Novel composite cathodes, eletrochemical cells comprising novel composite cathodes, and processes for fabricating same

Abstract

The present invention pertains to composite cathodes suitable for use in an electrochemical cell, said cathodes comprising: (a) an electroactive sulfur-containing cathode material, wherein said electroactive sulfur-containing cathode material, in its oxidized state, comprises a polysulfide moiety of the formula —S m —, wherein m is an integer equal to or greater than 3; and, (b) an electroactive transition metal chalcogenide composition, which encapsulates said electroactive sulfur-containing cathode material, and which retards the transport of anionic reduction products of said electroactive sulfur-containing cathode material, said electroactive transition metal chalcogenide composition comprising an electroactive transition metal chalcogenide having the formula M j Y k (OR) l wherein: M is a transition metal; Y is the same or different at each occurrence and is oxygen, sulfur, or selenium; R is an organic group and is the same or different at each occurrence; j is an integer ranging from 1 to 12; k is a number ranging from 0 to 72; and l is a number ranging from 0 to 72; with the proviso that k and l cannot both be 0. The present invention also pertains to methods of making such composite cathodes, cells comprising such composite cathodes, and methods of making such cells.

1 - 51 . (canceled)  
     
     
         52 . A rechargeable battery cell comprising: 
 a) an anode comprising a metal or an ion of a metal;    b) a cathode comprising a mixture of: 
 (i) an electrochemically active material comprising sulfur in the form of at least one of elemental sulfur, a sulfide of the metal, or a polysulfide of the metal, and  
 (ii) an electronically conductive material; and  
   c) a liquid electrolyte comprising a solvent for at least some discharge products of the positive electrode;    wherein the battery cell attains a utilization of 50-75% over 2-10 cycles.    
     
     
         53 . A rechargeable battery cell comprising: 
 d) an anode comprising a metal or an ion of a metal;    e) a cathode comprising a mixture of: 
 (i) an electrochemically active material comprising sulfur in the form of at least one of elemental sulfur, a sulfide of the metal, or a polysulfide of the metal, and  
 (ii) an electronically conductive material; and  
   f) a liquid electrolyte comprising a solvent for at least some discharge products of the positive electrode;    wherein the battery cell attains a utilization of 10-75% over 200 cycles.    
     
     
         54 . A rechargeable battery cell comprising: 
 a) an anode comprising a metal or an ion of a metal;    b) a cathode comprising a mixture of: 
 (i) an electrochemically active material comprising sulfur in the form of at least one of elemental sulfur, a sulfide of the metal, or a polysulfide of the metal, and  
 (ii) an electronically conductive material; and  
   c) a liquid electrolyte comprising a solvent for at least some discharge products of the positive electrode;    wherein the battery cell attains a utilization of 38-75% over 2-50 cycles.    
     
     
         55 . A rechargeable battery cell comprising: 
 a) a negative electrode including a metal or an ion of the metal;    b) a positive electrode comprising a mixture of: 
 (i) an electrochemically active material comprising sulfur in the form of at least one of elemental sulfur, a sulfide of the metal, or a polysulfide of the metal, and  
 (ii) an electronically conductive material; and  
   c) a liquid electrolyte including a solvent for at least some discharge products of the positive electrode; 
 wherein the battery cell is characterized by an initial capacity of at least 1172 mAh/g and has a utilization of at least 69.97%.  
   
     
     
         56 . A rechargeable battery cell comprising: 
 a) a negative electrode including a metal or an ion of the metal;    b) a positive electrode comprising a mixture of: 
 (i) an electrochemically active material comprising sulfur in the form of at least one of elemental sulfur, a sulfide of the metal, or a polysulfide of the metal, and  
 (ii) an electronically conductive material; and  
   c) a liquid electrolyte including a solvent for at least some discharge products of the positive electrode; 
 wherein the battery cell is characterized by a capacity of at least 1103 mAh/g and has a utilization of at least 65.85% after 20 cycles.  
   
     
     
         57 . A rechargeable battery cell comprising: 
 a) a negative electrode including a metal or an ion of the metal;    b) a positive electrode comprising a mixture of: 
 (i) an electrochemically active material comprising sulfur in the form of at least one of elemental sulfur, a sulfide of the metal, or a polysulfide of the metal, and  
 (ii) an electronically conductive material; and  
   c) a liquid electrolyte including a solvent for at least some discharge products of the positive electrode; 
 wherein the battery cell is characterized by a capacity of at least 850 mAh/g and has a utilization of at least 50.57% at the second cycle.  
   
     
     
         58 . A rechargeable battery cell comprising: 
 a) a negative electrode including a metal or an ion of the metal;    b) a positive electrode comprising a mixture of: 
 (i) an electrochemically active material comprising sulfur in the form of at least one of elemental sulfur, a sulfide of the metal, or a polysulfide of the metal, and.  
 (ii) an electronically conductive material; and  
   c) a liquid electrolyte including a solvent for at least some discharge products of the positive electrode; 
 wherein the battery cell is characterized by a capacity of at least 850 mAh/g and has a utilization of at least 50.57% at the second cycle.  
   
     
     
         59 . A rechargeable battery cell comprising: 
 a) a negative electrode including a metal or an ion of the metal;    b) a positive electrode comprising a mixture of: 
 (i) an electrochemically active material comprising sulfur in the form of at least one of elemental sulfur, a sulfide of the metal, or a polysulfide of the metal, and  
 (ii) an electronically conductive material; and  
   c) a liquid electrolyte including a solvent for at least some discharge products of the positive electrode; 
 wherein the battery cell is characterized by a capacity of at least 1387.5 mAh/g and has a utilization of at least) 82.84% at the 12th cycle.  
   
     
     
         60 . A rechargeable battery cell comprising: 
 a) a negative electrode including a metal or an ion of the metal;    b) a positive electrode comprising a mixture of: 
 (i) an electrochemically active material comprising sulfur in the form of at least one of elemental sulfur, a sulfide of the metal, or a polysulfide of the metal, and  
 (ii) an electronically conductive material; and  
   c) a liquid electrolyte including a solvent for at least some discharge products of the positive electrode; 
 wherein the battery cell is characterized by a capacity of at least 1300 mAh/g and has a utilization of at least 77.61% at the 18th cycle.  
   
     
     
         61 . A rechargeable battery cell comprising: 
 a) a negative electrode including a metal or an ion of the metal;    b) a positive electrode comprising a mixture of: 
 (i) an electrochemically active material comprising sulfur in the form of at least one of elemental sulfur, a sulfide of the metal, or a polysulfide of the metal, and  
 (ii) an electronically conductive material; and  
   c) a liquid electrolyte including a solvent for at least some discharge products of the positive electrode; 
 wherein the battery cell is characterized by a capacity of at least 850 mAh/g and has a utilization of at least 50.57% at the second cycle.  
   
     
     
         62 . A rechargeable battery cell comprising: 
 a) a negative electrode including a metal or an ion of the metal;    b) a positive electrode comprising a mixture of: 
 (i) an electrochemically active material comprising sulfur in the form of at least one of elemental sulfur, a sulfide of the metal, or a polysulfide of the metal, and  
 (ii) an electronically conductive material; and  
   c) a liquid electrolyte including a solvent for at least some discharge products of the positive electrode; 
 wherein the battery cell is characterized by a capacity of at least 750 mAh/g and has a utilization of at least 44.78% over 23 cycles.  
   
     
     
         63 . A rechargeable battery cell comprising: 
 a) a negative electrode including a metal or an ion of the metal;    b) a positive electrode comprising a mixture of: 
 (i) an electrochemically active material comprising sulfur in the form of at least one of elemental sulfur, a sulfide of the metal, or a polysulfide of the metal, and  
 (ii) an electronically conductive material; and  
   c) a liquid electrolyte including a solvent for at least some discharge products of the positive electrode; 
 wherein the battery cell is characterized by a capacity of at least 1000 mAh/g and has a utilization of at least 44.78% over the 7th through 22nd cycles.  
   
     
     
         64 . A rechargeable battery cell comprising: 
 a) a negative electrode including a metal or an ion of the metal;    b) a positive electrode comprising a mixture of: 
 (i) an electrochemically active material comprising sulfur in the form of at least one of elemental sulfur, a sulfide of the metal, or a polysulfide of the metal, and  
 (ii) an electronically conductive material; and  
   c) a liquid electrolyte including a solvent for at least some discharge products of the positive electrode; 
 wherein the battery cell is characterized by a capacity of at least 600 mAh/g and has a utilization of at least 35.82% over 61 cycles.  
   
     
     
         65 . A rechargeable battery cell comprising: 
 a) a negative electrode including a metal or an ion of the metal;    b) a positive electrode comprising a mixture of: 
 (i) an electrochemically active material comprising sulfur in the form of at least one of elemental sulfur, a sulfide of the metal, or a polysulfide of the metal, and  
 (ii) an electronically conductive material; and  
   c) a liquid electrolyte including a solvent for at least some discharge products of the positive electrode; 
 wherein the battery cell is characterized by a capacity of at least 525 mAh/g and has a utilization of at least 31.34% over 65 cycles.  
   
     
     
         66 . A rechargeable battery cell comprising: 
 a) a negative electrode including a metal or an ion of the metal;    b) a positive electrode comprising a mixture of: 
 (i) an electrochemically active material comprising sulfur in the form of at least one of elemental sulfur, a sulfide of the metal, or a polysulfide of the metal, and  
 (ii) an electronically conductive material; and  
   c) a liquid electrolyte including a solvent for at least some discharge products of the positive electrode; 
 wherein the battery cell is characterized by a capacity of at least 860 mAh/g and has a utilization of at least 51.3% over 10 cycles.  
   
     
     
         67 . A rechargeable battery cell comprising: 
 a) a negative electrode including a metal or an ion of the metal;    b) a positive electrode comprising a mixture of: 
 (i) an electrochemically active material comprising sulfur in the form of at least one of elemental sulfur, a sulfide of the metal, or a polysulfide of the metal, and  
 (ii) an electronically conductive material; and  
   c) a liquid electrolyte including a solvent for at least some discharge products of the positive electrode; 
 wherein the battery cell is characterized by first cycle capacity of 1265 mAh/g and has a utilization of 75.54%.  
   
     
     
         68 . A rechargeable battery cell comprising: 
 a) a negative electrode including a metal or an ion of the metal;    b) a positive electrode comprising a mixture of: 
 (i) an electrochemically active material comprising sulfur in the form of at least one of elemental sulfur, a sulfide of the metal, or a polysulfide of the metal, and  
 (ii) an electronically conductive material; and  
   c) a liquid electrolyte including a solvent for at least some discharge products of the positive electrode; 
 wherein the battery cell is characterized by a capacity of 1103 mAh/g and has a utilization of 65.85% at the 2 cycle  
   
     
     
         69 . A rechargeable battery cell comprising: 
 a) a negative electrode including a metal or an ion of the metal;    b) a positive electrode comprising a mixture of: 
 (i) an electrochemically active material comprising sulfur in the form of at least one of elemental sulfur, a sulfide of the metal, or a polysulfide of the metal, and  
 (ii) an electronically conductive material; and  
   c) a liquid electrolyte including a solvent for at least some discharge products of the positive electrode; 
 wherein the battery cell is characterized by a capacity of at least 956 mAh/g and has a utilization of at least 57.07% after 30 cycles.  
   
     
     
         70 . A rechargeable battery cell comprising: 
 a) a negative electrode including a metal or an ion of the metal;    b) a positive electrode comprising a mixture of: 
 (i) an electrochemically active material comprising sulfur in the form of at least one of elemental sulfur, a sulfide of the metal, or a polysulfide of the metal, and  
 (ii) an electronically conductive material; and  
   c) a liquid electrolyte including a solvent for at least some discharge products of the positive electrode; 
 wherein the battery cell is characterized by an initial capacity of around 1382 mAh/g and has a utilization of about 82.5%.  
   
     
     
         71 . A rechargeable battery cell comprising: 
 a) a negative electrode including a metal or an ion of the metal;    b) a positive electrode comprising a mixture of: 
 (i) an electrochemically active material comprising sulfur in the form of at least one of elemental sulfur, a sulfide of the metal, or a polysulfide of the metal, and  
 (ii) an electronically conductive material; and  
   c) a liquid electrolyte including a solvent for at least some discharge products of the positive electrode; 
 wherein the battery cell is characterized by a capacity of 738 mAh/g and has a utilization of 44.06% after 81 cycles.  
   
     
     
         72 . A rechargeable battery cell comprising: 
 a) a negative electrode including a metal or an ion of the metal;    b) a positive electrode comprising a mixture of: 
 (i) an electrochemically active material comprising sulfur in the form of at least one of elemental sulfur, a sulfide of the metal, or a polysulfide of the metal, and  
 (ii) an electronically conductive material; and  
   c) a liquid electrolyte including a solvent for at least some discharge products of the positive electrode; 
 wherein the battery cell is characterized by an initial capacity of 1270 mAh/g and has a utilization of 75.8%.  
   
     
     
         73 . A rechargeable battery cell comprising: 
 a) a negative electrode including a metal or an ion of the metal;    b) a positive electrode comprising a mixture of: 
 (i) an electrochemically active material comprising sulfur in the form of at least one of elemental sulfur, a sulfide of the metal, or a polysulfide of the metal, and  
 (ii) an electronically conductive material; and  
   c) a liquid electrolyte including a solvent for at least some discharge products of the positive electrode; 
 wherein the battery cell is characterized by a capacity of 380 to 450 mAh/g and has a utilization of 22.7 to 26.9% after 76 cycles.  
   
     
     
         74 . A rechargeable battery cell comprising: 
 a) a negative electrode including a metal or an ion of the metal;    b) a positive electrode comprising a mixture of: 
 (i) an electrochemically active material comprising sulfur in the form of at least one of elemental sulfur, a sulfide of the metal, or a polysulfide of the metal, and  
 (ii) an electronically conductive material; and  
   c) a liquid electrolyte including a solvent for at least some discharge products of the positive electrode; 
 wherein the battery cell is characterized by a capacity of 900 mAh/g and has a utilization of 53.7% after 4 cycles.  
   
     
     
         75 . A rechargeable battery cell comprising: 
 a) a negative electrode including a metal or an ion of the metal;    b) a positive electrode comprising a mixture of: 
 (i) an electrochemically active material comprising sulfur in the form of at least one of elemental sulfur, a sulfide of the metal, or a polysulfide of the metal, and  
 (ii) an electronically conductive material; and  
   c) a liquid electrolyte including a solvent for at least some discharge products of the positive electrode; 
 wherein the battery cell is characterized by a capacity of 880 mAh/g and has a utilization of 52.5% after 2 cycles.  
 (i) an electrochemically active material comprising sulfur in the form of at least one of elemental sulfur, a sulfide of the metal, or a polysulfide of the metal, and  
 (ii) an electronically conductive material; and  
   d) a liquid electrolyte comprising a solvent for at least some discharge products of said cathode,    wherein the battery cell attains a utilization of 38-75% over 2-50 cycles.    
     
     
         76 . The rechargeable battery cell of  claim 52 , wherein the anode comprises one or more materials selected from the group consisting of lithium metal, lithium-aluminum alloys, lithium-tin alloys, lithium-intercalated carbons, lithium-intercalated graphites, calcium metal, aluminum metal, sodium metal, and sodium alloys.  
     
     
         77 . The rechargeable battery cell of  claim 52 , wherein the cathode comprises one or more electronically conductive materials selected from the group consisting of conductive carbons, graphites, metal flakes, metal powders, and conductive polymers.  
     
     
         78 . The rechargeable battery cell of  claim 52 , wherein the cathode further comprises one or more of the materials selected from the group consisting of binder, electrolytes and conductive additives.  
     
     
         79 . The rechargeable battery cell of  claim 52 , wherein said cathode is disposed on a positive current collector.  
     
     
         80 . The rechargeable battery of  claim 53  wherein the positive electrode has a back boundry and a front boundry and the negative electrode has a front boundry, the electrolyte being between the front boundry of the positive electrode and the front boundry of the negative electrode, the distance between the back boundry of the positive electrode and the front boundry of the negative electrode being about 125 micrometers or less.  
     
     
         81 . The rechargeable battery of  claim 53  wherein the positive electrode has a back boundry and a front boundry and the negative electrode has a front boundry, the electrolyte being between the front boundry of the positive electrode and the front boundry of the negative electrode, the distance between the back boundry of the positive electrode and the front boundry of the negative electrode being about 75 micrometers or less.  
     
     
         82 . The rechargeable battery of  claim 53  wherein the positive electrode has a back boundry and a front boundry and the negative electrode has a front boundry, the electrolyte being between the front boundry of the positive electrode and the front boundry of the negative electrode, the distance between the back boundry of the positive electrode and the front boundry of the negative electrode being about 50 micrometers or less.  
     
     
         83 . The rechargeable battery of  claim 53  wherein the positive electrode has a back boundry and a front boundry and the negative electrode has a front boundry, the electrolyte being between the front boundry of the positive electrode and the front boundry of the negative electrode, the distance between the back boundry of the positive electrode and the front boundry of the negative electrode being about 150 micrometers or less.  
     
     
         84 . The rechargeable battery of  claim 53  wherein the positive electrode has a back boundry and a front boundry and the negative electrode has a front boundry, the electrolyte being between the front boundry of the positive electrode and the front boundry of the negative electrode, the distance between the back boundry of the positive electrode and the front boundry of the negative electrode being selected from one of the group consisting of: about 50 micrometers or less, up to about 75 micrometers or less, up to about 125 micrometers or less, and about 150 micrometers or less.  
     
     
         85 . A rechargeable battery cell comprising: 
 a) an anode comprising a metal or an ion of a metal;    b) a cathode comprising a mixture of: 
 (i) an electrochemically active material comprising sulfur in the form of at least one of elemental sulfur, a sulfide of the metal, or a polysulfide of the metal, and  
 (ii) an electronically conductive material; and  
   c) a liquid electrolyte comprising a solvent for at least some discharge products of the positive electrode; wherein the battery cell attains a utilization of 10-75% over 200 cycles and wherein the cell discharges at an average current density of at least about 0.5 mA/cm 2 .