US 20200028206A1 IN (19 ) United States (12 ) Patent Application Publication ( 10) Pub . No .: US 2020/0028206 A1 Zhu et al. (43 ) Pub . Date : Jan. 23, 2020 (54 ) SOLID OXYGEN -REDOX NANOCOMPOSITE Related U.S. Application Data MATERIALS (60 ) Provisional application No. 62 / 266,783 , filed on Dec. ( 71) Applicant: MASSACHUSETTS INSTITUTE OF 14 , 2015 , provisional application No. 62 / 360,909 , TECHNOLOGY, Cambridge , MA filed on Jul. 11, 2016 . (US ) Publication Classification (51 ) Int. Ci. (72 ) Inventors : Zhi Zhu , Malden , MA (US ) ; Ju Li, HOIM 10/0525 (2006.01 ) Weston , MA (US ) HOIM 4/38 ( 2006.01) HOIM 4/131 (2006.01 ) (52 ) U.S. CI. ( 73 ) Assignee : MASSACHUSETS INSTITUTE OF CPC .. HOIM 10/0525 ( 2013.01 ) ; HOLM 2004/027 TECHNOLOGY, Cambridge , MA ( 2013.01 ); HOTM 4/131 ( 2013.01 ) ; HOLM (US ) 4/38 ( 2013.01 ) (57 ) ABSTRACT (21 ) Appl. No .: 16 /061,441 A solid oxygen - redox nanocomposite material including an alkali metal oxide, peroxide, or superoxide , or alkaline earth ( 22 ) PCT Filed : Dec. 13 , 2016 metal oxide, peroxide , or superoxide core , and a catalytic nanoshell or skeleton surrounding the cores, as well as ( 86 ) PCT No .: PCT/ US16 /66338 methods of manufacture, are described . Additionally , sealed $ 371 ( c ) ( 1 ) , electrochemical devices including a solid oxygen -redox ( 2 ) Date : Jun . 12 , 2018 nanocomposite are also described . 22 COM 24 30 26 Co , 04 Skeleton Interface /Wetting Layer 28 Patent Application Publication Jan. 23 , 2020 Sheet 1 of 31 US 2020/0028206 A1 22 weeping 24 30 26 C0,0 Skeleton Interface /Wetting Layer 28 Fig . 1 Patent Application Publication Jan. 23 , 2020 Sheet 2 of 31 US 2020/0028206 A1 metal 6 salt 6 ( a ) ((b b ) 2 2 4 . 4 6 ( c ) ((dd ,, e e ) ) 2 2 o 8 4 alkali or alkaline earth metal oxide , peroxide , or superoxide core precipitated nanoshell 2 calcined nanoshell 8? Fig . 2 Patent Application Publication Jan. 23 , 2020 Sheet 3 of 31 US 2020/0028206 A1 INNS 02 caso 5 nm Fig . 3 Patent Application Publication Jan. 23 , 2020 Sheet 4 of 31 US 2020/0028206 A1 3.2 2.8 2.6 LilivsVoltageN 2.4 2,2 2.0 120 Alkg 200 300 600 Capacity Ah /kg Fig . 4 Patent Application Publication Jan. 23 , 2020 Sheet 5 of 31 US 2020/0028206 A1 CapacityAh/kg Efficiency19% 120 Alkg 20 60 80 100 120 140 160 180 200 Cycles Fig . 5 Patent Application Publication Jan. 23 , 2020 Sheet 6 of 31 US 2020/0028206 A1 3.6 3.5 5000 Akg 3.1 3.0 2.9 500 Akg LilivsV/Voltage 2.8 MScurrentIPA 2.7 2.6 5000 Alkg 2.5 2.4 500-2000 Alkg 2.3 2.2 m / z = 32 2.1 300 Capacity Ah /kg Fig . 6 Patent Application Publication Jan. 23 , 2020 Sheet 7 of 31 US 2020/0028206 A1 15 Currentlua 5 2.5 2.7 Voltage N vs Li* / Li Fig . 7 Patent Application Publication Jan. 23 , 2020 Sheet 8 of 31 US 2020/0028206 A1 Co 2p spectrum 2p 2010 After 15 Charge Intensitylau. wan After 15 Discharge 800 780 Binding Energy lev Fig . 8 Patent Application Publication Jan. 23 , 2020 Sheet 9 of 31 US 2020/0028206 A1 790 cm Discharge to 2.0V 3 900 Ahikg w 1 200 Ah kg Before charge A 700 800 Raman shift cm Fig . 9 Patent Application Publication Jan. 23 , 2020 Sheet 10 of 31 US 2020/0028206 A1 s Lizo con Location of Li202 a Li20L After 10th discharge After 1st Intensity After 7 $ 1 charge 30 35 50 55 60 2016 Fig . 10 Patent Application Publication Jan. 23 , 2020 Sheet 11 of 31 US 2020/0028206 A1 (911x 120 |( 111 ) NC67 after charge Standard LiO • Caculated Lio ....... 2 6 1 / d nm Fig . 11 Patent Application Publication Jan. 23 , 2020 Sheet 12 of 31 US 2020/0028206 A1 0.21 2.90 Standard samples L1,02 L1,0 . -2.74 Charged to 900 mAhg NC67 charging Charged to 600 mAng Charged to 400 mAhg is Discharged to 2.0 V met TARTIKLI ? unninition 30 25 20 15 10 5 0-5 -10-15-20-25-30 LiChemical Shift (ppm ) Fig . 12 Patent Application Publication Jan. 23 , 2020 Sheet 13 of 31 US 2020/0028206 A1 Olioz= 2.07848 Charge to 600 mAhlg carbon = 2.00289 Before charge 3100 3200 3300 3400 3500 3600 3700 Field / G Fig . 13 Patent Application Publication Jan. 23 , 2020 Sheet 14 of 31 US 2020/0028206 A1 3 . ******** V*** 2.64 vsLNVoltage 2.4 2.21 2.0 200 Capacity Ah / kg Fig . 14 Patent Application Publication Jan. 23 , 2020 Sheet 15 of 31 US 2020/0028206 A1 Wis Charge hode Anode 0 , 0 A c 42 Fig . 15 Patent Application Publication Jan. 23 , 2020 Sheet 16 of 31 US 2020/0028206 A1 9.2 attack 0 8 NNNNN TO Pres A2 A Fig . 16 Patent Application Publication Jan. 23 , 2020 Sheet 17 of 31 US 2020/0028206 A1 8 00 : 00ddd WWWWW Before charge Current(UA Sww . Sur 2.5 Voltage /V vs LIILI Fig . 17 Patent Application Publication Jan. 23 , 2020 Sheet 18 of 31 US 2020/0028206 A1 WE After Charge 2.06031 Before Charge 3200 3300 3400 3500 3600 3700 Field / G Fig . 18 Patent Application Publication Jan. 23 , 2020 Sheet 19 of 31 US 2020/0028206 A1 2 LilivsVoltageN 1.2 0.8 0.6 0.4 LIO & LI TI O 12 120 A /kg 0 200 500 Capacity Ah /kg Fig . 19 Patent Application Publication Jan. 23 , 2020 Sheet 20 of 31 US 2020/0028206 A1 800 80 CapacityAh/kg ColumbicEfficiency 200 0 20 80 Cycles Fig . 20 Patent Application Publication Jan. 23 , 2020 Sheet 21 of 31 US 2020/0028206 A1 3.4 3.2 E 3.0 2.8 2.6 LitilivsVoltageN 2.4 2.2 2.0 NC-67 1.8 Discharge capacity based on total weight of Li, O & C0,0 1.4 500 Capacity Ah /kg Fig . 21 Patent Application Publication Jan. 23 , 2020 Sheet 22 of 31 US 2020/0028206 A1 100 A /kg 300 A /kg 500 A /kg CapacityAh/kg ON I NC - 53 Capacity based on total weight of Li O & Co . Cycles Fig . 22 Patent Application Publication Jan. 23 , 2020 Sheet 23 of 31 US 2020/0028206 A1 CORO Cores 1 6.6 a 3 1979 Skeleton 1 : 2.08 S : 1.86 f 1 Fig . 23 Patent Application Publication Jan. 23 , 2020 Sheet 24 of 31 US 2020/0028206 A1 3.10 3.05 3.00 2.95 ruuruulwaranwwwww VoltageN 2.90 2.85 2.80 2.75 re 2.70 0 100 200 300 400 500 600 Capacity Ah /kg Fig . 24 Patent Application Publication Jan. 23 , 2020 Sheet 25 of 31 US 2020/0028206 A1 3.0 2.8 2.6 Discharge after overcharge 15 days LitilivsVoltageN 2.4 2.2 2.0 10th day 419 day 21 day Discharge after shelved Recovery 1.8 0 0 20 30 40 50 60 70 90 100 110 Capacity retention / % Fig . 25 Patent Application Publication Jan. 23 , 2020 Sheet 26 of 31 US 2020/0028206 A1 10 3.4 5 3.2 0 ,0232 3.0 Co , miz = 14 -5 3 2.8 -10 MScurrent/pA VoltageN 2.6 -15 2.4 -20 2.2 constant current 100 mAg -25 2.0 -30 0 200 400 600 800 1000 Time /min Fig . 26 Patent Application Publication Jan. 23 , 2020 Sheet 27 of 31 US 2020/0028206 A1 2.5 25 2.0 1.5 amely Co , m /z 14 -25 Current/mA 1.0 Negative MSCurrentOA 0.5 0.0 -75 Positive Positive -0.5 2.5 3.0 2.5 2.5 3.0 Voltage N Fig . 27 Patent Application Publication Jan. 23 , 2020 Sheet 28 of 31 US 2020/0028206 A1 790 Li0 , 1130 Lio ,2 Discharged to 2 : 0V ???? -?? /- 1 ??????? Charged to 900 mAhg ???????? ?? ???????? .. Charged to 400 mang ???www.www.hig?????? Before charge 2 wagen ?? . 700 750 800 850 900 1100 1200 1300 Raman shift / cm -1 Fig . 28 Patent Application Publication Jan. 23 , 2020 Sheet 29 of 31 US 2020/0028206 A1 Before charge L1,0 (111 ) 300 mAh / g 500 mAh / g L1,0 (111 ) After 10 cycles Fig . 29 Patent Application Publication Jan. 23 , 2020 Sheet 30 of 31 US 2020/0028206 A1 Simulation result 4 . 2 -2 -4 -6 -8 24 *** ini Fig . 30 Patent Application Publication Jan. 23 , 2020 Sheet 31 of 31 US 2020/0028206 A1 8 7 *+11 6 Current/uA R = 0.9943 Equation? ya + b * x Weight No Weighting Residual 0.04288 Sum of Pearson's e 0.9981 Adj. R -Squar 0.9943 3 ***11154 TTY Value Standard Erro Intercept 0.87273 0.18762 Slope 0.64031 0.02797 2 3 4 5 6 7 8 9 10 11 Scan Rate / (mV / s ) 1/2 Fig . 31 US 2020/0028206 A1 Jan. 23 , 2020 1 SOLID OXYGEN - REDOX NANOCOMPOSITE non - limiting embodiments when considered in conjunction MATERIALS with the accompanying figures . [ 0008 ] In cases where the present specification and a CROSS - REFERENCE TO RELATED document incorporated by reference include conflicting and / APPLICATIONS or inconsistent disclosure , the present specification shall [0001 ] This application claim the benefit of priority under control. If two or more documents incorporated by reference 35 U.S.C. § 119 ( e ) of U.S. provisional application No. include conflicting and /or inconsistent disclosure with 62/ 266,783 , filed Dec. 14 , 2015 , and U.S. provisional appli respect to each other, then the document having the later cation No.