-sized circular specimen and then a weight of the specimen was recorded. Then, an electrode was formed to be appropriate for welding and then a weight thereof was recorded. The result was welded on a lower portion of a 2032 coin cell and then, exhausting was performed thereon in a vacuum oven at a temperature of 250° C. for 5 hours. Then, a lithium electrode (positive electrode), a polyethylene separator (Star 20) that had a thickness of 20 μm, and an electrolytic solution including 1.15M LiPF6 and a mixture including ethylene carbonate (EC), ethyl methyl carbonate (EMC) and diethyl carbonate (DEC) (volumetric ratio of EM:EMC:DEC was 3:3:4) were assembled to manufacture a battery (assembly density: 1.3 g/cc, thickness: 40 nm, L/L:4).
Example 5
A lithium battery was manufactured in the same manner as in Example 4, except that instead of the negative active material prepared according to Example 1, the negative active material prepared according to Example 2 was used.
Example 6
A lithium battery was manufactured in the same manner as in Example 4, except that instead of the negative active material prepared according to Example 1, the negative active material prepared according to Example 3 was used.
Comparative Example 4
A lithium battery was manufactured in the same manner as in Example 4, except that instead of the negative active material prepared according to Example 1, the negative active material prepared according to Comparative Example 1.
Comparative Example 5
A lithium battery was manufactured in the same manner as in Example 4, except that instead of the negative active material prepared according to Example 1, the negative active material prepared according to Comparative Example 2 was used.
Evaluation Example
Evaluation Example 1
Crystallinity Test (XRD Experiment
A XRD test was performed on each of the carbonaceous cores prepared according to Preparation Examples 1 and 2 and Comparative Preparation Examples 1 and 3, and results thereof are shown in FIG. 8A, 8B, and Table 1. The test was performed using a CuK-alpha characteristic X-ray wavelength of 1.541 Å.
A peak with respect to a surface (002) of each of the carbonaceous cores prepared according to Preparation Examples 1 and 2 and Comparative Preparation Examples 1 and 3 was identified, Bragg angle 2θ of and a full width at half maximum measured from the peak, and an interlayer spacing (d002) and a crystallite size measured from the full width at half maximum are shown in Table 1.












TABLE 1









Full width at
Crystallite



Bragg angle
Interlayer
half maximum
size



2θ (°)
spacing (Å)
(°)
(nm)




















Preparation
26.45
3.365
0.4
26.5


Example 1


Preparation
26.40
3.365
0.45
26.1


Example 2


Comparative
26.60
3.345
0.145
59.5


Preparation


Example 1


Comparative
13
6.9
0.43
18.1


Preparation


Example 3









Referring to the X-ray diffraction analysis results, the carbonaceous cores prepared according to Preparation Examples 1 and 2 have similar crystallinity to each other, and the crystallinity of the carbonaceous cores prepared according to Preparation Examples 1 and 2 is distinguished from the crystallinity of the carbonaceous cores prepared according to Comparative Preparation Examples 1 and 3.
Evaluation Example 2
Residual Sulfur Content Evaluation
A sulfur content of each of the negative active materials prepared according to Examples 1 and 3 and Comparative Examples 1 and 2 was measured by using an inductively coupled plasma mass spectrometry (ELAN DRC-e, Perkin Elmer product). Results thereof are shown in Table 2 below.









TABLE 2







Residual sulfur content (ppm)



















Example 1
1563



Example 3
607



Comparative
200



Example 1



Comparative
1500



Example 2










Referring to Table 2, it was confirmed that the sulfur content of the negative active material prepared according to Example 1 is greater than those of the negative active materials prepared according to Example 3 and Comparative Example 1.
Evaluation Example 3
High Rate Characteristics Evaluation
The lithium batteries manufactured according to Examples 4 and 6 and Comparative Examples 4 and 5 were left at room temperature (25° C.) for 20 hours, and then, a formation process was carried out by repeatedly performing a ring including 0.01 V constant current (CC)/constant voltage (CV) 0.01 C cut-off charging at a charge rate of 0.2 C and 1.5 V cut-off discharging at a discharge rate of 0.2 C.
Then, while the charge rate was maintained at 0.2 C, the discharge rate was changed to 0.2 C, 0.5 C, 1 C, 2 C, and 4 C and a capacity was evaluated. In this regard, discharge amounts at the respective discharge rates are relative values with respect to the discharge capacity during the formation process, and results thereof are shown in FIG. 10.
Referring to FIG. 10, it was confirmed that the lithium batteries manufactured according to Examples 4 and 6 retain excellent discharge characteristics even when the charge and discharge rate is increased. The lithium batteries manufactured according to Examples 4 and 6 exhibited much better high rate characteristics than those of the lithium batteries manufactured according to Comparative Examples 4 and 5.
As described above, according to the one or more of the above embodiments, a negative active material includes a carbonaceous material that has a plate structure with high crystallinity, and includes a core including the carbonaceous material, and an amorphous carbon layer disposed on a non-cracked portion of a surface of the core. Due to the inclusion of the carbonaceous material, a specific surface area is increased and thus lithium ions are easily intercalated and deintercalated. Accordingly, a lithium battery including the negative active material has improved input and output characteristics and high rate characteristics.
It should be understood that the example embodiments described therein should be considered in a descriptive sense only and not for purposes of limitation. Descriptions of features or aspects within each embodiment should typically be considered as available for other similar features or aspects in other embodiments.

## Claims

1. A negative active material comprising a carbonaceous material that has a peak with respect to a surface (002) at a Bragg angle 2θ of 26.4°±0.1° in an X-ray diffraction spectrum, has a full width at half maximum of the peak with respect to the surface (002) of from about 0.2° to about 0.6°, has an interlayer spacing (d002) of the surface (002) measured by X-ray diffraction of from about 3.36 Å to about 3.37 Å, and has a crystallite size measured from the full width at half maximum of the peak with respect to the surface (002) of from about 10 nm to about 45 nm.

2. The negative active material of claim 1, wherein the carbonaceous material has a crystalloid plate structure.

3. The negative active material of claim 1, wherein the negative active material comprises:
a core comprising a carbonaceous material; and
an amorphous carbon layer disposed on a non-cracked portion of a surface of the core.

4. The negative active material of claim 3, wherein the amorphous carbon layer is a pitch coating.

5. The negative active material of claim 3, wherein the negative active material is spherical or oval, and a longer direction particle size thereof d50 is from about 1 μm to about 40 μm.

6. The negative active material of claim 3, wherein the core comprises voids.

7. The negative active material of claim 3, wherein the core has cracks at a surface thereof extending from the voids present inside the core.

8. The negative active material of claim 7, wherein at least a portion of the voids comprises amorphous carbon.

9. The negative active material of claim 3, wherein a sulfur content of the core is from about 1000 ppm to about 2000 ppm.

10. The negative active material of claim 3, wherein a BET specific surface area of the negative active material is from about 10 m2/g to about 60 m2/g.

11. The negative active material of claim 3, wherein the negative active material further comprises metal nanoparticles.

12. The negative active material of claim 11, wherein the metal nanoparticles are selected from the group consisting of silicon (Si), tin (Sn), nickel (Ni), and a mixture thereof.

13. The negative active material of claim 11, wherein the size of the metal nanoparticles is from about 1 nm to about 500 nm.

14. A method of preparing a negative active material, the method comprising:
preparing a carbonaceous core;
forming cracks at a portion of a surface of the carbonaceous core; and
forming an amorphous carbon layer on the carbonaceous core having the cracked surface portion,
wherein the carbonaceous core has a peak with respect to a surface (002) at a Bragg angle 2θ of 26.4°±0.1° in an X-ray diffraction spectrum, has a full width at half maximum of the peak with respect to the surface (002) of from about 0.2° to about 0.6°, has an interlayer spacing (d002) of the surface (002) measured by X-ray diffraction of from about 3.36 Å to about 3.37 Å, and has a crystallite size measured from the full width at half maximum of the peak with respect to the surface (002) of from about 10 nm to about 45 nm.

15. The method of claim 14, wherein the preparing of the carbonaceous core comprises:
preparing a carbonaceous material having a crystalloid plate structure; and
forming the carbonaceous material in a spherical shape.

16. The method of claim 15, wherein the preparing of the carbonaceous core having the crystalloid plate structure comprises:
expanding graphite by using an expanding agent; and
heat treating the graphite.

17. The method of claim 16, wherein the expanding agent comprises at least one selected from the group consisting of a sulfuric acid, a nitric acid, a hydrochloric acid, an acetic acid, and a perchloric acid.

18. The method of claim 16, wherein an amount of the expanding agent is from about 1 to about 80 parts by weight based on 100 parts by weight of the graphite.

19. The method of claim 16, wherein the heat treatment is performed at a temperature of from about 200° C. to about 400° C.

20. The method of claim 14, wherein the forming of cracks at a portion of a surface of the carbonaceous core comprises heat treating at a temperature of from 800° C. to 1000° C.

21. The method of claim 14, wherein the forming of the amorphous carbon layer comprises heat treating at a temperature of from about 700° C. to about 2000° C.

22. A lithium battery comprising:
a positive electrode comprising a positive active material;
a negative electrode comprising a negative active material comprising a carbonaceous material that has a peak with respect to a surface (002) at a Bragg angle 2θ of 26.4°±0.1° in an X-ray diffraction spectrum, has a full width at half maximum of the peak with respect to the surface (002) of from about 0.2° to about 0.6°, has an interlayer spacing (d002) of the surface (002) measured by X-ray diffraction of from about 3.36 Å to about 3.37 Å, and has a crystallite size measured from the full width at half maximum of the peak with respect to the surface (002) of from about 10 nm to about 45 nm; and
an electrolytic solution interposed between the positive and negative electrodes.