IP Library › Granted Patent US 12,293,852
Granted Patent B2
US 12,293,852 · App. 17/694,174 · Granted May 6, 2025

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

Inventors: Ju Li (Weston, MA); Andrea Maurano (Somerville, MA); Yuming Chen (Cambridge, MA); Ziqiang Wang (Cambridge, MA); So Yeon Kim (Cambridge, MA)
Assignee: Massachusetts Institute of Technology
H01B1/02H01B1/06H01M4/485H01M4/505H01M4/525H01M10/0565H01M2300/0082H01M2300/0085
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Quick Facts
Patent No.
US 12,293,852
App. No.
17/694,174
Granted
May 6, 2025
Kind
B2
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.

Claims (78)

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).

Assignments (2)
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Jun 16, 2022
From: LI, JU; CHEN, YUMING; WANG, ZIQIANG; KIM, SO YEON
To: MASSACHUSETTS INSTITUTE OF TECHNOLOGY
Reel/Frame 060227/0511 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Jun 16, 2022
From: MAURANO, ANDREA
To: SAMSUNG ELECTRONICS CO., LTD.
Reel/Frame 060227/0535 →
Continuity (3)
Continuation In Part 16499656
Provisional Application 62734564 · Sep 21, 2018
Related Publication 20220208410A1 · Jun 30, 2022
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