# US 2019/0318882 A1 · Hybrid lithium-ion battery-capacitor (h-libc) energy storage devices

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- Number: US 2019/0318882 A1
- Document ID: US20190318882A1
- Status: Published application
- Kind: A1
- Application number: 16/385,626
- Filed: 2019-04-16
- Published: 2019-10-17
- Earliest claimed: 2018-04-16
- Applicants: Florida State University Research Foundation, Inc.; General Capacitor, LLC
- Inventors: Wanjun Ben Cao; Jin Yan; Xujie Chen; Jian-Ping Zheng; Annadanesh Shellikeri; Mark Andrew Hagen
- Web page: https://patentgrep.com/patent/US20190318882A1

## 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 11/38: Carbon pastes or blends; Binders or additives therein
- H01G 11/46: Metal oxides
- H01G 11/50: specially adapted for lithium-ion capacitors, e.g. for lithium-doping or for intercalation
- H01G 11/52: Separators
- H01G 11/60: characterised by the solvent
- H01G 11/62: characterised by the solute, e.g. salts, anions or cations therein
- H01G 11/86: specially adapted for electrodes (carbonisation or activation of carbon for the manufacture of electrodes H01G11/34)
- 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)

## Abstract

A hybrid lithium-ion battery-capacitor (H-LIBC) energy storage device includes a hybrid composite cathode electrode having a lithium ion battery (LIB) cathode active material and a lithium ion capacitor (LIC) cathode active material. An anode electrode having a surface is pre-loaded and pressed with a lithium (Li) thin film source. The anode electrode is pre-lithiated with the lithium film source by positioning the Li film source on the surface of anode electrode after electrolyte filling and soaking processes, A separator and an organic solvent electrolytic solution including a lithium salt electrolyte are also provided. A method of making a hybrid lithium-ion battery-capacitor and a method of making a hybrid composite cathode for a hybrid lithium-ion battery-capacitor are also disclosed.

## Claims

### Claim 1

A hybrid lithium-ion battery-capacitor (H-LIBC) energy storage device comprising:
a hybrid composite cathode electrode comprising a lithium ion battery (LIB) cathode active material and a lithium ion capacitor (LIC) cathode active material, an anode electrode having a surface and comprising a thin lithium (Li) film source, a separator and an organic solvent electrolytic solution comprising a lithium salt electrolyte;
wherein the anode electrode is pre-lithiated with the lithium film source by positioning and pressing the Li film source on the surface of anode electrode after electrolyte filling and soaking processes, and further wherein the mass of the Li film source is calculated by the equation:
m
Li
=
xm
A

c
A


1
-
m
B

c
B
-
m
c

c
c

(
V
max
-
V
c
-
OCV
)
3.6
c
Li
where mLi is the Li film source mass to be pre-lithiated on the surface of the anode (g), cLi is the specific capacity of lithium and is 3,860 mAh/g, mA is the anode active layer weight (g), mB is the Li-ion battery (LIB) active material weight (g), mC is the Li-ion capacitor (LIC) active material weight (g), cA1 is the first lithium intercalation (1st discharge) specific capacity (mAh/g) of the anode electrode, cB is the specific capacity (mAh/g) of the LIB active material, cC is the specific capacitance (F/g) of the LIC active material, Vmax is the maximum operating voltage of H-LIBC, Vc-OCV is the open-circuit voltage of LIC activated material is from 2.5 V to 3.2 V, and x is between 0.5 to 1.0,
and wherein the capacity ratio γC:A of the hybrid composite cathode electrode to the anode electrode is from 0.14 to 1.13, and the specific surface area of the LIC cathode active material is greater than 1,000 m2/g.

### Claim 2 (depends on 1)

The H-LIBC energy storage device of claim 1, wherein the LIB cathode active material comprises a lithium metal oxide.

### Claim 3 (depends on 2)

The H-LIBC energy storage device of claim 2, wherein the lithium metal oxide comprises at least one selected from the group consisting of lithium metal oxide comprising LiCoO2 (lithium cobalt oxide), LiNi0.8Co0.15Al0.05O2 (NCA), LiNi0.5Mn0.3Co0.2O2 (NMC532), LiNi0.6Mn0.2Co0.2O2 (NMC622), LiNi0.8Mn0.1Co0.1O2 (NMC811), and LiFePO4 (LFP).

### Claim 4 (depends on 1)

The H-LIBC energy storage device of claim 1, wherein the LIC cathode active material in the hybrid composite cathode electrode comprises at least one selected from the group consisting of activated carbon (AC) and carbon black (CB).

### Claim 5 (depends on 1)

The H-LIBC energy storage device of claim 1, wherein the mass ratio of the LIC cathode active material to the LIB cathode active material in the hybrid composite cathode electrode is from 0.1 to 9.0.

### Claim 6 (depends on 1)

The H-LIBC energy storage device of claim 1, wherein the hybrid composite cathode electrode is fabricated by a dry method manufacturing process, wherein the binder used in said dry method manufacturing process includes polytetrafluoroethylene (PTFE).

### Claim 7 (depends on 1)

The H-LIBC energy storage device according to claim 1, wherein the active layer porosity of the hybrid composite cathode electrode is from 20% to 75%.

### Claim 8 (depends on 1)

The H-LIBC energy storage device according to claim 1, wherein the anode electrode active material comprises at least one selected from the group consisting of hard carbon, graphite, and soft carbon.

### Claim 9 (depends on 8)

The H-LIBC energy storage device of claim 8, wherein the mass median diameter (D50) particle size of the anode electrode active material is from 1 μm to 10 μm.

### Claim 10 (depends on 1)

The H-LIBC energy storage device of claim 1, wherein the anode electrode comprises styrene-butadiene rubber (SBR) and carboxymethyl cellulose (CMC) as binders, and wherein the mass ratio of SBR binder to CMC binder is from 1:5 to 5:1.

### Claim 11 (depends on 1)

The H-LIBC energy storage device of claim 1, wherein the thickness of the Li film source is from 2 μm to 40 μm.

### Claim 12 (depends on 1)

The H-LIBC energy storage device of claim 1, wherein the capacity ratio γC:A of the hybrid composite cathode to the anode electrode is described by the equation:
γ
C
:
A
=
m
B

c
B
+
m
C

c
C

(
V
max
-
V
min
)
3.6
m
A

c
Ar
where Vmin is the minimum operating voltage of the H-LIBC, and car is the reversible lithium intercalation and de-intercalation specific capacity (mAh/g) of the anode active material layer.

### Claim 13 (depends on 1)

The H-LIBC energy storage device of claim 1, wherein the peak open circuit voltage of the H-LIBC energy storage device during the first 5 hours of an electrolyte soaking process is from 2.4 V to 3.0 V.

### Claim 14 (depends on 1)

The H-LIBC energy storage device of claim 1, wherein the H-LIBC energy storage device comprises a H-LIBC laminate cell.

### Claim 15 (depends on 1)

The H-LIBC energy storage device of claim 1, wherein the anode electrode is double sided, and each side of the double sided anode is pre-lithiated with the Li film source after electrolyte filling and soaking processes.

### Claim 16 (depends on 15)

The H-LIBC energy storage device of claim 15, wherein the amount of Li pre-lithiated onto the surface of the anode to fully pre-lithiate the anode is 4 to 12% based upon the Li pre-lithiated mass/anode active layer mass.

### Claim 17 (depends on 15)

The H-LIBC energy storage device of claim 15, wherein the anode electrode active material comprises at least one selected from the group consisting of hard carbon, graphite, and soft carbon.

### Claim 18 (depends on 15)

The H-LIBC energy storage device of claim 15, wherein the mass median diameter (D50) particle size of the anode electrode active material is from 1 μm to 10 μm.

### Claim 19 (depends on 15)

The H-LIBC energy storage device of claim 15, wherein the anode electrode comprises styrene-butadiene rubber (SBR) and carboxymethyl cellulose (CMC) as binders, and wherein the mass ratio of SBR binder to CMC binder is from 1:5 to 5:1.

### Claim 20

A method for making a hybrid composite cathode for a H-LIBC, comprising the steps of:
providing a lithium metal oxide, activated carbon and a binder as dry powders;
mixing the lithium metal oxide, activated carbon and binder to create a homogenous cathode dry powder mixture;
pressing the cathode dry powder mixture at a temperature of at least 50° C. to produce a free-standing cathode film;
laminating the cathode film onto a current collector by passing the cathode film and the current collector through the gap of two rollers maintained at a temperature of at least 100° C.

### Claim 21

A method of making a hybrid lithium-ion battery-capacitor H-LIBC, comprising the steps of:
preparing a hybrid composite cathode by the steps of:
providing a lithium metal oxide, activated carbon and a binder as dry powders;
mixing the lithium metal oxide, activated carbon and binder to create a homogenous cathode dry powder mixture;
pressing the cathode dry powder at a temperature of at least 50° C. to produce a free-standing cathode film;
laminating the cathode film onto a current collector by passing the cathode film and the current collector through the gap of two rollers maintained at a temperature of at least 100° C.;
preparing an anode by the steps of:
providing an anode active material having a surface, and a thin Li film source;
pre-positioned and pressing on the surface of anode electrode, wherein the mass of the Li film source is calculated by the equation:
m
Li
=
xm
A

c
A


1
-
m
B

c
B
-
m
c

c
c

(
V
max
-
V
c
-
OCV
)
3.6
c
Li
where mLi is the Li source mass to be pre-lithiated on the surface of the anode (g), cLi is the specific capacity of lithium and is 3,860 mAh/g, mA is the anode active layer weight (g), mB is the Li-ion battery (LIB) active material weight (g), mC is the Li-ion capacitor (LIC) active material weight (g), cA1 is the first lithium intercalation (1st discharge) specific capacity (mAh/g) of the anode electrode, cB is the specific capacity (mAh/g) of the LIB active material, cC is the specific capacitance (F/g) of the LIC active material layer, Vmax is the maximum operating voltage of H-LIBC, Vc-OCV is the open-circuit voltage of LIC activated material is from 2.5 V to 3.2 V, and x is between 0.5 to 1.0
providing a separator;
providing an electrolytic solution comprising a lithium salt electrolyte;
combining the hybrid composite cathode, the pre-lithiated anode, the separator and the electrolyte to form a H-LIBC energy storage device.