Disordered rock-salt battery cathode composition and syntheses thereof

Patent metadata

Field	Value
Publication number	US-2025174649-A1
Application number	US-202418897372-A
Country	US
Kind code	A1
Filing date	Sep 26, 2024
Priority date	Nov 29, 2023
Publication date	May 29, 2025
Grant date	—

Abstract

A cathode material has the chemical formula Li 4+δ M x1 M′ y1 M″ z1 O 8 or Li 2+δ M x2 M′ y2 M″ z2 O 4 where 0≤δ≤1, x1, y1, z1 are integers (+/−0.5) and x1+y1+z1=4, and x2, y2, z2 are integers (+/−0.05) and x2+y2+z2=2. A method for discovering a cathode material includes estimating synthesizability for a plurality of cathode material compositions, selecting a first subset of cathode material compositions from the plurality of cathode material compositions as a function of the estimated synthesizability and metal-ion diffusion availability, estimating voltage discharge, charge capacity, and oxygen stability for the first subset of cathode material compositions, and selecting a second subset of cathode material compositions from the first subset plurality of cathode material compositions as a function of the estimated voltage discharge, charge capacity, and oxygen stability.

First claim

What is claimed is:

1 . A cathode for a Li ion battery, the cathode comprising:
a cathode material with the chemical formula Li 4+δ M x1 M′ y1 M″ z1 O 8 or Li 2+δ M x2 M′ y2 M″ z2 O 4 where 0≤δ≤1, x1, y1, z1 are integers (+/−0.05) and x1+y1+z1=4, x2, y2, z2 are integers (+/−0.05) and x2+y2+z2=2, and M, M′, and M″ are elements selected independently from hafnium (Hf), magnesium (Mg), aluminum (Al), scandium (Sc), titanium (Ti), vanadium (V), chromium (Cr), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), gallium (Ga), zirconium (Zr), niobium (Nb), ruthenium (Ru), tin (Sn), and antimony (Sb).

2 . The cathode according to claim 1 , wherein the cathode material is selected from the group consisting of Li 2+δ TiVO 4 , Li 2+δ VFeO 4 , Li 4+δ HfTiV 2 O 8 , Li 4+δ VFe 2 SnO 8 , Li 4+δ ScV 2 FeO 8 , Li 4+δ CrFeNi 2 O 8 , Li 4+δ Mn 2 CoRuO 8 , Li 4+δ Mn 2 NiRuO 8 , Li 4+δ CrFe 2 NiO 8 , Li 4+δ HfCrFe 2 O 8 , Li 4+δ ZrV 3 O 8 , Li 4+δ Mn 2 NiSbO 8 , Li 4+δ Mn 2 CoSbO 8 , Li 4+δ Cr 2 FeCuO 8 , Li 4+δ Cr 2 FeNiO 8 , Li 4+δ TiCrFe 2 O 8 , Li 4+δ HfV 3 O 8 , Li 4+δ Mn 2 FeRuO 8 , Li 4+δ MnCrNi 2 O 8 , Li 4+δ Cr 2 GaFeO 8 , Li 4+δ ZrCrFe 2 O 8 , Li 4+δ Ti 2 VCrO 8 , Li 4+δ ZrV 2 FeO 8 , Li 4+δ FeCo 2 RuO 8 , Li 4+δ Fe 2 CoRuO 8 , Li 4+δ CrFe 2 SnO 8 , Li 4+δ CrFe 2 CuO 8 , Li 4+δ Fe 2 NiSbO 8 , Li 4+δ ScMnV 2 O 8 , Li 4+δ ScTiV 2 O 8 , Li 4+δ MnV 2 FeO 8 , Li 4+δ MnCo 2 RuO 8 , Li 4+δ HfV 2 FeO 8 , Li 4+δ TiCr 2 CuO 8 , Li 4+δ TiV 3 O 8 , Li 4+δ ScCr 2 NiO 8 , Li 4+δ Mn 2 CrFeO 8 , Li 4+δ V 2 FeSnO 8 , Li 4+δ TiVFe 2 O 8 , Li 4+δ Cr 2 CuNiO 8 , Li 4+δ MnNbFe 2 O 8 , Li 4+δ NbFe 2 NiO 8 , Li 4+δ V 2 GaFeO 8 , Li 4+δ V 3 FeO 8 , Li 4+δ AlV 2 FeO 8 , Li 4+δ CrNi 2 SnO 8 , and Li 4+δ TiCrNi 2 O 8 .

3 . The cathode according to claim 1 , wherein the cathode material comprises Li 4+δ CrFeNi 2 O 8 , Li 4+δ CrFe 2 NiO 8 , Li 4+δ TiCrNi 2 O 8 , Li 4+δ Cr 2 FeNiO 8 , Li 4+δ Cr 2 FeCuO 8 , Li 4+δ Cr 2 GaFeO 8 , Li 4+δ TiCr 2 CuO 8 , and Li 2+δ CrCuO 4 .

4 . The cathode according to claim 1 , wherein the cathode material is selected from the group consisting of Li 4+δ CrFeNi 2 O 8 , Li 4+δ CrFe 2 NiO 8 , Li 4+δ TiCrNi 2 O 8 , Li 4+δ Cr 2 FeNiO 8 , Li 4+δ Cr 2 FeCuO 8 , Li 4+δ Cr 2 GaFeO 8 , Li 4+δ TiCr 2 CuO 8 , and Li 2+δ CrCuO 4 .

5 . The cathode according to claim 4 , wherein the cathode material comprises a crystal structure selected from the group consisting of a disordered-rock-salt crystal structure, a layered crystal structure, and combinations thereof.

6 . The cathode according to claim 5 , wherein the cathode material is Li 4+δ CrFeNi 2 O 8 .

7 . The cathode according to claim 5 , wherein the cathode material is Li 4+δ CrFe 2 NiO 8 .

8 . The cathode according to claim 5 , wherein the cathode material is Li 4+δ TiCrNi 2 O 8 .

9 . The cathode according to claim 5 , wherein the cathode material is Li 4+δ Cr 2 FeCuO 8 .

10 . The cathode according to claim 5 , wherein the cathode material is Li 4+δ Cr 2 GaFeO 8 .

11 . The cathode according to claim 5 , wherein the cathode material is Li 4+δ TiCr 2 CuO 8 .

12 . The cathode according to claim 5 , wherein the cathode material is Li 2+δ CrCuO 4 .

13 . A method comprising:
estimating synthesizability and metal-ion diffusion availability for a plurality of cathode material compositions with the chemical formula Li 4+δ M x1 M′ y1 M″ z1 O 8 or Li 2+δ M x2 M′ y2 M″ z2 O 4 where 0≤δ<1, x1+y1+z1=4, x2+y2+z2=2, and M, M′, and M″ are at least two different cation elements; selecting a first subset of cathode material compositions from the plurality of cathode material compositions as a function of the estimated synthesizability and metal-ion diffusion availability; estimating voltage discharge, charge capacity, and oxygen stability for the first subset of cathode material compositions; selecting a second subset of cathode material compositions from the first subset of cathode material compositions as a function of the estimated voltage discharge, charge capacity, and oxygen stability; and synthesizing and evaluating at least one of the second subset of cathode material compositions.

14 . The method according to claim 13 , wherein M, M′, and M″ are selected independently from hafnium (Hf), magnesium (Mg), aluminum (Al), scandium (Sc), titanium (Ti), vanadium (V), chromium (Cr), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), gallium (Ga), zirconium (Zr), niobium (Nb), ruthenium (Ru), tin (Sn), and antimony (Sb).

15 . The method according to claim 14 further comprising:
determining available oxidation states of the at least two different cation elements for the plurality of cathode material compositions;
determining octahedral coordination preference of the at least two cation elements for the plurality of cathode material compositions;
selecting a first subset of cathode material compositions from the plurality of cathode material compositions as a function of charge balance and cation redox capability;
designing disordered, layered, spinel-like, and γ-LiFeO 2 -like cation ordering crystal structures for the first subset of cathode material compositions;
performing first principle energy calculations for each of the disordered, layered, spinel-like, and γ-LiFeO 2 -like cation ordering crystal structures for each of the subset cathode material compositions;
predicting long-range order and/or short-range order for as a function of the first principle energy calculations for each of the disordered, layered, spinel-like, and γ-LiFeO 2 -like cation ordering crystal structures for each of the subset cathode material compositions; and
selecting the second subset of cathode material compositions from the first subset of cathode material compositions as a function of the predicted long rang order and/or short-ranger order.

16 . The method according to claim 15 further comprising:
estimating a charge capacity of each of the second subset of cathode material compositions as a function of oxidation state values for each element of each of the second subset of cathode material compositions; and
estimating an oxygen stability of each of the second subset of cathode material compositions as a function of oxygen vacancy formation energy calculations for each of the second subset of cathode material compositions.

17 . The method according to claim 16 further comprising:
selecting a third subset of cathode material compositions from the second subset of cathode material compositions as a function of the estimated charge capacity and the estimated oxygen stability of each of the second subset of cathode material compositions; and
synthesizing the third subset of cathode material compositions.

18 . The method according to claim 17 , wherein the second subset of cathode material compositions comprises Li 2+δ TiVO 4 , Li 2+δ VFeO 4 , Li 4+δ HfTiV 2 O 8 , Li 4+δ VFe 2 SnO 8 , Li 4+δ ScV 2 FeO 8 , Li 4+δ CrFeNi 2 O 8 , Li 4+δ Mn 2 CoRuO 8 , Li 4+δ Mn 2 NiRuO 8 , Li 4+δ CrFe 2 NiO 8 , Li 4+δ HfCrFe 2 O 8 , Li 4+δ ZrV 3 O 8 , Li 4+δ Mn 2 NiSbO 8 , Li 4+δ Mn 2 CoSbO 8 , Li 4+δ Cr 2 FeCuO 8 , Li 4+δ Cr 2 FeNiO 8 , Li 4+δ TiCrFe 2 O 8 , Li 4+δ HfV 3 O 8 , Li 4+δ Mn 2 FeRuO 8 , Li 4+δ MnCrNi 2 O 8 , Li 4+δ Cr 2 GaFeO 8 , Li 4+δ ZrCrFe 2 O 8 , Li 4+δ Ti 2 VCrO 8 , Li 4+δ ZrV 2 FeO 8 , Li 4+δ FeCo 2 RuO 8 , Li 4+δ Fe 2 CoRuO 8 , Li 4+δ CrFe 2 SnO 8 , Li 4+δ CrFe 2 CuO 8 , Li 4+δ Fe 2 NiSbO 8 , Li 4+δ ScMnV 2 O 8 , Li 4+δ ScTiV 2 O 8 , Li 4+δ MnV 2 FeO 8 , Li 4+δ MnCo 2 RuO 8 , Li 4+δ HfV 2 FeO 8 , Li 4+δ TiCr 2 CuO 8 , Li 4 ,TiV 3 O 8 , Li 4+δ ScCr 2 NiO 8 , Li 4+δ Mn 2 CrFeO 8 , Li 4+δ V

Assignees

• Toyota Res Inst Inc
• Toyota Motor Co Ltd
• Univ Northwestern

Inventors

• Torrisi Steven Bartholomew Joseph
• Wolverton Christopher
• Zhu Yizhou
• Liu Tzu-Chen
• Baldassarri Bianca
• Salgado-Casanova Adolfo
• Aykol Muratahan
• Yubuchi So
• Yamasaki Hisatsugu
• Yoshida Jun

Classifications

• H01M4/485

  of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy (H01M4/505, H01M4/525 take precedence) · CPC title

• H01M4/505

  of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy · CPC title

• C01G49/009

  Compounds containing iron, with or without oxygen or hydrogen, and containing two or more other elements · CPC title

• C01G49/0018 Primary

  Mixed oxides or hydroxides, (C01G49/0009 takes precedence) · CPC title

• H01M2004/028

  Positive electrodes · CPC title