This application claims priority to and the benefit of Korean Patent Application No. 10-2017-0180037, filed on Dec. 26, 2017, in the Korean Intellectual Property Office, and all the benefits accruing therefrom under 35 U.S.C. § 119, the content of which is incorporated herein in its entirety by reference.
The present disclosure relates to a lithium secondary battery, and more particularly, to a lithium secondary battery wherein a thickness change due to lithium may be reduced during charge or discharge.
Secondary batteries, which are rechargeable, unlike primary batteries which cannot be recharged, are widely used for various electronic devices such as cellular phones, notebook computers, and camcorders. Particularly, lithium secondary batteries provide a higher voltage and have a higher energy density per unit weight than nickel-cadmium batteries and nickel-hydrogen batteries, and thus, a demand therefor is increasing.
During charge of a lithium secondary battery, lithium at a cathode moves to an anode and thus lithium metal is generated at the anode, thereby increasing the thickness of the anode. On the contrary, during discharge, lithium leaves the anode, and thus, the thickness of the anode decreases. To increase an electrodeposition density of lithium and the charging and discharging efficiency of the lithium secondary battery, it would be desirable to reduce the thickness change of the anode during charge and discharge of the battery.
Provided is a lithium secondary battery of which an electrodeposition density of lithium and charging and discharging efficiency may be increased by reducing a thickness change due to lithium during charge and discharge.
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.
According to an aspect of an embodiment, a lithium secondary battery includes: a lithium secondary cell including a surface parallel to an electrode surface; a single-body pressing structure configured to apply pressure to the surface of the lithium secondary cell, wherein the pressing structure is configured to contract and expand in response to a change of volume of the lithium secondary cell; and a housing that accommodates the lithium secondary cell and the pressing structure, wherein an area of a surface of the lithium secondary battery which is parallel to the electrode surface is less than an area of a surface of the lithium secondary battery which is orthogonal to the electrode surface.
The pressing structure may include a pressure jig and a case encapsulating the pressure jig, and a side surface of the case along a contracting-expanding direction may have a modulated shape to permit the pressing structure to contract or expand in response to a change of volume of the lithium secondary cell.
The pressure jig may include a spring, an elastic alloy, a flexible polymer, or a combination thereof.
The pressure jig may include a spring that generates an elastic force in the contracting-expanding direction.
The pressure jig may include a metal sheet having a convex shape in the contracting-expanding direction, and an end of the metal sheet may be fixed to the case.
Two metal sheets may be fixed to the case such that convex parts of the two metal sheets face each other.
The metal sheet may be fixed to the case.
The case may include a metal, a polymeric material, or a combination thereof, which does not corrode when in contact with an electrolyte solution.
The pressing structure may be disposed at an upper side, a lower side, or a middle of the lithium secondary battery, and the upper side, the lower side, and the middle may be in a direction orthogonal to the electrode surface of the lithium secondary cell.
The pressing structure may be sealed.
The contracting-expanding direction may be orthogonal to the surface of the lithium secondary cell.
The modulated shape may include a pleated shape to permit the pressing structure to contract or expand in response to a change of volume of the lithium secondary cell.
The modulated shape may include a sliding shape to permit the pressing structure to contract or expand in response to a change of volume of the lithium secondary cell.
The lithium secondary battery may include a plurality of lithium secondary cells.
The pressing structure may be between lithium secondary cells in a direction orthogonal to the surface of the lithium secondary cell.
These and/or other aspects will become apparent and more readily appreciated from the following description of the embodiments, taken in conjunction with the accompanying drawings in which:
Reference will now be made in detail to embodiments, examples of which are illustrated in the accompanying drawings, wherein like reference numerals refer to like elements throughout, and the thickness or size of each component may be exaggerated for convenience of description. In this regard, the present embodiments may have different forms and should not be construed as being limited to the descriptions set forth herein. Accordingly, the embodiments are merely described below, by referring to the figures, to explain aspects. As used herein, expressions such as “at least one of,” when preceding a list of elements, modify the entire list of elements and do not modify the individual elements of the list.
It will be understood that when an element is referred to as being “on” another element, it can be directly on the other element or intervening elements may be present therebetween. In contrast, when an element is referred to as being “directly on” another element, there are no intervening elements present.
The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting. As used herein, the singular forms “a,” “an,” and “the” are intended to include the plural forms, including “at least one,” unless the content clearly indicates otherwise. “At least one” is not to be construed as limiting “a” or “an.” “Or” means “and/or.” As used herein, the term “and/or” includes any and all combinations of one or more of the associated listed items. It will be further understood that the terms “comprises” and/or “comprising,” or “includes” and/or “including” when used in this specification, specify the 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.
Furthermore, relative terms, such as “lower” or “bottom” and “upper” or “top,” may be used herein to describe one element's relationship to another element as illustrated in the Figures. It will be understood that relative terms are intended to encompass different orientations of the device in addition to the orientation depicted in the Figures. For example, if the device in one of the figures is turned over, elements described as being on the “lower” side of other elements would then be oriented on “upper” sides of the other elements. The exemplary term “lower,” can therefore, encompasses both an orientation of “lower” and “upper,” depending on the particular orientation of the figure. Similarly, if the device in one of the figures is turned over, elements described as “below” or “beneath” other elements would then be oriented “above” the other elements. The exemplary terms “below” or “beneath” can, therefore, encompass both an orientation of above and below.
“About” or “approximately” as used herein is inclusive of the stated value and means 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 (i.e., the limitations of the measurement system). For example, “about” can mean within one or more standard deviations, or within ±30%, 20%, 10% or 5% of the stated value.
Unless otherwise defined, all terms (including technical and scientific terms) used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this disclosure belongs. It will be further understood that terms, such as those defined in commonly used 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.
Exemplary embodiments are described herein with reference to cross section illustrations that are schematic illustrations of idealized embodiments. As such, variations from the shapes of the illustrations as a result, for example, of manufacturing techniques and/or tolerances, are to be expected. Thus, embodiments described herein should not be construed as limited to the particular shapes of regions as illustrated herein but are to include deviations in shapes that result, for example, from manufacturing. For example, a region illustrated or described as flat may, typically, have rough and/or nonlinear features. Moreover, sharp angles that are illustrated may be rounded. Thus, the regions illustrated in the figures are schematic in nature and their shapes are not intended to illustrate the precise shape of a region and are not intended to limit the scope of the present claims.
A “cell” refers to a single electrochemical cell.
A “battery” refers to one or more cells, wherein a plurality of cells may be connected in series, parallel, or a combination thereof.
To increase an electrodeposition density of lithium and the charging and discharging efficiency of the lithium secondary battery, the thickness change due to lithium during charge and discharge of the battery is desirably reduced.
Hereinafter, a lithium secondary battery according to embodiments will be described in further detail with reference to the accompanying drawings.
Referring to
According to an embodiment, the lithium secondary battery cell 30 may have a narrow and long shape in which an area of a first surface 11 of the lithium secondary battery 10 which is parallel to an electrode surface 31 is less than an area of a second surface 12 of the lithium secondary battery 10 which is orthogonal to the electrode surface 31.
In an embodiment, referring to
The lithium secondary cell 30 may have a structure in which a plurality of unit cells are stacked, the unit cell including an anode layer, a separator, and a cathode layer. An electrolyte may be provided, e.g., filled, between the cathode layer and the anode layer. The electrode surface 31 may be a surface of at least any one of the anode layer and the cathode layer, or may be a surface parallel to a surface of the cathode layer and the anode layer of the unit cell, which includes the anode layer, the separator, and the cathode layer.
The cathode layer may include a cathode active material. For example, the cathode active material may include a lithium (Li)-containing oxide. The Li-containing oxide may be an oxide containing Li and a transition metal. The Li-containing oxide may be, according to an embodiment, LiMO2, wherein M denotes a metal, for example, cobalt (Co), nickel (Ni), manganese (Mn), or a combination thereof. For example, the Li-containing oxide may be LiCoO2. The cathode active material may include ceramic and may have, a polycrystalline or a single crystalline structure. However, the detailed materials for the cathode active material described above are only illustrative, and other cathode active materials may be used.
The anode layer may include lithium metal. A lithium metal thin film may be used for the anode layer including lithium metal. As another example, the anode layer including a lithium metal may include a current collector and an anode active material layer disposed on the current collector. In this case, the anode active material layer may include, for example, a metal, a transition metal oxide, a non-transition metal oxide, a carbon-based material, a silicon-based material, or the like which is alloyable with lithium, or a combination thereof. Lithium metal is mentioned. Herein, detailed materials for an anode active material are not limited thereto.
The separator is inserted between the anode layer and the cathode layer and may be an insulating thin film having a high ion transmittance and a high mechanical strength. The separator may be, for example, a sheet or non-woven fabric made of an olefin-group-containing polymer such as polypropylene, a glass fiber, polyethylene, or the like. The separator may comprise, for example, polyethylene, polypropylene, polyvinylidene fluoride, or a combination thereof, and may be in the form of a multi-layer film thereof (two or more layers). When a solid polymer electrolyte is used for the electrolyte, the solid polymer electrolyte may also be used for the separator.
An electrolyte solution may be filled between the anode layer and the cathode layer of the lithium secondary cell 30. The electrolyte solution may include a liquid electrolyte, a solid electrolyte, or a combination thereof. The liquid electrolyte may comprise a suitable salt and solvent. The lithium salt may be, for example, LiSCN, LiN(CN)2, LiClO4, LiBF4, LiAsF6, LiPF6, LiCF3SO3, LiC(CF3SO2)3, LiN(SO2C2F5)2, Li N(SO2CF3)2, LiN(SO2F)2, LiSbF6, LiPF3(CF2CF3)3, LiPF3(CF3)3, LiB(C2O4)2, or a combination thereof. An amount of the lithium salt may be about 0.5 molar (M) to about 2M. The solvent may be a carbonate-based solvent, such as ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, or a combination thereof. The electrolyte solution may include a solid electrolyte such as Li3PO4, Li3PO4-xNx, LiBO2-xNx, Li3PO4Nx, LiBO2Nx, Li4SiO4—Li3PO4, Li4SiO4—Li3VO4, or Li7La3Zr2O12 (“LLZO”). The electrolyte solution may include a solid polymer electrolyte. Materials for the electrolyte solution may be variously changed.
In the lithium secondary battery 10 according to an embodiment, a plurality of lithium secondary cells 30 may be stacked such that an area of a surface 11 of the lithium secondary battery 10 parallel to the electrode surface 31 is less than an area of a surface 12 of the lithium secondary battery 10 orthogonal to the electrode surface 31.
The lithium secondary battery 10 may comprise any suitable number of lithium secondary cells 30. A quantity of lithium secondary cells 30 may be 2 to 100,000, for example, 10 to 80,000, 20 to 70,000, 30 to 60,000, or 40 to 50,000, or 5 to 1000, 7 to 500, or 10 to 250. The lithium secondary cells 30 may be stacked such that the area of a surface 11 of the lithium secondary battery 10 parallel to the electrode surface 31 is less than the area of a surface 12 of the lithium secondary battery 10 orthogonal to the electrode surface 31.
In the lithium secondary battery 10, during charge, lithium ions in the cathode layer move to the anode layer, thereby increasing the thickness of the anode layer, and on the contrary, during discharge, lithium ions move from the anode layer to the cathode layer, thereby decreasing the thickness of the anode layer.
During such charging and discharging of the lithium secondary battery 10, it would be desirable to increase an electrodeposition density of lithium by applying pressure to the lithium secondary cell 30 to minimize a thickness change of the lithium secondary cell 30.
The pressing structure 50 may reduce a thickness change during charge and discharge by pressing the lithium secondary cell 30 on a surface parallel to the electrode surface 31 of the lithium secondary cell 30.
The pressing structure 50 may have an effective, e.g., actual pressing, area corresponding to the electrode surface 31 and may be provided so as to contract or expand according to a relative pressing force applied to the lithium secondary cell 30. Herein, the effective, e.g., actual pressing, area of the pressing structure 50 may be less than or greater than the area of the electrode surface 31. As used herein, “pressing force” or “relative pressing force” refers to a positive or negative, e.g., increase or decrease of, pressure applied, e.g., to a lithium secondary cell 30.
As shown in
Referring to
The pressing structure 50 may be sealed so as not to come in contact with the electrolyte solution and the like of the lithium secondary cell 30, and to this end, the case 55 of the pressing structure 50 may be formed of a metal, a polymeric material, or a combination thereof, which is not corroded when in contact with the electrolyte solution of the lithium secondary cell 30.
To enable the pressing structure 50 to contract or expand, side surfaces of the case 55 along the contracting-expanding direction may be formed to have a modulated shape such as pleated shape as shown in
The pressure jig 51 may include at least one of a spring, an elastic alloy, and a flexible polymer.
For example, the pressure jig 51 may include at least one spring 151 disposed so as to have an elastic force in the contracting-expanding direction as shown in
As other examples, the pressure jig 51 may include at least one metal sheet 251 and 253 of a convex shape in a direction along or in the contracting-expanding direction as shown in
As shown in
As shown in
As another example, the pressure jig 51 may be formed of a flexible polymer 351 having a mesh form as shown in
Although only the case 150 in which the pressure jig 51 is sealed is shown in
Although
Although
For example, the pressing structure 50 may be disposed so as to press the lithium secondary battery cell 30 from a lower side as shown in
Alternatively, the pressing structure 50 may be provided so as to press the lithium secondary cell 30 from a lower side and an upper side as shown in
As is further described above, in the lithium secondary battery 10 according to an embodiment, the pressing structure 50 may be located at an upper side, at a lower side, at both sides, in the middle, or the like to act as a buffer in response to a volume change of the lithium secondary cell 30 during charge and discharge and to increase an electrodeposition density of lithium during charge by pressing the lithium secondary cell 30.
In the lithium secondary battery 10 according to an embodiment, the pressing structure 50 presses the lithium secondary cell 30 in a small area, and thus the pressing structure 50 may be formed so as to occupy a relatively small volume, e.g., of several %, for example, about 4.5%, of a total volume of the lithium secondary battery 10. In an embodiment, the pressing structure 50 occupies about 1% to about 20%, about 2% to about 16%, or about 4% to about 8% of a total volume of the lithium secondary battery 10. In addition, for example, when the cathode layer is about 65 micrometers (pm) thick, the anode layer may be about 50 μm thick, the separator may be about 30 μm thick, the solid electrolyte may be about 150 μm thick, and the current collector may be about 30 μm thick, a unit cell of the lithium secondary battery cell 30 may have a thickness of 325 μm, and thus an increasing thickness during charge may be about 15 μm.
According to the lithium secondary battery 10 according to an embodiment, as shown in the left image of
Therefore, according to the lithium secondary battery 10 according to an embodiment, since constant pressure is applied to the lithium secondary cell 30 by means of the pressing structure 50, a thickness change due to lithium may be minimized during charge and discharge, and a lithium electrodeposition density may be increased, and thus charging and discharging efficiency may be increased.
That is, according to the lithium secondary battery 10 according to an embodiment, since constant pressure may be applied to the lithium secondary cell 30 in both a state in which a volume of the lithium secondary cell 30 expands, e.g., increases, during charge and a state in which a volume of the lithium secondary cell 30 contracts, e.g., decreases, during discharge, a lithium electrodeposition density during charge may be increased, and lithium ions move to the cathode layer during discharge, and thus charging and discharging efficiency may be increased.
As shown in
Like the lithium secondary battery 10 according to an embodiment, the lithium secondary battery 10′ of the comparative example may include the lithium secondary cell 30′, a single-body pressing structure 50′, and a housing 20′ that accommodates the lithium secondary cell 30′ and the single-body pressing structure 50′.
When the lithium secondary battery 10 according to the embodiment of
That is, compared with the lithium secondary battery 10′ of the comparative example , in the lithium secondary battery 10 according to an embodiment, by applying pressure to a narrower surface to press a cell at higher pressure, a density of lithium electrodeposited on an anode layer may be increased, and a uniform surface state and pressure distribution may be maintained over the entire surface of an electrode layer, and thus cell charging and discharging efficiency may be increased, and even when a solid electrolyte is used, the lithium electrodeposition density may be increased.
In addition, compared with the lithium secondary battery 10′ of the comparative example, the lithium secondary battery 10 according to an embodiment has a smaller volume which the pressing structure 50 occupies, and thus the lithium secondary battery 10 may be improved relative to the lithium secondary battery 10′, for example, an energy density of the lithium secondary battery 10 may be improved relative to lithium secondary battery 10′.
According to a lithium secondary battery of the present disclosure, since a constant pressure may be applied to a lithium secondary cell by a pressing structure in both a state in which a volume of the lithium secondary cell expands during charge of the lithium secondary battery and a state in which a volume of the lithium secondary battery cell contracts during discharge of the lithium secondary battery, a thickness change due to lithium may be minimized during charge and discharge of the lithium secondary battery and a lithium electrodeposition density during charge may be increased. Thus, charging and discharging efficiency of the lithium secondary battery may be increased.
It should be understood that embodiments described herein should be considered in a descriptive sense only and not for purposes of limitation. Descriptions of features or aspects within each embodiment should typically be considered as available for other similar features or aspects in other embodiments.
While one or more embodiments have been described with reference to the figures, it will be understood by those of ordinary skill in the art that various changes in form and details may be made therein without departing from the spirit and scope as defined by the following claims.
Number | Date | Country | Kind |
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10-2017-0180037 | Dec 2017 | KR | national |