# US 11,309,544 B2 · High power, extended temperature range-capable, highly abuse overcharge and discharge tolerant rechargeable battery cell and pack

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- Number: US 11,309,544 B2
- Document ID: US11309544B2
- Status: Granted
- Kind: B2
- Application number: 16/383,079
- Filed: 2019-04-12
- Published: 2020-10-15
- Granted: 2022-04-19
- Earliest claimed: 2019-04-12
- Assignees: CAMX Power LLC
- Applicants: CAMX Power LLC
- Inventors: Kenan Sahin; David Ofer; Daniel Kaplan; Suresh Sriramulu
- Web page: https://patentgrep.com/patent/US11309544B2

## CPC

- 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
- 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)
- H01M 4/623: {fluorinated polymers}
- H01M 4/661: {Metal or alloys, e.g. alloy coatings (H01M4/669 take precedence)}
- H01M 10/0525: Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
- H01M 50/417: Polyolefins
- H01M 50/434: Ceramics
- H01M 50/446: Composite material consisting of a mixture of organic and inorganic materials
- H01M 50/451: comprising layers of only organic material and layers containing inorganic material
- H01M 2300/004: Three solvents
- Y02E 60/10: Energy storage using batteries
- 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

## Abstract

Provided are electrochemical secondary cells that exhibit excellent abuse tolerance, deep discharge and overcharge conditions including at extreme temperatures and remain robust and possess excellent performance. Cells as provided herein include: a cathode a polycrystalline cathode electrochemically active material including the formula Li1+xMO2+y, wherein −0.9≤x≤0.3, −0.3≤y≤0.3, and wherein M includes Ni at 80 atomic percent or higher relative to total M, the cathode electrochemically active material comprising a non-uniform distribution of Co; an anode including an anode electrochemically active material of the formula Li4+aTi5O12+b wherein −0.3≤a≤3.3, −0.3≤b≤0.3; and wherein the anode and the cathode each independently include a current collector substrate comprising aluminium.

## Claims

### Claim 1

An electrochemical cell comprising:
a cathode, the cathode comprising a polycrystalline cathode electrochemically active material comprising the formula Li1+xMO2+y, wherein −0.9≤x≤0.3, −0.3≤y≤0.3, and wherein M comprises Ni at 80 atomic percent or higher relative to total M, the cathode electrochemically active material comprising a non-uniform distribution of Co;
an anode comprising an anode electrochemically active material of the formula Li4+aTi5O12+b wherein −0.3≤a≤3.3, −0.3≤b≤0.3; and
wherein the anode and the cathode each independently comprising a current collector substrate comprising aluminium, and
wherein the electrochemical cell is characterized by a substantially unchanged voltage to capacity profile following puncture by a blunt 2 mm diameter stainless steel nail at a speed of 1 cm/sec.

### Claim 2 (depends on 1)

The electrochemical cell of claim 1 wherein the electrochemical cell is characterized by substantially unchanged performance following 1000 cycles and subsequent storage for 33 months at 0V condition.

### Claim 3 (depends on 1)

The electrochemical cell of claim 1 wherein the electrochemical cell is characterized by a 10C capacity decline of less than 10% following cycling 1,000 times between 2.43 V and 1.33 V in a 45° C. oven at 10C charge rate and 10C discharge rate without external constraints.

### Claim 4 (depends on 1)

The electrochemical cell of claim 1 wherein the electrochemical cell is characterized by delivery of over 30% capacity when discharged to 1.2 V at a rate of 3.3C at negative 50 degrees Celsius.

### Claim 5 (depends on 1)

The electrochemical cell of claim 1, capable of being charged at a rate of at least 1C at negative 50 degrees Celsius.

### Claim 6 (depends on 1)

The electrochemical cell of claim 1 wherein the anode and cathode are in a pouch cell.

### Claim 7 (depends on 1)

The electrochemical cell of claim 1 further comprising a separator comprising a ceramic, the ceramic in the form of a coating on a separator surface or as a filler within the separator.

### Claim 8 (depends on 7)

The electrochemical cell of claim 7 wherein the ceramic is a ceramic oxide, optionally aluminum oxide.

### Claim 9 (depends on 1)

The electrochemical cell of claim 1 further comprising a separator comprising a porous polyolefin.

### Claim 10 (depends on 1)

The electrochemical cell of claim 1 wherein the area ratio of anode to cathode is less than or equal to 1, or wherein a capacity ratio of anode to cathode is less than or equal to 1, or both.

### Claim 11 (depends on 1)

The electrochemical cell of claim 1 further comprising an electrolyte comprising a solvent and a salt.

### Claim 12 (depends on 11)

The electrochemical cell of claim 11 wherein the electrolyte comprises LiPF6 salt in a mixture of propylene carbonate, ethyl methyl carbonate, and methyl butyrate.

### Claim 13 (depends on 1)

The electrochemical cell of claim 1 wherein the anode and the cathode comprise a PVdF binder.

### Claim 14 (depends on 1)

The electrochemical cell of claim 1 wherein the cathode electrochemically active material includes a plurality of crystallites and a grain boundary between the plurality of crystallites, wherein a concentration of cobalt, aluminum, or both is higher in the grain boundary than in a center of the adjacent crystallites.

### Claim 15 (depends on 1)

The electrochemical cell of claim 1 wherein M in the formula Li1+xMO2+y comprises Ni and one or more metals selected from the group consisting of Mg, Sr, Co, Al, Ca, Cu, Zn, Mn, V, Ba, Zr, Ti, Cr, Fe, Mo, B, and any combination thereof.

### Claim 16 (depends on 1)

The electrochemical cell of claim 1 wherein the cathode electrochemically active material comprises Ni and one or more of Mg, Co, or Al.

### Claim 17

An electrochemical pouch cell comprising:
a cathode, the cathode comprising a cathode electrochemically active polycrystalline material comprising the formula Li1+xMO2+y, wherein −0.9≤x≤0.3, −0.3≤y≤0.3, and wherein M comprises Ni at 80 atomic percent or higher relative to total M, wherein the cathode electrochemically active material includes a plurality of crystallites and a grain boundary between the plurality of crystallites, wherein the concentration of cobalt, aluminum, or both is higher in the grain boundary than in the center of the adjacent crystallites;
two or more anodes comprising an anode electrochemically active material of the formula Li4+aTi5O12+b wherein −0.3≤a≤3.3, −0.3≤b≤0.3;
wherein the anode and the cathode independently further comprise a PVdF binder intermixed with the anode electrochemically active material and the cathode electrochemically active material respectively;
the anode and the cathode each independently further comprise a current collector substrate comprising aluminium, wherein the cathode current collector is coated with respective electrochemically active material on two sides;
a porous polyolefin separator;
an electrolyte comprising a lithium salt and a carbonate solvent;
wherein the two or more anodes are terminal layers of a stack of electrodes;
wherein an area ratio of anode to cathode is less than or equal to 1; and
wherein a capacity ratio of anode to cathode is less than 1, and
wherein the electrochemical cell is characterized by a substantially unchanged voltage to capacity profile following puncture by a blunt 2 mm diameter stainless steel nail at a speed of 1 cm/sec.

### Claim 18 (depends on 17)

The electrochemical cell of claim 17 wherein the electrochemical cell is characterized by substantially unchanged performance following 1000 cycles and subsequent storage for 33 months at 0 V condition.

### Claim 19 (depends on 17)

The electrochemical cell of claim 17 wherein the unconstrained electrochemical cell is characterized by a 10C capacity decline of less than 10% following cycling 1,000 times between 2.43 V and 1.33 V in a 45° C. oven at 10C charge rate and 10C discharge rate.

### Claim 20 (depends on 17)

The electrochemical cell of claim 17 wherein the electrochemical cell is characterized by delivery of over 40% capacity when discharged to 1.2 V at a rate of 3.3C at −50° C. and charged at 1C rate at −50° C.

### Claim 21 (depends on 17)

The electrochemical cell of claim 17 wherein the separator comprises a ceramic, the ceramic in the form of a coating on a separator surface or as a filler within the separator.

### Claim 22 (depends on 21)

The electrochemical cell of claim 21 wherein the ceramic is a ceramic oxide, optionally aluminum oxide.

### Claim 23 (depends on 17)

The electrochemical cell of claim 17 wherein M in the formula Li1+xMO2+y comprises Ni and one or more metals selected from the group consisting of Mg, Sr, Co, Al, Ca, Cu, Zn, Mn, V, Ba, Zr, Ti, Cr, Fe, Mo, B, and any combination thereof.

### Claim 24 (depends on 17)

The electrochemical cell of claim 17 wherein the cathode electrochemically active material comprises Ni and one or more of Mg, Co, or Al.