Anode for solid-state secondary battery, solid-state secondary battery including the same, and method of preparing the same

Patent metadata

Field	Value
Publication number	US-2024258533-A1
Application number	US-202318493459-A
Country	US
Kind code	A1
Filing date	Oct 24, 2023
Priority date	Oct 28, 2022
Publication date	Aug 1, 2024
Grant date	—

Abstract

An anode for a solid-state secondary battery, the anode including: a three-dimensional porous current collector including a plurality of pores having a lithiophilic property, and having a porosity of about 10 percent to about 99 percent, based on a total volume of the three-dimensional current collector, wherein pores of the plurality of the pores have a size and a pitch, and a ratio of the size to the pitch is about 0.1 to about 0.9; and a first anode active material layer disposed on a first side of the three-dimensional porous current collector, wherein the first anode active material layer is disposed in at least a portion of the pores of the three-dimensional porous current collector.

First claim

What is claimed is:

1 . An anode for a solid-state secondary battery, the anode comprising:
a three-dimensional porous current collector comprising a plurality of pores having a lithiophilic property, and having a porosity of about 10 percent to about 99 percent, based on a total volume of the three-dimensional porous current collector, wherein pores of the plurality of the pores have a size and a pitch, and a ratio of the size to the pitch is about 0.1 to about 0.9; and a first anode active material layer disposed on a first side of the three-dimensional porous current collector, wherein the first anode active material layer is disposed in at least a portion of the pores of the three-dimensional porous current collector.

2 . The anode of claim 1 , wherein the size of the pores of the three-dimensional porous current collector is about 0.1 micrometer to about 100 micrometers.

3 . The anode of claim 1 , wherein the pitch between the pores of the three-dimensional porous current collector is about 0.1 micrometer to about 100 micrometers.

4 . The anode of claim 1 , wherein the ratio of the size to the pitch of the pores of the three-dimensional porous current collector is about 0.2 to about 0.5.

5 . The anode of claim 1 , wherein a horizontal cross-section of the pore has a circular shape, an oval shape, a triangular shape, a square shape, a rectangular shape, a hexagonal shape, or a combination thereof.

6 . The anode of claim 1 ,
further comprising a lithiophilic coating layer on a surface of the plurality of the pores of the three-dimensional porous current collector, wherein the lithiophilic coating layer is an oxide layer comprising copper, nickel, aluminum, stainless steel, titanium, iron, cobalt, or a combination thereof.

7 . The anode of claim 1 , wherein the three-dimensional porous current collector has an oxygen peak at a binding energy of about 525 electronvolts to about 535 electronvolts, when analyzed by X-ray photoelectron spectroscopy, after sputtering on the three-dimensional porous current collector at 1.1 kilovolts or greater.

8 . The anode of claim 1 , wherein the three-dimensional porous anode current collector comprises copper, nickel, aluminum, stainless steel, titanium, iron, cobalt, or a combination thereof.

9 . The anode of claim 1 , wherein the three-dimensional porous anode current collector is in a form of a foil, a foam, or a mesh.

10 . The anode of claim 1 , wherein the first anode active material layer comprises:
a carbonaceous anode active material; a mixture of a carbonaceous anode active material and a first metal, a metalloid, or a combination thereof; a composite of a carbonaceous anode active material and the first metal, the metalloid, or a combination thereof; or a combination thereof.

11 . The anode of claim 10 ,
wherein the carbonaceous anode active material comprises amorphous carbon, and the first metal or the metalloid comprises indium, silicon, gallium, tin, aluminum, titanium, zirconium, niobium, germanium, antimony, bismuth, gold, platinum, palladium, magnesium, silver, zinc, nickel, iron, cobalt, chromium, cesium, cerium, sodium, potassium, calcium, yttrium, bismuth, tantalum, hafnium, barium, vanadium, strontium, lanthanum, or a combination thereof.

12 . The anode of claim 1 , further comprising an interlayer on a first side of the first anode active material layer opposite to a second side of the first anode active material on which the three-dimensional porous current collector is disposed,
wherein the interlayer comprises a metal or a metal alloy, which is capable of forming an alloy or a compound with lithium.

13 . The anode of claim 12 , wherein the metal alloy comprises a third element and a fourth element, and is represented by the formula M3M4,
wherein in a solution of pH 7 or less, the third element is soluble as an ion and the fourth element is insoluble, wherein the third element is Li, Na, K, Rb, Cs, Mg, Ca, Sr, Ba, Sc, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Al, Ge, Y, Zr, Hf, Nb, Tc, Rh, Cd, In, B, Si, P, F, Cl, Br, I, S, As, Sb, Bi, Ta, Re, Hg, TI, Pb, or a combination thereof, optionally in combination with C, N, or a combination thereof, and the fourth element is Ti, Mo, Ru, Pd, Ag, Sn, Se, Te, W, Os, Ir, Pt, Au, or a combination thereof.

14 . The anode of claim 12 , wherein the interlayer comprises a Ge x Te y alloy wherein 0<x≤3 and 0<y≤2, a Sb x Te y alloy wherein 0<x<1 and 0<y<1, a Ge x Se y alloy wherein 0<x≤1 and 0<y≤1, a Te x Ga y alloy wherein 0<x≤3 and 0<y≤2, Te x Zn y wherein 0<x≤1 and 0<y≤2, Te x Bi y wherein 0<x≤3 and 0<y≤2, Te x Sb y wherein 0<x≤3 and 0<y≤2, Te x Bi y wherein 0<x≤6 and 0<y≤14, Te x Au y wherein 0<x≤2 and 0<y≤1, Te 3 As 4 wherein 0<x≤3 and 0<y≤4, Te 3 As 2 wherein 0<x≤3 and 0<y≤2, Te x Sn y wherein 0<x≤1 and 0<y≤1, Te x Sr y wherein 0<x≤1 and 0<y≤1, Te x Y y wherein 0<x≤3 and 0<y≤2, Te x Zr y wherein 0<x≤5 and 0<y≤1, Te x Nb y wherein 0<x≤2 and 0<y≤1, Te x Mo y wherein 0<x≤2 and 0<y≤1, Te x Ag y wherein 0<x≤1 and 0<y≤2, Te x In y wherein 0<x≤3 and 0<y≤2, Te x Sn y wherein 0<x≤1 and 0<y≤1, Te x Pd y wherein 0<x$2 and 0<y≤1, Bi x —Sb y —Te z wherein 0<x≤4, 0<y≤4, and 0<z≤4, Bi x —Se y —Te z wherein 0<x≤4, 0<y≤4, and 0<z≤4, Se x —Sb y —Te z wherein 0<x≤4, 0<y≤4, and 0<z≤4, Ge x —Sb y —Te z wherein 0<x≤4, 0<y≤4 and 0<z≤4, Ge x —Sb y —Se z —Te k wherein 0<x≤4, 0<y≤4, 0<z≤4 and 0<k≤4, or a combination thereof.

15 . The anode of claim 1 , further comprising a second anode active material layer between the three-dimensional porous current collector and the first anode active material layer,
wherein the second anode active material layer comprises a second metal material, and the second metal material is lithium, a second metal, a lithium alloy, or a combination thereof.

16 . A solid-state secondary battery comprising:
a cathode; the anode of claim 1 ; and a solid electrolyte between the cathode and the anode.

17 . The solid-state secondary battery of claim 16 , wherein the solid-state secondary battery has a cell thickness change of 25 percent or less.

18 . A method of preparing a solid-state secondary battery, the method comprising:
providing a three-dimensional porous current collector, which has a porosity of about 10 percent to about 99 percent, based on a total volume of the three-dimensional porous current collector, and comprises a plurality of pores extending along a thickness direction,
wherein pores of the plurality of the pores have a size and a pitch and a ratio of the size to the pitch is about 0.1 to about 0.9;
disposing a first anode active material layer on a first side of the three-dimensional porous current collector to prepare an anode; providing a cathode; disposing a solid electrolyte on the cathode; and disposing the anode on the solid electrolyte opposite the cathode
wherein the first anode active material layer faces the solid electrolyte, to prepare the solid-state secondary battery.

19 . The method of claim 18 ,
wherein the first anode active material layer on the first side of the three-dimensional porous current collector is a first portion, and the method further comprises disposing a second portion of the first anode active material layer on the solid electrolyte, wherein the first portion of the first anode active material layer disposed on the three-dimensional porous current collector has a first thickness, the second portion of the first anode active material layer disposed on the solid electrolyte has a second thickne

Assignees

• Samsung Electronics Co Ltd

Inventors

• Lee Myungjin
• Kim Jirae
• Shon Jeongkuk
• Kim Yongsu
• Kim Jusik
• Jung Changhoon

Classifications

• H01M2004/027

  Negative electrodes · CPC title

• H01M2004/021

  Physical characteristics, e.g. porosity, surface area · CPC title

• H01M4/661 Primary

  Metal or alloys, e.g. alloy coatings (H01M4/669 take precedence) · CPC title

• H01M4/587

  for inserting or intercalating light metals · CPC title

• H01M10/0585

  of accumulators having only flat construction elements, i.e. flat positive electrodes, flat negative electrodes and flat separators · CPC title