Patent Application
20250149569
The present disclosure relates to a negative electrode active material, a method for manufacturing a negative electrode active material, a negative electrode composition, a negative electrode for a lithium secondary battery including the same, and a lithium secondary battery including a negative electrode.
Due to the rapid increase in the use of fossil fuels, the demand for the use of alternative energy or clean energy is increasing, and as part thereof, the fields that are being studied most actively are the fields of power generation and power storage using an electrochemical reaction.
At present, a secondary battery is a representative example of an electrochemical device that utilizes such electrochemical energy, and the range of use thereof tends to be gradually expanding.
Along with the technology development and the increase in demand for mobile devices, the demand for secondary batteries as an energy source is sharply increasing. Among such secondary batteries, lithium secondary batteries having high energy density and voltage, long cycle life, and low self-discharging rate have been commercialized and widely used. In addition, research is being actively conducted on a method for manufacturing a high-density electrode having a higher energy density per unit volume as an electrode for such a high-capacity lithium secondary battery.
In general, a secondary battery includes a positive electrode, a negative electrode, an electrolyte, and a separator. The negative electrode includes a negative electrode active material for intercalating and deintercalating lithium ions to and from the positive electrode, and silicon-based particles having a high discharge capacity may be used as the negative electrode active material.
In particular, according to the demand for high density energy batteries in recent years, research is being actively conducted on a method for increasing a capacity by using together a silicon-based compound such as Si/C and SiOx having a capacity 10 times or higher than that of a graphite-based material, as a negative electrode active material. However, as compared with graphite that is typically used, a silicon-based compound that is a high-capacity material has a large capacity but undergoes rapid volume expansion during charging, thereby disconnecting a conductive path to degrade battery characteristics.
Accordingly, in order to address a problem occurring when the silicon-based compound is used as the negative electrode active material, methods of suppressing the volume expansion itself such as a method of controlling a driving potential, a method of additionally further coating a thin film on an active material layer and a method of controlling a particle diameter of a silicon-based compound, or various measures for preventing a conductive path from being disconnected have been discussed. However, the above methods may rather deteriorate the performance of a battery, and thus, the application thereof is limited, so that there is still a limitation in commercializing the manufacture of a negative electrode battery having a high content of a silicon-based compound.
Therefore, there is a need for conducting research on a silicon-based active material itself capable of preventing a conductive path from being damaged due to volume expansion of a silicon-based compound, even when the silicon-based active material is used as a negative electrode active material in order to improve capacity performance.
Japanese Patent Application Publication No. 2009-080971
In the case of a silicon-based active material fabricated by a chemical processing method rather than a conventional pulverization processing method, particularly, a silicon-based active material grown through crystal nucleation, it was found through research that a specific surface area and a roughness can be controlled. Regarding this, it was confirmed that, when a range of the specific surface area is controlled within a certain range, during the intercalation and deintercalation reactions of lithium, the reactions occurs uniformly and stress applied to the silicon-based active material is reduced.
The present disclosure relates to a negative electrode active material, a method for manufacturing a negative electrode active material, a negative electrode composition, a negative electrode for a lithium secondary battery including the same, and a lithium secondary battery including a negative electrode capable of addressing the above-described problems.
An exemplary embodiment of the present specification provides a negative electrode active material including a silicon-based active material having a specific surface area of 0.30 m2/g or greater and 4.00 m2/g or less, wherein the silicon-based active material includes Si and optionally SiOx (0<x<2), and includes 70 parts by weight or more of Si on the basis of 100 parts by weight of the silicon-based active material.
Another exemplary embodiment provides a method for manufacturing a negative electrode active material, the method including: depositing a silicon-based active material on a substrate by chemically reacting a silane gas; growing the silicon-based active material through crystal nucleation; and obtaining the silicon-based active material deposited on the substrate and grown through crystal nucleation, wherein the silicon-based active material has a specific surface area of 0.30 m2/g or greater and 4.00 m2/g or less.
Still another exemplary embodiment provides a negative electrode composition including: the negative electrode active material according to the present disclosure; a negative electrode conductive material; and a negative electrode binder.
Yet another exemplary embodiment provides a negative electrode for a lithium secondary battery including: a negative electrode current collector layer; and a negative electrode active material layer provided on one surface or both surfaces of the negative electrode current collector layer, wherein the negative electrode active material layer includes the negative electrode composition according to the present disclosure or a cured product thereof.
Finally, there is provided a lithium secondary battery including a positive electrode; the negative electrode according to the present disclosure; a separator between the positive electrode and the negative electrode; and an electrolyte.
The negative electrode active material according to an exemplary embodiment of the present disclosure includes the silicon-based active material grown through chemical method and crystal nucleation, unlike the existing pulverization processing method, and thus, having a specific surface area of a certain range or more.
The negative electrode active material of the present disclosure includes Si and optionally SiOx (0<x<2) as the silicon-based active material, and includes 70 parts by weight or more of Si on the basis of 100 parts by weight of the silicon-based active material, i.e., has a pure Si active material, and resolves the problem of volume expansion upon charging and discharging, which is a problem when using the silicon-based active material, by controlling the specific surface area of the silicon-based active material within the certain range.
In other words, by using a silicon-based active material having a specific surface area which satisfies the specific range according to the present disclosure, the silicon-based active material has a rough surface of a larger specific surface area as compared to particles with the same particle size, thereby increasing a bonding force with the binder and resulting in reduction of cracks of an electrode upon repeating charge and discharge cycles. In addition, at the time of intercalation and deintercalation reactions of lithium during the charging/discharging, the reactions can occur uniformly and stress applied to the silicon-based active material can be reduced, so that breakage of particles can be reduced, and thus, the life maintenance rate of the electrode can be improved.
Before describing the present disclosure, some terms are first defined.
When one part “includes”, “comprises” or “has” 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.
In the present specification, ‘p to q’ means a range of ‘p or more and q or less’.
In this specification, the “specific surface area” is measured by the BET method, and specifically, is calculated from a nitrogen gas adsorption amount at a liquid nitrogen temperature (77K) by using BELSORP-mino II available from BEL Japan, Inc. That is, in the present disclosure, the BET specific surface area may refer to the specific surface area measured by the above measurement method.
In the present specification, “Dn” refers to a particle size distribution, and refers to a particle diameter at the n % point in the cumulative distribution of the number of particles according to the particle diameter. That is, D50 is a particle diameter (average particle diameter) at the 50% point in the cumulative distribution of the number of particles according to the particle diameter, D90 is a particle diameter at the 90% point in the cumulative distribution of the number of particles according to the particle diameter, and D10 is a particle diameter at the 10% point in the cumulative distribution of the number of particles according to the particle diameter. Meanwhile, the average particle diameter may be measured using a laser diffraction method. Specifically, after powder to be measured is dispersed in a dispersion medium, the resultant dispersion is introduced into a commercially available laser diffraction particle size measurement apparatus (for example, Microtrac S3500) in which a difference in a diffraction pattern according to the particle size is measured, when a laser beam passes through particles, and then a particle size distribution is calculated.
In an exemplary embodiment of the present disclosure, the particle size or particle diameter may mean an average diameter or representative diameter of each grain constituting the metal powder.
In the present specification, the description “a polymer includes a certain monomer as a monomer unit” means that the monomer participates in a polymerization reaction and is included as a repeating unit in the polymer. In the present specification, when a polymer includes a monomer, this is interpreted as the same as that the polymer includes a monomer as a monomer unit.
In the present specification, it is understood that the term ‘polymer’ is used in a broad sense including a copolymer unless otherwise specified as ‘a homopolymer’.
In the present specification, a weight-average molecular weight (Mw) and a number-average molecular weight (Mn) are polystyrene converted molecular weights measured by gel permeation chromatography (GPC) while employing, as a standard material, a monodispersed polystyrene polymer (standard sample) having various degrees of polymerization commercially available for measuring a molecular weight. In the present specification, a molecular weight refers to a weight-average molecular weight unless particularly described otherwise.
Hereinafter, embodiments of the present disclosure will be described in detail with reference to the drawings so that one skilled in the art can readily implement the present disclosure. However, the present disclosure may be embodied in various different forms, and is not limited to the following descriptions.
An exemplary embodiment of the present specification provides a negative electrode active material including a silicon-based active material having a specific surface area of 0.30 m2/g or greater and 4.00 m2/g or less, wherein the silicon-based active material includes Si and optionally SiOx (0<x<2), and includes 70 parts by weight or more of Si on the basis of 100 parts by weight of the silicon-based active material.
The negative electrode active material of the present disclosure includes Si and optionally SiOx (0<x<2) as the silicon-based active material, and includes 70 parts by weight or more of Si on the basis of 100 parts by weight of the silicon-based active material, i.e., has a pure Si active material, and resolves the problem of volume expansion upon charging and discharging, which is a problem when using the silicon-based active material, by controlling the specific surface area of the silicon-based active material within the certain range.
In other words, by using a silicon-based active material having a specific surface area which satisfies the specific range according to the present disclosure, the silicon-based active material has a rough surface of a larger specific surface area as compared with particles with the same particle size, thereby increasing a bonding force with the binder, and leading to reduction of cracks of an electrode upon repeating charge and discharge cycles. In addition, at the time of the intercalation and deintercalation reactions of lithium during the charging/discharging, the reactions can occur uniformly and stress applied to the silicon-based active material can be reduced, so that breakage of particles can be reduced, and thus, the life maintenance rate of the electrode can be improved.
In an exemplary embodiment of the present disclosure, the silicon-based active material may include Si and optionally SiOx (0<x<2), and may include Si in an amount of 70 parts by weight or more on the basis of 100 parts by weight of the silicon-based active material.
In an exemplary embodiment of the present disclosure, the silicon-based active material may include Si, and include 70 parts by weight or more of Si on the basis of 100 parts by weight of the silicon-based active material.
In another exemplary embodiment, Si may be included in amount of 70 parts by weight or more, preferably 80 parts by weight or more, and more preferably 90 parts by weight or more, and 100 parts by weight or less, preferably 99 parts by weight or less, and more preferably 95 parts by weight or less on the basis of 100 parts by weight of the silicon-based active material.
In an exemplary embodiment of the present disclosure, pure silicon (Si) particles may be particularly used as the silicon-based active material. The use of pure silicon (Si) particles as the silicon-based active material may mean that, on the basis of 100 parts by weight of the total silicon-based active material as described above, pure Si particles not bonded to other particles or elements are included within the above range.
In an exemplary embodiment of the present disclosure, the silicon-based active material may be formed of silicon-based particles having 100 parts by weight of Si on the basis of 100 parts by weight of the silicon-based active material.
In an exemplary embodiment of the present disclosure, the silicon-based active material may include a metal impurity, and in this case, the impurity is metal that may be generally included in the silicon-based active material, and specifically, a content thereof may be 0.1 part by weight or less on the basis of 100 parts by weight of the silicon-based active material.
The capacity of the silicon-based active material is significantly higher than that of a graphite-based active material that is typically used, so that there have been more attempts to apply the same. However, the volume expansion rate of the silicon-based active material during charging/discharging is high, so that only a small amount thereof is mixed and used with a graphite-based active material.
Therefore, in the present disclosure, only the silicon-based active material is used as a negative electrode active material in order to improve capacity performance, and at the same time, in order to address the problems as described above, rather than controlling the compositions of the conductive material and the binder, the specific surface area (surface roughness) of the silicon-based active material itself is controlled to solve the existing problems.
In an exemplary embodiment of the present disclosure, the negative electrode active material may include a silicon-based active material having a specific surface area of 0.30 m2/g or greater and 4.00 m2/g or less.
In another exemplary embodiment, the silicon-based active material may have a specific surface area of 0.30 m2/g or greater, preferably 0.31 m2/g or greater, and more preferably 0.32 m2/g or greater. The silicon-based active material may satisfy a range of a specific surface area of 4.00 m2/g or less, preferably 2.50 m2/g or less, and more preferably 2.20 m2/g or less. The specific surface area may be measured according to DIN 66131 (using nitrogen).
The silicon-based active material has the specific surface area described above, and the specific surface area of the silicon-based active material may be controlled by changing a process condition of a manufacturing process and a growth condition of the silicon-based active material described below. That is, when the negative electrode active material is manufactured using the manufacturing method according to the present disclosure, the rough surface results in a larger specific surface area, as compared with particles with the same particle size. In this case, the above range is satisfied, and thus, the bonding force with the binder increases, leading to reduction in cracks of an electrode due to repeating charge and discharge cycles.
In addition, the lithium ions can be uniformly intercalated during intercalation of lithium ions, resulting in reduction in stress applied during intercalation of lithium ions into the silicon particles, and accordingly, reduction in breakage of the particles. As a result, characteristics capable of improving the life stability of the negative electrode are obtained. If the specific surface area is less than the above range, the surface is formed smooth even with the same particle size, resulting in a decrease in the bonding force with the binder, and cracks of the electrode. In this case, lithium ions are non-uniformly intercalated into the particles, resulting in an increase in the stress due to the ion intercalation, and breakage of particles. In an exemplary embodiment of the present disclosure, Si has a crystal grain size of 200 nm or less. When the silicon-based active material having a crystal grain size satisfying the above range is used, at the time of the intercalation and deintercalation reactions of lithium during the charging/discharging, the reactions can occur uniformly and stress applied to the silicon-based active material can be reduced, so that breakage of particles can be reduced, and thus, the life maintenance rate of the electrode can be improved.
In the present disclosure, the crystal grain refers to a crystal particle in a metal or material, which is a collection of microscopically irregular shapes, and the crystal grain size may mean a diameter of the observed crystal grain particle. That is, in the present disclosure, the crystal grain size means a size of a domain sharing the same crystal direction in a particle, and has a different concept from a particle size or a size of a particle diameter expressing a size of a material.
In another exemplary embodiment, the crystal grain size of the silicon-based active material may be 200 nm or less, preferably 130 nm or less, more preferably 110 nm or less, still more preferably 100 nm or less, specifically 95 nm or less, and more specifically 91 nm or less. The crystal grain size of the silicon-based active material may have a range of 1 nm or greater, preferably 3 nm or greater.
Si has the crystal grain size described above, and the crystal grain size may be controlled by changing a process condition in a manufacturing process described below. In this case, when the above range is satisfied, the crystal grain boundaries are widely distributed, and thus, the lithium ions can be uniformly intercalated during intercalating of lithium ions, thereby reducing the stress applied during intercalating of lithium ions into the silicon particles, and accordingly, mitigating breakage of the particles. As a result, characteristics capable of improving the life stability of the negative electrode are obtained. If the crystal grain size exceeds the above range, the crystal grain boundaries within the particles are narrowly distributed, and in this case, the lithium ions are non-uniformly intercalated into the particles, leading to large stress during the intercalating of ions, and accordingly, breakage of particles.
In an exemplary embodiment of the present disclosure, there is provided the negative electrode active material in which the silicon-based active material includes a crystal structure having a crystal grain size distribution of 1 nm or greater and 200 nm or less, and an area ratio of the crystal structure based on a total area of the silicon-based active material is 5% or less.
In another exemplary embodiment, the area ratio of the crystal structure based on the total area of the silicon-based active material may be 5% or less, or 3% or less, and 0.1% or greater.
That is, the silicon-based active material according to the present disclosure has a crystal grain size of 200 nm or less, is formed so that the size of one crystal structure is small, and may satisfy the above area ratio. Accordingly, the distribution of the crystal grain boundaries may be widened, and accordingly, the above-described effects may be exhibited.
In an exemplary embodiment of the present disclosure, there is provided the negative electrode active material in which the silicon-based active material satisfies a range in Equation 1 below.
The measurement of Equation 1 above can be performed using a particle shape analyzer. Specifically, the silicon-based active material according to the present disclosure may be scattered on a glass plate through air injection, and then a shape of 10,000 silicon-based active material particles in a photograph taken by orthographically projecting the scattered silicon-based active material particles may be measured. In this case, Equation 1 is a value expressing an average of 10,000 particles. Equation 1 according to the present disclosure can be measured from the above image, and Equation 1 can be expressed as sphericity (circularity) of the silicon-based active material.
In another expression, X1 may refer to an actual area of the silicon-based active material, and Y1 may refer to an area of a spherical particle with the same circumference as the silicon-based active material.
In an exemplary embodiment of the present disclosure, the sphericity of the silicon-based active material may be 0.960 or less, for example, 0.957 or less. The sphericity of the silicon-based active material may be 0.8 or higher, for example, 0.9 or higher, specifically 0.93 or higher, more specifically 0.94 or higher, for example, 0.941 or higher.
In an exemplary embodiment of the present disclosure, there is provided the negative electrode active material in which the silicon-based active material satisfies a range in Equation 2 below.
The measurement of Equation 2 above can be performed using a particle shape analyzer. Specifically, the silicon-based active material according to the present disclosure may be scattered on a glass plate through air injection, and then a shape of 10,000 silicon-based active material particles in a photograph may be measured by taking an orthographic projection image of the scattered silicon-based active material. In this case, Equation 2 is a value expressing an average of 10,000 particles. Equation 2 according to the present disclosure can be measured from the above image, and Equation 2 can be expressed as convexity of the silicon-based active material.
In another expression, Y2 may refer to an actual circumference of the silicon-based active material, and X2 may refer to a circumference of a circumscribed figure of the silicon-based active material.
In an exemplary embodiment of the present disclosure, a range of X2/Y≤50.996, preferably X2/Y2≤0.995 may be satisfied, and a range of 0.8≤x2/Y2, preferably 0.9≤x2/Y2, more preferably 0.95≤x2/Y2, specifically 0.98≤x2/Y2 may be satisfied.
The smaller the value of Equation 1 or Equation 2, the greater the roughness of the silicon-based active material may be meant. As the silicon-based active material with the above range is used, the bonding force with the binder increases, leading to reduction in cracks of the electrode due to the repeating of the charge/discharge cycle.
In an exemplary embodiment of the present disclosure, the negative electrode active material does not have a structure including pores, but satisfies Equations 1 and 2 and has an irregularity shape on an external surface. That is, the negative electrode active material may have an irregularity shape on an external surface rather than an internal pore shape.
In an exemplary embodiment of the present disclosure, the silicon-based active material may include silicon-based particles having a particle size distribution of 0.01 μm or greater and 30 μm or less.
The description ‘the silicon-based active material includes silicon-based particles having a particle size distribution of 0.01 μm or greater and 30 μm or less’ means including a plurality of individual silicon-based particles having a particle size within the above range, and the number of silicon-based particles included is not limited.
When the silicon-based particle is spherical, the particle size thereof can be expressed as its diameter. However, even when the silicon-based particle has a shape other than spherical, the particle size can be measured in contrast to the case of the spherical shape, and the particle size of the individual silicon-based particle can be measured by a method that is generally known in the art.
An average particle diameter (D50 particle size) of the silicon-based active material of the present disclosure may be 3 μm to 10 μm, specifically 5.5 μm to 8 μm, and more specifically 6 μm to 7 μm. When the average particle diameter is within the above range, a specific surface area of the particles is within a suitable range, so that a viscosity of a negative electrode slurry is formed within an appropriate range. Accordingly, the particles constituting the negative electrode slurry are smoothly dispersed. In addition, when the size of the silicon-based active material has a value equal to or greater than the lower limit value of the range, a contact area between the silicon particles and the conductive material is excellent due to the composite made of the conductive material and the binder in the negative electrode slurry, so that a sustaining possibility of the conductive network increases, thereby increasing the capacity retention rate. In the meantime, when the average particle diameter satisfies the above range, excessively large silicon particles are excluded, so that a surface of the negative electrode is formed smooth. Accordingly, a current density non-uniformity phenomenon during charging and discharging can be prevented.
In an exemplary embodiment of the present disclosure, the silicon-based active material may be present, for example, in a crystalline or amorphous form, and is preferably not porous. The silicon particles are preferably spherical or splinter-shaped particles. Alternatively, but less preferably, the silicon particles may also have a fiber structure or be present in the form of a silicon-containing film or coating.
In an exemplary embodiment of the present disclosure, there is provided a negative electrode composition including the negative electrode active material described above, a negative electrode conductive material, and a negative electrode binder.
In an exemplary embodiment of the present disclosure, there is provided the negative electrode composition in which the negative electrode active material is included in an amount of 40 parts by weight or more on the basis of 100 parts by weight of the negative electrode composition.
In another exemplary embodiment, the negative electrode active material may be included in an amount of 40 parts by weight or more, preferably 60 parts by weight or more, more preferably 65 parts by weight or more, and further preferably 70 parts by weight or more, and 95 parts by weight or less, preferably 90 parts by weight or less, and more preferably 85 parts by weight or less, on the basis of 100 parts by weight of the negative electrode composition.
The negative electrode composition according to the present disclosure does not degrade the performance of the negative electrode and has excellent output characteristics in charging and discharging, even when the silicon-based active material having a significantly high capacity is used within the above range, by using the negative electrode active material satisfying the specific surface area and capable of controlling the volume expansion rate during charging and discharging.
In the related art, it is general to use only graphite-based compounds as the negative electrode active material. However, in recent years, as the demand for high-capacity batteries is increasing, attempts to mix and use silicon-based compounds are increasing in order to increase capacity. However, in the case of a silicon-based active material, even when the characteristics of the silicon-based active material itself are adjusted as described above, the volume may rapidly expand during the charging/discharging, thereby causing some problems of damaging the conductive path formed in the negative electrode active material layer.
Therefore, in an exemplary embodiment of the present disclosure, the negative electrode conductive material may include one or more selected from the group consisting of a point-like conductive material, a planar conductive material and a linear conductive material.
In an exemplary embodiment of the present disclosure, the point-like conductive material refers to a point-like or spherical conductive material that may be used for improving conductivity of the negative electrode, and has conductivity without causing a chemical change. Specifically, the point-like conductive material may be one or more species selected from the group consisting of natural graphite, artificial graphite, carbon black, acetylene black, Ketjen black, channel black, furnace black, lamp black, thermal black, conductive fiber, fluorocarbon, aluminum powder, nickel powder, zinc oxide, potassium titanate, titanium oxide, and a polyphenylene derivative, and preferably may include carbon black in terms of high conductivity and excellent dispersibility.
In an exemplary embodiment of the present disclosure, the point-like conductive material may have a BET specific surface area of 40 m2/g or greater and 70 m2/g or less, preferably 45 m2/g or greater and 65 m2/g or less, and more preferably 50 m2/g or greater and 60 m2/g or less.
In an exemplary embodiment of the present disclosure, a content of the functional group (volatile matter) of the point-like conductive material may satisfy a range of 0.01% or more and 1% or less, preferably 0.01% or more and 0.3% or less, and more preferably 0.01% or more and 0.1% or less.
In particular, when the content of the functional group of the point-like conductive material satisfies the above range, a functional group is present on a surface of the point-like conductive material, so that the point-like conductive material can be smoothly dispersed in a solvent when water is used as the solvent. In particular, in the present disclosure, as the specific silicon-based active material is used, a functional group content of the point-like conductive material can be lowered, which exhibits an excellent effect in improving dispersibility.
In an exemplary embodiment of the present disclosure, the point-like conductive material having the content of the functional group within the range described above is included together with the silicon-based active material, and the content of the functional group can be adjusted according to a degree of heat treatment of the point-like conductive material.
In an exemplary embodiment of the present disclosure, a particle diameter of the point-like conductive material may be 10 nm to 100 nm, preferably 20 nm to 90 nm, and more preferably 20 nm to 60 nm.
In an exemplary embodiment of the present disclosure, the conductive material may include a planar conductive material.
The planar conductive material improves conductivity by increasing surface contact between silicon particles in the negative electrode, and at the same time, can serve to suppress disconnection of the conductive path due to the volume expansion. The planar conductive material may be expressed as a plate-like conductive material or a bulk-type conductive material.
In an exemplary embodiment of the present disclosure, the planar conductive material may include one or more selected from the group consisting of plate-like graphite, graphene, graphene oxide, and graphite flake, and preferably may be plate-like graphite.
In an exemplary embodiment of the present disclosure, the average particle diameter (D50) of the planar conductive material may be 2 μm to 7 μm, specifically 3 μm to 6 μm, and more specifically 3.5 μm to 5 μm. When the above range is satisfied, the sufficient particle size results in easy dispersion without causing an excessive increase in viscosity of the negative electrode slurry. Therefore, the dispersion effect is excellent when dispersing using the same equipment and time.
In an exemplary embodiment of the present disclosure, there is provided the negative electrode composition in which the planar conductive material has D10 of 0.5 μm or greater and 2.0 μm or less, D50 of 2.5 μm or greater and 3.5 μm or less and D90 of 6.5 μm or greater and 15.0 μm or less.
In an exemplary embodiment of the present disclosure, for the planar conductive material, a planar conductive material with a high specific surface area having a high BET specific surface area or a planar conductive material with a low specific surface area may be used.
In an exemplary embodiment of the present disclosure, for the planar conductive material, a planar conductive material with a high specific surface area or a planar conductive material with a low specific surface area may be used without limitation. However, in particular, the planar conductive material according to the present disclosure can be affected to some extent in the electrode performance by the dispersion effect, so that a planar conductive material with a low specific surface area that does not cause a problem in dispersion is used particularly preferably.
In an exemplary embodiment of the present disclosure, the planar conductive material may have a BET specific surface area of 0.25 m2/g or greater.
In another exemplary embodiment, the planar conductive material may have a BET specific surface area of 1 m2/g or greater and 500 m2/g or less, preferably 5 m2/g or greater and 300 m2/g or less, and more preferably 5 m2/g or greater and 250 m2/g or less.
For the planar conductive material of the present disclosure, a planar conductive material with a high specific surface area or a planar conductive material with a low specific surface area may be used.
In another exemplary embodiment, the planar conductive material is a planar conductive material with a high specific surface area, and the BET specific surface area may satisfy a range of 50 m2/g or greater and 500 m2/g or less, preferably 80 m2/g or greater and 300 m2/g or less, and more preferably 100 m2/g or greater and 300 m2/g or less.
In another exemplary embodiment, the planar conductive material is a planar conductive material with a low specific surface area, and the BET specific surface area may satisfy a range of 1 m2/g or greater and 40 m2/g or less, preferably 5 m2/g or greater and 30 m2/g or less, and more preferably 5 m2/g or greater and 25 m2/g or less.
Other conductive materials may include linear conductive materials such as carbon nanotubes. The carbon nanotubes may be bundle-type carbon nanotubes. The bundle-type carbon nanotubes may include a plurality of carbon nanotube units. Specifically, the term ‘bundle type’ herein refers to, unless otherwise specified, a bundle or rope-shaped secondary shape in which a plurality of carbon nanotube units are aligned side by side in such an orientation that longitudinal axes of the carbon nanotube units are substantially the same, or are entangled. The carbon nanotube unit has a graphite sheet having a cylindrical shape with a nano-sized diameter, and has an sp2 bonding structure. In this case, the characteristics of a conductor or a semiconductor may be exhibited depending on the rolled angle and structure of the graphite sheet. As compared with entangled-type carbon nanotubes, the bundle-type carbon nanotubes can be more uniformly dispersed during the manufacture of the negative electrode, and can form more smoothly a conductive network in the negative electrode to improve the conductivity of the negative electrode.
In an exemplary embodiment of the present disclosure, there is provided the negative electrode composition in which the negative electrode conductive material is included in an amount of 20 parts by weight or less on the basis of 100 parts by weight of the negative electrode composition.
In another exemplary embodiment, the negative electrode conductive material may be included in an amount of 0.1 part by weight or more and 20 part by weight or less, preferably 1 part by weight or more and 20 parts by weight or less, more preferably 5 part by weight or more and 15 parts by weight or less, and most preferably 6 parts by weight or more and 13 parts by weight or less, on the basis of 100 parts by weight of the negative electrode composition.
The negative electrode conductive material according to the present disclosure has a completely different configuration from that of a positive electrode conductive material that is applied to the positive electrode. That is, the negative electrode conductive material according to the present disclosure serves to hold the contact between silicon-based active materials of which volume expansion of the electrode is very large upon charging and discharging, and the positive electrode conductive material serves to impart some conductivity while serving as a buffer when roll-pressed, and is completely different from the negative electrode conductive material of the present disclosure in terms of configuration and role.
In addition, the negative electrode conductive material according to the present disclosure is applied to a silicon-based active material, and has a completely different configuration from that of a conductive material that is applied to a graphite-based active material. That is, since a conductive material that is used for an electrode having a graphite-based active material simply has smaller particles than the active material, the conductive material has characteristics of improving output characteristics and imparting some conductivity, and is completely different from the negative electrode conductive material that is applied together with the silicon-based active material as in the present disclosure, in terms of configuration and role.
In an exemplary embodiment of the present disclosure, the planar conductive material that is used as the negative electrode conductive material described above has a different structure and role from those of the carbon-based active material that is generally used as the negative electrode active material. Specifically, the carbon-based active material that is used as the negative electrode active material may be artificial graphite or natural graphite, and refers to a material that is processed and used into a spherical or point-like shape so as to facilitate storage and release of lithium ions.
On the other hand, the planar conductive material that is used as the negative electrode conductive material is a material having a plane or plate-like shape, and may be expressed as plate-like graphite. That is, the planar conductive material is a material that is included so as to maintain a conductive path in the negative electrode active material layer, and means a material for securing a conductive path in a planar shape inside the negative electrode active material layer, rather than playing a role in storing and releasing lithium.
That is, in the present disclosure, the use of plate-like graphite as a conductive material means that graphite is processed into a planar or plate-like shape and used as a material for securing a conductive path rather than playing a role in storing or releasing lithium. In this case, the negative electrode active material included together has high-capacity characteristics with respect to storing and releasing lithium, and serves to store and release all lithium ions transferred from the positive electrode.
On the other hand, in the present disclosure, the use of a carbon-based active material as an active material means that the carbon-based active material is processed into a point-like or spherical shape and used as a material for storing or releasing lithium.
That is, in an exemplary embodiment of the present disclosure, artificial graphite or natural graphite, which is a carbon-based active material, has a point-like shape, and a BET specific surface area thereof may satisfy a range of 0.1 m2/g or greater and 4.5 m2/g or less. In addition, plate-like graphite, which is a planar conductive material, has a planar shape, and a BET specific surface area thereof may be 5 m2/g or greater.
In an exemplary embodiment of the present disclosure, the negative electrode binder may include at least one selected from the group consisting of polyvinylidenefluoride-hexafluoropropylene copolymer (PVDF-CO-HFP), polyvinylidenefluoride, polyacrylonitrile, polymethylmethacrylate, polyvinyl alcohol, carboxymethylcellulose (CMC), starch, hydroxypropylcellulose, regenerated cellulose, polyvinylpyrrolidone, tetrafluoroethylene, polyethylene, polypropylene, polyacrylic acid, ethylene-propylene-diene monomer (EPDM), sulfonated EPDM, styrene butadiene rubber (SBR), fluoro rubber, poly acrylic acid, and the above-described materials in which a hydrogen is substituted with Li, Na, Ca, etc., and may also include various copolymers thereof.
The negative electrode binder according to an exemplary embodiment of the present disclosure serves to hold the active material and the conductive material in order to prevent distortion and structural deformation of the negative electrode structure in volume expansion and relaxation of the silicon-based active material. When such roles are satisfied, all of the general binders can be applied. Specifically, an aqueous binder may be used, and more specifically, a PAM-based binder may be used.
In an exemplary embodiment of the present disclosure, the negative electrode binder may be included in an amount of 30 parts by weight or less, preferably 25 parts by weight or less, and more preferably 20 parts by weight or less, and 5 parts by weight or more, and 10 parts by weight or more, on the basis of 100 parts by weight of the negative electrode composition.
An exemplary embodiment of the present disclosure provides a method for manufacturing a negative electrode active material, the method including: depositing a silicon-based active material on a substrate by chemically reacting a silane gas; growing the silicon-based active material through crystal nucleation; and obtaining the silicon-based active material deposited on the substrate, wherein the silicon-based active material has a specific surface area of 0.30 m2/g or greater and 4.00 m2/g or less.
According to an example, the silane gas may include one or more gas selected from monosilane, dichlorosilane, and trichlorosilane, and specifically, may be a trichlorosilane gas.
In an exemplary embodiment of the present disclosure, the step of growing the silicon-based active material through crystal nucleation may be performed under temperature conditions of 800° C. or higher, preferably 800° C. to 1300° C. This is a lower temperature than the existing gas atomizing method in which heating is performed at 1600° C. or higher in order to melt Si. In addition, the growing of the silicon-based active material through crystal nucleation may be performed under a pressure of 100 Pa to 150 Pa. Due to such a low pressure, a silicon growth rate is reduced, and as a result, formation of small crystal grains can be achieved.
In the related art, a silicon-based active material was fabricated by pulverizing MG-silicon (metallurgical grade silicon), which is a lump of silicon, with physical force. When manufactured in this way, the crystal grain size generally exceeds a range of 100 nm and a surface is smooth, resulting in a specific surface area of less than 0.30 m2/g. When simply manufacturing a silicon-based active material by the method of the related art, it is difficult to secure life stability of the negative electrode because the specific surface area cannot be controlled.
However, the method for manufacturing a negative electrode active material according to the present disclosure includes gasifying a silicon lump into a silane gas through a chemical reaction as described above and then growing the silicon-based active material through crystal nucleation to form silicon particles. Accordingly, it was possible to obtain a silicon-based active material that satisfies the specific surface area range according to the present disclosure.
In an exemplary embodiment of the present disclosure, there is provided a negative electrode for a lithium secondary battery including: a negative electrode current collector layer; and a negative electrode active material layer including the negative electrode composition according to the present disclosure or a cured product thereof formed on one surface or both surfaces of the negative electrode current collector layer.
In an exemplary embodiment of the present disclosure, the negative electrode for a lithium secondary battery may be formed by applying and drying a negative electrode slurry including the negative electrode composition to one surface or both surfaces of the negative electrode current collector layer.
In this case, the negative electrode slurry may include the negative electrode composition described above, and a slurry solvent
In an exemplary embodiment of the present disclosure, a solid content of the negative electrode slurry may satisfy a range of 5% or more and 40% or less.
In another exemplary embodiment, the solid content of the negative electrode slurry may satisfy a range of 5% or more and 40% or less, preferably 7% or more and 35% or less, and more preferably 10% or more and 30% or less.
The solid content of the negative electrode slurry may mean a content of the negative electrode composition included in the negative electrode slurry, and may mean a content of the negative electrode composition on the basis of 100 parts by weight of the negative electrode slurry.
When the solid content of the negative electrode slurry satisfies the above range, the viscosity is appropriate during formation of the negative electrode active material layer, so that particle aggregation of the negative electrode composition is minimized to efficiently form the negative electrode active material layer.
In an exemplary embodiment of the present disclosure, the slurry solvent may be used without limitation as long as it can dissolve the negative electrode composition, and specifically, water or NMP may be used.
In an exemplary embodiment of the present disclosure, the negative electrode current collector layer generally has a thickness of 1 μm to 100 μm. Such negative electrode current collector layer is not particularly limited as long as it has high conductivity without causing a chemical change in the battery. For example, copper, stainless steel, aluminum, nickel, titanium, fired carbon, copper or stainless steel each surface-treated with carbon, nickel, titanium, silver, or the like, an aluminum-cadmium alloy, or the like may be used. In addition, the negative electrode current collector layer may have microscopic irregularities formed on a surface to enhance a coupling force of the negative electrode active material, and may be used in various forms such as a film, a sheet, a foil, a net, a porous body, a foamed body, or a non-woven fabric body.
In an exemplary embodiment of the present disclosure, there is provided the negative electrode for a lithium secondary battery in which a thickness of the negative electrode current collector layer is 1 μm or greater and 100 μm or less and a thickness of the negative electrode active material layer is 5 μm or greater and 500 μm or less.
However, the thickness may be variously modified depending on a type and use of the negative electrode used, and is not limited thereto.
In an exemplary embodiment of the present disclosure, a porosity of the negative electrode active material layer may satisfy a range of 10% or greater and 60% or less.
In another exemplary embodiment, the porosity of the negative electrode active material layer may satisfy a range of 10% or greater and 60% or less, preferably 20% or greater and 50% or less, and more preferably 30% or greater and 45% or less.
The porosity varies depending on compositions and contents of the silicon-based active material, conductive material and binder included in the negative electrode active material layer, and in particular, satisfies the range described above when the silicon-based active material according to the present disclosure and the conductive material are included in the specific compositions and contents, so that the electrode has electrical conductivity and resistance within appropriate ranges.
An exemplary embodiment of the present disclosure provides a lithium secondary battery including a positive electrode; the negative electrode for a lithium secondary battery according to the present disclosure; a separator provided between the positive electrode and the negative electrode; and an electrolyte.
The secondary battery according to the exemplary embodiment of the present specification may particularly include the negative electrode for a lithium secondary battery described above. Specifically, the secondary battery may include a negative electrode, a positive electrode, a separator interposed between the positive electrode and the negative electrode, and an electrolyte, and the negative electrode is the same as the negative electrode described above. Since the negative electrode has been described above, a detailed description thereof is 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 it has conductivity without causing a chemical change in the battery. For example, stainless steel, aluminum, nickel, titanium, fired carbon, aluminum or stainless steel each surface treated with carbon, nickel, titanium, silver, or the like, or the like may be used. In addition, the positive electrode current collector may typically have a thickness of 3 to 500 μm, and a surface of the current collector may be formed with microscopic irregularities to enhance adhesion of the positive electrode active material. 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 foamed body, and a non-woven fabric body.
The positive electrode active material may be a positive electrode active material that is typically used. Specifically, the positive electrode active material may be a layered compound such as a lithium cobalt oxide (LiCoO2) and a 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≤c≤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 represented by chemical formula LiNi1-c2Mc2O2 (where M is at least one selected from the group consisting of Co, Mn, Al, Cu, Fe, Mg, B, and Ga, and satisfies 0.01≤c2≤0.3); a lithium manganese composite oxide represented by chemical formula LiMn2-c3Mc3O2 (where M is at least one selected from the group consisting of Co, Ni, Fe, Cr, Zn and Ta, and satisfies 0.01≤c3≤0.1) or Li2Mn3MO8 (where M is at least one selected from the group consisting of Fe, Co, Ni, Cu and Zn); LiMn2O4 in which a part of Li of the chemical formula is substituted with an alkaline earth metal ion, or 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 positive electrode active material described above.
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 electronic conductivity without causing a chemical change in a battery. Specific examples may include graphite such as natural graphite and 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 powders or metal fibers 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 polyphenylene derivative, or the like, and any one thereof or a mixture of two or more thereof may be used.
In addition, the positive electrode binder serves to improve bonding between particles of the positive electrode active material and adhesion between the positive electrode active material and the positive electrode current collector. Specific examples may include polyvinylidene fluoride (PVDF), vinylidene fluoride-hexafluoropropylene copolymer (PVDF-CO-HFP), polyvinyl alcohol, polyacrylonitrile, carboxymethylcellulose (CMC), starch, hydroxypropylcellulose, regenerated cellulose, polyvinylpyrrolidone, tetrafluoroethylene, polyethylene, polypropylene, ethylene-propylene-diene polymer (EPDM), sulfonated-EPDM, styrene butadiene rubber (SBR), fluoro rubber, or various copolymers thereof, and the like, and any one thereof or a mixture of two or more thereof may be used.
The separator serves to separate the negative electrode and the positive electrode and to provide a movement path of lithium ions, in which any separator may be used as the separator without particular limitation as long as it is typically used in a secondary battery, and particularly, a separator having high moisture-retention ability for an electrolyte as well as a low resistance to the movement of electrolyte ions may be preferably used. Specifically, a porous polymer film, for example, a porous polymer film manufactured from 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 having two or more layers thereof may be used. In addition, a typical porous non-woven fabric, for example, a non-woven fabric formed of high melting point glass fibers, polyethylene terephthalate fibers, or the like may be used. Furthermore, a coated separator including a ceramic component or a polymer material may be used to secure heat resistance or mechanical strength, and the separator having a single layer or multilayer structure may be selectively used.
Examples of the electrolyte may include an organic liquid electrolyte, an inorganic liquid electrolyte, a solid polymer electrolyte, a gel-type polymer electrolyte, a solid inorganic electrolyte, or a molten-type inorganic electrolyte that may be used in the manufacturing of the lithium secondary battery, but are not limited thereto.
Specifically, the electrolyte may include a non-aqueous organic solvent and a metal salt.
As the non-aqueous organic solvent, for example, an aprotic organic solvent such as N-methyl-2-pyrrolidinone, propylene carbonate, ethylene carbonate, butylene carbonate, dimethyl carbonate, diethyl carbonate, gamma-butyrolactone, 1,2-dimetoxy ethane, tetrahydrofuran, 2-methyltetrahydrofuran, dimethyl sulfoxide, 1,3-dioxolane, formamide, dimethylformamide, dioxolane, acetonitrile, nitromethane, methyl formate, methyl acetate, phosphoric acid triester, trimethoxy methane, dioxolane derivative, sulfolane, methyl sulfolane, 1,3-dimethyl-2-imidazolidinone, propylene carbonate derivative, tetrahydrofuran derivative, ether, methyl propionate, or ethyl propionate may be used.
In particular, among the carbonate-based organic solvents, ethylene carbonate and propylene carbonate, which are cyclic carbonates, are high-viscosity organic solvents and can be preferably used because they have high permittivity to dissociate a lithium salt well. When the cyclic carbonate is mixed with a linear carbonate with low viscosity and low permittivity, such as dimethyl carbonate or diethyl carbonate, in a suitable ratio and used, an electrolyte having high electric conductivity may be prepared, and therefore, may be more preferably used.
A lithium salt may be used as the metal salt, and the lithium salt is a material that is readily soluble in the non-aqueous electrolyte, in which, for example, one or more species selected from the group consisting of F−, Cl−, I−, NO3−, N(CN)2-, BF4−, ClO4−, PF6−, (CF3)2PF4−, (CF3)3PF3−, (CF3)4PF2−, (CF3)5 PF−, (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− may be used as an anion of the lithium salt.
One or more additives, for example, a haloalkylene carbonate-based compound such as difluoroethylene carbonate, pyridine, triethylphosphite, triethanolamine, cyclic ether, ethylenediamine, n-glyme, hexaphosphoric 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 the electrolyte for the purpose of improving life characteristics of the battery, suppressing a decrease in battery capacity, improving discharge capacity of the battery, and the like, in addition to the above-described electrolyte components.
An exemplary embodiment of the present disclosure provides a battery module including the secondary battery as a unit cell, and a battery pack including the same. Since the battery module and the battery pack include the secondary battery having high capacity, high-rate capability, and high cycle characteristics, the battery module and the battery pack may be used as a power source of a medium to 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.
Hereinafter, preferred examples will be provided for better understanding of the present disclosure. It will be apparent to one skilled in the art that the examples are only provided to illustrate the present disclosure and various modifications and alterations are possible within the scope and technical spirit of the present disclosure. Such modifications and alterations naturally fall within the scope of claims included herein.
In this case, through process condition control (condition selection for controlling the specific surface area in Table 1 within the ranges of the crystal nucleation temperature and pressure, and control of the specific surface area by controlling the temperature and pressure conditions), the specific surface area of the silicon-based active materials of Examples 1 to 6 could be controlled, and the results are shown in Table 1.
In Comparative Example 2, the silicon lump, which is MG-Si, was pulverized using physical force, melted, and gas atomized, and a strong base etching method was used to form a silicon-based active material with pores. In this case, each information was as shown in Table 1 above.
In addition, in Comparative Example 3, the vapor-deposited silicon-based active material was treated with a strong base to mainly form pores in the particles rather than forming irregularities on a surface. This resulted in a larger specific surface area, as compared with other Comparative Examples and Examples, Equation 1 (circularity) showing an increased value as compared with Examples 1 to 6 of the present disclosure, and Equation 2 (convexity) showing a reduced value.
This is because, in Comparative Example 3, like Comparative Example 2, the roughness is greatly increased due to the pores formed on the smooth surface, but the particles, which are close to elliptical, are shaved and rounded.
As shown in Table 1, the silicon of Examples 1 to 6 had a specific surface area of 0.30 m2/g or greater.
For reference, in Comparative Example 3 in which pores were formed inside the silicon-based active material rather than having an irregularity shape protruding from the surface of the silicon-based active material, as in Comparative Example 1, the silicon-based active material with a smooth surface was formed, and the pores were formed by the strong base etching method. As a result, it can be seen that the specific surface area was larger and the value of Equation 1 was larger, as compared with Examples 1 to 6. It is believed that this is because when pores are formed, as the roughness of the existing smooth surface increases, Equation 2 (Convexity) decreases, but during the etching process, some particles close to the elliptical shape are shaved and rounded.
A negative electrode slurry was prepared by adding a negative electrode active material including the silicon-based active material of Table 1, a negative electrode conductive material, and polyacrylamide as a binder to distilled water as a solvent for formation of a negative electrode slurry in a weight ratio of 80:10:10 (solid concentration: 25 wt %).
Specifically, the negative electrode conductive material was carbon black (specific surface area: 45 m2/g, diameter: 30 to 50 nm).
As a specific mixing method, after dispersing the negative electrode conductive material, the binder and water at 2500 rpm for 30 minutes with a homo mixer, the silicon-based active material was added to the dispersion, which was then dispersed at 2500 rpm for 30 minutes to fabricate a negative electrode slurry.
The negative electrode slurry was coated on both surfaces of a copper current collector (thickness: 8 μm) serving as a negative electrode current collector with a loading amount of 85 mg/25 cm2, which was then roll-pressed and dried in a vacuum oven at 130° C. for 10 hours to form a negative electrode active material layer (thickness: 33 μm), which was prepared as a negative electrode (thickness of negative electrode: 41 μm, porosity of negative electrode: 40.0%).
A positive electrode slurry was prepared by adding LiNi0.6Co0.2Mn0.2O2 (average particle diameter (D50): 15 μm) as a positive electrode active material, carbon black (product name: Super C65, manufacturer: Timcal) as a conductive material, and polyvinylidene fluoride (PVdF) as a binder to N-methyl-2-pyrrolidone (NMP) as a solvent for formation of a positive electrode slurry in a weight ratio of 97:1.5:1.5 (solid concentration: 78 wt %).
The positive electrode slurry was coated on both surfaces of an aluminum current collector (thickness: 12 μm) serving as a positive electrode current collector with a loading amount of 537 mg/25 cm2, which was then roll-pressed and dried in a vacuum oven at 130° C. for 10 hours to form a positive electrode active material layer (thickness: 65 μm), whereby a positive electrode was manufactured (thickness of the positive electrode: 77 μm, porosity: 26%).
A lithium secondary battery was manufactured by interposing a polyethylene separator between the positive electrode and the negative electrode of the Examples and the Comparative Examples and injecting an electrolyte.
The electrolyte was obtained by adding vinylene carbonate to an organic solvent, in which fluoroethylene carbonate (FEC) and diethyl carbonate (DEC) were mixed in a volume ratio of 10:90, in an amount of 3 wt. % on the basis of a total weight of the electrolyte and adding LiPF6 as a lithium salt to a concentration of 1M.
For the secondary batteries including the negative electrodes manufactured in the Examples and Comparative Examples, the life and capacity retention rate were evaluated using an electrochemical charging and discharging device. The in-situ cycle test was conducted on the secondary battery at 4.2-3.0 V 1 C/0.5 C, and during the test, 0.33 C/0.33 C charging/discharging (4.2-3.0 V) was performed every 50 cycles to measure the capacity retention rate.
As can be seen in Table 2, when checking the capacity retention rates according to the cycles of Examples 1 to 6, Comparative Examples 1 to 3, it could be confirmed that the capacity retention rate of Comparative Example 1 was lower than those of the Examples. This corresponds to results that, when the specific surface area of the silicon-based active material satisfies the range according to the present disclosure, the reactions can occur uniformly during the intercalation and deintercalation reactions of lithium at the time of charging/discharging, the stress applied to the silicon-based active material can be reduced to reduce breakage of the particles, and accordingly, the life retention rate of the electrode is improved.
In the test in Experimental Example 1, the capacity retention rate was measured by charging/discharging (4.2-3.0V) at 0.33 C/0.33 C every 50 cycles, and then the resistance increase rate was compared and analyzed by discharging the battery with a pulse of 2.5 C at SOC50 to measure the resistance.
For the evaluation of the resistance increase rate measurement, data at 200 cycles was each calculated, and the results are shown in Table 3 below.
According to Tables 2 and 3, it could be confirmed that the life characteristics and resistance change of the battery using silicon prepared in Examples 1 to 6 as a negative electrode active material were excellent.
Additionally, Comparative Example 2 had the specific surface area smaller than that of the present disclosure, and corresponds to a structure with internal pores rather than the external irregularity shape. In this case, it could be confirmed that the effect was determined excellent, as compared with Comparative Example 1 where the specific surface area significantly deviated from the range of the present disclosure, but the life performance was lower and the resistance change was larger due to the internal pore shape, as compared with the Examples of the present disclosure.
For reference, in Comparative Example 3 in which pores were formed inside the silicon-based active material rather than having an irregularity shape protruding from the surface of the silicon-based active material, as in Comparative Example 2, the silicon-based active material with a smooth surface was formed, and the pores were formed by the strong base etching method. As a result, it can be confirmed that the specific surface area was larger and the value of Equation 1 was larger, as compared with Examples 1 to 6. In this case, as in Comparative Example 2, it could be confirmed that the life performance was lower and the resistance change was larger due to the internal pore shape, as compared with the Examples of the present disclosure.
| Number | Date | Country | Kind |
|---|---|---|---|
| 10-2022-0097513 | Aug 2022 | KR | national |
| 10-2023-0100381 | Aug 2023 | KR | national |
This application is a National Phase entry pursuant to 35 U.S.C. § 371 of International Application No. PCT/KR2023/011329 filed on Aug. 2, 2023, and claims priority to and the benefit of Korean Patent Application No. 10-2022-0097513 filed on Aug. 4, 2022, the disclosures of which are incorporated herein by reference in their entirety.
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/KR2023/011329 | 8/2/2023 | WO |
