Hybrid electrochemical cell

• US 10,211,495 B2
• Filed: 06/16/2015
• Issued: 02/19/2019
• Est. Priority Date: 06/16/2014
• Status: Active Grant

• Current Assignee: Regents of the University of California (University of California)
• Original Assignee: Regents of the University of California (University of California)
• Inventors: El-Kady, Maher F., Kaner, Richard B.
• Primary Examiner(s): Marks, Jacob B
• Application Number:
  US15/319,286
• Publication Number:
  US 20170149107A1
• Time in Patent Office: 1,344 Days
• CPC Class Codes: H01G 11/02 using combined reduction-oxidation reactions, e.g. redox arrangement or solion
• CPC Class Codes: H01G 11/04 Hybrid capacitors
• CPC Class Codes: H01G 11/06 with one of the electrodes allowing ions to be reversibly doped thereinto, e.g. lithium ion capacitors [LIC]
• CPC Class Codes: H01G 11/08 Structural combinations, e.g. assembly or connection, of hybrid or EDL capacitors with other electric components, at least one hybrid or EDL capacitor being the main component
• CPC Class Codes: H01G 11/26 characterised by their structure, e.g. multi-layered, porosity or surface features
• CPC Class Codes: H01G 11/30 characterised by their material
• CPC Class Codes: H01G 11/32 Carbon-based
• CPC Class Codes: H01G 11/46 Metal oxides
• CPC Class Codes: H01G 11/50 specially adapted for lithium-ion capacitors, e.g. for lithium-doping or for intercalation
• CPC Class Codes: H01G 11/52 Separators
• CPC Class Codes: H01G 11/86 specially adapted for electrodes carbonisation or activation of carbon for the manufacture of electrodes H01G11/34
• CPC Class Codes: H01M 10/052 Li-accumulators
• CPC Class Codes: H01M 10/0525 Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
• CPC Class Codes: H01M 10/30 Nickel accumulators H01M10/34 takes precedence
• CPC Class Codes: H01M 10/345 Gastight metal hydride accumulators
• CPC Class Codes: H01M 14/00 Electrochemical current or voltage generators not provided for in groups H01M6/00 - H01M12/00; Manufacture thereof
• CPC Class Codes: H01M 4/13 Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
• CPC Class Codes: H01M 4/386 Silicon or alloys based on silicon
• CPC Class Codes: H01M 4/485 of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy H01M4/505, H01M4/525 take precedence
• CPC Class Codes: H01M 4/505 of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
• CPC Class Codes: H01M 4/525 : of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
• CPC Class Codes: H01M 4/5825 : Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
• CPC Class Codes: H01M 4/587 : for inserting or intercalating light metals
• CPC Class Codes: Y02E 60/10 : Energy storage using batteries
• CPC Class Codes: Y02E 60/13 : Energy storage using capacitors

Abstract

Disclosed is a hybrid electrochemical cell with a first conductor having at least one portion that is both a first capacitor electrode and a first battery electrode. The hybrid electrochemical cell further includes a second conductor having at least one portion that is a second capacitor electrode and at least one other portion that is a second battery electrode. An electrolyte is in contact with both the first conductor and the second conductor. In some embodiments, the hybrid electrochemical cell further includes a separator between the first conductor and the second conductor to prevent physical contact between the first conductor and the second conductor, while facilitating ion transport between the first conductor and the second conductor.

Claims

1. A hybrid electrochemical cell comprising:

a) a first conductor having at least one portion that is both a first capacitor electrode and a first battery electrode;

b) a second conductor having at least one portion that is a second capacitor electrode comprising a layered metal oxide positive electrode and at least one other portion that is a second battery electrode comprising an activated carbon positive electrode; and

c) an electrolyte in contact with both the first conductor and the second conductor, wherein the hybrid electrochemical cell comprises at least one of a lithium-ion material and a lithium-ion chemistry.

2. The hybrid electrochemical cell of claim 1 further comprising a separator between the first conductor and the second conductor that is configured in a manner to prevent or reduce physical contact between the first conductor and the second conductor and that facilitates ion transport between the first conductor and the second conductor.

3. The hybrid electrochemical cell of claim 1 wherein the first battery electrode comprises hard carbon, silicon alloy, composite alloy, or any combination thereof.

4. The hybrid electrochemical cell of claim 1 wherein the second battery electrode comprises lithium cobalt oxide, lithium manganese oxide, lithium nickel oxide, lithium nickel manganese cobalt oxide, lithium nickel cobalt aluminum oxide, lithium titanium oxide, lithium iron phosphate, or any combination thereof.

5. The hybrid electrochemical cell of claim 1 wherein the second capacitor electrode comprises an interconnected corrugated carbon-based network (ICCN).

6. The hybrid electrochemical cell of claim 5 wherein the interconnected corrugated carbon-based network (ICCN) electrode comprises a plurality of expanded and interconnected carbon layers that include a corrugated carbon layer.

7. The hybrid electrochemical cell of claim 1 wherein the second capacitor electrode is redox active to store charge via intercalation pseudo-capacitance.

8. The hybrid electrochemical cell of claim 7 wherein the second capacitor electrode comprises niobium pentoxide.

9. The hybrid electrochemical cell of claim 1 integrated as a micro-hybrid electrochemical cell with an implantable medical device, a smart card, a radio frequency identification (RFID) tag, a wireless sensor, a wearable electronic device, an energy harvester, a solar cell, or any combination thereof.

10. The hybrid electrochemical cell of claim 1 wherein the second capacitor electrode and the second battery electrode have electrode digits with a length L, a width W, and an interspace I.

11. The hybrid electrochemical cell of claim 10, wherein the length L is about 4000 μ

m to about 5000 μ

m, the width W is about 300 μ

m to around about 1800 μ

m, and the interspace I is about 100 μ

m to about 200 μ

m.

12. The hybrid electrochemical cell of claim 10, wherein the length L is around about 0.5 cm to about 1.5 cm, the width W ranges from around about 0.05 cm to about 0.2 cm, and the interspace I is about 0.01 cm to about 0.05 cm.

13. The hybrid electrochemical cell of claim 1 wherein the hybrid electrochemical cell comprises nickel-cadmium (Ni—

Cd) and/or nickel-metal hydride (Ni-MH) chemistries.

14. The hybrid electrochemical cell of claim 1 wherein energy density of the hybrid electrochemical cell ranges between 20 watt-hour/kilogram (Wh/kg) to around about 200 Wh/kg.

15. The hybrid electrochemical cell of claim 1 wherein power density of the hybrid electrochemical cell ranges between nearly 1,000 watt /kilogram (W/kg) to about 10,000 W/kg.

16. A method of manufacturing a micro-hybrid electrochemical cell comprising lithium-ion (Li-Ion) material, the method comprising growing porous positive and negative electrode materials on interconnected corrugated carbon-based network (ICCN) interdigitated patterns, wherein an ICCN pattern is created using a consumer-grade optical disc burner drive, comprising a series of steps of:

a) a first step, wherein a graphite oxide (GO) dispersion in water is dropcast onto an optical disc and dried in air to form a GO film;

b) a second step, wherein a micro-pattern made with imaging or drafting software is directly printed onto the GO coated optical disc, and wherein the GO film absorbs energy from a laser and is converted into an ICCN pattern;

c) a third step, wherein anode and cathode materials are sequentially electrodeposited on the ICCN pattern, and voltage-controlled and current-controlled electrodeposition is used to ensure conformal coating of active materials throughout the three-dimensional (3D) structure of the ICCN;

d) a fourth step, wherein a nickel-tin alloy, silicon, or graphite micro-particles are electrodeposited onto the ICCN pattern corresponding to an anode; and

e) a fifth step, wherein a drop of electrolyte is added to provide ions that allow continuous electron flow when the micro-hybrid electrochemical cell is under load.

17. A method of manufacturing a micro-hybrid electrochemical cell relying on nickel-cadmium (Ni—

Cd) and/or nickel-metal hydride (Ni-MH) chemistries, the method comprising growing porous positive and negative electrode materials on interconnected corrugated carbon-based network (ICCN) interdigitated patterns, wherein an ICCN pattern is created using an optical disc burner drive, comprising a series of steps of;

a) a first step, wherein a graphite oxide (GO) dispersion in water is dropcast onto an optical disc and dried in air to form a GO film;

b) a second step, wherein a micro-pattern made with imaging or drafting software is directly printed onto the GO-coated optical disc, and wherein the GO film absorbs energy from a laser and is converted into an ICCN pattern;

c) a third step, wherein voltage-controlled and current-controlled electrodeposition is used to ensure conformal coating of active materials throughout the three-dimensional (3D) structure of ICCN, and a metal is electrodeposited on ICCN microelectrodes making up a second battery electrode that forms a portion of an anode;

d) a fourth step, wherein cadmium hydroxide (Cd(OH)2) is added to the ICCN corresponding to the anode; and

e) a fifth step, wherein a drop of electrolyte is added to provide ions that allow continuous electron flow when the micro-hybrid electrochemical cell is under load.