Solid-state electrolytes including lithiated zeolite particles and lithium-containing materials and methods of forming the same
A solid-state electrolyte for an electrochemical cell that cycles lithium ions is provided. The solid-state electrolyte includes a sintered layer that includes a plurality of lithiated zeolite particles having pores and a lithium-containing material disposed in at least a portion of the pores of the lithiated zeolite particles. For example, each lithiated zeolite particle has a porosity greater than or equal to about 20 vol. % to less than or equal to about 80 vol. %, and the lithium-containing material occupies greater than or equal to about 20% to less than or equal to about 80% of a total porosity of each lithiated zeolite particle. In certain instances, the sintered layer further includes a superionic additive that is also disposed in a portion of the pores of the lithiated zeolite particles, such that the sintered layer has an ionic conductivity between about 1×10 −5 S·cm −1 and about 1×10 −1 S·cm −1 .
1 . A solid-state electrolyte for an electrochemical cell that cycles lithium ions, the solid-state electrolyte being a sintered layer and comprising:
a plurality of lithiated zeolite particles defining a plurality of pores, each lithiated zeolite particle of the plurality of lithiated zeolite particles having a porosity greater than or equal to about 20 vol. % to less than or equal to about 80 vol. %; and
a lithium-containing material being disposed in at least a portion of the plurality of pores of the lithiated zeolite particles, the lithium-containing material occupying greater than or equal to about 20% to less than or equal to about 80% of a total porosity of each lithiated zeolite particle.
2 . The solid-state electrolyte of claim 1 , wherein the lithiated zeolite particles defining the plurality of lithiated zeolite particles have an average particle size greater than or equal to about 100 nanometers to less than or equal to about 5 micrometers, and an average pore diameter for each lithiated zeolite particle is greater than or equal to about 0.1 nanometer to less than or equal to about 2 nanometers.
3 . The solid-state electrolyte of claim 1 , wherein the lithiated zeolite particles are defined by linked AlO 2 and SiO 2 tetrahedral units and extra-framework cations dispersed among the tetrahedral units, the extra-framework cations comprising greater than or equal to about 10 wt. % of lithium ions, and the linked AlO 2 and SiO 2 tetrahedral units having an aluminum to silicon ratio greater than or equal to about 0.2.
4 . The solid-state electrolyte of claim 1 , wherein an average particle size of the lithium-containing material is greater than or equal to about 0.1 nanometer to less than or equal to about 2 nanometers.
5 . The solid-state electrolyte of claim 1 , wherein the lithium-containing material is selected from the group consisting of: lithium phosphate, lithium nitrate, lithium fluoride, lithium oxide, lithium peroxide, lithium lanthanum titanate, thio-LISICON, sulfide glass ceramics and combinations thereof.
6 . The solid-state electrolyte of claim 1 , wherein the sintered layer comprises:
greater than or equal to about 20 wt. % to less than or equal to about 80 wt. % of the lithiated zeolite particles; and
greater than or equal to about 20 wt. % to less than or equal to about 80 wt. % of the lithium-containing material.
7 . The solid-state electrolyte of claim 1 , wherein
the portion of the pores of the lithiated zeolite particles is a first portion of the pores of the lithiated zeolite particles, and
the sintered layer further comprises:
a superionic additive also disposed in a second portion of the pores of the lithiated zeolite particles.
8 . The solid-state electrolyte of claim 7 , wherein the sintered layer has an ionic conductivity greater than or equal to about 1×10 −5 S·cm −1 to less than or equal to about 1×10 −1 S·cm −1 .
9 . The solid-state electrolyte of claim 7 , wherein the sintered layer comprises greater than or equal to about 20 wt. % to less than or equal to about 80 wt. % of the superionic additive.
10 . The solid-state electrolyte of claim 7 , wherein the superionic additive is selected from the group consisting of: Li 10 GeP 2 S 12 , Li 7 La 3 Zr 2 O 12 , Li 3 N, LiB 11 H 14 , LiBH 4 , Li 2+x Zr 1−x M x Cl 6 where M is In, Sc, or a combination thereof and 1 wt. %≤x≤40 wt. %, and combinations thereof.
11 . An electrochemical cell that cycles lithium ions, the electrochemical cell comprising:
a first electrode comprising a positive electroactive material;
a second electrode comprising a negative electroactive material; and
a solid-state electrolyte physically separating the first and second electrodes, the solid-state electrolyte being a sintered layer and comprising:
a plurality of lithiated zeolite particles defining a plurality of pores, each lithiated zeolite particle of the plurality of lithiated zeolite particles having a porosity greater than or equal to about 20 vol. % to less than or equal to about 80 vol. %; and
a lithium-containing material being disposed in at least a portion of the plurality of pores of the lithiated zeolite particle, the lithium-containing material occupying greater than or equal to about 20% to less than or equal to about 80% of a total porosity of each lithiated zeolite particle.
12 . The electrochemical cell of claim 11 , wherein the lithium-containing material is selected from the group consisting of: lithium phosphate, lithium nitrate, lithium fluoride, lithium oxide, lithium peroxide, lithium lanthanum titanate, thio-LISICON, sulfide glass ceramics and combinations thereof.
13 . The electrochemical cell of claim 11 , wherein the lithiated zeolite particles are defined by linked AlO 2 and SiO 2 tetrahedral units and extra-framework cations dispersed among the tetrahedral units, the extra-framework cations comprising greater than or equal to about 10 wt. % of the lithium ions, and the linked AlO 2 and SiO 2 tetrahedral units having an aluminum to silicon ratio greater than or equal to about 0.2.
14 . The electrochemical cell of claim 11 ,
wherein the solid-state electrolyte further comprises greater than or equal to about 20 wt. % to less than or equal to about 60 wt. % of a superionic additive also disposed in the pores of the lithiated zeolite particles.
15 . The electrochemical cell of claim 14 , wherein the superionic additive is selected from the group consisting of: Li 10 GeP 2 S 12 , Li 7 La 3 Zr 2 O 12 , Li 3 N, LiB 11 H 14 , LiBH 4 , Li 2+x Zr 1−x M x Cl 6 , where M is In, Sc, or a combination thereof and 1 wt. %≤x≤40 wt. %, and combinations thereof.
16 . A method for forming a solid-state electrolyte layer for use in an electrochemical cell that cycles lithium ions, the method comprising:
obtaining a plurality of lithiated zeolite particles having pores, each lithiated zeolite particle of the plurality of lithiated zeolite particles having a porosity greater than or equal to about 20 vol. % to less than or equal to about 80 vol. %, the lithiated zeolite particles defining a zeolite powder;
impregnating at least a portion of the pores with a lithium-containing material to form impregnated lithium zeolite particles, the lithium-containing material occupying greater than or equal to about 20% to less than or equal to about 80% of a total porosity of each lithiated zeolite particle;
heating the impregnated lithium zeolite particles to a first temperature greater than or equal to about 200° C. to less than or equal to about 600° C. to remove any gaseous byproducts and to form a pre-sintered zeolite powder;
applying a first pressure to the pre-sintered zeolite powder to form a pellet; and
heating the pellet to a second temperature greater than or equal to about 800° C. to less than or equal to about 1,200° C. while applying a second pressure greater than 0 MPa to less than or equal to about 50 MPa to form a sintered body that defines the solid-state electrolyte layer.
17 . The method of claim 16 , wherein the lithium-containing material comprises lithium nitrate and the impregnating comprises:
contacting lithium nitrate to water to form an aqueous solution;
contacting the aqueous solution to the lithiated zeolite particles to form an admixture; and
heating the admixture to precipitate the lithium nitrate within the portion of the pores of the lithiated zeolite particles forming the impregnated lithium zeolite particles.
18 . The method of claim 16 , wherein the lithium-containing material comprises lithium phosphate and the impregnating comprises:
contacting the lithiated zeolite particles with a (NH 4 ) 3 PO 4 solution such that the (NH 4 ) 3 PO 4 solution enters into the portion of the pores of the lithiated zeolite particles; and
contacting LiOH to the lithiated zeolite particles including the (NH 4 ) 3 PO 4 solution such that Li 3 PO 4 forms within the portion of the pores thereby forming the impregnated lithium zeolite particles.