Mixed ionic-electronic conductive materials for alkali metal transport during battery cycling, and batteries incorporating same

Patent metadata

Field	Value
Publication number	US-12293852-B2
Application number	US-202217694174-A
Country	US
Kind code	B2
Filing date	Mar 14, 2022
Priority date	Sep 21, 2018
Publication date	May 6, 2025
Grant date	May 6, 2025

Abstract

A mixed ionic-electronic conductor (MIEC) in contact with a solid electrolyte includes a material having a bandgap less than 3 eV. The material includes an end-member phase directly connected to an alkali metal by a tie-line in an equilibrium phase diagram. The material is thermodynamically stable with a solid electrolyte. The MIEC includes plurality of open pores, formed within the MIEC, to facilitate motion of the alkali metal to at least one of store the alkali metal in the plurality of open pores or release the alkali metal from the plurality of open pores. The solid electrolyte has an ionic conductivity to ions of the alkali metal greater than 1 mS cm −1 , a thickness less than 100 μm, and comprises at least one of a ceramic or a polymer.

First claim

The invention claimed is:

1. A mixed ionic-electronic conductor (MIEC) in contact with a solid electrolyte comprising:
a material having a bandgap less than 3 eV, the material comprising an end-member phase directly connected to an alkali metal by a tie-line in an equilibrium phase diagram, and the material being thermodynamically stable with the solid electrolyte; and
a plurality of open pores, formed within the MIEC, to facilitate motion of the alkali metal to at least one of store the alkali metal in the plurality of open pores or release the alkali metal from the plurality of open pores,
wherein the solid electrolyte has an ionic conductivity to ions of the alkali metal greater than 1 mS cm −1 , a thickness less than 100 μm, and comprises at least one of a ceramic or a polymer.

2. The MIEC of claim 1 , wherein the material excludes any lanthanides.

3. The MIEC of claim 1 , wherein the material excludes any rare earth metals.

4. The MIEC of claim 1 , wherein:
the solid electrolyte comprises the polymer; and
the polymer comprises at least one of, a polyacetal, a polyolefin, a poly (alkylene oxide), a polymethacrylate, a polycarbonate, a polystyrene, a polyester, a polyamide, a polyimide, a polyarylate, a polyarylsulfone, a polyethersulfone, a polyphenylene sulfide, a polyvinyl chloride, a polysulfone, a polytetrafluoroethylene, a polyetherketone, a polybenzoxazole, a polyphthalide, a polyanhydride, a polyvinyl ether, a polyvinyl thioether, a polyvinyl alcohol, a polyvinyl ketone, a polyvinyl halide, a polyvinyl nitrile, a polyvinyl ester, a polysulfonate, a polysulfide, a polythioester, a polysulfonamide, a polyurea, a polyphosphazene, a polysilazane, a polyurethane, an ethylene propylene diene rubber, a fluorinated ethylene propylene, a perfluoroalkoxyethylene, a polychlorotrifluoroethylene, or a polyvinylidene fluoride.

5. The MIEC of claim 1 , wherein:
the solid electrolyte comprises the ceramic; and
the ceramic comprises at least one of:
Li 7 La 3 Zr 2 O 12 ;
Li 3 OX wherein X is at least one of Cl, Br, or I;
Li 3 SX wherein X is at least one of Cl, Br, or I;
Li 1.3 Al 0.3 Ti 1.7 (PO 4 ) 3 ;
Li 10 MP 2 S 12 wherein M is at least one of Ge, Si, or Sn;
Li 3 PS 4 ;
Li 7 P 3 S 11 ;
Li 3 N;
Li 2 S;
LiBH 4 ;
Li 3 BO 3 ;
Li 2 S—P 2 S 5 ;
Li 2 S—P 2 S 5 -L4SiO 4 ;
Li 2 S—Ga 2 S 3 -GeS 2 ;
Li 2 S—Sb 2 S 3 -GeS 2 ;
Li 3.25 —Ge 0.25 —P 0.75 S 4 ;
(La 1-x Li x )TiO 3 wherein 0<x<1;
Li 6 La 2 CaTa 2 O 12 ;
Li 6 La 2 ANb 2 O 12 wherein A is at least one of Ca, Sr, or Ba;
Li 6 La 3 Zr 1.5 WO 12 ;
Li 6.5 La 3 Zr 1.5 TaO 12 ;
Li 6.625 Al 0.25 La 3 Zr 2 O 12 ;
Li 3 BO 2.5 N 0.5 ;
Li 9 SiAlO 8 ;
Li 1 +x Al x Ge 2-x (PO 4 ) 3 wherein 0<x<1;
Li 1 +x Al x Ti 2-x (PO 4 ) 3 wherein 0<x<1;
Li 1+x Ti 2-x Al x Si y (PO 4 ) 3-y wherein 0<x<1 and 0≤y<1;
LiAl x Zr 2-x (PO 4 ) 3 wherein 0<x<2;
LiTi x Zr 2-x (PO 4 ) 3 wherein 0<x<2;
Li 6 PS 5 X, wherein X is at least one of Cl, Br, or I; or
Li 7 In x Sc 0.666-x Cl 4 wherein 0≤x≤0.666.

6. An anode comprising:
the mixed ionic-electronic conductor (MIEC) of claim 1 ,
wherein the MIEC does not reversibly store and release the alkali metal.

7. The anode of claim 6 , wherein:
the MIEC has a thickness of about 0.5 μm to about 67 μm;
the MIEC has a porosity greater than 45%; and
the anode has an areal capacity of about 6+0.5 mAh cm −2 .

8. The anode of claim 6 , further comprising the alkali metal.

9. A battery comprising:
the anode of claim 6 ; and
the solid electrolyte.

10. An anode comprising a mixed ionic-electronic conductor (MIEC), the MIEC comprising:
at least one of A x B y , A x B y C z , or A x B y C z D w ; and
a plurality of open pores, formed within the MIEC, to facilitate motion of an alkali metal to at least one of store the alkali metal in the plurality of open pores or release the alkali metal from the plurality of open pores,
wherein:
the MIEC does not reversibly store and release the alkali metal;
the at least one of A x B y , A x B y C z , or A x B y C z D w comprises an end-member phase directly connected to an alkali metal by a tie-line in an equilibrium phase diagram;
A is the alkali metal;
at least one of B, C, or D is at least one of an alkaline earth metal, a group 13 element, Sc, Y, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Fe, Co, Ni, Cu, Zn, Cd, Hg, C, N, Si, Sn, Pb, Bi, La, Ce, Nd, Sm, Eu, Gd, Ho, Er, or Yb; and
x, y, z, and w each have a value of about 1 to about 149.

11. The anode of claim 10 , wherein B, C, and D is each at least one of the alkaline earth metal, the group 13 element, Sc, Y, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Fe, Co, Ni, Cu, Zn, Cd, Hg, C, N, Si, Sn, Pb, Bi, La, Ce, Nd, Sm, Eu, Gd, Ho, Er, or Yb.

12. The anode of claim 10 , wherein B is the alkaline earth metal.

13. The anode of claim 10 , wherein B is the group 13 element.

14. The anode of claim 10 , wherein B is a period 4 transition metal.

15. The anode of claim 10 , wherein B is a period 5 transition metal.

16. The anode of claim 10 , wherein B is a period 6 transition metal.

17. The anode of claim 10 , wherein B is a lanthanide.

18. The anode of claim 10 , wherein the alkali metal comprises at least one of lithium (Li), sodium (Na), or potassium (K).

19. An anode, comprising:
a mixed ionic-electronic conductor (MIEC) comprising Ti w AlC y Ni z ; and
a plurality of open pores, formed within the MIEC, to facilitate motion of an alkali metal to at least one of store the alkali metal in the plurality of open pores or release the alkali metal from the plurality of open pores,
wherein x, y, z, and w each have a value less than or equal to 8.

20. A battery comprising:
the anode of claim 19 ; and
a solid electrolyte, coupled to a portion of the MIEC, the solid electrolyte comprising polyethylene oxide (PEO).

Assignees

• Massachusetts Inst Technology

Inventors

• Li Ju
• Maurano Andrea
• Chen Yuming
• Wang Ziqiang
• Kim So Yeon

Classifications

• H01M10/0565

  Polymeric materials, e.g. gel-type or solid-type · CPC title

• H01M2300/0082

  Organic polymers · CPC title

• H01M4/505

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

• H01B1/06

  mainly consisting of other non-metallic substances · CPC title

• H01M2300/0085

  Immobilising or gelification of electrolyte · CPC title