Granted Patent
B2
US 12,381,207 · App. 17/601,191 · Granted Aug 5, 2025
Desodiated sodium transition metal oxides for primary batteries
Assignee:
President and Fellows of Harvard College
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Abstract
The invention provides primary batteries that incorporate a desodiated sodium transition metal oxide into the positive electrode (a cathode). Batteries of the invention using a desodiated sodium transition metal oxide in the cathode exhibit discharge voltages, battery capacities, and energy densities higher than a traditional Zn—MnO 2 dry cell battery, such as a commercially available AA battery. These batteries are also advantageous over comparable lithium ion batteries due to the high abundance and low cost of sodium precursor materials with similar electrical performance.
Claims (16)
1. A primary battery comprising:
(a) a negative electrode comprising a metal and an oxide of the metal;
(b) a positive electrode comprising a desodiated sodium transition metal oxide of the formula Na x MO 2 ; and
(c) an electrolyte,
wherein 0<x≤1.5 and M is one or more transition metal atoms.
2. The battery of claim 1 , wherein the one or more transition metal atoms are selected from the group consisting of Ni, Co, Fe, Mn, Rh, Pt, Cu, Mo, W, and a combination thereof.
3. The battery of claim 2 , wherein the one or more transition metal atoms are selected from the group consisting of Ni, Co, Fe, Mn, and a combination thereof.
4. The battery of claim 1 , wherein the desodiated sodium transition metal oxide further comprises an alkali metal or alkaline earth metal atom.
5. The battery of claim 1 , wherein the negative electrode comprises elemental zinc.
6. The battery of claim 5 , wherein the negative electrode further comprises zinc oxide.
7. The battery of claim 1 , wherein the electrolyte comprises 1M to 9M hydroxide.
8. The battery of claim 1 , wherein the electrolyte further comprises zinc oxide.
9. The battery of claim 1 , wherein the desodiated sodium transition metal oxide is desodiated from NaNiO 2 , NaCoO 2 , NaFeO 2 , NaMnO 2 , Na 0.67 MnO 2 , NaFe 0.24 Ni 0.76 O 2 , NaFe 0.35 Ni 0.65 O 2 , NaFe 0.5 Ni 0.5 O 2 , NaFe 0.5 Co 0.5 O 2 , Na 0.67 Fe 0.5 Mn 0.5 O 2 , NaFe 0.4 Mn 0.2 Ni 0.2 O 2 , NaFe y Mn 1-y O 2 (0.05≤y≤0.5), Na 0.67 Ni 1/3 Mn 2/3 O 2 , NaFe 1/3 Ni 1/3 Mn 1/3 O 2 , Na 0.67 Mg 0.23 Mn 0.72 O 2 , Na 0.67 Mg 0.205 Fe 0.05 Ni 0.1 Mn 0.645 O 2 , Na 0.67 Mg 0.23 Ni 0.05 Mn 0.72 O 2 , Na 0.67 Mg 0.28 Ni 0.05 Mn 0.67 O 2 , Na 0.67 Mg 0.205 Ni 0.125 Mn 0.67 O 2 , Na 0.67 Mg 0.205 Fe 0.05 Mn 0.745 O 2 , Na 0.67 Mg 0.28 Fe 0.1 Mn 0.62 O 2 , Na 0.67 Mg 0.24 Fe 0.18 Mn 0.58 O 2 , Na 0.67 Mg 0.205 Fe 0.05 Co 0.05 Mn 0.645 O 2 , Na 0.7 Ni 1.1 O 2 , Na 0.55 Ni 1.15 O 2 , Na 0.75 Li 0.1 Ni 0.15 (Fe 0.35 Ni 0.65 ) 0.9 O 2 , Na 0.6 Li 0.1 Ni 0.2 (Fe 0.35 Ni 0.65 ) 0.9 O 2 , Na x Fe 0.35 Ni 0.75 O 2 (0.6≤x≤0.9), or Na x Fe y Ni z O 2 , (0.5≤x≤1, 0≤y≤0.5, 1≤z≤1.3).
10. The battery of claim 1 , wherein the desodiated sodium transition metal oxide is one or more of Na 0.4 NiO 2 , Na 0.29 NiO 2 , Na 0.24 NiO 2 , Na 0.38 CoO 2 , Na 0.25 CoO 2 , Na 0.79 FeO 2 , Na 0.5 FeO 2 , Na 0.2 MnO 2 , Na 0.12 MnO 2 , Na 0.15 MnO 2 , Na 0.25 MnO 2 , Na 0.4 MnO 2 , Na 0.34 Fe 0.24 Ni 0.76 O 2 , Na 0.25 Fe 0.24 Ni 0.76 O 2 , Na 0.13 Fe 0.24 Ni 0.76 O 2 , Na 0.33 Fe 0.35 Ni 0.65 O 2 , Na 0.24 Fe 0.35 Ni 0.65 O 2 , Na 0.05 Fe 0.35 Ni 0.65 O 2 , Na 0.45 Fe 0.5 Ni 0.5 O 2 , Na 0.35 Fe 0.5 Ni 0.5 O 2 , Na 0.25 Fe 0.5 Ni 0.5 O 2 , Na 0.18 Fe 0.5 Co 0.5 O 2 , Na 0.27 Fe 0.5 Co 0.5 O 2 , Na 0.32 Fe 0.5 Mn 0.5 O 2 , Na 0.25 Fe 0.5 Mn 0.5 O 2 , Na 0.19 Fe 0.5 Mn 0.5 O 2 , Na 0.09 Ni 1/3 Mn 2/3 O 2 , Na 0.36 Fe 1/3 Ni 1/3 Mn 1/3 O 2 , Na 0.23 Fe 1/3 Ni 1/3 Mn 1/3 O 2 , Na 0.17 Fe 1/3 Ni 1/3 Mn 1/3 O 2 , Na 0.46 Mg 0.28 Mn 0.72 O 2 , Na 0.42 Mg 0.28 Mn 0.72 O 2 , Na 0.39 Mg 0.28 Mn 0.72 O 2 , Na 0.35 Mg 0.28 Mn 0.72 O 2 , Na 0.32 Mg 0.28 Mn 0.72 O 2 , Na 0.28 Mg 0.28 Mn 0.72 O 2 , Na 0.27 Mg 0.28 Mn 0.72 O 2 , Na 0.25 Mg 0.28 Mn 0.72 O 2 , Na 0.45 Mg 0.205 Fe 0.05 Ni 0.1 Mn 0.645 O 2 , Na 0.38 Mg 0.205 Fe 0.05 Ni 0.1 Mn 0.645 O 2 , Na 0.36 Mg 0.205 Fe 0.05 Ni 0.1 Mn 0.645 O 2 , Na 0.34 Mg 0.205 Fe 0.05 Ni 0.1 Mn 0.645 O 2 , Na 0.31 Mg 0.205 Fe 0.05 Ni 0.1 Mn 0.645 O 2 , Na 0.33 Mg 0.23 Ni 0.05 Mn 0.72 O 2 , Na 0.29 Mg 0.23 Ni 0.05 Mn 0.72 O 2 , Na 0.35 Mg 0.28 Ni 0.05 Mn 0.67 O 2 , Na 0.32 Mg 0.28 Ni 0.05 Mn 0.67 O 2 , Na 0.33 Mg 0.2 O 5 Ni 0.125 Mn 0.6 O 2 , Na 0.29 Mg 0.205 Ni 0.125 Mn 0.602 , Na 0.33 Mg 0.205 Fe 0.05 Mn 0.745 O 2 , Na 0.29 Mg 0.205 Fe 0.05 Mn 0.745 O 2 , Na 0.35 Mg 0.2 O 5 Fe 0.05 Co 0.05 Mn 0.645 O 2 , Na 0.32 Mg 0.205 Fe 0.05 Co 0.05 Mn 0.645 O 2 .
11. The battery of claim 1 , wherein the desodiated sodium transition metal oxide is one or more of Na 0.29 NiO 2 , Na 0.33 Fe 0.35 Ni 0.65 O 2 , Na 0.24 Fe 0.35 Ni 0.65 O 2 , Na 0.19 Fe 0.5 Mn 0.5 O 2 , Na 0.32 Mg 0.28 Mn 0.72 O 2 , Na 0.28 Mg 0.28 Mn 0.72 O 2 , Na 0.34 Mg 0.2 O 5 Fe 0.05 Ni 0.1 Mn 0.645 O 2 , Na 0.31 Mg 0.2 O 5 Fe 0.05 Ni 0.1 Mn 0.645 O 2 .
12. The battery of claim 1 , wherein the desodiated sodium transition metal oxide is Na 0.24 H 0.76 Fe 0.35 Ni 0.65 O 2 .
Assignments (1)
ASSIGNMENT OF ASSIGNOR'S INTEREST
Recorded Jan 20, 2023
From: HAI, LI; LI, XIN; WANG, YICHAO
To: PRESIDENT AND FELLOWS OF HARVARD COLLEGE
Reel/Frame 062433/0013 →
Continuity (2)
Provisional Application
62829278
· Apr 4, 2019
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Zhu et al., “Origin of Outstanding Stability in the Lithium Solid Electrolyte Materials: Insights from Thermodynamic Analyses Based on First-Principles Calculations,” ACS Appl Mater Interfaces. 7(42):23685-23693 (Oct. 6…
[cited by applicant]
Zhu et al., “Strategies Based on Nitride Materials Chemistry to Stabilize Li Metal Anode,” Adv Sci. 4(8):1600517 (Mar. 3, 2017) (11 pages).
[cited by applicant]