Electrolyte formulations and additives for iron anode electrochemical systems

Patent metadata

Field	Value
Publication number	US-2022367911-A1
Application number	US-202217661256-A
Country	US
Kind code	A1
Filing date	Apr 28, 2022
Priority date	Apr 29, 2021
Publication date	Nov 17, 2022
Grant date	—

Abstract

Systems, methods, and devices of various aspects include using tin and/or antimony as an additive to an electrolyte and/or electrode in an electrochemical system, such as a battery, having an iron-based anode. In some aspects, the addition of tin and/or antimony may improve cycling of the iron-based anode. Systems, methods, and devices of various aspects include using high hydroxide concentration electrolyte in an electrochemical system, such as a battery. In some aspects, a high hydroxide concentration electrolyte may increase the stored amount of charge stored in the cell (i.e., the capacity of the battery material) and/or decrease the overpotential (i.e., increase the voltage) of the battery.

First claim

1 . A battery, comprising:
a first electrode, comprising direct reduced iron (DRI) or another sponge iron powder; an electrolyte; and a second electrode, wherein the first electrode or the electrolyte includes an additive containing an element that has a low hydrogen evolution reaction (HER) activity and/or improves charging of the first electrode.

2 . The battery of claim 1 , wherein the element comprises tin and/or antimony.

3 . The battery of claim 2 , wherein the additive comprises sodium stannate trihydrate (Na 2 SnO 3 .3H 2 O), metallic tin, potassium stannate trihydrate (K 2 SnO 3 .3H 2 O), tin oxide (SnO 2 ), cylindrite (Pb 3 Sn 4 FeSb 2 S 14 ), copper iron tin sulfide (Cu 2 FeSnS 4 ), lead-tin alloys (60/40 Sn/Pb solder, 63/37 Sn/Pb solder, Terne I alloy: 10-20% Sn, balance Pb), zinc-tin alloys (Terne II alloy: 10-20% Sn, balance Zn), or tin sulfide (SnS or SnS 2 ).

4 . The battery of claim 2 , wherein the element comprises tin.

5 . The battery of claim 1 , wherein the additive is in the electrolyte in a concentration of 0.1 mM or greater.

6 - 12 . (canceled)

13 . The battery of claim 5 , wherein the additive is in the electrolyte at or below a saturation limit.

14 . The battery of claim 1 , wherein the additive is in the first electrode in an amount from about 0.1 wt % of the first electrode to about 20 wt % of the first electrode.

15 . (canceled)

16 . (canceled)

17 . The battery of claim 14 , wherein the additive is in the first electrode in an amount of about 1 wt % of the first electrode to 10 wt % of the first electrode.

18 . The battery of claim 1 , wherein the electrolyte comprises lithium hydroxide (LiOH), potassium hydroxide (KOH) and/or sodium hydroxide (NaOH), and optionally sodium sulfide (Na 2 S).

19 . The battery of claim 1 , wherein the additive is plated on the second electrode.

20 . The battery of claim 1 , wherein the additive is disposed in a reservoir suspended in the electrolyte.

21 . The battery of claim 1 , wherein the additive comprises antimony.

22 . The battery of claim 1 , wherein the electrolyte includes a sulfide.

23 . The battery of claim 22 , wherein the sulfide concentration in the electrolyte is between 0.001 M and 0.5 M.

24 . The battery of claim 1 , wherein the electrolyte does not include a sulfide.

25 . The battery of claim 1 , wherein the additive is at least partially a solid.

26 . The battery of claim 25 , wherein a surface area of the solid is selected to provide a level of reactivity such that there is a constant flux of additive into the liquid electrolyte phase and/or to maintain the additive concentration in the liquid electrolyte phase at or above a selected concentration.

27 . A battery, comprising:
a first electrode, comprising direct reduced iron (DRI) or another sponge iron powder; an electrolyte comprising a hydroxide; and a second electrode, wherein the first electrode or the electrolyte further comprises an additive, said additive comprising at least one of tin, lead, or antimony.

28 . The battery of claim 27 , wherein a total hydroxide concentration in the electrolyte is about 6 M or greater.

29 . The battery of claim 27 , wherein a total hydroxide concentration in the electrolyte is greater than 7 M.

30 . The battery of claim 29 , wherein the total hydroxide concentration in the electrolyte is greater than 7 M and less than or equal to 11 M.

31 . The battery of claim 30 , wherein the electrolyte includes greater than 6 M of combined KOH and NaOH and greater than or equal to 0.05 M of LiOH.

32 . The battery of claim 30 , wherein the electrolyte includes greater a concentration of KOH, NaOH, and LiOH such that a molar concentration of KOH is greater than a molar concentration of NaOH and the molar concentration of NaOH is greater than a molar concentration of LiOH.

33 . The battery of claim 27 , wherein the total hydroxide concentration in the electrolyte is greater than 7 M and less than 10 M.

34 . The battery of claim 27 , wherein the total hydroxide concentration in the electrolyte is greater than 7.5 M and less than 9.5 M.

35 . The battery of claim 33 , wherein the electrolyte includes KOH.

36 . The battery of claim 27 , wherein the electrolyte includes at least 0.05 M of LiOH.

37 . The battery of claim 27 , wherein the electrolyte includes any one or more of KOH, NaOH, LiOH, RbOH, CsOH, FrOH, Be(OH) 2 , Ca(OH) 2 , Mg(OH) 2 , Sr(OH) 2 , Ra(OH) 2 , Ba(OH) 2 and mixtures thereof.

38 . The battery of claim 27 , wherein the electrolyte includes a sulfide.

39 . The battery of claim 38 , wherein the sulfide concentration in the electrolyte is between 0.001 M and 0.5 M.

40 . The battery of claim 27 , wherein the electrolyte does not include a sulfide.

41 - 46 . (canceled)

47 . A method of operating a battery having an iron-based electrode, comprising:
adding an additive of an additive containing an element that has a low hydrogen evolution reaction (HER) activity and/or improves charging of the first electrode to the battery; and/or adding a hydroxide to the battery.

48 . The method of claim 47 , further comprising adding one or more organic additives to an electrolyte of the battery.

49 . The method of claim 48 , wherein the one or more organic additives comprise one or more alkyl polyglucosides.

50 . The method of claim 47 , further comprising incorporating tin into a current collector of the battery.

51 . The method of claim 47 , further comprising, prior to reduction of sponge iron, incorporating selected additives into a powder mixture that is used to produce the sponge iron.

52 . The method of claim 47 , further comprising adding a HOR catalyst to the battery.

53 . The method of claim 47 , further comprising trapping hydrogen in a soluble or quasi-soluble form.

54 . The method of claim 47 , further comprising:
adding additives to the anode and/or electrolyte to reduce migration of sulfide to the positive electrode or consume the sulfide or sulfate released from the anode; and/or adding anion-selective membranes or separators to impede migration of specific ions.

55 . The method of claim 54 , wherein the additives and/or anion-selective membranes or separators comprise lignin and its derivatives, such as lignosulfonate.

56 - 63 . (canceled)

64 . The battery of claim 1 , wherein the electrolyte includes one or more organic additives.

65 . The battery of claim 64 , wherein the one or more organic additives comprise one or more alkyl polyglucosides.

66 . The battery of claim 1 , further comprising a current collector having incorporated tin therein.

67 . The battery of claim 1 , wherein the DRI or another sponge iron powder comprises selected additives that were incorporated into a powder mixture that was used to produce the DRI or another sponge iron powder.

68 . The battery of claim 1 , further comprising a HOR catalyst and/or a hydrogen getter.

Assignees

• Form Energy Inc

Inventors

• Thompson Annelise Christine
• Gibson Michael Andrew
• Woodford William Henry
• Eisenach Rebecca Marie
• Newhouse Jocelyn Marie
• Perkins Nicholas Reed
• Taylor Olivia Claire
• Schroder Kjell William
• Thomas-Alyea Karen

Classifications

• Y02E60/10

  Energy storage using batteries · CPC title

• H01M4/383

  Hydrogen absorbing alloys · CPC title

• H01M4/0404

  by coating on electrode collectors · CPC title

• H01M10/052

  Li-accumulators · CPC title

• H01M10/0567 Primary

  characterised by the additives · CPC title