Method of improving cycle-life of a lithium metal secondary battery
The invention provides a method of improving the cycle-life of a lithium metal secondary battery. The method comprises implementing an anode-protecting layer between an anode active material layer and a porous separator/electrolyte, wherein the anode-protecting layer or cathode-protecting layer comprises a conductive sulfonated elastomer composite having from 0.01% to 50% by weight of a conductive reinforcement material dispersed in a sulfonated elastomeric matrix material and the protecting layer has a thickness from 1 nm to 100 μm, a fully recoverable tensile strain from 2% to 500%, a lithium ion conductivity from 10 −7 S/cm to 5×10 −2 S/cm, and an electrical conductivity from 10 −7 S/cm to 100 S/cm when measured at room temperature.
1. A method of improving a cycle-life of a lithium metal secondary battery, not including a lithium-sulfur battery or lithium-selenium battery, said method comprising implementing an anode-protecting layer between an anode active material layer and a porous separator/electrolyte, wherein said anode-protecting layer comprises a conductive sulfonated elastomer composite having from greater than 20% to 50% by weight of a conductive reinforcement material dispersed in a sulfonated elastomeric matrix material and said layer of conductive sulfonated elastomer composite has a thickness from 1 nm to 100 μm, a fully recoverable tensile strain from 2% to 500%, a lithium ion conductivity from 10 −7 S/cm to 5×10 −2 S/cm, and an electrical conductivity from 10 −7 S/cm to 100 S/cm when measured at room temperature, wherein said conductive sulfonated elastomer composite comprises a sulfonated elastomer composite network having a rotaxane structure, wherein said sulfonated elastomeric matrix material contains a material selected from the group consisting of sulfonated versions of natural polyisoprene, synthetic polyisoprene, polybutadiene, chloroprene rubber, polychloroprene, nitrile rubber, ethylene propylene rubber, metallocene-based poly(ethylene-co-octene) elastomer, poly(ethylene-co-butene) elastomer, epichlorohydrin rubber, silicone rubber, fluorosilicone rubber, polyether block amides, ethylene-vinyl acetate, protein resilin, protein elastin, ethylene oxide-epichlorohydrin copolymer, polyurethane, urethane-urea copolymer, and combinations thereof.
2. The method of claim 1 , wherein said step of implementing an anode-protecting layer is conducted by depositing a layer of a sulfonated elastomer composite onto one primary surface of the anode active material layer to form a protected anode, optionally compressing said protected anode to improve a contact between said anode-protecting layer and said anode active material layer, followed by combining the protected anode, the separator/electrolyte, and the cathode together to form said lithium metal secondary battery.
3. The method of claim 1 , wherein said step of implementing an anode-protecting layer is conducted by depositing a layer of first sulfonated elastomer composite onto one primary surface of the separator to form a coated separator, followed by combining the anode, the coated separator, the cathode, and the electrolyte together to form the lithium metal secondary battery.
4. The method of claim 1 , wherein said step of implementing an anode-protecting layer is conducted by forming a layer of a sulfonated elastomer composite, followed by laminating the anode layer, the layer of sulfonated elastomer composite, the separator layer, the cathode layer, along with the electrolyte to form the lithium metal secondary battery, wherein an optional compressive stress is applied to improve a contact between said anode-protecting layer and said anode active material layer during or after said laminating step.
5. The method of claim 1 , wherein said sulfonated elastomer matrix further contains from 0.1% to 50% by weight of a lithium ion-conducting additive dispersed therein.
6. The method of claim 5 , wherein said lithium ion-conducting additive is selected from the group consisting of Li 2 CO 3 , Li 2 O, Li 2 C 2 O 4 , LiOH, LiX, ROCO 2 Li, HCOLi, ROLi, (ROCO 2 Li) 2 , (CH 2 OCO 2 Li) 2 , Li 2 S, Li x SO y , and combinations thereof, wherein X=F, Cl, I, or Br, R=a hydrocarbon group, 0<x≤1 and 1≤y≤4.
7. The method of claim 5 , wherein said lithium ion-conducting additive is selected from the group consisting of lithium perchlorate (LiClO 4 ), lithium hexafluorophosphate (LiPF 6 ), lithium borofluoride (LiBF 4 ), lithium hexafluoroarsenide (LiAsF 6 ), lithium trifluoro-metasulfonate (LiCF 3 SO 3 ), bis-trifluoromethyl sulfonylimide lithium [LiN(CF 3 SO 2 ) 2 ] lithium bis(oxalato) borate (LiBOB), lithium oxalyldifluoroborate (LiBF 2 C 2 O 4 ), lithium oxalyldifluoroborate (LiBF 2 C 2 O 4 ), lithium nitrate (LiNO 3 ), Li-fluoroalkyl-phosphates [LiPF 3 (CF 2 CF 3 ) 3 ], lithium bisperfluoro-ethysulfonylimide (LiBETI), lithium bis(trifluoromethanesulfonyl) imide, lithium bis(fluorosulfonyl) imide, lithium trifluoromethanesulfonimide (LiTFSI), an ionic liquid-based lithium salt, and combinations thereof.
8. The method of claim 1 , wherein said electrolyte is selected from a polymer electrolyte, polymer gel electrolyte, composite electrolyte, ionic liquid electrolyte, organic liquid electrolyte, solid-state electrolyte, and combinations thereof.
9. The method of claim 1 , wherein said cathode active material is selected from the group consisting of inorganic materials, organic materials, polymeric materials, and combinations thereof, and said inorganic material does not include sulfur or alkali metal polysulfide.
10. The method of claim 9 , wherein said inorganic material is selected from the group consisting of metal oxides, metal phosphates, metal silicides, metal selenides, transition metal sulfides, and combinations thereof.
11. The method of claim 10 , wherein said metal oxide contains a vanadium oxide selected from the group consisting of VO 2 , Li x VO 2 , V 2 O 5 , Li x V 2 O 5 , V 3 O 8 , Li x V 3 O 8 , Li x V 3 O 7 , V 4 O 9 , Li x V 4 O 9 , V 6 O 13 , Li x V 6 O 13 , their doped versions, their derivatives, and combinations thereof, wherein 0.1<x<5.
12. The method of claim 10 , wherein said metal oxide or metal phosphate is selected from the group consisting of a layered compound LiMO 2 , spinel compound LiM 2 O 4 , olivine compound LiMPO 4 , silicate compound Li 2 MSiO 4 , tavorite compound LiMPO 4 F, borate compound LiMBO 3 , and combinations thereof, wherein M is a transition metal or a mixture of multiple transition metals.
13. The method of claim 10 , wherein said inorganic material is selected from the group consisting of: (a) bismuth selenide or bismuth telluride, (b) transition metal dichalcogenide or trichalcogenide, (c) sulfide, selenide, or telluride of niobium, zirconium, molybdenum, hafnium, tantalum, tungsten, titanium, cobalt, manganese, iron, nickel, or a transition metal; (d) boron nitride, and (e) combinations thereof.
14. The method of claim 9 , wherein said inorganic material is selected from the group consisting of lithium cobalt oxide, lithium nickel oxide, lithium manganese oxide, lithium vanadium oxide, lithium-mixed metal oxide, lithium iron phosphate, lithium manganese phosphate, lithium vanadium phosphate, lithium mixed metal phosphate, lithium metal silicide, and combinations thereof.
15. The method of claim 9 , wherein said inorganic material is selected from a metal fluoride or metal chloride including the group consisting of CoF 3 , MnF 3 , FeF 3 , VF 3 , VOF 3 , TiF 3 , BiF 3 , NiF 2 , FeF 2 , CuF 2 , CuF, SnF 2 , AgF, CuCl 2 , FeCl 3 , MnCl 2 , and combinations thereof.
16. The method of claim 9 , wherein said inorganic material is selected from a lithium transition metal silicate, denoted as Li 2 MSiO 4 or Li 2 Ma x Mb y SiO 4 , wherein M and Ma are selected from Fe, Mn, Co, Ni, V, or VO; Mb is selected from Fe, Mn, Co, Ni, V, Ti, Al, B, Sn, or Bi; and x+y≤1.
17. The method of claim 9 , wherein said inorganic material is selected from the group consisting of a transition metal dichalcogenide, a transition metal trichalcogenide, and combinations thereof.
18. The method of claim 9 , wherein said inorganic material is selected from the group consisting of TiS 2 , TaS 2 , MoS 2 , NbSe 3 , MnO 2 , CoO 2 , an iron oxide, a vanadium oxide, and combinations thereof.
19. A method of improving a cycle-life of a lithium metal secondary battery, not including a lithium-sulfur battery or lithium-selenium battery, said method comprising implementing an anode-protecting layer between an anode active material layer and a porous separator/electrolyte, wherein said anode-protecting layer comprises a conductive sulfonated elastomer composite having from greater than 20% to 50% by weight of a conductive reinforcement material dispersed in a sulfonated elastomeric matrix material and said layer of conductive sulfonated elastomer composite has a thickness from 1 nm to 100 μm, a fully recoverable tensile strain from 2% to 500%, a lithium ion conductivity from 10 −7 S/cm to 5×10 −2 S/cm, and an electrical conductivity from 10 −7 S/cm to 100 S/cm when measured at room temperature, wherein said sulfonated elastomer matrix further contains from 0.1% to 50% by weight of a lithium ion-conducting additive dispersed therein, wherein said conductive sulfonated elastomer composite comprises a sulfonated elastomer composite network having a rotaxane structure, wherein said lithium ion-conducting additive is selected from the group consisting of poly(methyl methacrylate) (PMMA), poly bis-methoxy ethoxyethoxide-phosphazene, polydimethylsiloxane, a sulfonated derivative thereof, and combinations thereof.