Solid state catholytes and electrolytes for energy storage devices

• US 9,819,024 B2
• Filed: 01/11/2017
• Issued: 11/14/2017
• Est. Priority Date: 05/15/2013
• Status: Active Grant

• Current Assignee: Quantumscape Battery Incorporated
• Original Assignee: Quantumscape Corporation
• Inventors: Chao, Cheng-Chieh, Chen, Zhebo, Holme, Tim, Mayer, Marie A., Riley, Jr., Gilbert N.
• Primary Examiner(s): HARRIS, GARY D
• Application Number:
  US15/404,179
• Publication Number:
  US 20170149065A1
• Time in Patent Office: 307 Days
• Field of Search: 429144, 429322
• CPC Class Codes: C01B 33/00 Silicon; Compounds thereof C01B6/00, C01B21/00, C01B23/00 take precedence; persilicates C01B15/14; carbides C01B32/956
• CPC Class Codes: C01P 2006/40 Electric properties
• CPC Class Codes: C04B 2235/3203 Lithium oxide or oxide-forming salts thereof
• CPC Class Codes: C04B 2235/428 Silicon
• CPC Class Codes: C04B 2235/446 Sulfides, tellurides or selenides
• CPC Class Codes: C04B 2235/447 Phosphates or phosphites, e.g. orthophosphate or hypophosphite
• CPC Class Codes: C04B 35/547 based on sulfides or selenides or tellurides
• CPC Class Codes: C04B 35/6261 Milling
• CPC Class Codes: C04B 35/6262 of calcined, sintered clinker or ceramics
• CPC Class Codes: C04B 35/62645 Thermal treatment of powders or mixtures thereof other than sintering
• CPC Class Codes: H01M 10/0525 Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
• CPC Class Codes: H01M 10/056 characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
• CPC Class Codes: H01M 10/0562 Solid materials
• CPC Class Codes: H01M 2220/20 Batteries in motive systems, e.g. vehicle, ship, plane
• CPC Class Codes: H01M 2220/30 Batteries in portable systems, e.g. mobile phone, laptop
• CPC Class Codes: H01M 2300/0068 inorganic
• CPC Class Codes: H01M 2300/0071 Oxides
• CPC Class Codes: H01M 2300/0074 Ion conductive at high temperature
• CPC Class Codes: H01M 4/131 Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
• CPC Class Codes: H01M 4/136 Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
• CPC Class Codes: H01M 4/366 : as layered products
• CPC Class Codes: H01M 4/505 : of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
• CPC Class Codes: H01M 4/525 : of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
• CPC Class Codes: H01M 4/582 : Halogenides
• CPC Class Codes: H01M 4/5825 : Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
• CPC Class Codes: H01M 4/62 : Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
• CPC Class Codes: H01M 4/624 : Electric conductive fillers
• CPC Class Codes: H01M 50/46 : Separators, membranes or diaphragms characterised by their combination with electrodes
• CPC Class Codes: Y02E 60/10 : Energy storage using batteries
• CPC Class Codes: Y02P 70/50 : Manufacturing or production processes characterised by the final manufactured product
• CPC Class Codes: Y02T 10/70 : Energy storage systems for electromobility, e.g. batteries

Abstract

The present invention provides an energy storage device comprising a cathode region or other element. The device has a major active region comprising a plurality of first active regions spatially disposed within the cathode region. The major active region expands or contracts from a first volume to a second volume during a period of a charge and discharge. The device has a catholyte material spatially confined within a spatial region of the cathode region and spatially disposed within spatial regions not occupied by the first active regions. In an example, the catholyte material comprises a lithium, germanium, phosphorous, and sulfur (“LGPS”) containing material configured in a polycrystalline state. The device has an oxygen species configured within the LGPS containing material, the oxygen species having a ratio to the sulfur species of 1:2 and less to form a LGPSO material. The device has a protective material formed overlying exposed regions of the cathode material to substantially maintain the sulfur species within the catholyte material. Also included is a novel dopant configuration of the Li_aMP_bS_c (LMPS) [M=Si, Ge, and/or Sn] containing material.

Claims

1. A method of making a catholyte material, comprising providing catholyte precursor materials;

ball milling the catholyte precursor materials;

annealing the catholyte precursor materials to form a catholyte; and

ball milling the catholyte to a median particle size of less than about 1 um and greater than 20 nm;

wherein the catholyte precursor materials are selected from LiS, P₂Ss, SiS₂, Si, S, and combinations thereof.

2. The method of claim 1, wherein the annealing is at 500°

C. to 600°

C.

3. The method of claim 1, wherein the annealing is at 400°

C. to 600°

C.