Protection layers for metal anodes

Patent metadata

Field	Value
Publication number	US-2017263935-A1
Application number	US-201515517126-A
Country	US
Kind code	A1
Filing date	Oct 5, 2015
Priority date	Oct 6, 2014
Publication date	Sep 14, 2017
Grant date	—

Abstract

A protection layer is formed on a highly-reactive substantially-pure metal anode to a thickness of between 1 nm and 200 nm, inclusive, using atomic layer deposition (ALD). The ALD protection layer allows the conduction of ions of the metal of the anode therethrough but suppresses electron transport therethrough. The ALD protection layer may also be effective to inhibit passage of air and/or water therethrough. The ALD protection layer can allow more relaxed purity requirements for subsequent battery assembly, electrolyte specifications, and/or cathode gas purity. Fabrication methods for the protection layers, protected metal anodes, and systems and devices incorporating such protected metal anodes are also disclosed herein.

First claim

1 . A battery comprising:
an anode consisting essentially of a pure metal selected from Group I and Group II materials, or mixtures of pure metals selected from Group I and Group II materials; a cathode; an electrolyte disposed between the anode and the cathode; and a protection layer formed on the anode by atomic layer deposition, wherein the protection layer allows ions of the pure metal or metals to pass therethrough while inhibiting electron passage therethrough.

2 - 3 . (canceled)

4 . The battery of claim 1 ,
wherein the pure metal or metals of the anode includes one or more of Li, Na, Mg, Al, and Ca, and wherein the protection layer comprises a metal oxide, a metal phosphate, or a hybrid inorganic-organic material.

5 . The battery of claim 4 , wherein the protection layer comprises at least one of Al 2 O 3 , TiO 2 , V 2 O 5 , L 3 PO 4 , Li x PO y N z (LiPON), Li x Al y Ti z P (LATP), an alucone, and a titanocone.

6 . The battery of claim 1 ,
wherein the protection layer comprises a solid electrolyte or a material that reacts with the metal or metals of the anode to form a solid electrolyte.

7 - 14 . (canceled)

15 . The battery of claim 1 ,
wherein the cathode comprises carbon, sulfur, oxygen, air, a metal oxide, or a metal sulfide, and wherein the electrolyte comprises an organic electrolyte, liquid electrolyte, a gel electrolyte, or a solid electrolyte.

16 - 18 . (canceled)

19 . The battery of claim 1 , wherein the protection layer comprises islands separated from each other by gaps, and further comprising a solid electrolyte interphase formed in the gaps by interaction of the anode and the electrolyte such that primary ionic transport of the metal or metals of the anode is substantially through the protection layer islands.

20 . An electrochemical electrode comprising:
a structure consisting essentially of a pure metal selected from Group I and Group II materials, or mixtures of pure metals selected from Group I and Group II materials; and a protection layer formed on the structure by atomic layer deposition, wherein the protection layer allows ions of the pure metal or metals to pass therethrough while inhibiting passage of at least air and water therethrough.

21 . The electrochemical electrode of claim 20 , wherein the protection layer inhibits electron passage therethrough.

22 - 23 . (canceled)

24 . The electrochemical electrode of claim 20 ,
wherein the pure metal or metals of the structure includes one or more of Li, Na, Mg, Al, and Ca, and wherein the protection layer comprises a metal oxide, a metal phosphate, or a hybrid inorganic-organic material.

25 . The electrochemical electrode of claim 24 , wherein the protection layer comprises at least one of Al 2 O 3 , TiO 2 , V 2 O 5 , Li 3 PO 4 , Li x PO y N z (LiPON) , Li x Al y Ti z P (LATP), an alucone, and a titanocone.

26 . The electrochemical electrode of claim 20 ,
wherein the protection layer comprises a solid electrolyte or a material that reacts with the metal or metals of the structure to form a solid electrolyte.

27 - 28 . (canceled)

29 . The electrochemical electrode of claim 20 , wherein the protection layer comprises at least one layer with a composition or property that varies in a thickness direction of the at least one layer.

30 - 92 . (canceled)

93 . A fabrication method comprising:
depositing a protection layer on a substrate by an atomic layer deposition process comprising:
(a) flowing a lithium tert-butoxide (LiOtBu) into contact with the substrate;
(b) flowing an oxidant into contact with the substrate;
(c) flowing trimethylphosphate (TMP) into contact with the substrate; and
(d) flowing nitrogen (N 2 ) into contact with the substrate.

94 . The fabrication method of claim 93 , wherein the oxidant in (b) comprises deionized water (H 2 O), ethylene glycol, or dimethyl sulfoxide.

95 . (canceled)

96 . The fabrication method of claim 93 , wherein the substrate has a hydroxyl-terminated surface on which the protection layer is deposited

97 . The fabrication method of claim 93 , wherein (a)-(d) are repeated to yield a desired thickness for the deposited protection layer.

98 . (canceled)

99 . The fabrication method of claim 97 , wherein in repeating (a)-(d), variations are introduced such that a composition or property of the deposited protection layer varies in a thickness direction thereof.

100 - 103 . (canceled)

104 . The fabrication method of claim 93 ,
wherein the substrate is formed of a substantially pure metal selected from Group I and Group II materials, or mixtures of substantially pure metals selected from Group I and Group II materials, and wherein the substantially pure metal or metals of the electrochemical electrode includes one or more of Li, Na, Mg, Al, and Ca.

105 - 108 . (canceled)

109 . The fabrication method of claim 93 ,
wherein an intermediate layer is between the deposited protection layer and the substrate, wherein the intermediate layer is a thin layer of oxide or other species that does not interfere with ion transport of metal or metals of the substrate, and the fabrication method further comprising, prior to the depositing the protection layer, forming the intermediate layer on the substrate.

110 - 111 . (canceled)

112 . The fabrication method of claim 93 , wherein (d) comprises flowing nitrogen (N 2 ) gas into contact with the substrate, with the nitrogen gas excited in a plasma discharge.

113 - 120 . (canceled)

Assignees

• Univ Maryland

Inventors

• Kozen Alexander C
• Schroeder Marshall A
• Rubloff Gary W
• Hu Liangbing
• Noked Malakhi
• Lee Sang Bok

Classifications

• H01M10/0525

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

• H01M4/366

  as layered products · CPC title

• H01M4/62 Primary

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

• H01M2004/027

  Negative electrodes · CPC title

• Y02E60/10

  Energy storage using batteries · CPC title