# US 10,865,493 B2 · Synthesis of lithium manganese dioxide micro/nanostructures

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- Number: US 10,865,493 B2
- Document ID: US10865493B2
- Status: Granted
- Kind: B2
- Application number: 16/109,407
- Filed: 2018-08-22
- Published: 2019-05-09
- Granted: 2020-12-15
- Earliest claimed: 2017-08-22
- Applicants: Sepideh Behboudikhiavi; Mehran Javanbakht; Sayed Ahmad Mozaffari; Mehdi Ghaemi
- Inventors: Sepideh Behboudikhiavi; Mehran Javanbakht; Sayed Ahmad Mozaffari; Mehdi Ghaemi
- Web page: https://patentgrep.com/patent/US10865493B2

## CPC

- C25D 9/06: by anodic processes
- C01G 45/1228: of the type (MnO2)-, e.g. LiMnO2 or Li(MxMn1-x)O2
- C25D 13/02: with inorganic material
- C25D 13/18: using modulated, pulsed, or reversing current
- H01M 4/505: of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
- 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
- C01P 2004/03: obtained by SEM
- 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 2004/32: Spheres
- C01P 2006/12: Surface area
- C01P 2006/16: Pore diameter
- C01P 2006/17: Pore diameter distribution
- C01P 2006/40: Electric properties
- Y02E 60/10: Energy storage using batteries
- C25D: PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- 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)
- H01M: PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- 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

A method for synthesizing mesoporous lithium manganese dioxide micro/nanostructures, in accord with an implementation, includes preparing an aqueous metal salt solution by dissolving a lithium ion source and a manganese ion source in water, and subjecting the aqueous metal salt solution to an anodic electrodeposition process. The anodic electrodeposition process may include transferring the aqueous metal salt solution to an electrodeposition bath comprising an anode electrode and a cathode electrode, such that the anode electrode and the cathode electrode are immersed in the transferred aqueous metal salt solution, and applying a pulse reverse current through the electrodeposition bath to obtain lithium manganese dioxide deposited on a surface of the anode electrode.

## Claims

### Claim 1

A method for synthesizing mesoporous lithium manganese dioxide micro/nanostructures, the method comprising:
preparing an aqueous metal salt solution by dissolving a lithium ion source and a manganese ion source in water; and
subjecting the aqueous metal salt solution to an anodic electrodeposition process by:
transferring the aqueous metal salt solution to an electrodeposition bath containing an anode electrode and a cathode electrode, the anode electrode and the cathode electrode being immersed in the transferred aqueous metal salt solution; and
applying a pulse reverse current through the electrodeposition bath to obtain lithium manganese dioxide deposited on a surface of the anode electrode.

### Claim 2 (depends on 1)

The method according to claim 1, wherein applying the pulse reverse current through the electrodeposition bath includes applying a modulated pulse reverse current with an anodic duty cycle adjustable between 20% and 90%, a cathodic duty cycle adjustable between 3% and 50%, and a frequency adjustable between 5 Hz and 500 Hz.

### Claim 3 (depends on 2)

The method according to claim 2, wherein applying the modulated pulse reverse current includes applying the modulated pulse reverse current with an adjustable anodic pulse width of between 5 μs and 100 ms and an adjustable cathodic pulse width of between 1 μs and 95 ms.

### Claim 4 (depends on 3)

The method according to claim 3, wherein applying the modulated pulse reverse current includes applying the modulated pulse reverse current with an adjustable anodic peak current density and an adjustable cathodic peak current density of between 100 μAdm−2 and 10 Adm−2.

### Claim 5 (depends on 1)

The method according to claim 1, wherein subjecting the aqueous metal salt solution to the anodic electrodeposition process further includes concurrently stirring the aqueous metal salt solution in the electrodeposition bath.

### Claim 6 (depends on 5)

The method according to claim 5, wherein stirring the aqueous metal salt solution in the electrodeposition bath includes stirring the aqueous metal salt solution in the electrodeposition bath with a speed of 20 to 600 rpm.

### Claim 7 (depends on 1)

The method according to claim 1, further comprising adjusting pH of the aqueous metal salt solution to between 2.0 and 6.5.

### Claim 8 (depends on 1)

The method according to claim 1, further comprising removing the obtained lithium manganese dioxide from the surface of the anode electrode.

### Claim 9 (depends on 1)

The method according to claim 1, further comprising:
heating the obtained lithium manganese dioxide at a first temperature in a range of 100° C. to 200° C.;
increasing the first temperature to a second temperature with a slope of between 1° C./min. and 10° C./min.; and
heating the obtained lithium manganese dioxide at the second temperature in a range of 300° C. to 500° C.

### Claim 10 (depends on 9)

The method according to claim 9, wherein heating the obtained lithium manganese dioxide at the first temperature in a range of 100° C. to 200° C. includes heating the obtained lithium manganese dioxide at the first temperature in a range of 100° C. to 200° C. for a first period of 60 min. to 12 hours.

### Claim 11 (depends on 9)

The method according to claim 9, wherein heating the obtained lithium manganese dioxide at the second temperature in a range of 300° C. to 500° C. includes heating the obtained lithium manganese dioxide at the second temperature in a range of 300° C. to 500° C. for a second period of 180 min. to 14 hours.

### Claim 12 (depends on 1)

The method according to claim 1, wherein temperature of the electrodeposition bath is kept between 70° C. and 100° C.

### Claim 13 (depends on 1)

The method according to claim 1, wherein applying the pulse reverse current through the electrodeposition bath includes applying the pulse reverse current through the electrodeposition bath for a period of 30 min. to 24 hours.

### Claim 14 (depends on 1)

The method according to claim 1, wherein the lithium salt is selected from the group consisting of lithium hydroxide, lithium carbonate, lithium sulfate, lithium nitrate, lithium bromide, lithium chloride, lithium perchlorate, lithium acetate, lithium oxalate, and combinations thereof.

### Claim 15 (depends on 1)

The method according to claim 1, wherein the manganese salt is selected from the group consisting of manganese bromide, manganese carbonate, manganese chloride, manganese nitrate, manganese sulfate, manganese perchlorate, manganese acetate and manganese oxalate, and combinations thereof.

### Claim 16 (depends on 1)

The method according to claim 1, wherein adjusting pH of the aqueous metal salt solution between 2.0 and 6.5 includes adding a specific amount of an acid solution, the acid solution selected from the group consisting of sulfuric acid, hydrochloric acids, acetic acid, perchloric acid, and combinations thereof.

### Claim 17 (depends on 1)

The method according to claim 1, wherein the cathode electrode includes a sheet made of any one of lead, stainless steel, graphite, platinum, platinum-coated substrates, gold, and gold-coated substrates.

### Claim 18 (depends on 1)

The method according to claim 1, wherein the anode electrode includes a sheet made of any one of titanium, stainless steel, platinum, platinum-coated substrates, gold, and gold-coated substrates.