Patent Application
20250183284
The present disclosure relates to a negative electrode active material, a negative electrode including the same, a secondary battery including the same and a method for preparing a negative electrode active material.
Recently, with the rapid spread of electronic devices using batteries such as mobile phones, notebook-sized computers, and electric vehicles, the demand for small and lightweight secondary batteries having relatively high capacity is rapidly increasing. In particular, lithium secondary batteries are lightweight and have high energy density, and thus have attracted attention as driving power sources for mobile devices. Accordingly, research and development efforts to improve the performance of lithium secondary batteries have been actively conducted.
In general, a lithium secondary battery includes a positive electrode, a negative electrode, a separator interposed between the positive electrode and the negative electrode, an electrolyte, an organic solvent and the like. Further, for the positive electrode and the negative electrode, an active material layer including each of a positive electrode active material and a negative electrode active material may be formed on a current collector. In general, lithium-containing metal oxides such as LiCoO2 and LiMn2O4 have been used as the positive electrode active material for the positive electrode, and lithium-free carbon-based active materials and silicon-based active materials have been used as the negative electrode active material for the negative electrode.
Among the negative electrode active materials, the silicon-based active material is attracting attention because the silicon-based active material has a high capacity and excellent high-speed charging characteristics compared to the carbon-based active material. However, the silicon-based active material has a disadvantage in that the initial efficiency is low because the degree of volume expansion/contraction due to charging/discharging is large and the irreversible capacity is large.
Meanwhile, among the silicon-based active materials, a silicon-based oxide, specifically, a silicon-based oxide represented by SiOx (0<x<2) has an advantage in that the degree of volume expansion/contraction due to charging/discharging is low compared to other silicon-based active materials such as silicon (Si). However, the silicon-based oxide still has a disadvantage in that the initial efficiency is lowered depending on the presence of the irreversible capacity.
In this regard, studies have been continuously conducted to reduce irreversible capacity and improve initial efficiency by doping or intercalating a metal such as Li, Al, and Mg into silicon-based oxides. However, in the case of a negative electrode slurry including a metal-doped silicon-based oxide as a negative electrode active material, there is a problem in that the metal oxide formed by doping the metal reacts with moisture to increase the pH of the negative electrode slurry and change the viscosity thereof, and accordingly, there is a problem in that the state of the prepared negative electrode becomes poor and the charge/discharge efficiency of the negative electrode is reduced.
Accordingly, there is a need for the development of a negative electrode active material capable of improving the phase stability of a negative electrode slurry including a silicon-based oxide and improving the charge/discharge efficiency of a negative electrode prepared therefrom.
The present disclosure relates to a negative electrode active material, a negative electrode including same, a secondary battery including same and a method for preparing a negative electrode active material.
An exemplary embodiment of the present disclosure provides a negative electrode active material including: silicon-based particles including SiOx (0<x<2) and a lithium (Li) compound; a first carbon layer on at least a part of a surface of the silicon-based particles; a second carbon layer on at least a part of a surface of the first carbon layer; lithium fluoride (LiF); and carbon fluoride (CFa, 0<a<4).
An exemplary embodiment of the present disclosure provides a negative electrode including the negative electrode active material.
An exemplary embodiment of the present disclosure provides a secondary battery including the negative electrode.
An exemplary embodiment of the present disclosure provides a method for preparing the negative electrode active material, the method including: forming silicon-based particles including SiOx (0<x<2) and a Li compound and having a first carbon layer formed on at least a part of a surface thereof; forming a second carbon layer on at least a part of a surface of the first carbon layer; and treating the silicon-based particles with a fluorine plasma.
A negative electrode active material according to an exemplary embodiment of the present disclosure includes: silicon-based particles including SiOx (0<x<2) and a Li compound; a first carbon layer on at least a part of a surface of the silicon-based particles; a second carbon layer on at least a part of a surface of the first carbon layer; LiF; and CFa (0<a<4), and there is an advantageous effect that water-based processability of an electrode slurry is improved when the negative electrode active material of the present disclosure is used. Specifically, LiF is hardly dissolved in water, and thus can efficiently passivate silicon-based particles in a water-based slurry, and LiF acts as an artificial SEI layer during driving a battery so as to provide an effect of improving service life performance of the battery. CFa (0<a<4) can suppress a reaction of moisture and a negative electrode active material in the water-based slurry by increasing hydrophobicity of the carbon layer, and thus, can effectively passivate the silicon-based particles.
In addition, since the negative electrode active material includes two carbon layers, passivation effect of particles can be improved by maximizing the hydrophobicity of the carbon layer during fluorine plasma treatment.
Therefore, a negative electrode including the negative electrode active material according to an exemplary embodiment of the present disclosure and a secondary battery including the negative electrode have an advantageous effect of improving discharge capacity, initial efficiency, resistance performance and/or service life characteristics of the battery.
Hereinafter, the present specification will be described in more detail.
When one part “includes” one constituent element in the present specification, unless otherwise specifically described, this does not mean that another constituent element is excluded, but means that another constituent element may be further included.
When one member is disposed “on” another member in the present specification, this includes not only a case where the one member is brought into contact with another member, but also a case where still another member is present between the two members.
Terms or words used in the specification should not be interpreted as being limited to typical or dictionary meaning and should be interpreted with a meaning and a concept which conform to the technical spirit of the present disclosure based on the principle that an inventor can appropriately define a concept of a term in order to describe his/her own invention in the best way.
Singular expressions of the terms used in the present specification include plural expressions unless they have definitely opposite meanings in the context.
In the present specification, the crystallinity of a structure included in a negative electrode active material may be confirmed by X-ray diffraction analysis, the X-ray diffraction analysis may be performed using an X-ray diffraction (XRD) analyzer (trade name: D4-endavor, manufacturer: Bruker), and in addition to the analyzer, an apparatus used in the art may be appropriately employed.
In the present specification, the presence or absence of an element and the content of the element in a negative electrode active material can be confirmed by ICP analysis, and the ICP analysis may be performed using an inductively coupled plasma atomic emission spectrometer (ICPAES, Perkin Elmer 7300).
In the present specification, an average particle diameter (D50) may be defined as a particle diameter corresponding to 50% of a cumulative volume in a particle size distribution curve (graph curve of the particle size distribution map) of the particles. The average particle diameter (D50) may be measured using, for example, a laser diffraction method. The laser diffraction method can generally measure a particle diameter of about several mm from the submicron region, and results with high reproducibility and high resolution may be obtained.
Hereinafter, preferred exemplary embodiments of the present disclosure will be described in detail. However, the exemplary embodiments of the present disclosure may be modified into various other forms, and the scope of the present disclosure is not limited to the exemplary embodiments which will be described below.
An exemplary embodiment of the present disclosure provides a negative electrode active material including: silicon-based particles including SiOx (0<x<2) and a Li compound; a first carbon layer provided on at least a part of a surface of the silicon-based particles; a second carbon layer provided on at least a part of a surface of the first carbon layer; LiF; and CFa (0<a<4).
The negative electrode active material according to an exemplary embodiment of the present disclosure includes silicon-based particles. The silicon-based particles include SiOx (0<x<2) and a Li compound.
The SiOx (0<x<2) may correspond to a matrix in the silicon-based particle. The SiOx (0<x<2) may be in a form including Si and/or SiO2, and Si may also form a phase. That is, “x” corresponds to a number ratio of O per Si included in SiOx (0<x<2). When the silicon-based particles include SiOx (0<x<2), a discharge capacity of a secondary battery may be improved.
The Li compound may correspond to a matrix in the silicon-based composite particle. The Li compound may be present in the form of at least one of a lithium atom, a lithium silicate, a lithium silicide, and a lithium oxide in the silicon-based particle. When the silicon-based particles include the Li compound, there is an effect that an initial efficiency is improved.
The Li compound is in a form in which the silicon-based particles are doped with the compound, and may be distributed on the surface and/or inside of the silicon-based particle. The Li compound is distributed on the surface and/or inside of the silicon-based particle, and thus may control the volume expansion/contraction of the silicon-based particles to an appropriate level, and may serve to prevent damage to the active material. Further, the Li compound may be contained in terms of reducing the ratio of the irreversible phase (for example, SiO2) of the silicon-based oxide particles to increase the efficiency of the active material.
In an exemplary embodiment of the present disclosure, the Li compound may be present in the form of a lithium silicate. The lithium silicate is represented by LiaSibOc (2≤a≤4, 0<b≤2, 2≤c≤5) and may be classified into crystalline lithium silicate and amorphous lithium silicate. The crystalline lithium silicate may be present in the form of at least one lithium silicate selected from the group consisting of Li2SiO3, Li4SiO4 and Li2Si2O5 in the silicon-based particles, and the amorphous lithium silicate may consist of a complex structure in the form of LiaSibOc (2≤a≤4, 0<b≤2, 2≤c≤5), and are not limited to the forms.
In an exemplary embodiment of the present disclosure, Li may be included in an amount of 0.1 parts by weight to 40 parts by weight or 0.1 parts by weight to 25 parts by weight based on total 100 parts by weight of the negative electrode active material. Specifically, the Li may be included in an amount of 1 part by weight to 25 parts by weight, more specifically 2 parts by weight to 20 parts by weight. There is a problem in that as the content of Li is increased, the initial efficiency is increased, but the discharge capacity is decreased, so that when the content satisfies the above range, appropriate discharge capacity and initial efficiency may be implemented.
The content of the Li element can be confirmed by ICP analysis. Specifically, after a predetermined amount (about 0.01 g) of the negative electrode active material is aliquoted, the negative electrode active material is completely decomposed on a hot plate by transferring the aliquot to a platinum crucible and adding nitric acid, hydrofluoric acid, or sulfuric acid thereto. Thereafter, a reference calibration curve is prepared by measuring the intensity of a standard liquid prepared using a standard solution (5 mg/kg) in an intrinsic wavelength of an element to be analyzed using an inductively coupled plasma atomic emission spectrometer (ICPAES, Perkin-Elmer 7300). Thereafter, a pre-treated sample solution and a blank sample are each introduced into the apparatus, an actual intensity is calculated by measuring each intensity, the concentration of each component relative to the prepared calibration curve is calculated, and then the contents of the elements of the prepared negative electrode active material may be analyzed by converting the total sum so as to be the theoretical value.
In an exemplary embodiment of the present disclosure, the silicon-based particles may include an additional metal atom. The metal atom may be present in the form of at least one of a metal atom, a metal silicate, a metal silicide, and a metal oxide in the silicon-based particle. The metal atom may include at least one selected from the group consisting of Mg, Li, Al and Ca. Accordingly, the initial efficiency of the negative electrode active material may be improved.
In an exemplary embodiment of the present disclosure, the silicon-based particles have a first carbon layer on at least a part of a surface thereof. In this case, the first carbon layer may be in the form of covering at least a portion of the surface, that is, partially covering the surface of the particle, or covering the entire surface of the particle. By the first carbon layer, conductivity is imparted to the negative electrode active material, and the initial efficiency, service life characteristics, and battery capacity characteristics of the secondary battery may be improved.
In an exemplary embodiment of the present disclosure, a second carbon layer may be formed on at least a part of a surface of the first carbon layer. When two carbon layers are provided as described above, reaction of the silicon-based particles or lithium by-products with water may be effectively prevented by passivating the particles more easily, and passivation characteristics may be improved by maximizing the hydrophobicity of the carbon layer during a fluorine plasma treatment.
In an exemplary embodiment of the present disclosure, the first carbon layer and the second carbon layer include amorphous carbon.
Furthermore, the first carbon layer and the second carbon layer may further include crystalline carbon.
The crystalline carbon may further improve the conductivity of the negative electrode active material. The crystalline carbon may include at least one selected from the group consisting of fullerene, carbon nanotubes, and graphene.
The amorphous carbon may suppress the expansion of the silicon-based particles by appropriately maintaining the strength of the carbon layer. The amorphous carbon may be a carbon-based material formed using a carbonized material of at least one selected from the group consisting of tar, pitch and other organic materials, or formed by depositing a hydrocarbon as a source of a chemical vapor deposition method.
The carbonized material of the other organic materials may be a carbonized material of sucrose, glucose, galactose, fructose, lactose, mannose, ribose, aldohexose, ketohexose or combinations thereof.
The hydrocarbon may be a substituted or unsubstituted aliphatic or alicyclic hydrocarbon, or a substituted or unsubstituted aromatic hydrocarbon. The aliphatic or alicyclic hydrocarbon of the substituted or unsubstituted aliphatic or alicyclic hydrocarbon may be methane, ethane, ethylene, acetylene, propane, butane, butene, pentane, isobutane, hexane, or the like. Examples of the aromatic hydrocarbon of the substituted or unsubstituted aromatic hydrocarbon include benzene, toluene, xylene, styrene, ethylbenzene, diphenylmethane, naphthalene, phenol, cresol, nitrobenzene, chlorobenzene, indene, coumarone, pyridine, anthracene, phenanthrene, or the like.
In an exemplary embodiment of the present disclosure, the first carbon layer and the second carbon layer may be an amorphous carbon layer.
In an exemplary embodiment of the present disclosure, the total content of the first carbon layer and the second carbon layer may be 1 part by weight to 50 parts by weight, 1 part by weight to 30 parts by weight, or 1 part by weight to 20 parts by weight, based on 100 parts by weight of the negative electrode active material. More specifically, the total content may be 1 part by weight to 15 parts by weight, 2 parts by weight to 10 parts by weight, 3 parts by weight to 7 parts by weight or 4 parts by weight to 6 parts by weight. When the above range is satisfied, it is possible to prevent a decrease in the capacity and efficiency of the negative electrode active material.
In an exemplary embodiment of the present disclosure, the first carbon layer may be included in an amount of 0.5 parts by weight to 5 parts by weight, 1 part by weight to 5 parts by weight, 2 parts by weight to 5 parts by weight, 2 parts by weight to 4.5 parts by weight or 2 parts by weight to 4 parts by weight, based on 100 parts by weight of the negative electrode active material. More specifically, the first carbon layer may be included in an amount of 3 parts by weight to 4 parts by weight. When the above range is satisfied, it is possible to prevent a decrease in the capacity and efficiency of the negative electrode active material.
In an exemplary embodiment of the present disclosure, the second carbon layer may be included in an amount of 0.5 parts by weight to 5 parts by weight, 1 part by weight to 5 parts by weight, specifically 1.5 parts by weight to 3 parts by weight, and more specifically 2 parts by weight to 3 parts by weight, based on 100 parts by weight of the negative electrode active material. When the above range is satisfied, it is possible to prevent a decrease in the capacity and efficiency of the negative electrode active material and effectively passivate the negative electrode active material.
In an exemplary embodiment of the present disclosure, each of the first carbon layer and the second carbon layer may have a thickness of 1 nm to 500 nm, specifically 5 nm to 300 nm. When the above range is satisfied, the conductivity of the negative electrode active material is improved, the volume change of the negative electrode active material is readily suppressed, and side reactions between an electrolyte solution and the negative electrode active material are suppressed, so that there is an effect that the initial efficiency and/or service life of a battery is/are improved.
Specifically, the carbon layer may be formed by a chemical vapor deposition (CVD) method using at least one hydrocarbon gas selected from the group consisting of methane, ethane and acetylene.
In an exemplary embodiment of the present disclosure, the negative electrode active material may include lithium fluoride (LiF) and carbon fluoride (CFa, 0<a<4).
Specifically, after the first carbon layer is formed on the at least a part of a surface of the silicon-based particles and the second carbon layer is formed on the at least a part of a surface of the first carbon layer during the preparation of the negative electrode active material, F may be introduced into the surface of silicon-based particles provided with the two carbon layers through fluorine plasma treatment. In this process, LiF may be formed by introducing F into a lithium by-product generated when the silicon-based particles are doped with Li, and F may be introduced into the carbon of a carbon layer provided on the surface of the silicon-based particles and the resulting product may be present in the form of CFa (0<a<4).
LiF formed as described above is hardly soluble in water and can efficiently passivate the silicon-based particles in a water-based slurry and can prevent the Li compound included in the silicon-based particles from being eluted and the slurry from becoming basic, and thereby providing an effect of improving the water-based processability of the slurry. In addition, LiF acts as an artificial SEI layer during driving a battery to have an effect of improving service life performance of the battery.
In an exemplary embodiment of the present disclosure, the negative electrode active material may comprise LiF and CFa (0<a<4) provided on the silicon-based particles.
In an exemplary embodiment of the present disclosure, LiF and CFa (0<a<4) may be provided on the outermost surface of the negative electrode active material.
LiF may be provided on the surface of the silicon-based particles, inside the first carbon layer, on the surface of the first carbon layer, inside the second carbon layer, or on the surface of the second carbon layer. Specifically, LiF may be provided on at least a part of the first or second carbon layer, or on at least a part on a region in which the first or second carbon layer is not provided on the surface of the silicon-based particles. LiF may be formed at a position where lithium by-products or lithium silicate are or is present in the negative electrode active material, but is not limited thereto.
LiF may be in the form of being partially coated on the surface or being coated on the entire surface. Examples of a shape of the LiF include an island type, a thin film type, or the like, but the shape of the LiF is not limited thereto.
Further, LiF may be provided on the surface of the silicon-based particles by introducing F into the Li compound included in the silicon-based particles.
CFa (0<a<4) may be provided inside the first carbon layer, on the surface of the first carbon layer, inside the second carbon layer, or on the surface of the second carbon layer.
Specifically, CFa (0<a<4) is formed by introducing F into the surface of the first or second carbon layer, and has a structure including a C—F bond. That is, CFa (0<a<4) may be located inside the first or second carbon layer, or located on the surface of the first or second carbon layer, and specifically, may be mainly located near the surface of the second carbon layer.
F is introduced into the surface of the first or second carbon layer to form CFa (0<a<4), so that it is possible to effectively passivate particles because the overall hydrophobicity of the carbon layer is increased to suppress a reaction of moisture and a negative electrode active material in a water-based slurry.
In an exemplary embodiment of the present disclosure, the negative electrode active material may further include silicon fluoride (SiFb, 0<b<4). When F is introduced to the surface of the silicon-based particles through fluorine plasma treatment, F may also be introduced into the silicon-based particles, and may be present in the form of SiFb (0<b<4) by forming Si—F bonds with the silicon inside the particles. The SiFb (0<b<4) may be located inside the silicon-based particles or may be located on the surface of the silicon-based particles, and specifically, may be mainly located near the surface of the silicon-based particles.
Components included in the negative electrode active material may be confirmed through X-ray diffraction analysis (XRD) or X-ray photoelectron spectroscopy (XPS).
In the present disclosure, the content (atomic percentage, at %) and atomic ratio of the element on the surface of the negative electrode active material can be confirmed through XPS (Nexsa ESCA System, Thermo Fisher Scientific (ESCA-02)).
Specifically, after a survey scan spectrum and a narrow scan spectrum are obtained for each sample, the survey scan spectrum and the narrow scan spectrum may be obtained while performing a depth profile. The depth profile may be performed up to 3000 seconds using monatomic Ar ions, and the measurement and data processing conditions are as follows.
In an exemplary embodiment of the present disclosure, the depth profile of the X-ray photoelectron spectroscopy (XPS) may be measured by performing the spectroscopy under the X-ray source of the monochromated Al K α at 0.09 nm/s for up to 3000 seconds.
In an exemplary embodiment of the present disclosure, Li, Si, C, N, O, or F may be detected during the analysis of the negative electrode active material by X-ray photoelectron spectroscopy.
Hereinafter, the content of elements by X-ray photoelectron spectroscopy is based on the total 100 at % of the total elements measured based on 100s, where the “100s” is a time period of 100 seconds spent collecting data, i.e., the duration for which the electrons emitted from the sample are collected by the detector to accumulate the signal.
In an exemplary embodiment of the present disclosure, the content of F may be 10 at % or more according to a surface analysis of the negative electrode active material by X-ray photoelectron spectroscopy, and the content of Li may be less than 10 at %.
Specifically, the content of F may be 10 at % or more and 50 at % or less, 15 at % or more and 40 at % or less, 20 at % or more and 40 at % or less, or 25 at % or more and 35 at % or less, or 20 at % or more and 30 at % or less. The lower limit of the content of F may be 10 at %, 15 at %, 20 at %, 22 at %, 24 at %, or 25 at %, and the upper limit thereof may be 50 at %, 45 at %, 40 at %, 35 at %, or 33 at %.
When the F element satisfies the aforementioned content on the surface of the negative electrode active material, there is an effect that F can be sufficiently introduced into the negative electrode active material to remove lithium by-products and effectively introduce F into the carbon layer, and the water-based processability is improved by preventing the negative electrode active material in the aqueous slurry from reacting with moisture or lithium by-products from being eluted.
When the content of F is equal to or more than the lower limit of the above range, a passivation effect may appear because the amount of F introduced to the surface of the negative electrode active material is appropriate, and when the content of F is equal to or less than the upper limit of the above range, it is possible to prevent a decrease in viscosity by preventing the generation of a large number of unstable F bonds such as C—F and Si—F to suppress the generation of HF in the water-based slurry and the decomposition of components such as CMC by HF.
In an exemplary embodiment of the present disclosure, the content of Li may be less than 10 at % according to a surface analysis of the negative electrode active material by X-ray photoelectron spectroscopy. Specifically, the content of Li may be 0.1 at % or more and less than 10 at %, 0.5 at % or more and 7 at % or less, 1 at % or more and 5 at % or less, 1 at or more and 3 at % or less, or 1.5 at % or more and 2.5 at % or less. The lower limit of the content of Li may be 0.1 at %, 0.5 at %, 1 at %, 1.5 at %, or 2 at %, and the upper limit thereof may be 9.9 at %, 7 at %, 5 at %, 4 at %, 3 at %, or 2.5 at %.
When the Li element on the surface of the negative electrode active material satisfies the content described above, a second carbon layer is uniformly formed, so that when the second carbon layer is applied to water-based processes, there is an effect of suppressing gas generation by minimizing contact with water. When the content of Li is equal to or more than the lower limit of the above range, an appropriately formed carbon layer acts as a resistor for lithium diffusion during the operation of a battery to prevent the performance of the battery from deteriorating, and when the content of Li is equal to or less than the upper limit of the above range, a uniform carbon layer is formed, so that gas generation during water-based processes is suppressed because a large amount of Li is exposed to the surface.
In an exemplary embodiment of the present disclosure, the content of Si may be 7 at % or less according to a surface analysis of the negative electrode active material by X-ray photoelectron spectroscopy. Specifically, the content of Si may be 0.1 at % or more and 7 at % or less, 0.5 at % or more and 5 at % or less, 1 at % or more and 4 at % or less, 1.5 at % or more and 3.5 at % or less, or 1.5 at % or more and 3 at % or less. The lower limit of the content of Si may be 0.1 at %, 0.5 at %, 1 at %, or 1.5 at %, and the upper limit thereof may be 7 at %, 5 at %, 4 at %, 3.5 at %, or 3 at %.
When the Si element on the surface of the negative electrode active material satisfies the content described above, an appropriately uniform carbon layer is formed, so that contact with water is minimized because Si is not exposed, thereby having an effect of improving water-based processability. When the content of Si is equal to or more than the lower limit of the above range, it is possible to prevent the deterioration in battery performance due to other components other than Si present on the surface acting as a resistor during battery operation, and when the content is equal to or less than the upper limit of the above range, gas generation due to the contact of Si with water may be prevented.
In an exemplary embodiment of the present disclosure, the content of C may be 50 at % or more according to a surface analysis of the negative electrode active material by X-ray photoelectron spectroscopy. Specifically, the content of C may be 50 at % or more and 80 at % or less, 55 at % or more and 75 at % or less, 55 at % or more and 70 at % or less, or 60 at % or more and 70 at % or less. The lower limit of the content of C may be 50 at %, 55 at %, or 60 at %, and the upper limit thereof may be 80 at %, 75 at %, or 70 at %.
When the C element on the surface of the negative electrode active material satisfies the content described above, a uniform carbon layer is formed, so that there is an effect of alleviating gas generation due to a passivation effect. When the content of C is equal to or less than the lower limit of the above range, the uniformity is increased, so that the chance of contact with water is lowered, and gas generation in water-based processes is prevented, and when the content is equal to or less than the upper limit of the above range, it is possible to prevent the deterioration in battery performance due to an excessive increase in resistance during battery operation with an appropriate amount of carbon layer, and it is also possible to prevent gas generation due to the contact of Si with water.
In an exemplary embodiment of the present disclosure, the content of 0 may be 15 at % or less according to a surface analysis of the negative electrode active material by X-ray photoelectron spectroscopy. Specifically, the content of O may be 0.1 at % or more and 15 at % or less, 0.1 at % or more and 10 at % or less, 0.3 at % or more and 5 at % or less, 0.3 at % or more and 3 at % or less, or 0.5 at % or more and 2.5 at % or less. The lower limit of the content of O may be 0.1 at %, 0.3 at %, 0.5 at %, 0.7 at %, or 0.8 at %, and the upper limit thereof may be 15 at %, 10 at %, 5 at %, 3 at %, or 2.5 at %.
When the O element on the surface of the negative electrode active material satisfies the content described above, an appropriate amount of F is introduced to reduce 0, thereby increasing the non-hydrophilicity of the surface, so that there is an effect of suppressing gas generation in water-based processes because the contact with water is blocked to maximize the passivation effect. When the content of O is equal to or more than the lower limit of the above range, it is possible to suppress the generation of HF due to the bonding of unstable F elements, thereby preventing a rapid decrease in viscosity by suppressing the decomposition reaction of materials such as CMC in the slurry. When the content of O is equal to or less than the upper limit of the above range, the hydrophilicity is reduced, so that gas generation may be prevented because the surface does not easily react with water.
When the negative electrode active material of the present disclosure satisfies the above element content range, F is sufficiently introduced into the negative electrode active material, so that lithium by-products are easily removed, and simultaneously, LiF is formed, and F is effectively introduced into the carbon layer to form CFa, and there is an effect that the water-based processability is improved by preventing the negative electrode active material in the water-based slurry from reacting with moisture or lithium by-products from being eluted because the amounts of LiF and CFa produced are appropriate.
In an exemplary embodiment of the present disclosure, an atomic ratio of F relative to O (F/O ratio) may be 1 or more according to a surface analysis of the negative electrode active material by X-ray photoelectron spectroscopy. Specifically, the atomic ratio may be 1 or more and 50 or less, 5 or more and 50 or less, or 10 or more and 40 or less. When the above range is satisfied, F is appropriately introduced into the surface of the negative electrode active material to easily form LiF and CFa, so that there is an effect that slurry processability and service life performance are remarkably improved because silicon-based particles are easily passivated in the slurry and LiF acts as an artificial SEI layer during the driving of the battery. When the content is equal to or more than the lower limit of the above range, the content is advantageous in a passivation effect because the amount of F introduced to the surface of the negative electrode active material is sufficient, and when the content is equal to or less than the upper limit of the above range, it is possible to prevent a remarkable decrease in viscosity by preventing the generation of a large number of unstable F bonds such as C—F and Si—F to suppress the generation of HF in the water-based slurry and the decomposition of components such as CMC in the slurry by HF.
In an exemplary embodiment of the present disclosure, an atomic ratio of C relative to Li (C/Li ratio) may be more than 10 according to a surface analysis of the negative electrode active material by X-ray photoelectron spectroscopy. Specifically, the atomic ratio may be 15 or more and 50 or less, 20 or more and 40 or less, or 25 or more and 35 or less. When the above range is satisfied, the content of LiF and CFa located on the surface of the negative electrode active material is appropriate, so that there is an effect that slurry processability and service life performance are remarkably improved because silicon-based particles may be easily passivated in the slurry and LiF acts as an artificial SEI layer during the driving of the battery. When the atomic ratio is equal to or more than the lower limit of the above range, the carbon layer may be appropriately formed and may prevent a deterioration in battery performance as the carbon layer serves as a resistor for lithium diffusion during battery operation, and when the atomic ratio is equal to or less than the upper limit of the above range, the uniformity of the carbon layer is increased, so that it is possible to prevent gas generation in water-based processes as a large amount of Li is exposed to the surface.
In an exemplary embodiment of the present disclosure, the negative electrode active material may satisfy the following Equation A.
In Equation A, each element content is from a surface analysis of the negative electrode active material by X-ray photoelectron spectroscopy, and is based on a total of 100 at % of all elements measured based on 100s.
Specifically, the {(content of F element)×(content of C element)}/{(content of Li element)×(content of Si element)×(content of 0 element)} may be 50 or more, 80 or more, 100 or more, or 120 or more, and may be 1000 or less, 800 or less, 700 or less, or 600 or less.
When the above range is satisfied, the content of CFa (0<a<4) including C—F bonds on the surface of the negative electrode active material is increased, so that the passivation effect of the particles may be excellent because the hydrophobicity of the carbon layer is maximized.
In an exemplary embodiment of the present disclosure, the content of CFa (0<a<4) may be higher than the content of LiF. In general, during the process of forming the first carbon layer on the silicon-based particles, and then doping the silicon-based particles with lithium, the lithium by-products are mainly present on the first carbon layer. Thereafter, when a second carbon layer is provided on the first carbon layer, and then the silicon-based particles are treated with fluorine plasma, the content of CFa (0<a<4) may be higher than the content of LiF because F is preferentially introduced into the carbon layer. When the content of CFa (0<a<4) is higher than the content of LiF as described above, the hydrophobicity of the carbon layer is maximized, so that the passivation effect of particles may be excellent.
In an exemplary embodiment of the present disclosure, a lithium by-product may be present on the silicon-based particles. Specifically, the lithium by-product may be present on the surface of the silicon-based particles or present on the surface of the carbon layer.
Specifically, the lithium by-product may mean a lithium compound remaining near the surface of the silicon-based particles or the carbon layer after preparing the silicon-based particles. As described above, even after the acid treatment process, a lithium by-product which has not been reacted with the acid may remain.
The lithium by-product may include one or more selected from the group consisting of Li2O, LiOH and Li2CO3. As in the above-described reaction, LiF may be formed in the lithium by-products during the fluorine plasma treatment, and unreacted lithium by-products may be present on the silicon-based particles.
Whether the lithium by-product is present can be confirmed through X-ray diffraction analysis (XRD) or X-ray photoelectron spectroscopy (XPS).
The lithium by-product may be included in an amount of 5 parts by weight or less based on total 100 parts by weight of the negative electrode active material. Specifically, the lithium by-product may be included in an amount of 0.01 parts by weight to 5 parts by weight, 0.05 parts by weight to 2 parts by weight, or 0.1 parts by weight to 1 part by weight. More specifically, the lithium by-product may be included in an amount of 0.1 parts by weight to 0.8 parts by weight or 0.1 parts by weight to 0.5 parts by weight. When the content of the lithium by-product satisfies the above range, side reactions in the slurry may be reduced, and the water-based processability may be improved by lowering the change in viscosity. When the content is equal to or less than the upper limit of the above range, it is possible to minimize the occurrence of water-based processability problems due to the occurrence of side reactions or the changes in viscosity by preventing the slurry from becoming basic during formation of the slurry.
For the content of the lithium by-product, the amount of the lithium by-product may be calculated after measuring the amount of a HCl solution in a specific interval where the pH changes during the process of titrating an aqueous solution including the negative electrode active material with the HCl solution using a titrator.
The negative electrode active material may have an average particle diameter (D50) of 0.1 μm to 30 μm, specifically 1 μm to 20 μm, and more specifically 1 μm to 10 μm. When the above range is satisfied, the active material during charging and discharging is ensured to be structurally stable, and it is possible to prevent a problem in that the volume expansion/contraction level also becomes large as the particle diameter is excessively increased, and to prevent a problem in that the initial efficiency is reduced because the particle diameter is excessively small.
The negative electrode active material may have a BET specific surface area of 1 m2/g to 100 m2/g, specifically 1 m2/g to 70 m2/g, more specifically 1 m2/g to 50 m2/g, and for example, 2 m2/g to 30 m2/g. When the above range is satisfied, side reactions with an electrolyte solution during the charging and discharging of a battery may be reduced, so that the service life characteristics of the battery may be improved.
An exemplary embodiment of the present disclosure provides a method for preparing the negative electrode active material, the method including: forming silicon-based particles including SiOx (0<x<2) and a Li compound and having a first carbon layer provided on at least a part of the surface thereof; providing a second carbon layer on at least a part of the first carbon layer; and treating the silicon-based particles with fluorine plasma.
The silicon-based particles may be formed through forming preliminary particles by heating and vaporizing a Si powder and a SiO2 powder under vacuum, and then depositing the vaporized mixed gas; forming a carbon layer on a surface of the formed preliminary particles; and mixing the preliminary particles on which the carbon layer is formed with a Li powder, and then heat-treating the resulting mixture.
Specifically, the mixed powder of the Si powder and the SiO2 powder may be heat-treated at 1300° C. to 1800° C., 1400° C. to 1800° C. or 1400° C. to 1600° C. under vacuum.
The formed preliminary particles may have a form of SiO.
The first carbon layer may be formed using a chemical vapor deposition (CVD) method using a hydrocarbon gas or by a method of carbonizing a material which is a carbon source.
Specifically, the first carbon layer may be formed by introducing the formed preliminary particles into a reaction furnace, and then subjecting a hydrocarbon gas to chemical vapor deposition (CVD) at 600 to 1,200° C. The hydrocarbon gas may be at least one hydrocarbon gas selected from the group including methane, ethane, propane and acetylene, and may be heat-treated at 900° C. to 1,000° C.
The mixing of the preliminary particles on which the first carbon layer is formed with the Li powder, and then heat-treating of the resulting mixture may be performed at 700° C. to 900° C. for 4 hours to 6 hours, and specifically at 800° C. for 5 hours.
The silicon-based particles may include a Li silicate, a Li silicide, a Li oxide, or the like as the above-described Li compound.
The particle size of the silicon-based particles may be adjusted by a method such as a ball mill, a jet mill, or an air current classification, and the method is not limited thereto.
A lithium compound (lithium by-product) is provided on at least a part of the surface of the silicon-based particles provided with the first carbon layer as described above. Specifically, in the process of preparing the above-described silicon-based particles by forming the preliminary particles including SiOx (0<x<2), forming a first carbon layer on the preliminary particles, and then doping the preliminary particles with Li, a lithium compound, which is a lithium by-product formed by unreacted lithium, remains near the surface of the silicon-based particles.
In an exemplary embodiment of the present disclosure, the method for preparing a negative electrode active material includes providing a second carbon layer on at least a part of a surface of the first carbon layer.
The second carbon layer may be formed using a chemical vapor deposition (CVD) method using a hydrocarbon gas or by a method of carbonizing a material which is a carbon source.
Specifically, the second carbon layer may be formed by introducing the preliminary particles provided with the first carbon layer into a reaction furnace, and then subjecting a hydrocarbon gas to chemical vapor deposition (CVD) at less than 800° C. The hydrocarbon gas may be at least one hydrocarbon gas selected from the group including methane, ethane, propane and acetylene, and may be heat-treated at 600° C. to less than 800° C. for 2 hours to 4 hours. For example, the forming of the second carbon layer may be performed under heat-treatment conditions of 700° C. and 3 hours in an acetylene or propane gas atmosphere.
By performing a heat treatment at less than 800° C. as described above to enhance the degree of amorphization of the second carbon layer, the second carbon layer may be formed. Since the remaining lithium by-product may be effectively covered by enhancing the degree of amorphization of the second carbon layer, there is an effect of minimizing the side reaction with moisture and there is an effect that the rapid charging performance is improved. Conversely, when the degree of amorphization of the second carbon layer is low, that is, the degree of crystallization is high, the size of Si crystal grains is increased because carbon coating is performed at a relatively high temperature, so that there is a disadvantage in that the service life performance deteriorates.
By forming two carbon layers as described above, side reactions caused by unreacted lithium compounds may be suppressed, and the hydrophobicity of the carbon layer may be maximized when fluorine is introduced in the fluorine plasma step to be described below.
In an exemplary embodiment of the present disclosure, the method for preparing the negative electrode active material includes treating the silicon-based particles with fluorine plasma.
The treating of the silicon-based particles with fluorine plasma includes: putting the silicon-based particles into a plasma chamber, and then injecting CF4 gas into the plasma chamber; increasing pressure in the plasma chamber; and forming a plasma in the plasma chamber.
The plasma treatment may be performed using an RF plasma.
Specifically, the pressure in the chamber may be adjusted to 0.01 torr to 0.1 torr before injecting the CF4 gas into the chamber. Preferably, the pressure may be adjusted to 0.05 torr to 0.09 torr or 0.07 torr.
Thereafter, in the increasing of the pressure in the chamber, the pressure in the chamber may be adjusted to 0.1 torr to 0.5 torr. Specifically, the pressure may be adjusted to 0.15 torr to 0.3 torr or 0.2 torr.
The forming of the plasma in the chamber may be performed by applying power to the chamber. Specifically, the power may be 50 W to 300 W, 80 W to 250 W or 100 W to 200 W.
The plasma may be maintained for 1 minute to 10 minutes. Preferably, the power may be maintained for 3 minutes to 8 minutes, 5 minutes to 7 minutes or 6 minutes.
When the plasma treatment is performed while satisfying the above range, F may be introduced into the negative electrode active material in an appropriate content.
After F is introduced into the negative electrode active material by forming plasma in the chamber, vacuum is released at normal pressure, and then the sample may be collected.
The fluorine plasma treatment step may be repeated two or more times, preferably twice.
When F is introduced into the negative electrode active material by a dry method using plasma as in the present disclosure, the lithium inside the silicon-based particles including the Li compound is not dissolved, thereby further improving passivation characteristics. In contrast, when F is introduced by a method such as hydrothermal synthesis or solvothermal synthesis, the surface of the silicon-based particles becomes porous, thereby reducing the passivation effect.
As described above, through the fluorine plasma treatment, there is an effect that F is introduced into the lithium by-products formed during doping of silicon-based particles with lithium to form LiF, and the formed LiF easily blocks the reaction between water and the lithium compound or silicon-based particles, and acts as an artificial SEI layer during the driving of the battery to improve service life performance.
Furthermore, F is introduced into the surface of the carbon layer to form CFa (0<a<4), so that it is possible to effectively passivate particles because the hydrophobicity of the carbon layer is increased to suppress a reaction of moisture and a negative electrode active material in a water-based slurry.
The negative electrode according to an exemplary embodiment of the present disclosure may include the above-described negative electrode active material.
Specifically, the negative electrode may include a negative electrode current collector and a negative electrode active material layer disposed on the negative electrode current collector. The negative electrode active material layer may include the negative electrode active material. Furthermore, the negative electrode active material layer may further include a binder, a thickener and/or a conductive material.
The negative electrode active material layer may be formed by applying a negative electrode slurry including a negative electrode active material, a binder, a thickener and/or a conductive material to at least one surface of a current collector and drying and rolling the current collector.
The negative electrode slurry may further include an additional negative electrode active material.
As the additional negative electrode active material, a compound capable of reversible intercalation and deintercalation of lithium may be used. Specific examples thereof include a carbonaceous material such as artificial graphite, natural graphite, graphitized carbon fiber, and amorphous carbon; a metallic compound alloyable with lithium such as Si, Al, Sn, Pb, Zn, Bi, In, Mg, Ga, Cd, a Si alloy, a Sn alloy, or an Al alloy; a metal oxide which may be undoped and doped with lithium such as SiOβ (0<β<2), SnO2, vanadium oxide, lithium titanium oxide, and lithium vanadium oxide; or a composite including the metallic compound and the carbonaceous material such as a Si—C composite or a Sn—C composite, and the like, and any one thereof or a mixture of two or more thereof may be used. Furthermore, a metallic lithium thin film may be used as the negative electrode active material. Alternatively, both low crystalline carbon and high crystalline carbon, and the like may be used as the carbon material. Typical examples of the low crystalline carbon include soft carbon and hard carbon, and typical examples of the high crystalline carbon include irregular, planar, flaky, spherical, or fibrous natural graphite or artificial graphite, Kish graphite, pyrolytic carbon, mesophase pitch-based carbon fibers, meso-carbon microbeads, mesophase pitches, and high-temperature fired carbon such as petroleum or coal tar pitch derived cokes.
The additional negative electrode active material may be a carbon-based negative electrode active material.
In an exemplary embodiment of the present disclosure, a weight ratio of the negative electrode active material and the additional negative electrode active material included in the negative electrode slurry may be 10:90 to 90:10, specifically 10:90 to 50:50.
The negative electrode slurry may include a solvent for forming a negative electrode slurry. Specifically, the solvent for forming a negative electrode slurry may include at least one selected from the group consisting of distilled water, ethanol, methanol, and isopropyl alcohol, specifically distilled water in terms of facilitating the dispersion of the components.
A negative electrode slurry including the negative electrode active material according to an exemplary embodiment of the present disclosure may have a pH of 7 to 11 at 25° C. When the pH of the negative electrode slurry satisfies the above range, there is an effect that the rheological properties of the slurry are stabilized. In contrast, when the pH of the negative electrode slurry is less than 7 or exceeds 11, there is a problem in that carboxymethyl cellulose (CMC) used as a thickener is decomposed, resulting in a decrease in the viscosity of the slurry and a deterioration in the degree of dispersion of the active material included in the slurry.
The negative electrode current collector is sufficient as long as the negative electrode current collector has conductivity without causing a chemical change to the battery, and is not particularly limited. For example, as the current collector, it is possible to use copper, stainless steel, aluminum, nickel, titanium, fired carbon, or aluminum or stainless steel whose surface is treated with carbon, nickel, titanium, silver, and the like. Specifically, a transition metal, such as copper or nickel which adsorbs carbon well, may be used as a current collector. Although the current collector may have a thickness of 6 μm to 20 μm, the thickness of the current collector is not limited thereto.
The binder may include at least one selected from the group consisting of a polyvinylidene fluoride-hexafluoropropylene copolymer (PVDF-co-HFP), polyvinylidene fluoride, polyacrylonitrile, polymethylmethacrylate, polyvinyl alcohol, carboxymethyl cellulose (CMC), starch, hydroxypropyl cellulose, regenerated cellulose, polyvinylpyrrolidone, polytetrafluoroethylene, polyethylene, polypropylene, polyacrylic acid, an ethylene-propylene-diene monomer (EPDM), a sulfonated EPDM, styrene butadiene rubber (SBR), fluorine rubber, polyacrylic acid and a material in which the hydrogen thereof is substituted with Li, Na, Ca, or the like, and may also include various copolymers thereof.
The conductive material is not particularly limited as long as the conductive material has conductivity without causing a chemical change to the battery, and for example, it is possible to use graphite such as natural graphite or artificial graphite; carbon black such as acetylene black, Ketjen black, channel black, furnace black, lamp black, and thermal black; a conductive fiber such as carbon fiber or metal fiber; a conductive tube such as a carbon nanotube; a metal powder such as a fluorocarbon powder, an aluminum powder, and a nickel powder; a conductive whisker such as zinc oxide and potassium titanate; a conductive metal oxide such as titanium oxide; a conductive material such as polyphenylene derivatives, and the like.
The thickener may be carboxymethyl cellulose (CMC) and is not limited thereto, and a thickener used in the art may be appropriately employed.
In an exemplary embodiment of the present disclosure, a weight ratio of the negative electrode active material and the additional negative electrode active material included in the negative electrode slurry may be 1:99 to 30:70, specifically 5:95 to 30:70 or 10:90 to 20:80.
In an exemplary embodiment of the present disclosure, the entire negative electrode active material may be included in the negative electrode slurry in an amount of 60 parts by weight to 99 parts by weight, specifically 70 parts by weight to 98 parts by weight, based on total 100 parts by weight of the solid content of the negative electrode slurry.
In an exemplary embodiment of the present disclosure, the binder may be included in an amount of 0.5 parts by weight to 30 parts by weight, specifically 1 part by weight to 20 parts by weight, based on total 100 parts by weight of the solid content of the negative electrode slurry.
In an exemplary embodiment of the present disclosure, the conductive material may be included in an amount of 0.5 parts by weight to 25 parts by weight, specifically 1 part by weight to 20 parts by weight, based on total 100 parts by weight of the solid content of the negative electrode slurry.
In an exemplary embodiment of the present disclosure, the thickener may be included in an amount of 0.5 parts by weight to 25 parts by weight, specifically 0.5 parts by weight to 20 parts by weight, and more preferably 1 part by weight to 20 parts by weight based on total 100 parts by weight of the solid content of the negative electrode slurry.
The negative electrode slurry according to an exemplary embodiment of the present disclosure may further include a solvent for forming a negative electrode slurry. Specifically, the solvent for forming a negative electrode slurry may include at least one selected from the group consisting of distilled water, ethanol, methanol, and isopropyl alcohol, specifically distilled water in terms of facilitating the dispersion of the components.
In an exemplary embodiment of the present disclosure, the solid content weight of the negative electrode slurry may be 20 parts by weight to 75 parts by weight, specifically 30 parts by weight to 70 parts by weight, based on total 100 parts by weight of the negative electrode slurry.
A secondary battery according to an exemplary embodiment of the present disclosure may include the above-described negative electrode according to an exemplary embodiment. Specifically, the secondary battery may include the above-described negative electrode, a positive electrode, a separator between the positive electrode and the negative electrode, and an electrolyte solution. Since the negative electrode has been previously described, a specific description thereof will be omitted.
The positive electrode may include a positive electrode current collector and a positive electrode active material layer formed on the positive electrode current collector and including the positive electrode active material.
In the positive electrode, the positive electrode current collector is not particularly limited as long as the positive electrode current collector has conductivity without causing a chemical change to the battery, and for example, it is possible to use stainless steel, aluminum, nickel, titanium, fired carbon, or aluminum or stainless steel whose surface is treated with carbon, nickel, titanium, silver, and the like. Further, the positive electrode current collector may typically have a thickness of 3 to 500 μm, and the adhesion of the positive electrode active material may also be enhanced by forming fine irregularities on the surface of the current collector. For example, the positive electrode current collector may be used in various forms such as a film, a sheet, a foil, a net, a porous body, a foam body, and a non-woven fabric body.
The positive electrode active material may be a typically used positive electrode active material. Specifically, the positive electrode active material includes: a layered compound such as lithium cobalt oxide (LiCoO2) and lithium nickel oxide (LiNiO2) or a compound substituted with one or more transition metals; a lithium iron oxide such as LiFe3O4; a lithium manganese oxide such as chemical formula Li1+c1Mn2-c1O4 (0≤c1≤0.33), LiMnO3, LiMn2O3, and LiMnO2; a lithium copper oxide (Li2CuO2); a vanadium oxide such as LiV3O8, V2O5, and Cu2V2O7; a Ni site type lithium nickel oxide expressed as chemical formula LiNi1-c2Mc2O2 (here, M is at least one selected from the group consisting of Co, Mn, Al, Cu, Fe, Mg, B and Ga, and c2 satisfies 0.01≤c2≤0.5); a lithium manganese composite oxide expressed as chemical formula LiMn2-c3Mc3O2 (here, M is at least any one selected from the group consisting of Co, Ni, Fe, Cr, Zn and Ta, and c3 satisfies 0.01≤c3≤0.1) or Li2Mn3MO8 (here, M is at least any one selected from the group consisting of Fe, Co, Ni, Cu and Zn); LiMn2O4 in which Li of the chemical formula is partially substituted with an alkaline earth metal ion, and the like, but is not limited thereto. The positive electrode may be Li-metal.
The positive electrode active material layer may include a positive electrode conductive material and a positive electrode binder together with the above-described positive electrode active material.
In this case, the positive electrode conductive material is used to impart conductivity to the electrode, and can be used without particular limitation as long as the positive electrode conductive material has electron conductivity without causing a chemical change to a battery to be constituted. Specific examples thereof include graphite such as natural graphite or artificial graphite; a carbon-based material such as carbon black, acetylene black, Ketjen black, channel black, furnace black, lamp black, thermal black, and carbon fiber; metal powder or metal fiber such as copper, nickel, aluminum, and silver; a conductive whisker such as zinc oxide and potassium titanate; a conductive metal oxide such as titanium oxide; or a conductive polymer such as a polyphenylene derivative, and any one thereof or a mixture of two or more thereof may be used.
Alternatively, the positive electrode binder serves to improve the bonding between positive electrode active material particles and the adhesion between the positive electrode active material and the positive electrode current collector. Specific examples thereof may include polyvinylidene fluoride (PVDF), a polyvinylidene fluoride-hexafluoropropylene copolymer (PVDF-co-HFP), polyvinyl alcohol, polyacrylonitrile, carboxymethyl cellulose (CMC), starch, hydroxypropyl cellulose, regenerated cellulose, polyvinylpyrrolidone, polytetrafluoroethylene, polyethylene, polypropylene, an ethylene-propylene-diene monomer (EPDM), a sulfonated EPDM, styrene-butadiene rubber (SBR), fluorine rubber, or various copolymers thereof, and any one thereof or a mixture of two or more thereof may be used.
The separator separates the negative electrode and the positive electrode and provides a passage for movement of lithium ions, and can be used without particular limitation as long as the separator is typically used as a separator in a secondary battery, and in particular, a separator having an excellent ability to retain moisture of an electrolyte solution as well as low resistance to ion movement in the electrolyte solution is preferable. Specifically, it is possible to use a porous polymer film, for example, a porous polymer film formed of a polyolefin-based polymer such as an ethylene homopolymer, a propylene homopolymer, an ethylene/butene copolymer, an ethylene/hexene copolymer, and an ethylene/methacrylate copolymer, or a laminated structure of two or more layers thereof. In addition, a typical porous non-woven fabric, for example, a non-woven fabric made of a glass fiber having a high melting point, a polyethylene terephthalate fiber, and the like may also be used. Furthermore, a coated separator including a ceramic component or a polymeric material may be used to secure heat resistance or mechanical strength and may be selectively used as a single-layered or multi-layered structure.
Examples of the electrolyte solution include an organic liquid electrolyte, an inorganic liquid electrolyte, a solid polymer electrolyte, a gel-type polymer electrolyte, a solid inorganic electrolyte, a molten-type inorganic electrolyte, and the like, which can be used in the preparation of a lithium secondary battery, but are not limited thereto.
Specifically, the electrolyte solution may include a non-aqueous organic solvent and a metal salt.
As the non-aqueous organic solvent, it is possible to use, for example, an aprotic organic solvent, such as N-methyl-2-pyrrolidinone, propylene carbonate, ethylene carbonate, butylene carbonate, dimethyl carbonate, diethyl carbonate, γ-butyrolactone, 1,2-dimethoxy ethane, tetrahydrofuran, 2-methyl tetrahydrofuran, dimethyl sulfoxide, 1,3-dioxolane, formamide, dimethylformamide, dioxolane, acetonitrile, nitromethane, methyl formate, methyl acetate, phosphate triester, trimethoxy methane, a dioxolane derivative, sulfolane, methyl sulfolane, 1,3-dimethyl-2-imidazolidinone, a propylene carbonate derivative, a tetrahydrofuran derivative, ether, methyl propionate, and ethyl propionate.
In particular, among the carbonate-based organic solvents, cyclic carbonates ethylene carbonate and propylene carbonate may be preferably used because the cyclic carbonates have high permittivity as organic solvents of a high viscosity and thus dissociate a lithium salt well, and such a cyclic carbonate may be more preferably used since the cyclic carbonate may be mixed with a linear carbonate of a low viscosity and low permittivity such as dimethyl carbonate and diethyl carbonate in an appropriate ratio and used to prepare an electrolyte solution having a high electric conductivity.
As the metal salt, a lithium salt may be used, the lithium salt is a material which is easily dissolved in the non-aqueous electrolyte solution, and for example, as an anion of the lithium salt, it is possible to use one or more selected from the group consisting of F−, Cl−, I−, NO3−, N(CN)2−, BF4−, ClO4−, PF6−, (CF3)2PF4−, (CF3)3PF3″, (CF3)4PF2−, (CF3)5PF−, (CF3)6P−, CF3SO3−, CF3CF2SO3−, (CF3SO2)2N−, (FSO2)2N−, CF3CF2(CF3)2CO−, (CF3SO2)2CH−, (SF5)3C−, (CF3SO2)3C−, CF3(CF2)7SO3−, CF3CO2−, CH3CO2−, SCN− and (CF3CF2SO2)2N−.
In the electrolyte solution, for the purpose of improving the service life characteristics of a battery, suppressing the decrease in battery capacity, and improving the discharge capacity of the battery, one or more additives, such as, for example, a halo-alkylene carbonate-based compound such as difluoroethylene carbonate, pyridine, triethylphosphite, triethanolamine, cyclic ether, ethylenediamine, n-glyme, hexamethyl phosphoric triamide, a nitrobenzene derivative, sulfur, a quinone imine dye, N-substituted oxazolidinone, N,N-substituted imidazolidine, ethylene glycol dialkyl ether, an ammonium salt, pyrrole, 2-methoxy ethanol, or aluminum trichloride may be further included in addition to the above electrolyte solution constituent components.
According to still another exemplary embodiment of the present disclosure, provided are a battery module including the secondary battery as a unit cell, and a battery pack including the same. The battery module and the battery pack include the secondary battery which has high capacity, high rate properties, and cycle properties, and thus, may be used as a power source of a medium-and-large sized device selected from the group consisting of an electric vehicle, a hybrid electric vehicle, a plug-in hybrid electric vehicle, and a power storage system.
After 94 g of a powder, in which Si and SiO2 were mixed at a molar ratio of 1:1, was mixed in a reaction furnace, the resulting mixture was heated under vacuum at a sublimation temperature of 1,400° C. Thereafter, a mixed gas of the vaporized Si and SiO2 was reacted in a cooling zone in a vacuum state having a cooling temperature of 800° C. and condensed into a solid phase. Next, particles having a size of 6 μm were prepared by pulverizing the aggregated particles using a ball mill for 3 hours. Thereafter, the particles were positioned in a hot zone of a CVD apparatus while maintaining an inert atmosphere by flowing Ar gas, and methane was blown into the hot zone at 900° C. using Ar as a carrier gas and reacted at 10-1 torr for 5 hours to form a first carbon layer on the particle surface. Thereafter, 6 g of Li metal powder was added to the carbon layer-formed particles and mixed, and then an additional heat treatment at a temperature of 800° C. in an inert atmosphere was performed to obtain silicon-based particles including a Li compound, on which the first carbon coating layer was formed on the surface thereof.
The silicon-based particles obtained above were placed in a reactor, and acetylene was blown into the hot zone of 700° C. using Ar as a carrier gas and allowed to react at 10-1 torr for 3 hours to obtain a silicon-based particle on which a second carbon layer was formed on the surface thereof.
After 10 g of the silicon-based particles with the second carbon layer formed thereon were spread thinly to a thickness of about 3 mm and put into an RF plasma chamber, CF4 gas was injected under 0.07 torr to increase the internal pressure of the plasma chamber to 0.2 torr. Thereafter, a plasma was formed by applying a power of 150 W to the plasma chamber, the plasma was maintained for 6 minutes, vacuum was released to normal pressure, and then the resulting product was obtained. The above process was further repeated twice (three times in total) to obtain the negative electrode active material of Example 1.
A negative electrode active material of Example 2 was obtained by preparation in the same manner as in Example 1, except that the intensity of power applied was 200 W during the formation of plasma.
A negative electrode active material of Example 3 was obtained by preparation in the same manner as in Example 1, except that the intensity of power applied was 100 W during the formation of plasma.
A negative electrode active material of Comparative Example 1 was obtained by preparation in the same manner as in Example 1, except that the second carbon layer was not formed and the plasma treatment was not performed.
A negative electrode active material of Comparative Example 2 was obtained by preparation in the same manner as in Example 1, except that the second carbon layer was formed but the plasma treatment was not performed.
Silicon-based particles with a second carbon layer formed thereon were obtained by preparation in the same manner as in Example 1, except that the plasma treatment was not performed.
After the silicon-based particles and a 0.1 M HF solution were mixed at a weight ratio of 1:7, the resulting solution was stirred for 1 hour, filtered, dried, and heat-treated at 300° C. to prepare a negative electrode active material having a LiF layer introduced onto the surface thereof.
The content of the carbon layer was analyzed using a CS-analyzer (CS-800, Eltra).
The content of the Li atom was confirmed by an ICP analysis using an inductively coupled plasma atomic emission spectrometer (ICP-OES, AVIO 500 from Perkin-Elmer 7300).
The content (at %) and atomic ratio of the element on the surface of the negative electrode active material were confirmed through XPS (Nexsa ESCA System, Thermo Fisher Scientific (ESCA-02)).
Specifically, a survey scan spectrum and a narrow scan spectrum were obtained for each sample, and then the survey scan spectrum and the narrow scan spectrum were obtained while performing a depth profile. Depth profile was performed up to 3000 seconds using Monatomic Ar ion. Measurement and data processing conditions are as follows.
Under the above conditions, the content (at %) and atomic ratio of each element were calculated based on the total content of 100 at % of the measured elements based on 100s.
The compositions of the negative electrode active materials prepared in the Examples and Comparative Examples are shown in the following Table 1.
A mixture of the composite negative electrode active material prepared in Example 1 as the negative electrode material and graphite (average particle diameter (D50): 20 μm) as the carbon-based active material at a weight ratio of 20:80 was used.
The negative electrode material, styrene-butadiene rubber (SBR) as a binder, Super C65 as a conductive material, and carboxymethyl cellulose (CMC) as a thickener were mixed at a weight ratio of 96:2:1:1, and the resulting mixture was added to distilled water as a solvent for forming a negative electrode slurry to prepare a negative electrode slurry.
One surface of a copper current collector (thickness: 15 μm) as a negative electrode current collector was coated with the negative electrode slurry in a loading amount of 3.6 mAh/cm2, and the copper current collector was roll-pressed and dried in a vacuum oven at 130° C. for 10 hours to form a negative electrode active material layer (thickness: 50 μm), which was employed as a negative electrode according to Example 1 (thickness of the negative electrode: 65 μm).
Furthermore, the negative electrodes of Examples 2 and 3 and Comparative Examples 1 to 3 were manufactured in the same manner as in Example 1, except that the negative electrode active materials of Examples 2 and 3 and Comparative Examples 1 to 3 were used, respectively, instead of the negative electrode active material of Example 1.
A lithium metal foil was prepared as a positive electrode.
Coin-type half cells of Examples 1 to 3 and Comparative Examples 1 to 3 were manufactured, respectively, by interposing a porous polyethylene separator between the negative electrodes of Examples 1 to 3 and Comparative Examples 1 to 3 manufactured above and the positive electrode and injecting an electrolyte solution thereinto.
As the electrolyte solution, a product obtained by dissolving 0.5 wt % of vinylene carbonate (VC) in a solution of ethyl methyl carbonate (EMC) and ethylene carbonate (EC) mixed at a volume ratio of 7:3, and dissolving LiPF6 at a concentration of 1 M was used.
The discharge capacities, initial efficiencies and cycle capacity retention rates of the secondary batteries manufactured in Examples 1 to 3 and Comparative Examples 1 to 3 were evaluated using an electrochemical charger/discharger.
The cycle capacity retention rate was evaluated at a temperature of 25° C., the first and second cycles were charged and discharged at 0.1 C, and the third and subsequent cycles were charged and discharged at 0.5 C (charging conditions: CC/CV, 5 mV/0.005 C cut-off, discharging conditions: CC, 1.5 V cut off).
The discharge capacity (mAh/g) and initial efficiency (%) were derived from the results during one-time charge/discharge.
The capacity retention rate was calculated as follows.
(In the equation, N is an integer of 1 or higher.)
The 50th cycle capacity retention rate (%) is shown in the following Table 2.
A mixture of the negative electrode active material prepared in each of the Examples and the Comparative Examples as the negative electrode material and graphite (average particle diameter (D50): 20 μm) as the carbon-based active material at a weight ratio of 15:85 was used.
The negative electrode material, styrene-butadiene rubber (SBR) as a binder, Super C65 as a conductive material, and carboxymethyl cellulose (CMC) as a thickener were mixed at a weight ratio of 96:2:1:1, and the resulting mixture was added to distilled water as a solvent for forming a negative electrode slurry to prepare a negative electrode slurry.
The negative electrode slurry was each placed in a 7-mL volume aluminum pouch and sealed.
A difference between the weight of the aluminum pouch containing the negative electrode slurry in the air and the weight of the aluminum pouch containing the negative electrode slurry in water at 23° C. was determined, and a volume of gas immediately after preparing the negative electrode slurry was measured by dividing the difference by the density of water at 23° C.
Next, after the aluminum pouch containing the negative electrode slurry was stored at 60° C. for 7 days, a difference between the weight of the aluminum pouch containing the negative electrode slurry in the air and the weight of the aluminum pouch containing the negative electrode slurry in water at 60° C. was determined, and a volume of gas after storing the negative electrode slurry for 7 days was measured by dividing the difference by the density of water at 60° C.
A difference between the volume of gas measured after storing the negative electrode slurry for 7 days and the volume of gas measured immediately after preparing the negative electrode slurry was defined as an amount of gas generated, and is shown in the following Table 2.
The negative electrode active material according to the present disclosure includes silicon-based particles including SiOx (0<x<2) and a Li compound; a first carbon layer; a second carbon layer; LiF; and CFa (0<a<4), and it could be confirmed that in Examples 1 to 3 using the negative electrode active material of the present disclosure, discharge capacity, initial efficiency, and capacity retention rate were excellent, and the amount of gas generated in the slurry was either zero or remarkably low. This result seems to be provided by the negative electrode active material of the present disclosure which is provided with two carbon layers that prevent lithium by-products from reacting with moisture and CFa (0<a<4) maximizing hydrophobicity of the two carbon layers to effectively passivate particles in the water-based slurry.
In contrast, in Comparative Example 1, the negative electrode active material included only one carbon layer and did not include LiF and CFa (0<a<4), and thus it could be confirmed that moisture in the slurry easily reacted with the silicon-based particles and the lithium by-product to generate gas, and the discharge capacity, initial efficiency and capacity retention rate were decreased.
In Comparative Example 2, the negative electrode active material included two carbon layers, but did not include LiF and CFa (0<a<4), and thus it could be confirmed that the discharge capacity, initial efficiency and capacity retention rate were decreased because the reactivity of moisture and silicon-based particles was still high.
In Comparative Example 3, the surface of the negative electrode active material was coated with LiF, and the silicon-based particles were passivated by LiF, but the degree of passivation was low, and thus it could be confirmed that the amount of gas generated was still large, and the discharge capacity, initial efficiency and capacity retention rate were not improved.
Therefore, in the present disclosure, the overall water-based processability, discharge capacity, efficiency, and capacity retention rate could be remarkably improved by providing the negative electrode active material including the silicon-based particles, LiF, and CFa (0<a<4), and having the two carbon layers.
| Number | Date | Country | Kind |
|---|---|---|---|
| 10-2022-0134148 | Oct 2022 | KR | national |
This application is a National Phase entry pursuant to 35 U.S.C. § 371 of International Application No. PCT/KR2023/013551 filed on Sep. 11, 2023, and claims priority to and the benefit of Korean Patent Application No. 10-2022-0134148 filed on Oct. 18, 2022, the entire contents of which are incorporated herein by reference.
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/KR2023/013551 | 9/11/2023 | WO |
