Conductive polymeric compositions for lithium batteries

Abstract

Novel chain polymers comprising weakly basic anionic moieties chemically bound into a polyether backbone at controllable anionic separations are presented. Preferred polymers comprise orthoborate anions capped with dibasic acid residues, preferably oxalato or malonato acid residues. The conductivity of these polymers is found to be high relative to that of most conventional salt-in-polymer electrolytes. The conductivity at high temperatures and wide electrochemical window make these materials especially suitable as electrolytes for rechargeable lithium batteries.

1 - 40 . (canceled) 
   
   
       41 . A method of making an electrochemical cell, comprising:
 assembling an anode and a cathode in a case; and   disposing an electrolyte between the anode and the cathode to form the electrolytic cell, wherein the electrolyte provides an electrical conduction path through the electrochemical cell, and wherein the electrolyte comprises a plurality of polyanionic polymer chains forming a solid polymer having a negatively charged surface, each polyanionic polymer chain having a formula:
   M b   +k [AL] p   −q    
   wherein:
 AL is a repeat unit in the chain wherein AL includes the formula: 
   
     
       
         
         
             
             
         
       
       
         
           wherein X is a Group III element; 
           O is oxygen, 
           Y includes a formula OC(CR 1   2 ) a CO, SO 2 , aryl, phenyl, and R 1 -substituted phenyl, wherein a ranges from 0 to 5, 
           R 1  is selected from the group consisting of alkyl 1,3 tetra(trifluoromethyl)ethylene dialato, halo 1,3 tetra (trifluoromethyl)ethylene dialato, and silane-co-tetraethleneglycalato, 
           L comprises n spacer groups z, z is selected from the group consisting of alkyl, R 2 -substituted alkyl, alkoxy and R 2 -substituted alkoxy, 
           wherein R 2  is selected from the group consisting of hydrogen, halo, alkyl, alkoxy, phenyl, and substituted phenyl, wherein n ranges from about 1 to 30, and 
         
         p is the number of repeating units in the polymer, 
         q is charge on the anion, 
         M +  is a cation, 
         b is the repeat number of compounds with a positive charge, 
         k is the charge on the compound with a positive charge, and bk equals qp. 
       
     
   
   
       42 . The method of  claim 41 , wherein p is a number from 1 to 3. 
   
   
       43 . The method of  claim 41 , wherein the M +k  is selected from the group consisting of hydrogen, Group I metals, Group II metals, NR 3   4  and PR 3   4 , and wherein R 3  is selected from the group consisting of hydrogen, alkyl, and halo, and wherein k ranges from 1 to 3. 
   
   
       44 . The method of  claim 41 , wherein the repeating spacer groups include a polysiloxane having the formula Si[(CR 4   3 ) 2 ]—O(CR 4   2 CR 4   2 O)] w , wherein w ranges from about 2 to 50, and wherein R 4  is selected from the group consisting of hydrogen and alkyl. 
   
   
       45 . The method of  claim 41 , wherein A comprises a borate anion having two oxygens bound to a dibasic acid residue and two oxygens bound to polymeric chain groups L, wherein spacer group z is [(CR 2   2 ) x (CR 2   2 O)], and wherein x ranges from 0 to 50. 
   
   
       46 . The method of  claim 41 , wherein the polyanionic polymer chain is selected from the group consisting of poly[lithium oxalato oligo(ethylene glycolato)n orthoborate], poly [lithium oxalate oligo(propylene glycolato)n orthoborate], poly [lithium malonato oligo(ethyleneglycolato)n orthoborate], and poly [lithium malonato oligo(propylene glycolato)n orthoborate], and wherein n is 3,5, 9 or 14. 
   
   
       47 . The method of  claim 41 , wherein the solid polymer further has chemical bonds between polymer chains. 
   
   
       48 . The method of  claim 41 , wherein the polyanionic polymer chain includes a plasticizer. 
   
   
       49 . A method of making an electrochemical cell, comprising:
 assembling an anode and a cathode in a case; and   disposing an electrolyte between the anode and the cathode to form the electrolytic cell, wherein the electrolyte provides an electrical conduction path through the electrochemical cell, and wherein the electrolyte comprises a plurality of polyanionic polymer chains forming a solid polymer having a negatively charged surface, each polyanionic polymer chain having a formula:
   M b   +k [AL] p   −q    
   wherein:
 AL is a repeat unit in the chain, wherein 
 A is an anionic group including a Group III element, 
 L is a polymeric chain group chemically linked to A, the polymeric chain having repeating polyether spacer groups, the spacer groups providing distance between each anionic group, 
 p is the number of repeating units in the polymer, 
 q is charge on the anion, 
 M +  is a cation, 
 b is the repeat number of compounds with a positive charge, 
 k is the charge on the compound with a positive charge, and 
 bk equals pq. 
   
   
   
       50 . The method of  claim 49 , wherein AL of the polyanionic polymer chain includes the formula: 
     
       
         
         
             
             
         
       
       wherein X is a Group III element;
 O is oxygen, 
 Y includes a formula OC(CR 2 ) a CO, SO 2 , aryl, phenyl, and R-substituted phenyl, wherein a ranges from 0 to 5, 
 R is selected from the group consisting of alkyl 1,3 tetra(trifluoromethyl)ethylene dialato, halo 1,3 tetra(trifluoromethyl)ethylene dialato, and silane-co-tetraethyleneglycalato, 
 L comprises n spacer groups z, z is selected from the group consisting of alkyl, R-substituted alkyl, alkoxy and R-substituted alkoxy, 
 wherein R is selected from the group consisting of hydrogen, halo, alkyl, alkoxy, phenyl and substituted phenyl, wherein n ranges from about 1 to 30, and 
 p is a number from 1 to 3. 
 
     
   
   
       51 . The method of  claim 49 , wherein M +k  is selected from the group consisting of hydrogen, Group I metals, Group II metals, NR 3   4  and PR 3   4 , and wherein R 3  is selected from the group consisting of hydrogen, alkyl, and halo, and wherein k ranges from 1 to 3. 
   
   
       52 . The method of  claim 49 , wherein the repeating spacer groups include a polysiloxane having the formula Si[(CR 4   3 ) 2 ]—O(CR 4   2 CR 4   2 O)] w , wherein w ranges from about 2 to 50, and wherein R 4  is selected from the group consisting of hydrogen and alkyl. 
   
   
       53 . The method of  claim 49 , wherein A comprises a borate anion having two oxygens bound to a dibasic acid residue and two oxygens bound to polymeric chain groups L, and wherein [(CR 2   2 ) x (CR 2   2 O)], and wherein x ranges from about 0 to 50. 
   
   
       54 . The method of  claim 49 , wherein polyanionic polymer chain is selected from the group consisting of poly[lithium oxalate oligo(ethylene glycolato)n orthoborate], poly [lithium oxalate oligo(propylene glycolato)n orthoborate], poly [lithium malonato oligo(ethyleneglycolato)n orthoborate], and poly [lithium malonato oligo(propylene glycolato)n orthoborate], and wherein n is 3,5, 9 or 14. 
   
   
       55 . The method of  claim 49 , wherein the solid polymer further has chemical bonds between the polymeric chains. 
   
   
       56 . The method of  claim 49 , wherein the polyanionic polymer chain includes a plasticizer. 
   
   
       57 . An electrochemical cell, comprising:
 an anode;   a cathode; and   a means for providing an electrical conduction path between the anode and the cathode, wherein the conduction path comprises a plurality of polyanionic polymer chains forming a solid polymer having a negatively charged surface, each polyanionic polymer chain having a formula:
   M b   +k [AL] p   −q    
   wherein:
 AL is a repeat unit in the chain, wherein 
 A is an anionic group including a Group III element, 
 L is a polymeric chain group chemically linked to A, the polymeric chain having repeating polyether spacer groups, the spacer groups providing distance between each anionic group, 
 p is the number of repeating units in the polymer, 
 q is charge on the anion, 
 M +  is a cation, 
 b is the repeat number of compounds with a positive charge, 
 k is the charge on the compound with a positive charge, and 
 bk equals pq.