PATENT DOCUMENT

Publication Number: US-10847834-B1
Application Number: US-201816059609-A
Country: US
Kind Code: B1

Title: Corrosion resistant current collector for lithium metal anode

Abstract:
An anode for a lithium metal battery has a current collector formed of a flexible polymer substrate having an anode-facing surface, the polymer substrate formed of a polymer chemically compatible with lithium metal. A current pathway of a first conductive metal is embedded in the polymer substrate and has a terminal end extending from an end of the polymer substrate. Traces of a second conductive metal each have a current collecting portion at the anode-facing surface, the traces in electrical communication with the current pathway. Lithium metal is deposited onto the current collector.

Claims:
What is claimed is: 
     
       1. An anode for a lithium metal battery, comprising:
 a current collector comprising:
 a flexible polymer substrate having an anode-facing surface, the polymer substrate formed of a polymer chemically compatible with lithium metal; 
 a current pathway of a first conductive metal embedded in the polymer substrate and having a terminal end extending from an end of the polymer substrate; and 
 traces of a second conductive metal each having a current collecting portion, the traces in electrical communication with the current pathway, wherein the flexible polymer substrate has apertures through which respective current collecting portions are exposed at the anode-facing surface; and 
 
 lithium metal deposited onto the anode-facing surface and current collecting portions of the current collector. 
 
     
     
       2. The anode of  claim 1 , further comprising an adhesion promotor between the lithium metal and the current collector. 
     
     
       3. The anode of  claim 2 , wherein the adhesion promotor is aluminum oxide. 
     
     
       4. The anode of  claim 2 , wherein the adhesion promotor is a plasma treatment of the flexible polymer substrate. 
     
     
       5. The anode of  claim 1 , wherein a total area of current collecting portions is 20% or less than an area of the anode-facing surface. 
     
     
       6. An anode for a lithium metal battery, comprising:
 a current collector comprising:
 a flexible polymer substrate having an anode-facing surface, the polymer substrate formed of a polymer chemically compatible with lithium metal; 
 a current pathway of a first conductive metal embedded in the polymer substrate and having a terminal end extending from an end of the polymer substrate; and 
 traces of a second conductive metal each having a current collecting portion at the anode-facing surface, the traces in electrical communication with the current pathway; and 
 
 lithium metal deposited onto the anode-facing surface and current collecting portions of the current collector, wherein the current collecting portion is a contact point, and contact points are distributed across the anode-facing surface. 
 
     
     
       7. The anode of  claim 6 , wherein each contact point has a diameter between about 20 microns and about 1.0 mm. 
     
     
       8. The anode of  claim 1 , wherein the first conductive metal and the second conductive metal are both copper, and the traces form both current collecting portions and the current pathway. 
     
     
       9. The anode of  claim 1 , wherein the first conductive metal and the second conductive metal are both copper, and the current pathway is one or more copper strips. 
     
     
       10. The anode of  claim 1 , wherein the first conductive metal is copper and the second conductive metal is nickel. 
     
     
       11. The anode of  claim 10 , wherein the current pathway is one or more strips of copper. 
     
     
       12. The anode of  claim 1 , wherein each current collecting portion is coated with a conductive corrosion barrier material. 
     
     
       13. The anode of  claim 12 , wherein the corrosion barrier material is carbon. 
     
     
       14. The anode of  claim 12 , wherein the corrosion barrier material is aluminum nitride. 
     
     
       15. The anode of  claim 1 , wherein the current collector has a thickness of between 5 microns and 20 microns. 
     
     
       16. The anode of  claim 1 , wherein the polymer of the polymer substrate is one or more of polyether ether ketone, polyimide, polyamide, polyethylene, polyvinyl acetate and polypropylene. 
     
     
       17. A lithium metal battery, comprising:
 a cathode comprising a cathode active material and a cathode current collector; 
 a liquid electrolyte; 
 an anode current collector comprising:
 a flexible polymer substrate having an anode-facing surface, the polymer substrate formed of a polymer chemically compatible with lithium metal; 
 a current pathway of a first conductive metal embedded in the polymer substrate and having a terminal end extending from an end of the polymer substrate; and 
 traces of a second conductive metal each having a current collecting portion at the anode-facing surface, the traces in electrical communication with the current pathway; and 
 
 an anode comprising lithium metal deposited onto the anode-facing surface and current collecting portions of the current collector. 
 
     
     
       18. An anode for a lithium metal battery, comprising:
 a current collector comprising:
 a flexible polymer substrate having a first anode-facing surface and a second anode-facing surface opposite the first anode-facing surface, the polymer substrate formed of a polymer chemically compatible with lithium metal; 
 a current pathway of a first conductive metal embedded in the polymer substrate and having a terminal end extending from an end of the polymer substrate; and 
 traces of a second conductive metal each having a current collecting portion at one of the first anode-facing surface and the second anode-facing surface, the traces in electrical communication with the current pathway; and 
 
 lithium metal deposited onto the first anode-facing surface, the second anode-facing surface, and current collecting portions of the current collector, wherein the current collecting portion is a contact point, and contact points are distributed across each of the first anode-facing surface and the second anode-facing surface. 
 
     
     
       19. The anode of  claim 18 , wherein a total area of current collecting portions on each of the first anode-facing surface and the second anode-facing surface is 20% or less than an area of a respective anode-facing surface. 
     
     
       20. The anode of  claim 18 , wherein each contact point has a diameter between about 20 microns and about 1.0 mm.

Description:
CROSS-REFERENCE TO RELATED APPLICATIONS 
     This application claims the benefit of U.S. Provisional Application No. 62/563,792, filed on Sep. 27, 2017, the content of which is hereby incorporated by reference in its entirety for all purposes. 
    
    
     TECHNICAL FIELD 
     This application generally relates to a corrosion resistant current collector for lithium metal anodes in high energy density batteries. 
     BACKGROUND 
     Lithium metal can provide significant increases in energy density, but can be difficult to handle and integrate. Lithium is soft and is typically used with a copper foil backing to mechanically support the lithium and provide a means to conduct current from the cell. However, when two dissimilar metals such as lithium and copper are placed into electrical contact in the presence of an electrolyte, galvanic corrosion will occur. 
     SUMMARY 
     The disclosed embodiments provide an anode having a current collector for a lithium metal battery comprising a flexible polymer substrate having an anode-facing surface, the polymer substrate formed of a polymer chemically compatible with lithium metal. A current pathway of a first conductive metal is embedded in the polymer substrate and has a terminal end extending from an end of the polymer substrate. Traces of a second conductive metal each have a current collecting portion at the anode-facing surface, the traces in electrical communication with the current pathway. 
     In some embodiments, a total area of current collecting portions is 20% or less than an area of the anode-facing surface. 
     In some embodiments, the current collecting portion is a contact point, and contact points are evenly distributed across the anode-facing surface. 
     In some embodiments, each contact point has a diameter between about 20 microns and about 1.0 mm. 
     In some embodiments, the first conductive metal and the second conductive metal are both copper. 
     In some embodiments, the current pathway is one or more copper strips. 
     In some embodiments, the current pathway is formed of the traces extending through the polymer substrate to the terminal end. 
     In some embodiments, the first conductive metal is copper and the second conductive metal is nickel. 
     In some embodiments, each current collecting portion is coated with a conductive corrosion barrier material. 
     In some embodiments, the corrosion barrier material is carbon. 
     In some embodiments, the corrosion barrier material is aluminum nitride. 
     In some embodiments, the current collector has a thickness of between 5 microns and 10 microns. 
     In some embodiments, the polymer of the polymer substrate is one or more of polyether ether ketone, polyimide, polyamide, polyethylene, polyvinyl acetate and polypropylene. 
     Also disclosed herein are anodes for a lithium metal battery comprising a current collector, a flexible polymer substrate having a first anode-facing surface and a second anode-facing surface opposite the first anode-facing surface, the polymer substrate formed of a polymer chemically compatible with lithium metal, a current pathway of a first conductive metal embedded in the polymer substrate and having a terminal end extending from an end of the polymer substrate and traces of a second conductive metal each having a current collecting portion at one of the first anode-facing surface and the second anode-facing surface, the traces in electrical communication with the current pathway. Lithium metal is deposited onto the first anode-facing surface, the second anode-facing surface, and current collecting portions of the current collector. 
     In some embodiments, an adhesion promotor is between the lithium metal and the current collector. 
     In some embodiments, the adhesion promotor is aluminum oxide. 
     In some embodiments, the adhesion promotor is a plasma treatment of the flexible polymer substrate. 
     Also disclosed herein are lithium metal batteries having a cathode comprising a cathode active material and a cathode current collector; a liquid electrolyte; an anode current collector comprising a flexible polymer substrate having an anode-facing surface, the polymer substrate formed of a polymer chemically compatible with lithium metal, a current pathway of a first conductive metal embedded in the polymer substrate and having a terminal end extending from an end of the polymer substrate and traces of a second conductive metal each having a current collecting portion at the anode-facing surface, the traces in electrical communication with the current pathway; and an anode comprising lithium metal deposited onto the anode-facing surface and current collecting portions of the anode current collector. 
     Another aspect of the disclosed embodiments is a battery pack having a plurality of lithium metal batteries. 
    
    
     
       BRIEF DESCRIPTION OF THE DRAWINGS 
         FIG. 1A  is a plan view of an embodiment of a current collector as disclosed herein. 
         FIG. 1B  is a cross-sectional view of the current collector of  FIG. 1A  along line B. 
         FIG. 1C  is a plan cross-sectional view of the current collector of  FIG. 1B  along line C. 
         FIG. 2A  is a plan view of another embodiment of a current collector as disclosed herein. 
         FIG. 2B  is a cross-sectional view of the current collector of  FIG. 2A  along line B. 
         FIG. 2C  is a plan cross-sectional view of the current collector of  FIG. 2B  along line C. 
         FIG. 3A  is a cross-sectional view of another embodiment of a current collector as disclosed herein. 
         FIG. 3B  is a plan cross-sectional view of the current collector of  FIG. 3A  along line B. 
         FIG. 4  is an enlarged view of the circled section of  FIG. 1B . 
         FIG. 5  is a cross-sectional view of an anode as disclosed herein. 
         FIG. 6  is a cross-sectional view of another anode as disclosed herein. 
         FIG. 7  is a cross-section view of a lithium metal battery as disclosed herein. 
     
    
    
     DETAILED DESCRIPTION 
     When two dissimilar metals are placed into electrical contact in the presence of an electrolyte, galvanic corrosion will occur. In some high-energy density batteries, a lithium metal anode material is used with a copper current collector. Lithium has a galvanic potential of approximately −3.0 V and copper has a galvanic potential of approximately +0.8 V, so anodic corrosion of the lithium is expected. When a lithium metal layer on copper is used as the anode in a lithium metal battery, the galvanic corrosion initially begins at the edges where there are exposed lithium-copper junctions. The electrolyte can also penetrate the lithium grain boundaries, causing lithium corrosion at these boundaries. Eventually, the lithium will become porous and delaminate from the copper where the galvanic corrosion occurs. Obvious prevention measures would include removing the electrical connection, avoiding dissimilar metals or removing the electrolyte from the junction between the metals, none of which are possible in a battery. 
     The current collectors disclosed herein provide electrical contacts at discrete spots that are isolated from the liquid electrolyte that fills the cell. In this way, junctions of dissimilar metals that are exposed to electrolyte are significantly reduced, reducing the potential for galvanic corrosion in the anode, and thereby improving battery performance. 
       FIGS. 1A-1C  illustrate an embodiment of a current collector  100  for a lithium metal battery as disclosed herein. The current collector  100  is formed of a flexible polymer substrate  102  having an anode-facing surface  104 . A current pathway  106  is embedded in the polymer substrate  102  and has a terminal end  108  extending from an end  110  of the polymer substrate  102 . Traces  112  or vias in electrical communication with the current pathway  106  each have a current collecting portion  114  at the anode-facing surface  104 . 
     The current collectors disclosed herein are shown as double-sided, as seen in the side cross-sectional views. Each current collector has a second anode-facing surface  105  on its opposing side with traces  112  or vias in electrical communication with the current pathway  106 . The traces  112  on the opposing side of the current pathway  106  will have respective current collecting portions  114  at the second anode-facing surface  105 . Plan views of only one surface are included as the opposing surface will be similar or identical. Single-sided current collectors are contemplated herein. In other words, the traces  112  can be in electrical communication with the current pathway  106  on only one side of the current collector  100 . 
     The polymer substrate  102  is formed of a polymer chemically compatible with lithium metal. As used herein “chemically compatible” means that the polymer is non-reactive with lithium metal. Non-limiting examples include polyether ether ketone, polyimide, polyamide, polyethylene, polyvinyl acetate and polypropylene. The polymer substrate  102  can provide mechanical strength to the lithium metal anode material. 
     The current pathway  106  is a conductive metal that is embedded or encapsulated in the polymer substrate  102 . The current pathway  106  is not limited in its structure. The current pathway  106  can be a single strip or wire of the conductive metal of a size sufficient to electronically communicate with the traces  112 , as illustrated in  FIGS. 1A-1C . The current pathway  106  conducts current from traces  112  through the terminal end  108 . As another non-limiting example, the current collector  120  in  FIGS. 2A-2C  has a current pathway  126  of multiple strips or wires of the conductive metal, each in electrical communication with a respective portion of traces  112  and each carrying current through its respective terminal end  128 . As another non-limiting example, the current collector  130  in  FIGS. 3A and 3B  has a current pathway  136  that are extensions of each trace  112 , the trace  112  extending from the current collecting portion  114  (as illustrated in  FIG. 1B ) through the polymer substrate  102  and to terminal end  138 , which conducts the current from the cell. As another non-limiting example, the current pathway  106  can be a sheet of conductive metal. Each of the examples of the current pathway  106  provides a current pathway  106  that is fully encased in the polymer substrate  102  apart from the terminal end  108 . 
     The traces  112  are a conductive metal. The traces  112  and the current pathway  106  can be the same conductive metal. For example, the traces  112  and the current pathway  106  can both be copper or both be nickel. The traces  112  can be a different conductive metal than the conductive metal of the current pathway  106 . For example, the current pathway  106  can be copper while the traces  112  can be nickel. Nickel is less reactive with lithium in the presence of the electrolyte. Copper and nickel are non-limiting examples of conductive metals that can be used as each of the current pathway  106  and traces  112 . Nickel coated copper and other materials such as gold can also be used.  FIG. 1C  is a plan cross-sectional view along line C in  FIG. 1A  illustrating how the traces  112  communicate with the current pathway  106 . In an embodiment, the entire trace  112  can be nickel. In another embodiment, a distal portion of the trace  112  that is perpendicular to the anode-facing surface  104  can be nickel, i.e., a plug of nickel, with the remainder of the trace  112  connecting the plug to the current pathway  106 . 
     The traces  112  provide current collecting portions  114  that are discrete spots isolated from the liquid electrolyte that fills the cell. As illustrated in  FIG. 1B , the current collecting portions  114  are contact points, such as distal ends, of the traces  112  that are exposed through the anode-facing surface  104  of the polymer substrate  102 . As illustrated, these contact points are evenly distributed across the anode-facing surface  104 . The distribution shown in the figures is illustrative only and not meant to be limiting. Each contact point can have a diameter between about 20 microns and about 1.0 mm. The smaller the current collecting portion  114  of each trace  112 , the less likely the current collecting portion  114  will be exposed to the electrolyte in the cell. Having current collecting portions  114  of reduced size and increased number allows for isolated incidents of galvanic corrosion where the lithium metal is penetrated to the current collector by the electrolyte. The corrosion will occur at the discrete current collecting portion  114  but will not spread to other current collecting portions  114  due to the intervening polymer of the polymer substrate  102 . 
     The number and size of collecting portions  114  provides sufficient contact with the lithium metal to conduct the current required during operation. To ensure sufficient current collection and reduce potential sites for corrosion, a total area of the current collecting portions  114  can be 20% or less of an area of the anode-facing surface  104 . For example, the current collecting portions  114  can total between about 15% and 20% of the area of the anode-facing surface  104 . 
     The current collecting portions  114  of the traces  112  can have other configurations. For example, the current collecting portions  114  can be the traces  112  extending along the anode-facing surface  104  of the polymer substrate  102  and connecting with the terminal end  108  within the polymer substrate  102 . Other patterns of traces  112  are contemplated. 
       FIG. 4  is an enlarged view of section  4  circled in  FIG. 1B . As illustrated in  FIG. 4 , each current collecting portion  114  can be coated with a conductive corrosion barrier material  116  to further eliminate the potential for corrosion at the junction between the lithium, current collector metal and electrolyte. This barrier material  116  can be carbon or a material such as aluminum nitride, as non-limiting examples. 
     The current collector  100  can be manufactured by methods known to those skilled in the art. Processes can be either subtractive or additive. As a non-limiting example, metal foil can be used as the starting material and screen printed with the desired configuration. Material is removed based on the screen-printed design to form the current pathways  106  and/or traces  112 . As another example, the current pathway  106  can be printed, plated or deposited onto a polymer film and covered with additional polymer to form the polymer substrate  102 . Imprint lithography can be used to insert the traces  112  at the desired positions. 
     An anode  200  for a lithium metal battery is illustrated in  FIG. 5 . The anode  200  comprises the current collector  100  disclosed herein with lithium metal  220  deposited onto both the anode-facing surface  104  and current collecting portions  114  of the current collector  100 . A portion of encapsulation  224  is illustrated, with electrolyte  226  contained in the encapsulation  224 . As illustrated, there are no junctions of dissimilar metals exposed to the electrolyte  226  in the anode  200  disclosed herein.  FIG. 6  illustrates the anode  200  of  FIG. 5  with an adhesion promotor  222  used between the lithium metal  220  and the current collector  100  to ensure adhesion of the lithium metal  220  on the polymer used for the polymer substrate  102 . A non-limiting example of the adhesion promotor  222  is aluminum oxide. The anode-facing surface  104  of the polymer substrate  102  can also be plasma treated to improve the adhesion of the lithium metal  220  to the polymer substrate  102  of the current collector  100 . 
     An aspect of the disclosed embodiments is a lithium metal battery  300 , the layers of which are shown in cross-section in  FIG. 7 . The lithium metal battery  300  has an anode  302  as described herein with the current collector  304  representing disclosed current collector  100 . The anode layer  306  represents the lithium metal layer  220 . The lithium metal battery  300  also has a cathode  308  with a cathode current collector  310  and a cathode active material  312  disposed over the cathode current collector  310 . The cathode  308  and the anode  302  are separated by electrolyte and a separator  314 . 
     The cathode current collector  310  can be, for example, an aluminum sheet or foil. Cathode active materials  312  can include one or more lithium transition metal oxides which can be bonded together using binders and optionally conductive fillers such as carbon black. Lithium transition metal oxides can include, but are not limited to, LiCoO 2 , LiNiO 2 , LiNi 0.8 Co 0.15 Al 0.05 O 2 , LiMnO 2 , Li(Ni 0.5 Mn 0.5 )O 2 , LiNi x Co y Mn z O 2 , Spinel Li 2 Mn 2 O 4 , LiFePO 4  and other polyanion compounds, and other olivine structures including LiMnPO 4 , LiCoPO 4 , LiNi 0.5 Co 0.5 PO 4 , and LiMn 0.33 Fe 0.33 Co 0.33 PO 4 . 
     In some embodiments, the electrolyte may include a liquid electrolyte, a polymer ionic liquid, a gel electrolyte, or a combination thereof. The electrolyte can be an ionic liquid based electrolyte mixed with a lithium salt. The ionic liquid may be, for example, at least one selected from N-Propyl-N-methyl pyrrolidinium bis(fluorosulfonyl)imide, N-methyl-N-propylpyrrolidinium bis(trifluoromethanesulfonyl)imide, N-butyl-N-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide, 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide, and 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide. The salt can be or include, for example, a fluorosulfonyl (FS0) group, e.g., lithium bis(fluorosulfonyl)imide (LiN(FS0 2 ) 2 , (LiFSI), LiN(FS0 2 ) 2 , LiN(FS0 2 )(CF 3 S0 2 ), LiN(FS0 2 )(C 2 F 5 S0 2 ). In some embodiments, the electrolyte is or includes a cyclic carbonate (e.g., ethylene carbonate (EC) or propylene carbonate, a cyclic ether such as tetrahydrofuran (THF) or tetrahydropyran (TH), a glyme such as dimethoxyethane (DME), dimethyl carbonate (DMC) or diethoxyethane, an ether such as diethylether (DEE) or methylbutylether (MBE), their derivatives, and any combinations and mixtures thereof. 
     The foregoing descriptions of various embodiments have been presented only for purposes of illustration and description. They are not intended to be exhaustive or to limit the present invention to the forms disclosed. Accordingly, many modifications and variations will be apparent to practitioners skilled in the art.

Metadata:
Filing Date: 20180809
Publication Date: 20201124
Grant Date: 20201124
Priority Date: 20170927
Inventors: BROWN, KARL M.
RITCHIE, ALAN A.
Assignee: APPLE INC
CPC Classifications: [{"code": "H01M10/4235", "inventive": true, "first": false, "tree": "[]"}, {"code": "H01M10/052", "inventive": true, "first": false, "tree": "[]"}, {"code": "H01M4/668", "inventive": true, "first": false, "tree": "[]"}, {"code": "H01M4/628", "inventive": true, "first": false, "tree": "[]"}, {"code": "H01M4/134", "inventive": true, "first": true, "tree": "[]"}, {"code": "Y02E60/10", "inventive": false, "first": false, "tree": "[]"}, {"code": "H01M4/661", "inventive": true, "first": false, "tree": "[]"}, {"code": "H01M10/052", "inventive": true, "first": true, "tree": "[]"}, {"code": "H01M2004/021", "inventive": false, "first": false, "tree": "[]"}, {"code": "H01M2004/027", "inventive": false, "first": false, "tree": "[]"}, {"code": "H01M4/628", "inventive": true, "first": false, "tree": "[]"}, {"code": "H01M2004/028", "inventive": false, "first": false, "tree": "[]"}, {"code": "H01M2004/028", "inventive": false, "first": false, "tree": "[]"}, {"code": "H01M4/661", "inventive": true, "first": false, "tree": "[]"}, {"code": "H01M10/052", "inventive": true, "first": true, "tree": "[]"}, {"code": "H01M2004/027", "inventive": false, "first": false, "tree": "[]"}, {"code": "H01M2004/021", "inventive": false, "first": false, "tree": "[]"}, {"code": "H01M4/628", "inventive": true, "first": false, "tree": "[]"}]
Family ID: 73462037