Template-based methods of making and using ceramic solids and products and devices related thereto

Patent metadata

Field	Value
Publication number	US-2016293988-A1
Application number	US-201414169758-A
Country	US
Kind code	A1
Filing date	Jan 31, 2014
Priority date	Jan 31, 2013
Publication date	Oct 6, 2016
Grant date	—

Abstract

Various embodiments relate to a method comprising forming a template forming a template from a template precursor, wherein the template contains an entrapped ceramic precursor, which can be further processed to form a ceramic solid, such as an oxide ceramic solid. In one embodiment, the template precursor is a hydrogel precursor and the template is a hydrogel template. The hydrogel template can include, for example, agarose, chitosan, alginate or a photo-initiating receptive hydrogel template such as a functionalized poly(ethylene glycol). Various devices, including electrolyte interfaces and energy storage devices, as well as thermoelectric devices are also provided. In one embodiment, the oxide ceramic solid is a cubic garnet having a nominal formula of Li 7 La 3 Zr 2 O 12 (LLZO).

First claim

What is claimed is:

1 . A method of forming a wet gel comprising forming a hydrogel template from a hydrogel precursor, wherein the hydrogel template contains an entrapped ceramic precursor solution.

2 . The method of claim 1 wherein the forming comprises:
dissolving ceramic precursor components in a solvent to produce the ceramic precursor solution;
combining the ceramic precursor solution with the hydrogel precursor to produce a solubilized hydrogel template; and
gelling the solubilized hydrogel template to produce the wet gel comprising a hydrogel template containing the entrapped ceramic precursor solution.

3 . The method of claim 2 further comprising providing a molecule to the ceramic precursor solution capable of providing steric hindrance to the hydrogel template.

4 . The method of 2 wherein the solvent is a polar solvent.

5 . The method of claim 3 wherein the ceramic precursor components are metal salts.

6 . The method of claim 2 further comprising:
pre-heating the dried gel to produce a pre-heated ceramic precursor mixture;
milling the pre-heated ceramic precursor mixture to produce a pre-heated powder containing the ceramic precursor mixture; and
solidifying the pre-heated powder to produce a pre-heated solid formation containing the ceramic precursor mixture.

7 . The method of claim 2 further comprising:
calcining the pre-heated solid formation containing the ceramic precursor mixture to produce a calcined ceramic solid formation;
optionally milling the calcined ceramic solid formation to produce calcined ceramic powder; and
densifying the calcined ceramic powder to produce a densified ceramic solid.

8 . The method of claim 7 wherein the hydrogel precursor is a linear polysaccharide, a branched polyethylene imine, a 4-armed polyethylene glycol or a 6-armed polyethylene glycol.

9 . The method of claim 8 wherein the linear polysaccharide is selected from chitosan, alginate and agarose.

10 . The method of claim 9 wherein the hydrogel precursor is a thermally cross-linked hydrogel and the process further comprises drying the wet gel prior to producing the densified ceramic solid.

11 . The method of claim 10 wherein the thermally cross-linked polymer is agarose.

12 . The method of claim 7 wherein the hydrogel precursor is a non-thermally cross-linked hydrogel.

13 . The method of claim 12 wherein the non-thermally cross-linked hydrogel is alginate, chitosan or a functionalized poly(ethylene glycol).

14 . The method of claim 12 wherein method there is no drying of the wet gel and process time to produce the densified ceramic solid is reduced at least 33% as compared to a process which includes drying the wet gel.

15 . The method of claim 14 wherein the non-thermally cross-linked hydrogel is also a free-radical photopolymerizable hydrogel precursor and the gelling step is a photoinitated gelling step.

16 . The method of claim 15 wherein the free-radical photopolymerizable hydrogel precursor is a functionalized poly(ethylene glycol) (PEG).

17 . The method of claim 16 wherein the functionalized poly(ethylene glycol) is dimethacrylate (PEG).

18 . The method of claim 8 wherein the gelling step includes exposure of the template precursor solution to basic conditions.

19 . The method of claim 8 wherein the densified ceramic solid is an oxide ceramic solid.

20 . The method of claim 19 wherein the oxide ceramic solid is a sodium cobalt oxide, lithium cobalt oxide, lithium manganese nickel oxide, calcium cobalt oxide, calcium cobalt oxide with rare earth doping, lithium titanium oxide, and combinations thereof or a cubic garnet having an atomic formula comprising:
A x R y C z S a O 12 ,
wherein A is a first cationic species selected from H, Li, Na, Mg, Al, Sc and/or Ga and residing in an 8a, 16f, 32g, 24d, 48g or 96h site;
R is a second cationic species selected from La, Ba and/or Ce and residing in a 24c site; and
C is a third cationic species selected from Zr, Ta, Nb, Y or Hf and residing in the 16a site.

21 . The method of claim 20 wherein the cubic garnet has a nominal formula of Li 7 La 3 Zr 2 O 12 .

22 . The method of claim 2 wherein the forming comprises:
gelling the hydrogel precursor to produce the hydrogel template;
dissolving ceramic precursor components in a solvent to produce the ceramic precursor solution; and
combining the ceramic precursor solution with the hydrogel template to produce a wet gel comprising a hydrogel template containing the entrapped ceramic precursor solution.

23 . The method of claim 22 further comprising at least partially drying the hydrogel template prior to the combining step.

24 . A device comprising a densified ceramic solid produced by
calcining the pre-heated solid formation containing the ceramic precursor mixture to produce a calcined ceramic solid formation; optionally milling the calcined ceramic solid formation to produce calcined ceramic powder; and densifying the calcined ceramic powder to produce the densified ceramic solid.

25 . The device of claim 24 comprising an energy storage device or a thermoelectric device.

26 . The device of claim 25 wherein the energy storage device is a battery, fuel cell or semi-fuel cell and/or the thermoelectric device is a thermoelectric generator.

27 . The device of claim 25 comprising at least one electrode which includes hydrogen, lithium, sodium, magnesium, aluminum or gallium.

28 . A device comprising an oxide ceramic solid, wherein the oxide ceramic solid is a cubic garnet having an atomic formula comprising:
A x R y C z S a O 12 , wherein A is a first cationic species selected from H, Li, Na, Mg, Al, Sc and/or Ga and residing in an 8a, 16f, 32g, 24d, 48g or 96h site; R is a second cationic species selected from La, Ba and/or Ce and residing in a 24c site; and C is a third cationic species selected from Zr, Ta, Nb, Y or Hf and residing in the 16a site.

29 . The device of claim 28 wherein the cubic garnet has a nominal formula of Li 7 La 3 Zr 2 O 12 .

30 . The device of claim 28 comprising at least one electrode which includes hydrogen, lithium, sodium, magnesium, aluminum or gallium.

31 . A method of making an electrolyte interface comprising:
providing a slurry that includes an oxide ceramic compound having an atomic formula comprising: A x R y C z S a O 12 ,
wherein A is a first cationic species selected from H, Li, Na, Mg, Al and/or Ga and residing in an 8a, 16f, 32g, 24d, 48g or 96h site;
R is a second cationic species selected from La, Ba and/or Ce and residing in a 24c site; and
C is a third cationic species selected from Zr, Ta, Nb, Y or Hf and residing in the 16a site; and
providing an oxide ceramic electrolyte that includes a compound selected from A x R y C z S a O 12 ; forming at least one 3D feature on the oxide ceramic electrolyte, to provide an un-sintered electrolyte interface, wherein the 3D feature includes the slurry; and sintering the un-sintered electrolyte interface, to provide the electrolyte interface.

32 . A device comprising the electrolyte interface of claim 31 .

33 . The device of claim 32 comprising a battery, fuel cell or semi-fuel cell.

34 . The device of claim 32 comprising at l

Assignees

• Univ Michigan State

Inventors

• Sakamoto Jeffrey
• Thompson Travis
• Rangasamy Ezhiylmurugan
• Lynam Daniel A

Classifications

• C04B2235/3244

  Zirconium oxides, zirconates, hafnium oxides, hafnates, or oxide-forming salts thereof · CPC title

• C04B35/6365

  Cellulose or derivatives thereof · CPC title

• C01G53/54

  of the type (Mn2O4)-, e.g. Li(NixMn2-x)O4 or Li(MyNixMn2-x-y)O4 · CPC title

• C04B35/636

  Polysaccharides or derivatives thereof · CPC title

• H01M2008/1293

  Fuel cells with solid oxide electrolytes · CPC title