Patent Application
20240234733
This application claims priority to and the benefit of Korean Patent Application No. 10-2022-0136755, filed in the Korean Intellectual Property Office on Oct. 21, 2022, and Korean Patent Application No. 10-2023-0141539, filed in the Korean Intellectual Property Office on Oct. 20, 2023, the entire content of each of which is incorporated herein by reference.
One or more embodiments of the present disclosure relate to a method of manufacturing an electrode for a rechargeable lithium battery and an electrode manufactured therefrom, and a rechargeable lithium battery including the electrode.
A demand on/for portable electronics such as a laptop, a cellphone, and/or the like has sharply increased, and a demand on/for an electric vehicle, an electric cart, an electric wheelchair, a motorbike, and/or the like has also increased. Accordingly, research on a repetitively chargeable/dischargeable high performance rechargeable battery is actively being made.
As the gradual depletion of carbon energy and an interest in environmental conservation are increased, a demand on a hybrid electric vehicle (HEV), an electric vehicle (EV), and/or the like is being gradually increased around the world. Accordingly, ever-increasing interest and research on a vehicle battery as a core part of the HEV, the EV, and/or the like requires (or there is a desire for) the urgently development of high-rate charge technology to implement the fast charging of a battery. For example, the high-rate charge is very important in an EV having no additional energy source.
This description of the related art is provided only to provide certain background information of the present disclosure. Accordingly, statements made in this description of the related art are not admissions of prior art.
Studies on high-capacity active materials have been conducted for rechargeable lithium batteries with a focus on achieving enhanced electrochemical performance. However, the importance of the polymer binder utilized in the batteries has until now been underestimated because the polymer binder has a relatively low content (e.g., amount) in an electrode and negligible electrochemical properties.
Polymer binders are indispensable components (e.g., additives) that have a significant impact on the dispersibility of a slurry, the physicochemical properties of the electrode, and the subsequent electrochemical performance of a rechargeable lithium battery.
One or more aspects of some embodiments are directed toward a method of manufacturing an electrode for a rechargeable lithium battery which is capable of controlling a behavior of the polymer binder in the electrode to improve adhesion to the current collector, and improving electrochemical properties such as high-rate charging characteristics and/or cycle-life characteristics of the rechargeable lithium battery.
One or more aspects of some embodiments are directed toward an electrode manufactured according to the above manufacturing method and a rechargeable lithium battery including the same. Additional aspects will be set forth in part in the description which follows and, in part, will be apparent from the description, or may be learned by practice of the presented embodiments of the disclosure.
According to some embodiments, a method of manufacturing an electrode for a rechargeable lithium battery includes
According to other embodiments, an electrode for a rechargeable lithium battery manufactured by the disclosed manufacturing method is provided.
According to other embodiments, a rechargeable lithium battery including the electrode for the rechargeable lithium battery is provided.
The electrode manufactured according to the disclosed manufacturing method has improved electrochemical performance and can be utilized in (usefully applied to) a rechargeable lithium battery.
Hereinafter, specific embodiments will be described in more detail so that those of ordinary skill in the art can easily implement them. However, this disclosure may be embodied in many different forms and is not construed as limited to the example embodiments set forth herein. Rather, the present disclosure is intended to cover all modifications, equivalents, and alternatives falling within the spirit and scope of the present disclosure.
The terminology utilized herein is utilized to describe example embodiments only, and is not intended to limit the present disclosure, which is defined by the scope of claims. The singular expression includes the plural expression unless the context clearly dictates otherwise. As utilized herein, the phrase “combination thereof” refers to a mixture, laminate, composite, copolymer, alloy, blend, reaction product, and/or the like of the constituents. In the drawings, the thickness of layers, films, panels, regions, and/or the like, are exaggerated for clarity and like reference numerals designate like elements throughout the specification, and duplicative descriptions thereof may not be provided. It will be understood that if (e.g., when) an element such as a layer, film, region, or substrate is referred to as being “on” another element, it can be directly on the other element or intervening elements may also be present. In contrast, if (e.g., when) an element is referred to as being “directly on” another element, there are no intervening elements present. Accordingly, the embodiments are merely described by referring to the drawings, to explain aspects of the present description. In some embodiments, “layer” herein includes not only a shape formed on the whole surface if (e.g., when) viewed from a plan view, but also a shape formed on a partial surface.
Herein, “or” is not to be construed as an exclusive meaning, for example, “A or B” is construed to include A, B, A+B, and/or the like.
As utilized herein, the term “and/or” includes any and all combinations of one or more of the associated listed items.
Expressions such as “at least one of,” if (e.g., when) preceding a list of elements, modify the entire list of elements and do not modify the individual elements of the list.
As utilized herein, the term “substantially” and similar terms are utilized as terms of approximation and not as terms of degree, and are intended to account for the inherent deviations in measured or calculated values that would be recognized by those of ordinary skill in the art.
As utilized herein, the term “about” and similar terms, if (e.g., when) utilized herein in connection with a numerical value or a numerical range, are inclusive of the stated value and refer to within an acceptable range of deviation for the particular value as determined by one of ordinary skill in the art, considering the measurement in question and the error associated with measurement of the particular quantity (e.g., the limitations of the measurement system). For example, “about” may refer to within one or more standard deviations, or within ±30%, 20%, 10%, 5% of the stated value. Also, any numerical range recited herein is intended to include all sub-ranges of the same numerical precision subsumed within the recited range. For example, a range of “1.0 to 10.0” is intended to include all subranges between (and including) the recited minimum value of 1.0 and the recited maximum value of 10.0, that is, having a minimum value equal to or greater than 1.0 and a maximum value equal to or less than 10.0, such as, for example, 2.4 to 7.6. Any maximum numerical limitation recited herein is intended to include all lower numerical limitations subsumed therein and any minimum numerical limitation recited in this specification is intended to include all higher numerical limitations subsumed therein. Accordingly, Applicant reserves the right to amend this specification, including the claims, to expressly recite any sub-range subsumed within the ranges expressly recited herein.
If (e.g., when) it is described that an element is “on,” “connected to,” or “coupled to” another element, it will be understood that the element may be provided directly on another element or still another element may be interposed therebetween. On the other hand, if (e.g., when) it is described that an element is “directly on” another element, still another element is not interposed therebetween.
It will be understood that, although the terms “first,” “second,” and “third” may be utilized herein to describe one or more suitable elements, components, regions, layers, and/or sections, these elements, components, regions, layers, and/or sections should not be limited by these terms. These terms are only utilized to distinguish one element, component, region, layer, or section from another region, layer, or section. Thus, a first element, component, region, layer, or section described herein may be termed a second element, component, region, layer, or section without departing from the teachings of the present specification.
As utilized herein, the singular forms “a,” “an,” and “the” are intended to include the plural forms, including “at least one,” unless the content (e.g., amount) clearly indicates otherwise. As used herein, expressions such as “at least one,” “one of,” and “selected from,” if (e.g., when) preceding a list of elements, should not be construed as being limited to the singular, but may modify the entire list of elements and do not modify the individual elements of the list. For example, the expressions “at least one of a to c,” “at least one of a, b or c,” and “at least one of a, b and/or c” may indicate only a, only b, only c, both (e.g., simultaneously) a and b, both (e.g., simultaneously) a and c, both (e.g., simultaneously) b and c, all of a, b, and c, or variations thereof.
The terms “include,” “includes,” “including,” “comprise,” “comprises,” “comprising,” “having,” “has,” and/or “have” if (e.g., when) utilized in the detailed description, specify a presence of stated features, regions, integers, steps, operations, elements, and/or components, but do not preclude the presence or addition of one or more other features, regions, integers, steps, operations, elements, components, and/or groups thereof.
Spatially relative terms such as “beneath,” “below,” “lower,” “above,” and “upper” may be utilized herein to easily describe one element or feature's relationship to another element or feature. It will be understood that the spatially relative terms are intended to encompass different orientations of a device in utilization or operation in addition to the orientation illustrated in the drawing. For example, if (e.g., when) a device in the drawings is turned over, elements described as “below” or “beneath” other elements or features would then be “above” or “over” the other elements or features. Thus, the example term “below” may encompass both (e.g., opposite) orientations of above and below. The device may be otherwise oriented (rotated 90 degrees or at other orientations), and the spatially relative terms utilized herein may be interpreted accordingly.
As used herein, the terms “use,” “using,” and “used” may be considered synonymous with the terms “utilize,” “utilizing,” and “utilized,” respectively.
The term “may” will be understood to refer to “one or more embodiments of the present disclosure,” some of which include the described element and some of which exclude that element and/or include an alternate element. Similarly, alternative language such as “or” refers to “one or more embodiments of the present disclosure,” each including a corresponding listed item.
Unless otherwise defined, all terms (including chemical, technical and scientific terms) utilized herein have the same meaning as commonly understood by one of ordinary skill in the art to which the present disclosure belongs. In some embodiments, it will be further understood that terms, such as those defined in commonly utilized dictionaries, should be interpreted as having a meaning that is consistent with their meaning in the context of the relevant art and the present disclosure, and will not be interpreted in an idealized or overly formal sense unless expressly so defined herein.
In this context, “consisting essentially of” means that any additional components will not materially affect the chemical, physical, optical or electrical properties of the semiconductor film.
Further, in this specification, the phrase “on a plane,” or “plan view,” means viewing a target portion from the top, and the phrase “on a cross-section” means viewing a cross-section formed by vertically cutting a target portion from the side.
As utilized herein, the term “particle diameter” of particles refers to an average diameter if (e.g., when) particles are spherical and refers to an average major axis length if (e.g., when) particles are non-spherical. A particle diameter of particles may be measured utilizing a particle size analyzer (PSA). A “particle diameter” of particles is, for example, an “average particle diameter.” An average particle diameter refers to, for example, a median particle diameter (D50). The median particle diameter (D50) is a particle size corresponding to a 50% cumulative volume if (e.g., when) a particle size distribution measured through a laser diffraction method is calculated from particles having a smaller particle size. In some embodiments, a “particle diameter” or an “average particle diameter” may be measured from a transmission electron microscope (TEM) image, a scanning electron microscope (SEM) image, and/or the like.
D50 refers to a particle size corresponding to a 50% cumulative volume if (e.g., when) a particle size distribution measured through a laser diffraction method is calculated from particles having a smaller particle size.
D90 refers to a particle size corresponding to a 90% cumulative volume if (e.g., when) a particle size distribution measured through a laser diffraction method is calculated from particles having a smaller particle size.
D10 refers to a particle size corresponding to a 10% cumulative volume if (e.g., when) a particle size distribution measured through a laser diffraction method is calculated from particles having a smaller particle size.
In some embodiments, the term “group” may refer to a group (i.e., column) of elements in the periodic table of the elements according to the International Union of Pure and Applied Chemistry (“IUPAC”) Groups 1-18 group classification system. In some embodiments, the term “group” may refer to a chemical functional group, e.g., an “alkyl group.”
The term “electrode active material” as utilized herein refers to an electrode material that may undergo lithiation and delithiation.
The term “negative electrode active material” as utilized herein refers to a negative electrode material that may undergo lithiation and delithiation.
The terms “lithiate” and “lithiating” as utilized herein refer to a process of adding lithium to an electrode active material.
The terms “delithiate” and “delithiating” as utilized herein refer to a process of removing lithium from an electrode active material.
The terms “charge” and “charging” as utilized herein refer to a process of providing electrochemical energy to a battery.
The terms “discharge” and “discharging” as utilized herein refer to a process of removing electrochemical energy from a battery.
The term “positive electrode” as utilized herein refers to an electrode at which electrochemical reduction and lithiation occur during a discharging process.
The term “negative electrode” as utilized herein refers to an electrode at which electrochemical oxidation and delithiation occur during a discharging process.
Hereinafter, a method of manufacturing an electrode for a rechargeable lithium battery according to one or more embodiments will be described.
The method of manufacturing an electrode for a rechargeable lithium battery includes
The electrode active material may be a negative electrode active material or a positive electrode active material.
The negative electrode active material may include a carbon-based negative electrode active material that is a material that reversibly intercalates/deintercalates lithium ions, a silicon-carbon composite, or a combination thereof.
The carbon-based negative electrode active material may include crystalline carbon, amorphous carbon, or a combination thereof. The crystalline carbon may be graphite such as non-shaped, sheet-shaped, flake-shaped, sphere-shaped, or fiber-shaped natural graphite or artificial graphite. The amorphous carbon may be a soft carbon, a hard carbon, a mesophase pitch carbonization product, calcined coke, and/or the like.
The carbon-based negative electrode active material may have an average particle diameter (D50) of, for example about 1 μm to about 50 μm, for example about 1 μm to about 40 μm, about 1 μm to about 30 μm, about 1 μm to about 25 μm, about 1 μm to about 20 μm, about 2 μm to about 50 μm, about 5 μm to about 50 μm, about 10 μm to about 50 μm, or about 15 μm to about 50 μm. If (e.g., when) the carbon-based negative electrode active material with the particle diameter ranges is utilized, energy density may be increased, while sufficient voids between particles may be concurrently (e.g., simultaneously) secured. Herein, the average particle diameter is obtained by randomly selecting 20 carbon-based negative electrode active material particles from an electron microscope image of the electrode to measure each particle diameter and obtain a particle diameter distribution therefrom and then, taking a particle diameter (D50) at 50 volume % of a cumulative volume from the particle diameter distribution.
The silicon-carbon composite may include a silicon-based material and amorphous carbon or crystalline carbon in addition to the silicon-based material and the amorphous carbon. Herein, the silicon-based material may be silicon (Si) or a silicon oxide (SiOx, 0<x<2).
If (e.g., when) the silicon-carbon composite includes the silicon-based material and the amorphous carbon, the silicon-carbon composite may be an assembly of the silicon-based material and the amorphous carbon or the silicon-based material coated with the amorphous carbon on the surface. Herein, the silicon-based material and the amorphous carbon may be mixed in a weight ratio of about 1:99 to about 60:40.
If (e.g., when) the silicon-carbon composite includes the crystalline carbon in addition to the silicon-based material and the amorphous carbon, the crystalline carbon and the silicon-based material are assembled to form an assembly, on which the amorphous carbon may be coated. Herein, a content (e.g., amount) of the silicon-based material may be about 1 wt % to about 60 wt %, or for example, about 3 wt % to about 60 wt % based on 100 wt % of the total silicon-based negative electrode active material. In some embodiments, in the silicon-based negative electrode active material, a content (e.g., amount) of the amorphous carbon may be about 20 wt % to about 60 wt % based on 100 wt % of the total silicon-based negative electrode active material, and a content (e.g., amount) of the crystalline carbon may be about 20 wt % to about 60 wt % based on 100 wt % of the total silicon-based negative electrode active material.
The silicon (e.g., of the silicon-carbon composite and/or the silicon-based material) may have a particle diameter of about 10 nm to about 30 μm but according to an embodiment, about 10 nm to about 1000 nm, and according to another embodiment, about 20 nm to about 150 nm.
If (e.g., when) the amorphous carbon is coated to form a layer, the amorphous carbon may have a thickness of about 5 nm to about 100 nm.
The water-soluble binder may include a rubber-based binder, a polymer resin binder, or a combination thereof. The rubber-based binder may include, for example a styrene-butadiene rubber, an acrylated styrene-butadiene rubber, an acrylonitrile-butadiene rubber, an acrylic rubber, a butyl rubber, a fluorine rubber, or a combination thereof. The polymer resin binder may include, for example polyethylene oxide, polyvinylpyrrolidone, polyacrylonitrile, an ethylene propylene diene copolymer, polyvinylpyridine, chlorosulfonated polyethylene, latex, a polyester resin, an acrylic resin, a phenol resin, an epoxy resin, a polyvinyl alcohol, or a combination thereof.
The water-soluble binder may be included in an amount of about 0.1 wt % to about 10 wt %, for example about 0.5 wt % to about 5 wt %, or about 1 wt % to about 3 wt %, based on 100 wt % of the negative electrode active material layer.
The ionic polymer may be a cellulose-based compound. The ionic polymer may have a negative charge in an aqueous medium. By applying an electric field that induces positive charges to the current collector, electrostatic attraction is generated toward the bottom of the negative electrode, thereby suppressing the migration behavior of the ionic polymer having a negative charge.
The cellulose-based compound may include, for example carboxylmethyl cellulose, hydroxypropylmethyl cellulose, methyl cellulose, an alkali metal salt thereof, or a combination thereof. The alkali metal may be Li, Na, K, and/or the like. The ionic polymer may be included in an amount of about 0.1 wt % to about 3 wt %, or about 0.1 wt % to about 1.5 wt % based on 100 wt % of the negative electrode active material layer.
The negative electrode active material layer may include other negative electrode active materials in addition to the negative electrode active material described above. For example, the negative electrode active material layer may further include a silicon-based negative electrode active material and/or a tin-based negative electrode active material. In this case, the capacity of the negative electrode can be maximized or increased.
The silicon-based negative electrode active material may include silicon, SiOx (0<x<2), a Si-Q alloy (where Q is selected from among an alkali metal, an alkaline-earth metal, a Group 13 element, a Group 14 element (excluding Si), a Group 15 element, a Group 16 element, a transition metal, a rare earth element, and a combination thereof).
The tin-based negative electrode active material may be, for example tin, tin oxide (e.g., SnOx (0<x≤2 or 1<x≤2)), a Sn—R alloy (where R is selected from among an alkali metal, an alkaline-earth metal, a Group 13 element, a Group 14 element (excluding Sn), a Group 15 element, a Group 16 element, a transition metal, a rare earth element, and a combination thereof), or a combination thereof. The elements Q and R may include, for example, Mg, Ca, Sr, Ba, Ra, Sc, Y, Ti, Zr, Hf, Rf, V, Nb, Ta, Db, Cr, Mo, W, Sg, Tc, Re., Bh, Fe, Pb, Ru, Os, Hs, Rh, Ir, Pd, Pt, Cu, Ag, Au, Zn, Cd, B, Al, Ga, Sn, In, TI, Ge, P, As, Sb, Bi, S, Se, Te, and/or Po.
The silicon-based negative electrode active material and/or tin-based negative electrode active material may be included in an amount of about 0 wt % to about 60 wt %, about 1 wt % to about 50 wt %, about 1 wt % to about 40 wt %, about 1 wt % to about 30 wt %, or about 5 wt % to about 20 wt % based on 100 wt % of the negative electrode active material in the negative electrode active material layer. Herein, a cost may not only be reduced, but also high capacity may be achieved.
In the negative electrode active material layer, a content (e.g., amount) of the negative electrode active material may be about 80 wt % to about 99.5 wt %, for example, about 85 wt % to about 99 wt %, about 90 wt % to about 99 wt %, or about 95 wt % to about 98 wt % based on a total weight of the negative electrode active material layer.
The negative electrode active material layer may optionally include a conductive material in addition to the negative electrode active material and the polymer binder. The conductive material may be utilized to impart conductivity (e.g., electrical conductivity) to the electrode. Any material that does not cause chemical change (e.g., does not cause an undesirable chemical change in the rechargeable lithium battery) and that conducts electrons can be utilized in the battery. Non-limiting examples thereof may include a carbon-based material such as natural graphite, artificial graphite, carbon black, acetylene black, ketjen black, a carbon fiber, a carbon nanofiber, and a carbon nanotube; a metal-based material including copper, nickel, aluminium, silver, and/or the like in a form of a metal powder or a metal fiber; a conductive polymer such as a polyphenylene derivative; or a mixture thereof. The conductive material may be included in an amount of about 0.1 wt % to about 10 wt %, for example, about 0.5 wt % to about 5 wt %, or about 1 wt % to about 3 wt % based on 100 wt % of the negative electrode active material layer.
A thickness of the negative electrode active material layer is not particularly limited but may be about 20 μm to about 500 μm according to intended uses or standards, for example, about 20 μm to about 300 μm, about 20 μm to about 200 μm, or about 30 μm to about 100 μm.
The current collector is not particularly limited but may be, for example, a copper foil, a nickel foil, a stainless steel foil, a titanium foil, or a polymer substrate coated with a conductive metal.
Hereinafter, a method of manufacturing the negative electrode for a rechargeable lithium battery will be described with reference to
In
The CMC/SBR polymer binder is an aqueous binder that is widely utilized in aqueous negative electrode systems. CMC is a cellulose derivative including p-linked glucopyranose monomers with varying degrees of substitution (DS) of carboxymethyl (—CH2COOH) groups. The carboxymethyl groups of CMC, which are derived from hydroxyl (—OH) groups on cellulose, contribute to the aqueous solubility of CMC compared with insoluble cellulose. The carboxymethyl and hydroxyl groups of CMC form hydrogen bonding with water, allowing CMC to act as a thickener in an aqueous slurry. The carboxymethyl group of CMC can be dissociated into a carboxylate anion (—CH2COO−) in an aqueous medium. Therefore, CMC adsorbed on a graphite surface via hydrophobic interaction creates a negative charge on graphite, making an electrostatically repulsive force between graphite particles. This repulsive force can improve the dispersibility of a slurry by suppressing the agglomeration of graphite particles.
SBR is a synthetic rubber including styrene and butadiene units. Because SBR has high flexibility, excellent or suitable heat resistance, and a strong binding force, a negative electrode fabricated with SBR could have enhanced physicochemical properties. For example, the aromatic ring of SBR interacts with the Cu current collector, providing adhesion strength between the negative electrode film and Cu, and acting as a primary binder in the negative electrode.
As shown in
As shown in
If (e.g., when) the electric field is applied during the drying process, the migration behavior of the polymer binder may be effectively suppressed or reduced in the negative electrode 20, so that the polymer binder may be uniformly distributed in the longitudinal direction. The binder uniformly distributed in the negative electrode may improve Li-ion kinetics and electrochemical performance (e.g., constant current charge capacity, cycle-life characteristics) of rechargeable lithium batteries. In other words, the electric field-treated negative electrode may improve Li-ion kinetics and reduce an overvoltage during the lithiation process and exhibit fast charging performance and improved cycle stability, compared with a non-electric field-treated negative electrode 20′ of
If (e.g., when) the electric field is applied, a voltage applied herein may be greater than or equal to about 1 kV, greater than or equal to about 2 kV, greater than or equal to about 3 kV, greater than or equal to about 4 kV, greater than or equal to about 5 kV, or greater than or equal to about 6 kV and less than or equal to about 25 kV, less than or equal to about 24 kV, less than or equal to about 23 kV, less than or equal to about 22 kV, less than or equal to about 21 kV, or less than or equal to about 20 kV. Within the ranges, sufficient charges are introduced into the current collector to suppress or reduce the migration behavior of the polymer binder.
The negative electrode manufactured in the above manufacturing method has improved electrochemical performance and thus may be usefully applied to rechargeable lithium batteries.
If (e.g., when) analyzed with a contact angle analysis equipment (Phoenix 300, SEO, Suwon, South Korea (contact angle analyzer)), the negative electrode may have a contact angle with respect to the (e.g., corresponding) electrolyte of less than or equal to about 60 degrees, for example, less than or equal to about 55 degrees, or less than or equal to about 50 degrees.
The MacMullin number (NM) of the negative electrode calculated utilizing Equation 1 may be less than or equal to about 26.5 or less than or equal to about 26.
wherein Rion is the ionic resistance of the negative electrode (Ω), A is an area of the electrode (cm2), σo is the ionic conductivity of the electrolyte (S cm−1), and d is the thickness of the electrode (μm). Rion is obtained from EIS (Electrochemical Impedance Spectroscopy) analysis at an open-circuit voltage of a cell with a frequency range of 100 kHz to 1 Hz and an amplitude of 20 mV by using Potentiostat (ZIVE BP2A, Won-ATech Co., Ltd., Korea). The ionic conductivity is measured at room temperature (25° C.).
The descriptions of the negative electrode can be equally applied to the positive electrode manufactured by utilizing a water-soluble binder and an ionic polymer as a binder and applying an electric field.
A positive electrode for a rechargeable lithium battery may include a current collector and a positive electrode active material layer on the current collector. The positive electrode active material layer includes a positive electrode active material and a polymer binder, and the polymer binder may include a water-soluble binder and an ionic polymer. The water-soluble binder and the ionic polymer are as described above.
For example, the positive electrode may further include an additive that can serve as a sacrificial positive electrode.
The positive electrode active material may include a compound (lithiated intercalation compound) that is capable of intercalating and deintercalating lithium. For example, at least one of a composite oxide of lithium and a metal selected from among cobalt, manganese, nickel, and combinations thereof may be utilized.
The composite oxide may be a lithium transition metal composite oxide. Specific examples of the composite oxide may include lithium nickel-based oxide, lithium cobalt-based oxide, lithium manganese-based oxide, lithium iron phosphate-based compound, cobalt-free lithium nickel-manganese-based oxide, or a combination thereof.
As an example, the following compounds represented by at least one selected from among the following chemical formulas LiaA1-bXbO2-cDc (0.90≤a≤1.8, 0≤b≤0.5, and 0≤c≤0.05); LiaMn2-bXbO4-cDc (0.90≤a≤1.8, 0≤b≤0.5, and 0≤c≤0.5); LiaN1-b-cCobXcO2-αDα(0.90≤a≤1.8, 0≤b≤0.5, 0≤c≤0.5, and 0<α<2); LiaNi1-b-cMnbXcO2-αDα (0.90≤a≤1.8, 0≤b≤0.5, 0≤c≤0.5, and 0<α<2); LiaNibCocL1dGeO2 (0.90≤a≤1.8, 0≤b≤0.9, 0≤c≤0.5, 0≤d≤0.5, and 0≤e≤0.1); LiaNiGbO2 (0.90≤a≤1.8 and 0.001≤b≤0.1); LiaCoGbO2 (0.90≤a≤1.8 and 0.001≤b≤0.1); LiaMn1-bGbO2 (0.90≤a≤1.8 and 0.001≤b≤0.1); LiaMn2GbO4 (0.90≤a≤1.8 and 0.001≤b≤0.1); LiaMn1-gGgPO4 (0.90≤a≤1.8 and 0≤g≤0.5); Li(3-f)Fe2(PO4)3 (0≤f≤2); and LiaFePO4 (0.90≤a≤1.8) may be utilized as the lithium transition metal composite oxide.
In the above chemical formulas, A may be Ni, Co, Mn, or a combination thereof; X may be Al, Ni, Co, Mn, Cr, Fe, Mg, Sr, V, a rare earth element or a combination thereof; D may be 0, F, S, P, or a combination thereof; G may be Al, Cr, Mn, Fe, Mg, La, Ce, Sr, V, or a combination thereof; and L 1 may be Mn, Al, or a combination thereof.
The positive electrode active material may be, for example, a high nickel-based positive electrode active material having a nickel content (e.g., amount) of greater than or equal to about 80 mol %, greater than or equal to about 85 mol %, greater than or equal to about 90 mol %, greater than or equal to about 91 mol %, or greater than or equal to about 94 mol % and less than or equal to about 99 mol % based on 100 mol % of the metal excluding lithium in the lithium transition metal composite oxide. The high-nickel-based positive electrode active material may be capable of realizing high capacity and can be applied to a high-capacity, high-density rechargeable lithium battery.
An amount of the positive electrode active material may be about 90 wt % to about 99.5 wt % based on 100 wt % of the positive electrode active material layer. Amounts of the binder and the conductive material may be about 0.5 wt % to about 5 wt %, respectively, based on 100 wt % of the positive electrode active material layer.
The positive electrode active material layer may further include a conductive material. The conductive material may be utilized to impart conductivity (e.g., electrical conductivity) to the electrode. Any material that does not cause chemical change (e.g., does not cause an undesirable chemical change in the rechargeable lithium battery) and conducts electrons can be utilized in the battery. Examples of the conductive material may include a carbon-based material such as natural graphite, artificial graphite, carbon black, acetylene black, ketjen black, a carbon fiber, a carbon nanofiber, and/or carbon nanotube; a metal-based material containing copper, nickel, aluminium, silver, and/or the like, in a form of a metal powder or a metal fiber; a conductive polymer such as a polyphenylene derivative; or a mixture thereof.
Al may be utilized as the current collector, but is not limited thereto.
Some embodiments provide a rechargeable lithium battery including a negative electrode, a positive electrode, and an electrolyte. In the rechargeable lithium battery, the negative electrode may be a negative electrode manufactured by applying an electric field as described above, and/or the positive electrode may be a positive electrode manufactured by applying an electric field as described above.
The electrolyte may include a non-aqueous organic solvent and a lithium salt.
The non-aqueous organic solvent serves as a medium for transmitting ions taking part in the electrochemical reaction of a battery.
The non-aqueous organic solvent may be a carbonate-based, ester-based, ether-based, ketone-based, or alcohol-based solvent, an aprotic solvent, or a combination thereof.
The carbonate-based solvent may include dimethyl carbonate (DMC), diethyl carbonate (DEC), dipropyl carbonate (DPC), methylpropyl carbonate (MPC), ethylpropyl carbonate (EPC), methylethyl carbonate (MEC), ethylene carbonate (EC), propylene carbonate (PC), butylene carbonate (BC), and/or the like.
The ester-based solvent may include methyl acetate, ethyl acetate, n-propyl acetate, dimethyl acetate, methyl propionate, ethyl propionate, decanolide, mevalonolactone, valerolactone, caprolactone, and/or the like.
The ether-based solvent may include dibutyl ether, tetraglyme, diglyme, dimethoxyethane, 2-methyltetrahydrofuran, 2,5-dimethyltetrahydrofuran, tetrahydrofuran, and/or the like. In some embodiments, the ketone-based solvent may include cyclohexanone, and/or the like. The alcohol-based solvent may include ethanol, isopropyl alcohol, and/or the like and the aprotic solvent may include nitriles such as R—CN (wherein R is a C2 to C20 linear, branched, or cyclic hydrocarbon group, a double bond, an aromatic ring, or an ether bond), and/or the like; amides such as dimethylformamide; dioxolanes such as 1,3-dioxolane, 1,4-dioxolane, and/or the like; sulfolanes, and/or the like.
The non-aqueous organic solvents may be utilized alone or in combination of two or more.
In some embodiments, if (e.g., when) utilizing a carbonate-based solvent, a cyclic carbonate and a chain carbonate may be mixed and utilized, and the cyclic carbonate and the chain carbonate may be mixed in a volume ratio of about 1:1 to about 1:9.
The lithium salt dissolved in the organic solvent supplies lithium ions in a battery, enables a basic operation of a rechargeable lithium battery, and improves transportation of the lithium ions between positive and negative electrodes. Examples of the lithium salt include at least one selected from among LiPF6, LiBF4, LiSbF6, LiAsF6, LiClO4, LiAlO2, LiAlCl4, LiPO2F2, LiCl, LiI, LiN(SO3C2F6)2, Li(FSO2)2N (lithium bis(fluorosulfonyl)imide, LiFSI), LiC4F9SO3, LiN(CxF2x+1SO2)(CyF2y+1SO2) (wherein x and y are integers of 1 to 20), lithium trifluoromethane sulfonate, lithium tetrafluoroethanesulfonate, lithium difluorobis(oxalato)phosphate (LiDFOB), and lithium bis(oxalato) borate (LiBOB).
Depending on the type or kind of the rechargeable lithium battery, a separator may be present between the positive electrode and the negative electrode. The separator may include polyethylene, polypropylene, polyvinylidene fluoride, or a multilayer film of two or more layers thereof, and a mixed multilayer film such as a polyethylene/polypropylene two-layer separator, polyethylene/polypropylene/polyethylene three-layer separator, polypropylene/polyethylene/polypropylene three-layer separator, and/or the like.
The separator may include a porous substrate and a coating layer including an organic material, an inorganic material, or a combination thereof on one or both (e.g., simultaneously) surfaces of the porous substrate.
The porous substrate may be a polymer film including any one selected polymer polyolefin such as polyethylene and polypropylene, polyester such as polyethylene terephthalate and polybutylene terephthalate, polyacetal, polyamide, polyimide, polycarbonate, polyether ketone, polyarylether ketone, polyetherimide, polyamideimide, polybenzimidazole, polyethersulfone, polyphenylene oxide, a cyclic olefin copolymer, polyphenylene sulfide, polyethylene naphthalate, a glass fiber, TEFLON, and polytetrafluoroethylene, or a copolymer or mixture of two or more thereof.
The organic material may include a polyvinylidene fluoride-based polymer or a (meth)acrylic polymer.
The inorganic material may include inorganic particles selected from among Al2O3, SiO2, TiO2, SnO2, CeO2, MgO, NiO, CaO, GaO, ZnO, ZrO2, Y2O3, SrTiO3, BaTiO3, Mg(OH)2, boehmite, and a combination thereof, but is not limited thereto.
The organic material and the inorganic material may be mixed in one coating layer, or a coating layer including an organic material and a coating layer including an inorganic material may be stacked.
The rechargeable lithium battery may be classified into cylindrical, prismatic, pouch, or coin-type or kind batteries, and/or the like depending on their shape. FIGS. 2 to 5 are schematic views illustrating rechargeable lithium batteries according to some embodiments.
The rechargeable lithium battery according to one or more embodiments may be applied to automobiles, mobile phones, and/or one or more suitable types (kinds) of electric devices, as non-limiting examples.
The following Examples and Comparative Examples are provided in order to highlight characteristics of one or more embodiments, but it will be understood that the Examples and Comparative Examples are not to be construed as limiting the scope of the embodiments, nor are the Comparative Examples to be construed as being outside the scope of the embodiments. Further, it will be understood that the embodiments are not limited to the particular details described in the Examples and Comparative Examples.
Graphite, a silicon-carbon composite, a 1.0 wt % CMC aqueous solution, and a 40% SBR emulsion in a weight ratio of 87.0:10.8:1:1.2 based on a solid content (e.g., amount) were added to water to prepare a slurry for forming a negative electrode active material layer. The silicon-carbon composite was an assembly containing Si, graphite, and amorphous carbon (pitch carbide) in a weight ratio of 30:40:30.
The slurry for forming a negative electrode active material layer was mixed at 2000 rpm with a Thinky mixer for 6 minutes. The obtained slurry for forming a negative electrode active material layer was coated with a loading amount of 13 milligram per square centimeter (mg/cm2) on a Cu current collector (a thickness: 8 micrometer (μm)) by utilizing a doctor blade.
The coated electrode was immediately moved to a space where an electric field was applied according to a voltage (3 kilovolt (kV)) and then, dried at 110° C. for 10 minutes.
If (e.g., when) the voltage was applied, a distance between two electrodes was maintained at 15 centimeter (cm). After the drying, the negative electrode was calendered to achieve a target density of 1.68 gram per cubic centimeter (g/cc).
Each negative electrode was manufactured in substantially the same manner as in Example 1A except that the applied voltage was changed into 7 kV, 10 kV, 15 kV, and 20 kV, for Examples 2A, 3A, 4A, and 5A, respectively.
A negative electrode was manufactured in substantially the same manner as in Example 1A except that the applied voltage was set to 0 kV to conduct no electric field treatment process.
The negative electrodes of Comparative Example 1A and Examples 1A to 5A were evaluated with respect to adhesion between negative electrode active material layer and Cu current collector by conducting a 180° peeling test. The 180° peeling test is a method of indirectly predicting a binder distribution in an electrode, based on the observation that less migration creates higher adhesion. The adhesion strength of the negative electrodes was measured by utilizing a universal testing machine (AGS-J, Shimadzu Corp., Tokyo, Japan).
The analysis results of the negative electrodes of Examples 1A to 5A and Comparative Example 1A are shown in
In order to analyze longitudinal binder distributions of the negative electrode treated with no electric field (“with no electric field” indicated as (w/o)) according to Comparative Example 1A and the negative electrode treated with an electric field according to Example 5A (“with an electric field” indicated as (w)), peel strength was obtained by scratching the negative electrode surface toward the inner layer every 15 μm, utilizing an surface and interface cutting analysis system (SAICAS). The results are shown in Table 1 and
Referring to Table 1 and
Accordingly, referring to Table 1 and
An electrolyte permeability test of the negative electrodes of Example 5A and Comparative Example 1A was performed by dropping 20 milligram (mg) of an electrolyte (fluoroethylene carbonate additive (10 wt % of FEC (Starlyte from Panax Etec Co., Ltd., Busan, Korea) in EC/DMC/DEC: 1/1/2 volume %) in ethylene carbonate/dimethyl carbonate/diethyl carbonate containing 1.5 M LiPF6 onto the negative electrode surfaces of Example 5A and Comparative Example 1A. Herein, the time taken for the electrolyte to completely permeate each of the negative electrodes was measured. The results are shown in
Referring to
In general, electrolyte permeability is closely related to binder and pore distributions of a negative electrode, which plays an important role in electrochemical characteristics.
A binder on the negative electrode surface may limit electrolyte transfer through pores of the negative electrode to slow down a speed of Li-ion kinetics and deteriorate electrochemical performance of rechargeable lithium batteries.
In order to analyze affinity between the electrolyte and the negative electrode surface, a contact angle of the negative electrode with a droplet of the electrolyte (prepared by dissolving 1.5 M LiPF6 in ethylene carbonate/dimethyl carbonate/diethyl carbonate (EC/DMC/DEC: 1/1/2 in a volume ratio and adding a fluoroethylene carbonate additive (10 wt % FEC, Starlyte from Panax Etec Co., Ltd., Busan, Korea) thereto) was more than 5 times measured by utilizing a contact angle analysis equipment (Phoenix 300, SEO, Suwon, South Korea (contact angle analyzer)). One contact angle with one electrolyte droplet among them is shown in
Referring to
In order to assess (e.g., explain) electrolyte transport through pores of the negative electrodes, an electrochemical impedance spectroscopy (EIS) analysis of a negative electrode symmetric (2032 circular) cell fabricated by utilizing the same negative electrode as a working electrode and a counter electrode was conducted. The EIS (Electrochemical Impedance Spectroscopy) analysis was conducted at an open-circuit voltage of each cell with a frequency range of 100 kilohertz (kHz) to 1 hertz (Hz) and an amplitude of 20 millivolt (mV) by utilizing Potentiostat (ZIVE BP2A, Won-ATech Co., Ltd., Korea). The results are shown in
Referring to
In order to clarify the electrolyte transport in the negative electrodes regardless of a thickness of the negative electrodes, the MacMullin number (NM) was calculated and provided in
wherein Rion is the ionic resistance of the negative electrode (Ω), A is an area of the electrode (square centimeter (cm2)), σo is the ionic conductivity of the electrolyte (siemens per centimeter (S cm−1)), and d is the thickness of the electrode (μm).
Parameters required to calculate the NM's of the negative electrodes of Example 5A and Comparative Example 1A are listed in Table 2.
In Table 2, the ionic conductivity of the electrolyte was obtained from the electrolyte manufacturer (Starlyte from Panax Etec Co., Ltd., Busan, Korea). The electrode thickness was measured using a micrometer (SM293-025, Sincon).
Referring to
Each of the electrodes of Examples 1A to 5A and Comparative Example 1A, before manufactured into a half-cell, was dried at 130° C. for 4 hours under vacuum. Each (2032 circular) coin type or kind half-cell according to Examples 1H to 5H and Comparative Example 1H was manufactured by utilizing a lithium metal (a thickness: 200 μm) as a counter electrode.
Electrochemical characteristics of the coin type or kind half-cells of Examples 1H to 5H and Comparative Example 1H were evaluated by utilizing a battery cycle tester (TOSCAT 3000, Toyo System, Tokyo Co., Ltd., Japan).
Referring to
In order to analyze discharge (lithiation) capacity characteristics according to application of the electric field, a voltage profile was measured, while a discharge C-rate was increased to 0.5 C, 1.0 C, and 2.0 C, and the results are shown in
Herein, the charge C-rate was set at 0.2 C. In order to clarify the Li-ion kinetics during the discharge, termination conditions of discharge patterns of the half-cells were set at a voltage range of −0.5 V and areal capacity of 5.5 milliampere hour per square centimeter (mAh/cm).
Referring to (a), (c), and (e) of
Each of the negative electrode half-cells was discharged (lithiated) at 0 V after the formation cycle and then, disassembled in a glove box filled with Ar. Each of the negative electrodes obtained therefrom was thoroughly washed with dimethyl carbonate and dried. Top view images of the recovered negative electrodes were examined with a field emission scanning electron microscope (FE-SEM, JSM-7600F, JEOL Ltd., Tokyo, Japan). The results are shown in
In the negative electrode of the half-cell of Comparative Example 1H, no lithium plating was observed on the negative electrode surface during the discharge at 0.5 and 1.0 C, but at 2.0 C, lithium plating was observed on the negative electrode surface (
However, in the negative electrode of the half-cell of Example 5H, because the binder behavior was controlled or selected during the drying by utilizing the electric field to improve the ion resistance, no Li plating appeared at all the discharge C-rates of 0.5, 1.0, and 2.0. This refers to excellent or suitable discharge (lithiation) characteristics at high C-rates (
Each of the electrodes of Example 1A to 5A and Comparative Example 1A, before being manufactured into a full cell, was dried at 130° C. for 4 hours under vacuum. LiNi0.8Co0.1Al0.1O2 (NCA), a PVdF binder, and carbon black were mixed in N-methyl pyrrolidone at a weight ratio of 97:1.5:1.5 to prepare a slurry for forming a positive electrode active material layer, and then coated on an Al foil, dried, and compressed to manufacture a positive electrode having an areal capacity of 5 mAh/cm2. Each full cell was manufactured at an N/P ratio of 1.1/1 utilizing the positive electrode and each negative electrode prepared in Examples 1A to 5A and Comparative Example 1A.
Referring to
The high-rate charging test results of the full cells of Example 5F and Comparative Example 1F are shown in
Referring to
This result shows that high-rate charging characteristics were improved by utilizing the electric field-treated negative electrode to improve Li-ion kinetics.
In order to evaluate cycle-life characteristics, each of the full cells of Example 5F and Comparative Example 1F was 70 cycles charged and discharged at 1.0 C, and the results are shown in
Referring to
Likewise, the full cells of Example 5F and Comparative Example 1F were also evaluated at 2.0 C for 100 cycles after the formation cycle, and the results are shown in
Referring to
On the other hand, the full cell of Comparative Example 1F exhibited a substantially continuous decrease in capacity and thus capacity retention of 79.4% at the 40th cycle to capacity retention of 66.4% at the 100th cycle.
The EIS evaluation results of the full cells of Example 5F and Comparative Example 1F at 2.0 C after 100 cycles are shown in
It is confirmed that an electric field may be applied during the drying process to suppress or reduce binder migration behaviors and resultantly, improve Li-ion kinetics and high-rate charging characteristics of rechargeable lithium batteries.
A battery manufacturing system including a battery electrode manufacturing device, a battery management system (BMS) device, and/or any other relevant devices or components according to embodiments of the present invention described herein may be implemented utilizing any suitable hardware, firmware (e.g. an application-specific integrated circuit), software, or a combination of software, firmware, and hardware. For example, the various components of the device may be formed on one integrated circuit (IC) chip or on separate IC chips. Further, the various components of the device may be implemented on a flexible printed circuit film, a tape carrier package (TCP), a printed circuit board (PCB), or formed on one substrate. Further, the various components of the device may be a process or thread, running on one or more processors, in one or more computing devices, executing computer program instructions and interacting with other system components for performing the various functionalities described herein. The computer program instructions are stored in a memory which may be implemented in a computing device using a standard memory device, such as, for example, a random access memory (RAM). The computer program instructions may also be stored in other non-transitory computer readable media such as, for example, a CD-ROM, flash drive, or the like. Also, a person of skill in the art should recognize that the functionality of various computing devices may be combined or integrated into a single computing device, or the functionality of a particular computing device may be distributed across one or more other computing devices without departing from the scope of the present disclosure.
While this disclosure has been described in connection with what is presently considered to be practical example embodiments, it is to be understood that the present disclosure is not limited to the disclosed embodiments. In contrast, it is intended to cover one or more suitable modifications and equivalent arrangements included within the spirit and scope of the appended claims and equivalents thereof.
| Number | Date | Country | Kind |
|---|---|---|---|
| 10-2022-0136755 | Oct 2022 | KR | national |
| 10-2023-0141539 | Oct 2023 | KR | national |
| Number | Date | Country | |
|---|---|---|---|
| 20240136530 A1 | Apr 2024 | US |
