All-solid-state secondary battery

Patent metadata

Field	Value
Publication number	US-2019260065-A1
Application number	US-201916280610-A
Country	US
Kind code	A1
Filing date	Feb 20, 2019
Priority date	Feb 20, 2018
Publication date	Aug 22, 2019
Grant date	—

Abstract

An all-solid-state secondary battery including: a positive electrode active material layer including a positive electrode active material and a sacrificial positive electrode material having an oxidation-reduction potential which is less than a discharge voltage of the positive electrode active material; and a negative electrode active material layer including a negative electrode active material including an element alloyable with lithium or that forms a compound with lithium; and a solid electrolyte layer between the positive electrode active material layer and the negative electrode active material layer, wherein the sacrificial positive electrode material includes a sacrificial active material and a conductive agent.

First claim

What is claimed is:

1 . An all-solid-state secondary battery comprising:
a positive electrode active material layer comprising:
a positive electrode active material, and
a sacrificial positive electrode material having an oxidation-reduction potential which is less than a discharge voltage of the positive electrode active material;
a negative electrode active material layer comprising a negative electrode active material comprising an element alloyable with lithium or that forms a compound with lithium; and a solid electrolyte layer between the positive electrode active material layer and the negative electrode active material layer, wherein the sacrificial positive electrode material comprises a sacrificial active material and a conductive agent.

2 . The all-solid-state secondary battery of claim 1 , wherein the sacrificial positive electrode material has an ionic conductivity of about 1×10 −7 Siemens per centimeter or greater.

3 . The all-solid-state secondary battery of claim 1 , wherein the sacrificial positive electrode material has an electrical resistivity of about 1×10 10 Ohms·centimeter or less.

4 . The all-solid-state secondary battery of claim 1 , wherein the sacrificial active material comprises a sulfide solid electrolyte material.

5 . The all-solid-state secondary battery of claim 4 , wherein the sulfide solid electrolyte material comprises Li 2 S—P 2 S 5 .

6 . The all-solid-state secondary battery of claim 4 , wherein the sulfide solid electrolyte material comprises a sulfide represented by Formula 1:
x LiX-(1- x )( y Li 2 S-(1- y )P 2 S 5 )  Formula 1
wherein, in Formula 1, 0≤x≤0.5, 0.6≤y≤0.9, and X is Cl, Br, I, or a combination thereof.

7 . The all-solid-state secondary battery of claim 6 , wherein 0.1≤x≤0.5, and 0.6≤y≤0.9.

8 . The all-solid-state secondary battery of claim 6 , wherein x=0, and 0.4≤y≤0.9.

9 . The all-solid-state secondary battery of claim 1 , wherein an amount of the sacrificial positive electrode material in the positive electrode active material layer is about 1 mass percent or greater to about 30 mass percent or less, based on a total mass of the positive electrode active material.

10 . The all-solid-state secondary battery of claim 1 , wherein the conductive agent of the sacrificial positive electrode material comprises a carbonaceous material.

11 . The all-solid-state secondary battery of claim 1 , wherein a weight ratio of the sacrificial active material to the conductive agent in the sacrificial positive electrode material is in a range of about 99:1 to about 50:50.

12 . The all-solid-state secondary battery of claim 1 , wherein the sacrificial active material is a sulfide solid electrolyte material, and the conductive agent is a carbonaceous material.

13 . The all-solid-state secondary battery of claim 1 , wherein the positive electrode active material comprises a lithium salt having a layered rock-salt structure, the lithium salt comprising Li and an element comprising Ni, Co, Mn, Al, or a combination thereof.

14 . The all-solid-state secondary battery of claim 1 , wherein the positive electrode active material comprises a lithium transition metal oxide represented by
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, and wherein x, y, and z are each independently selected for LiNi x Co y Al z O 2 and LiNi x Co y Mn z O 2 .

15 . The all-solid-state secondary battery of claim 14 , wherein the positive electrode active material comprises a lithium transition metal oxide represented by
LiNi x Co y Al z O 2 or LiNi x Co y Mn z O 2 wherein 0.7<x<1, 0<y<0.3, 0<y<0.3, and x+y+z=1, and wherein x, y, and z are each independently selected for LiNi x Co y Al z O 2 and LiNi x Co y Mn z O 2 .

16 . The all-solid-state secondary battery of claim 1 , wherein prior to charging, the negative electrode active material layer does not comprise lithium.

17 . The all-solid-state secondary battery of claim 1 , wherein a lithium amount per unit area of the negative electrode active material layer is 0 weight percent or greater to about 5 weight percent or less, based on a total lithium content per unit area of the positive electrode active material layer.

18 . The all-solid-state secondary battery of claim 1 , wherein a ratio of an initial charge capacity of the negative electrode active material layer to an initial charge capacity of the positive electrode active material layer satisfies Equation 1:
0.002< b/a< 0.5  Equation 1
wherein a is the charge capacity of the positive electrode active material layer and b is the charge capacity of the negative electrode active material layer.

19 . The all-solid-state secondary battery of claim 1 , wherein the negative electrode active material is beryllium (Be), magnesium (Mg), aluminium (Al), silicon (Si), calcium (Ca), scandium (Sc), chromium (Cr), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), zinc (Zn), gallium (Ga), germanium (Ge), arsenic (As), strontium (Sr), yttrium (Y), zirconium (Zr), niobium (Nb), molybdenum (Mo), technetium (Tc), rhodium (Rh), palladium (Pd), silver (Ag), cadmium (Cd), indium (In), tin (Sn), antimony (Sb), tellurium (Te), barium (Ba), hafnium (Hf), tantalum (Ta), tungsten (W), rhenium (Re), iridium (Ir), platinum (Pt), gold (Au), mercury (Hg), thallium (TI), lead (Pb), bismuth (Bi), or a combination thereof.

20 . The all-solid-state secondary battery of claim 19 , wherein the negative electrode active material layer further comprises amorphous carbon.

21 . An all-solid-state secondary battery comprising:
a positive electrode active material layer comprising a positive electrode active material; a negative electrode active material layer comprising a negative electrode active material comprising an element alloyable with lithium or that forms a compound with lithium, a lithium alloy, a lithium compound, or a combination thereof; a lithium metal layer comprising a lithium metal precipitate; and a solid electrolyte layer between the positive electrode active material layer and the negative electrode active material layer.

22 . The all-solid-state secondary battery of claim 21 , wherein the positive electrode active material layer further comprises a sacrificial positive electrode material having an oxidation-reduction potential which is less than a discharge voltage of the positive electrode active material, and wherein the sacrificial positive electrode material comprises a sacrificial active material and a conductive agent.

23 . The all-solid-state secondary battery of claim 21 , wherein the negative electrode active material is beryllium (Be), magnesium (Mg), aluminium (Al), silicon (Si), calcium (Ca), scandium (Sc), chromium (Cr), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), zinc (Zn), gallium (Ga), germanium (Ge), arsenic (As), strontium (Sr), yttrium (Y), zirconium (Zr), niobium (Nb), molybdenum (Mo), technetium (Tc), rhodium (Rh), palladium (Pd), silver (Ag), cadmium (Cd), indium (In), tin (Sn), antimony (Sb), tellurium (Te), barium (Ba), hafnium (Hf), tantalum (Ta), tungsten (W), rhenium (Re), iridium (Ir), platinum (Pt), gold (Au), mercury (Hg), thallium (TI), lead (Pb), bismuth (Bi), or a combination thereof.

24 . The all-solid-state secondary battery of claim 21 , wherein the negative electrode active material layer further comprises amorphous carbon.

2

Assignees

• Samsung Electronics Co Ltd

Inventors

• Yashiro Nobuyoshi
• Ito Seitaro
• Shiratsuchi Tomoyuki
• Aihara Yuichi

Classifications

• H01M4/131 Primary

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

• H01M4/5815

  Sulfides · CPC title

• H01M4/381

  Alkaline or alkaline earth metals elements (H01M4/40 takes precedence) · CPC title

• H01M4/362

  Composites · CPC title

• H01M4/625

  Carbon or graphite · CPC title