Lithium metal battery

Patent metadata

Field	Value
Publication number	US-2017062829-A1
Application number	US-201615230593-A
Country	US
Kind code	A1
Filing date	Aug 8, 2016
Priority date	Aug 31, 2015
Publication date	Mar 2, 2017
Grant date	—

Abstract

A lithium metal battery including: a lithium metal anode; a protective layer disposed on the lithium metal anode, the protective layer including: a polymer and at least one selected from a metal salt including a Group 1 and Group 2 element and a nitrogen-containing additive; a cathode; and a liquid electrolyte disposed between the protective layer and the cathode, the liquid electrolyte including an organic solvent, wherein the at least one selected from metal salt and a nitrogen-containing additive comprising a Group 1 element or Group 2 element is insoluble in the organic solvent of the liquid electrolyte.

First claim

What is claimed is:

1 . A lithium metal battery comprising:
a lithium metal anode; a protective layer disposed on the lithium metal anode, the protective layer comprising: i) a polymer and ii) at least one selected from a metal salt comprising a Group 1 or a Group 2 element and a nitrogen-containing additive; a cathode; and a liquid electrolyte disposed between the protective layer and the cathode, the liquid electrolyte comprising an organic solvent, wherein the at least one selected from metal salt and a nitrogen-containing additive comprising a Group 1 element or Group 2 element is insoluble in the organic solvent of the liquid electrolyte.

2 . The lithium metal battery of claim 1 , wherein the metal salt comprises at least one selected from Cs, Rb, K, Ba, Sr, Ca, Na, and Mg.

3 . The lithium metal battery of claim 1 , wherein the metal salt is at least one selected from Cs(bis(trifluoromethylsulfonyl)imide), CsNO 3 , CsPF 6 , Cs(bis(fluorosulfonyl)imide), CsAsF 6 , CsClO 4 , CsBF 4 , Rb(bis(trifluoromethylsulfonyl)imide), RbNO 3 , RbPF 6 , Rb(bis(fluorosulfonyl)imide), RbAsF 6 , RbClO 4 , RbBF 4 , K(bis(trifluoromethylsulfonyl)imide), KNO 3 , KPF 6 , K(bis(fluorosulfonyl)imide), KAsF 6 , KClO 4 , KBF 4 , Na(bis(trifluoromethylsulfonyl)imide), NaNO 3 , NaPF 6 , Na(bis(fluorosulfonyl)imide), NaAsF 6 , NaClO 4 , NaBF 4 , Ba(bis(trifluoromethylsulfonyl)imide) 2 , Ba(NO 3 ) 2 , Ba(PF 6 ) 2 , Ba(bis(fluorosulfonyl)imide) 2 , Ba(AsF 6 ) 2 , Ba(ClO 4 ) 2 , Ba(BF 4 ) 2 , Sr(bis(trifluoromethylsulfonyl)imide) 2 , Sr(NO 3 ) 2 , Sr(PF 6 ) 2 , Sr(bis(fluorosulfonyl)imide) 2 , Sr(AsF 6 ) 2 , Sr(ClO 4 ) 2 , Sr(BF 4 ) 2 , Ca(bis(trifluoromethylsulfonyl)imide) 2 , Ca(NO 3 ) 2 , Ca(PF 6 ) 2 , Ca(bis(fluorosulfonyl)imide) 2 , Ca(AsF 6 ) 2 , Ca(ClO 4 ) 2 , Ca(BF 4 ) 2 , Mg(bis(trifluoromethylsulfonyl)imide) 2 , Mg(NO 3 ) 2 , Mg(PF 6 ) 2 , Mg(bis(fluorosulfonyl)imide) 2 , Mg(AsF 6 ) 2 , Mg(ClO 4 ) 2 , and Mg(BF 4 ) 2 .

4 . The lithium metal battery of claim 1 , wherein the nitrogen-containing additive is at least one selected from an inorganic nitrate, an organic nitrate, an inorganic nitrite, an organic nitrite, an organic nitro compound, an organic nitroso compound, an N—O compound, and lithium nitride.

5 . The lithium metal battery of claim 4 , wherein the inorganic nitrate is at least one selected from lithium nitrate, potassium nitrate, cesium nitrate, barium nitrate, and ammonium nitrate,
the organic nitrate is at least one selected from a C1 to C20 dialkyl imidazolium nitrate, guanidine nitrate, ethyl nitrate, propyl nitrate, butyl nitrate, pentyl nitrate, and octyl nitrate, the organic nitrite is at least one selected from ethyl nitrite, propyl nitrite, butyl nitrite, pentyl nitrite, and octyl nitrite, the organic nitro compound is at least one selected from nitromethane, nitropropane, nitrobutane, nitrobenzene, dinitrobenzene, nitrotoluene, dinitrotoluene, and nitropyridine, and the N—O compound is at least one selected from pyridine N-oxide, C1 to C20 alkylpyridine N-oxide, and tetramethyl piperidine N-oxyl.

6 . The lithium metal battery of claim 1 , wherein an amount of the metal salt and the nitrogen-containing additive in the protective layer is from about 0.1 part to about 100 parts by weight, based on 100 parts by weight of the polymer.

7 . The lithium metal battery of claim 1 ,
wherein the protective layer comprises the metal salt and the nitrogen-containing additive, wherein an amount of the metal salt is from about 0.01 part to about 99.99 parts by weight, based on 100 parts by weight of the polymer, and wherein an amount of the nitrogen-containing additive is from about 0.01 part to about 99.99 parts by weight, based on 100 parts by weight of the polymer.

8 . The lithium metal battery of claim 1 ,
wherein the protective layer comprises the metal salt and the nitrogen-containing additive, and wherein a mixed weight ratio of the metal salt to the nitrogen-containing additive is from about 1:9 to about 9:1.

9 . The lithium metal battery of claim 1 , wherein the polymer is at least one copolymer selected from a homopolymer, a block copolymer, and a graft copolymer.

10 . The lithium metal battery of claim 9 , wherein the homopolymer is at least one selected from polyvinyl alcohol, polymethylmethacrylate, polymethylacrylate, polyethylmethacrylate, polyethylacrylate, polypropylmethacrylate, polypropylacrylate, polybutylacrylate, polybutylmethacrylate, polypentylmethacrylate, polypentylacrylate, polycyclohexylmethacrylate, polycyclohexylacrylate, polyhexylmethacrylate, polyhexylacrylate, poly(glycidylacrylate), polyglycidylmethacrylate, and polyvinylidene fluoride.

11 . The lithium metal battery of claim 1 , wherein the polymer is a block copolymer comprising a first polymer block and a second polymer block,
wherein the first polymer block comprises at least one selected from polystyrene, hydrogenated polystyrene, polymethacrylate, poly(methyl methacrylate), polyvinylpyridine, polyvinyl cyclohexane, polyimide, polyamide, polyethylene, polybutylene, polypropylene, poly(4-methyl 1-pentene), poly(butylene terephthalate), poly(isobutyl methacrylate), poly(ethylene terephthalate), polydimethylsiloxane, polyvinylidene fluoride, polymaleic acid, poly(maleic anhydride), polymethacrylic acid, poly(tert-butyl vinyl ether), poly(cyclohexyl methacrylate), poly(cyclohexyl vinyl ether), and polydivinylbenzene; or a polymer comprising at least two repeating units of these polymers, and wherein the second polymer block is at least one selected from polyethylene oxide, polypropylene oxide, polymethylmethacrylate, polyethylmethacrylate, polydimethylsiloxane, polyacrylic acid, polymethacrylic acid, polymethylacrylate, polyethylacrylate, poly-2-ethylhexyl acrylate, polybutyl methacrylate, poly-2-ethylhexylmethacrylate, poly(decyl acrylate), polyethylene vinyl acetate, polyimide, polyamine, polyamide, poly(C1 to C20 alkyl carbonate), polynitrile, polyphosphazine, polyolefin, polydiene, polyisoprene, polybutadiene, polychloroprene, polyisobutylene, polyurethane, polyethylene, polybutylene, and polypropylene.

12 . The lithium metal battery of claim 1 , wherein the lithium metal battery further comprises an ion-conductive thin film disposed between the lithium metal anode and the protective layer.

13 . The lithium metal battery of claim 1 , wherein an amount of the at least one of a metal salt and a nitrogen-containing additive in the protective layer increases in a direction from the liquid electrolyte towards the lithium metal anode.

14 . The lithium metal battery of claim 1 , wherein the protective layer further comprises at least one selected from an inorganic particle, an ionic liquid, a polymer ionic liquid, and an oligomer.

15 . The lithium metal battery of claim 14 , wherein the inorganic particle comprises at least one selected from SiO 2 , TiO 2 , ZnO, Al 2 O 3 , BaTiO 3 , a cage-structured silsesquioxane, and a metal-organic framework.

16 . The lithium metal battery of claim 14 , wherein an amount of the inorganic particle is from about 1 part to about 40 parts by weight, based on 100 parts by weight of the polymer.

17 . The lithium metal battery of claim 14 , wherein the ionic liquid is at least one compound each comprising:
i) a cation selected from an ammonium cation, a pyrrolidinium cation, a pyridinium cation, a pyrimidinium cation, an imidazolium cation, a piperidinium cation, a pyrazolium cation, an oxazolium cation, a pyridazinium cation, a phosphonium cation, a sulfonium cation, and a triazolium cation; and ii) an anion selected from BF 4 −

Assignees

• Samsung Electronics Co Ltd
• Samsung Sdi Co Ltd

Inventors

• Ryu Saebom
• Lee Yonggun
• Park Joungwon
• Sugimoto Toshinori

Classifications

• H01M10/4235

  Safety or regulating additives or arrangements in electrodes, separators or electrolyte (H01M10/4242 takes precedence) · CPC title

• H01M4/366

  as layered products · CPC title

• H01M10/058 Primary

  Construction or manufacture · CPC title

• H01M4/628 Primary

  Inhibitors, e.g. gassing inhibitors, corrosion inhibitors · CPC title

• H01M4/62

  Selection of inactive substances as ingredients for active masses, e.g. binders, fillers · CPC title