CN103682317A - Li2MnO3 nanowire as well as preparation method and application thereof - Google Patents

Li2MnO3 nanowire as well as preparation method and application thereof Download PDF

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Publication number
CN103682317A
CN103682317A CN201310721584.7A CN201310721584A CN103682317A CN 103682317 A CN103682317 A CN 103682317A CN 201310721584 A CN201310721584 A CN 201310721584A CN 103682317 A CN103682317 A CN 103682317A
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China
Prior art keywords
nano wire
mno
li2mno3
nanowire
lithium battery
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Pending
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CN201310721584.7A
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Chinese (zh)
Inventor
魏明灯
吴小敏
费海龙
李亚峰
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Fuzhou University
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Fuzhou University
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Priority to CN201310721584.7A priority Critical patent/CN103682317A/en
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G45/00—Compounds of manganese
    • C01G45/12—Manganates manganites or permanganates
    • C01G45/1221—Manganates or manganites with a manganese oxidation state of Mn(III), Mn(IV) or mixtures thereof
    • C01G45/125—Manganates or manganites with a manganese oxidation state of Mn(III), Mn(IV) or mixtures thereof of the type[MnO3]n-, e.g. Li2MnO3, Li2[MxMn1-xO3], (La,Sr)MnO3
    • C01G45/1257—Manganates or manganites with a manganese oxidation state of Mn(III), Mn(IV) or mixtures thereof of the type[MnO3]n-, e.g. Li2MnO3, Li2[MxMn1-xO3], (La,Sr)MnO3 containing lithium, e.g. Li2MnO3, Li2[MxMn1-xO3
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention discloses a Li2MnO3 nanowire as well as a preparation method and application thereof. The molten-salt growth method is adopted to synthesize the Li2MnO3 nanowire at the a lower temperature, wherein the diameter of the Li2MnO3 nanowire is 5-25 nm, and the length of the Li2MnO3 nanowire ranges from hundreds of nanometers to a few microns. The Li2MnO3 nanowire is used as the positive pole of a lithium battery. A one-dimensional nano material is an excellent lithium battery electrode material. The invention provides a method for preparing a high purity Li2MnO3 nanowire for the first time, and the advantages of convenience for operation, low cost and good reproducibility are realized; the Li2MnO3 nanowire prepared through the method is high in purity and excellent in performance.

Description

A kind of Li 2mnO 3nano wire and its preparation method and application
Technical field
The invention belongs to anode material of lithium battery preparation field, be specifically related to a kind of Li 2mnO 3nano wire and its preparation method and application.
Background technology
Since last century, lithium battery was succeeded in developing, lithium battery is widely used, but will obtain good cycle, and it is scientist's research emphasis that specific capacity height waits the good anode material of lithium battery of chemical property all the time.Present industrial conventional positive electrode, as LiCoO 2, LiNiO 2, LiMnO 2, their capacity is not high, only has 120 mAh/g left and right.Along with the rise of nano material, monodimension nanometer material is considered to a kind of very promising li-ion electrode materials, and positive electrode is the bottleneck of lithium ion battery.Also there is not at present preparation Li 2mnO 3the Patents report of nano wire.
Summary of the invention
The object of the present invention is to provide a kind of Li 2mnO 3nano wire and its preparation method and application, provides a kind of highly purified Li for preparing first 2mnO 3the method of nano wire, it is easy and simple to handle, cost is low, purity is high, excellent performance, favorable reproducibility.
For achieving the above object, the present invention adopts following technical scheme:
A kind of Li 2mnO 3the diameter of nano wire is 5-25nm, and length is that hundreds of nanometer is to several microns.
Adopt molten salt growth method synthetic Li at a lower temperature 2mnO 3nano wire.Comprise the following steps:
(1) 0.2g manganous fluoride is mixed with 10g sodium nitrate after mill even, in 540 ℃ of calcinings 3 hours, washing, absolute ethyl alcohol filtered each 3 times, dried 4 hours, obtained Mn for 70 ℃ 2o 3presoma nano wire;
(2) by 0.1gMn 2o 3after presoma nano wire mixes with 5g lithium nitrate, mill is even, then by reaction condition calcining, washing, alcohol wash and the oven dry of step (1), obtains highly purified Li 2mnO 3nano wire.
Described manganous fluoride is to be obtained by hydrofluoric acid and manganese carbonate reaction.
Described Li 2mnO 3nano wire is as lithium battery anode.
Lithium battery assembling: in mass ratio: Li 2mnO 3nano wire: polytetrafluoroethylene: after super carbon=7:2:1 mixed grinding, be coated in equably 0.25 cm 2aluminium foil on do positive pole, reference electrode and electrode is to lithium metal, electrolyte is by 1M LiPF 6eC+DMC+EMC solution; All assembling process all carry out in glove box; In described EC+DMC+EMC solution, the volume ratio of EC, DMC, EMC is 1:1:1.
Remarkable advantage of the present invention is: a kind of highly purified Li for preparing is provided first 2mnO 3the method of nano wire, it is easy and simple to handle, cost is low, purity is high, excellent performance, and favorable reproducibility, with this high-purity Li 2mnO 3the lithium battery that nano wire obtains as lithium battery anode has very high specific capacity, in current density, is 0.02 Ag -1under discharge and recharge after 27 circles, discharge capacity has reached 159 mAh/g.
Accompanying drawing explanation
Fig. 1 is Li 2mnO 3the SEM figure (a) of nano wire and TEM figure (b).
Fig. 2 is Li 2mnO 3the discharge curve of nano line electrode material (c) and specific discharge capacity (d).
Embodiment
It is 5-25nm left and right that the present invention has synthesized diameter at a lower temperature by simple molten salt growth method, and length is that hundreds of nanometer is to the highly purified Li of several microns of left and right 2mnO 3nano wire.
With this high-purity Li 2mnO 3the lithium battery that nano wire obtains as lithium battery anode has very high specific capacity, in current density, is 0.02 Ag -1under discharge and recharge 27 circles after discharge capacity reached 159 mAh/g, other same provisional capital is under very low current density, to present lower specific capacity.
High-purity Li 2mnO 3the preparation method of nano wire is that after 0.2g manganous fluoride (obtaining with hydrofluoric acid and manganese carbonate reaction) is mixed with 10g sodium nitrate, mill is even, and in 540 ℃ of calcinings 3 hours, washing, absolute ethyl alcohol filtered each 3 times, dried 4 hours, obtained Mn for 70 ℃ 2o 3presoma nano wire, after then its 0.1g being mixed with 5g lithium nitrate, mill is even obtains high-purity Li by above-mentioned same step and reaction condition again 2mnO 3nano wire.
Lithium battery assembling: Li in mass ratio 2mnO 3nano wire: polytetrafluoroethylene: be coated in equably 0.25 cm after super carbon=7:2:1 mixed grinding 2aluminium foil on do positive pole, reference electrode and electrode is to lithium metal, electrolyte is by 1M LiPF 6eC+DMC+EMC (EC/DMC/EMC=1/1/1 v/v) solution.All assembling process all carry out in glove box.
From (a) figure, can find out Li 2mnO 3the length of nano wire probably in hundreds of nanometer in scope between several microns, the about 5-25 nanometer of diameter; From (b) figure, can find out Li 2mnO 3the degree of crystallinity of nano wire is very high; From (c) figure, can find out Li 2mnO 3nano line electrode material discharging specific capacity is fallen after rising, and first circle specific discharge capacity is up to 160 mAh/g; From (d) figure, can find out, be 0.02 Ag in current density -1under discharge and recharge 27 circles after discharge capacity reached 159 mAh/g, and cycle performance is fine.
The foregoing is only preferred embodiment of the present invention, all equalizations of doing according to the present patent application the scope of the claims change and modify, and all should belong to covering scope of the present invention.

Claims (6)

1. a Li 2mnO 3nano wire, is characterized in that: described Li 2mnO 3the diameter of nano wire is 5-25nm, and length is that hundreds of nanometer is to several microns.
2. prepare Li as claimed in claim 1 for one kind 2mnO 3the method of nano wire, is characterized in that: adopt molten salt growth method synthetic Li at a lower temperature 2mnO 3nano wire.
3. Li according to claim 2 2mnO 3the preparation method of nano wire, is characterized in that: comprise the following steps:
(1) 0.2g manganous fluoride is mixed with 10g sodium nitrate after mill even, in 540 ℃ of calcinings 3 hours, washing, absolute ethyl alcohol filtered each 3 times, dried 4 hours, obtained Mn for 70 ℃ 2o 3presoma nano wire;
(2) by 0.1gMn 2o 3after presoma nano wire mixes with 5g lithium nitrate, mill is even, then by reaction condition calcining, washing, alcohol wash and the oven dry of step (1), obtains highly purified Li 2mnO 3nano wire.
4. Li according to claim 3 2mnO 3the preparation method of nano wire, is characterized in that: described manganous fluoride is to be obtained by hydrofluoric acid and manganese carbonate reaction.
5. a Li as claimed in claim 1 2mnO 3the application of nano wire, is characterized in that: described Li 2mnO 3nano wire is as lithium battery anode.
6. Li according to claim 5 2mnO 3the application of nano wire, is characterized in that: lithium battery assembling: in mass ratio: Li 2mnO 3nano wire: polytetrafluoroethylene: after super carbon=7:2:1 mixed grinding, be coated in equably 0.25 cm 2aluminium foil on do positive pole, reference electrode and electrode is to lithium metal, electrolyte is by 1M LiPF 6eC+DMC+EMC solution; All assembling process all carry out in glove box; In described EC+DMC+EMC solution, the volume ratio of EC, DMC, EMC is 1:1:1.
CN201310721584.7A 2013-12-25 2013-12-25 Li2MnO3 nanowire as well as preparation method and application thereof Pending CN103682317A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104022277A (en) * 2014-05-16 2014-09-03 武汉理工大学 Li2MnO3 nanowire, preparation method and application thereof
CN104084202A (en) * 2014-07-14 2014-10-08 北京工业大学 In-situ molten salt preparation method and application of Ag/Mn2O3 nanowire catalyst
CN111172743A (en) * 2020-01-16 2020-05-19 浙江大学 Method for rapidly preparing composite metal oxide nano film material at low temperature

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20060099508A1 (en) * 2000-06-22 2006-05-11 The University Of Chicago Lithium metal oxide electrodes for lithium cells and batteries
CN1817800A (en) * 2006-01-26 2006-08-16 合肥工业大学 Synthesis of series nanometer lithium and manganese oxide for lithium ion battery

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20060099508A1 (en) * 2000-06-22 2006-05-11 The University Of Chicago Lithium metal oxide electrodes for lithium cells and batteries
CN1817800A (en) * 2006-01-26 2006-08-16 合肥工业大学 Synthesis of series nanometer lithium and manganese oxide for lithium ion battery

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
XIAOMIN WU等: "Facile synthesis of Li2MnO3 nanowires for lithium-ion battery cathodes", 《NEW JOURNAL OF CHEMISTRY》 *

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104022277A (en) * 2014-05-16 2014-09-03 武汉理工大学 Li2MnO3 nanowire, preparation method and application thereof
CN104022277B (en) * 2014-05-16 2016-01-06 武汉理工大学 Li 2mnO 3nano wire and its preparation method and application
CN104084202A (en) * 2014-07-14 2014-10-08 北京工业大学 In-situ molten salt preparation method and application of Ag/Mn2O3 nanowire catalyst
CN104084202B (en) * 2014-07-14 2016-04-13 北京工业大学 A kind of Ag/Mn 2o 3the fuse salt original position preparation method of nano-wire catalyst and application
CN111172743A (en) * 2020-01-16 2020-05-19 浙江大学 Method for rapidly preparing composite metal oxide nano film material at low temperature
CN111172743B (en) * 2020-01-16 2021-10-19 浙江大学 Method for rapidly preparing composite metal oxide nano film material at low temperature

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Application publication date: 20140326