Electrochemical apparatus with barrier layer protected substrate

• US 20080003496A1
• Filed: 06/15/2005
• Published: 01/03/2008
• Est. Priority Date: 08/09/2002
• Status: Abandoned Application

• Current Assignee: Sapurast Research LLC
• Original Assignee: Sapurast Research LLC
• Inventors: Snyder, Shawn, Emerson, Brian, McGraw, Jeanne, Neudecker, Bernd
• Application Number:
  US11/374,282
• Publication Number:
  US 20080003496A1
• Time in Patent Office: Days
• US Class Current: 429/122
• CPC Class Codes: H01M 10/0436 Small-sized flat cells or batteries for portable equipment
• CPC Class Codes: H01M 10/052 Li-accumulators
• CPC Class Codes: H01M 10/0562 Solid materials
• CPC Class Codes: H01M 10/0585 of accumulators having only flat construction elements, i.e. flat positive electrodes, flat negative electrodes and flat separators
• CPC Class Codes: H01M 2004/021 Physical characteristics, e.g. porosity, surface area
• CPC Class Codes: H01M 50/24 adapted for protecting batteries from their environment, e.g. from corrosion thermal insulation H01M10/658
• CPC Class Codes: H01M 6/40 Printed batteries , e.g. thin film batteries
• CPC Class Codes: Y02E 60/10 Energy storage using batteries

Abstract

The present invention relates generally to fabricating well performing thin-film batteries onto metallic substrates, polymeric substrates, and doped and undoped silicon substrates. More specifically, the invention may include fabricating an appropriate diffusion barrier layer between the substrate and the battery part of the present invention that separates said two parts chemically during the entire battery fabrication process and the operation and storage conditions of the electrochemical apparatus during its entire lifetime. In one embodiment of the present invention, thin-film batteries fabricated onto a thin, flexible, stainless steel foil substrate using an appropriate diffusion layer show uncompromised electrochemical performance compared to thin-film batteries fabricated onto ceramic substrates when using a 700° C. post-deposition anneal process for the LiCoO₂ positive cathode.

Claims

1-264. -264. (canceled)

265. An electrochemical apparatus comprising a substrate further comprising a first side, a first electrochemically active cell on said first side, and a first barrier layer on said first side which chemically separates said first electrochemically active cell from said substrate, and wherein:

(a) said first barrier layer is not a pure oxide;

(b) said substrate is not selected from the group Zr and Ti;

(c) said substrate is not Al that is coated with metals or semi-metals selected from the group V, Mn, Mg, Fe, Ge, Cr, Ni, Zn, and Co;

(d) said first electrochemically active cell is not equipped with a Li_xV₂O_y cathode wherein 0<

x≦

100 and 0<

y≦

5;

(e) said first electrochemically active cell is not a solar battery;

(f) said barrier layer comprises an electrically insulating material; and

(g) said substrate is selected from the group consisting of metallic substrate, polymeric substrate, and doped or undoped silicon substrate.

266. The electrochemical apparatus of claim 265 wherein said barrier layer separates chemically said electrochemically active cell from said substrate by virtue of:

(a) its chemical inertness to said electrochemically active cell and said substrate; and

(b) its diffusion blocking properties relative to the electrons or the ions of any of the chemical elements of said electrochemically active cell and said substrate;

during the entire fabrication of said electrochemically active cell onto said substrate and during all operation and storage conditions of said electrochemical apparatus.

267. The electrochemical apparatus of claim 265 wherein:

(a) said barrier layer comprises an electrically conducting or electrically semi-conducting material;

(b) the electrical separation of the positive cathode and the negative anode is given either by the negative part of said electrochemically active cell not making contact to said barrier layer or the positive part of said electrochemically active cell not making contact to said barrier layer;

(c) said negative part of said electrochemically active cell comprises the negative anode, the anode current collector, and the negative terminal; and

(d) said positive part of said electrochemically active cell comprises the positive cathode, the cathode current collector, and the positive terminal.

268. The electrochemical apparatus of claim 265 wherein said barrier layer comprises a plurality of individual sub-layers that are selected from the group of electrically conducting, electrically insulating, and electrically semi-conducting materials and wherein the positive part of said electrochemically active cell is not in electrical contact with the negative part.

269. The electrochemical apparatus of claim 268 wherein said sub-layers exhibit all the same shape and area size.

270. The electrochemical apparatus of claim 268 wherein at least one of said sub-layers exhibits a different shape and area size than the other sub-layers.

271. The electrochemical apparatus of claim 265 wherein said barrier layer is adapted to cover said substrate only partially so that at least the positive part of said electrochemically active cell is separated from said substrate.

272. The electrochemical apparatus of claim 265 wherein said barrier layer is adapted to cover said substrate only partially so that at least the negative part of said electrochemically active cell is chemically separated from said substrate.

273. The electrochemical apparatus of claim 268 wherein said barrier layer and said individual sub-layers comprises a chemical compound selected from the group of metals, semi-metals, alloys, borides, carbides, diamond, diamond-like carbon, silicides, nitrides, phosphides, fluorides, chlorides, bromides, iodides, or from the group of any multinary compounds composed of borides, carbides, silicides, nitrides, phosphides, oxides, fluorides, chlorides, bromides, and iodides.

274. The electrochemical apparatus of claim 268 wherein said barrier layer and said individual sub-layers is selected from the group consisting of a single phase of crystalline, nano-crystalline, amorphous, or glassy material or any poly phase mixture or composite.

275. The electrochemical apparatus of claim 265 wherein said electrochemically active cell comprises a battery that operates based on lithium chemistry, thus comprising lithium metal batteries, lithium-ion batteries, and lithium free batteries.

276. The electrochemical apparatus of claim 265 wherein said electrochemically active cell comprises a positive thin-film cathode that is either deposited by a vacuum vapor deposition process or by a non-vacuum vapor deposition process and wherein the thickness of said positive thin-film cathode comprises less than 200 micro-meters.

277. The electrochemical apparatus of claim 276 wherein:

(a) said positive thin-film cathodes comprises single crystallites having a size of at least

(b) said electrochemically active cell further comprises a thin-film solid-state electrolyte having a thickness of less than 100 micro-meters;

(c) the thickness of said substrate is within the range of 0.1 micro-meters to 1 cm; and

(d) the thickness of said barrier layer ranges from 0.01 micro-meters to 1 mm.

278. The electrochemical apparatus of claim 265 wherein said electrochemically active cell comprises a thin-film negative anode selected from the group of lithium metal, lithium-ion anode, or a metal that does not form inter-metallic compounds with lithium and wherein the thickness of said thin-film negative anode is less than 200 micro-meters.

279. The electrochemical apparatus of claim 265 wherein said electrochemically active cell comprises a battery that operates based on lithium chemistry, thus comprising lithium metal batteries, lithium-ion batteries, and lithium-free batteries.

280. An electrochemical apparatus comprising a substrate with a first side, a first electrochemically active cell on said first side, and a first barrier layer on said first side which is adapted to chemically separate said first electrochemically active cell from said substrate;

and with a second side, a second electrochemically active cell on said second side, and a second barrier layer on said second side which chemically separates said second electrochemically active cell from said substrate and wherein;

(a) said barrier layers on both substrate sides are not pure oxides;

(b) said substrate is not selected from the group Zr and Ti;

(c) said substrate does not comprise Al that is coated with metals or semi-metals selected from the group V, Mn, Mg, Fe, Ge, Cr, Ni, Zn, and Co;

(d) said electrochemically active cells on both substrate sides are not equipped with a Li_xV₂O_y cathode wherein 0<

x≦

100 and 0<

y≦

5;

(e) said electrochemically active cells on both substrate sides are not solar batteries; and

(f) said substrate is selected from the group consisting of metallic substrate, polymeric substrate, and doped or undoped silicon substrate.

and wherein said barrier layers on both sides of said substrate separate chemically said electrochemically active cells from said substrate by virtue of;

(g) the chemical inertness of said first barrier layer on said first side of said substrate relative to said first electrochemically active cell on said first side of said substrate and relative to said substrate;

(h) the chemical inertness of said second barrier layer on said second side of said substrate relative to said second electrochemically active cell on said second side of said substrate and relative to said substrate;

(i) the diffusion blocking properties of said first barrier layer on said first side of said substrate relative to the electrons or the ions of any of the chemical elements of said first electrochemically active cell on said first side of said substrate; and

(j) the diffusion blocking properties of said second barrier layer on said second side of said substrate relative to the electrons or the ions of any of the chemical elements of said second electrochemically active cell on said second side of said substrate during the entire fabrication of said first electrochemically active cell on said first side of said substrate and said second electrochemically active cell on said second side of said substrate and during all operation and storage conditions of said electrochemical apparatus.

281. The method of fabricating an electrochemical apparatus comprising the following step sequence:

(a) providing a substrate with a first and a second side wherein said substrate is selected from the group consisting of metallic substrate, polymeric substrate, and doped or undoped silicon substrate;

(b) depositing a first barrier layer on said first side;

(c) depositing a second barrier layer on said second side;

(d) fabricating a first electrochemically active cell on said first side on top of said first barrier layer, which in turn chemically separates said first electrochemically active cell from said substrate;

(e) fabricating a second electrochemically active cell on said second side on top of said second barrier layer, which in turn chemically separates said second electrochemically active cell from said substrate;

(f) wherein said first barrier layer and said second barrier layer are not selected to be a pure oxide;

(g) wherein said substrate is not selected from the group Zr and Ti;

(h) wherein said substrate is not selected to be Al that is coated with metals or semi-metals selected from the group V, Mn, Mg, Fe, Ge, Cr, Ni, Zn, and Co;

(i) wherein said first electrochemically active cell and said second electrochemically active cell are not equipped with a Li_xV₂O_y cathode wherein 0<

x≦

100 and 0<

y≦

5; and

(j) wherein said first electrochemically active cell and said second electrochemically active cell are not used as solar batteries.

282. The method of claim 281 wherein said steps of fabricating a first and/or a second electrochemically active cell comprises providing a positive cathode, and wherein said positive cathode of said first and/or second electrochemically cell is fabricated by an in-situ (during deposition) or ex-situ (post-deposition) temperature process between 100-1000°

C. in order to accomplish that the positive cathode comprises crystallites having a size of at least 100 Å

.