Glass ceramic with ion-conducting residual glass phase and process for the production thereof

Patent metadata

Field	Value
Publication number	US-2019241463-A1
Application number	US-201916266552-A
Country	US
Kind code	A1
Filing date	Feb 4, 2019
Priority date	Feb 2, 2018
Publication date	Aug 8, 2019
Grant date	—

Abstract

The present disclosure relates to a lithium ion-conducting glass ceramic which comprises a residual glass phase that is also ion-conducting, a process for the production thereof as well as its use in a battery. The glass ceramic according to the present disclosure comprises a main crystal phase which is isostructural to the NaSICon crystal phase, wherein the composition can be described with the following formula: Li1+x−yMy5+M2−x−y4+(PO4)3, wherein x is greater than 0 and at most 1, as well as greater than y. Y may take values of between 0 and 1. Here, the following boundary condition has to be fulfilled: (1+x−y)>1. Here, M represents a cation with io the valence of +3, +4 or +5. M3+is selected from Al, Y, Sc or B, wherein at least Al as trivalent cation is present. Independently thereof, M4+ is selected from Ti, Si or Zr, wherein at least Ti as tetravalent cation is present. Independently thereof, M5+ is selected from Nb, Ta or La.

First claim

What is claimed is:

1 . A lithium ion-conductive glass ceramic, wherein the glass ceramic comprises a crystal phase having the chemical composition
Li 1+x−y M y 5+ M x 3+ M 2−x−y 4+ (PO 4 ) 3 , wherein: M 3+ =a trivalent cation of one or more elements, M 4+ =a tetravalent cation of one or more elements, M 5+ =a pentavalent cation of one or more elements, x is greater than 0 and at most 1, x is greater than y, y is 0 to 1, wherein (1+x−y) is greater than 1, wherein at least Al 3+ as trivalent ion and at least Ti 4+ as tetravalent ion are contained, wherein the glass ceramic comprises a glass phase with an ionic conductivity of higher than 10 −5 S/cm, wherein the composition of the glass phase comprises Li 2 O, P 2 O 5 and B 2 O 3 and the content of B 2 O 3 has values of 0.2 mole % to 4 mole % and wherein the ratio of Al 2 O 3 /TiO 2 has values of between 0.05 to 0.1, and wherein the ratio of Al 2 O 3 /Li 2 O has values of between >0 and 0.25.

2 . The glass ceramic according to claim 1 , wherein the main crystal phase Li 1+x−y M y 5+ M x 3+ M 2−x−y (PO 4 ) 3 contains only Al 3+ as trivalent ion and only Ti 4+ as tetravalent ion.

3 . The glass ceramic according to claim 1 , wherein after the glass ceramic is ceramicized and/or sintered at a temperature of <1000° C., the glass ceramic has a total conductivity of higher than 10 −4 S/cm at 22° C.

4 . The glass ceramic according to claim 1 , wherein after the glass ceramic is ceramicized and/or sintered at a temperature of <900° C. the glass ceramic has a total conductivity of higher than 10 −4 S/cm at 22° C.

5 . The glass ceramic according to claim 1 , wherein the residual glass phase consists essentially of the components Li 2 O, B 2 O 3 and P 2 O 5 .

6 . The glass ceramic according to claim 1 , wherein the content of B 2 O 3 is from 0.3 mole % to 3 mole %.

7 . The glass ceramic according to claim 1 , wherein the content of B 2 O 3 is from 0.5 mole % to 2.5 mole %.

8 . The glass ceramic according to claim 1 , wherein the ratio of Al 2 O 3 /Li 2 O is less than 0.24.

9 . The glass ceramic according to one of the preceding claims, wherein the ratio of Al 2 O 3 /Li 2 O is less than 0.22.

10 . The glass ceramic according to claim 1 , wherein the glass ceramic comprises the following composition in mole %:
1-6% of Al 2 O 3 , 12-28% of Li 2 O, 32-42% of P 2 O 5 , 28-45% of TiO 2 , 0.2 %<B 2 O 3 <4%.

11 . The glass ceramic according to claim 1 , wherein the glass ceramic comprises the following composition in mole %:
2-5% of Al 2 O 3 , 15-20% of Li 2 O, 34-40% of P 2 O 5 , 36-42% of TiO 2 , 0.5% <B 2 O 3 <2.5%.

12 . The glass ceramic according to claim 1 , wherein the glass ceramic is substantially free of halides and/or arsenic and/or antimony and/or cadmium and/or chromium.

13 . The glass ceramic according to claim 1 , wherein the glass ceramic is free of GeO 2 .

14 . The glass ceramic according to claim 1 , wherein the glass ceramic is free of GaO 2 .

15 . The glass ceramic according to claim 1 , wherein the glass ceramic has a content of Fe 2 O 3 that is less than 0.2 mole %.

16 . The glass ceramic according to claim 1 , wherein the glass ceramic has a content of Fe 2 O 3 that is less than 0.1 mole %.

17 . The glass ceramic according to claim 1 , wherein, when the glass ceramic is in contact with a polymer electrolyte, the glass ceramic has a transfer resistance of lower than 1000Ω/cm 2 .

18 . A process for the production of a glass-ceramic electrolyte material with a main crystal phase of Li 1+x−y M y 5+ M x 3+ M 2−x−y 4+ (PO 4 ) 3 and a residual glass phase having a conductivity of higher than 10 −5 S/cm at 22° C. comprising the steps of:
a) melting the raw materials and homogenizing the starting glass,
b) casting and cooling the starting glass,
c) ceramicizing the starting glass at temperatures of between 750-1000° C.,
d) grinding the ceramicized starting glass to a powder, and
e) sintering the powder.

19 . The process for the production of a glass-ceramic electrolyte material according to claim 18 , wherein, during the ceramicizing step c), the starting glass is ceramicized at temperatures of between 850-950° C.

20 . The process for the production of a glass-ceramic electrolyte material according to claim 18 , wherein, during the sintering step e), the powder is mixed with an organic material.

21 . The process for the production of a glass-ceramic electrolyte material according to claim 18 , wherein, during the sintering step e), the powder is mixed with a polymer.

22 . A battery comprising the glass ceramic of claim 1 as a constituent, as an electrolyte, as part of an electrode, as an additive for a liquid electrolyte, as a constituent of a polymer electrolyte, as a constituent of a composite electrolyte, or as a coating on an electrode or a separator.

Assignees

• Schott Ag

Inventors

• Schneider Meike
• Roters Andreas
• Schumacher Jörg
• Samsinger Rolf

Classifications

• H01M4/134

  Electrodes based on metals, Si or alloys · CPC title

• C03C8/08

  containing phosphorus · CPC title

• H01M10/0525

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

• H01B1/08 Primary

  oxides · CPC title

• H01M4/624

  Electric conductive fillers · CPC title