US009660311B2  c12)  United States Patent  Visco et al.  (54)  AQUEOUS LITHIUM AIR BATTERIES  (IO)  Patent No.:  US 9,660,311 B2  May 23, 2017  (45)  Date of Patent:  (75)  Inventors:  Steven J. Visco,  Berkeley, CA (US);  Yevgeniy S. Nimon,  Danville, CA  (US);  Lutgard C. De Jonghe,  Lafayette, CA (US);  Alexei Petrov,  Walnut Creek, CA (US);  Nikolay  Goncharenko,  Walnut Creek, CA (US)  (73)  Assignee:  POLYPLUS BATTERY COMPANY,  Berkeley, CA (US)  ( *)  Notice:  Subject to any disclaimer, the term ofthis  patent is extended or adjusted under 35  U.S.C. 154(b) by 448 days.  (21)  Appl. No.:  13/588,911  Aug. 17, 2012  (22)  Filed:  (60)  Provisional application No. 61/525,634, filed on Aug.  19, 2011.  (51)  Int. Cl.  (52)  U.S. Cl.  CPC ....  H0JM 12108  (2013.01);  H0JM 2300/0005  (2013.01);  Y02E 60/128  (2013.01)  ( 58)  Field of Classification Search  CPC ......... H0lM 12/08; H0lM 2300/0005; H0lM  12/06; H01M 2004/024; Y02E 60/128  USPC ......................................... 429/405, 500, 535  See application file for complete search history.  (65)  Prior Publication Data  Related U.S. Application Data  OTHER PUBLICATIONS  FOREIGN PATENT DOCUMENTS  U.S. PATENT DOCUMENTS  (56)  References Cited  (57)  ABSTRACT  US 2013/0045428 Al  Feb. 21, 2013  International Search Report and Written Opinion dated Oct. 18,  2005 from International Application No. PCT/US2004/033372.  (Continued)  Primary Examiner  - Nicholas P D’  Aniello  Assistant Examiner  - Ling R Zeng  (74)  Attorney, Agent, or Firm  - Weaver Austin  Villeneuve & Sampson LLP  Aqueous Li/ Air secondary battery cells are configurable to  achieve high energy density and prolonged cycle life. The  cells include a protected a lithium metal or alloy anode and  an aqueous catholyte in a cathode compartment. The aque› ous catholyte comprises an evaporative-loss resistant and/or  polyprotic active compound or active agent that partakes in  the discharge reaction and effectuates cathode capacity for  discharge in the acidic region. This leads to improved  performance including one or more of increased specific  energy, improved stability on open circuit, and prolonged  cycle life, as well as various methods, including a method of  operating an aqueous Li/ Air cell to simultaneously achieve  improved energy density and prolonged cycle life.  31 Claims, 2 Drawing Sheets  H0JM  8122  H0JM 12108  (2006.01)  (2006.01)  EP  EP  0111214  11/1983  0694501  l/ 1996  (Continued)  (Continued)  3,528,856 A  3,607,417 A  3,615,835 A  3,625,769 A  3,679,540 A  9/1970 Ovshinsky  9/1971 McRae et al.  10/1971 Ovshinsky  12/1971 Lyall  7/1972 Zinnnerman et al.  3  2  7  4  6  5 