UChicago Argonne, LLC

Jason R Croy

Michael M Thackeray

Joong Sun Park

Eungje Lee

Jeffrey W Elam

Anil U Mane

Mahalingam Balasubramanian

Meinan He

Arturo Gutierrez

Brandon R Long

Jihyeon Gim

Khalil Amine

Zhengcheng Zhang

Sun-Ho Kang

Hakim H Iddir

Devika Choudhury

Jinhyup Han

Adam P Tornheim

Bryan T Yonemoto

A method for coating of lithium ion electrode materials via atomic layer deposition. The coated materials may be integrated in part as a dopant in the electrode itself via heat treatment forming a doped lithium electrode.

Modification of lithium ion electrode materials via atomic layer deposition techniques

Substantially defect-free layered lithium nickel oxide materials of Formula (I): Li(NiM)Oand Formula (II): LiNiMOare provided herein, wherein M is one or more metal selected from the group consisting of Co, Mn, Al, Mg, Ti, B, Zr, Nb, and Mo; 0≤x≤0.05; and 0≤y≤0.1, 0.97≤a≤1.03; 0.9≤b≤1; 0≤c≤0.1; and 0.97≤(b+c)≤1.03; and the material has a layered structure with no more than about 1.2 percent disorder between lithium and transition metal (TM) layers, as determined by structural refinement calculations on x-ray diffraction (XRD) data, compared to an ideal layered LiNiOstructure. The materials can be formed by heating Ni(OH)or NiO with lithium hydroxide at a temperature in the range of about 650 to 680° C.

Defect-free lithium nickel(3+) oxide materials for use in lithium batteries and method of preparation thereof

Cation-stabilized materials and compositions are described herein, which suppress the structural and electrochemical instability of lithium-metal-oxide spinel and lithiated lithium-metal-oxide spinel electrodes for lithium batteries, notably lithium-ion batteries. The lithium metal oxide electrode material comprises a disordered rock salt structure with partial lithiated-spinel character, wherein, for example, the disordered rock salt structure comprises a formula Li(M″M'″)O, which has the crystallographic formula: [LiM′″][M″M′″Li]Owherein 16c and 16d refer to the octahedral sites of the prototypic space group symmetry Fdm; M″ and M′″ are metal ions; 0<a≤0.5; and 0<b<0.5. These stabilized materials are useful as positive electrodes for lithium batteries in their own right or when used as a structural component to stabilize layered metal oxide electrode systems, such as a two-component layered-layered system or a multi-component layered-layered-spinel system.

Disordered rock salt electrodes for lithium batteries

The fabrication of robust interfaces between transition metal oxides and non-aqueous electrolytes is one of the great challenges of lithium ion batteries. Atomic layer deposition (ALD) of aluminum tungsten fluoride (AlWF) improves the electrochemical stability of LiCoO. AlWFthin films were deposited by combining trimethylaluminum and tungsten hexafluoride. in-situ quartz crystal microbalance and transmission electron microscopy studies show that the films grow in a layer-by-layer fashion and are amorphous nature. Ultrathin AlWFcoatings (<10 Å) on LiCoOsignificantly enhance stability relative to bare LiCoOwhen cycled to 4.4 V. The coated LiCoO2 exhibited superior rate capability (up to 400 mA/g) and discharge capacities at a current of 400 mA/g were 51% and 92% of the first cycle capacities for the bare and AlWFcoated materials. These results open new possibilities for designing ultrathin and electrochemically robust coatings of metal fluorides via ALD to enhance the stability of Li-ion electrodes.

Metal fluoride passivation coatings prepared by atomic layer deposition for Li-ion batteries

Stabilized layered lithium metal oxide cathode materials are described which include excess lithium, Ni, Mn, and at least one other metal ion. The materials comprise a layered LiMO-type material in which M comprises a combination of Ni, Mn, and at least one other metal ion that includes less than about 6 mol % Co; and which has about 1 to 6 percent excess lithium. In one embodiment, the stabilized lithium metal oxide cathode material comprises a composition having the empirical formula xLiMnO&#xb7;(1&#x2212;x)LiNiMnCoO, wherein 0&#x3c;x&#x2264;0.1; and 0&#x2264;&#x3b4;&#x2264;0.2. In another embodiment, the stabilized lithium metal oxide cathode material comprises a composition having the empirical formula Li[NiMnM']O, wherein M&#x2032; is one of more metal selected from the group consisting of Co, Al, Fe, Mg, and Ti; 0&#x3c;y&#x2264;0.02; 0.85&#x2264;a&#x2264;0.96; 0.03&#x2264;b&#x2264;0.1; and 0.01&#x2264;c&#x2264;0.1.

Low cobalt layered oxide materials for lithium ion battery electrodes

Electrode materials for electrochemical cells and batteries and methods of producing such materials are disclosed herein. The electrode materials comprise an active lithium metal oxide material prepared by: (a) contacting the lithium metal oxide material with an aqueous acidic solution containing one or more metal cations; and (b) heating the so-contacted lithium metal oxide from step (a) to dryness at a temperature below 200&#xb0; C. The metal cations in the aqueous acidic solution comprise one or more metal cations selected from the group consisting of an alkaline earth metal ion, a transition metal ion, and a main group metal ion.

Lithium battery electrodes

An electrode comprises an electrode core. A composite bilayer coating is conformally disposed on the electrode core. The composite bilayer coating comprises a first layer disposed on at least a portion of the electrode core. The first layer comprises a metal fluoride, a metal oxide or a metal sulfide. A second layer is disposed on the first layer and comprises a metal fluoride, a metal oxide or a metal sulfide.

Composite bilayer coatings for high capacity cathodes and anodes

A non-aqueous solvent composition for a lithium battery comprises a fluorinated solvent mixture that consists essentially of a 1,2-difluoroethylene carbonate and a fluoro-substituted dialkyl carbonate in a respective weight ratio of about 1:3 to about 1:1, and optionally up to about 30 wt % of an additional organic solvent. An electrolyte for a lithium ion battery comprises a lithium salt dissolved in a non-aqueous solvent composition comprising the fluorinated solvent mixture.

Polyfluorinated carbonate electrolyte for high-voltage lithium batteries

The fabrication of robust interfaces between transition metal oxides and non-aqueous electrolytes is one of the great challenges of lithium ion batteries. Atomic layer deposition (ALD) of aluminum tungsten fluoride (AlWF) improves the electrochemical stability of LiCoO. AlWFthin films were deposited by combining trimethylaluminum and tungsten hexafluoride. in-situ quartz crystal microbalance and transmission electron microscopy studies show that the films grow in a layer-by-layer fashion and are amorphous nature. Ultrathin AlWFcoatings (&#x3c;10 &#x212b;) on LiCoOsignificantly enhance stability relative to bare LiCoOwhen cycled to 4.4 V. The coated LiCoOexhibited superior rate capability (up to 400 mA/g) and discharge capacities at a current of 400 mA/g were 51% and 92% of the first cycle capacities for the bare and AlWFcoated materials. These results open new possibilities for designing ultrathin and electrochemically robust coatings of metal fluorides via ALD to enhance the stability of Li-ion electrodes.

An electrode material comprising a composite lithium metal oxide, which in an initial state has the formula: y[xLiMO.(1&#x2212;x)LiM'O].(1&#x2212;y)LiMnM&#x2033;O; wherein 0&#x2264;x&#x2264;1; 0.75&#x2264;y&#x3c;1; 0&#x3c;z&#x2264;2; 0&#x2264;d&#x2264;0.2; and z&#x2212;d&#x2264;2. M comprises one or more metal ions that together have an average oxidation state of +4; M&#x2032; comprises one or more metal ions that together have an average oxidation state of +3; and M&#x2033; comprises one or more metal ions that together with the Mn and any excess proportion of lithium, 'd', have a combined average oxidation state between +3.5 and +4. The LiMnM&#x2033;Ocomponent comprises a spinel structure, each of the LiMOand the LiM&#x2032;Ocomponents comprise layered structures, and at least one of M, M&#x2032;, and M&#x2033; comprises Co. Cells and batteries comprising the electrode material also are described.

Cobalt-stabilized lithium metal oxide electrodes for lithium batteries

Electrode materials for electrochemical cells and batteries and methods of producing such materials are disclosed herein. A method of preparing an active lithium metal oxide material suitable for use in an electrode for a lithium electrochemical cell comprises the steps of: (a) contacting the lithium metal oxide material with an aqueous acidic solution containing one or more metal cations; and (b) heating the so-contacted lithium metal oxide from step (a) to dryness at a temperature below 200&#xb0; C. The metal cations in the aqueous acidic solution comprise one or more metal cations selected from the group consisting of an alkaline earth metal ion, a transition metal ion, and a main group metal ion.

Surface treatment for lithium battery electrode materials

An electrode for a lithium-ion cell comprising a 'layered-spinel' composite oxide material is disclosed. The 'layered-spinel' can be a material of formula xLiMO.(1&#x2212;x)LiM'O, wherein 0&#x3c;x&#x3c;1; LiMOis a lithium metal oxide having a layered structure in which M comprises one or more transition metals and optionally lithium, and has a combined average oxidation state of +3; and LiM&#x2032;Ois a lithium metal oxide having a spinel structure, 1&#x2264;y&#x2264;1.33, 1.66&#x2264;z&#x2264;2, and M&#x2032; comprises one or more transition metals, and has a combined average metal oxidation state in the range of about +3.5 to about +4.

Layered-spinel electrodes for lithium batteries

The surface of a lithium ion cathode material (e.g., a lithium metal oxide material capable of releasing and accepting lithium ions during charging and discharging, respectively, of a lithium ion electrochemical cell) is coated with a lithium metal oxide (LMO) material comprising a high-valent metal to, inter alia, reduce interfacial resistance toward lithium exchange. Li-rich phases on the surface of the treated LMO particles allow for better lithium ion diffusion. The inclusion of elements that form phases with lithium and can substitute in the host structure allow for mixing across interfaces leading to more robust structures that better mimic epitaxial-type layers. Inclusion of doping elements in place of some of the high-valent metal in the surface-treating composition provides unexpectedly improved performance over surface treatments comprising lithium metal oxides that only include a high-valent metal.

High valent lithiated surface structures for lithium ion battery electrode materials

A structurally inhomogeneous lithium metal oxide material having the Formula (I): y[xLiMO&#x2022;(1-x)LiM'O]&#x2022;(1-y)LiM&#x2033;O; wherein 0&#x2264;x&#x2264;1; 0&#x3c;y&#x3c;1; 0&#x2264;d&#x2264;0.33; and wherein the LiM&#x2033;Ocomponent comprises a spinel structure, and each of the LiMOand the LiM&#x2032;components thereof comprise layered structures. Each of M, M&#x2032;, and M&#x2033; independently comprises one or more metal ions. The composition of the material of Formula (I) varies across the electrode particles by changing at least one of x, y, d, M, M&#x2032; and M&#x2033;. Electrodes, cells and batteries comprising the lithium metal oxide material are also described.

Stabilized electrodes for lithium batteries

The fabrication of robust interfaces between transition metal oxides and non-aqueous electrolytes is one of the great challenges of lithium ion batteries. Atomic layer deposition (ALD) of aluminum tungsten fluoride (AlWF) improves the electrochemical stability of LiCoO. AlWFthin films were deposited by combining trimethylaluminum and tungsten hexafluoride. in-situ quartz crystal microbalance and transmission electron microscopy studies show that the films grow in a layer-by-layer fashion and are amorphous nature. Ultrathin AlWFcoatings (&#x3c;10 &#x212b;) on LiCoOsignificantly enhance stability relative to bare LiCoOwhen cycled to 4.4 V. The coated LiCoO2 exhibited superior rate capability (up to 400 mA/g) and discharge capacities at a current of 400 mA/g were 51% and 92% of the first cycle capacities for the bare and AlWFcoated materials. These results open new possibilities for designing ultrathin and electrochemically robust coatings of metal fluorides via ALD to enhance the stability of Li-ion electrodes.

Growing community of inventors

Bolingbrook, IL, United States of America

Jason R Croy