Secondary battery and method of preparing the same

Patent metadata

Field	Value
Publication number	US-2021351411-A1
Application number	US-202117141373-A
Country	US
Kind code	A1
Filing date	Jan 5, 2021
Priority date	May 6, 2020
Publication date	Nov 11, 2021
Grant date	—

Abstract

A secondary battery includes a cathode layer including a cathode active material layer; an anode layer including an anode current collector and a metal layer disposed on the anode current collector; a solid electrolyte layer disposed between the cathode layer and the anode layer; and a graphite interlayer disposed between the solid electrolyte layer and the anode layer, wherein the interlayer comprises a graphite material having a crystallite size of about 1000 angstroms to about 1500 angstroms, when measured from a (110) diffraction peak, and having a hexagonal interplanar spacing about 500 angstroms to about 800 angstroms in a c-axis direction, when measured from a (002) diffraction peak, an aspect ratio of the graphite material is in a range of between about 0.44 and about 0.55.

First claim

What is claimed is:

1 . A secondary battery comprising:
a cathode layer comprising a cathode active material layer; an anode layer comprising an anode current collector and a metal layer disposed on the anode current collector; a solid electrolyte layer disposed between the cathode layer and the anode layer; and a graphite interlayer disposed between the solid electrolyte layer and the anode layer, wherein the graphite interlayer comprises a graphite material and a crystallite of the graphite material has a crystallite size of about 1000 angstroms to about 1500 angstroms measured from a (110) diffraction peak, when analyzed by X-ray diffraction, and has a hexagonal interplanar spacing about 500 angstroms to about 800 angstroms in a c-axis direction measured from a (002) diffraction peak, when analyzed by X-ray diffraction, and has an aspect ratio is in a range of about 0.44 to about 0.55.

2 . The secondary battery of claim 1 , wherein
the metal layer comprises at least one of lithium or a lithium alloy.

3 . The secondary battery of claim 1 , wherein
the graphite interlayer further comprises at least one of iron, zirconium, gold, platinum, palladium, silicon, silver, aluminum, bismuth, tin, or zinc.

4 . The secondary battery of claim 1 , wherein
the cathode active material layer comprises at least one of a lithium cobalt oxide, a lithium nickel oxide, a lithium nickel cobalt oxide, a lithium nickel cobalt aluminum oxide, a lithium nickel cobalt manganese oxide, a lithium manganate, or a lithium iron phosphate.

5 . The secondary battery of claim 1 , wherein the cathode active material layer comprises at least one of LiNi x Co y Al z O 2 or LiNi x Co y Mn z O 2 , wherein 0<x<1, 0<y<1, 0<z<1, and x+y+z=1.

6 . The secondary battery of claim 1 , wherein
the solid electrolyte layer comprises at least one of Li 3+x La 3 M 2 O 12 , wherein 0≤x≤10, Li 3 PO 4 , Li x Ti y (PO 4 ) 3 , wherein 0<x<2 and 0<y<3, Li x Al y Ti z (PO 4 ) 3 , wherein 0<x<2, 0<y<1, and 0<z<3, Li 1+x+y (Al a Ga 1−a ) x (Ti b Ge 1−b ) 2−x Si y P 3−y O 12 , wherein 0≤x≤1, 0≤y≤1, 0≤a≤1, and 0≤b≤1, Li x La y TiO 3 , wherein 0<x<2 and 0<y<3, a Li x M y P z S w , wherein M is at least one of Ge, Si, or Sn, and 0<x<4, 0<y<1, 0<z<1, and 0<w<5, Li x N y , wherein 0<x<4 and 0<y<2, Li x PO y N z , wherein 0<x<4, 0<y<5, and 0<z<4, a Li x Si y S z , wherein 0<x<3, 0<y<2, and 0<z<4, a Li x P y S z , wherein 0<x<3, 0<y<3, and 0<z<7, Li 2 O, LiF, LiOH, Li 2 CO 3 , LiAlO 2 , a Li 2 O—Al 2 O 3 —SiO 2 —P 2 O 5 —TiO 2 —GeO 2 , or a Li x La y M z O 12 , wherein M is at least one of Te, Nb, or Zr, and 1<x<5, 0<y<4, and 0<z<4.

7 . The secondary battery of claim 1 , wherein
a thickness of the solid electrolyte layer is in a range of about 10 micrometers to about 250 micrometers.

8 . The secondary battery of claim 1 , wherein the graphite interlayer further comprises a binder.

9 . The secondary battery of claim 9 , wherein the binder comprises at least one of polyvinylidene fluoride, polyvinyl alcohol, or a polyvinyl alcohol-polyacrylic acid copolymer, carboxymethyl cellulose, styrene-butadiene rubber and an amount of the binder is in a range of about 1 weight percent to about 10 weight percent, based on the total weight of the graphite interlayer.

10 . The secondary battery of claim 1 , wherein
the lithium alloy comprises at least one of a Li—Al alloy, a Li—Sn alloy, a Li—In alloy, a Li—Ag alloy, a Li—Au alloy, a Li—Zn alloy, a Li—Ge alloy, or a Li—Si alloy.

11 . The secondary battery of claim 1 , wherein the secondary battery is a lithium battery.

12 . The secondary battery of claim 1 , wherein
the cathode layer further comprises a cathode current collector disposed on a surface of the cathode active material layer.

13 . The secondary battery of claim 1 , wherein
a thickness of the graphite interlayer is in a range of about 0.1 micrometer to about 0.3 micrometer.

14 . A method of preparing a secondary battery, the method comprising:
providing a solid electrolyte layer; mechanically milling a surface of the solid electrolyte layer to provide a milled surface; contacting the solid electrolyte layer with an oxidizing gas to provide an oxidized solid electrolyte layer; drying the oxidized solid electrolyte layer in air to provide a dried solid electrolyte layer; coating a graphite interlayer on the milled surface of the solid electrolyte layer to provide a coated solid electrolyte layer; disposing a stack comprising a metal layer and an anode current collector on the coated solid electrolyte layer to form an anode layer; and disposing a cathode layer comprising a cathode active material layer on a surface of the dried solid electrolyte layer opposite to the anode layer to form a secondary battery, wherein the graphite interlayer comprises a graphite material and a crystallite of the graphite material has a crystallite size of about 1000 angstroms to about 1500 angstroms measured from a (110) diffraction peak, when analyzed by X-ray diffraction, and has a hexagonal interplanar spacing about 500 angstroms to about 800 angstroms in a c-axis direction measured from a (002) diffraction peak when analyzed by X-ray diffraction, and has an aspect ratio in a range of about 0.44 to about 0.55.

15 . The method of claim 14 , wherein
the coating of the graphite interlayer is provided by ink coating or pencil drawing.

16 . The method of claim 14 , wherein
the disposing of the stack comprising a metal layer and an anode current collector on the coated solid electrolyte layer further comprises cold isostatic pressing to dispose the stack comprising a metal layer and an anode current collector on the coated solid electrolyte layer.

17 . The method of claim 14 , wherein
the cathode active material layer comprises at least one of a lithium cobalt oxide, a lithium nickel oxide, a lithium nickel cobalt oxide, a lithium nickel cobalt aluminum oxide, a lithium nickel cobalt manganese oxide, a lithium manganate, or a lithium iron phosphate.

18 . The method of claim 14 , wherein
the solid electrolyte layer comprises at least one of Li 3+x La 3 M 2 O 12 , wherein 0≤x≤10, Li 3 PO 4 , Li x Ti y (PO 4 ) 3 , wherein 0<x<2 and 0<y<3, Li x Al y Ti z (PO 4 ) 3 , wherein 0<x<2, 0<y<1, and 0<z<3, Li 1+x+y (Al a Ga 1−a ) x (Ti b Ge 1−b ) 2−x Si y P 3−y O 12 , wherein 0≤x≤1, 0≤y≤1, 0≤a≤1, and 0≤b≤1, Li x La y TiO 3 , wherein 0<x<2 and 0<y<3, a Li x M y P z S w , wherein M is at least one of Ge, Si, or Sn, and 0<x<4, 0<y<1, 0<z<1, and 0<w<5, Li x N y , wherein 0<x<4 and 0<y<2, Li x PO y N z , wherein 0<x<4, 0<y<5, and 0<z<4, a Li x Si y S z , wherein 0<x<3, 0<y<2, and 0<z<4, a Li x P y S z , wherein 0<x<3, 0<y<3, and 0<z<7, Li 2 O, LiF, LiOH, Li 2 CO 3 , LiAlO 2 , a Li 2 O—Al 2 O 3 —SiO 2 —P 2 O 5 —TiO 2 —GeO 2 , or a Li x La y M z O 12 , wherein M is at least one of Te, Nb, or Zr, and 1<x<5, 0<y<4, and 0<z<4.

19 . The method of claim 14 , wherein
the metal layer comprises at least one of lithium or a lithium alloy.

20 . The method of claim 14 , wherein
the cathode layer further comprises a cathode current collector disposed on a surface of the cathode active material layer.

21 . The method of claim 14 , wherein
the graphite interlayer further comprises at least one of iron, zirconium, gold, platinum, palladium, silicon, silver, aluminum, bismuth, tin, or zinc.

22 . The method of claim 14 , wherein
a thickness of the graphite interlayer is in a range of about 0.1 micrometer to a

Assignees

• Samsung Electronics Co Ltd
• Corning Inc

Inventors

• Roev Victor
• Kim Kyounghwan
• Kim Sewon
• Kim Jusik
• Badding Michael Edward
• Lee Myungjin
• Chang Jaemyung
• Song Zhen

Classifications

• H01M2300/0071

  Oxides · CPC title

• H01M10/052

  Li-accumulators · CPC title

• H01M4/134

  Electrodes based on metals, Si or alloys · CPC title

• H01M4/131

  Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx · CPC title

• H01M4/382

  Lithium (H01M4/405 takes precedence) · CPC title