System and Method for Treating the Surface of Solid Electrolytes

Patent metadata

Field	Value
Publication number	US-2018301752-A1
Application number	US-201815943312-A
Country	US
Kind code	A1
Filing date	Apr 2, 2018
Priority date	Mar 31, 2017
Publication date	Oct 18, 2018
Grant date	—

Abstract

Disclosed are electrochemical devices, such as lithium battery electrodes, lithium ion conducting solid state electrolytes, and solid-state lithium metal batteries including these electrodes and solid state electrolytes. In one embodiment, a method for forming an electrochemical device is disclosed in which a precursor electrolyte is heated to remove at least a portion of a resistive surface region of the precursor electrolyte.

First claim

1 . A method for forming an electrochemical device, the method comprising:
(a) providing a precursor electrolyte having a resistive surface region; (b) heating the precursor electrolyte to remove at least a portion of the resistive surface region thereby forming a solid state electrolyte; and (c) placing the solid state electrolyte in contact with an electrode.

2 . The method of claim 1 , wherein the precursor electrolyte comprises a ceramic material having a formula of Li w A x M 2 Re 3-y O z wherein w is 5-7.5, wherein A is selected from B, Al, Ga, In, Zn, Cd, Y, Sc, Mg, Ca, Sr, Ba, and any combination thereof, wherein x is 0-2, wherein M is selected from Zr, Hf, Nb, Ta, Mo, W, Sn, Ge, Si, Sb, Se, Te, and any combination thereof, wherein Re is selected from lanthanide elements, actinide elements, and any combination thereof, wherein y is 0.01-0.75, wherein z is 10.875-13.125, and wherein the material has a garnet-type or garnet-like crystal structure.

3 . (canceled)

4 . The method of claim 1 , wherein the resistive surface region comprises LiOH.

5 . The method of claim 1 , wherein the resistive surface region comprises Li 2 CO 3 .

6 . The method of claim 1 , wherein step (b) further comprises heating at a temperature between 180° C. to 1000° C.

7 . The method of claim 6 , wherein the resulting interfacial resistance between the electrode and the solid state electrolyte is less than 500 ohm cm 2 .

8 . (canceled)

9 . (canceled)

10 . (canceled)

11 . (canceled)

12 . (canceled)

13 . The method of claim 1 , wherein the electrode comprises an anode.

14 . (canceled)

15 . The method of claim 1 , wherein step (c) further comprises depositing an interfacial layer on the solid state electrolyte, wherein the interfacial layer comprises a blocking metal, a semi-blocking metal, a non-blocking metal, or mixtures thereof.

16 . (canceled)

17 . (canceled)

18 . A method for forming a solid state electrolyte, the method comprising:
(a) providing a precursor electrolyte comprising an oxide of a metal, the precursor electrolyte having a resistive surface region; and (b) heating the precursor electrolyte at a temperature above a melting point of the metal to remove at least a portion of the resistive surface region thereby forming a solid state electrolyte.

19 . The method of claim 18 , wherein the precursor electrolyte comprises a ceramic material having a formula of Li w A x M 2 Re 3-y O z wherein w is 5-7.5, wherein A is selected from B, Al, Ga, In, Zn, Cd, Y, Sc, Mg, Ca, Sr, Ba, and any combination thereof, wherein x is 0-2, wherein M is selected from Zr, Hf, Nb, Ta, Mo, W, Sn, Ge, Si, Sb, Se, Te, and any combination thereof, wherein Re is selected from lanthanide elements, actinide elements, and any combination thereof, wherein y is 0.01-0.75, wherein z is 10.875-13.125, and wherein the material has a garnet-type or garnet-like crystal structure.

20 . (canceled)

21 . The method of claim 18 , wherein the resistive surface region comprises LiOH.

22 . (canceled)

23 . The method of claim 18 , wherein step (b) further comprises heating at a temperature between 350° C. and 650° C.

24 . The method of claim 18 , wherein the resulting interfacial resistance between the electrode and the solid state electrolyte is less than 25 ohm cm 2 .

25 . (canceled)

26 . (canceled)

27 . (canceled)

28 . The method of claim 18 , wherein the electrode comprises an anode.

29 . (canceled)

30 . (canceled)

31 . A method for forming a solid state electrolyte, the method comprising:
(a) providing a precursor electrolyte having a resistive surface region; and (b) removing at least a portion of the resistive surface region thereby forming a solid state electrolyte, wherein removing at least a portion of the resistive surface region comprises a chemical treatment, electropolishing, wet polishing, argon plasma etching, oxygen plasma cleaning, annealing, or exposure to high vacuum.

32 . The method of claim 31 , wherein the precursor electrolyte comprises a ceramic material having a formula of Li w A x M 2 Re 3-y O z wherein w is 5-7.5, wherein A is selected from B, Al, Ga, In, Zn, Cd, Y, Sc, Mg, Ca, Sr, Ba, and any combination thereof, wherein x is 0-2, wherein M is selected from Zr, Hf, Nb, Ta, Mo, W, Sn, Ge, Si, Sb, Se, Te, and any combination thereof, wherein Re is selected from lanthanide elements, actinide elements, and any combination thereof, wherein y is 0.01-0.75, wherein z is 10.875-13.125, and wherein the material has a garnet-type or garnet-like crystal structure.

33 . (canceled)

34 . The method of claim 31 , wherein the resistive surface region comprises LiOH.

35 . (canceled)

36 . The method of claim 31 , wherein the resulting interfacial resistance between the electrode and the solid state electrolyte is less than 25 ohm cm 2 .

37 . The method of claim 31 , wherein step (b) further comprises heating at a temperature between 400° C. to 600° C. under an inert gas atmosphere.

38 . (canceled)

39 . The method of claim 31 , wherein the electrode comprises an anode, wherein the anode consists essentially of lithium metal.

40 . (canceled)

41 . A method for forming a solid state electrolyte, the method comprising:
(a) providing a precursor electrolyte having a resistive surface region; (b) removing at least a portion of the resistive surface region by polishing, and (c) heating the precursor electrolyte thereby forming a solid state electrolyte.

42 . The method of claim 41 , wherein the precursor electrolyte comprises a ceramic material having a formula of Li w A x M 2 Re 3-y O z wherein w is 5-7.5, wherein A is selected from B, Al, Ga, In, Zn, Cd, Y, Sc, Mg, Ca, Sr, Ba, and any combination thereof, wherein x is 0-2, wherein M is selected from Zr, Hf, Nb, Ta, Mo, W, Sn, Ge, Si, Sb, Se, Te, and any combination thereof, wherein Re is selected from lanthanide elements, actinide elements, and any combination thereof, wherein y is 0.01-0.75, wherein z is 10.875-13.125, and wherein the material has a garnet-type or garnet-like crystal structure.

43 . (canceled)

44 . The method of claim 41 , wherein the resistive surface region comprises LiOH.

45 . (canceled)

46 . The method of claim 41 , wherein the resulting interfacial resistance between the electrode and the solid state electrolyte is less than 100 ohm cm 2 .

47 . The method of claim 41 , wherein step (b) comprises removing the portion of the resistive surface region by dry polishing.

48 . The method of claim 41 , wherein step (b) comprises removing the portion of the resistive surface region by wet polishing.

49 . The method of claim 41 , wherein step (c) comprises heating the precursor electrolyte in a temperature range of 200° C. to 500° C.

50 . The method of claim 49 , wherein the electrode is an anode consisting essentially of lithium metal.

Assignees

• Univ Michigan Regents

Inventors

• Sakamoto Jeffrey
• Thompson Travis
• Sharafi Asma

Classifications

• H01M2300/0071

  Oxides · CPC title

• H01M4/525

  of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy · CPC title

• H01M10/0585

  of accumulators having only flat construction elements, i.e. flat positive electrodes, flat negative electrodes and flat separators · CPC title

• C01P2002/30

  Three-dimensional structures · CPC title

• H01M4/5825

  Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines · CPC title