The present invention relates to solid-state batteries. More particularly, this invention relates to solid-state lithium batteries with electrodes that are infused with an ionically-conductive material and methods for forming such batteries.
As electronic devices continue to get smaller, while the performance thereof continues to improve, there is an ever growing need for smaller, lighter, and more powerful batteries that demonstrate suitable reliability and longevity. One possible solution for these batteries is solid-state lithium batteries.
Currently, high utilization of thin, solid-film lithium-cobalt oxide electrodes is limited when the electrode thickness exceeds about 4 micrometers (μm) due to, for example, low ionic conductivity and/or high Ohmic resistivity within the electrode. Films thicker than 4 micrometers show decreased utilization of the full capacity of the electrode at charge rates above C/5. Thus, the batteries suffer from a loss of overall energy.
One cause of this decreased utilization in relatively thick films is that the bulk ionic conductivity of the electrode is relatively small when compared to good ionic conductors such as liquid, gel, or polymer electrolytes. Thick films of low ionic conductance will exhibit substantial impedance which will limit the utilization of the electrode especially at high discharge rates (e.g., >C/5). In addition thick electrode layers may contain porosity, voids, or cracks. These can occur naturally during electrode fabrication by anisotropic densification (e.g., during annealing), stress cracking, free volume creation at grain boundaries, and other means. Porosity can further reduce ionic conductance by reducing the amount of conducting pathways through the electrode. These pores and voids may particularly be an issue when relatively fast and inexpensive methods are used to form the electrodes, such as screen printing, tape casting, and electrophoretic deposition.
To facilitate understanding, identical reference numerals have been used, where possible, to designate identical elements that are common to the figures. The drawings are not to scale and the relative dimensions of various elements in the drawings are depicted schematically and not necessarily to scale.
The techniques of the present invention can readily be understood by considering the following detailed description in conjunction with the accompanying drawings, in which:
A detailed description of one or more embodiments is provided below along with accompanying figures. The detailed description is provided in connection with such embodiments, but is not limited to any particular example. The scope is limited only by the claims, and numerous alternatives, modifications, and equivalents are encompassed. Numerous specific details are set forth in the following description in order to provide a thorough understanding. These details are provided for the purpose of example and the described techniques may be practiced according to the claims without some or all of these specific details. For the purpose of clarity, technical material that is known in the technical fields related to the embodiments has not been described in detail to avoid unnecessarily obscuring the description.
The term “horizontal” as used herein will be understood to be defined as a plane parallel to the plane or surface of the substrate, regardless of the orientation of the substrate. The term “vertical” will refer to a direction perpendicular to the horizontal as previously defined. Terms such as “above”, “below”, “bottom”, “top”, “side” (e.g. sidewall), “higher”, “lower”, “upper”, “over”, and “under”, are defined with respect to the horizontal plane. The term “on” means there is direct contact between the elements. The term “above” will allow for intervening elements.
In some embodiments, methods are provided for forming solid-state battery electrodes (and/or solid-state batteries) in such a way as to reduce the loss of ionic conductivity often associated with relatively thick electrodes (e.g., greater than 4 micrometer (μm)). In some embodiments, the ionic conductivity of the electrodes is improved by infusing a fluidic, ionically-conductive material into the electrodes, particularly the pores, voids, and other free volume formed in the electrodes. The fluidic, ionically-conductive material may include (or be made of) an ionic liquid, a flowable solid electrolyte material, or a combination thereof.
Still referring to
As shown in
Still referring to
Referring now to
In some embodiments, the fluidic, ionically-conductive material 108 includes a liquid, such as a lithium-conducting, room-temperature ionic liquid. Any ionic liquids that are both compatible with the material of the electrode (e.g., lithium-cobalt oxide) and have sufficient lithium ionic conductivity may be used. Additionally, it may be preferable that the ionic liquid(s) have low freezing points, low viscosities, and large electrochemical stability windows (e.g., do not react with lithium-cobalt oxide, etc.).
Examples of suitable ionic liquids include, but are not limited to, 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide, 1-ethoxymethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide, n-butyl-n-methyl pyrrolidinium bis(trifluoromethylsulfonylimide), n-propyl-n-methyl pyrrolidinium bis(trifluoromethylsulfonylimide), and the corresponding BF4 and PF6 salts. In some embodiments, the ionic liquid also includes a quantity of a lithium salt, such as lithium bis(trifluoromethane sulfonylimide, sufficient to obtain a 0.001 M to 1.0 M concentration (e.g., such a type and quantity of salt may be added to the ionic liquid before it is infused into the electrode 104).
The ionic liquid may be deposited onto (and/or infused within) the electrode 104 (e.g., through a side of the electrode 104 opposite the substrate 100) using any suitable method, such as bath immersion, spray coating, spin coating, puddle coating, brush coating, and rolling. Agitation, heat, sonication, or other energetic, or physical method, may be used to enhance the penetration of the ionic liquid into the electrode 104.
In some embodiments, the fluidic, ionically-conductive material 108 includes a solid material, such as a flowable solid electrolyte material. The flowable solid electrolyte material may have an ionic conductivity sufficient to allow thick electrodes (e.g., greater than 4 μm) to conduct ions though the entire thickness thereof, while also being “flowable” (i.e., able to be flowed into the voids 106 of the electrode 104). For example, solid electrolytes with low glass transition temperatures may be used such that the electrode 104 (and/or the substrate 100) may be heated and the electrolyte infused into the electrode, perhaps by also applying pressure to the solid electrolyte (e.g., “pressing” the electrolyte into the electrode).
In some embodiments, the flowable solid electrolyte is a lithium phosphorous sulfide or a related compound. One particular example is Li2S—P2S5. In some embodiments, the ratio of Li2S to P2S5 is 70:30 by weight. In embodiments in which the flowable solid electrolyte is a lithium phosphorous sulfide, the electrolyte may be suitably flowable at room temperature (e.g., 25° C.) under applied pressure.
Referring now to
The protective coating 110 may prevent the flowable solid electrolyte material from reacting with the material of the electrode 104, which may otherwise result in degradation of the performance (e.g., capacity) of the battery with repeated cycling. The protective coating 110 may be particularly beneficial when the electrode 104 includes lithium-cobalt oxide and the flowable solid electrolyte includes a lithium phosphorous sulfide.
After the electrode 104 has been infused with the flowable solid electrolyte or the ionic liquid, any excess or unwanted electrolyte material on the surface of the electrode 104 may be removed, which may effectively planarize the electrode 104. This process may be performed either mechanically (e.g., by polishing or other method), chemically (e.g. dissolution using a solvent treatment), or using a light ion etch. Additionally, the surface of the electrode 104 may be cleaned to, for example, enhance the adhesion of the solid electrolyte (described below) to the infused cathode material. Cleaning methods such as an oxygen plasma treatment, ozone treatment, an organic solvent, an argon ion treatment, or mechanical abrasion may be used.
Although not specifically shown, in some embodiments, the electrode 104 is formed such that the voids 106 manifest as pores. For example, the electrode 104 may be formed using a method in which the material contains some solids (e.g., powders mixed with a binder such as ethyl cellulose which are removed during sintering). Examples of such methods includes screen printing, stencil printing, doctor blading, tape casting, gravure printing, and other printing or casting methods. After the material of the electrode is deposited, a sintering process may be performed, for example, to increase the density of the material. This annealing may also be required in order to adjust the crystallographic orientation of the material of the electrode 104 for optimal performance.
The heating process may be performed in the same processing chamber in which the electrode 104 (and perhaps the current collector 502) is formed (i.e., “in situ”). Alternatively, the heating process may be performed in a different processing chamber than that used to form the electrode 104 (i.e., “ex situ”). In some embodiments, the electrode 104 is heated to a temperature of, for example, greater than about 600° C. (e.g., between about 600° C. and about 800° C.) during the heating process. The heating process may be performed in a gaseous environment including oxygen, nitrogen, argon, and/or hydrogen (e.g., 80% nitrogen, 20% oxygen, air/atmosphere, etc.) with either ambient humidity, or no humidity. In some embodiments, the heating process is performed for a duration of, for example, greater than 30 minutes (e.g., 30-60 minutes). The heating process may utilize a temperature ramp rate of, for example, between about 5° C. and about 10° C. per minute (e.g., starting from room temperature).
Such a process may result in electrode material containing pores due to anisotropic densification, stress cracking, and free volume creation at grain boundaries or other by other means. The fluidic, ionically-conductive material 108 (e.g., an ionic liquid or a flowable solid electrolyte) may then be infused into the pores in a manner similar those described above.
In some embodiments, the electrode material formed in such a manner (i.e., resulting in pores within the electrode 104) may form a first (or lower) portion of the electrode 104, and a second (or upper) portion of the electrode 104 is formed above. The second portion of the electrode 104 may be formed in a way that the material is deposited with a higher density that the density of the initially deposited material of the first portion of the electrode 104, such as sputtering. After the second portion of the electrode 104 is formed, the fluidic, ionically-conductive material 108 (e.g., an ionic liquid or a flowable solid electrolyte) may then be infused into the voids of the second portion of the electrode 104 in a manner similar those described above.
After the infusion of the fluidic, ionically-conductive material into the electrode 104, the substrate 100, the current collector 102, and the electrode 104 may be used to form a solid-state lithium battery in an otherwise convention manner. However, is should be understood that in some embodiments, the fluidic, ionically-conductive material 108 is infused into the electrode 104 through a side thereof that is adjacent to the substrate 100 (and/or the current collector 102), or through fluidically connected passageways either laterally across the substrate 100 but beneath the electrode 104 or vertically through the thickness of the substrate 100. This may be accomplished by using a porous substrate with an open pore structure, such as porous alumina or any standard substrate material that may be made into a porous form using known methods. In such embodiments, the infusion of the fluidic, ionically-conductive material 108 may be performed at any time after the formation of the electrode 104. For example, the infusion may performed after additional components of the solid-state battery (e.g., as described below) are formed (e.g., after anode is formed, but before the protective layer is formed).
The embodiment shown in
Still referring to
The various layers (or components) in the battery stack 608 may be formed sequentially (i.e., from bottom to top) above the substrate 602 using, for example, physical vapor deposition (PVD) and/or reactive sputtering processing, or any other processes (e.g., plating, sol-gel processes, etc.) that are suitable depending on the material(s), thicknesses, etc. Although the components may be described as being formed “above” the previous component (or the substrate), it should be understood that in some embodiments, each layer is formed directly on (and adjacent to) the previously provided/formed component. In some embodiments, additional components (or layers) may be included between the components shown in
Still referring to
The cathode (or first electrode) 614 is formed above the cathode current collector 612. Although not shown in detail in
As shown in
The anode (or second electrode) 618 is formed above the electrolyte 616. In some embodiments, the anode 618 includes (or is made of) lithium metal. The anode 618 may have a thickness of, for example, between 1.0 μm and 5.0 μm. In the depicted embodiment, the anode 618 is formed such that it covers an end of the electrolyte 616 opposite an exposed end of the cathode current collector 612.
The anode (or second) current collector 620 is formed above the anode 618. In some embodiments, the anode current collector 620 includes (or is made of) a conductive material that is thermodynamically and chemically stable with the material (e.g., lithium metal) of the anode 618. Suitable materials include scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, yttrium, zirconium, lanthanum, hafnium, molybdenum, tantalum, tungsten, titanium nitride, or a combination thereof.
The anode current collector 620 may have a thickness of, for example, between about 0.1 μm and about 3.0 μm. In the depicted embodiment, the anode current collector 620 is formed such that it covers both ends of the anode 618 and a portion thereof is formed directly on an exposed portion of the substrate 602.
The protective layer 622 is formed over the anode current collector 620. In some embodiments, the protective layer 622 includes (or is made of) a nitride, such as aluminum nitride or silicon nitride. The protective layer 622 may have a thickness of, for example, between about 1.0 μm and about 30 μm. As is shown in
During operation of the battery 600, when the battery 600 is allowed to discharge, lithium ions (i.e., Li+) migrate from the anode 618 to the cathode 614 by diffusing through the electrolyte 616. When the anode and cathode reactions are reversible, as for an intercalation compound or alloy, such as lithium-cobalt oxide, the battery 600 may be recharged by reversing the current. The difference in the electrochemical potential of the lithium determines the cell voltage. Electrical connections are made to the battery 600, for both discharging and charging, through the current collectors 612 and 620.
The performance of the battery 600 may be improved due to the method described above for forming the electrode (e.g., electrode 104 and/or cathode 614). In particular, the infusion of the fluidic, ionically-conductive material into the voids within the electrode improves the overall ionic conductivity of the electrode by adding highly ionically conducting pathways through the thickness of the electrode allowing much faster ionic transport within, through, and across the electrode . As a result, the thickness of the electrode may be increased (e.g., to over 10 μm), thus increasing the energy density and power density of the battery. Additionally, the infusion of the fluidic, ionically-conductive material may allow relatively fast and inexpensive methods to be used to form the electrode (e.g., screen printing, tape casting, electrophoretic deposition, etc.) while still maintaining desirable performance.
At block 704, a first electrode (e.g., a cathode) is formed above the first current collector. In some embodiments, the first electrode includes lithium and cobalt (e.g., lithium-cobalt oxide) and has a thickness of, for example, between about 5 μm and about 15 μm, such as about 10 μm (or more). The first electrode may be formed using PVD (e.g., sputtering), a sol-gel process, or any other suitable method. In some embodiments, the electrode includes a series of voids (e.g., cracks and/or pores), which may manifest during the deposition/formation process.
At block 706, a fluidic, ionically-conductive material is infused into the first electrode, particular the voids therein. In some embodiments, the fluidic, ionically-conductive material at least partially fills at least some of the voids, while in some embodiments, all of the voids are completely filed. The fluidic, ionically-conductive material includes may, for example, include a liquid, such as a lithium-conducting, room-temperature ionic liquid, or a flowable solid electrolyte.
Examples of ionic liquids include, but are not limited to, 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide, 1-ethoxymethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide, n-butyl-n-methyl pyrrolidinium bis(trifluoromethylsulfonylimide), n-propyl-n-methyl pyrrolidinium bis(trifluoromethylsulfonylimide), and BF4 and PF6 salts (e.g., those corresponding to the other listed ionic liquids). In some embodiments, the ionic liquid also includes a quantity of a lithium salt, such as lithium bis(trifluoromethane sulfonylimide, sufficient to obtain a 0.001 M to 1.0 M concentration. The flowable solid electrolyte may be a lithium phosphorous sulfide, such as Li2S—P2S5, or a related compound.
At block 708, an electrolyte is formed above the first electrode. The electrolyte may be a solid electrolyte formed, or deposited, using a PVD process. In some embodiments, the electrolyte includes LiPON and has a thickness of, for example, between about 1.0 μm and about 2.0 μm.
At block 710, a second electrode (e.g., an anode) is formed above the electrolyte. The second electrode may include lithium metal and have a thickness of, for example, between 1.0 μm and 5.0 μm. The second electrode may be formed using, for example, PVD (e.g., sputtering).
At block 712, a second current collector (e.g., an anode current collector) is formed above the second electrode. In some embodiments, the second current collector includes scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, yttrium, zirconium, lanthanum, hafnium, molybdenum, tantalum, tungsten, titanium nitride, or a combination thereof. The second current collector may have a thickness of, for example, between about 0.1 μm and about 3.0 μm. The second current collector may be formed using, for example, PVD (e.g., sputtering).
Although not shown in
Thus, in some embodiments, methods for forming a solid-state battery are provided. A first current collector is provided. A first electrode is formed above the first current collector. The first electrode has at least one void formed therein. A fluidic ionically-conductive material is infused into the at least one void within the first electrode. A solid electrolyte is formed above the first electrode. A second electrode is formed above the solid electrolyte. A second current collector is formed above the second electrode.
In some embodiments, methods for forming a solid-state battery are provided. A first current collector is provided. A first electrode is formed above the first current collector. The first electrode includes lithium and cobalt and has at least one void formed therein. A fluidic ionically-conductive material is infused into the at least one void within the first electrode. The fluidic ionically-conductive material includes at least one of an ionic liquid, a flowable solid electrolyte material, or a combination thereof. A solid electrolyte is formed above the first electrode. The solid electrolyte includes lithium-phosphorous oxynitride. A second electrode is formed above the solid electrolyte. A second current collector is formed above the second electrode.
In some embodiments, solid-state batteries are provided. The solid-state batteries include a first current collector. A first electrode is formed above the first current collector. The first electrode has at least one void formed therein. A fluidic ionically-conductive material is infused into the at least one void within the first electrode. A solid electrolyte is formed above the first electrode. A second electrode is formed above the solid electrolyte. A second current collector is formed above the second electrode.
Although the foregoing examples have been described in some detail for purposes of clarity of understanding, the invention is not limited to the details provided. There are many alternative ways of implementing the invention. The disclosed examples are illustrative and not restrictive.