CN110127767A - A kind of preparation method of multi-level flower-like manganese base nano-sheet lithium ion battery positive electrode - Google Patents
A kind of preparation method of multi-level flower-like manganese base nano-sheet lithium ion battery positive electrode Download PDFInfo
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- CN110127767A CN110127767A CN201910501172.XA CN201910501172A CN110127767A CN 110127767 A CN110127767 A CN 110127767A CN 201910501172 A CN201910501172 A CN 201910501172A CN 110127767 A CN110127767 A CN 110127767A
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- 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
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- 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
- C01G45/1207—Permanganates ([MnO]4-) or manganates ([MnO4]2-)
- C01G45/1214—Permanganates ([MnO]4-) or manganates ([MnO4]2-) containing alkali metals
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/006—Compounds containing, besides nickel, two or more other elements, with the exception of oxygen or hydrogen
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- H—ELECTRICITY
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- 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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- 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
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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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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- 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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
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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 multi-level flower-like manganese base nano-sheet lithium ion battery positive electrode.The solvent-thermal method that the present invention is assisted with hydrophily alcohol decomposes the CO of generation using precipitating reagent at high temperature2" bubble reaction " principle that bubble is formed in conjunction with metal salt, has synthesized metal carbonate.By being pre-sintered the metal oxide being decomposed to form as orientation template using carbonate, mixed with lithium salts, high temperature solid-phase sintering is prepared for multi-level flower-like pure phase spinel manganese base oxide nanometer sheet.Preparation method simple process of the present invention, it is easy to operate, be conducive to industrialized production, the multi-level flower-like manganese base nanometer sheet of preparation, maximized active site can not only be exposed, shorten ion/electron diffusion path, it may also be ensured that good structural stability, and inhibit the structural strain during repetitive cycling.Applied to lithium ion battery, the cycle life with excellent reversible lithium storage and overlength is a kind of very promising anode material for lithium-ion batteries with widespread commercialization application.
Description
Technical field
The invention proposes a kind of preparation methods of multi-level flower-like manganese base nano-sheet lithium ion battery positive electrode, belong to lithium
Ion battery nanostructure positive electrode synthesizes field.
Background technique
As electric car and hybrid vehicle are to the growth requirement of high-energy density and high power density, to having height
The exploration of the anode material for lithium-ion batteries of voltage and height ratio capacity becomes the focus of research.Spinel manganese base anode material because
Theoretical specific capacity with higher and quickly three-dimensional lithium ion diffusion admittance and receive significant attention, especially have stable
The LiNi of~4.7V high voltage platform0.5Mn1.5O4.However, the spinel manganese base anode material of block structure repeatedly lithium from
Can there are problems that serious capacity attenuation and poor high rate performance during sub- deintercalation.This major embodiment produces during the preparation process
Raw Mn3+Ion and impurity phase LixNi1-xO2And NixO.Wherein, by Mn3+Decompose the Mn generated2+It dissolves in the electrolyte, in height
Easily cause the collapsing of spinel manganese base anode material structure under temperature.Moreover, as final product LiNi0.5Mn1.5O4Second generated
Impurity phase but will deteriorate structure to reduce the cyclical stability of material.And compared with bulk material, construct multi-level nano-structure
These problems can be well solved to a certain extent.
As document report, compared with corresponding bulk material, in various energy fields, novel nano structure (0D, 1D, 2D)
Material usually has excellent physics and chemical property.Wherein, 2D material because of its two-dimensional transmission channel and high surface area more
Seem especially prominent.Designing, there is the lithium ion battery electrode material of two-dimensional structure to have become to realize height ratio capacity, long circulating
With the important means of outstanding high rate performance.The electrode material of two-dimensional structure can increase the contact area of electrode/electrolyte, exposure
Maximum active site, to promote e-/Li+The diffusion of ion.It is verified, there is 2D structure lithium ion electrode material to construction
Report much concentrate on researchs to negative electrode material, such as SnSe, Co3O4, graphene etc..In contrast, about 2D positive electrode
Report it is very limited, and the overwhelming majority all concentrate on synthesis LMPO4.This is because metal oxide cathode material is in lithium
Conventional during changing to need high-temperature calcination, this results in the 2D for being difficult to maintain presoma during phase transformation and crystal growth to tie
Structure.Therefore, the suitable preparation method for preparing two-dimensional structure metal oxide cathode material is found to be of great significance.In addition,
Extensive interest is also resulted in by the multilevel structure that the nanostructure of specific dimensions constructs.And combine nanostructure and micron knot
The positive electrode of three-dimensional (3D) structure that structure is assembled is even more to become research hotspot.This 3D multilevel structure not only contributes to electricity
The abundant infiltration for solving liquid extenuates the structural stress generated during lithium ion deintercalation, also can be very good to avoid in cyclic process
The reunion of caused nanostructure.Currently, for designing the 3D spinel manganese base anode material being assembled by 2D nanostructure still
In the presence of great challenge.
The present invention proposes that the multi-level flower-like structure being assembled by two-dimentional (2D) nanometer sheet is conducive to electrochemical reaction.It is this only
Special structure can not only expose maximized active site, shorten ion/electron diffusion path, it may also be ensured that good knot
Structure stability, and inhibit the structural strain during repetitive cycling.Particularly, the multi-level flower-like synthesized by template direction strategy
Pure phase spinel manganese base anode material nanometer sheet can meet simultaneously with excellent high rate performance and cyclical stability lithium ion
The demand for development of battery.
Summary of the invention
It is this only the purpose of the present invention is to propose to prepare a kind of multi-level flower-like manganese base nano-sheet lithium ion battery positive electrode
Special structure can not only expose maximized active site, shorten ion/electron diffusion path, it may also be ensured that good knot
Structure stability, and inhibit the structural strain during repetitive cycling, eventually becoming satisfaction has excellent high rate performance and circulation
The anode material for lithium-ion batteries of stability demand for development.
The purpose of the present invention can be realized by following scheme:
The preparation method of multi-level flower-like manganese base nano-sheet lithium ion battery positive electrode, includes the following steps:
(1) stoichiometrically, a certain amount of soluble manganese salt and nickel salt are weighed, is completely dissolved in hydrophilic solvent, obtains
To solution A.
(2) claim a certain amount of precipitating reagent to be added in solution A, be completely dissolved under stirring.
(3) after magnetic agitation 2 hours, it is proportionally slowly added to hydrophily alcoholic solution, is continuing stirring after ten minutes, shape
At mixed solution B.
(4) above-mentioned solution B is fitted into reaction kettle and carries out hydro-thermal reaction, at 100~200 DEG C, reacted 10~50 hours
Afterwards, room temperature is naturally cooled to, obtains the metal carbonate of manganese-based anode material after centrifuge separation is dry.
(5) gained metal carbonate is put into Muffle furnace, after pre-sintering 1~20 hour is carried out at 200~800 DEG C,
It is cooled to room temperature, forms the metal oxide template of manganese-based anode material, by its lithium salts with stoichiometric ratio in a small amount of second
It is small to be transferred in high temperature process furnances the heat treatment 1~20 at a temperature of 300~1000 DEG C by combination drying in alcoholic solution for this mixture
When, it is cooled to room temperature, manganese-based anode material required for being formed.
Solubility manganese salt according to the present invention is selected from one of manganese sulfate, manganese nitrate, manganese chloride, manganese acetate or several
Kind；Related soluble nickel salt is selected from one or more of nickel sulfate, nickel nitrate, nickel chloride, nickel acetate；Related lithium
Salt is selected from one or more of lithium carbonate, lithium hydroxide, lithium nitrate.Related hydrophilic solvent be deionized water, ethyl alcohol,
Isopropanol, ethylene glycol, glycerine, methanol, normal propyl alcohol, n-butanol, one of isobutanol or several.Related precipitating reagent
It can be urea, urotropine, ammonium hydrogen carbonate, sodium carbonate, sodium bicarbonate, one of ammonium carbonate or several.Institute
The hydrophily alcohol being related to be ethyl alcohol, isopropanol, ethylene glycol, glycerine, methanol, normal propyl alcohol, n-butanol, one of isobutanol or
Person is several.
Multi-level flower-like manganese base nanometer sheet prepared in accordance with the present invention, can expose maximized active site, shorten ion/
Electron diffusion path, it may also be ensured that good structural stability, and inhibit the structural strain during repetitive cycling, finally may be used
To have the anode material for lithium-ion batteries of excellent high rate performance and cyclical stability demand for development as satisfaction.
Detailed description of the invention
Fig. 1 is the X-ray diffractogram of nickel ion doped prepared by embodiment 1.
Fig. 2 is the scanning electron microscope diagram and transmission electricity after nickel ion doped presoma prepared by embodiment 2 is pre-sintered
Sub- microscope figure.
Fig. 3 is the scanning electron microscope diagram and projection electron microscope figure of nickel ion doped prepared by embodiment 3.
Fig. 4 is the cycle performance figure of nickel ion doped at higher current densities prepared by embodiment 4.
Fig. 5 is the cycle performance figure of LiMn2O4 at higher current densities prepared by embodiment 5.
Specific embodiment
Below with reference to embodiment, the present invention is further illustrated, but the present invention is not limited merely to following embodiment.
Embodiment 1
(1) it weighs 7.5mmol manganese acetate and 2.5mmol nickel acetate is completely dissolved in the deionized water of 50ml, obtain solution A.
(2) claim 2.12g urotropine to be added in solution A, be completely dissolved under stirring.
(3) after stirring 2h, it is proportionally slowly added to 20ml ethanol solution, it is molten to form mixing for after magnetic stirring for 10 minutes
Liquid B.
Above-mentioned solution B is fitted into reaction kettle, at 150 DEG C, reacts 24 hours, naturally cools to room temperature, be centrifugated
After drying, the metal carbonate of nickel lithium manganate cathode material is obtained.
Gained carbonate is put into Muffle furnace, 8h is pre-sintered at 400 DEG C, later with the lithium hydroxide of stoichiometric ratio
It is mixed in a small amount of ethanol solution, it is dry in baking oven, this mixture is transferred in high temperature process furnances hot at a temperature of 750 DEG C
Processing 6 hours is cooled to room temperature, nickel lithium manganate cathode material required for being formed.
Fig. 1 is the X-ray diffractogram of nickel ion doped prepared by this example, and nickel ion doped has highly crystalline as seen from the figure
Property；Fig. 2 is the scanning electron microscope diagram and transmission electron microscope after nickel ion doped presoma prepared by this example is pre-sintered,
Show that nickel ion doped forms 3D flower-like structure by 2D nanometer sheet in figure, and individually there are many porous structures on piece；Fig. 3
It is hereditary well after obtaining high-temperature heat treatment in figure for the scanning electron microscope diagram and transmission electron microscope of nickel ion doped
The appearance structure of presoma, as multi-level flower-like nanometer chip architecture；Fig. 4 is that nickel mangaic acid prepared by this example is close in 10C electric current
Degree, electrochemistry at room temperature recycle figure, and capacity is 122.0mAh g for the first time-1, after 500 times recycle, capacity retention ratio is
83.68%.
Embodiment 2
(1) it weighs 10mmol manganese acetate to be completely dissolved in the deionized water of 50ml, obtains solution A.
(2) claim 2.12g urotropine to be added in solution A, be completely dissolved under stirring.
(3) after stirring 2h, it is proportionally slowly added to 20ml ethanol solution, it is molten to form mixing for after magnetic stirring for 10 minutes
Liquid B.
(4) above-mentioned solution B is fitted into reaction kettle, at 150 DEG C, is reacted 24 hours, naturally cool to room temperature, centrifugation point
From obtaining manganese carbonate after drying.
Gained manganese carbonate is put into Muffle furnace, the pre-heat treatment 8h at 400 DEG C, later with the hydroxide of stoichiometric ratio
Lithium mixes in a small amount of ethanol solution, dry in baking oven, and this mixture is transferred in high temperature process furnances at a temperature of 700 DEG C
Heat treatment 8 hours is cooled to room temperature, manganate cathode material for lithium required for being formed.
Fig. 5 is that the electrochemistry of LiMn2O4 prepared by this example in 10C current density, at room temperature recycles figure, and capacity is for the first time
113.7mAh g-1, after 1000 times recycle, capacity retention ratio 88.12%.
Embodiment 3
(1) it weighs 10mmol manganese acetate to be completely dissolved in the deionized water of 40ml, obtains solution A.
(2) claim 2.12g urotropine to be added in solution A, be completely dissolved under stirring.
(3) after stirring 2h, it is proportionally slowly added to 30ml ethanol solution, it is molten to form mixing for after magnetic stirring for 10 minutes
Liquid B.
(4) above-mentioned solution B is fitted into reaction kettle, at 160 DEG C, is reacted 20 hours, naturally cool to room temperature, centrifugation point
From obtaining manganese carbonate after drying.
Gained manganese carbonate is put into Muffle furnace, the pre-heat treatment 8h at 400 DEG C, later with the hydroxide of stoichiometric ratio
Lithium mixes in a small amount of ethanol solution, dry in baking oven, and this mixture is transferred in high temperature process furnances at a temperature of 700 DEG C
Heat treatment 10 hours is cooled to room temperature, manganate cathode material for lithium required for being formed.
Embodiment 4
(1) it weighs 7.5mmol manganese acetate and 2.5mmol nickel acetate is completely dissolved in the deionized water of 40ml, obtain solution A.
(2) claim 2.12g urotropine to be added in solution A, be completely dissolved under stirring.
(3) after stirring 2h, it is proportionally slowly added to 30ml aqueous isopropanol, after magnetic stirring for 10 minutes form mixing
Solution B.
Above-mentioned solution B is fitted into reaction kettle, at 160 DEG C, reacts 15 hours, naturally cools to room temperature, be centrifugated
The metal carbonate of nickel lithium manganate cathode material is obtained after drying.
Gained carbonate is put into Muffle furnace, the pre-heat treatment 8h at 400 DEG C, later with the hydroxide of stoichiometric ratio
Lithium mixes in a small amount of ethanol solution, dry in baking oven, and this mixture is transferred in high temperature process furnances at a temperature of 750 DEG C
Heat treatment 10 hours is cooled to room temperature, nickel lithium manganate cathode material required for being formed.
Embodiment 5
(1) it weighs 7.5mmol manganese acetate and 2.5mmol nickel acetate is completely dissolved in the ethylene glycol of 50ml, obtain solution A.
(2) claim 2.12g urotropine to be added in solution A, be completely dissolved under stirring.
(3) after stirring 2h, it is proportionally slowly added to 20ml methanol solution, it is molten to form mixing for after magnetic stirring for 10 minutes
Liquid B.
Above-mentioned solution B is fitted into reaction kettle, at 180 DEG C, reacts 30 hours, naturally cools to room temperature, be centrifugated
The carbonate of nickel lithium manganate cathode material is obtained after drying.
Gained carbonate is put into Muffle furnace, the pre-heat treatment 6h at 500 DEG C, later with the hydroxide of stoichiometric ratio
Lithium mixes in a small amount of ethanol solution, dry in baking oven, and this mixture is transferred in high temperature process furnances at a temperature of 750 DEG C
Heat treatment 6 hours is cooled to room temperature, nickel lithium manganate cathode material required for being formed.
Embodiment 6
(1) it weighs 10mmol manganese acetate to be completely dissolved in the ethylene glycol of 40ml, obtains solution A.
(2) claim 2.12g urotropine to be added in solution A, be completely dissolved under stirring.
(3) after stirring 2h, it is proportionally slowly added to 30ml ethylene glycol solution, after magnetic stirring for 10 minutes form mixing
Solution B.
(4) above-mentioned solution B is fitted into reaction kettle, at 180 DEG C, is reacted 30 hours, naturally cool to room temperature, centrifugation point
From the manganese carbonate for obtaining manganate cathode material for lithium after drying.
Gained manganese carbonate is put into Muffle furnace, the pre-heat treatment 5h at 500 DEG C, later with the hydroxide of stoichiometric ratio
Lithium mixes in a small amount of ethanol solution, dry in baking oven, and this mixture is transferred in high temperature process furnances at a temperature of 700 DEG C
Heat treatment 6 hours is cooled to room temperature, manganate cathode material for lithium required for being formed.
Embodiment 7
(1) it weighs 10mmol manganese acetate to be completely dissolved in the ethyl alcohol of 40ml, obtains solution A.
(2) claim 2.12g urea to be added in solution A, be completely dissolved under stirring.
(3) after stirring 2h, it is proportionally slowly added to 30ml ethanol solution, it is molten to form mixing for after magnetic stirring for 10 minutes
Liquid B.
(4) above-mentioned solution B is fitted into reaction kettle, at 150 DEG C, is reacted 15 hours, naturally cool to room temperature, centrifugation point
From obtaining manganese carbonate after drying.
Manganese carbonate is put into Muffle furnace, the pre-heat treatment 8h at 400 DEG C exists with the lithium hydroxide of stoichiometric ratio later
It is mixed in a small amount of ethanol solution, it is dry in baking oven, this mixture is transferred in high temperature process furnances at a temperature of 700 DEG C at heat
Reason 8 hours is cooled to room temperature, manganate cathode material for lithium required for being formed.
Embodiment 8
(1) it weighs 8mmol manganese acetate and 2mmol nickel acetate is completely dissolved in the ethylene glycol of 50ml, obtain solution A.
(2) claim 2.12g urotropine to be added in solution A, be completely dissolved under stirring.
(3) after stirring 2h, it is proportionally slowly added to 20ml ethylene glycol solution, after magnetic stirring for 10 minutes form mixing
Solution B.
Above-mentioned solution B is fitted into reaction kettle, at 180 DEG C, reacts 20 hours, naturally cools to room temperature, be centrifugated
The metal carbonate of spinel manganese base anode material is obtained after drying.
Gained carbonate is put into Muffle furnace, the pre-heat treatment 6h at 500 DEG C, later with the hydroxide of stoichiometric ratio
Lithium mixes in a small amount of ethanol solution, dry in baking oven, and this mixture is transferred in high temperature process furnances at a temperature of 750 DEG C
Heat treatment 6 hours is cooled to room temperature, spinel manganese base anode material required for being formed.
Embodiment 9
(1) it weighs 8mmol manganese acetate and 2mmol nickel acetate is completely dissolved in the water of 20ml, obtain solution A.
(2) claim 2.12g urea to be added in solution A, be completely dissolved under stirring.
(3) after stirring 2h, it is proportionally slowly added to 50ml ethanol solution, it is molten to form mixing for after magnetic stirring for 10 minutes
Liquid B.
Above-mentioned solution B is fitted into reaction kettle, at 160 DEG C, reacts 20 hours, naturally cools to room temperature, be centrifugated
The carbonate of spinel manganese base anode material is obtained after drying.
Gained carbonate is put into Muffle furnace, the pre-heat treatment 6h at 500 DEG C, later with the hydroxide of stoichiometric ratio
Lithium mixes in a small amount of ethanol solution, dry in baking oven, and this mixture is transferred in high temperature process furnances at a temperature of 750 DEG C
Heat treatment 6 hours is cooled to room temperature, spinel manganese base anode material required for being formed.
Claims (9)
1. a kind of preparation method of multi-level flower-like manganese base nano-sheet lithium ion battery positive electrode, includes the following steps:
(1) stoichiometrically, a certain amount of soluble manganese salt and nickel salt are weighed, is completely dissolved in hydrophilic solvent, obtains molten
Liquid A.
(2) claim a certain amount of precipitating reagent to be added in solution A, be completely dissolved under stirring.
(3) after magnetic agitation 2 hours, it is proportionally slowly added to hydrophily alcoholic solution, is continuing stirring after ten minutes, is formed mixed
Close solution B.
(4) above-mentioned solution B is fitted into reaction kettle and carries out hydro-thermal reaction, at 100~200 DEG C, after reaction 10~50 hours, from
It is so cooled to room temperature, obtains the metal carbonate of manganese-based anode material after centrifuge separation is dry.
(5) gained metal carbonate is put into Muffle furnace, it is cooling after pre-sintering 1~20 hour is carried out at 200~800 DEG C
To room temperature, the metal oxide template of manganese-based anode material is formed, it is molten in a small amount of ethyl alcohol with the lithium salts of stoichiometric ratio
This mixture is transferred in high temperature process furnances and is heat-treated 1~20 hour at a temperature of 300~1000 DEG C by combination drying in liquid,
It is cooled to room temperature, manganese-based anode material required for being formed.
2. preparation method as described in claim 1, it is characterised in that: the molar ratio of the soluble manganese salt and nickel salt exists
10:0~0:10.
3. preparation method as described in claim 1, it is characterised in that: the soluble manganese salt be selected from manganese sulfate, manganese nitrate,
One or more of manganese chloride, manganese acetate；The soluble nickel salt is in nickel sulfate, nickel nitrate, nickel chloride, nickel acetate
One or more；The lithium salts is selected from one or more of lithium carbonate, lithium hydroxide, lithium nitrate.The hydrophily
Solvent is deionized water, ethyl alcohol, isopropanol, ethylene glycol, glycerine, methanol, normal propyl alcohol, n-butanol, one of isobutanol or
Person is several.
4. preparation method as described in claim 1, it is characterised in that: the precipitating reagent can be urea, hexamethylene
Tetramine, ammonium hydrogen carbonate, sodium carbonate, sodium bicarbonate, one of ammonium carbonate or several.
5. preparation method as described in claim 1, it is characterised in that: the hydrophily alcohol is ethyl alcohol, isopropanol, second two
Alcohol, glycerine, methanol, normal propyl alcohol, n-butanol, one of isobutanol or several.
6. preparation method as described in claim 1, it is characterised in that: the volume ratio of hydrophilic solvent and hydrophily alcoholic solution exists
2:5~5:2.
7. preparation method as described in claim 1, it is characterised in that: in step (4) the temperature control of hydro-thermal reaction 130~
200 DEG C, the reaction time is 10~50 hours.
8. preparation method as described in claim 1, it is characterised in that: the temperature of pre-sintering controls between 200~800 DEG C, burns
The time of knot is 1~20 hour.For the temperature of high-temperature heat treatment between 300~1000 DEG C, the time of sintering is 1~20 hour.
9. preparation method as described in claim 1, it is characterised in that: the manganese-based anode material of formation is multi-level flower-like nanometer sheet
Structure can be used as the positive electrode of lithium ion battery.
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| CN111668445A (en) * | 2020-06-01 | 2020-09-15 | 广东轻工职业技术学院 | Shape-controllable nickel manganese oxide electrode material and preparation method and application thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59182991A (en) * | 1983-03-31 | 1984-10-17 | Kinkidaigaku | Method for coloring and modifying anodic oxide film on aluminum |
| CN104852040A (en) * | 2015-04-21 | 2015-08-19 | 洛阳理工学院 | Preparation method of lithium nickel manganese oxide anode material for high-rate lithium ion battery |
| CN106082361A (en) * | 2016-06-03 | 2016-11-09 | 北京理工大学 | A kind of preparation method of anode material for lithium-ion batteries hollow porous nano/submicron multilevel hierarchy nickel ion doped |
| CN106299341A (en) * | 2016-10-11 | 2017-01-04 | 北京理工大学 | A kind of anode material for lithium-ion batteries chemistry symbiosis porous nano/multistage LiMn of submicron2o4/ LiNi0.5mn1.5o4cubical preparation method |
| CN106876682A (en) * | 2017-04-10 | 2017-06-20 | 中南大学 | A kind of manganese oxide with loose structure/nickel micron ball and its preparation and application |
-
2019
- 2019-06-11 CN CN201910501172.XA patent/CN110127767A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59182991A (en) * | 1983-03-31 | 1984-10-17 | Kinkidaigaku | Method for coloring and modifying anodic oxide film on aluminum |
| CN104852040A (en) * | 2015-04-21 | 2015-08-19 | 洛阳理工学院 | Preparation method of lithium nickel manganese oxide anode material for high-rate lithium ion battery |
| CN106082361A (en) * | 2016-06-03 | 2016-11-09 | 北京理工大学 | A kind of preparation method of anode material for lithium-ion batteries hollow porous nano/submicron multilevel hierarchy nickel ion doped |
| CN106299341A (en) * | 2016-10-11 | 2017-01-04 | 北京理工大学 | A kind of anode material for lithium-ion batteries chemistry symbiosis porous nano/multistage LiMn of submicron2o4/ LiNi0.5mn1.5o4cubical preparation method |
| CN106876682A (en) * | 2017-04-10 | 2017-06-20 | 中南大学 | A kind of manganese oxide with loose structure/nickel micron ball and its preparation and application |
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| CN111668445A (en) * | 2020-06-01 | 2020-09-15 | 广东轻工职业技术学院 | Shape-controllable nickel manganese oxide electrode material and preparation method and application thereof |
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