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

• US 20190318882A1
• Filed: 04/16/2019
• Published: 10/17/2019
• Est. Priority Date: 04/16/2018
• Status: Abandoned Application

• Current Assignee: SPEL Technologies Private Limited, Florida State University Research Foundation, Inc. (State University System of Florida)
• Original Assignee: General Capacitor LLC, Florida State University Research Foundation, Inc. (State University System of Florida)
• Inventors: Cao, Wanjun Ben, Yan, Jin, Chen, Xujie, Zheng, Jian-Ping, Shellikeri, Annadanesh, Hagen, Mark Andrew
• Application Number:
  US16/385,626
• Publication Number:
  US 20190318882A1
• Time in Patent Office: Days
• 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 11/24 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
• CPC Class Codes: H01G 11/38 Carbon pastes or blends; Binders or additives therein
• 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 11/60 characterised by the solvent
• CPC Class Codes: H01G 11/62 characterised by the solute, e.g. salts, anions or cations therein
• CPC Class Codes: H01G 11/86 specially adapted for electrodes carbonisation or activation of carbon for the manufacture of electrodes H01G11/34

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

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;

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 LiCoO₂ (lithium cobalt oxide), LiNi_0.8Co_0.15Al_0.05O₂ (NCA), LiNi_0.5Mn_0.3Co_0.2O₂ (NMC532), LiNi_0.6Mn_0.2Co_0.2O₂ (NMC622), LiNi_0.8Mn_0.1Co_0.1O₂ (NMC811), and LiFePO₄ (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 μ

m to 10 μ

m.

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 μ

m to 40 μ

m.

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

<sub>C;

A</sub> of the hybrid composite cathode to the anode electrode is described by the equation;

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 μ

m to 10 μ

m.

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;