UChicago Argonne, LLC

The University of Chicago

Sun-Ho Kang

Christopher S Johnson

Michael M Thackeray

Khalil Amine

Mahalingam Balasubramanian

John Thomas Vaughey

Jason R Croy

Lynn Trahey

Donghan Kim

A positive electrode is disclosed for a non-aqueous electrolyte lithium rechargeable cell or battery. The electrode comprises a lithium containing material of the formula NaLiNiMnMO, wherein M is a metal cation, x+y&#x3e;1, 0&#x3c;z&#x3c;0.5, 0&#x2264;z'&#x3c;0.5, y+x+1 is less than d, and the value of d depends on the proportions and average oxidation states of the metallic elements, Li, Na, Mn, Ni, and M, if present, such that the combined positive charge of the metallic elements is balanced by the number of oxygen anions, d. The inventive material preferably has a spinel or spinel-like component in its structure. The value of y preferably is less than about 0.2, and M comprises one or more metal cations selected preferably from one or more monovalent, divalent, trivalent or tetravalent cations, such as Mg, Co, Co, B, Ga, Fe, Fe, Al, and Ti. The electrode material can be synthesized using an ion-exchange reaction with a lithium salt in an organic-based solvent to partially replace sodium ions of a precursor material with lithium ions.

Electrode materials for rechargeable battery

This invention relates to methods of preparing positive electrode materials for electrochemical cells and batteries. It relates, in particular, to a method for fabricating lithium-metal-oxide electrode materials for lithium cells and batteries. The method comprises contacting a hydrogen-lithium-manganese-oxide material with one or more metal ions, preferably in an acidic solution, to insert the one or more metal ions into the hydrogen-lithium-manganese-oxide material; heat-treating the resulting product to form a powdered metal oxide composition; and forming an electrode from the powdered metal oxide composition.

Electrode structures and surfaces for Li batteries

A lithium-metal-oxide positive electrode having a layered or spinel structure for a non-aqueous lithium electrochemical cell and battery is disclosed comprising electrode particles that are protected at the surface from undesirable effects, such as electrolyte oxidation, oxygen loss or dissolution by one or more lithium-metal-polyanionic compounds, such as a lithium-metal-phosphate or a lithium-metal-silicate material that can act as a solid electrolyte at or above the operating potential of the lithium-metal-oxide electrode. The surface protection significantly enhances the surface stability, rate capability and cycling stability of the lithium-metal-oxide electrodes, particularly when charged to high potentials.

Surface protected lithium-metal-oxide electrodes

A positive electrode is disclosed for a non-aqueous electrolyte lithium rechargeable cell or battery. The electrode comprises a lithium containing material of the formula NaLiNiMnMO, wherein M is a metal cation, x+y&#x3e;1, 0&#x3c;z&#x3c;0.5, 0&#x2266;z'&#x3c;0.5, y+x+1 is less than d, and the value of d depends on the proportions and average oxidation states of the metallic elements, Li, Na, Mn, Ni, and M, if present, such that the combined positive charge of the metallic elements is balanced by the number of oxygen anions, d. The inventive material preferably has a spinel or spinel-like component in its structure. The value of y preferably is less than about 0.2, and M comprises one or more metal cations selected preferably from one or more monovalent, divalent, trivalent or tetravalent cations, such as Mg, Co, Co, B, Ga, Fe, Fe, Al, and Ti. The electrode material can be synthesized using an ion-exchange reaction with a lithium salt in an organic-based solvent to partially replace sodium ions of a precursor material with lithium ions.

A stabilized electrode comprising a metal oxide or lithium-metal-oxide electrode material is formed by contacting a surface of the electrode material, prior to cell assembly, with an aqueous or a non-aqueous acid solution having a pH greater than 4 but less than 7 and containing a stabilizing salt, to etch the surface of the electrode material and introduce stabilizing anions and cations from the salt into said surface. The structure of the bulk of the electrode material remains unchanged during the acid treatment. The stabilizing salt comprises fluoride and at least one cationic material selected from the group consisting of ammonium, phosphorus, titanium, silicon, zirconium, aluminum, and boron.

Surface stabilized electrodes for lithium batteries

The present invention provides an electrode material suitable for use as a cathode in a sodium electrochemical cell or battery, the electrode comprising a layered material of formula NaLiNiMnMO, wherein M comprises one or more metal cation, 0.24&#x2266;c/b&#x2266;0.5, 0&#x3c;d/b&#x2266;0.23, 0&#x2266;e/b&#x2266;0.45, 0&#x2266;f/b&#x2266;0.45, 0&#x2266;z/b&#x2266;0.45, the combined average oxidation state of the metal components (i.e., NaLiNiMnM) is in the range of about 3.9 to 5.2, and b is equal to (c+d+Ve+Xf+Yz)/2, wherein V is the average oxidation state of the Ni, X is the average oxidation state of the Mn, and Y is the average oxidation state of the M in the material. The combined positive charge of the metallic elements is balanced by the combined negative charge of the oxygen anions, the Na is predominately present in a sodium layer, and the Mn, Ni, and M are predominately present in a transition metal layer.

Electrode materials for sodium batteries

This invention provides lithium-rich compounds as precursors for positive electrodes for lithium cells and batteries. The precursors comprise a LiO-containing compound as one component, and a second charged or partially-charged component, selected preferably from a metal oxide, a lithium-metal-oxide, a metal phosphate or metal sulfate compound. LiO is extracted from the above-mentioned electrode precursors to activate the electrode either by electrochemical methods or by chemical methods. The invention also extends to methods for synthesizing and activating the precursor electrodes and to cells and batteries containing such electrodes.

Positive electrodes for lithium batteries

A method of stabilizing a metal oxide or lithium-metal-oxide electrode comprises contacting a surface of the electrode, prior to cell assembly, with an aqueous or a non-aqueous acid solution having a pH greater than 4 but less than 7 and containing a stabilizing salt, for a time and at a temperature sufficient to etch the surface of the electrode and introduce stabilizing anions and cations from the salt into said surface. The structure of the bulk of the electrode remains unchanged during the acid treatment. The stabilizing salt comprises fluoride and at least one cationic material selected from the group consisting of ammonium, phosphorus, titanium, silicon, zirconium, aluminum, and boron.

This invention provides a lithium-oxygen or lithium-air electrochemical cell comprising a negative electrode, an electrolyte, and a porous activated positive electrode comprising lithium-rich electrocatalytic materials suitable for use in lithium-oxygen (air) cells and batteries. The activated positive electrode is produced by activating a precursor electrode formed from a material comprising one or more metal oxide compounds of general formula xLiO.yMO, in which 0&#x3c;x&#x2266;4, 0&#x3c;y&#x2266;1, and 0&#x3c;z&#x2266;3, in which M is typically, but not exclusively, a transition metal, excluding LiMnOas a sole metal oxide compound in the precursor electrode. LiO is extracted from the above-mentioned precursors to activate the electrode either by electrochemical methods or by chemical methods. The invention extends to batteries containing such electrochemical cells.

Lithium-oxygen (AIR) electrochemical cells and batteries

An uncycled, preconditioned positive metal-oxide or lithium-metal-oxide electrode for a non-aqueous lithium electrochemical cell, the electrode being preconditioned in an aqueous or a non-aqueous solution containing stabilizing cations and anions that are etched into the electrode surface to form a protective layer. Methods of preconditioning the electrodes are disclosed as are electrochemical cells and batteries containing the electrodes.

An activated electrode for a non-aqueous electrochemical cell is disclosed with a precursor thereof a lithium metal oxide with the formula x{zLiMnO&#x2022;(1-z)LiM'O}.(1-x)LiMnMOfor 0&#x3c;x&#x3c;1; 0&#x2266;y&#x2266;0.5; and 0&#x3c;z&#x3c;1, comprised of layered zLiMnO.(1-z)LiM&#x2032;Oand spinel LiMnMOcomponents, physically mixed or blended with one another or separated from one another in a compartmentalized electrode, in which M is one or more metal ions, and in which M&#x2032; is selected from one or more first-row transition metal ions, The electrode is activated by removing lithium and lithia, from the precursor. A cell and battery are also disclosed incorporating the disclosed positive electrode.

Manganese oxide composite electrodes for lithium batteries

Processes are provided for making dense, spherical mixed-metal carbonate or phosphate precursors that are particularly well suited for the production of active materials for electrochemical devices such as lithium ion secondary batteries. Exemplified methods include precipitating dense, spherical particles of metal carbonates or metal phosphates from a combined aqueous solution using a precipitating agent such as ammonium hydrogen carbonate, sodium hydrogen carbonate, or a mixture that includes sodium hydrogen carbonate. Other exemplified methods include precipitating dense, spherical particles of metal phosphates using a precipitating agent such as ammonium hydrogen phosphate, ammonium dihydrogen phosphate, sodium phosphate, sodium hydrogen phosphate, sodium dihydrogen phosphate, or a mixture of any two or more thereof. Further provided are compositions of and methods of making dense, spherical metal oxides and metal phosphates using the dense, spherical metal precursors. Still further provided are electrodes and batteries using the same.

Processes for making dense, spherical active materials for lithium-ion cells

An activated electrode for a non-aqueous electrochemical cell is disclosed with a precursor thereof a lithium metal oxide with the formula x{zLiMnO.(1&#x2212;z)LiM'O}.(1&#x2212;x)LiMnMOfor 0&#x3c;x&#x3c;1; 0&#x2266;y&#x2266;0.5; and 0&#x3c;z&#x3c;1, comprised of layered zLiMnO.(1&#x2212;z)LiM&#x2032;Oand spinel LiMnMOcomponents, physically mixed or blended with one another or separated from one another in a compartmentalized electrode, in which M is one or more metal ions, and in which M&#x2032; is selected from one or more first-row transition metal ions, The electrode is activated by removing lithium and lithia, from the precursor. A cell and battery are also disclosed incorporating the disclosed positive electrode.

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Naperville, IL, United States of America

Sun-Ho Kang