US-20260128401-A1 - LONG LIFE SEALED ALKALINE SECONDARY BATTERIES

US20260128401A1US 20260128401 A1US20260128401 A1US 20260128401A1US-20260128401-A1

Abstract

In an aspect, provide is an alkaline rechargeable battery comprising: i) a battery container sealed against the release of gas up to at least a threshold gas pressure, ii) a volume of an aqueous alkaline electrolyte at least partially filling the container to an electrolyte level; iii) a positive electrode containing positive active material and at least partially submerged in the electrolyte; iv) an iron negative electrode at least partially submerged in the electrolyte, the iron negative electrode comprising iron active material; v) a separator at least partially submerged in the electrolyte provided between the positive electrode and the negative electrode; vi) an auxiliary oxygen gas recombination electrode electrically connected to the iron negative electrode by a first electronic component, ionically connected to the electrolyte by a first ionic pathway, and exposed to a gas headspace above the electrolyte level by a first gas pathway.

Inventors

Ai Quoc Pham
Sandeep Nijhawan
Aswin K. MANOHAR
Kevin Van GALLOWAY
Chenguang Yang
Eric E. BENSON
Lang McHARDY
Tim RACKERS

Assignees

FORM ENERGY, INC.

Dates

Publication Date: 20260507
Application Date: 20250612

Claims (14)

1 . (canceled)
2 . A rechargeable battery comprising: a container sealed against release of gas up to at least a predetermined threshold gas pressure; an aqueous alkaline electrolyte at least partially filling the container; a positive electrode including a positive active material at least partially submerged in the aqueous alkaline electrolyte; an iron negative electrode comprising iron active material and a sulfide compound, the iron active material and the sulfide compound at least partially submerged in the aqueous alkaline electrolyte; a separator at least partially submerged in the aqueous alkaline electrolyte between the positive electrode and the iron negative electrode; and a sulfide reservoir containing a sulfide-source material exposed to the aqueous alkaline electrolyte with a quantity of sulfide ions deliverable to the aqueous alkaline electrolyte at a rate slower than a rate of dissolution of the sulfide-source material in the aqueous alkaline electrolyte.
3 . The rechargeable battery of claim 2 , wherein the sulfide-source material comprises a metal sulfide.
4 . The rechargeable battery of claim 3 , wherein the metal sulfide is iron sulfide.
5 . The rechargeable battery of claim 2 , wherein the sulfide-source material is disposed in the iron negative electrode.
6 . The rechargeable battery of claim 2 , wherein the sulfide reservoir comprises an encapsulation material, the sulfide-source material is disposed in the encapsulation material, and the encapsulation material is dissolvable in the aqueous alkaline electrolyte at a slower rate than the rate of dissolution of the sulfide-source material in the aqueous alkaline electrolyte.
7 . The rechargeable battery of claim 6 , wherein the encapsulation material comprises a metal oxide.
8 . The rechargeable battery of claim 7 , wherein the encapsulation material comprises one or more of zinc oxide, aluminum oxide, bismuth oxide, or copper oxide.
9 . The rechargeable battery of claim 6 , wherein the encapsulation material comprises one or more of silicon oxide, silicon dioxide, a polymer, polyvinyl alcohol, or polyethylene.
10 . The rechargeable battery of claim 6 , wherein the sulfide reservoir is insoluble in the aqueous alkaline electrolyte.
11 . The rechargeable battery of claim 10 , wherein the sulfide reservoir is submerged in the aqueous alkaline electrolyte.
12 . The rechargeable battery of claim 11 , wherein the sulfide reservoir includes a separator bag submerged in the aqueous alkaline electrolyte.
13 . The rechargeable battery of claim 2 , wherein the sulfide reservoir is electrically connected to the positive electrode by an intermittently-openable electrical connection.
14 . The rechargeable battery of claim 13 , wherein the intermittently-openable electrical connection is intermittently-openable based on temperature.

Description

CROSS REFERENCE TO RELATED APPLICATIONS This application is a continuation of U.S. patent application Ser. No. 18/182,776, filed Mar. 13, 2023, which is a continuation of U.S. patent application Ser. No. 16/957,917, filed Jun. 25, 2020 (issued as U.S. Pat. No. 11,611,115), which claims priority to International Application No. PCT/US2018/067662, filed on Dec. 27, 2018, which claims the benefit of and priority to U.S. Provisional Patent Application No. 62/611,946, filed Dec. 29, 2017, with the entire contents of each of these applications hereby incorporated by reference herein. FIELD This invention generally relates to alkaline batteries and in some embodiments more particularly to gas recombination methods and apparatus in sealed alkaline secondary batteries. SUMMARY OF THE INVENTION Provided herein are systems and methods for batteries and components thereof, for example, sealed batteries, such as sealed alkaline rechargeable batteries, providing enhanced performance including longer battery life, increased discharge and cycling performance and enhanced battery safety. In some embodiments, the battery systems and methods utilize auxiliary electrodes for the recombination of gas generated during charging or discharging, for example, by chemical combustion of stoichiometric quantities of oxygen and hydrogen, by electrochemical reduction of oxygen gas and/or by electrochemical oxidation of hydrogen gas. Multiple auxiliary electrodes may be included in some embodiments for the recombination of different gases generated during charging or discharging of the electrochemical cell. The systems and methods are versatile and may be used with a variety of electrode, separator and electrolyte components and compositions, including alkaline rechargeable batteries, such as iron-containing batteries including nickel-iron batteries. In some embodiments, the systems and methods further include batteries, such as sealed alkaline rechargeable batteries, incorporating one or more auxiliary electrodes that are capable of depolarizing the negative or positive electrode, for example, in a manner that avoids, or minimizes, the loss of certain electrode additives, such as a sulfide species. In some embodiments, the systems and methods further include batteries, such as sealed alkaline rechargeable batteries, characterized by an arrangement of the positive electrode, negative electrode or both provided in uniform contact with a separator so as to eliminate, or minimize, spaces or structures in which gas bubbles may form, accumulate or travel, for example, in a manner to cause any gases formed to efficiently interact with the counter-electrode so as to encourage direct recombination, such as direct recombination of oxygen gas on the negative electrode. In some embodiments, the systems and methods further include batteries, such as sealed alkaline rechargeable batteries, incorporating a positive electrode and/or negative electrode containing a hydrophobic polymer for enhancing transport of gases generated upon charging or discharging the battery to a counter electrode or auxiliary gas recombination electrode. In an aspect, provided is an alkaline rechargeable battery comprising: i) a battery container sealed against the release of gas up to at least a threshold gas pressure, ii) a volume of an aqueous alkaline electrolyte at least partially filling the container to an electrolyte level; iii) a positive electrode containing positive active material and at least partially submerged in the electrolyte; iv) an iron negative electrode at least partially submerged in the electrolyte, the iron negative electrode comprising iron active material; v) a separator at least partially submerged in the electrolyte provided between the positive electrode and the negative electrode; vi) an auxiliary oxygen gas recombination electrode electrically connected to the iron negative electrode by a first electronic component, ionically connected to the electrolyte by a first ionic pathway, and exposed to a gas headspace above the electrolyte level by a first gas pathway. In some embodiments, the iron negative electrode further comprises one or more sulfide compounds, the one or more sulfide compounds being soluble in the electrolyte. In some embodiments, the sulfide compound comprises one or more metal sulfides. In some embodiments, the one or more metal sulfides comprise an iron sulfide, such as FeS, ZnS, CuS, MnS in powder or granular form added to the electrode, or iron sulfide (e.g., FeS, Fe3S4, Fe2S3 and/or other forms) generated in situ as a reaction product or intermediary upon cycling the battery. In some embodiments, the one or more metal sulfides is iron sulfide. In embodiments, the auxiliary oxygen gas recombination electrode electrochemically reduces oxygen gas in the gas headspace. In embodiments, while electrochemically reducing oxygen gas in the gas headspace the auxiliary oxygen gas recombination electrode depolarizes the negative electrode