This application is directed to a secondary battery with an improved battery separator, particularly a battery separator that may be reduce or eliminate metal-ion contamination in a secondary battery, particularly a secondary battery susceptible to metal-ion contamination.
Commonly used electrode materials for a secondary battery may contain transition metals including iron (Fe), manganese (Mn), nickel (Ni), cobalt (Co), aluminum (Al), chrome (Cr), molybdenum (Mo), tin (Sn), and others. For example, some exemplary electrode materials may include Lithium Nickel Cobalt Manganese Oxide (NMC or NCM), Lithium Iron Phosphate (LFP), Lithium Nickel Manganese Spinel (LMNO), Lithium Nickel Cobalt Aluminum Oxide (NCA), Lithium Manganese Oxide (LMO), Lithium Cobalt Oxide (LCO), or combinations thereof. Some of these electrode materials interact with the electrolyte resulting in the presence of transition metal ions in the electrolyte. Under the right conditions, these metal ions maybe reduced to their metal form. This metal plating will result in, among other things, dendrite growth. When dendrites grow through the separator, connecting both electrodes, a short results. Poisoning of a graphite electrode may also result, for example, from plating of transition metal ions on the electrode. This may reduce the useful life of the battery.
Another source of metal contamination may be metallic equipment, e.g., brushes, rollers, etc. used to manufacture battery parts and/or batteries. Metallic equipment may be a source of cobalt, copper, zinc, chrome, or iron ions in the battery.
In view of the foregoing, methods to reduce, eliminate, or mitigate metal contamination in a battery may be desirable.
In one aspect, a secondary battery that generates or comprises metal ion contaminants selected from, but not limited to, copper ions, manganese ions, nickel ions, cobalt ions, iron ions, chrome ions, molybdenum ions, tin ions, or combinations thereof is described. Metal ion contaminants may be generated from the battery's electrode material. For example, the battery's cathode material may comprise Lithium Nickel Cobalt Manganese Oxide (NMC or NCM), Lithium Iron Phosphate (LFP), Lithium Nickel Manganese Spinel (LMNO), Lithium Nickel Cobalt Aluminum Oxide (NCA), Lithium Manganese Oxide (LMO), Lithium Cobalt Oxide (LCO), or combinations thereof. Alternatively or additionally, presence of metal ion contaminants may be due to metallic equipment, e.g., brushes, rollers, etc., used in the battery manufacture process. The secondary battery described herein may have reduced or eliminated metal contamination issues, due to the use of a separator as described herein, compared to batteries where the separator is not used.
The secondary battery described herein may comprise the following components: an anode, a cathode, a coated or uncoated battery separator comprising a trap layer between the anode and the cathode, and an electrolyte. The battery separator may comprise a trap layer that is part of the separator. For example, the trap layer may be in the middle of the battery separator or on a side of the battery separator that is closest to the anode. Alternatively or in addition to a trap layer being part of the battery separator, a trap layer may be provided as a coating or as one layer of a coating on a side of the battery separator that faces the anode.
With regard to embodiments where the trap layer is part of the separator, the potential difference of the trap layer vs. Li+/Li is in the range from +0.0V to +5.0V, from +0.0V to +4.0V, from +0.0V to +3.5V, from +0.0V to +3.0V, from +0.0V to +2.5V, from +0.0V to +2.0V, from +0.0V to +1.5V, or from +0.0V to 1.0V.
In embodiments where the trap layer is part of the separator, the trap layer may have a bulk or volume resistivity of 104 to 109 ohms-cm, 105 to 109 ohms-cm, 106 to 109 ohms-cm, 107 to 109 ohms-cm, or 108 to 109 ohms-cm. In some preferred embodiments, the bulk or volume resistivity may be from 104 to 109 ohms-cm, 104 to 108 ohms-cm or from 104 to 107 ohms-cm. Particularly preferred resistivity may be 104 to 108 ohms-cm or from 104 to 107 ohms-cm.
In some embodiments, the trap layer may be incorporate as part of the separator through a lamination process, a co-extrusion process, or a combination of a lamination and a co-extrusion process.
With regard to embodiments where the trap layer is part of the separator, the trap layer may comprise carbon and a polymer. The carbon may be a conductive carbon in some embodiments. The carbon may be selected from carbon black, acetylene black, carbon nanotubes, graphene, or combinations thereof. In some other embodiments where the trap layer is part of the separator, the trap layer may comprise a conductive polymer. For example, the conductive polymer may be a poly-acetylene, a poly-thiophene, a poly-aniline, a poly-pyrrole, or combinations thereof.
With regard to embodiments where the trap layer is provided as a coating or as one layer of a coating, the potential difference of the trap layer vs. Li+/Li is in the range from +0.0V to +5.0V, from +0.0V to +4.0V, from +0.0V to +3.5V, from +0.0V to +3.0V, from +0.0V to +2.5V, from +0.0V to +2.0V, from +0.0V to +1.5V, or from +0.0V to 1.0V.
In embodiments where the trap layer is provided as a coating or as one layer of a coating, the trap layer may have a bulk or volume resistivity of 104 to 109 ohms-cm, 104 to 108 ohms-cm, or 104 to 107 ohms-cm.
With regard to embodiments where the trap layer is provided as a coating or as one layer of a coating, the trap layer may comprise carbon and a polymer. The carbon may be a conductive carbon in some embodiments. The carbon may be selected from carbon black, acetylene black, carbon nanotubes, graphene, or combinations thereof. In some other embodiments where the trap layer is provided as a coating or as one layer of a coating, the trap layer may comprise a conductive polymer. For example, the conductive polymer may be a poly-acetylene, a poly-thiophene, a poly-aniline, a poly-pyrrole, or combinations thereof.
Disclosed herein is a secondary battery that has or is susceptible to metal contamination and has improved useful life due at least in part to the separator utilized therein. The battery may comprise, consist of, or consist essentially of, an anode, a cathode, a separator between the anode and the cathode, and an electrolyte. The separator may be a coated separator or an uncoated separator, and a trap layer may be part of the separator, part of the coating, or both part of the separator and part of the coating. Where the trap layer is part of the separator, it is preferably in the middle of the separator or on a side of the separator closest to the anode. When the trap layer is part of a coating (trap layer coating), it is part of a coating on an anode-facing side of the separator. Examples of secondary batteries according to some embodiments described herein are shown in
Cathode
The cathode of the secondary battery described herein is not so limited, but may preferably be a cathode-material that generates metal ion contamination in the battery. For example, the cathode material may transition-metal-containing compounds that can be used for the cathode. In some embodiments, the cathode material may be selected from Lithium Nickel Cobalt Manganese Oxide (NMC or NCM), Lithium Iron Phosphate (LFP), Lithium Nickel Manganese Spinel (LMNO), Lithium Nickel Cobalt Aluminum Oxide (NCA), Lithium Manganese Oxide (LMO), Lithium Cobalt Oxide (LCO), or combinations thereof.
Anode
The Anode material of the secondary battery described herein is not so limited, and may be any anode-material for use in a secondary battery. In some preferred embodiments, the anode material may be one susceptible to metal-ion contamination in the cell such as graphite.
Electrolyte
The electrolyte material of the secondary battery described herein is not so limited, and any electrolyte suitable for use in a secondary battery may be used. In some preferred embodiments, the electrolyte is a liquid electrolyte.
Separator
The separator herein may be one of the following: an uncoated separator comprising a trap layer, a coated separator where the coating comprises a trap layer, a coated separator where the separator comprises a trap layer, or a coated separator where the coating and the separator comprise a trap layer
Uncoated Separator Comprising a Trap Layer
The uncoated separator Comprising a Trap Layer may be a porous membrane with one or more trap layers therein. The one or more trap layers may be external layers, see
The uncoated separator with a trap layer may, in preferred embodiments, be a microporous membrane.
The uncoated separator with a trap layer may be formed by any method, but in preferred embodiments, the uncoated separator with a trap layer may be formed by a dry-stretch method such as the Celgard dry-stretch method. A dry-stretch method may comprise, consist of, or consist essentially of an extrusion (or co-extrusion) step, an annealing step, and a stretching (uniaxially or biaxially) step. A dry-stretch method does not utilize solvents or oils, or uses only minimal amounts. The uncoated separator with a trap layer may also be formed by a wet process that does utilize solvents and/or oils. For example, solvents and/or oils may be used for pore formation in a wet process.
Coated Separator with Trap Layer
The coated separator may comprise the following: a separator with a trap layer as described hereinabove (see also
The separator without a trap layer is not so limited and may be any porous or microporous membrane suitable for use as a battery separator. In some preferred embodiments, the separator without a trap layer may comprise, consist of, or consist essentially of one or more polyolefins, including polypropylene, polyethylene, copolymers thereof, or mixtures thereof. The separator without a trap layer may be a monolayer membrane, a bilayer membrane, a trilayer membrane, or a multilayer membrane. The separator without a trap layer may be formed by any method, but in preferred embodiments, the separator without a trap layer may be formed by a dry-stretch method such as the Celgard dry-stretch method. A dry-stretch method may comprise, consist of, or consist essentially of an extrusion (or co-extrusion) step, an annealing step, and a stretching (uniaxially or biaxially) step. A dry-stretch method does not utilize solvents or oils, or uses only minimal amounts. The separator without a trap layer may also be formed by a wet process that does utilize solvents and/or oils. For example, solvents and/or oils may be used for pore formation in a wet process.
Trap Layer
The trap layer, whether part of the separator, part of the coating, or both part of the separator and part of the coating, may have a potential difference vs. Li+/Li that is in the range of +0.0V to +5.0V, +0.0V to +4.5V, from +0.0V to +4.0V, from +0.0V to +3.5V, from +0.0V to +3.0V, from +0.0V to +2.5V, from +0.0V to +2.0V, from +0.0V to +1.5V, or from or from +0.0V to 1.0V. For example, for the trap layer to be able to trap copper ions, the potential difference would have to be +3.38. Li+/Li is at −3.04V relative to H2/2H+, Cu2+/Cu is at +0.34V, so the trap layer would have to be at a potential difference of at least +3.38 V relative to Li+/Li to trap the copper ions.
The trap layer, whether part of the separator, part of the coating, or both part of the separator and part of the coating, has a bulk or volume resistivity of 10 to 109 ohms-cm, 10 to 108 ohms-cm, 10 to 107 ohms-cm, 10 to 106 ohms-cm, 10 to 105 ohms-cm, 10 to 104 ohms-cm, 10 to 103 ohms-cm, or 10 to 102 ohms-cm. In some preferred embodiments, a resistivity from 104 to 109 ohms-cm, 104 to 108 ohms-cm, or 104 to 107 ohms-cm may be preferred. As shown in
In some preferred embodiments, the trap layer may comprise, consist of, or consist essentially of carbon and a polymer. In some particularly preferred embodiments, the carbon may be a conductive carbon such as carbon nanotubes. In some embodiments, the carbon is selected from carbon black, acetylene black, carbon nanotubes, graphene, or combinations thereof.
In other preferred embodiments, trap layer may comprise, consist of, or consist essentially of a conductive polymer. The conductive polymer may be selected from a poly-acetylene, a poly-thiophene, a poly-aniline, a poly-pyrrole, or combinations thereof.
Table 1 below shows the reduction potential for certain transition metal ions and gives the minimum potential difference vs. Li+/Li which the trap layer must have to trap each of the listed metal ions. Trapping of the transition metal ions may mean plating of the ions on the trap layer surface.
A polypropylene and a trap layer material comprising polypropylene and carbon nanotubes is co-extruded to form a battery separator like that shown in
A trap layer coating is formed on a polypropylene monolayer battery separator to form a structure like that shown in
Example 3 is like Example 1 except the trap layer material comprises a conductive polymer, not polypropylene and carbon nanotubes.
Example 4 is like Example 2 except the trap layer comprises a conductive polymer, not carbon nanotubes and a polymer binder.
Examples 5 and 6, and Comparative Example 1, were prepared by coating a slurry having a composition as shown in Table 2 onto a surface of a 16 micron polyolefin tri-layer battery separator. The coating in each Example was 4 microns thick.
Cells were formed using the separators of Examples 5, 6, and 7. The Cell configuration was as follows. The cell structure was a laminated cell (36 mAh). Electrode size was 50 mm×30 mm. The cathode material was NCM111 and the anode material was graphite. The electrolyte was EC/EMC=1/2, 1M LiPF6, VC1 wt %. A 50 um copper particle was placed on cathode electrode to simulate contamination metal. A schematic drawing of this cell is in
Charging and discharging conditions are as follows. Charge conditions are 4.2V CCCV 1 mA 0.2 mA cut off. Aging was 3 days (checked voltage drop by internal short circuit). Temperature was 25° C.
Results are shown in
This application is a 371 U.S. Application claiming priority to PCT/US2021/041193, filed Jul. 10, 2021, which claims priority to U.S. Provisional Patent Application Ser. No. 63/051,742, filed Jul. 15, 2020, which is hereby fully incorporated by reference herein.
Filing Document | Filing Date | Country | Kind |
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PCT/US2021/041193 | 7/10/2021 | WO |
Number | Date | Country | |
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63051742 | Jul 2020 | US |