Lfp as initiator of in-battery polymerization of conducting polymers for high-rate-charging cathodes

Patent metadata

Field	Value
Publication number	US-2018166680-A1
Application number	US-201715836993-A
Country	US
Kind code	A1
Filing date	Dec 11, 2017
Priority date	Dec 11, 2016
Publication date	Jun 14, 2018
Grant date	—

Abstract

Cathodes for a fast charging lithium ion battery, processes for manufacturing thereof and corresponding batteries are provided. Cathode formulations comprise spinel and/or layered structure cathode material with 5-10% of cathode material having an olivine-based structure as polymerization initiator, binder material, and monomer and/or oligomer material selected to polymerize into a conductive polymer upon partial delithiation of the olivine-based structure cathode material during at least a first charging cycle of a cell having a cathode made of the cathode formulation. When the cathode is used in a battery, polymerization is induced in-situ (in-cell) during first charging cycle(s) of the battery to provide a polymer matrix which is evenly dispersed throughout the cathode.

First claim

1 . A cathode, prepared from a cathode formulation comprising:
cathode material having spinel or layered structure, up to 10 wt % cathode material having an olivine-based structure, binder material, and monomer and/or oligomer material selected to polymerize into a conductive polymer upon partial delithiation of the olivine-based structure cathode material during at least a first charging cycle of a cell having the cathode, wherein: the monomer and/or oligomer material is in monomer and/or oligomer form in the cathode in its pristine form prior to the first charging cycle of the cell, the partial delithiation is carried out electrochemically during the first charging cycle of the cell, and following the first charging cycle of the cell, the monomer and/or oligomer material is at least partly polymerized.

2 . The cathode of claim 1 , wherein the cathode material consists of at least one of: LCO formulations (based on LiCoO 2 ), NMC formulations (based on lithium nickel-manganese-cobalt), NCA formulations (based on lithium nickel cobalt aluminum oxides), LMO formulations (based on LiMn 2 O 4 ) and LMN formulations (based on lithium manganese-nickel oxides).

3 . The cathode of claim 1 , wherein the olivine-based structure cathode material comprises LFP (LiFePO 4 ).

4 . The cathode of claim 1 , wherein the olivine-based structure cathode material is A z MXO 4 wherein A is Li, alone or partially replaced by at most 10% of Na and/or K; 0≤z≤1, M is at least 50% of Fe(II) or Mn(II) or mixture thereof; and XO 4 is PO 4 , alone or partially replaced by at most 10 mol % of at least one group selected from SO 4 and SiO 4 .

5 . The cathode of claim 1 , wherein the cathode material further comprises a carbon coating.

6 . The cathode of claim 1 , wherein the monomer and/or oligomer material comprises monomers of at least one of pyrrole, aniline, thiophene, phenyl mercaptan, furan, phenol, ethylenedioxythiophene, styrenesulfonate and oligomers thereof.

7 . The cathode of claim 6 , wherein at least one ring in the monomers is substituted with one or more straight, branched or bridged alkyl, alkenyl, oxa-alkyl, oxa-alkenyl, aza-alkyl, aza-alkenyl, thia-alkyl, thia-alkenyl, sila-alkyl, sila-alkenyl, aryl, aryl-alkyl, alkyl-aryl, alkenyl-aryl, dialkylamino or dialkylazo group, comprising 1-30 carbon atoms.

8 . The cathode of claim 1 , wherein the monomer and/or oligomer material comprises a combination of monomers and oligomers.

9 . The cathode of claim 1 , wherein the binder material comprises at least one of: carboxymethyl cellulose (CMC), polyvinylidene difluoride (PVDF), polyacrylic acid (PAA), polyethylene oxide (PEO), polyvinyl alcohol (PVA) and alginate.

10 . The cathode of claim 1 , comprising 70-90% of the spinel or layered structure cathode material, 5-10% of the olivine-based structure cathode material, 1-10% of the binder material and 1-10% of the monomer and/or oligomer material.

11 . The cathode of claim 1 , comprising 85-93% of the cathode material, 5% of the olivine-based structure cathode material, 1-5% of the binder material and 1-5% of the monomer and/or oligomer material.

12 . A cell comprising the cathode of claim 1 .

13 . A cell comprising:
an anode, electrolyte, a separator, and a cathode comprising:
cathode material having spinel or layered structure,
up to 10 wt % cathode material having an olivine-based structure,
binder material, and
a conductive polymer formed during at least a first charging cycle of the cell from monomer and/or oligomer material selected to polymerize into the conductive polymer upon partial delithiation of the cathode material,
wherein:
the monomer and/or oligomer material is in monomer and/or oligomer form in the cathode in its pristine form prior to the first charging cycle of the cell,
the partial delithiation is carried out electrochemically during the first charging cycle of the cell, and
following the first charging cycle of the cell, the monomer and/or oligomer material is at least partly polymerized.

14 . The cell of claim 13 , wherein the cathode material consists of at least one of: LCO formulations (based on LiCoO 2 ), NMC formulations (based on lithium nickel-manganese-cobalt), NCA formulations (based on lithium nickel cobalt aluminum oxides), LMO formulations (based on LiMn 2 O 4 ) and LMN formulations (based on lithium manganese-nickel oxides).

15 . The cell of claim 13 , having a charging curve, in at least a first charging thereof, which comprises a local peak at a specified potential which corresponds to a polymerization reaction of the monomer and/or oligomer material in presence of the partially delithiated olivine-based structure cathode material.

16 . A method comprising configuring, for in-situ polymerization, a cathode made of cathode material having spinel or layered structure, by adding to the cathode material up to 10 wt % cathode material having an olivine-based structure and monomer and/or oligomer material selected to polymerize into a conductive polymer upon partial delithiation of the olivine-based structure cathode material during at least a first charging cycle of a cell with the cathode,
wherein the monomer and/or oligomer material is in monomer and/or oligomer form in the cathode in its pristine form prior to the first charging cycle of the cell, the partial delithiation is carried out electrochemically during the first charging cycle of the cell, and following the first charging cycle of the cell, the monomer and/or oligomer material is at least partly polymerized.

17 . The method of claim 16 , further comprising polymerizing the monomer and/or oligomer material during the at least first charging cycle of the cell.

18 . The method of claim 16 , wherein the monomer and/or oligomer material comprises monomers and oligomers, and the method further comprises polymerizing the monomers and the oligomers during the at least first charging cycle of the cell.

19 . The method of claim 16 , further comprising operating the cell at a charging and/or discharging rate of at least 5C.

20 . The method of claim 16 , wherein the cathode material having spinel or layered structure consists of at least one of: LCO formulations (based on LiCoO 2 ), NMC formulations (based on lithium nickel-manganese-cobalt), NCA formulations (based on lithium nickel cobalt aluminum oxides), LMO formulations (based on LiMn 2 O 4 ) and LMN formulations (based on lithium manganese-nickel oxides).

Assignees

• Storedot Ltd

Inventors

• Ophir Carmit
• Brakha Libi

Classifications

• C08G2261/3221

  containing one or more nitrogen atoms as the only heteroatom, e.g. pyrrole, pyridine or triazole · CPC title

• H01M4/466

  Magnesium based · CPC title

• H01M10/049

  Processes for forming or storing electrodes in the battery container · CPC title

• H01M4/366

  as layered products · CPC title

• C08G61/124

  with a five-membered ring containing one nitrogen atom in the ring · CPC title