CN108455674A - A kind of preparation method of spindle bodily form LiMn2O4 hollow pipe - Google Patents
A kind of preparation method of spindle bodily form LiMn2O4 hollow pipe Download PDFInfo
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- CN108455674A CN108455674A CN201711500186.7A CN201711500186A CN108455674A CN 108455674 A CN108455674 A CN 108455674A CN 201711500186 A CN201711500186 A CN 201711500186A CN 108455674 A CN108455674 A CN 108455674A
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- limn2o4
- hollow pipe
- lithium
- manganese
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- 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
- C01G45/1242—Manganates or manganites with a manganese oxidation state of Mn(III), Mn(IV) or mixtures thereof of the type [Mn2O4]-, e.g. LiMn2O4, Li[MxMn2-x]O4
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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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
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/30—Particle morphology extending in three dimensions
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
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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
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
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- 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 kind of preparation methods of spindle bodily form LiMn2O4 hollow pipe, using soluble lithium salt, bivalent soluble manganese salt and potassium permanganate as raw material, it is precipitating reagent by template, urea of naphthalene, pass through hydro-thermal reaction and calcining, obtain spindle-shaped LiMn2O4 hollow pipe, the length of 200 800nm.The present invention obtains presoma as template using the easy sublimation characteristics of naphthalene by hydro-thermal reaction, presoma is calcined again, naphthalene occurs distillation and is escaped from lithium manganate material, and LiMn2O4 further increases crystallinity at high temperature, finally obtains spindle-shaped LiMn2O4 hollow pipe.The spindle bodily form LiMn2O4 hollow pipe can be used as anode material of lithium battery, improve the specific capacity and power density of lithium battery, have a good application prospect.
Description
Technical field
The present invention relates to a kind of preparation methods of lithium manganate material, having spindle-shaped LiMn2O4 more particularly to one kind
The preparation method of hollow pipe.
Background technology
In recent years, various electronic equipment rapid developments, the requirement for battery is higher and higher, has both required battery to have sufficiently large
Capacity, it is also necessary to its over numerous cycles have smaller decaying.In numerous battery types, lithium ion battery is considered
Most potential battery.Also, lithium battery has also begun to take shape in the market, arrives electric vehicle greatly, small to notebook, hand
Machine all be unable to do without lithium battery.
LiMn2O4 (LiMn2O4) due to have the characteristics that voltage it is high, it is cheap, resourceful, with it is environmental-friendly, become
One of most promising anode material for lithium-ion batteries obtains widely studying and applying.Currently, the method master of synthetic lithium manganate
There are high temperature solid-state method, melt impregnation, hydrothermal synthesis method, sol-gal process, spray drying process etc..Wherein, solid phase method technique
Simply, but synthesising reacting time is long, and product uniformity is poor, and sol-gal process needs a large amount of organic reagents, and environmental pollution is big,
And spray drying process etc. is higher to equipment requirement.Hydro-thermal method is a kind of widely used method in existing preparation method.
As cell positive material, the chemical property of LiMn2O4 and the preparation process of material, crystal structure, crystallite dimension
With pattern etc., there is larger relationship.
In recent years, how LiMn2O4 and its chemical property is improved, had been a hot spot of research.Such as application No. is
201610047742.9 Chinese patent application discloses a kind of method for the LiMn2O4 preparing high-purity；Application No. is
201610971181.1 Chinese patent application, disclose a kind of promotion manganate cathode material for lithium chemical property at high temperature
The method of stability.For another example applicant formerly submit application No. is 201710159408.7 Chinese patent applications, be logical
Water-soluble amino acid is crossed as precipitating reagent and soft template, promotes the development of LiMn2O4 crystal structure, being formed has ten four sides
The lithium manganate material of the bodily form, to improve its chemical property.
On the basis of existing result of study, the relationship between the pattern of LiMn2O4 and its chemical property is determined, and
The relationship between preparation method and pattern is studied, for preparing high performance lithium manganate material, and then breaks through existing battery skill
The problem of art, has great importance.
Invention content
The purpose of the present invention is to provide a kind of preparation methods of spindle bodily form LiMn2O4 hollow pipe.
The purpose of the present invention is achieved through the following technical solutions：
A kind of preparation method of spindle bodily form LiMn2O4 hollow pipe, includes the following steps：
(1) soluble lithium salt is configured to the lithium salt solution of 0.5-1mol/L with deionized water；By bivalent soluble manganese salt
The ratio for being 2-3: 1 according to molar ratio with potassium permanganate is uniformly mixed, is then configured to manganese salt solution with deionized water, described
The total concentration of manganese ion is 1-1.2mol/L in manganese salt solution；The urea liquid for being 0.5mol/L with deionized water compound concentration；
(2) naphthalene is added in absolute ethyl alcohol, stirring forms uniform solution；
(3) lithium salt solution in step (1) is added in hydrothermal reaction kettle, addition is hydrothermal reaction kettle volume
, the ethanol solution of naphthalene is then added, stirs evenly to form albescent suspension, wherein mole of naphthalene and lithium ion
Than being 1: 1-2；
(4) again under stirring conditions, manganese salt solution and urea in step (1) is added into shallow white suspension successively
Solution obtains reaction precursor liquid, wherein the volume of the reaction precursor liquid is the 2/3-3/4 of hydrothermal reaction kettle volume；
(5) hydrothermal reaction kettle is sealed, 1~3h of hydro-thermal reaction, is then separated by solid-liquid separation at 140-180 DEG C, consolidates what is obtained
Body product is washed 2-3 times with absolute ethyl alcohol and deionized water respectively, and then drying obtains presoma at 70-90 DEG C；
(6) presoma is calcined to 30min-1h at 260-320 DEG C to get to spindle bodily form LiMn2O4 hollow pipe.
Preferably, the soluble lithium salt is one or more in lithium nitrate, lithium acetate, lithium chloride, and the divalent can
Dissolubility manganese salt is one or more in manganese nitrate, manganese acetate, manganese chloride.
Preferably, in the step (4), it is 2-2.2 to control the ratio between the integral molar quantity of manganese ion and the mole of lithium ion:
1。
Technical solution according to the invention, obtained product is spindle bodily form LiMn2O4 hollow pipe namely both ends are in needle point
The length of the hollow pipe of shape, hollow pipe is 200-800nm.
Naphthalene, as template, is first dissolved in absolute ethyl alcohol by technical solution disclosed by the invention using the easy sublimation characteristics of naphthalene
It is middle to form uniform solution, it is then added in lithium salt solution, to improve the uniformity that naphthalene disperses in lithium salt solution, that is, carries
The high degree that is uniformly dispersed of template, contributes to follow-up hydrothermal reaction to carry out that tiny product is obtained by the reaction as nucleation site.
Hydro-thermal reaction is carried out after manganese salt solution and urea liquid is added, operation is simple, and the main component of the presoma of formation is manganese
Sour lithium and naphthalene, using high-temperature calcination, naphthalene occur distillation is escaped from lithium manganate material, meanwhile, LiMn2O4 at high temperature into
One step improves its crystallinity.
The present invention rationally controls the dosage of lithium, manganese using naphthalene as template, the template of appropriate amount is added and as precipitation
The urea of agent forms spindle bodily form LiMn2O4 hollow pipe by hydrothermal step and calcining step.
Obtained hammer body shape LiMn2O4 hollow pipe is used as anode material of lithium battery, due to this special hollow tubular shape
Looks have larger surface area, it helps the transfer of lithium ion, this improves the specific capacity of lithium battery and power density,
It has a good application prospect.
Description of the drawings
Fig. 1 is the TEM figures for the spindle bodily form LiMn2O4 hollow pipe that embodiment 1 obtains；
Fig. 2 is the TEM figures for the spindle bodily form LiMn2O4 hollow pipe that embodiment 2 obtains.
Specific implementation mode
It is the specific implementation mode of the present invention below, the present invention to be explained and illustrated.
Embodiment 1
A kind of preparation method of spindle bodily form LiMn2O4 hollow pipe, includes the following steps：
(1) lithium nitrate is prepared to the lithium salt solution of 0.5mol/L with deionized water；By manganese acetate and potassium permanganate according to rubbing
Then you are configured to manganese salt solution, manganese ion is total in the manganese salt solution than being uniformly mixed for 3: 1 ratio with deionized water
A concentration of 1mol/L；The urea liquid for being 0.5mol/L with deionized water compound concentration；
(2) naphthalene is added in absolute ethyl alcohol, stirring forms uniform solution；
(3) lithium salt solution in step (1) is added in hydrothermal reaction kettle, addition is hydrothermal reaction kettle volume
1/4, the ethanol solution of naphthalene is then added, stirs evenly to form albescent suspension, wherein the molar ratio of naphthalene and lithium ion is 1
∶1；
(4) again under stirring conditions, manganese salt solution and urea in step (1) is added into shallow white suspension successively
Solution obtains reaction precursor liquid, wherein the volume of the reaction precursor liquid be hydrothermal reaction kettle volume 3/4, manganese ion it is total
The ratio between mole and the mole of lithium ion are 2: 1；
(5) hydrothermal reaction kettle is sealed, hydro-thermal reaction 3h, is then separated by solid-liquid separation at 140 DEG C, by obtained solid product point
It is not washed 3 times with absolute ethyl alcohol and deionized water, then drying obtains presoma at 90 DEG C；
(6) presoma is calcined to 1h at 260 DEG C to get to spindle bodily form LiMn2O4 hollow pipe.
The TEM for the spindle bodily form LiMn2O4 hollow pipe that Fig. 1 is schemes, it can be seen from the figure that the length of product is
200-600nm or so is in hollow tubular.
Embodiment 2
A kind of preparation method of spindle bodily form LiMn2O4 hollow pipe, includes the following steps：
(1) lithium acetate and lithium chloride are prepared to the lithium salt solution of 1mol/L with deionized water；By manganese nitrate and potassium permanganate
The ratio for being 2: 1 according to molar ratio is uniformly mixed, and is then configured to manganese salt solution with deionized water, in the manganese salt solution manganese from
The total concentration of son is 1.2mol/L；The urea liquid for being 0.5mol/L with deionized water compound concentration；
(2) naphthalene is added in absolute ethyl alcohol, stirring forms uniform solution；
(3) lithium salt solution in step (1) is added in hydrothermal reaction kettle, addition is hydrothermal reaction kettle volume
1/5, the ethanol solution of naphthalene is then added, stirs evenly to form albescent suspension, wherein the molar ratio of naphthalene and lithium ion is 1
∶2；
(4) again under stirring conditions, manganese salt solution and urea in step (1) is added into shallow white suspension successively
Solution obtains reaction precursor liquid, wherein the volume of the reaction precursor liquid be hydrothermal reaction kettle volume 3/4, manganese ion it is total
The ratio between mole and the mole of lithium ion are 2.2: 1；
(5) hydrothermal reaction kettle is sealed, hydro-thermal reaction 1h, is then separated by solid-liquid separation at 180 DEG C, by obtained solid product point
It is not washed 3 times with absolute ethyl alcohol and deionized water, then drying obtains presoma at 70 DEG C；
(6) presoma is calcined to 30min at 320 DEG C to get to spindle bodily form LiMn2O4 hollow pipe.
The TEM for the spindle bodily form LiMn2O4 hollow pipe that Fig. 1 is schemes, it can be seen from the figure that the length of product is
500-800nm or so is in hollow tubular.
Claims (4)
1. a kind of preparation method of spindle bodily form LiMn2O4 hollow pipe, which is characterized in that the preparation method includes the following steps：
(1) soluble lithium salt is configured to the lithium salt solution of 0.5-1mol/L with deionized water；By bivalent soluble manganese salt and height
The ratio that potassium manganate is 2-3: 1 according to molar ratio is uniformly mixed, is then configured to manganese salt solution, the manganese salt with deionized water
The total concentration of manganese ion is 1-1.2mol/L in solution；The urea liquid for being 0.5mol/L with deionized water compound concentration；
(2) naphthalene is added in absolute ethyl alcohol, stirring forms uniform solution；
(3) lithium salt solution in step (1) is added in hydrothermal reaction kettle, addition is the 1/5- of hydrothermal reaction kettle volume
1/4, the ethanol solution of naphthalene is then added, stirs evenly to form albescent suspension, wherein the molar ratio of naphthalene and lithium ion is 1
∶1-2；
(4) again under stirring conditions, the manganese salt solution in step (1) is added into shallow white suspension successively and urea is molten
Liquid obtains reaction precursor liquid, wherein the volume of the reaction precursor liquid is the 2/3-3/4 of hydrothermal reaction kettle volume；
(5) hydrothermal reaction kettle is sealed, 1~3h of hydro-thermal reaction, is then separated by solid-liquid separation at 140-180 DEG C, and obtained solid is produced
Object is washed 2-3 times with absolute ethyl alcohol and deionized water respectively, and then drying obtains presoma at 70-90 DEG C；
(6) presoma is calcined to 30min-1h at 260-320 DEG C to get to spindle bodily form LiMn2O4 hollow pipe.
2. a kind of preparation method of spindle bodily form LiMn2O4 hollow pipe according to claim 1, which is characterized in that it is described can
Dissolubility lithium salts is one or more in lithium nitrate, lithium acetate, lithium chloride, and the bivalent soluble manganese salt is manganese nitrate, acetic acid
It is one or more in manganese, manganese chloride.
3. a kind of preparation method of spindle bodily form LiMn2O4 hollow pipe according to claim 1 or 2, which is characterized in that institute
It states in step (4), it is 2-2.2: 1 to control the ratio between the integral molar quantity of manganese ion and the mole of lithium ion.
4. according to a kind of preparation method of spindle bodily form LiMn2O4 hollow pipe of claim 1-3 any one of them, feature exists
In the length of the spindle bodily form LiMn2O4 hollow pipe is 200-800nm.
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| CN201711500186.7A CN108455674B (en) | 2017-12-26 | 2017-12-26 | Preparation method of spindle-shaped lithium manganate hollow tube battery positive electrode material |
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| CN201711500186.7A CN108455674B (en) | 2017-12-26 | 2017-12-26 | Preparation method of spindle-shaped lithium manganate hollow tube battery positive electrode material |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102205989A (en) * | 2011-03-25 | 2011-10-05 | 江苏国泰锂宝新材料有限公司 | Preparation method for cathode material LiMn2O4 of cell |
| US8911904B2 (en) * | 2012-10-05 | 2014-12-16 | Ut-Battelle, Llc | Mesoporous metal oxide microsphere electrode compositions and their methods of making |
| CN104538623A (en) * | 2015-01-20 | 2015-04-22 | 河北工业大学 | Preparation method for sphere-like lithium nickel manganese oxide positive electrode material |
| CN105983383A (en) * | 2015-02-15 | 2016-10-05 | 江苏海四达电源股份有限公司 | Apparatus for preparing lithium ion battery positive electrode material lithium nickel cobalt manganese oxide precursor |
-
2017
- 2017-12-26 CN CN201711500186.7A patent/CN108455674B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102205989A (en) * | 2011-03-25 | 2011-10-05 | 江苏国泰锂宝新材料有限公司 | Preparation method for cathode material LiMn2O4 of cell |
| US8911904B2 (en) * | 2012-10-05 | 2014-12-16 | Ut-Battelle, Llc | Mesoporous metal oxide microsphere electrode compositions and their methods of making |
| CN104538623A (en) * | 2015-01-20 | 2015-04-22 | 河北工业大学 | Preparation method for sphere-like lithium nickel manganese oxide positive electrode material |
| CN105983383A (en) * | 2015-02-15 | 2016-10-05 | 江苏海四达电源股份有限公司 | Apparatus for preparing lithium ion battery positive electrode material lithium nickel cobalt manganese oxide precursor |
Non-Patent Citations (2)
| Title |
|---|
| F.X. WANG ET AL.: ""Nanoporous LiMn2O4 spinel prepared at low temperature as cathode material for aqueous supercapacitors"", 《JOURNAL OF POWER SOURCES》 * |
| 徐烨明等: ""一种新型有机模板硫酸铈晶体的水热合成"", 《中国稀土学报》 * |
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