Nanocomposite particles of conversion chemistry and mixed electronic ionic conductor materials

Patent metadata

Field	Value
Publication number	US-2016164135-A1
Application number	US-201514827105-A
Country	US
Kind code	A1
Filing date	Aug 14, 2015
Priority date	Dec 5, 2014
Publication date	Jun 9, 2016
Grant date	—

Abstract

Positive electrode films for a Li-secondary battery are provided. The films include composite particles including a mixed electronic ionic conductor (MEIC), a metal fluoride (MF), and optionally an electrically conductive additive comprising carbon. The films include a catholyte and a binder that are both in contact with the composite particle surfaces but not contained therein. The composite particles are characterized by a porosity of less than about 15% v/v at 25° C. Methods of forming positive electrode films for a Li-secondary battery are also provided. Methods of forming positive electrode films including annealed composite particles for a Li-secondary battery are also provided. The methods include preparing a composite including a mixed electronic ionic conductor (MEIC) including a member selected from metal oxides, metal sulfides, metal halides, metal oxyhalides, and combinations thereof, a nanodimensioned metal fluoride (MF), optionally a binder, and optionally an electrically conductive additive comprising carbon.

First claim

1 . A positive electrode film comprising:
composite particles; a catholyte; and a binder;
wherein the composite particles comprise a mixed electronic ionic conductor (MEIC) and a metal fluoride (MF);
wherein the composite particles optionally comprise an electrically conductive additive comprising carbon;
wherein the catholyte and binder contact outer surfaces of the composite particles but are not contained therein; and
wherein the composite particles are characterized by a porosity of less than about 15% v/v.

2 . The positive electrode film of claim 1 , wherein the composite particles comprise an electrically conductive additive comprising carbon.

3 . The positive electrode film of claim 1 , wherein the MEIC is selected from the group consisting of carbon (C), MoS x wherein 0<x≦3, MoS 2 , MoS, LiV 3 O 8 , LiV 3 O 6 , MoOF, MoO 3−x wherein 0≦x≦1, Li x VO y wherein 0 <x< 2 y and 1≦y≦2.5, V 2 O 5 , Mn a O b wherein 1≦a≦2 and 1≦b≦7, MnO, Mn 3 O 4 , Mn 2 O 3 , MnO 2 , LiAlCl 4 , LISICON, NASICON, Na 1+x Zr 2 Si x P 3−x O 12 wherein x in each instance is 0<x<3 and optionally wherein Na, Zr and/or Si is replaced by isovalent elements, NASICON-structured phosphates, Li c Na c V 2 (PO 4 ) 3 wherein c in each instance is independently 0<c<1, Li d Na d M e M′ f (PO 4 ) 3 wherein d in each instance is independently 0≦d≦2, and 0≦e≦2, 0≦f≦2, and M and M′ are metals selected from the group consisting of V, Nb, Ta, Cr, Fe, Al, Co, Ni, and Cu, Li g MM′(SO 4 ) 3 where M and M′ are transition metals and g is selected so that a compound is charge neutral, and LiMXO 4 where X is Ge, Si, Sb, As, or P, Li h NaV 2 (PO 4 ) 3 , Li h Na 2 FeV(PO 4 ) 3 , Li h FeTi(PO 4 ) 3 , and Li h TiNb(PO 4 ) 3 , and Li h FeNb(PO 4 ) 3 , wherein 0≦h≦1.

4 . The positive electrode film of claim 1 , wherein the MEIC or carbon are coated on the MF.

5 . The positive electrode film of claim 1 , wherein the MEIC and the MF are nanodimensioned.

6 - 10 . (canceled)

11 . The positive electrode film of claim 1 , wherein the MF is selected from the group consisting of LiF, Li z FeF 3 , Li z CuF 2 , Li z NiF 2 , Li z NiF 2.5 , Li z NiF 3 , Li z CoF 2 , Li z CoF 3 , Li z MnF 2 , and Li z MnF 3 , wherein 0≦z≦3.

12 . The positive electrode film of claim 1 , wherein the MF is Li d MF g , wherein d and g are, independently in each instance, selected from within a range of 0 to 3, and wherein M is a metal selected from Fe, Cu, Ni, Co, Mn, alloys thereof, or combinations thereof.

13 - 14 . (canceled)

15 . The positive electrode film of claim 1 , wherein the MF is doped with a dopant selected from the group consisting of oxygen, carbon, a metal selected from the group consisting of Li, Mg, Al, Si, Ca, Ti, V, Cr, Mn, Mo, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Ba, and Hf, a metal oxide of said metal, a cation of said metal, a metal fluoride of said metal, and combinations thereof.

16 . The positive electrode film of claim 15 , wherein the dopant is selected from the group consisting of Li 2 O, Cu, CuF 2 , MoO 2 , MoO 3 , NiF 2 , ZrF 4 , CaF 2 , and AlF 3 .

17 - 18 . (canceled)

19 . The positive electrode film of claim 1 , wherein the catholyte is selected from the group consisting of LSS, LTS, LXTS, LXPS, LXPSO, and Li-stuffed garnet, where X is Si, Ge, Sn, As, Al, or combinations thereof.

20 . The positive electrode film of claim 1 , wherein the catholyte is LXPS and is substantially free of oxygen, where X is Si, Ge, Sn, Al, or combinations thereof.

21 . The positive electrode film of claim 1 , wherein the catholyte is LXPS and has an oxygen content between about 0 and 10 atomic %, where X is Si, Ge, Sn, As, Al, or combinations thereof.

22 - 38 . (canceled)

39 . The positive electrode film of claim 1 , wherein a weight ratio of the MEIC to the MF in the composite particles is between about 8:92 to 17:83 w/w.

40 - 95 . (canceled)

96 . A Li-secondary battery positive electrode film comprising:
composite particles; a catholyte; and a binder;
wherein the composite particles comprise a mixed electronic ionic conductor (MEIC) and a conversion chemistry material;
wherein the composite particles optionally comprise an electrically conductive additive comprising carbon;
wherein the catholyte and binder contact outer surfaces of the composite particles but are not contained therein; and
wherein the composite particles are characterized by a porosity of less than about 15% v/v at 25° C.

97 - 160 . (canceled)

161 . A method for forming a positive electrode film, the method comprising:
preparing a composite comprising:
a mixed electronic ionic conductor (MEIC) comprising a member selected from the group consisting of metal oxides, metal sulfides, metal halides, metal oxyhalides, and combinations thereof;
a nanodimensioned metal fluoride (MF);
optionally a binder; and
optionally an electrically conductive additive comprising carbon;
milling the composite to form a milled composite having a characteristic dimension of about 300 nm to 100 μm; heating the milled composite to a temperature of about 150° C. to 600° C. for about 2 to 10 hours to form an annealed composite; optionally cooling the annealed composite to room temperature; preparing a slurry by mixing the annealed composite with a catholyte and optionally a binder; casting the slurry as the positive electrode film; heating the positive electrode film to a temperature of about 80° C. to 400° C.; and applying a pressure to the positive electrode film.

162 - 165 . (canceled)

166 . The method of claim 161 , wherein preparing the composite comprises individually milling the MEIC, the MF, optional binder, and optional electrically conductive additive prior to combining the MEIC, the MF, optional binder, and optional electrically conductive additive.

167 - 169 . (canceled)

170 . The method of claim 161 , wherein milling the composite comprises wet milling the MEIC, the MF, optional binder, and optional electrically conductive additive in a solvent selected from the group consisting of methanol, ethanol, isopropanol, butanol, pentanol, hexanol, toluene, toluene:ethanol, acetone, N-methyl-2-pyrrolidone (NMP), diacetone alcohol, ethyl acetate, hexane, nonane, dodecane, and combinations thereof.

171 - 173 . (canceled)

174 . The method of claim 161 , wherein the milled composite is heated to a temperature selected from the group consisting of about 300° C., 325° C., 350° C., 375° C., 400° C., 425° C., 450° C., 475° C., and 500° C.

175 - 188 . (canceled)

189 . The method of claim 161 , further comprising coating the milled composite prior to heating the milled composite.

190 . The method of claim 161 , further comprising coating the annealed composite prior to preparing the slurry.

191 - 267 . (canceled)

Assignees

• Quantumscape Corp

Inventors

• Fasching Rainer J
• Hudson Will
• Loveness Ghyrn E
• Tulsky Eric
• Winoto Adrian
• Yang Aram
• Allenic Arnold

Classifications

• H01M2220/20

  Batteries in motive systems, e.g. vehicle, ship, plane · CPC title

• H01M10/0525

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

• H01M4/405

  Alloys based on lithium · CPC title

• H01M4/136

  Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy · CPC title

• H01M2300/0068

  inorganic · CPC title