Capacity regenerable excess electrolyte Zn ion battery

Patent metadata

Field	Value
Publication number	US-11469452-B2
Application number	US-202017001300-A
Country	US
Kind code	B2
Filing date	Aug 24, 2020
Priority date	Nov 12, 2019
Publication date	Oct 11, 2022
Grant date	Oct 11, 2022

Abstract

Battery systems, methods of in-situ grid-scale battery construction, and in-situ battery regeneration methods are disclosed. The battery system features controllable capacity regeneration for grid-scale energy storage. The battery system includes a battery comprising a plurality of cells. Each cell includes a cathode comprising cathode electrode materials disposed on a first current collector, an anode comprising anode electrode materials disposed on a second current collector, a separator or spacer disposed between the cathode and the anode an electrolyte to fill the battery in the spaces between electrodes. The battery system includes a battery system controller, wherein the battery system controller is configured to selectively charge and discharge the battery at a normal cutoff voltage and wherein the battery system controller is further configured to selectively charge and discharge the battery at a capacity regeneration voltage as part of a healing reaction to generate active electrode materials.

First claim

What is claimed is:

1. A battery system with controllable capacity regeneration for energy storage, comprising:
a Zn-ion battery comprising a plurality of cells, each cell comprising:
a cathode comprising cathode electrode materials disposed on a first current collector;
an anode comprising anode electrode materials disposed on a second current collector;
a separator or spacer disposed between the cathode and the anode;

an electrolyte to fill the battery in the spaces between electrodes, wherein the electrolyte includes a Mn salt additive; and
a battery system controller, wherein the battery system controller is configured to:
measure a battery system voltage;
determine if the battery system voltage is at a capacity regeneration threshold;
selectively charge and discharge the battery system, and
if the voltage of the battery system is at or below the capacity regeneration threshold, then perform a capacity regeneration healing reaction by increasing the cut-off voltage to a capacity regeneration voltage and controlling a battery temperature, wherein the capacity regeneration healing reaction comprises a chemical reaction at the electrode-electrolyte interface that generates electrochemically active electrode materials; and wherein the capacity regeneration healing reaction is performed while the battery is being charged.

2. The battery system of claim 1 , wherein one or more of the first current collector and second current collector comprise conductive materials selected from the group consisting of carbon paper, carbon cloth, carbon felt, carbon foil, carbon foam, conductive polymers, metal sheet, metal mesh, mesh screen, metal foam, wherein metal in the metal sheet, metal mesh, metal screen, or metal foam includes one or more of Ni, carbon steel, Cr, copper, aluminum, and stainless steel.

3. The battery system of claim 1 , wherein one or more of the first current collector and second current collector comprise a surface coated in one or more of carbon black, conductive graphite, carbon nanotube, activated carbon, amorphous carbon, conductive polymer, metal particles, Ni, Cr, copper, aluminum, stainless steel.

4. The battery system of claim 1 , wherein, one or more of the cathode electrode materials and anode electrode materials further comprises polymer binders selected from the group consisting of Polyvinylidene fluoride (PVDF), Polytetrafluoroethylene (PTFE), Polyvinyl butyral (PVB), Carboxymethyl cellulose (CMC), Styrene-Butadiene Rubber (SBR), Poly(ethylene oxide) (PEO); and further wherein the polymer binders are dissolved and mixed in solvents comprising one or more of N-Methyl-2-Pyrrolidone (NMP), ethanol, acetone, and water.

5. The method in claim 4 , wherein the polymer binders are coated onto one or more of the first current collector and second current collector through one or more of brush painting, spin coating, blade coating, dip coating, and sonication assisted dip coating.

6. The battery system of claim 1 , wherein one or more of the cathode electrode materials and anode electrode materials are disposed on one or more of the first current collectors and second current collector by one or more of brush painting, spin coating, blade coating, dip-coating, electroplating, pulse electroplating, electrodeposition, constant voltage electrodeposition, constant current electrodeposition, pulse electrodeposition, cyclic voltammetric deposition, and electrophoretic deposition.

7. The battery system of claim 1 , wherein the cathode electrode materials comprise one or more of manganese oxide, nickel oxide, vanadium oxide, titanium oxide, iron oxide and further wherein the cathode electrode materials further comprise metal doping selected from the group consisting of aluminum, nickel, lead, magnesium, boron, cobalt, titanium, chromium, vanadium; and
wherein the anode electrode materials further comprise one or more anion doping materials selected from the group consisting of fluorine, chorine, sulfur, and nitrogen.

8. The battery system of claim 1 , wherein the anode electrode materials comprises one or more of zinc, aluminum, copper, nickel, lead, magnesium, boron, cobalt, titanium, chromium, vanadium, carbon nanotube, carbon black, amorphous carbon, activated carbon, hard carbon, polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), conductive polymers, and sodium vanadium phosphate.

9. The battery system of claim 1 , wherein the electrolyte comprises:
solvents selected from the group consisting of water and organic solvents;
additive cations selected from the group consisting of Zn2+, Mn2+, proton, Al3+, Na+, K+, Mg2+, Ni2+, Cu2+, Fe3+, Co2+, Ca2+, and NH4+; and
anions selected from the group consisting of PO 4 3− , SO 4 2− , CH3COO—, Cl—, F—, Br—, NO3-, and BO 3 3− .

10. The battery system of claim 1 , wherein the separator comprises one or more of filter paper, fiberglass paper, fiber cloths, cellulose, wood fibers, polyethylene separator, and plastic mesh.

11. The battery system of claim 1 , wherein the battery system controller is configured to control the capacity regeneration healing reaction by altering one or more battery operating conditions selected from the group consisting of a cut-off voltage, a cut-off capacity, a constant voltage step, a constant current, and a current density.

12. The battery system of claim 1 , wherein the battery system controller is configured to control the capacity regeneration healing reaction by, at least in part, controlling a relative charging and discharging time.

13. The battery system of claim 1 , wherein the battery system controller is configured to control the capacity regeneration healing reaction by, at least in part, controlling a ratio and type of electrolyte ions.

14. The battery system of claim 1 , wherein the battery system controller is configured to control the capacity regeneration healing reaction by, at least in part, controlling a temperature.

15. The battery system of claim 1 , wherein the electrolyte is filled as flooded type or porous and gel separator-soaked type between electrodes wherein the distance between the electrodes is between 0.1 mm and 10 mm to elongate the healing reaction and capacity regeneration effect.

16. The battery system of claim 1 , wherein electrolyte is used for carrying ions involving in the capacity regeneration healing reaction.

17. The battery system of claim 1 , wherein the electrolyte includes Zn ions.

18. The battery system of claim 1 , wherein the capacity regeneration voltage is above a normal cutoff voltage.

19. The battery system of claim 18 , wherein the normal cutoff voltage is around 1.7V.

20. The battery system of claim 18 , wherein the capacity regeneration voltage is above 1.8V.

Assignees

• Hunt Energy Entpr Llc

Inventors

• Kong Fantai
• Griffin Mark
• Lim Jin-Myoung

Classifications

• H01M50/60

  Arrangements or processes for filling or topping-up with liquids; Arrangements or processes for draining liquids from casings · CPC title

• H01M50/409

  Separators, membranes or diaphragms characterised by the material · CPC title

• H02J7/875

  Charging or discharging for charge maintenance, battery initiation or rejuvenation · CPC title

• H01M10/46

  Accumulators structurally combined with charging apparatus (circuits for charging H02J7/00) · CPC title

• Y02E60/10

  Energy storage using batteries · CPC title