# US 2020/0403237 A1 · Positive manganese lithium oxide-stabilised electrode for a secondary lithium battery and a method for producing same

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- Number: US 2020/0403237 A1
- Document ID: US20200403237A1
- Status: Published application
- Kind: A1
- Application number: 16/975,177
- Filed: 2018-12-18
- Published: 2020-12-24
- Earliest claimed: 2018-05-24
- Assignees: Instituto Tecnologico De Santo Domingo
- Applicants: Instituto Tecnologico De Santo Domingo
- Inventors: Melvin Arias; Lorenzo Caputi; Isaias Martinez; Parra Santana; Noel Upia
- Web page: https://patentgrep.com/patent/US20200403237A1

## CPC

- H01M 4/505: of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
- C01G 37/006: {Compounds containing chromium, with or without oxygen or hydrogen, and containing two or more other elements}
- C01G 45/1228: of the type (MnO2)-, e.g. LiMnO2 or Li(MxMn1-x)O2
- C01G 45/1242: of the type (Mn2O4)-, e.g. LiMn2O4 or Li(MxMn2-x)O4
- C01G 49/0072: {containing manganese}
- C01G 53/42: containing alkali metals, e.g. LiNiO2
- H01M 4/525: of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
- H01M 10/0525: Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
- C01P 2002/32: spinel-type (AB2O4)
- C01P 2002/54: one element only
- C01P 2002/72: by d-values or two theta-values, e.g. as X-ray diagram
- C01P 2002/82: by IR- or Raman-data
- C01P 2004/03: obtained by SEM
- C01P 2004/10: extending in one dimension, e.g. needle-like
- C01P 2004/16: Nanowires or nanorods, i.e. solid nanofibres with two nearly equal dimensions between 1-100 nanometer
- C01P 2004/24: Nanoplates, i.e. plate-like particles with a thickness from 1-100 nanometer
- C01P 2006/40: Electric properties
- H01M 2004/028: {Positive electrodes}
- Y02E 60/10: Energy storage using batteries
- H01M: PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- C01G: COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F (metal hydrides {monoborane, diborane or addition complexes thereof} C01B6/00; salts of oxyacids of halogens C01B11/00; peroxides, salts or peroxyacids C01B15/00; thiosulfates, dithionites, polythionates C01B17/64; compounds containing selenium, or tellurium C01B19/00; binary compounds of nitrogen with metals C01B21/06; azides C01B21/08; {compounds containing nitrogen, other non-metals and metal C01B21/082}; metal amides C01B21/092; nitrites C01B21/50; {compounds of noble gases C01B23/0005}; phosphides C01B25/08; salts of oxyacids of phosphorus C01B25/16; carbides C01B32/90; compounds containing silicon C01B33/00; compounds containing boron C01B35/00; compounds having molecular sieve properties but not having base-exchange properties C01B37/00; compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites, C01B39/00; cyanides C01C3/08; salts of cyanamide C01C3/16; thiocyanates C01C3/20)
- C01P: INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- Y02E: REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION

## Abstract

The present invention provides the compound LiMn2--x-yNaxMyO4/Na1-zMnLizMtO2/Na2CO3, to be used as a positive electrode for rechargeable lithium ion battery, where M is a metal or metalloid, 0.0≤x≤0.5; 0.0≤y≤0.5; 0.1≤z≤0.5; 0.0≤t≤0.3; as well as the method for producing it. The synthesis process includes disolving or mixing the precursor metals and then calcining them in air or controlled atmosphere in a temperature range between 250° C. and 1000° C., and for a time range of 0.5 h to 72 h to obtain the composite proposed with the interaction of its three present phases, presenting a high retention capacity during repeated loading/unloading cycles and excellent discharge capacity both at room temperature and up to 55° C.

## Claims

### Claim at position 1

1-13. (canceled)

### Claim 14

A method for producing a positive manganese lithium oxide stabilized electrode for a secondary lithium battery, the method comprising the steps of:
producing a three phases compound including lithium manganese oxide with spinel structure (LiMn2-x-yNaxMyO4, where M is a metal, and for 0.0≤x≤0.5; 0.0≤y≤0.5), sodium manganese oxide-lithium (Na1-z-tMnLizMtO2, where 0.1≤z≤0.5; 0.0≤t≤0.3), and sodium carbonate (Na2CO3);
wherein a molar ratio between lithium (Li), manganese (Mn), sodium (Na) and metal (M) selected from the group consisting of Li, Sr, Mg, Ni, Cr, Fe, Al, Co, Cu, Ga, In, Ca, Ti, Zn, Si; which is indicated by Li:Mn:Na:M; in the ratio of 1:2-nM: nna: nM;
wherein 0.01≤nna≤0.5; 0.0≤nM≤0.5, in a polymer solution or a mixture of the precursors and then subjected to a heat treatment of 250° C. to 1000° C. in an air or inert atmosphere or a combination of both.

### Claim 15 (depends on 14)

The method according to claim 14, wherein the compound is a powder.

### Claim 16 (depends on 14)

The method according to claim 14, wherein the compound is a micro and nano fibers, rods, needles, or composite porous plates.

### Claim 17

A positive manganese lithium oxide stabilized electrode for a secondary lithium battery comprising a compound including LiMn2-x-yNaxMyO4/Na1-zMnLizMtO2/Na2CO3, wherein 0.0≤x≤0.5; 0.0≤y≤0.5; 0.1≤z≤0.5; 0.0≤t≤0.3; and M is selected from the group consisting of Li, Sr, Mg, Ni, Cr, Fe, Al, Co, Cu, Ga, In, Ca, Ti, and Zn; Yes.

### Claim 18 (depends on 17)

The positive manganese lithium oxide stabilized electrode according to claim 17, wherein the compound is micro and nano fibers of the active material stabilized to be used as positive electrode in rechargeable lithium-ion batteries, and comprises LiMn2-x-yNaxMyO4/Na1-zMnLizMtO2/Na2CO3 where 0.0≤x≤0.5; 0.0≤y≤0.5; 0.1≤z≤0.5; 0.0≤t≤0.3, and M is selected from the group consisting of Li, Sr, Mg, Ni, Cr, Fe, Al, Co, Cu, Ga, In, Ca, Ti, and Zn.

### Claim 19 (depends on 17)

The positive manganese lithium oxide stabilized electrode according to claim 17, wherein the compound is nano bars of the active material stabilized to be used as positive electrode in rechargeable lithium-ion batteries comprises LiMn2-x-yNaxMyO4/Na1-zMnLizMtO2/Na2CO3; where 0.0≤x≤0.5; 0.0≤y≤0.5; 0.1≤z≤0.5; 0.0≤t≤0.3; and M is selected from the group consisting of Li, Sr, Mg, Ni, Cr, Fe, Al, Co, Cu, Ga, In, Ca, Ti, and Zn.

### Claim 20 (depends on 17)

The positive manganese lithium oxide stabilized electrode according to claim 17, wherein the compound is micro and nano needles of the active material stabilized to be used as positive electrode in rechargeable lithium-ion batteries and comprises LiMn2-x-yNaxMyO4/Na1-zMnLizMtO2/Na2CO3; where 0.0≤x≤0.5; 0.0≤y≤0.5; 0.1≤z≤0.5; 0.0≤t≤0.3; and M is selected from the group consisting of Li, Sr, Mg, Ni, Cr, Fe, Al, Co, Cu, Ga, In, Ca, Ti, and Zn.

### Claim 21 (depends on 17)

The positive manganese lithium oxide stabilized electrode according to claim 17, wherein the compound is porous micro and nano plates of the active material stabilized to be used as positive electrode in rechargeable lithium-ion batteries and comprises LiMn2-x-yNaxMyO4/Na1-zMnLizMtO2/Na2CO3; where 0.0≤x≤0.5; 0.0≤y≤0.5; 0.1≤z≤0.5; 0.0≤t≤0.3; and M is selected from the group consisting of Li, Sr, Mg, Ni, Cr, Fe, Al, Co, Cu, Ga, In, Ca, Ti, and Zn.

### Claim 22

A method for the production of a positive manganese lithium oxide stabilized electrode for a secondary lithium battery, the method comprising the steps of:
producing a three phases compound including lithium manganese oxide with spinel structure (LiMn2-x-yNaxMyO4, where M is a metal, and for 0.0≤x≤0.5; 0.0≤y≤0.5), sodium manganese oxide lithium (Na1-z-tMnLizMtO2, where 0.1≤z≤0.5; 0.0≤t≤0.3), and sodium carbonate (Na2CO3) from mixing LiMn2O4 and Na2CO3 spinel in a range of 200° C. to 700° C. in a time range of 0.1 h to 20 h in an air atmosphere.

### Claim 23 (depends on 22)

The method according to claim 22, wherein the compound is a powder of the stabilized active material to be used as a positive electrode in rechargeable lithium-ion batteries and comprises LiMn2-xNaxO4/Na1-zMnLizO2/Na2CO3; where 0.0≤x≤0.5; 0.0≤y≤0.5; 0.1≤z≤0.5; 0.0≤t≤0.3.

### Claim 24 (depends on 22)

The method according to claim 22, wherein the compound is nano bars of the stabilized active material to be used as a positive electrode in rechargeable lithium-ion batteries and comprises LiMn2-xNaxO4/Na1-zMnLizO2/Na2CO3; where 0.0≤x≤0.5; 0.0≤y≤0.5; 0.1≤z≤0.5; 0.0≤t≤0.3.

### Claim 25 (depends on 22)

The method according to claim 22, wherein the compound are micro and nano particles, fibers, bars, needles, porous plates of the stabilized active material to be used as a positive electrode in rechargeable lithium-ion batteries and comprises LiMn2-xNaxO4/Na1-zMnLizO2/Na2CO3; where 0.0≤x≤0.5; 0.0≤y≤0.5; 0.1≤z≤0.5; 0.0≤t≤0.3.