Seasonal energy storage technologies based on rechargeable batteries

Patent metadata

Field	Value
Publication number	US-2022393230-A1
Application number	US-202117330305-A
Country	US
Kind code	A1
Filing date	May 25, 2021
Priority date	May 25, 2021
Publication date	Dec 8, 2022
Grant date	—

Abstract

Rechargeable batteries include a NiyFe1-y cathode where 0≤y≤1, an anode comprising a current collector, a porous separator positioned between the cathode and the anode, and an electrolyte comprising MAlX4, wherein M is Na, Li, K, or a combination thereof, and X is Cl, Br, I, or a combination thereof, and wherein the electrolyte is a solid at temperatures less than 50° C. The batteries are temperature activated. The electrolyte temperature is increased above its melting point while charging and reduced below the melting point for energy storage, such as seasonal energy storage. The electrolyte temperature is increased above the melting point again to discharge the battery.

First claim

1 . A rechargeable battery, comprising:
a cathode comprising Ni y Fe 1-y where 0≤y≤1; an anode comprising a current collector; a porous separator positioned between the cathode and the anode; and an electrolyte comprising MAlX 4 , wherein M is Na, Li, K, or a combination thereof, and X is Cl, Br, I, or a combination thereof, the porous separator impregnated with the electrolyte, wherein the electrolyte is a solid at temperatures less than 50° C.

2 . The rechargeable battery of claim 1 , wherein the electrolyte comprises Na a1 Li a2 K a3 AlCl b1 Br b2 I b3 , where:
a1+a2+a3=1, where 0≤a1≤1, 0≤a2≤1, and 0≤a3≤1; and b1+b2+b3=4, where 0≤b1≤4, 0≤b2≤4, and 0≤b3≤4.

3 . The rechargeable battery of claim 1 , wherein:
(i) the electrolyte comprises NaAlCl 4 ; or (ii) the cathode comprises Ni; or (iii) both (i) and (ii).

4 . The rechargeable battery of claim 1 , wherein the cathode comprises porous nickel granules having an average size of 0.5 mm to 2 mm.

5 . The rechargeable battery of claim 1 , wherein the rechargeable battery further comprises sulfur.

6 . The rechargeable battery of claim 1 , wherein:
(i) the cathode further comprises Ni y Fe 1-y X 2 ; or (ii) the anode further comprises Al and MX; or (iii) the rechargeable battery further comprises greater than 0 mol % and up to 10 mol % sulfur relative to moles of Ni y Fe 1-y in the cathode; or (iv) any combination of (i), (ii), and (iii).

7 . The rechargeable battery of claim 1 , further comprising a container containing the cathode, the anode, the porous separator, and the electrolyte, the container comprising:
an upper portion; a lower portion; and a compressible gasket between the upper portion and the lower portion.

8 . The rechargeable battery of claim 1 , wherein:
the cathode further comprises Ni y Fe 1-y X 2 ; and the anode further comprises Al and MX, wherein M is Na, Li, K, or a combination thereof, and X is Cl, Br, I, or a combination thereof.

9 . The rechargeable battery of claim 8 , wherein the electrolyte comprises Na a1 Li a2 K a3 AlCl b1 Br b2 I b3 , where:
a1+a2+a3=1, where 0≤a1≤1, 0≤a2≤1, and 0≤a3≤1; and b1+b2+b3=4, where 0≤b1≤4, 0≤b2≤4, and 0≤b3≤4.

10 . The rechargeable battery of claim 8 , wherein:
(i) the electrolyte comprises NaAlCl 4 ; or (ii) the cathode comprises NiCl 2 and Ni; or (iii) the anode comprises Al and NaCl; or (iv) any combination of (i), (ii), and (iii).

11 . The rechargeable battery of claim 8 , wherein the rechargeable battery further comprises sulfur.

12 . The rechargeable battery of claim 8 , wherein:
(i) the anode comprises 50 mol % to 130 mol % MX relative to moles of Ni y Fe 1-y in the cathode; or (ii) the rechargeable battery comprises greater than 0 mol % and up to 10 mol % sulfur relative to moles of Ni y Fe 1-y X 2 and Ni y Fe 1-y in the cathode; or (iii) both (i) and (ii).

13 . The rechargeable battery of claim 8 , further comprising a container containing the cathode, the anode, the porous separator, and the electrolyte, the container comprising:
an upper portion; a lower portion; and a compressible gasket between the upper portion and the lower portion.

14 . A method, comprising:
storing energy in a rechargeable battery by
providing a rechargeable battery comprising a cathode comprising Ni y Fe 1-y where 0≤y≤1, an anode comprising a current collector, a porous separator positioned between the cathode and the anode, and an electrolyte comprising MAlX 4 , wherein M is Na, Li, K, or a combination thereof, and X is Cl, Br, I, or a combination thereof, the porous separator impregnated with the electrolyte, wherein the electrolyte is a solid at temperatures less than 50° C.;
heating the electrolyte to a temperature T 1 , wherein the temperature T 1 is above a melting point of the electrolyte, thereby melting the electrolyte;
charging the temperature-activated rechargeable battery while maintaining the temperature of the electrolyte at or greater than the temperature T 1 ; and
allowing the electrolyte to cool to a temperature T 2 , wherein the temperature T 2 is below the melting point of the electrolyte, thereby solidifying the electrolyte and storing energy in the temperature-activated rechargeable battery.

15 . The method of claim 14 , wherein charging the rechargeable battery comprises:
supplying a current to the rechargeable battery, wherein the current is sufficient to create an oxidation-reduction reaction in the electrolyte; and maintaining the current until the oxidation-reduction reaction reaches a desired cut-off voltage.

16 . The method of claim 15 , wherein the current is from 1 mA to 5 mA.

17 . The method of claim 14 , further comprising:
releasing stored energy from the rechargeable battery by
heating the electrolyte to a temperature T 3 , wherein the temperature T 3 is above a melting point of the electrolyte, thereby melting the electrolyte, and
discharging the rechargeable battery while maintaining the temperature of the electrolyte at or greater than the temperature T 3 , thereby releasing some or all of the stored energy from the temperature-activated rechargeable battery.

18 . The method of claim 14 , wherein:
the electrolyte comprises NiAlCl 4 ; the temperature T 1 is greater than 160° C.; and the temperature T 2 is less than 150° C.

19 . The method of claim 14 , wherein the temperature T 2 is ambient temperature.

20 . The method of claim 14 , wherein the rechargeable battery, when maintained at or below the temperature T 2 , has:
(i) a capacity retention of at least 99% of an initial charged capacity after two weeks; or (ii) a capacity retention of at least 95% of an initial charged capacity after four weeks; or (iii) both (i) and (ii).

21 . A method of making a rechargeable battery, the method comprising:
sintering cathode material particles to remove surface oxidation and produce porous granules, the granules comprising Ni y Fe 1-y where 0≤y≤1; combining the granules with molten MAlX 4 , wherein M is Na, Li, K, or a combination thereof, and X is Cl, Br, I, or a combination thereof to provide a Ni y Fe 1-y /MAlX 4 mixture; placing a porous separator on an upper surface of the Ni y Fe 1-y /MAlX 4 mixture; placing additional MAlX 4 combined with 0 mol % to 10 mol % sulfur, relative to moles of the Ni y Fe 1-y , on the porous separator; melting the additional MAlX 4 , thereby impregnating the porous separator with the additional MAlX 4 ; placing a current collector on an upper surface of the porous separator while the MAlX 4 is molten; and cooling the MAlX 4 to solidify the MAlX 4 .

22 . The method of claim 21 , wherein the granules are combined with molten MAlX 4 in a container, the method further comprising:
(i) evacuating gas from the container containing granules and molten MAlX 4 ; or (ii) applying pressure to the porous separator to remove gas from pores of the porous separator while impregnating the porous separator with the additional MAlX 4 ; or (iii) both (i) and (ii).

23 . The method of claim 21 , further comprising, prior to placing the porous separator on the upper surface of the Ni y Fe 1-y /MAlX 4 mixture:
cooling the Ni y Fe 1-y /MAlX 4 mixture to solidify the molten MAlX 4 ; and comminuting the Ni y Fe 1-y /MAlX 4 mixture to provide grounds having an average size of 0.1 to 2 mm.

24 . The method of claim 21 , further comprising, activating the cathod

Assignees

• Battelle Memorial Institute

Inventors

• Li Guosheng
• Sprenkle Vincent L
• Li Minyuan M
• Reed David M
• Polikarpov Evgueni

Classifications

• Y02E60/10

  Energy storage using batteries · CPC title

• H01M10/0561 Primary

  the electrolyte being constituted of inorganic materials only · CPC title

• H01M4/134 Primary

  Electrodes based on metals, Si or alloys · CPC title

• H01M10/443

  in response to temperature · CPC title

• H01M2004/028

  Positive electrodes · CPC title