# US 12,014,872 B2 · Hybrid electrodes and electrochemical cells and modules utilizing the same

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- Number: US 12,014,872 B2
- Document ID: US12014872B2
- Status: Granted
- Kind: B2
- Application number: 17/050,084
- Filed: 2018-04-23
- Published: 2021-03-04
- Granted: 2024-06-18
- Earliest claimed: 2018-04-23
- Assignees: GM Global Technology Operations LLC
- Applicants: GM Global Technology Operations LLC
- Inventors: Haijing Liu; Xiaochao Que; Dewen Kong; Jianfeng Wang
- Web page: https://patentgrep.com/patent/US12014872B2

## CPC

- H01G 11/06: with one of the electrodes allowing ions to be reversibly doped thereinto, e.g. lithium ion capacitors [LIC]
- H01G 11/24: characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
- H01G 11/28: arranged or disposed on a current collector; Layers or phases between electrodes and current collectors, e.g. adhesives
- H01G 11/30: characterised by their material
- H01G 11/46: Metal oxides
- H01G 11/50: specially adapted for lithium-ion capacitors, e.g. for lithium-doping or for intercalation
- H01G 11/66: Current collectors
- H01M 4/13: Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M 4/48: of inorganic oxides or hydroxides
- H01M 10/0525: Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
- H01M 10/0585: of accumulators having only flat construction elements, i.e. flat positive electrodes, flat negative electrodes and flat separators
- H01M 10/0587: of accumulators having only wound construction elements, i.e. wound positive electrodes, wound negative electrodes and wound separators
- H01M 12/00: Hybrid cells; Manufacture thereof (hybrid capacitors H01G11/00)
- H01M 2004/027: {Negative electrodes}
- H01M 2004/028: {Positive electrodes}
- Y02E 60/10: Energy storage using batteries
- Y02E 60/13: Energy storage using capacitors
- Y02P 70/50: Manufacturing or production processes characterised by the final manufactured product
- Y02T 10/70: Energy storage systems for electromobility, e.g. batteries
- H01G: CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE (selection of specified materials as dielectric H01B3/00; capacitors having potential barriers H10D1/62, H10K10/10)
- H01M: PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- Y02E: REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02P: CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02T: CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION

## Abstract

Hybrid electrochemical cells and modules include an anode two-sided current collector a coated with host material in anode region(s) and a cathode two-sided current collector coated with active material in cathode region(s), and one or more of the anode current collector and the cathode current collector is coated with capacitor material in one or more distinct, non-overlapping capacitor regions. A hybrid anode and/or cathode can include gaps between capacitor regions and anode regions and cathode regions. The capacitor material applied to an electrode is different from the host or active material thereof. Active material includes lithium metal oxides and lithium metal phosphates such as LiFePO4, Li(NixMnyCoz)O2, and/or LiMn2O4; host material includes graphite, silicon, silicon-Li/Sn/Cu alloys, Si/Co/Fe/TiSn oxides, and low-surface area carbon; and capacitor material includes activated carbon, metal oxides, and metal sulfides.

## Claims

### Claim 1

A hybrid electrochemical cell comprising:
an anode having an anode current collector with two anode sides, wherein:
each of the two anode sides is coated in one or more anode regions with an anode host material and in one or more first capacitor regions with a first capacitor material;
the one or more anode regions and the one or more first capacitor regions define one or more anode gaps between the anode host material and the first capacitor material; and
the one or more anode gaps each has a width of about 0.01 millimeters to about 5 millimeters; and
a cathode having a cathode current collector with two cathode sides, wherein:
each of the two cathode sides is coated in one or more cathode regions with a cathode active material and in one or more second capacitor regions with a second capacitor material;
the one or more cathode regions and the one or more second capacitor regions define one or more cathode gaps between the cathode active material and the second capacitor material; and
the one or more cathode gaps each has the width of about 0.01 millimeters to about 5 millimeters.

### Claim 2 (depends on 1)

The hybrid electrochemical cell of claim 1, wherein:
the one or more first capacitor regions of the anode are distinct from and do not overlap the one or more anode regions; and
the one or more second capacitor regions of the cathode are distinct from and do not overlap the one or more cathode regions.

### Claim 3 (depends on 1)

The hybrid electrochemical cell of claim 1, wherein the first capacitor material and/or the second capacitor material comprises one or more of activated carbon, graphite, carbon aerogel, carbide-derived carbon, graphene, graphene oxide, carbon nanotubes, lead oxide, germanium oxide, cobalt oxide, nickel oxide, copper oxide, iron oxide, manganese oxide, ruthenium oxide, rhodium oxide, palladium oxide, chromium oxide, molybdenum oxide, tungsten oxide, niobium oxide, TiS2, NiS, Ag4Hf3S8, CuS, FeS, and FeS2.

### Claim 4 (depends on 3)

The hybrid electrochemical cell of claim 3, wherein:
the first capacitor material applied to the anode current collector is different from the anode host material; and
the second capacitor material applied to the cathode current collector is different from the cathode active material.

### Claim 5 (depends on 1)

The hybrid electrochemical cell of claim 1, wherein the anode host material comprises one or more of lithium titanate, TiNb2O7, silicon, one or more silicon-lithium alloys, one or more silicon-tin alloys, one or more silicon-copper alloys, one or more silicon oxides, one or more cobalt oxides, one or more iron oxides, one or more titanium oxides, tin, one or more tin oxides, hard carbon, soft carbon, and graphite.

### Claim 6 (depends on 1)

The hybrid electrochemical cell of claim 1, wherein
the cathode active material comprises one or more lithium metal oxides.

### Claim 7 (depends on 1)

The hybrid electrochemical cell of claim 1, wherein:
the cathode active material comprises one or more of lithium iron phosphate, lithium nickel-manganese-cobalt oxide, and spinel-structured lithium manganese oxide;
the anode host material comprises one or more of graphite, silicon, and one or more silicon oxides; and
the first capacitor material and/or the second capacitor material comprises activated carbon.

### Claim 8

A hybrid electrochemical cell comprising:
an anode having an anode current collector with two anode sides, wherein:
each of the two anode sides is coated in a plurality of anode regions with an anode host material and in one or more first capacitor regions with a first capacitor material;
a first anode end of the anode includes a first anode region of the plurality of anode regions;
a first anode side of the anode current collector in the first anode region is partially coated with the anode host material;
a second anode side of the anode current collector in the first anode region is uncoated;
a second anode end of the anode includes a second anode region of the plurality of anode regions;
the first anode side of the anode current collector in the second anode region is partially coated with the anode host material;
the second anode side of the anode current collector in the second anode region is fully coated with the anode host material;
the first anode region and the second anode region are on opposite sides of the anode current collector;
the plurality of anode regions and the one or more first capacitor regions define a plurality of anode gaps between the anode host material and the first capacitor material; and
the plurality of anode gaps each have a width of about 0.01 millimeters to about 5 millimeters;
an anode electrode tab directly connected to the first anode side of the anode current collector within the first anode region;
a cathode having a cathode current collector with two cathode sides, wherein:
each of the two cathode sides of the cathode current collector is coated in a plurality of cathode regions with a cathode active material and in one or more second capacitor regions with a second capacitor material;
a first cathode end of the cathode includes a first cathode region of the plurality of cathode regions;
each of the two cathode sides of the cathode current collector in the first cathode region is partially uncoated;
a second cathode end of the cathode includes a second cathode region of the plurality of cathode regions;
each of the two cathode sides of the cathode current collector in the second cathode region is fully coated with the cathode active material;
the first cathode region is aligned with the first anode region;
the plurality of cathode regions and the one or more second capacitor regions define a plurality of cathode gaps between the cathode active material and the second capacitor material; and
the plurality of cathode gaps each have the width of about 0.01 millimeters to about 5 millimeters; and
a cathode electrode tab directly connected to the cathode current collector within the first cathode region.

### Claim 9 (depends on 8)

The hybrid electrochemical cell of claim 8, wherein the first capacitor material and/or the second capacitor material comprises one or more of activated carbon, graphite, carbon aerogel, carbide-derived carbon, graphene, graphene oxide, carbon nanotubes, lead oxide, germanium oxide, cobalt oxide, nickel oxide, copper oxide, iron oxide, manganese oxide, ruthenium oxide, rhodium oxide, palladium oxide, chromium oxide, molybdenum oxide, tungsten oxide, niobium oxide, TiS2, NiS, Ag4Hf3S8, CuS, FeS, FeS2, poly (3-methyl thiophene), polyaniline, polypyrrole, poly(paraphenylene), polyacene, polythiophene, and polyacetylene.

### Claim 10 (depends on 8)

The hybrid electrochemical cell of claim 8, wherein:
the cathode active material comprises one or more of lithium iron phosphate, lithium nickel-manganese-cobalt oxide, and spinel-structured lithium manganese oxide;
the anode host material comprises one or more of graphite, silicon, and one or more silicon oxides; and
the first capacitor material and/or the second capacitor material comprises activated carbon.

### Claim 11 (depends on 8)

The hybrid electrochemical cell of claim 8, wherein
the anode host material comprises one or more of lithium titanate, TiNb2O7, silicon, one or more silicon-lithium alloys, one or more silicon-tin alloys, one or more silicon-copper alloys, one or more silicon oxides, one or more cobalt oxides, one or more iron oxides, one or more titanium oxides, tin, one or more tin oxides, hard carbon, soft carbon, and graphite.

### Claim 12 (depends on 8)

The hybrid electrochemical cell of claim 8, wherein
the cathode active material comprises one or more lithium metal oxides.

### Claim 13

A hybrid electrochemical module comprising:
a plurality of stacked or wound electrode pairs, each electrode pair comprising:
an anode having an anode current collector with two sides, wherein:
each side of the two sides is coated in one or more anode regions with an anode host material and in one or more first capacitor regions with a first capacitor material;
the one or more anode regions and the one or more first capacitor regions define one or more anode gaps between the anode host material and the first capacitor material; and
the one or more anode gaps each has a width of about 0.01 millimeters to about 5 millimeters; and
a cathode having a cathode current collector with two cathode sides, wherein:
each of the two sides is coated in one or more cathode regions with a cathode active material and in one or more second capacitor regions with a second capacitor material;
the one or more cathode regions and the one or more second capacitor regions define one or more cathode gaps between the cathode active material and the second capacitor material; and
the one or more cathode gaps each has the width of about 0.01 millimeters to about 5 millimeters.

### Claim 14 (depends on 13)

The hybrid electrochemical module of claim 13, wherein
the first capacitor material and/or the second capacitor material comprises one or more of activated carbon, graphite, carbon aerogel, carbide-derived carbon, graphene, graphene oxide, carbon nanotubes, lead oxide, germanium oxide, cobalt oxide, nickel oxide, copper oxide, iron oxide, manganese oxide, ruthenium oxide, rhodium oxide, palladium oxide, chromium oxide, molybdenum oxide, tungsten oxide, niobium oxide, TiS2, NiS, Ag4Hf3S8, CuS, FeS, and FeS2.

### Claim 15 (depends on 13)

The hybrid electrochemical module of claim 13, wherein
a thickness of the first capacitor material, the second capacitor material, the anode host material, and the cathode active material is about 20 micrometers to about 200 micrometers.

### Claim 16 (depends on 13)

The hybrid electrochemical module of claim 13, wherein:
a first width of the one or more anode regions and/or the one or more cathode regions is about 25 millimeters to about 500 millimeters; and
a second width of the one or more capacitor regions is about 5 millimeters to about 400 millimeters.

### Claim 17 (depends on 13)

The hybrid electrochemical module of claim 13, wherein:
the cathode active material comprises one or more of lithium iron phosphate, lithium nickel-manganese-cobalt oxide, and spinel-structured lithium manganese oxide;
the anode host material comprises one or more of graphite, silicon, and one or more silicon oxides; and
the first capacitor material and/or the second capacitor material comprises activated carbon.

### Claim 18 (depends on 1)

The hybrid electrochemical cell of claim 1, wherein
a thickness of the first capacitor material, the second capacitor material, the anode host material, and the cathode active material is about 20 micrometers to about 200 micrometers.

### Claim 19 (depends on 13)

The hybrid electrochemical module of claim 13, wherein
the anode host material comprises one or more of lithium titanate, TiNb2O7, silicon, one or more silicon-lithium alloys, one or more silicon-tin alloys, one or more silicon-copper alloys, one or more silicon oxides, one or more cobalt oxides, one or more iron oxides, one or more titanium oxides, tin, one or more tin oxides, hard carbon, soft carbon, and graphite.

### Claim 20 (depends on 13)

The hybrid electrochemical module of claim 13, wherein
the cathode active material comprises one or more lithium metal oxides.