Patent Application
20250105254
The present disclosure relates to a negative electrode for a secondary battery and a secondary battery including the same.
A secondary battery is universally applied not only to a portable device, but also to an electric vehicle (EV) or a hybrid electric vehicle (HEV) that is driven by an electrical driving source.
The secondary battery is attracting attention as a new energy source to improve eco-friendliness and energy efficiency because of the primary advantage that the use of fossil fuels can be dramatically reduced and the advantage that no by-products are generated from the use of energy.
In general, a secondary battery includes a positive electrode, a negative electrode, a separator interposed between the positive electrode and the negative electrode, an electrolyte, and the like. In addition, the electrode such as a positive electrode and a negative electrode may have an electrode active material layer provided on a current collector.
As utilization of the secondary battery increases, various battery performances are required. Attempts have been made to appropriately compose an electrode active material layer in order to improve battery performance. Some performances of the battery may be improved depending on selection or combination of materials, but some performances may rather deteriorate. Accordingly, research on the selection or combination of appropriate materials is necessary depending on the performance of the secondary battery to be improved.
An aspect of the present invention has been made in an effort to provide a negative electrode capable of providing a secondary battery with rapid charge performance and improved life, and a secondary battery including the same.
An exemplary embodiment of the present invention provides a negative electrode for a secondary battery including a current collector; a first negative electrode active material layer provided on the current collector and including a silicon carbon composite; and a second negative electrode active material layer provided on the first negative electrode active material layer and including a silicon oxide, wherein a ratio (D50,2nd/D50,1st) Of an average particle diameter (D50,2nd) of the silicon oxide to an average particle diameter (D50,1st) of the silicon carbon composite is 0.75 to 1.5.
Another exemplary embodiment of the present invention provides a secondary battery including the negative electrode for a secondary battery described above, a positive electrode, and a separator.
According to the exemplary embodiments described in the present specification, the silicon carbon composite and the silicon oxide, which have different efficiency and swelling characteristics, among silicon-based active materials, are arranged at specific positions in the two negative electrode active material layers, making it possible to provide a secondary battery with excellent rapid charge performance and improved life.
Hereinafter, the present invention will be described in more detail for better understanding of the present invention. The present invention may be implemented in various different forms, and is not limited to the exemplary embodiments described herein. The terms or words used throughout the specification and the claims should not be construed as being limited to their ordinary or dictionary meanings, but construed as having meanings and concepts consistent with the technical idea of the present invention, based on the principle that an inventor may properly define the concepts of the words or terms to best explain the invention.
It will be further understood that the terms “comprises”, “includes” or “have” when used in the present specification specify the presence of stated features, integers, steps, constitutional elements and/or combinations thereof, but do not preclude the presence or addition of one or more other features, integers, steps, constitutional elements, and/or combinations thereof.
Further, it will be understood that when an element such as a layer is referred to as being “on” another element, it can be “directly on” the other element or an intervening element may also be present. In contrast, when an element is referred to as being “directly on” another element, there are no intervening elements present. Further, when an element is referred to as being “on” a reference portion, the element is positioned above or below the reference portion, and it does not necessarily mean that the element is positioned “above” or “on” in a direction opposite to gravity.
In the present specification, descriptions referred to only as “active material layer” without first and second expressions may be applied to both the first and second active material layers.
A negative electrode for a secondary battery according to an exemplary embodiment of the present specification includes a current collector; a first negative electrode active material layer provided on the current collector and including a silicon carbon composite; and a second negative electrode active material layer provided on the first negative electrode active material layer and including a silicon oxide, wherein a ratio (D50,2nd/D50,1st) Of an average particle diameter (D50,2nd) of the silicon oxide to an average particle diameter (D50,1st) of the silicon carbon composite is 0.75 to 1.5.
Recently, attempts have been made to design batteries by arranging silicon-based active materials in a negative electrode in order to improve rapid charge, which is the biggest requirement for automobile batteries. However, the present inventors have found that when a silicon-based active material with large swelling is arranged in an upper layer of the negative electrode, the upper layer is intensively used during charging and discharging, leading to significant deterioration in the silicon-based active material present in the upper layer and poor life characteristics. Accordingly, the present inventors have found that when two types of silicon-based active materials with different efficiency and swelling characteristics are used and arranged at specific positions in two negative electrode active material layers, a battery with excellent rapid and charge improved life characteristics can be provided, whereby an embodiment of the present invention has been achieved.
Specifically, the negative electrode for a secondary battery according to the above exemplary embodiment includes silicon carbon a composite among silicon-based active materials in a first negative electrode active material layer arranged adjacent to a current collector, and a silicon oxide in a second negative electrode active material layer arranged farther from the current collector. Silicon oxide has relatively low efficiency but has long-life characteristics, and silicon carbon composite has high efficiency characteristics. Therefore, silicon oxide and silicon carbon composite are arranged in the upper and lower layers of the two negative electrode active material layers, respectively, leading to excellent rapid charge performance and improved life characteristics.
In addition, a ratio (D50,2nd/D50,1st) of an average particle diameter (D50,2nd) of the silicon oxide to an average particle diameter (D50,1st) of the silicon carbon composite may be 0.75 to 1.5, 0.9 to 1.1, or 0.9 to 1.
If the average particle diameter of the silicon oxide and the average particle diameter of the silicon carbon composite deviate from the above range, a pore structure is heterogeneous, thus impairing the mobility of lithium ions, and the reactivities of the first negative electrode active material layer and the second negative electrode active material layer are different, thus having an adverse effect on the battery life.
According to an exemplary embodiment, the silicon carbon composite included in the first negative electrode active material layer has a discharge efficiency of 85% to 95%. Additionally, the silicon oxide included in the second negative electrode active material layer has a discharge efficiency of 75% to 85%.
The discharge efficiency of the negative electrode active materials may be measured as follows.
First, a negative electrode slurry is prepared by adding the negative electrode active material, Super-C (registered trademark) as a conductive material, carboxy methylcellulose (CMC) as a thickener, and a styrene-butadiene rubber (SBR) binder polymer to water at a weight ratio of 95:1:1:3. A copper foil is coated with the negative electrode slurry, punched and rolled to have an area of 1.4875 cm2, and then dried to prepare a negative electrode. The negative electrode and lithium metal as a counter electrode are used to prepare an electrode assembly with a polypropylene separator interposed between both the electrodes. A non-aqueous electrolyte solution is prepared by adding 1M LiPF6 to an organic solvent in which ethylene carbonate and ethyl methyl carbonate are mixed at a volume ratio of 3:7 and vinylene carbonate is added to a concentration of 1 wt %. Then, the non-aqueous electrolyte solution is injected into the electrode assembly to prepare a coin-type secondary half-cell (coin half cell; CHC).
When charging the negative electrode coin-type secondary half-cell (CHC) prepared above, a constant current is applied up to 0.005 V at a rate of 0.2 C by a constant current constant voltage (CC—CV) method, and then the current is controlled by a constant voltage at 0.005 V. During discharge, the discharge efficiency may be measured by cutting-off at 1.5 V by a constant current (CC) method at a rate of 0.2 C. The discharge efficiency can be calculated as discharge capacity/charge capacity*100.
In the present specification, the silicon carbon composite is a composite of Si and C, may be expressed as a Si/C-based active material, and is distinguished from silicon carbide expressed as SiC. The silicon carbon composite may be a composite of silicon, graphite, and the like, and may form a structure in which a core composite of silicon, graphite, and the like is surrounded by graphene, amorphous carbon or the like. In the silicon carbon composite, silicon may be nano silicon.
In the present specification, the silicon oxide may be expressed as SiOx (0≤x<2). The silicon oxide may be a silicon-based composite particle including SiOx (0<x<2) and a pore.
The SiOx (0<x<2) corresponds to a matrix in the silicon-based composite particle. The SiOx (0<x<2) may be a form of including Si and SiO2, and the Si may form a phase. That is, x corresponds to a ratio of the number of O to Si included in the SiOx (0<x<2). When the silicon-based composite particle includes the SiOx (0<x<2), a discharge capacity of a secondary battery can be improved.
The silicon-based composite particle may further include at least one of an Mg compound and a Li compound. The Mg compound and the Li compound may correspond to a matrix in the silicon-based composite particle.
The Mg compound and/or the Li compound may be present in the Siox (0<x<2) and/or on a surface of the SiOx (0<x<2). The initial efficiency of the battery can be improved by the Mg compound and/or the Li compound.
The Mg compound may include at least one selected from the group consisting of Mg silicate, Mg silicide, and Mg oxide. The Mg silicate may include at least one of Mg2SiO4 and MgSiO3. The Mg silicide may include Mg2Si. The Mg oxide may include MgO.
In an exemplary embodiment of the present specification, the Mg element may be included in an amount of 0.1 wt % to 20 wt % or 0.1 wt % to 10 wt % on the basis of 100 wt % of a total of the silicon-based active material. Specifically, the Mg element may be included in an amount of 0.5 wt % to 8 wt % or 0.8 wt % to 4 wt %. When the above range is satisfied, the Mg compound can be included in an appropriate content in the silicon-based active material, so the volume change of the silicon-based active material during charging and discharging of the battery can be easily suppressed, and the discharge capacity and initial efficiency of the battery can be improved.
The Li compound may include at least one selected from the group consisting of Li silicate, Li silicide, and Li oxide. The Li silicate may include at least one of Li2SiO3, Li4SiO4 and Li2Si2O5. The Li silicide may include Li7Si2. The Li oxide may include Li2O.
In an exemplary embodiment of the present invention, the Li compound may include a form of lithium silicate. The lithium silicate is represented by LiaSibOc (2≤a≤4, 0<b≤2, 2≤c≤5) and may be divided into crystalline lithium silicate and amorphous lithium silicate. The crystalline lithium silicate may be present in the silicon-based composite particle in a form of at least one lithium silicate selected from the group consisting of Li2SiO3, Li4SiO4 and Li2Si2O5, and the amorphous lithium silicate may be a form of LiaSibOc (2a≤4, 0<b≤2, 2≤c≤5). However, the present invention is not limited thereto.
In an exemplary embodiment of the present specification, the Li element may be included in an amount of 0.1 wt % to 20 wt % or 0.1 wt % to 10 wt % on the basis of 100 wt % of a total of the silicon-based active material. Specifically, the Li element may be included in an amount of 0.5 wt % to 8 wt %, and more specifically, 0.5 wt % to 4 wt %. When the above range is satisfied, the Li compound can be included in an appropriate content in the silicon-based active material, so the volume change of the negative electrode active material during charging and discharging of the battery can be easily suppressed, and the discharge capacity and initial efficiency of the battery can be improved.
The content of the Mg element or Li element can be confirmed through inductively coupled plasma (ICP) analysis. For the ICP analysis, a predetermined amount (about 0.01 g) of a negative electrode active material is precisely aliquoted, transferred to a platinum crucible, and completely decomposed on a hot plate by adding nitric acid, hydrofluoric acid and sulfuric acid thereto. Then, by using an inductively coupled plasma atomic emission spectrometer (ICP-AES, Perkin-Elmer 7300), a reference calibration curve is obtained by measuring the intensity of a standard liquid, which has been prepared using a standard solution (5 mg/kg), at an intrinsic wavelength of the Mg element or Li element. Subsequently, a pre-treated sample solution and a blank sample are introduced into the spectrometer, and by measuring the intensity of each component to calculate an actual intensity, calculating the concentration of each component based on the obtained calibration curve, and then performing a conversion such that the sum of the calculated concentrations of the components is equal to a theoretical value, the Mg element or Li element content in the prepared silicon-based active material can be analyzed.
In an exemplary embodiment of the present specification, a carbon layer may be provided on a surface of the silicon-based composite particle and/or inside the pore. Conductivity is imparted to the silicon-based composite particle by the carbon layer, so that the initial efficiency, life characteristics, and battery capacity characteristics of a secondary battery including the negative electrode active material including the silicon-based composite particle can be improved. A total amount of the carbon layer included may be 5 wt % to 40 wt % on the basis of 100 wt % of a total of the silicon-based composite particle.
In an exemplary embodiment of the present specification, the carbon layer may include at least one of amorphous carbon or crystalline carbon.
An average particle diameter (D50) of the silicon-based active material may be 2 μm to 15 μm, specifically 3 μm to 12 μm, and more specifically 4 μm to 10μ. When the above range is satisfied, a side reaction between the silicon-based composite particle and the electrolyte solution is controlled, and the discharge capacity and initial efficiency of the battery can be effectively implemented.
In the present specification, the average particle diameter (D50) may be defined as a particle diameter corresponding to 50% of the cumulative volume in the particle diameter distribution curve of particles. The average particle diameter (D50) may be measured using, for example, a laser diffraction method. In the laser diffraction method, in general, particle diameters ranging from a submicron range to several millimeters can be measured, and results with high reproducibility and high resolvability can be obtained.
According to an exemplary embodiment, the silicon carbon composite in the first negative electrode active material layer may be included in an amount of 1 wt % to 20 wt % based on 100 wt % of the first negative electrode active material layer, and the silicon oxide in the second negative electrode active material layer may be included in an amount of 1 wt % to 20 wt % based on 100 wt % of the second negative electrode active material layer. When the content of the silicon carbon composite or silicon oxide in the first or second negative electrode active material layer is 1 wt % or more, the capacity gain becomes a certain level or higher, so that the advantage of using these materials can be exhibited, and when the content is 20 wt % or less, excessive swelling is prevented, which is advantageous for life and battery characteristics and is also price competitive from a cost perspective.
According to an exemplary embodiment, the first negative electrode active material layer and the second negative electrode active material layer further include a carbon-based active material. The carbon-based active material may be graphite, and the graphite may be natural graphite, artificial graphite, or a mixture thereof. The carbon-based active material may be included in an amount of 80 parts by weight or more and 99 parts by weight or less on the basis of 100 parts by weight of a total of the negative electrode active material included in each negative electrode active material layer.
In an exemplary embodiment of the present specification, the negative electrode active material may be included in an amount of 80 parts by weight or more and 99.9 parts by weight or less, preferably 90 parts by weight or more and 99.9 parts by weight or less, more preferably 95 parts by weight or more and 99.9 parts by weight or less, and most preferably 98 parts by weight or more and 99.9 parts by weight or less on the basis of 100 parts by weight of each negative electrode active material layer.
According to an additional exemplary embodiment of the present specification, the negative electrode active material layer may further include a negative electrode binder, in addition to the silicon-based active material and the carbon-based active material.
The negative electrode binder may serve to improve adhesion between particles of the negative electrode active material and adhesive force between particles of the negative electrode active material and the negative electrode current collector. For the negative electrode binder, those known in the art may be used. Non-limiting examples thereof may include at least one selected from the group consisting of polyvinylidenefluoride-hexafluoropropylene copolymer (PVDF-co-HFP), polyvinylidenefluoride, polyacrylonitrile, polymethylmethacrylate, polyvinyl alcohol, (CMC), starch, carboxymethylcellulose hydroxypropylcellulose, regenerated cellulose, polyvinylpyrrolidone, polytetrafluoroethylene, polyethylene, polypropylene, polyacrylic acid, ethylene-propylene-diene monomer (EPDM), sulfonated EPDM, styrene butadiene rubber (SBR), fluoro rubber, poly acrylic acid, and the above-mentioned materials in which a hydrogen is substituted with Li, Na, Ca, etc., and may also include various copolymers thereof.
The negative electrode binder may be included in an amount of 0.1 part by weight or more and 20 parts by weight or less, for example, preferably 0.3 part by weight or more and 20 parts by weight or less, and more preferably 0.5 part by weight or more and 10 parts by weight or less on the basis of 100 parts by weight of the negative electrode active material layer.
The negative electrode active material layer may not include a conductive material, but may further include a conductive material if necessary. The conductive material included in the negative electrode active material layer is not particularly limited as long as it has conductivity without causing a chemical change in the battery, and for example, graphite such as natural graphite or artificial graphite; carbon black such as acetylene black, Ketjen black, channel black, furnace black, lamp black, and thermal black; a conductive fiber such as a carbon fiber and a metal fiber; a conductive tube such as a carbon nanotube; metal powders such as fluorocarbon, aluminum, and nickel powders; a conductive whisker such as zinc oxide and potassium titanate; a conductive metal oxide such as titanium oxide; a conductive material such as polyphenylene derivative, and the like may be used. A content of the conductive material in the negative electrode active material layer may be 0.01 part by weight to 20 parts by weight, and preferably 0.03 part by weight to 18 parts by weight on the basis of 100 parts by weight of the negative electrode active material layer.
In an exemplary embodiment of the present specification, a thickness of each of the first and second negative electrode active material layers may be 10 μm or greater and 150 μm or less. A weight loading amount of each of the first and second negative electrode active material layers may be 50 to 300 mg/25 cm2. The weight loading amount is a weight based on solid content after drying.
In an exemplary embodiment of the present specification, the negative electrode current collector is not particularly limited as long as it has conductivity without causing a chemical change in the battery. For example, for the current collector, copper, 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. Specifically, transition metals that adsorb carbon well, such as copper and nickel, may be used for the current collector. A thickness of the current collector may be 1 μm to 500 μm. However, the thickness of the current collector is not limited thereto.
An additional exemplary embodiment of the present specification provides a secondary battery including the negative electrode according to the above-described exemplary embodiments, a positive electrode, and a separator.
In an exemplary embodiment of the present specification, 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. A thickness of the positive electrode active material layer may be 20 μm or greater and 500 μm or less.
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 1 to 500 μm, and a surface of the current collector may be formed with microscopic irregularities to enhance adhesive force 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.
In an exemplary embodiment of the present specification, the positive electrode may include a lithium composite transition metal compound including nickel (Ni) and cobalt (Co), as an active material. The lithium composite transition metal compound may further include at least one of manganese and aluminum. The lithium composite transition metal compound may include 80 mol % or more, for example, 80 mol % or more and less than 100 mol % of nickel among metals other than lithium.
In an exemplary embodiment, the positive electrode active material in 100 parts by weight of the positive electrode active material layer may be included in an amount of 80 parts by weight or more and 99.9 parts by weight or less, preferably 90 parts by weight or more and 99.9 parts by weight or less, more preferably 95 parts by weight or more and 99.9 parts by weight or less, and most preferably 98 parts by weight or more and 99.9 parts by weight or less.
According to a further exemplary embodiment of the present specification, the positive electrode active material layer according to the exemplary embodiment described above may further include a positive electrode binder and a conductive material.
The positive electrode binder may serve to improve adhesion between particles of the positive electrode active material and adhesive force between particles of the positive electrode active material and the positive electrode current collector. For the positive electrode binder, those known in the art may be used. Non-limiting examples thereof may include polyvinylidene fluoride (PVDF), vinylidene fluoride-hexafluoropropylene copolymer (PVDF-co-HFP), polyvinyl alcohol, polyacrylonitrile, carboxymethylcellulose (CMC), starch, hydroxypropylcellulose, regenerated cellulose, polyvinylpyrrolidone, polytetrafluoroethylene, polyethylene, polypropylene, ethylene-propylene-diene polymer (EPDM), sulfonated-EPDM, styrene butadiene rubber (SBR), fluoro rubber, various copolymers thereof, and the like, and any one thereof or a mixture of two or more thereof may be used.
The positive electrode binder may be included in an amount of 0.1 part by weight or more and 50 parts by weight or less, for example, preferably 0.3 part by weight or more and 35 parts by weight or less, and more preferably 0.5 part by weight or more and 20 parts by weight or less on the basis of 100 parts by weight of the positive electrode active material layer.
The conductive material included in the positive electrode active material layer is used to impart conductivity to the electrode, and can be used without particular limitation as long as the 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.
Specifically, in an exemplary embodiment, the conductive material may include one or more of a single-walled carbon nanotube (SWCNT) and a multi-walled carbon nanotube (MWCNT). The conductive material may be included in an amount of 0.1 part by weight or more and 2 parts by weight or less, for example, preferably 0.3 part by weight or more and 1.5 parts by weight or less, and more preferably 0.5 part by weight or more and 1.2 parts by weight or less on the basis of 100 parts by weight of the composition for a positive electrode active material layer.
The positive electrode and the negative electrode can be manufactured according to a conventional method for manufacturing a positive electrode and a negative electrode, except using the positive electrode and negative electrode active materials described above. Specifically, the electrodes can be manufactured by applying a composition for active material layer formation, including the above-described active material and, optionally, a binder and a conductive material, onto a current collector, followed by drying and rolling. In this case, the types and contents of the positive electrode and negative electrode active materials, the binder, and the conductive material are as described above. The solvent may be a solvent commonly used in the art, such as dimethyl sulfoxide (DMSO), isopropyl alcohol, N-methylpyrrolidone (NMP), acetone, or water, and any one thereof or a mixture of two or more thereof may be used. A used amount of the solvent is sufficient if it can dissolve or disperse the active material, the conductive material, and the binder in consideration of an applied thickness of a slurry and a manufacturing yield, and then, allows for a viscosity capable of exhibiting excellent thickness uniformity when applied to manufacture a positive electrode and a negative electrode. Alternatively, the positive electrode and the negative electrode may be manufactured by laminating, on a current collector, film a obtained by casting the composition for active material layer formation on a separate support and peeling off it from the support.
The separator serves to separate the negative electrode and the positive electrode and to provide a migration 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 solution as well as a low resistance against migration 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 usual 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 and 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 solution, 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)5PF—, (CF3)6P—, CF3SO3—, CF3CF2SO3—, (CF3SO2)2N—, (FSO2)2N—, CF3CF2 (CF3)2CO—, (CF3SO2)2CH—, (SF5)3C—, (CF3SO2)3C—, CF3 (CF2)7SO3—, CF3CO2—, CH3CO2—, SCN— and (CF3CF2SO2)2N— 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.
A secondary battery according to an exemplary embodiment of the present invention includes an assembly including a positive electrode, a negative electrode, a separator, and an electrolyte, and may be a lithium secondary battery.
A further exemplary embodiment of the present invention provides a battery module including the aforementioned secondary battery as a unit cell, and a battery pack including the battery module. 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.
Since the secondary battery according to the exemplary embodiments of the present invention stably exhibits excellent discharge capacity, output characteristics, and cycle performance, the secondary battery can be used as a power source of a portable device such as a mobile phone, a laptop computer, and a digital camera as well as 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. For example, the battery module or battery pack may be used as a power source of a medium to large sized device of any one or more of a power tool; an electric vehicle including an electric vehicle (EV), a hybrid electric vehicle, and a plug-in hybrid electric vehicle (PHEV); or a power storage system.
Hereinafter, preferred examples will be provided for better understanding of the present invention. It will be apparent to one skilled in the art that the examples are only provided to illustrate the present invention and various modifications and alterations are possible within the scope and technical spirit of the present invention. Such modifications and alterations naturally fall within the scope of claims included herein.
A first negative electrode active material layer was formed by coating a composition for formation of a first negative electrode active material layer including a negative electrode active material (content of silicon carbon composite: 5 parts by weight based on 100 parts by weight of negative electrode active material) including a silicon carbon composite (discharge efficiency: 90%, D50:10 μm) and a carbon-based active material (including artificial graphite and natural graphite), a conductive material (including carbon black, CNT), a binder (SBR), and a thickener (CMC) at a weight ratio of 95.9:1.0:2.0:1.1 to a thickness of 70 μm in a dry state on a copper foil (thickness 10 μm) and then drying the same. Then, a second negative electrode active material layer was formed by coating a composition for formation of a second negative electrode active material layer including a negative electrode active material (content of SiO: 5 parts by weight based on 100 parts by weight of the negative electrode active material) including SiO (discharge efficiency: 80%, D50:10 μm) and a carbon-based active material (including artificial graphite and natural graphite), a conductive material (including carbon black, CNT), a binder (SBR), and a thickener (CMC) at a weight ratio of 94.9:1.0:3.0:1.1 to a thickness of 70 μm in a dry state on the first negative electrode active material layer and drying the same, whereby a negative electrode was prepared.
A positive electrode was prepared by coating a composition for formation of a positive electrode active material layer including lithium nickel-based oxide single particles of Li1.0Ni0.84Co0.08Mn0.08O2, a conductive material (CNT), and a binder (PVDF) at a weight ratio of 97:1:2 to a thickness of 130 μm in a dry state on an aluminum foil with a thickness of 15 μm and drying the same.
A battery was prepared by stacking the positive electrode and the negative electrode with a separator interposed therebetween and injecting an electrolyte solution. The electrolyte solution included 1M LiPF6, ethylene carbonate (EC)/ethylmethyl carbonate (EMC) (volume ratio 3/7), and vinylene carbonate (VC)/propane sultone (PS) (included in amounts of 3 parts by weight and 1.5 parts by weight based on 100 parts by weight of the electrolyte, respectively).
In order to check the rapid charge life performance of the prepared battery, the battery was subjected to a cycle of constant current (charging to 4.1V at 2.00 and constant current (CC) discharging (2.5V-cut) at 0.33 C at room temperature (25° C.). The capacity retention rate after 100 cycles is shown in Table 1 below.
The same procedure as in Example was performed except that SiO was included in the first negative electrode active material layer instead of silicon carbon composite.
As shown in Table 1, it could be confirmed that, in the Example, the capacity retention rate was significantly higher, compared to the Comparative Example, and thus the rapid charge life performance was excellent.
| Number | Date | Country | Kind |
|---|---|---|---|
| 10-2022-0132114 | Oct 2022 | KR | national |
| 10-2023-0135780 | Oct 2023 | KR | national |
The present application is a national phase entry under 35 U.S.C. § 371 of International Application No. PCT/KR2023/015831, filed on Oct. 13, 2023, which claims priority from Korean Patent Application No. 10-2022-0132114, filed on Oct. 14, 2022, and Korean Patent Application No. 10-2023-0135780, filed on Oct. 12, 2023, all of which are incorporated herein by reference.
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/KR2023/015831 | 10/13/2023 | WO |
