Composite electrolyte, protective film including composite electrolyte, protected negative electrode including the protective film, and lithium metal battery including the protected negative electrode

Abstract

A composite electrolyte includes: a positively charged particle, a particle that is positively charged by having a coordinate bond with a cation, or a combination thereof; and a lithium salt.

1 - 34 . (canceled) 
     
     
         35 . A composite electrolyte, comprising:
 a particle that is positively charged by a coordinate bond with a cation; and   a lithium salt,   wherein the particle comprises:   a core comprising an organic particle; and   a functional group bound to the core via a covalent bond,   wherein the functional group comprises a functional group that is bound to the cation by the coordinate bond,   wherein an average particle size of the particle is about 10 nanometers to about 100 micrometers, and   wherein the functional group that is bound to the cation by the coordinate bond is represented by Formula 2:   
       
         
           
           
               
               
           
         
       
       wherein, in Formula 2,
 X is O, S, or a covalent bond, 
 Z is N or B, 
 R 5 , and R 6  are each independently hydrogen, a C 1 -C 20  alkyl group that is unsubstituted or substituted with a halogen, a C 2 -C 20  alkenyl group that is unsubstituted or substituted with a halogen, a C 2 -C 20  alkynyl group that is unsubstituted or substituted with a halogen, a C 5 -C 20  aryl group that is unsubstituted or substituted with a halogen, or a C 2 -C 20  heteroaryl group that is unsubstituted or substituted with a halogen, and 
 R 7  is a C 1 -C 20  alkylene group that is unsubstituted or substituted with a halogen. 
 
     
     
         36 . The composite electrolyte of  claim 35 , wherein a monomeric compound that provides the functional group that is bound to the cation by the coordinate bond is a base, and
 wherein a pKa value of a conjugate acid of the monomeric compound is 12 or less.   
     
     
         37 . The composite electrolyte of  claim 35 , wherein the functional group that is bound to the cation by the coordinate bond is represented by one of Formulae 11 to 18, or a combination thereof: 
       
         
           
           
               
               
           
         
       
     
     
         38 . The composite electrolyte of  claim 35 , wherein the particle comprises a polystyrene homopolymer, a copolymer comprising a styrene repeating unit, a polymethyl (meth)acrylate, a copolymer comprising a repeating unit having a crosslinkable functional group, a crosslinked polymer thereof, or a combination thereof 
     
     
         39 . The composite electrolyte of  claim 35 , wherein the particle comprises a polystyrene homopolymer, a poly(styrene-divinylbenzene) copolymer, a poly(methyl methacrylate-divinylbenzene) copolymer, a poly(ethyl methacrylate-divinylbenzene) copolymer, a poly(pentyl methacrylate-divinylbenzene) copolymer, a poly(butyl methacrylate-divinylbenzene) copolymer, a poly(propyl methacrylate-divinylbenzene) copolymer, a poly(styrene-ethylene butylene-styrene) copolymer, a poly(styrene-methyl methacrylate) copolymer, a poly(styrene-acrylonitrile) copolymer, a poly(styrene-vinylpyridine) copolymer, a poly(acrylonitrile-butadiene-styrene) copolymer, a poly(acrylonitrile-ethylene-propylene-styrene) copolymer, a poly(methyl methacrylate-acrylonitrile-butadiene-styrene) copolymer, a poly((C 1 -C 9  alkyl) methacrylate-butadiene-styrene) copolymer, a poly(styrene-(C 1 -C 9  alkyl) acrylate) copolymer, a poly(acrylonitrile-styrene-(C 1 -C 9  alkyl) acrylate) copolymer, or a combination thereof, a crosslinked structure thereof, or a combination thereof. 
     
     
         40 . The composite electrolyte of  claim 35 , wherein the particle comprises a microsphere having an average diameter of about 0.5 micrometer to about 50 micrometers. 
     
     
         41 . The composite electrolyte of  claim 35 , wherein the lithium salt comprises LiSCN, LiN(CN) 2 , LiClO 4 , LiBF 4 , LiAsF 6 , LiPF 6 , LiCF 3 SO 3 , LiC(CF 3 SO 2 ) 3 , LiN(SO 2 C 2 F 5 ) 2 , LiN(SO 2 CF 3 ) 2 , LiN(SO 2 F) 2 , LiSbF 6 , LiPF 3 (CF 2 CF 3 ) 3 , LiPF 3 (CF 3 ) 3 , LiB(C 2 O 4 ) 2 , or a combination thereof. 
     
     
         42 . The composite electrolyte of  claim 35 , further comprising a polymer. 
     
     
         43 . The composite electrolyte of  claim 42 , wherein the polymer comprises polyethylene oxide, polyvinylidene fluoride, polyvinylidene fluoride-hexafluoropropylene, a poly(styrene-b-ethylene oxide) block copolymer, poly(styrene-butadiene), poly(styrene-isoprene-styrene), a poly(styrene-b-divinylbenzene) block copolymer, a poly(styrene-ethylene oxide-styrene) block copolymer, or a combination thereof. 
     
     
         44 . The composite electrolyte of  claim 35 , wherein a lithium ion mobility of the composite electrolyte is greater than a lithium ion mobility of a comparable composite electrolyte comprising the lithium salt and not comprising the particle. 
     
     
         45 . A protective film, comprising the composite electrolyte of  claim 35 . 
     
     
         46 . The protective film of  claim 45 , further comprising a crosslinked product of a polymerizable oligomer located between the particles. 
     
     
         47 . The protective film of  claim 46 , wherein the polymerizable oligomer comprises diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol diacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, ethoxylated trimethylolpropane triacrylate, acrylate-functionalized ethylene oxide, 1,6-hexanediol diacrylate, ethoxylated neopentyl glycol diacrylate, propoxylated neopentyl glycol diacrylate, allyl methacrylate, trimethylol propane triacrylate, trimethylol propane trimethacrylate, pentaerythritol triacrylate, ethoxylated/propoxylated trimethylolpropane triacrylate, glyceryl propoxylated triacrylate, tris(2-hydroxyethyl) isocyanurate triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, or a combination thereof. 
     
     
         48 . The protective film of  claim 46  further comprising a liquid electrolyte comprising a lithium salt and an organic solvent. 
     
     
         49 . The protective film of  claim 48 , wherein the organic solvent comprises ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, fluoroethylene carbonate, γ-butyrolactone, dimethoxyethane, diethoxyethane, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, polyethylene glycol dimethyl ether, succinonitrile, sulfolane, dimethyl sulfone, ethyl methyl sulfone, diethyl sulfone, adiponitrile, tetraethylene glycol dimethyl ether, 1,1,2,2-tetrafluoroethyl 2,2,3,3-tetrafluoropropyl ether, or a combination thereof. 
     
     
         50 . The protective film of  claim 45 , further comprising an ionic liquid, a metal salt comprising a Group 1 element of the Periodic Table of Elements, a metal salt comprising a Group 2 element of the Periodic Table of Elements, a nitrogen-containing additive, boron nitride, an ion conductive polymer, or a combination thereof. 
     
     
         51 . A lithium battery comprising:
 a positive electrode;   a protected negative electrode comprising lithium metal or a lithium metal alloy, and a protective film on the lithium metal or a lithium metal alloy; and   an electrolyte located between the positive electrode and the protected negative electrode,   wherein the protective film comprises a composite electrolyte comprising:   a positively charged particle, a particle that is positively charged by having a coordinate bond with a cation, or a combination thereof; and   a lithium salt.   
     
     
         52 . The lithium battery of  claim 51 , wherein the electrolyte comprises a liquid electrolyte, a solid electrolyte, a gel electrolyte, a polymer ionic liquid, a separator, or a combination thereof. 
     
     
         53 . The lithium battery of  claim 51 , further comprising:
 a monolayer structure comprising a first liquid electrolyte layer in contact with the protective film of the protected negative electrode, or   a monolayer structure comprising a first liquid electrolyte layer comprising a separator in contact with the protective film of the protected negative electrode, wherein a first liquid electrolyte is impregnated in the separator.   
     
     
         54 . The lithium battery of  claim 51 , further comprising
 a multi-layer structure comprising:
 a first liquid electrolyte layer comprising; 
 a separator in contact with the protective film of the protected negative electrode, wherein a first liquid electrolyte is impregnated in the separator; 
 a second solid electrolyte layer in contact with the first liquid electrolyte layer and comprising a ceramic conductor; and 
 a second liquid electrolyte layer in contact with the second solid electrolyte layer, or 
   a multi-layer structure comprising:
 a first solid electrolyte layer in contact with the protective film of the protected negative electrode and comprising the composite electrolyte; 
 a second solid electrolyte layer in contact with the first solid electrolyte layer and comprising a ceramic conductor; and 
 a second liquid electrolyte layer in contact with the second solid electrolyte layer, or 
   a multi-layer structure comprising:
 a first solid electrolyte layer in contact with the protective film of the protected negative electrode and comprising the composite electrolyte; 
 a first liquid electrolyte comprising a separator in contact with the first solid electrolyte, wherein a first liquid electrolyte is impregnated in the separator; 
 a second solid electrolyte layer in contact with the first liquid electrolyte layer and comprising a ceramic conductor; and 
 a second liquid electrolyte layer in contact with the second solid electrolyte layer.