Anodic Dendritic Growth Suppression System for Secondary Lithium Batteries
Provided herein are methods for manufacturing lithium-metal anode [ 18] assemblies for thin-film, thick-film and hulk secondary batteries that use liquid or gel-type electrolytes [ 14], and lithium-metal anode [ 18] assemblies for thick-film and bulk secondary batteries that use solid electrolytes [ 18]. These methods involve electrolytic formation of a lithium metal anode [ 18] between a protecting lithium-stable, solid electrolyte [ 18] material and an eieethcaiiy-Gonductive substance [ 20 ]. Secondary lithium_ batteries made by these methods aw also provided.
1 . An anode assembly designed in use to be a component of a secondary lithium battery, said anode assembly comprising:
a. an electronically-conductive substrate;
b. a lithium metal anode in contact with said substrate; and
c. an electronically-insulating, lithium ion-conducting, lithium-stable, solid electrolyte covering said lithium metal anode.
2 . The anode assembly of claim 1 designed to be a component of a thin-film secondary lithium battery wherein said lithium metal anode has a thickness of between about 0.2 and about 2 μm.
3 . The anode assembly of claim 1 designed in use to be a component of a thick-film lithium secondary battery; wherein said lithium metal anode has a thickness of between about 2 and about 10 μm.
4 . The anode assembly of claim 1 designed in use to be a component of a bulk lithium secondary battery; wherein said lithium metal anode has a thickness of between about 10 and about 100 μm.
5 . The anode assembly of any of claims 1 - 4 wherein said substrate is comprised of a material selected from the group consisting of stainless steel, iron, gold, copper, transition metals that do not form intermetallic compounds with lithium, and glass or a plastic onto which an electrically-conductive film has been deposited.
6 . The anode assembly of any of claims 1 - 5 wherein said electronically-insulating, lithium ion-conducting, lithium-stable, solid electrolyte is made of a material selected from the group consisting of lithium silicates, lithium borates, lithium aluminates, phosphates, lithium phosphorus oxynitrides, lithium silicosulfides, lithium borosulfides, lithium aluminosulfides, and lithium phosphosulfides.
7 . The anode assembly of claim 6 wherein said electronically-insulating, lithium ion-conducting, lithium-stable, solid electrolyte is made of Lipon.
8 . A thick-film or bulk secondary lithium battery comprising the anode assembly of any of claims 1 - 7 .
9 . A thin-film battery comprising the anode assembly of any of claims 1 - 7 and additionally comprising a liquid or gel-type electrolyte.
10 . A method of making an anode assembly for a lithium-metal secondary battery, said method comprising:
a. providing an electronically-conductive substrate;
b. at least partially covering said substrate with an electronically-insulating, lithium ion-conducting, lithium-stable, solid electrolyte material;
c. providing a lithium-containing cathode material;
d. providing an electrolyte bath sized to receive said cathode material and said substrate that is at least partially covered with said solid electrolyte material;
e. placing said cathode and said substrate that is at least partially covered with said solid electrolyte material into said electrolyte bath; and
f. flowing an electrical current between said substrate and said cathode, whereby a lithium metal anode is deposited on said substrate through said solid electrolyte material.
11 . The method of claim 10 wherein said substrate is comprised of a material selected the group consisting of stainless steel, iron, gold, copper, transition metals that do not form intermetallic compounds with lithium, and glass or a plastic onto which an electrically-conductive film has been deposited.
12 . The method of claim 10 or 11 wherein said electronically-insulating, lithium ion-conducting, lithium-stable, solid electrolyte material is selected from the group consisting of lithium silicates, lithium borates, lithium aluminates, lithium phosphates, lithium phosphorusoxynitrides, lithium silicosulfides, lithium borosulfides, lithium aluminosulfides, and lithium phosphosulfides.
13 . The method of any of claims 10 - 12 wherein said electronically-insulating, lithium ion-conducting, lithium-stable, solid electrolyte material is Lipon.
14 . The method of any of claims 10 - 13 wherein said lithium-containing cathode material is selected from the group consisting of lithium vanadate, lithium manganate, lithium nickelate, and lithium cobaltate.
15 . The method of any of claims 10 - 14 wherein said electrolyte bath is a container comprising an electrolyte solution selected from the group consisting of: LiClO 4 —PC, LiPF 6 -EC-DMC, and LiBF 4 -EMC.
16 . The method of any of claims 10 - 15 wherein said lithium metal anode is deposited to a thickness of between about 100 nm and about 2 μm.
17 . The method of any of claims 10 - 15 wherein said lithium metal anode is deposited to a thickness of between about 2 μm and about 10 μm.
18 . The method of any of claims 10 - 15 wherein said lithium metal anode is deposited to a thickness of between about 10 μm and about 100 μm.
19 . A secondary lithium battery comprising the anode assembly made by the method of any of claims 10 - 18 comprising a liquid or gel-type electrolyte, wherein said lithium metal anode is prevented from contact with said liquid or gel-type electrolyte by said electronically-insulating, lithium ion-conducting, lithium-stable, solid electrolyte material.
20 . A thick-film or bulk secondary lithium battery made by the method of any of claims 10 - 18 comprising a solid electrolyte as the only electrolyte, wherein said solid electrolyte is comprised entirely of said electronically-insulating, lithium ion-conducting, lithium-stable, solid electrolyte material; or is comprised of one or more second solid electrolyte material(s), in contact with said electronically-insulating, lithium ion-conducting, lithium-stable, solid electrolyte material.
21 . An electrically-powered device comprising the secondary battery of claim 19 or 20 .
22 . A method of providing an electric current to a device comprising:
a. placing in operative electrical connection with said device, a secondary lithium battery comprising:
i. a lithium metal anode;
ii. a liquid or gel-type electrolyte; and
iii. a lithium-stable, electrically insulating, lithium-ion-conducting solid electrolyte material covering said lithium metal anode so as to prevent contact between said anode and said liquid or gel-type electrolyte; and
b. activating said battery to provide an electrical current to said device.
23 . A method of providing an electric current to a device comprising:
a. placing in operative electrical connection with said device, a thick-film or bulk secondary lithium battery comprising:
i. a lithium metal anode;
ii. an electrically-insulating, lithium-ion-conducting, lithium-stable, solid first electrolyte covering said lithium metal anode; and
iii. a solid-state second electrolyte in contact with said lithium-stable solid first electrolyte;
wherein said first electrolyte prevents direct contact between said anode and said liquid second electrolyte; and
b. activating said battery to provide an electrical current to said device.
24 . A method of recharging a lithium battery comprising flowing an electric current into an anode of a secondary lithium battery that comprises:
a. a lithium metal anode;
b. a liquid or gel-type electrolyte; and
c. a lithium-stable, electrically insulating, lithium-ion-conducting solid electrolyte layer situated between said anode and said liquid or gel-type electrolyte so as to prevent contact therebetween;
whereby dendrite formation on said lithium metal anode is prevented.