Lithium secondary ion battery

Patent metadata

Field	Value
Publication number	US-2017256786-A1
Application number	US-201715447759-A
Country	US
Kind code	A1
Filing date	Mar 2, 2017
Priority date	Mar 3, 2016
Publication date	Sep 7, 2017
Grant date	—

Abstract

A lithium ion secondary battery including: a cathode layer including at least a halogen-containing sulfide catholyte including a sulfide catholyte and a halide, and a conducting material; a solid electrolyte layer; and an anode layer, wherein the halogen-containing sulfide catholyte in the cathode layer can be reversibly oxidized and reduced.

First claim

What is claimed is:

1 . A lithium ion secondary battery comprising:
a cathode layer comprising
at least a halogen-containing sulfide catholyte comprising a sulfide catholyte and a halide, and
a conducting material;
a solid electrolyte layer; and an anode layer, wherein the halogen-containing sulfide catholyte in the cathode layer can be reversibly oxidized and reduced.

2 . The lithium ion secondary battery of claim 1 , wherein the halogen-containing sulfide catholyte showing the oxidation and reduction capacity has a reversible oxidation and reduction potential of about 1 Volt to about 3.5 Volts vs. Li/Li + .

3 . The lithium ion secondary battery of claim 1 , wherein the halogen-containing sulfide catholyte has a greater discharge capacity than a discharge capacity of the sulfide catholyte.

4 . The lithium ion secondary battery of claim 1 , wherein the lithium ion secondary battery has a discharge capacity of 200 milliampere hours per gram or more after being charged at a voltage of 1.3 Volts vs. Li/Li + .

5 . The lithium ion secondary battery of claim 1 , wherein the halogen-containing sulfide catholyte has an average particle diameter of about 0.01 μm to about 30 μm.

6 . The lithium ion secondary battery of claim 1 , wherein an amount of the halogen-containing sulfide catholyte is in the range of about 30 weight percent to about 95 weight percent, based on a total weight of the cathode layer.

7 . The lithium ion secondary battery of claim 1 , wherein a capacity retention of the lithium secondary ion battery after 50 cycles of charging and discharging in a voltage range of about 1.3 Volts to about 3.1 Volts vs. Li/Li + is 95% or more.

8 . The lithium ion secondary battery of claim 1 , wherein a coulombic efficiency of the lithium secondary ion battery after 50 cycles of charging and discharging in the voltage range of about 1.3 Volts to about 3.1 Volts vs. Li/Li + is 95% or more.

9 . The lithium ion secondary battery of claim 1 , wherein the lithium ion secondary battery does not comprise another cathode active material which is different from the halogen-containing sulfide catholyte.

10 . The lithium ion secondary battery of claim 1 , wherein the cathode layer further comprises another cathode active material which is different from the halogen-containing sulfide catholyte.

11 . The lithium ion secondary battery of claim 10 , wherein the halogen-containing sulfide catholyte has a reversible oxidation-reduction potential range that partially or completely overlaps a reversible oxidation-reduction potential range of the other cathode active material.

12 . The lithium ion secondary battery of claim 10 , wherein the reversible oxidation-reduction potential range of the other cathode active material at least partially overlaps a reversible oxidation-reduction potential range of the halogen-containing sulfide catholyte in the range of 1 Volts to 3.5 Volts vs. Li/Li + .

13 . The lithium ion secondary battery of claim 10 , wherein the reversible oxidation-reduction potential of the other cathode active material is 3.5 Volts vs. Li/Li + or less.

14 . The lithium ion secondary battery of claim 10 , wherein the reversible oxidation-reduction potential of the other cathode active material is 2.5 Volts vs. Li/Li + or less.

15 . The lithium ion secondary battery of claim 10 , wherein, a combination of the other cathode active material and the halogen-containing sulfide catholyte has a greater discharge capacity than a discharge capacity of the other cathode active material.

16 . The lithium ion secondary battery of claim 10 , wherein the other cathode active material comprises LiMO 4 wherein M is Fe, Mn, Ni, or Cu, Li 4/3 Ti 5/3 O 4 , Bi 2 O 3 , Bi 2 Pb 3 O 5 , CuO, V 6 O 13 , LiV 6 O 13 , NbSe 3 , LiNbSe 3 , TiS 2 , FeS, FeS 2 , CuS, Ni 3 S 2 , LiTiS 2 , LiMoS 2 , S, Li 2 S, V 2 O 5 , or a combination thereof.

17 . The lithium ion secondary battery of claim 10 ,
wherein the other cathode active material is sulfur, and wherein the lithium ion secondary battery has a discharge capacity of 1,700 milliampere hours per gram or more charged to a cut-off voltage of 1.3 Volts vs. Li/Li + .

18 . The lithium ion secondary battery of claim 10 , wherein a capacity retention after 50 cycles of charging and discharging in the voltage range of 1.3 Volts to about 3.1 Volts vs. Li/Li + is 95% or more.

19 . The lithium ion secondary battery of claim 10 , wherein a coulombic efficiency after 50 cycles of charging and discharging in the voltage range of 1.3 Volts to about 3.1 Volts vs. Li/Li + is 95% or more.

20 . The lithium ion secondary battery of claim 1 , wherein the sulfide catholyte comprises Li 2 S—P 2 S 5 , Li 2 S—P 2 S 5 —Li 2 O, Li 2 S—SiS 2 , Li 2 S—SiS 2 —B 2 S 3 , Li 2 S—B 2 S 3 , Li 2 S—P 2 S 5 —Z m S n wherein m and n are each an integer and Z is one of Fe, Zn, Ge and Ga, Li 2 S—GeS 2 , Li 2 S—SiS 2 —Li 3 PS 4 , and Li 2 S—SiS 2 —Li p MO q wherein p and q are each a positive number and M is P, Si, Ge, B, Al, Ga, or In, or a combination thereof.

21 . The lithium ion secondary battery of claim 1 , wherein the sulfide catholyte is pLi 2 S-(1-q)5P 2 S 5 wherein 0.50≦p≦0.90.

22 . The lithium ion secondary battery of claim 1 , wherein the sulfide catholyte is 0.75Li 2 S-0.25P 2 5 5 .

23 . The lithium ion secondary battery of claim 1 , wherein the halide is LiX, wherein X comprises Cl, Br, I, or a combination thereof.

24 . The lithium ion secondary battery of claim 1 , wherein the halogen-containing sulfide catholyte is aLiX-(100-a)(0.75Li 2 S-0.25P 2 S 5 ), wherein 0<a<50, and X is Cl, Br, or I.

25 . The lithium ion secondary battery of claim 1 , wherein the halide is LiI.

26 . The lithium ion secondary battery of claim 1 , wherein the halogen-containing sulfide catholyte is 35LiI-65(0.75Li 2 S-0.25P 2 S 5 ).

Assignees

• Samsung Electronics Co Ltd

Inventors

• Ito Seitaro
• Aihara Yuichi

Classifications

• H01M4/131

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

• H01M10/0525

  Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries · CPC title

• H01M4/136 Primary

  Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy · CPC title

• H01M2004/028

  Positive electrodes · CPC title

• H01M4/485

  of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy (H01M4/505, H01M4/525 take precedence) · CPC title