CN116783729A - Negative electrode active material, negative electrode comprising same, secondary battery comprising same, and method for manufacturing negative electrode active material - Google Patents
Negative electrode active material, negative electrode comprising same, secondary battery comprising same, and method for manufacturing negative electrode active material Download PDFInfo
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- CN116783729A CN116783729A CN202280012345.1A CN202280012345A CN116783729A CN 116783729 A CN116783729 A CN 116783729A CN 202280012345 A CN202280012345 A CN 202280012345A CN 116783729 A CN116783729 A CN 116783729A
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Landscapes
- Battery Electrode And Active Subsutance (AREA)
Abstract
The present application relates to a negative electrode active material, a negative electrode including the same, a secondary battery including the same, and a method of manufacturing the negative electrode active material.
Description
Technical Field
The present application claims priority and benefit from korean patent application nos. 10-2021-0107525 and 10-2022-0008564, filed in the korean intellectual property office on day 13 of 2021 and day 20 of 2022, respectively, the entire contents of which are incorporated herein by reference.
The present application relates to a negative electrode active material, a negative electrode including the same, a secondary battery including the same, and a method of preparing the negative electrode active material.
Background
Recently, with the rapid spread of electronic devices using batteries, such as mobile phones, notebook computers, and electric vehicles, the demand for small and lightweight secondary batteries having relatively high capacity has rapidly increased. In particular, lithium secondary batteries are lightweight and have high energy density, and thus have been attracting attention as driving power sources for mobile devices. Accordingly, research and development efforts have been actively conducted to improve the performance of the lithium secondary battery.
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, active material layers each containing a positive electrode active material and a negative electrode active material may be formed on the current collector. Typically, lithium-containing metal oxides such as LiCoO are used 2 And LiMn 2 O 4 As the positive electrode active material for the positive electrode, a carbon-based active material and a silicon-based active material that do not contain lithium are used as the negative electrode active material for the negative electrode.
Among the negative electrode active materials, silicon-based active materials have been attracting attention because of their high capacity and excellent high-rate charging characteristics as compared with carbon-based active materials. However, the silicon-based active material has a disadvantage in that initial efficiency is low because the degree of volume expansion/contraction caused by charge/discharge is large and irreversible capacity is large.
On the other hand, in the silicon-based active material, silicon-based oxide, specifically, siO x (0<x<2) The silicon-based oxide is shown to have an advantage in that the degree of volume expansion/contraction caused by charge/discharge is low compared to other silicon-based active materials such as silicon (Si). However, silicon seriesThe oxide also has a disadvantage in that the initial efficiency is lowered according to the presence of irreversible capacity.
In this regard, studies have been continuously conducted to reduce the irreversible capacity and improve the initial efficiency by doping or embedding metals such as Li, al, and Mg in silicon-based oxides. However, in the case of an anode slurry containing a metal-doped silicon-based oxide as an anode active material, there is a problem in that pH of the anode slurry is increased and viscosity thereof is changed by reacting a metal oxide formed by doping a metal with moisture, and thus, there is a problem in that the state of the prepared anode is deteriorated and the anode charge/discharge efficiency is lowered.
Therefore, there is a need to develop an anode active material capable of improving the phase stability of an anode slurry containing a silicon-based oxide and improving the charge/discharge efficiency of an anode prepared therefrom.
Korean patent No. 10-0794192 relates to a method for preparing a carbon-coated silicon-graphite composite negative electrode material for a lithium secondary battery and a method for preparing a secondary battery comprising the same, but has limitations in solving the above-described problems.
[ related art literature ]
[ patent literature ]
(patent document 1) Korean patent No. 10-0794192
Disclosure of Invention
Technical problem
The present invention relates to a negative electrode active material, a negative electrode including the same, a secondary battery including the same, and a method of preparing the negative electrode active material.
Technical proposal
An exemplary embodiment of the present invention provides a negative active material including: silicon-based particles comprising SiO x (0<x<2) And a Li compound, and the silicon-based particles have a carbon layer provided on at least a part of the surface thereof; and a layer comprising LiF disposed on at least a portion of the silicon-based particles, wherein F is relative to the original of O during analysis by X-ray photoelectron spectroscopy (XPS)The sub-ratio (F/O ratio) is 0.45 or more and the atomic ratio of F to C (F/C ratio) is 0.5 or less.
An exemplary embodiment of the present invention provides a method of preparing a negative active material, the method including: forming silicon-based particles comprising SiO x (0<x<2) And a Li compound, and the silicon-based particles have a carbon layer provided on at least a part of the surface thereof; and forming a layer including LiF on at least a portion of the silicon-based particles by reacting the silicon-based particles with an HF solution.
An exemplary embodiment of the present invention provides a negative electrode including the negative electrode active material.
An exemplary embodiment of the present invention provides a secondary battery including the negative electrode.
Advantageous effects
The anode active material according to an exemplary embodiment of the present invention can enhance aqueous workability by effectively removing lithium byproducts formed when doping silicon-based particles with Li, and can improve service life performance by providing a LiF-containing layer on the silicon-based particles to function as an artificial SEI layer. Further, since the atomic ratio of F to O (F/O ratio) is 0.45 or more and the atomic ratio of F to C (F/C ratio) is 0.5 or less on the particle surface, the aqueous workability can be significantly improved.
Accordingly, the anode including the anode active material according to one exemplary embodiment of the present invention and the secondary battery including the anode have the effect of improving the discharge capacity, initial efficiency, resistance performance, and/or service life characteristics of the battery.
Detailed Description
Hereinafter, the present specification will be described in more detail.
In this specification, when a component "includes" one constituent element, unless specifically stated otherwise, this does not mean to exclude another constituent element, but means that another constituent element may be further included.
In this specification, when one member is provided "on" another member, this includes not only the case where one member is in contact with another member but also the case where another member is present between the two members.
The terms or words used in the present specification should not be construed as limited to conventional or dictionary meanings, but interpreted with meanings and concepts conforming to the technical gist of the present invention based on the principle that the inventor is able to properly define concepts of terms so as to describe his/her invention in the best manner.
As used in this specification, the singular expression of a term includes the plural expression unless the context clearly indicates to the contrary.
In this specification, crystallinity of a structure included in the anode active material can be confirmed by X-ray diffraction analysis, which can be performed using an X-ray diffraction (XRD) analyzer (trade name: D4-endavor, manufacturer: bruker), and equipment used in the art may be appropriately employed in addition to the equipment.
In this specification, the presence or absence of an element in the anode active material and the content of the element can be confirmed by ICP analysis, which can be performed using an inductively coupled plasma atomic emission spectrometer (ICPAES, perkin Elmer 7300).
In the present specification, the average particle diameter (D 50 ) Can be defined as the particle size corresponding to 50% cumulative volume in the particle size distribution curve (graphical curve of the particle size distribution map) of the particles. Average particle diameter (D) 50 ) Can be measured using, for example, laser diffraction. Laser diffraction methods are generally capable of measuring particle diameters from the submicron region to about several mm, and can obtain results with high reproducibility and high resolution.
Hereinafter, preferred exemplary embodiments of the present invention will be described in detail. However, the exemplary embodiment of the present invention may be modified into various other forms, and the scope of the present invention is not limited to the exemplary embodiment to be described below.
< negative electrode active Material >
One of the inventionAn exemplary embodiment provides a negative active material including: silicon-based particles comprising SiO x (0<x<2) And a Li compound, and a carbon layer is provided on at least a part of the surface of the silicon-based particles; and a layer containing LiF provided on at least a part of the silicon-based particles, wherein an atomic ratio of F to O (F/O ratio) is 0.45 or more and an atomic ratio of F to C (F/C ratio) is 0.5 or less during analysis by X-ray photoelectron spectroscopy (XPS).
The anode according to an exemplary embodiment of the present invention includes silicon-based particles. The silicon-based particles contain SiO x (0<x<2) And a Li compound, and the silicon-based particles may have a carbon layer provided on at least a part of the surface thereof.
The SiO is x (0<x<2) May correspond to the matrix in the silicon-based particles. The SiO is x (0<x<2) Can be in the form of a composition comprising Si and SiO 2 In the form of (2), the Si may also form a phase. That is, x corresponds to SiO x (0<x<2) The number ratio of O to Si contained in the alloy. When the silicon-based particles contain SiO x (0<x<2) When this is done, the discharge capacity of the secondary battery can be improved.
In one exemplary embodiment of the present invention, the silicon-based particles may include a Li compound.
The Li compound may correspond to a dopant in the silicon-based particles. The Li compound may be present in the silicon-based particles in the form of at least one of a lithium atom, a lithium silicate, a lithium silicide, and a lithium oxide. When the silicon-based particles contain Li compounds, there is an effect of improving the initial efficiency.
The Li compound exists in a form in which the silicon-based particles are doped with the lithium compound, and may be distributed on the surface and/or inside the silicon-based particles. The Li compound is distributed on the surface and/or inside of the silicon-based particles, and thus the volume expansion/contraction of the silicon-based particles can be controlled to a proper level, and can be used to prevent damage to the active material. In addition, the irreversible phase of the silicon-based oxide particles is reduced (for example For example, siO 2 ) The Li compound may be contained in terms of increasing the efficiency of the active material.
In one exemplary embodiment of the present invention, the Li compound may exist in the form of lithium silicate. The lithium silicate is composed of Li a Si b O c (2≤a≤4，0<b.ltoreq.2, 2.ltoreq.c.ltoreq.5), and may be classified into crystalline lithium silicate and amorphous lithium silicate. The crystalline lithium silicate may be selected from the group consisting of Li 2 SiO 3 、Li 4 SiO 4 And Li (lithium) 2 Si 2 O 5 At least one lithium silicate in the group consisting of amorphous lithium silicate may be present in the silicon-based particles in the form of Li a Si b O c (2≤a≤4，0<b.ltoreq.2, 2.ltoreq.c.ltoreq.5), and is not limited to the form.
In one exemplary embodiment of the present invention, the content of Li may be 0.1 to 40 parts by weight or 0.1 to 25 parts by weight with respect to 100 parts by weight of the total of the anode active materials. Specifically, the content of Li may be 1 to 25 parts by weight, more specifically 2 to 20 parts by weight. There is a problem in that as the Li content increases, the initial efficiency increases, but the discharge capacity decreases, so that when the content satisfies the above range, a suitable discharge capacity and initial efficiency can be achieved.
The content of Li element can be confirmed by ICP analysis. Specifically, after a predetermined amount (about 0.01 g) of the anode active material was separated, the anode active material was completely decomposed on a hot plate by transferring the sample to a platinum crucible and adding nitric acid, hydrofluoric acid, or sulfuric acid thereto. Thereafter, a reference calibration curve was prepared by measuring the intensity of a standard solution prepared using a standard solution (5 mg/kg) at the inherent wavelength of the element to be analyzed using an inductively coupled plasma atomic emission spectrometer (ICPAES, perkin-Elmer 7300). Thereafter, the pretreated sample solution and the blank sample are each introduced into the apparatus, the actual strength is calculated by measuring each strength, the concentration of each component is calculated with respect to the prepared calibration curve, and then the elemental content of the prepared anode active material can be analyzed by converting the sum into a theoretical value.
In one exemplary embodiment of the present invention, the silicon-based particles may contain additional metal atoms. The metal atom may be present in the silicon-based particles in the form of at least one of a metal atom, a metal silicate, a metal silicide, and a metal oxide. The metal atom may include at least one selected from the group consisting of Mg, li, al, and Ca. Thereby, the initial efficiency of the anode active material can be improved.
The silicon-based particles according to an exemplary embodiment of the present invention have a carbon layer disposed on at least a portion of the surface thereof. In this case, the carbon layer may be in the form of coating on at least a portion of the surface, i.e., partially coating on the surface of the particles, or coating on the entire surface of the particles. The negative electrode active material is given conductivity by the carbon layer, and initial efficiency, service life characteristics, and battery capacity characteristics of the secondary battery can be improved.
In an exemplary embodiment of the present invention, the carbon layer includes an amorphous phase.
In one exemplary embodiment of the present invention, the carbon layer comprises amorphous carbon.
Furthermore, the carbon layer may additionally contain crystalline carbon.
The crystalline carbon may further improve the conductivity of the anode active material. The crystalline carbon may include at least one selected from the group consisting of fullerenes, carbon nanotubes, and graphene.
The amorphous carbon can suppress expansion of the silicon-based particles by appropriately maintaining the strength of the carbon layer. The amorphous carbon may be a carbide of at least one selected from the group consisting of tar, pitch, and other organic materials, or may be a carbon-based material formed using hydrocarbon as a source of a chemical vapor deposition method.
The carbide of the other organic material may be a carbide of sucrose, glucose, galactose, fructose, lactose, mannose, ribose, aldohexose or aldohexose, and a carbide of an organic material selected from a combination 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 in the substituted or unsubstituted aromatic hydrocarbon include benzene, toluene, xylene, styrene, ethylbenzene, diphenylmethane, naphthalene, phenol, cresol, nitrobenzene, chlorobenzene, indene, coumarone, pyridine, anthracene, phenanthrene, and the like.
In one exemplary embodiment of the present invention, the carbon layer may be contained in an amount of 0.1 to 50 parts by weight, 0.1 to 30 parts by weight, or 0.1 to 20 parts by weight with respect to 100 parts by weight of the total of the anode active materials. More specifically, the carbon layer may be contained in an amount of 0.5 to 15 parts by weight, 1 to 10 parts by weight, or 1 to 5 parts by weight. When the above range is satisfied, the capacity and efficiency of the anode active material can be prevented from being lowered.
In an exemplary embodiment of the present invention, the thickness of the carbon layer may be 1nm to 500nm, and particularly 5nm to 300nm. When the above range is satisfied, the conductivity of the anode active material is improved, the volume change of the anode active material is easily suppressed, and the side reaction between the electrolyte and the anode active material is suppressed, so that there is an effect of improving the initial efficiency and/or the service life of the battery.
Specifically, the carbon layer may be formed by a Chemical Vapor Deposition (CVD) method by using at least one hydrocarbon gas selected from the group consisting of methane, ethane, and acetylene.
The anode active material according to an exemplary embodiment of the present invention includes a LiF-containing layer disposed on at least a portion of the silicon-based particles.
The LiF-containing layer may be in the form of a coating on at least a portion of the silicon-based particles in which the surface is provided with a carbon layer. That is, the LiF-containing layer may be in the form of a partial coating on the surface of the particles or coating on the entire surface of the particles. Examples of the shape of the LiF-containing layer include an island type, a thin film type, and the like, but the shape of the LiF-containing layer is not limited thereto.
The LiF-containing layer can be disposed on at least a portion of the carbon layer. That is, the LiF-containing layer is adjacently coated on the carbon layer, thereby being configured to contain SiO x (0<x<2) And Li compound-carbon layer-the form of particles of the LiF-containing layer.
The LiF-containing layer can be disposed on a layer containing SiO x (0<x<2) And on the areas on the particle surfaces of the Li compound where the carbon layers are not provided. That is, the LiF-containing layer is adjacently coated on the SiO-containing layer x (0<x<2) And Li compound, thereby can be set to contain SiO-containing particles x (0<x<2) And particles of Li compound-LiF.
The LiF-containing layer may be a LiF layer composed of LiF. Alternatively, the LiF-containing layer mainly contains LiF, and may contain a small amount of impurities such as lithium compounds in addition to LiF.
Whether LiF is contained in the anode active material can be confirmed by X-ray diffraction analysis (XRD) or X-ray photoelectron spectroscopy (XPS).
In an exemplary embodiment of the present invention, the LiF-containing layer may be formed by a material selected from the group consisting of Li 2 O, liOH and Li 2 CO 3 One or more lithium compounds of the group consisting of are formed by reaction with HF. The formed LiF is uniformly formed on the surface of the particles, preferably forming a layer on the surface (upper portion) of the lithium byproduct, thereby easily blocking the reaction between water and lithium compound, and functioning as an artificial SEI layer during driving of the battery, thereby having an effect of improving the service life performance.
Specifically, the LiF-containing layer may be formed by preparing silicon-based particles and then acid-treating lithium compounds, i.e., lithium byproducts, remaining near the surface of the silicon-based particles or the carbon layer with HF.
In one exemplary embodiment of the present invention, the lithium compound may be selected from the group consisting of Li 2 O, liOH and Li 2 CO 3 More than one kind of the group.
When the lithium compound is reacted with HF, the LiF-containing layer can be produced by one or more reactions in the following formulas (1) to (3).
(1) LiOH + HF → LiF + H 2 O
(2) Li 2 O + 2HF → 2LiF + H 2 O
(3) Li 2 CO 3 + 2HF → 2LiF + H 2 CO 3
The LiF-containing layer produced as described above is hardly soluble in water, and can effectively passivate silicon-based particles in the aqueous slurry, and has an effect of improving the aqueous processability by preventing the Li compound contained in the silicon-based particles from eluting. In addition, the LiF-containing layer functions as an artificial SEI layer during driving of the battery, thereby having an effect of improving the service life performance of the battery.
In the present invention, the content and atomic ratio of the element on the surface of the anode active material can be confirmed by XPS (Nexsa ESCA system, samer femto technology company (Thermo Fisher Scientific) (ESCA-02)).
Specifically, after the full-scan spectrum (survey scan spectrum) and the narrow-scan spectrum (narrow scan spectrum) of each sample are obtained, the full-scan spectrum and the narrow-scan spectrum may be obtained while depth profile (depth profile) is performed. Depth profiles of up to 3000 seconds can be made using monoatomic Ar ions, with the measurement and data processing conditions as follows.
-an X-ray source: monochromatic Al K alpha (1486.6 eV)
X-ray spot size: 400 μm
-a sputter gun: monoatomic Ar (energy: 1000eV, flow: low, grating width: 2 mm)
Etch rate: for Ta 2 O 5 0.09nm/s
-an operating mode: CAE (constant analyzer energy) mode
-full scan: with an energy of 200eV and an energy level of 1eV
Narrow scan: scanning mode, energy of 50eV, energy level of 0.1eV
-charge compensation: flood gun closing
-SF：Al THERMO1
-ECF：TPP-2M
Background subtraction: shirley
In one exemplary embodiment of the invention, the depth profile of X-ray photoelectron spectroscopy (XPS) may be measured by performing spectroscopy at 0.09nm/s for up to 3000 seconds under an X-ray source of monochromatic alkα.
In one exemplary embodiment of the present invention, when the anode active material is analyzed by X-ray photoelectron spectroscopy (XPS), an atomic ratio of F to O (F/O ratio) is 0.45 or more. Specifically, the atomic ratio may be 0.48 or more, 0.55 or more, 0.6 or more, or 0.7 or more and 20 or less, 15 or less, 10 or less, 5 or less, 3 or less, 2 or less, 1.5 or less, or 1.2 or less.
In one exemplary embodiment of the present invention, when the anode active material is analyzed by X-ray photoelectron spectroscopy (XPS), an atomic ratio of F to C (F/C ratio) is 0.5 or less. Specifically, the atomic ratio may be 0.4 or less, 0.3 or less, 0.25 or less, or 0.22 or less and more than 0, 0.05 or more, 0.08 or more, or 0.1 or more.
When the above F/O ratio and F/C ratio are satisfied, liF is uniformly coated on the silicon-based particles, the particle coverage increases, thus improving passivation effect, and lithium by-products are easily removed, and at the same time, exposure of lithium by-products can be easily prevented, thus having an effect of effectively improving aqueous workability and improving capacity, efficiency and/or life performance of the battery.
In contrast, when the negative electrode active material does not satisfy the F/O ratio and/or the F/C ratio, the particle coverage is low, liF is formed to be partially thick, so that it is difficult to passivate the particles, and the aqueous workability is deteriorated due to the lithium byproduct being easily exposed, and thus there is a problem that the battery characteristics are also deteriorated.
Therefore, when the F/O ratio and the F/C ratio of the anode active material satisfy the above ranges, the optimal battery characteristics can be exhibited.
In one exemplary embodiment of the present invention, when the anode active material is analyzed by X-ray photoelectron spectroscopy (XPS), F may be 0.1 atomic% to 0.3 atomic% with respect to 100 atomic% of the total element.
In an exemplary embodiment of the present invention, when the anode active material is analyzed by X-ray photoelectron spectroscopy (XPS), O may be 5 to 14 or 8 to 13.5 at% with respect to 100 at% of the total element.
In an exemplary embodiment of the present invention, C may be 50 to 65 or 55 to 61 at% with respect to 100 at% of the total element when the anode active material is analyzed by X-ray photoelectron spectroscopy (XPS).
In one exemplary embodiment of the present invention, si may be 6 to 8 atomic% or 7 to 8 atomic% with respect to 100 atomic% of the total element when the anode active material is analyzed by X-ray photoelectron spectroscopy (XPS).
In one exemplary embodiment of the present invention, when the anode active material is analyzed by X-ray photoelectron spectroscopy (XPS), li may be 10 to 25 at% or 10 to 20 at% with respect to 100 at% of the total elements.
In one exemplary embodiment of the present invention, the LiF-containing layer may be contained in an amount of 0.5 parts by weight or more and 5 parts by weight or less with respect to 100 parts by weight of the total of the anode active materials. Specifically, the LiF-containing layer may be contained in an amount of 0.7 parts by weight or more, 0.8 parts by weight or more and 4 parts by weight or less, 3 parts by weight or less, or 2.5 parts by weight or less.
In one exemplary embodiment of the present invention, the content of LiF may be 0.5 parts by weight or more and 5 parts by weight or less with respect to 100 parts by weight total of the anode active material. Specifically, the content of LiF may be 0.7 parts by weight or more, 0.8 parts by weight or more and 4 parts by weight or less, 3 parts by weight or less, or 2.5 parts by weight or less.
When the content of LiF satisfies the above range, a layer is sufficiently formed on the surface (upper portion) of the lithium byproduct, thereby easily blocking the reaction between water and lithium compound, and functioning as an artificial SEI layer during driving of the battery, thereby having an effect of improving service life performance.
In contrast, when the content of LiF is less than 0.5 parts by weight, the content of LiF is so low that there is a problem in that the particles cannot be properly passivated and the lithium by-product reacts with moisture, resulting in poor aqueous workability.
In one exemplary embodiment of the present invention, a lithium compound (lithium byproduct) may be present between the silicon-based particles and the LiF-containing layer.
Specifically, the lithium compound (by-product) may refer to a lithium compound remaining near the surface of the silicon-based particles or the carbon layer after the silicon-based particles are prepared. As described above, even after the acid treatment process, lithium by-products that have not reacted with the acid may remain.
The lithium compound may comprise a material selected from the group consisting of Li 2 O, liOH and Li 2 CO 3 More than one kind of the group. As in the above reaction, the lithium compound reacts with HF to form a LiF-containing layer, and a lithium compound (lithium by-product) generated from residual lithium that does not react with HF may exist between the silicon-based particles and the LiF-containing layer.
The presence or absence of a lithium compound between the silicon-based particles and the LiF-containing layer can be confirmed by X-ray diffraction analysis (XRD) or X-ray photoelectron spectroscopy (XPS).
The content of the lithium compound (by-product) may be 5 parts by weight or less with respect to 100 parts by weight of the total of the anode active materials. Specifically, the content of the lithium compound (by-product) may be 0.01 to 5 parts by weight, 0.05 to 2 parts by weight, or 0.1 to 1 part by weight. More specifically, the content of the lithium compound (by-product) may be 0.1 to 0.8 parts by weight or 0.1 to 0.5 parts by weight. When the content of the lithium by-product satisfies the above range, side reactions in the slurry can be reduced, and the aqueous workability can be improved by reducing the viscosity change. In contrast, when the content of the lithium by-product is higher than the above range, there are problems in that the slurry becomes alkaline during the formation of the slurry, causing side reactions or viscosity changes, and in that the aqueous process is problematic.
The content of the lithium compound (by-product) may be calculated by measuring the amount of HCl solution in a specific interval of pH change during titration of an aqueous solution containing a negative electrode active material with HCl solution using a titrator, and then calculating the amount of lithium by-product.
The average particle diameter (D50) of the anode active material may be 0.1 μm to 30 μm, specifically 1 μm to 20 μm, more specifically 1 μm to 10 μm. When the above range is satisfied, structural stability of the active material during charge and discharge is ensured, it is possible to prevent the problem that the volume expansion/contraction level also becomes large due to an excessive increase in particle diameter, and the problem that the initial efficiency is lowered due to an excessively small particle diameter.
< preparation method of negative electrode active Material >
An exemplary embodiment of the present invention provides a method of preparing a negative active material, the method including: forming silicon-based particles comprising SiO x (0<x<2) And a Li compound, and the silicon-based particles have a carbon layer provided on at least a part of the surface thereof; and forming a layer including LiF on at least a portion of the silicon-based particles by reacting the silicon-based particles with an HF solution.
The silicon-based particles may be formed by: by mixing Si powder with SiO 2 Heating and gasifying the powder under vacuum to form preliminary particles, and then depositing the gasified mixed gas; forming a carbon layer on the surface of the formed preliminary particles; and the preliminary particles having the carbon layer formed thereon are mixed with Li powder, and then the resulting mixture is heat-treated.
Specifically, si powder and SiO may be used 2 The mixed powder of the powders is heat treated under vacuum at 1300 to 1800 ℃, 1400 to 1800 ℃, or 1400 to 1600 ℃.
The formed preliminary particles may have the form of SiO.
The carbon layer may be formed by using Chemical Vapor Deposition (CVD) using a hydrocarbon gas or by a method of carbonizing a material as a carbon source.
Specifically, the carbon layer may be formed by introducing the formed preliminary particles into a reaction furnace and then performing Chemical Vapor Deposition (CVD) on a hydrocarbon gas at 600 to 1200 ℃. The hydrocarbon gas may be at least one hydrocarbon gas selected from the group consisting of methane, ethane, propane, and acetylene, and may be heat-treated at 900 to 1000 ℃.
After mixing the preliminary particles having the carbon layer formed thereon with the Li powder, the heat treatment of the resultant mixture may be performed at 700 to 900 ℃ for 4 to 6 hours, specifically, at 800 ℃ for 5 hours.
The silicon-based particles may contain Li silicate, li silicide, li oxide, or the like as the 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 air classification, and the method is not limited thereto.
The lithium compound (lithium by-product) is provided on at least a part of the surface of the silicon-based particles provided with the carbon layer as described above. Specifically, in the process of forming a material containing SiO x (0<x<2) In the process of preparing the above-mentioned silicon-based particles by forming a carbon layer on the preliminary particles and then doping the preliminary particles with Li, lithium compounds, i.e., lithium by-products formed from unreacted lithium remain near the surfaces of the silicon-based particles.
In one exemplary embodiment of the present invention, the method of preparing the anode active material includes forming a layer including LiF on at least a portion of the silicon-based particles by reacting the silicon-based particles with an HF solution.
Specifically, in order to suppress side reactions due to unreacted lithium compounds, formation of a layer containing LiF on at least a part of the silicon-based particles may be performed.
The LiF formed preferentially forms a layer on the surface (upper portion) of the lithium byproduct, thereby easily blocking the reaction between water and lithium compound, and functions as an artificial SEI layer during driving of the battery, thereby having an effect of improving service life performance.
In one exemplary embodiment of the invention, forming the LiF-containing layer on at least a portion of the silicon-based particles by reacting the silicon-based particles with an HF solution comprises reacting the lithium compound disposed on at least a portion of the silicon-based particles with an HF solution.
Specifically, the LiF-containing layer may be formed by reacting a lithium compound disposed on at least a portion of the silicon-based particles with an HF solution.
The LiF-containing layer can be produced by reacting HF with a lithium compound (Li 2 O, liOH and Li 2 CO 3 ) And reacting to form the catalyst.
When the lithium compound is reacted with an HF solution, the LiF-containing layer can be produced by one or more reactions of the following formulas (1) to (3).
(1) LiOH + HF → LiF + H 2 O
(2) Li 2 O + 2HF → 2LiF + H 2 O
(3) Li 2 CO 3 + 2HF → 2LiF + H 2 CO 3
The HF solution may be 0.03M to 0.3M, specifically 0.05M to 0.2M.
The silicon-based particles and HF solution may be mixed in an amount of 1:1 to 1:10, specifically 1:5 to 1:10 weight ratio.
After mixing the silicon-based particles and the HF solution, heat treatment may be performed at 200 to 500 ℃, specifically 250 to 350 ℃.
When a layer containing LiF is formed by a chemical reaction of a lithium compound with LiF as described above, liF is uniformly formed on the surface of particles, and the formed LiF preferentially forms a layer on the surface (upper portion) of a lithium byproduct, thereby easily blocking the reaction between water and the lithium compound, and functioning as an artificial SEI layer during driving of a battery, thereby having an effect of improving service life performance.
< cathode >
The anode according to an exemplary embodiment of the present invention may include the anode active material described above.
Specifically, the anode may include an anode current collector and an anode active material layer disposed on the anode current collector. The anode active material layer may contain the anode active material. In addition, the anode active material layer may further include a binder, a thickener, and/or a conductive material.
The anode active material layer may be formed by applying an anode slurry including an anode 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 anode slurry may further contain an additional anode active material.
As the additional anode active material, a compound capable of reversibly intercalating and deintercalating lithium may be used. Specific examples thereof include carbonaceous materials such as artificial graphite, natural graphite, graphitized carbon fibers and amorphous carbon; a metal compound that can be alloyed with lithium, such as Si, al, sn, pb, zn, bi, in, mg, ga, cd, si alloy, sn alloy or Al alloy; metal oxides which may be undoped and doped with lithium, e.g. SiO β (0<β<2)、SnO 2 Vanadium oxide, lithium titanium oxide, and lithium vanadium oxide; or a composite material containing a metal compound and a carbonaceous material, such as a si—c composite material or a sn—c composite material, and the like, and any one or a mixture of two or more thereof may be used. In addition, a metallic lithium thin film may be used as the anode active material. Alternatively, both low crystalline carbon and high crystalline carbon 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 natural graphite or artificial graphite in an irregular, planar, flaky, spherical or fibrous shape, floating graphite, pyrolytic carbon, mesophase pitch-based carbon fiber, mesophase carbon microbeads, mesophase pitch and high-temperature calcined carbon such as coke derived from petroleum or coal tar pitch.
The additional anode active material may be a carbon-based anode active material.
In one exemplary embodiment of the present invention, the weight ratio of the anode active material and the additional anode active material included in the anode slurry may be 10:90 to 90:10, specifically 10:90 to 50:50.
the negative electrode slurry may contain a negative electrode slurry-forming solvent. Specifically, the negative electrode slurry-forming solvent may contain at least one selected from the group consisting of distilled water, ethanol, methanol, and isopropanol, and in terms of promoting dispersion of the components, distilled water is specific.
The anode current collector is not particularly limited as long as the anode current collector has conductivity without causing chemical changes to the battery. For example, as the current collector, copper, stainless steel, aluminum, nickel, titanium, fired carbon, or aluminum or stainless steel material whose surface is surface-treated with carbon, nickel, titanium, silver, or the like may be used. In particular, a transition metal such as copper or nickel, which well adsorbs carbon, may be used as the current collector. Although the thickness of the current collector may be 6 μm to 20 μm, the thickness of the current collector is not limited thereto.
The adhesive may comprise at least one selected from the group consisting of: polyvinylidene fluoride-hexafluoropropylene copolymer (PVDF-co-HFP), polyvinylidene fluoride, polyacrylonitrile, polymethyl methacrylate, polyvinyl alcohol, carboxymethyl cellulose (CMC), starch, hydroxypropyl cellulose, regenerated cellulose, polyvinylpyrrolidone, polytetrafluoroethylene, polyethylene, polypropylene, polyacrylic acid, ethylene-propylene-diene monomer (EPDM), sulfonated EPDM, styrene-butadiene rubber (SBR), fluororubber, polyacrylic acid, and materials in which hydrogen thereof is replaced with Li, na, ca, or the like may also contain various copolymers thereof.
The conductive material is not particularly limited as long as the conductive material has conductivity without causing chemical changes to the battery, for example, graphite such as natural graphite or artificial graphite may be used; carbon blacks such as acetylene black, ketjen black, channel black, furnace black, lamp black, and thermal black; conductive fibers such as carbon fibers or metal fibers; conductive tubes such as carbon nanotubes; fluorocarbon powder; metal powders such as aluminum powder and nickel powder; conductive whiskers such as zinc oxide and potassium titanate; conductive metal oxides such as titanium oxide; conductive materials 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 suitably employed.
< Secondary Battery >
The secondary battery according to an exemplary embodiment of the present invention may include the above-described negative electrode according to an exemplary embodiment. 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, the negative electrode being identical to the above-described negative electrode. Since the anode has been previously described, a detailed 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 a 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 chemical changes to the battery, and for example, stainless steel, aluminum, nickel, titanium, sintered carbon, or a material surface-treated with carbon, nickel, titanium, silver, or the like may be used. In addition, the thickness of the positive electrode current collector may be generally 3 to 500 μm, and the adhesion of the positive electrode active material may be further 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, and a nonwoven fabric body.
The positive electrode active material may be a commonly used positive electrode active material. Specifically, the positive electrode active material includes: layered compounds such as lithium cobalt oxide (LiCoO) 2 ) And lithium nickel oxide (LiNiO) 2 ) Or a compound substituted with more than one transition metal; lithium iron oxides such as LiFe 3 O 4 The method comprises the steps of carrying out a first treatment on the surface of the Lithium manganese oxide as chemical formula Li 1+c1 Mn 2-c1 O 4 (0≤c1≤0.33)、LiMnO 3 、LiMn 2 O 3 And LiMnO 2 The method comprises the steps of carrying out a first treatment on the surface of the Lithium copper oxide (Li) 2 CuO 2 ) The method comprises the steps of carrying out a first treatment on the surface of the Vanadium oxides such as LiV 3 O 8 、V 2 O 5 And Cu 2 V 2 O 7 The method comprises the steps of carrying out a first treatment on the surface of the Ni-site lithium nickel oxide, expressed as chemical formula LiNi 1-c2 M c2 O 2 (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.ltoreq.c2.ltoreq.0.3); lithium manganese composite oxide, expressed as chemical formula LiMn 2- c3 M c3 O 2 (where M is at least one selected from the group consisting of Co, ni, fe, cr, zn and Ta, and c3 satisfies 0.01.ltoreq.c3.ltoreq.0.1) or Li 2 Mn 3 MO 8 (here, M is at least one selected from the group consisting of Fe, co, ni, cu and Zn); liMn 2 O 4 Wherein Li and the like in the chemical formula are partially replaced with alkaline earth metal ions, 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.
In this case, the positive electrode conductive material is used to impart conductivity to the electrode, and may be used without particular limitation as long as the positive electrode conductive material has electron conductivity without causing chemical changes in the battery to be constituted. Specific examples thereof include graphite such as natural graphite or artificial graphite; carbon-based materials 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; conductive whiskers such as zinc oxide and potassium titanate; conductive metal oxides such as titanium oxide; or a conductive polymer such as a polyphenylene derivative, and any one or a mixture of two or more thereof may be used.
Alternatively, the positive electrode binder is used to improve the bonding between the 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), polyvinylidene fluoride-hexafluoropropylene copolymer (PVDF-co-HFP), polyvinyl alcohol, polyacrylonitrile, carboxymethyl cellulose (CMC), starch, hydroxypropyl cellulose, regenerated cellulose, polyvinylpyrrolidone, polytetrafluoroethylene, polyethylene, polypropylene, ethylene-propylene-diene monomer (EPDM), sulfonated EPDM, styrene-butadiene rubber (SBR), fluororubber, or various copolymers thereof, and any one or a mixture of two or more thereof may be used.
The separator separates the anode and the cathode and provides a passage for movement of lithium ions, and may be used without particular limitation as long as the separator is a separator that is generally used in a secondary battery, and in particular, a separator that is excellent in the ability of the electrolyte to retain moisture and low in resistance to movement of ions in the electrolyte is preferable. Specifically, 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 may be used. In addition, a conventional porous nonwoven fabric such as a nonwoven fabric made of high-melting glass fiber, polyethylene terephthalate fiber, or the like can also be used. In addition, a coated separator including a ceramic component or a polymer material may be used to secure heat resistance or mechanical strength, and may be selectively used as a single-layer or multi-layer structure.
Examples of the electrolyte include, but are not limited to, organic liquid electrolytes, inorganic liquid electrolytes, solid polymer electrolytes, gel-type polymer electrolytes, solid inorganic electrolytes, molten inorganic electrolytes, and the like, which can be used in the preparation of lithium secondary batteries.
In particular, the electrolyte may comprise a non-aqueous organic solvent and a metal salt.
As the nonaqueous organic solvent, for example, an aprotic organic solvent such as N-methyl-2-pyrrolidone, propylene carbonate, ethylene carbonate, butylene carbonate, dimethyl carbonate, diethyl carbonate, γ -butyrolactone, 1, 2-dimethoxyethane, tetrahydrofuran, 2-methyltetrahydrofuran, dimethyl sulfoxide, 1, 3-dioxolane, formamide, dimethylformamide, dioxolane, acetonitrile, nitromethane, methyl formate, methyl acetate, phosphotriester, trimethoxymethane, dioxolane derivatives, sulfolane, methyl sulfolane, 1, 3-dimethyl-2-imidazolidinone, propylene carbonate derivatives, tetrahydrofuran derivatives, ethers, methyl propionate, and ethyl propionate can be used.
In particular, among the carbonate-based organic solvents, ethylene carbonate and propylene carbonate as cyclic carbonates may be preferably used because cyclic carbonates have a high dielectric constant as high-viscosity organic solvents and thus dissociate lithium salts well, and when the cyclic carbonates are mixed with linear carbonates having low viscosity and low dielectric constant such as dimethyl carbonate and diethyl carbonate in a suitable ratio, an electrolyte having high conductivity can be prepared, and thus such a combined use is more preferable.
As the metal salt, a lithium salt which is a material easily dissolved in a nonaqueous electrolytic solution, for example, as an anion of the lithium salt, one or more selected from the group consisting of: f (F) - 、Cl - 、I - 、NO 3 - 、N(CN) 2 - 、BF 4 - 、ClO 4 - 、PF 6 - 、(CF 3 ) 2 PF 4 - 、(CF 3 ) 3 PF 3 - 、(CF 3 ) 4 PF 2 - 、(CF 3 ) 5 PF - 、(CF 3 ) 6 P - 、CF 3 SO 3 - 、CF 3 CF 2 SO 3 - 、(CF 3 SO 2 ) 2 N - 、(FSO 2 ) 2 N - 、CF 3 CF 2 (CF 3 ) 2 CO - 、(CF 3 SO 2 ) 2 CH - 、(SF 5 ) 3 C - 、(CF 3 SO 2 ) 3 C - 、CF 3 (CF 2 ) 7 SO 3 - 、CF 3 CO 2 - 、CH 3 CO 2 - 、SCN - Sum (CF) 3 CF 2 SO 2 ) 2 N - 。
In the electrolyte, for the purpose of improving the service life characteristics of the battery, suppressing the decrease in the battery capacity and improving the discharge capacity of the battery, one or more additives such as halogenated alkylene carbonate compounds such as difluoroethylene carbonate, pyridine, triethyl phosphite, triethanolamine, cyclic ether, ethylenediamine, N-glyme, hexamethylphosphoric triamide, nitrobenzene derivatives, sulfur, quinone imine dyes, N-substitutedOxazolidinone, N-substituted imidazolidine, ethylene glycol dialkyl ether, ammonium salts, pyrrole, 2-methoxyethanol or aluminum trichloride.
According to still another exemplary embodiment of the present invention, there are provided 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 secondary batteries having high capacity, high rate characteristics, and cycle characteristics, and thus may be used as a power source for medium-to-large devices selected from the group consisting of electric vehicles, hybrid electric vehicles, plug-in hybrid electric vehicles, and electric power storage systems.
Modes for carrying out the application
Hereinafter, the present specification will be described in detail with reference to examples for specifically describing the present specification. However, the embodiments according to the present specification may be modified in various forms, and the scope of the present application should not be construed as being limited to only the embodiments described in detail below. Embodiments of the present application are provided to more fully explain the present description to those skilled in the art.
< examples and comparative examples >
Example 1
Wherein the ratio of 1:1 is mixed with Si and SiO in a molar ratio of 2 And 94g of the powder obtained was mixed in a reaction furnace, and the resulting mixture was heated under vacuum at a sublimation temperature of 1400 ℃. Thereafter, gasifyingSi and SiO 2 The mixed gas of (2) is reacted in a cooling zone at a cooling temperature of 800 ℃ in a vacuum state and condensed into a solid phase. Next, particles having a size of 6 μm were prepared by pulverizing the aggregated particles for 3 hours using a ball mill. Thereafter, while maintaining an inert atmosphere by flowing Ar gas, the particles were placed in a hot zone of a CVD apparatus, methane was blown into the hot zone at 900℃using Ar as a carrier gas, at 10 -1 The reaction was carried out for 5 hours under the support, thereby forming a carbon layer on the surface of the particles. Thereafter, 6g of Li metal powder was added to the particles formed with the carbon layer and mixed, and then, additional heat treatment was performed at a temperature of 800 ℃ in an inert atmosphere to prepare silicon-based particles containing Li.
The silicon-based particles and 0.1M HF solution were mixed in a ratio of 1:7 weight ratio, the resulting solution was stirred for 1 hour, filtered, dried, and heat-treated at 300 c to prepare a negative active material incorporating a LiF layer.
Example 2
A negative electrode active material was prepared in the same manner as in example 1, except that a 0.15M HF solution was used.
Example 3
A negative electrode active material was prepared in the same manner as in example 1, except that a 0.05M HF solution was used.
Example 4
A negative electrode active material was prepared in the same manner as in example 1, except that a 0.2M HF solution was used.
Comparative example 1
A negative electrode active material was prepared in the same manner as in example 1, except that the introduction of the LiF layer was not performed.
Comparative example 2
Except that during the introduction of the LiF layer, liF powder and silicon-based particles were mixed at 1.5:100, and then introducing a LiF layer to the surface of the silicon-based particles by a ball mill, in the same manner as in example 1.
Comparative example 3
Except that during the introduction of the LiF layer, liF powder and silicon-based particles were mixed in a ratio of 0.4:100, and then introducing a LiF layer to the surface of the silicon-based particles by a ball mill, in the same manner as in example 1.
< measurement of carbon layer content >
The content of the carbon layer was analyzed using a CS analyzer (CS-800, eltra).
< measurement of content and atomic ratio of element by X-ray photoelectron Spectroscopy (XPS) >)
The content (atomic%) and the atomic ratio of the element on the surface of the anode active material were confirmed by XPS (Nexsa ESCA system, samer feishi technologies (Thermo Fisher Scientific) (ESCA-02)).
Specifically, a full-scan spectrum and a narrow-scan spectrum of each sample are obtained, and then the full-scan spectrum and the narrow-scan spectrum are obtained while performing depth distribution. Depth distribution was performed for up to 3000 seconds using monoatomic Ar ions, and measurement and data processing conditions were as follows.
-an X-ray source: monochromatic Al K alpha (1486.6 eV)
X-ray spot size: 400 μm
-a sputter gun: monoatomic Ar (energy: 1000eV, flow: low, grating width: 2 mm)
Etch rate: for Ta 2 O 5 0.09nm/s
-an operating mode: CAE (constant analyzer energy) mode
-full scan: with an energy of 200eV and an energy level of 1eV
Narrow scan: scanning mode, energy of 50eV, energy level of 0.1eV
-charge compensation: flood gun closing
-SF：Al THERMO1
-ECF：TPP-2M
Background subtraction: shirley
As a result of the above measurement, the content and the atomic ratio of each element were calculated with respect to 100 atomic% total content of the measured element.
< measurement of Li content in negative electrode active Material >
The content of Li atoms was confirmed by ICP analysis using an inductively coupled plasma atomic emission spectrometer (ICP-OES, AVIO 500 from Perkin-Elmer 7300).
< analysis of LiF content >
Samples of 20ml to 200ml were dispensed into a corning tube and eluted by shaking with 30g of ultra pure water for 24 hours. In this case, additional dilutions were made, if necessary, to bring the sample concentration within the standard material calibration curve (1 mg/kg). After measuring the F content using IC6000 (sameidie technologies, thermo Fisher Scientific) under the following analysis conditions, the LiF content was calculated from the measured F content.
[ analysis conditions ]
-column: ionPacAS18 (4X 250 mm), ionPacAG18 (4X 50 mm)
Eluent type KOH (30.5 mM), eluent flow: 1 mL/min
-a detector: suppression type conductivity detector, SRS current: 76mA, injection volume: 25 μl of
The constitution of the anode active materials prepared in examples and comparative examples is shown in table 1 below.
TABLE 1
< experimental example: evaluation of discharge capacity, initial efficiency and service life (Capacity Retention Rate) characteristics ]
Manufacturing of negative electrode
As the negative electrode material, the composite negative electrode active material prepared in example 1 and graphite (average particle diameter (D50): 20 μm) as a carbon-based active material were used in an amount of 15:85 weight percent of the mixture.
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 in an amount of 96:2:1:1, and adding the resultant mixture 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 measured at 3.6mAh/cm 2 The negative electrode slurry was coated with the support amount of (c), and the copper current collector was rolled and dried in a vacuum oven at 130 ℃ for 10 hours to form a negative electrode active material layer (thickness: 50 μm), which was used as a negative electrode according to example 1 (thickness of negative electrode: 65 μm).
Further, the negative electrodes of examples 2 to 4 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 to 4 and comparative examples 1 to 3 were used instead of the negative electrode active material of example 1, respectively.
Manufacturing of secondary battery
A lithium metal foil was prepared as a positive electrode.
Coin-type half cells of examples 1 to 4 and comparative examples 1 to 3 were manufactured by interposing a porous polyethylene separator between the negative electrodes of examples 1 to 4 and comparative examples 1 to 3 manufactured as above and the positive electrodes described above and injecting an electrolyte thereinto, respectively.
As the electrolyte, a solution prepared by dissolving 0.5 wt% of Vinylene Carbonate (VC) in a solution of 7:3 in a volume ratio of Ethylene Methyl Carbonate (EMC) and Ethylene Carbonate (EC) and dissolving LiPF at a concentration of 1M 6 And the product obtained.
Evaluation of discharge capacity, initial efficiency and service life (Capacity Retention Rate) characteristics
The discharge capacities, initial efficiencies, and cyclic capacity retention rates of the secondary batteries fabricated in examples 1 to 4 and comparative examples 1 to 3 were evaluated using electrochemical chargers/dischargers.
The cycle capacity retention was carried out at a temperature of 25℃with the first cycle and the second cycle charged and discharged at 0.1C and the third cycle and subsequent cycles charged and discharged at 0.5C (charge conditions: CC/CV,5mV/0.005C off, discharge conditions: CC,1.5V off).
The discharge capacity (mAh/g) and initial efficiency (%) were derived from the results of one charge/discharge.
The capacity retention was calculated as follows.
Capacity retention (%) = { (discharge capacity of nth cycle)/(discharge capacity of 1 st cycle) } ×100
(in this formula, N is an integer of 1 or more.)
The 50 th cycle capacity retention (%) is shown in table 2 below.
TABLE 2
| Battery cell | Discharge capacity (mAh/g) | Initial efficiency (%) | Capacity retention (%) |
| Example 1 | 506 | 91.2 | 93.1 |
| Example 2 | 506 | 91.3 | 93.6 |
| Example 3 | 506 | 91.2 | 92.8 |
| Example 4 | 506 | 91.1 | 91.6 |
| Comparative example 1 | 502 | 85.6 | 76.5 |
| Comparative example 2 | 503 | 87.8 | 84.6 |
| Comparative example 3 | 506 | 88.2 | 86.1 |
Examples 1 to 4 have LiF-containing layers disposed on silicon-based particles and satisfy F/O ratio of 0.45 or more and F/C ratio of 0.5 or less, and it was confirmed that discharge capacity, initial efficiency and capacity retention rate were excellent because LiF-containing layers can be uniformly coated on the surfaces of silicon-based particles, thereby blocking the reaction between lithium by-products and moisture.
In contrast, as in comparative example 1, when no LiF layer was provided on the surface of the silicon-based particles, it was confirmed that the discharge capacity, initial efficiency, and capacity retention rate of the battery were deteriorated because the aqueous slurry was degraded in the working procedure due to the reaction between the lithium by-product of the anode active material and moisture.
In the case of comparative example 2, a layer containing LiF was formed on the silicon-based particles, but the F/C ratio showed a high value of 0.62. As is clear from this, liF is partially formed to be thick, particles are not easily passivated, lithium by-products are easily exposed, and thus the aqueous workability is poor, and it is confirmed that the discharge capacity, initial efficiency, and capacity retention rate of the battery are deteriorated.
In the case of comparative example 3, a layer containing LiF was formed on the surface of the silicon-based particles, but the content of LiF was low, and the F/C ratio showed a low value of 0.4. As is clear from this, liF is partially formed on the particles, the particles are not easily passivated, lithium by-products are easily exposed, and thus the aqueous workability is poor, and it is confirmed that the discharge capacity, initial efficiency, and capacity retention rate of the battery are deteriorated.
Claims (13)
1. A negative electrode active material, the negative electrode active material comprising:
silicon-based particles comprising SiO x And Li compound, wherein 0<x<2, and the silicon-based particles have a carbon layer provided on at least a part of the surface thereof; and
a layer comprising LiF disposed on at least a portion of the silicon-based particles,
wherein an atomic ratio of F to O (F/O ratio) is 0.45 or more and an atomic ratio of F to C (F/C ratio) is 0.5 or less during analysis by X-ray photoelectron spectroscopy (XPS).
2. The anode active material according to claim 1, wherein an atomic ratio of F to O (F/O ratio) is 0.48 or more and 2 or less when the anode active material is analyzed by X-ray photoelectron spectroscopy (XPS).
3. The anode active material according to claim 1, wherein an atomic ratio of F to C (F/C ratio) is greater than 0 and 0.3 or less when the anode active material is analyzed by X-ray photoelectron spectroscopy (XPS).
4. The anode active material according to claim 1, wherein the content of the LiF-containing layer is 0.5 to 5 parts by weight with respect to 100 parts by weight in total of the anode active material.
5. The anode active material according to claim 1, wherein a lithium compound is present between the silicon-based particles and the LiF-containing layer.
6. The anode active material according to claim 5, wherein the lithium compound contains a metal selected from the group consisting of Li 2 O, liOH and Li 2 CO 3 More than one kind of the group.
7. The anode active material according to claim 1, wherein the LiF-containing layer is formed by a material selected from the group consisting of Li 2 O, liOH and Li 2 CO 3 And the reaction of more than one lithium compound in the group with HF.
8. The anode active material according to claim 1, wherein the content of Li is 0.1 to 40 parts by weight with respect to 100 parts by weight of the total of the anode active material.
9. The anode active material according to claim 1, wherein the content of the carbon layer is 0.1 to 50 parts by weight with respect to 100 parts by weight in total of the anode active material.
10. A method of producing the anode active material according to any one of claims 1 to 9, the method comprising:
forming silicon-based particles comprising SiO x And Li compound, wherein 0<x<2, and the silicon-based particles have a carbon layer provided on at least a part of the surface thereof; and
a layer comprising LiF is formed on at least a portion of the silicon-based particles by reacting the silicon-based particles with an HF solution.
11. The method of claim 10, wherein the forming a LiF-containing layer on at least a portion of the silicon-based particles by reacting the silicon-based particles with an HF solution comprises reacting the lithium compound disposed on at least a portion of the silicon-based particles with the HF solution.
12. A negative electrode comprising the negative electrode active material according to any one of claims 1 to 9.
13. A secondary battery comprising the negative electrode according to claim 12.
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| KR10-2021-0107525 | 2021-08-13 | ||
| KR10-2022-0008564 | 2022-01-20 | ||
| KR1020220008564A KR20230025316A (en) | 2021-08-13 | 2022-01-20 | Negative electrode active material, negative electrode comprising same, secondary battery comprising same, and method for preparing negative electrode active material |
| PCT/KR2022/010143 WO2023018025A1 (en) | 2021-08-13 | 2022-07-12 | Negative electrode active material, negative electrode including same, secondary battery including same, and method for manufacturing negative electrode active material |
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