HYBRID LITHIUM-ION BATTERY-CAPACITOR (H-LIBC) ENERGY STORAGE DEVICES

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 m Li is the Li film source mass to be pre-lithiated on the surface of the anode (g), c Li is the specific capacity of lithium and is 3,860 mAh/g, m A is the anode active layer weight (g), m B is the Li-ion battery (LIB) active material weight (g), m C is the Li-ion capacitor (LIC) active material weight (g), c A1 is the first lithium intercalation (1st discharge) specific capacity (mAh/g) of the anode electrode, c B is the specific capacity (mAh/g) of the LIB active material, c C is the specific capacitance (F/g) of the LIC active material, V max is the maximum operating voltage of H-LIBC, V c-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 γ C: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 m 2 /g.

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

3 . 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 LiCoO 2 (lithium cobalt oxide), LiNi 0.8 Co 0.15 Al 0.05 O 2 (NCA), LiNi 0.5 Mn 0.3 Co 0.2 O 2 (NMC532), LiNi 0.6 Mn 0.2 Co 0.2 O 2 (NMC622), LiNi 0.8 Mn 0.1 Co 0.1 O 2 (NMC811), and LiFePO 4 (LFP).

4 . 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).

5 . 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.

6 . 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).

7 . 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%.

8 . 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.

9 . 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.

10 . 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.

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

12 . The H-LIBC energy storage device of claim 1 , wherein the capacity ratio γ C: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 V min 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.

13 . 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.

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

15 . 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.

16 . 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.

17 . 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.

18 . 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.

19 . 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.

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.

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 m Li is the Li source mass to be pre-lithiated on the surface of the anode (g), c Li is the specific capacity of lithium and is 3,860 mAh/g, m A is the anode active layer weight (g), m B is the Li-ion battery (LIB) active material weight (g), m C is the Li-ion capacitor (LIC) active material weight (g), c A1 is the first lithium intercalation (1st discharge) specific capacity (mAh/g) of the anode electrode, c B is the specific capacity (mAh/g) of the LIB active material, c C is the specific capacitance (F/g) of the LIC active material layer, V max is the maximum operating voltage of H-LIBC, V c-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.