Multivalent metal salts for lithium ion cells having oxygen containing electrode active materials

Patent metadata

Field	Value
Publication number	US-2017077503-A1
Application number	US-201515123626-A
Country	US
Kind code	A1
Filing date	Mar 5, 2015
Priority date	Mar 5, 2014
Publication date	Mar 16, 2017
Grant date	—

Abstract

A material and method for a surface-treated electrode active material for use in a lithium ion battery is provided. The surface-treated electrode active material includes an ionically conductive layer comprising a multivalent metal present as a direct conformal layer on at least a portion of the outer surface of the electrode active material. The surface-treated electrode active material improves the capacity retention and cycle life as well as reduces undesirable reactions at the surface of the electrode active material.

First claim

1 . A surface-treated electrode active material for use in a lithium ion battery, comprising:
an electrode active material having an outer surface; and an ionically conductive layer comprising a multivalent metal wherein the ionically conductive layer is a direct conformal layer on the outer surface of the electrode active material.

2 . The surface-treated electrode active material of claim 1 , wherein the electrode active material is an anode comprising a lithiated metal oxide wherein the metal is selected from the group consisting of titanium, tin, niobium, vanadium, zirconium, indium, iron, and copper.

3 . The surface-treated electrode active material of claim 1 , wherein the electrode active material is a cathode comprising a lithiated metal oxide, wherein the metal oxide is selected from a group consisting of vanadium oxide, manganese oxide, iron oxide, cobalt oxide, nickel oxide, aluminum oxide, silicon oxide or a combination thereof; a lithium metal silicide; a lithium metal sulfide; a lithium metal phosphate; a lithium mixed metal phosphate; and lithium insertion compounds with olivine structure such as Li x MXO 4 , where M is a transition metal selected from Fe, Mn, Co, Ni, and a combination thereof, X is selected from P, V, S, Si and combinations thereof, and the value of x is between about 0 and 2.

4 . The surface-treated electrode active material of claim 1 , wherein the multivalent metal has a hydrogen overvoltage potential of more than 0.4V.

5 . The surface-treated electrode active material of claim 1 , wherein the multivalent metal is selected from the group consisting of: Ba, Ca, Ce, Co, Cu, La, Mg, Mn, Ni, Nb, Ag, Ti, Al, Zn, Pb, Fe, Hg, Cr, Cd, Sn, Pb, Sb, and Bi.

6 . The surface-treated electrode active material of claim 5 , wherein the multivalent metal is provided by a multivalent metal salt comprising an ion of the multivalent metal and a negative ion wherein the negative ion is selected from the group consisting of: hexafluorophosphate ion; tetrafluoroborate ion; chlorate ion; C(SO 2 CF 3 ) 3 − ion; PF 4 (CF 3 ) 2 − ion; PF 3 (C 2 F 5 ) 3 − ion; PF 3 (CF 3 ) 3 − ion; PF 3 (iso-C 3 F 7 ) 3 − ion; PF 5 (iso-C 3 F 7 ) − ion; imide ion wherein the imide ion is selected from one of bis(fluorosulfuryl) imide ion, bis(trifluoromethanesulfonyl) imide ion, bis(perfluoroethylsulfonyl) imide ion, linear imide ions having a general structure N(—SO 2 —R) 2 − , wherein at least one R is a fluorinated alkyl having a chain length of from 1 to 8, cyclic imide ions having a general structure N(—SO 2 —R—) − , wherein R is fluorinated alkyl having a chain length of from 1 to 8; methide ion having a general structure C(—SO 2 —R) 3 − , wherein R is a fluorinated alkyl with a chain length of from 0 to 8; bisoxalatoborate; and difluorooxalatoborate.

7 . The surface-treated electrode active material of claim 6 , further comprising an amount of the multivalent metal salt between 0.2% by weight to 20% by weight relative to a weight of the electrode active material.

8 . The surface-treated electrode active material of claim 1 , wherein the multivalent metal is selected based on the multivalent metal electrochemical potential being higher than a potential of the electrode active material versus lithium.

9 . The surface-treated electrode active material of claim 1 , wherein the multivalent metal is in at least a partially reduced form on the outer surface of the electrode active material.

10 . A non-aqueous electrolyte, comprising:
at least one non-aqueous solvent; one or more lithium containing salts, selected from LiPF 6 , LiBF 4 , LiClO 4 LiAsF 6 , LiN(CF 3 SO 2 ) 2 , LiN(C 2 F 5 SO 2 ) 2 , LiCF 3 SO 3 , LiC(CF 3 SO 2 ) 3 , LiPF 4 (CF 3 ) 2 , LiPF 3 (C 2 F 5 ) 3 , LiPF 3 (CF 3 ) 3 , LiPF 3 (iso-C 3 F 7 ) 3 , LiPF 5 (iso-C 3 F 7 ), lithium salts having cyclic alkyl groups and combinations thereof; and a multivalent metal salt having a concentration between about 0.01M and 0.2M wherein the multivalent metal salt comprises a multivalent metal ion having a valance of at least +2.

11 . The non-aqueous electrolyte of claim 10 , wherein the multivalent metal salt is selected from the group consisting of manganese bis(trifluoromethanesulfonyl) imide (Mn(N(SO 2 CF 3 ) 2 ) 2 ), magnesium bis(trifluoromethanesulfonyl) imide (Mg(N(SO 2 CF 3 ) 2 ) 2 ), calcium bis(trifluoromethanesulfonyl) imide (Ca(N(SO 2 CF 3 ) 2 ) 2 ), cobalt bis(trifluoromethanesulfonyl)imide (Co(N(SO 2 CF 3 ) 2 ) 2 ), nickel bis(trifluoromethanesulfonyl) imide (Ni(N(SO 2 CF 3 ) 2 ) 2 ), copper bis(trifluoromethanesulfonyl) imide (Cu(N(SO 2 CF 3 ) 2 ) 2 ), zinc bis(trifluoromethanesulfonyl) imide (Zn(N(SO 2 CF 3 ) 2 ) 2 ), cesium bis(trifluoromethanesulfonyl)imide (Cs(N(SO 2 CF 3 ) 2 ) 2 ), barium bis(trifluoromethanesulfonyl) imide (Ba(N(SO 2 CF 3 ) 2 ) 2 ), lanthanum bis(trifluoromethanesulfonyl)imide (La(N(SO 2 CF 3 ) 2 ) 2 ), and cerium bis(trifluoromethanesulfonyl)imide (Ce(N(SO 2 CF 3 ) 2 ) 2 ).

12 . The non-aqueous electrolyte of claim 10 , wherein the multivalent metal salt comprises a multivalent metal ion and a negative ion wherein the multivalent metal ion is selected from the group consisting of Ba, Ca, Ce, Co, Cu, La, Mg, Mn, Ni, Nb, Ag, Ti, Al, Zn, Pb, Fe, Hg, Cr, Cd, Sn, Pb, Sb, and Bi; and wherein the negative ion is selected from the group consisting of hexafluorophosphate ion; tetrafluoroborate ion; chlorate ion; C(SO 2 CF 3 ) 3 − ion; PF 4 (CF 3 ) 2 − ion; PF 3 (C 2 F 5 ) 3 − ion; PF 3 (CF 3 ) 3 − ion; PF 3 (iso-C 3 F 7 ) 3 − ion; PF 5 (iso-C 3 F 7 ) − ion; imide ion wherein the imide ion is selected from one of bis(fluorosulfuryl) imide ion, bis(trifluoromethanesulfonyl) imide ion, bis(perfluoroethylsulfonyl) imide ion, linear imide ions having a general structure N(—SO 2 —R) 2 − , wherein at least one R is a fluorinated alkyl having a chain length of from 1 to 8, cyclic imide ions having a general structure N(—SO 2 —R—) − , wherein R is fluorinated alkyl having a chain length of from 1 to 8; methide ion having a general structure C(—SO 2 —R) 3 − , wherein R is a fluorinated alkyl with a chain length of from 0 to 8; bisoxalatoborate; and difluorooxalatoborate.

13 . The non-aqueous electrolyte of claim 10 , wherein the concentration of the multivalent salt is between 0.05M to 0.10M.

14 . A non-aqueous electrolyte battery, comprising:
a cathode comprising a positive electrode active material in contact with a cathode current collector; an anode comprising a negative electrode active material in contact with an anode current collector; a separator positioned between the anode and the cathode; an electrolyte solution being in ionically conductive contact with the anode and the cathode, the electrolyte comprising at least one salt, at least one solvent, and at least one multivalent metal salt; an ionically conductive layer comprising a multivalent metal on at least one of the positive electrode active material or the negative electrode active material.

15 . The non-aqueous electrolyte battery of claim 14 , wherein the anode comprise a negative electrode active material comprising a lithiated metal oxide, wherein the metal is selected from the group consisting of titanium, tin, niobium, vanadium, zirconium, indium, iron, and copper; and
the cathode comprises a positive electrode active material comprising a lithiated metal oxide, wherein the metal oxide is selected from the group consisting of vanadium oxide, manganese oxide, iron oxide, cobalt oxide, nickel oxide, aluminum oxide, silicon oxide or a combination thereof; a lithium metal silicide; a lithium metal sulfide; a lithium metal phosphate; a lith

Assignees

• A123 Systems Llc

Inventors

• Erickson Michael
• Tikhonov Konstantin

Classifications

• H01M2300/0025

  Organic electrolyte · CPC title

• H01M4/366 Primary

  as layered products · CPC title

• H01M4/525

  of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy · CPC title

• H01M4/505

  of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy · CPC title

• H01M4/485 Primary

  of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy (H01M4/505, H01M4/525 take precedence) · CPC title