CN105514375B - A kind of carbon coating Na0.55Mn2O4·1.5H2O nanocomposite and preparation method thereof - Google Patents
A kind of carbon coating Na0.55Mn2O4·1.5H2O nanocomposite and preparation method thereof Download PDFInfo
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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
- H01M4/362—Composites
- H01M4/366—Composites as layered products
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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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- 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
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- 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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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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Abstract
The present invention relates to a kind of carbon coating Na0.55Mn2O4·1.5H2O nanocomposite and preparation method thereof.Na0.55Mn2O4·1.5H2O is the spherical structure being made of nanometer rods, and is uniformly wrapped in amorphous carbon layer.Preparation：(1) tetraethyl orthosilicate (TEOS) hydrolysis is added in the alcoholic solution of the manganese dioxide nano-rod after sour surface modification and obtains the composite material of core-shell structure of coated with silica manganese dioxide；Carbon coating is carried out to the sample that step (1) obtains, the composite material after being carbonized；Composite powder sample after carbonization is slowly added in the sodium hydroxide solution of excessive heat, is stirred to react.Carbon coating Na provided by the invention0.55Mn2O4·1.5H2O nanocomposite has high specific capacity, excellent high rate performance and cycle performance, is with a wide range of applications in lithium ion battery electrode material and other electrochemical technology fields.
Description
Technical field
The invention belongs to manganese base oxysalt field of material preparation, and in particular to a kind of carbon coating Na0.55Mn2O4 .1.5H2O nanometers
Composite material and preparation method.
Background technique
Nowadays, as new energy represent lithium ion secondary battery be widely used in mobile communication, laptop,
On the portable electronic devices such as miniature camera.In today that electric car is paid more and more attention, lithium ion battery be its most
One of important energy supply material；Meanwhile good application is also shown in fields such as satellite, space flight and aviation and Space Militaries
Prospect and potential economic benefit power, these applications are so that lithium ion secondary battery has become the heat of current scientific and technical research
One of point.But it is limited to the development of electrode material, cycle life is short, fast charging and discharging ability difference and higher cost etc. lack
Point hinders the development of lithium ion battery, and lithium ion battery still also has greatly improved sky in energy density and power density
Between.
Commercialization graphite cathode theoretical specific capacity at present（~372 mAh/g）Low, the service life is short, become further increase lithium from
The bottleneck of sub- battery energy density is not able to satisfy the needs of power battery development, thus develop it is novel have high-energy density,
The negative electrode material of power density seems extremely urgent.In recent years, Mn based material greatly excited the interest of researchers, wherein
The oxygen-containing salt material of manganese base is due to its special tunnel or layer structure, it is considered to be a kind of very potential lithium battery anode material
Material, and applied in sodium-ion battery, but very few using reporting so far in terms of cathode.
In recent years, the preparation in relation to such material still has many relevant reports.Such as document Journal of Solid
State Chemistry, 1971,3,1-l1 report a kind of synthesis NaxMn02The method of compound, and it has been delivered in oxygen
Study of Phase Diagram in gas, showing the substance, there are the object phases of three kinds of layer structures.Document Journal of Solid State
Chemistry has carried out more research in detail, this method to iodine reduction method in 2001,156,331-338 and has used
NaMn04 .H20 and NaI is raw material, weighs a certain amount of reactant mixing in proportion, dilute HCl is added dropwise under stiring and adjusts pH value,
After stirring 24 h, products therefrom is filtered, washed and is dried, after calcine 24 h at 300~900 DEG C and obtain NaxMn02。
In addition, the above-mentioned oxygen-containing salt material of manganese base directly applies to lithium ion battery negative material, there are also related scholars
Correlative study is carried out.Such as document J. Chem. Mater, K has been prepared in 2005,17,47002Mn8O16This material
And it is applied to lithium cell negative pole, it is 505 mAh/g that its first circle charge specific capacity is measured at 60 mA/g of current density.
Irvine et al. reports M2SnO4Cycle performance of this material under low current density（J. Power Sources 2001,
223,97-98), by Mn2SnO4With Mg2SnO4、Co2SnO4Both materials compare, and find Mn2SnO4Cycle performance is most
It is excellent, furthermore Zn2SnO4The reversible specific capacity of this new material reaches 500 mAh/g（Solid State Ionics, 2000,
135, 163）, but cycle performance and bad.
But the oxygen-containing salt material of manganese systems mentioned in most of document or patent is the tunnel or layer structure of birnessite, separately
Outer synthetic method higher cost, production efficiency is low, and the material conductivity of synthesis is poor, and cycle performance is unsatisfactory, to influence
Application and development of the above-mentioned material in terms of lithium ion battery, therefore, the present invention is directed to seek a kind of novel manganese base oxysalt
Material and preparation method thereof.
Summary of the invention
It is an object of the invention to be directed to the deficiency and defect of the existing oxygen-containing salt material of manganese base, a kind of novel carbon packet is provided
Cover Na0.55Mn2O4 .1.5H2O nanocomposite and preparation method thereof.
For achieving the above object, the present invention adopts the following technical scheme that：
Carbon coating Na is provided0.55Mn2O4 .1.5H2O nanocomposite, Na0.55Mn2O4 .1.5H2O is to be made of nanometer rods
Spherical structure, and be uniformly wrapped in amorphous carbon layer.
A kind of carbon coating Na is provided0.55Mn2O4 .1.5H2The preparation method of O nanocomposite, includes the following steps：
（1）It disperses the manganese dioxide nano-rod after sour surface modification in alcohol or alcohol-water mixture, is added just
Tetraethyl orthosilicate and tetraethyl orthosilicate hydrolytic accelerating agent, stirring, the coated with silica for keeping surface negatively charged to surface band
On the manganese dioxide nano-rod of positive charge, then through deionized water centrifuge washing and drying, coated with silica titanium dioxide is obtained
Manganese nanometer rods；
（2）To step（1）In sample carry out carbon coating：Carbon source is added in alcohol or alcohol-water mixture, then by step
（1）Middle gained nucleocapsid coated with silica manganese dioxide nano-rod is scattered in the solution, ultrasound, after stirring a period of time, through going
Ionized water centrifuge washing is dry；Then gained compound is subjected to high-temperature heat treatment under reproducibility or inert atmosphere, it is naturally cold
But, the composite material after being carbonized；
（3）Carbon coating Na0.55Mn2O4 .1.5H2The preparation of O nanocomposite：By step（2）In carbonization after it is compound
Material powder sample is slowly added in the sodium hydroxide solution of excessive heat, is stirred to react, most dry through deionized water centrifuge washing afterwards
It is dry, obtain carbon coating Na0.55Mn2O4 .1.5H2O nanocomposite.
Further, step（1）In mixing time be 3-5 h；Step（2）Mixing time be 12-24 h；Step
（3）Mixing time be 18-24 h.
Further, step（1）Described in surface be modified as：Manganese dioxide nano-rod is added in the solution containing acid,
Ultrasound makes its dispersion, then dry through deionized water centrifuge washing.
Further, step（1）The acid is inorganic acid hydrochloric acid, sulfuric acid, perchloric acid, nitric acid and organic acid dodecane
Any one of base sulfonic acid, phytic acid, oxalic acid, citric acid, dodecyl benzene sulfonic acid, camphorsulfonic acid and naphthalene sulfonic acids.
Further, step（1）The volume of the acid and the amount ratio of manganese dioxide nano-rod are 200~900 μ L：
0.087~0.435 g.
Further, step（1）The amount ratio of the tetraethyl orthosilicate and manganese dioxide nano-rod is 0.1868-
0.7472g：0.087~0.435 g.
Further, step（1）The hydrolytic accelerating agent is ammonium hydroxide, the volume of ammonium hydroxide and the dosage of tetraethyl orthosilicate
Than for 1ml：0.1868-0.7472g.
Further, step（1）The alcohol be ethyl alcohol, ethylene glycol, isopropanol, in polyalcohol any one or it is a kind of
Above combination；Alcohol-water mixture is ethyl alcohol, ethylene glycol, isopropanol, any one or more than one combination in polyalcohol
With deionized water with volume ratio for 1:4~4:1 mixing.
Further, step（2）The carbon source is one of citric acid, sucrose, chitosan.
Further, step（2）The mass ratio of middle carbon source and nucleocapsid coated with silica manganese dioxide powder is：0.1~
0.5 g:40~160 mg.
Further, step（2）The reducing atmosphere is the mixed gas for being nitrogen containing 5% hydrogen, remaining gas,
Inert atmosphere is nitrogen, argon atmosphere.
Further, step（2）The high-temperature heat treatment refers in the tubular type for being full of above-mentioned gas one of which gas
In furnace, with 5~15 DEG C/min heating rate, 5~10 hours are kept the temperature after being raised to 450~750 DEG C of target temperatures.
Further, step（3）The heating bath temperature is 40~90 DEG C.
Further, drying temperature is 60 ~ 80 DEG C.
Compared with prior art, the beneficial effects of the present invention are：
1) present invention dexterously utilizes manganese dioxide and silica sintered characteristic at high temperature, is made with silica
For template, it will first be reacted again with sodium hydroxide after manganese dioxide and silica sintering, generate Na0.55Mn2O4 .1.5H2O；Technique
It is simple controllable, it is low in cost, it is easy to accomplish industrialization.
2) carbon coating Na provided by the invention0.55Mn2O4 .1.5H2Na in O nanocomposite0.55Mn2O4 .1.5H2O is in receive
The spherical structure of rice stick composition, and be uniformly wrapped in amorphous carbon layer.The present invention, which passes through, introduces carbon-coating, and will
Na0.55Mn2O4 .1.5H2O amorphous carbon layer effectively wraps up and is isolated to get up, and can promote material conductivity, overcome
Na0.55Mn2O4 .1.5H2O in charge and discharge process due to embedding lithium cause the destruction of structure caused by volume expansion, dusting, reunion and
The problem of causing capacity to be decayed rapidly.Therefore, prepared composite material makees electrode material, and capacity is high, has excellent structure
Stability, cyclical stability and high rate performance have huge application potential in electrode material of secondary lithium ion battery field.
Detailed description of the invention:
Fig. 1 is the XRD photo of 1 products obtained therefrom of embodiment；
Fig. 2 is the TEM photo of 1 products obtained therefrom of embodiment；
Fig. 3 is the cycle performance photo of the simulated battery of 1 products obtained therefrom of embodiment preparation；
Fig. 4 is the high rate performance photo of the simulated battery of 1 products obtained therefrom of embodiment preparation.
Specific embodiment:
It is described further below with case is embodied to technical solution of the present invention, but the present invention obtains protection scope not
It is limited to this.
Embodiment 1
1) manganese dioxide prepared by 0.1 g hydro-thermal method is weighed（MnO2）Nanometer rods measure the hydrochloric acid of 400 μ L（HCl）,
It is separately added into 50 mL deionized waters, after being ultrasonically treated 30 minutes with ultrasonic cleaner, through deionized water centrifuge washing 3 times
And it is dry at 80 DEG C；100 mL ethanol solutions are dispersed by above-mentioned powder（Alcohol water ratio is 4:1）In, it is separately added into 1 mL's
The tetraethyl orthosilicate of ammonia spirit and 0.4 mL（28.4%）, after magnetic agitation 3 hours, simultaneously through deionized water centrifuge washing 3 times
It is dry at 80 DEG C, obtain core-shell structure coated with silica manganese dioxide nano-rod；
The preparation of manganese dioxide nano-rod hydro-thermal method and pre-treatment step are as follows：1.35 g manganese sulfate monohydrates are weighed respectively
（MnSO4·H2O）With 1.83 g ammonium persulfates（(NH4)2S2O8）It is dissolved in 70 mL water, stirring is transferred to 100 mL after 30 minutes poly-
In tetrafluoroethene reaction kettle, hydro-thermal reaction 12 hours at 140 DEG C are dry after deionized water centrifuge washing 3 times, for use.
2) by the citric acid of 0.2 g（CA）10 mL ethanol solutions are added（Alcohol water ratio is 4:1）In, then weigh 40 mg's
Step（1）The powder-like of middle preparation is scattered in the solution, and after being ultrasonically treated 30 minutes with ultrasonic cleaner, magnetic agitation 24 is small
When, it is through deionized water centrifuge washing 3 times and dry at 80 DEG C；Gained compound is placed in the tube furnace full of nitrogen, with
The heating rate of 5 DEG C/min keeps the temperature 5 hours at 650 DEG C, to tube furnace natural cooling, obtains black powder；
3) by the sodium hydroxide of 0.8 g（NaOH）It is added in 20 mL deionized waters, heating water bath is to after 90 DEG C, by step
（2）The black powder of middle preparation is slowly added to, after magnetic agitation 18 hours, through deionized water centrifuge washing 3 times and at 80 DEG C
Dry, obtaining powder is carbon coating Na0.55Mn2O4 .1.5H2O nanocomposite.Fig. 1 is the X-ray diffraction of the material
（XRD）Figure compares, products therefrom Na with standard card0.55Mn2O4 .1.5H2O, carbon material fail to show due to partial amorphism
Diffraction maximum, and without other impurity；Fig. 2 is the transmission electron microscope of the product（TEM）Photo, it can be found that being
Na0.55Mn2O4 .1.5H2O is the spherical structure being made of nanometer rods, and is uniformly wrapped in amorphous carbon layer.
With a kind of resulting carbon coating Na of embodiment 10.55Mn2O4 .1.5H2Electricity is made in O nanocomposite as follows
Pole：
With 7：2：1 mass ratio weighs carbon coating Na respectively0.55Mn2O4 .1.5H2O nanocomposite：Acetylene black：Poly- four
Vinyl fluoride（PVDF）, after grinding, the N-Methyl pyrrolidone of designated volume is added（NMP）Ultrasonic treatment 1 hour, is coated uniformly on
Electrode is made on copper foil, uses metal lithium sheet for anode, electrolyte is 1 mol/L LiPF6 /EC-DMC（Volume ratio is 1:1）,
Polypropylene micropore diaphragm is diaphragm（Celgard 2300）, it is assembled into half-cell.Fig. 3 is that the battery that the composite material is assembled into exists
Long-time cyclic curve under the current density of 1 A/g in 0.01 ~ 3.0 V voltage range, it can be found that the combination electrode material
Specific capacity be in apparent growth trend, have extraordinary cyclical stability；From fig. 4, it can be seen that the combination electrode material
With good high rate performance, even if experience high current density charge and discharge, when being restored to low current density, charge specific capacity energy
Enough basic recoveries.
Embodiment 2
1) 0.1 g manganese dioxide is weighed（MnO2）Nanometer rods measure the sulfuric acid of 200 μ L, are separately added into 50 mL deionizations
It is after twenty minutes with ultrasonic cleaner ultrasonic treatment, through deionized water centrifuge washing 3 times and dry at 60 DEG C in water；It will be upper
It states powder and is scattered in 80 mL ethylene glycol solutions（Alcohol water ratio is 2:1）In, the ammonia spirit and 0.2 mL for being separately added into 1 mL are just
Tetraethyl orthosilicate, it is through deionized water centrifuge washing 3 times and dry at 60 DEG C after magnetic agitation 5 hours, obtain core-shell structure
Coated with silica manganese dioxide nano-rod；
2) 20 mL ethylene glycol solutions are added in the sucrose of 0.1 g（Alcohol water ratio is 2:1）In, the step of then weighing 40 mg
（1）The powder-like of middle preparation is scattered in the solution, after twenty minutes with ultrasonic cleaner ultrasonic treatment, magnetic agitation 22 hours,
It is through deionized water centrifuge washing 3 times and dry at 60 DEG C；Gained compound is placed in the tube furnace full of argon gas, with 10
DEG C/heating rate of min, 8 hours are kept the temperature at 450 DEG C, to tube furnace natural cooling, obtains black powder；
3) by the sodium hydroxide of 0.14 g（NaOH）It is added in 30 mL deionized waters, heating water bath will be walked to after 40 DEG C
Suddenly（2）The black powder of middle preparation is slowly added to, after magnetic agitation 20 hours, through deionized water centrifuge washing 3 times and in 60 DEG C
Lower drying, obtaining powder is a kind of carbon coating Na0.55Mn2O4 .1.5H2O nanocomposite.
Embodiment 3
1) 0.087 g manganese dioxide is weighed（MnO2）Nanometer rods, measure 500 μ L oxalic acid, be separately added into 50 mL go from
It is after ten minutes with ultrasonic cleaner ultrasonic treatment, through deionized water centrifuge washing 3 times and dry at 70 DEG C in sub- water；It will
Above-mentioned powder is scattered in 90 mL aqueous isopropanols（Alcohol water ratio is 1:1）In, it is separately added into the ammonia spirit and 0.2 mL of 1 mL
Tetraethyl orthosilicate, it is through deionized water centrifuge washing 3 times and dry at 70 DEG C after magnetic agitation 4 hours, obtain nucleocapsid knot
Structure coated with silica manganese dioxide nano-rod；
2) 30 mL aqueous isopropanols are added in the chitosan of 0.3 g（Alcohol water ratio is 1:1）In, then weigh the step of 80 mg
Suddenly（1）The powder-like of middle preparation is scattered in the solution, and after ten minutes with ultrasonic cleaner ultrasonic treatment, magnetic agitation 20 is small
When, it is through deionized water centrifuge washing 3 times and dry at 70 DEG C；Gained compound is placed in the tube furnace full of hydrogen, with
The heating rate of 5 DEG C/min keeps the temperature 5 hours at 550 DEG C, to tube furnace natural cooling, obtains black powder；
3) by the sodium hydroxide of 0.3 g（NaOH）It is added in 40 mL deionized waters, heating water bath is to after 60 DEG C, by step
（2）The black powder of middle preparation is slowly added to, after magnetic agitation 22 hours, through deionized water centrifuge washing 3 times and at 70 DEG C
Dry, obtaining powder is a kind of carbon coating Na0.55Mn2O4 .1.5H2O nanocomposite.
Embodiment 4
1) 0.087 g manganese dioxide is weighed（MnO2）Nanometer rods measure the hydrochloric acid of 200 μ L（HCl）, it is separately added into 50 mL
In deionized water, after twenty minutes with ultrasonic cleaner ultrasonic treatment, done through deionized water centrifuge washing 3 times and at 80 DEG C
It is dry；100 mL glycerin solutions are dispersed by above-mentioned powder（Alcohol water ratio is 1:2）In, be separately added into 1 mL ammonia spirit and
The tetraethyl orthosilicate of 0.4 mL, it is through deionized water centrifuge washing 3 times and dry at 80 DEG C after magnetic agitation 3 hours, it obtains
To core-shell structure coated with silica manganese dioxide nano-rod；
2) 10 mL glycerin solutions are added in the sucrose of 0.2 g（Alcohol water ratio is 1:2）In, the step of then weighing 80 mg
（1）The powder-like of middle preparation is scattered in the solution, after ten minutes with ultrasonic cleaner ultrasonic treatment, magnetic agitation 18 hours,
It is through deionized water centrifuge washing 3 times and dry at 80 DEG C；Gained compound is placed in the tube furnace full of nitrogen, with 15
DEG C/heating rate of min, 10 hours are kept the temperature at 750 DEG C, to tube furnace natural cooling, obtains black powder；
3) by the sodium hydroxide of 0.5 g（NaOH）It is added in 40 mL deionized waters, heating water bath is to after 90 DEG C, by step
（2）The black powder of middle preparation is slowly added to, after magnetic agitation 24 hours, through deionized water centrifuge washing 3 times and at 80 DEG C
Dry, obtaining powder is a kind of carbon coating Na0.55Mn2O4 .1.5H2O nanocomposite.
Embodiment 5
1) 0.2 g manganese dioxide is weighed（MnO2）Nanometer rods measure the sulfuric acid of 500 μ L, are separately added into 50 mL deionizations
It is through deionized water centrifuge washing 3 times and dry at 70 DEG C after being ultrasonically treated 30 minutes with ultrasonic cleaner in water；It will be upper
It states powder and is scattered in 80 mL ethanol solutions（Alcohol water ratio is 1:4）In, it is separately added into the ammonia spirit of 1 mL and the positive silicon of 0.4 mL
Sour tetra-ethyl ester, it is through deionized water centrifuge washing 3 times and dry at 70 DEG C after magnetic agitation 4 hours, obtain core-shell structure two
Silica coats manganese dioxide nano-rod；
2) 30 mL ethanol solutions are added in the chitosan of 0.1 g（Alcohol water ratio is 1:4）In, the step of then weighing 40 mg
（1）The powder-like of middle preparation is scattered in the solution, after being ultrasonically treated 30 minutes with ultrasonic cleaner, magnetic agitation 20 hours,
It is through deionized water centrifuge washing 3 times and dry at 70 DEG C；Gained compound is placed in the tube furnace full of argon gas, with 15
DEG C/heating rate of min, 5 hours are kept the temperature at 550 DEG C, to tube furnace natural cooling, obtains black powder；
3) by the sodium hydroxide of 0.3 g（NaOH）It is added in 20 mL deionized waters, heating water bath is to after 40 DEG C, by step
（2）The black powder of middle preparation is slowly added to, after magnetic agitation 18 hours, through deionized water centrifuge washing 3 times and at 70 DEG C
Dry, obtaining powder is a kind of carbon coating Na0.55Mn2O4 .1.5H2O nanocomposite.
Embodiment 6
1) 0.2 g manganese dioxide is weighed（MnO2）Nanometer rods measure the hydrochloric acid of 600 μ L（HCl）, it is separately added into 50 mL and goes
It is after ten minutes with ultrasonic cleaner ultrasonic treatment, through deionized water centrifuge washing 3 times and dry at 60 DEG C in ionized water；
100 mL aqueous isopropanols are dispersed by above-mentioned powder（Alcohol water ratio is 4:1）In, it is separately added into the ammonia spirit and 0.6 of 1 mL
The tetraethyl orthosilicate of mL, it is through deionized water centrifuge washing 3 times and dry at 60 DEG C after magnetic agitation 5 hours, obtain core
Shell structure coated with silica manganese dioxide nano-rod；
2) by the citric acid of 0.1 g（CA）20 mL aqueous isopropanols are added（Alcohol water ratio is 4:1）In, then weigh 120
The step of mg（1）The powder-like of middle preparation is scattered in the solution, after ten minutes with ultrasonic cleaner ultrasonic treatment, magnetic agitation
It is 22 hours, through deionized water centrifuge washing 3 times and dry at 60 DEG C；Gained compound is placed in the tube furnace full of hydrogen
In, with the heating rate of 5 DEG C/min, 10 hours are kept the temperature at 450 DEG C, to tube furnace natural cooling, obtains black powder；
3) by the sodium hydroxide of 0.14 g（NaOH）It is added in 30 mL deionized waters, heating water bath will be walked to after 90 DEG C
Suddenly（2）The black powder of middle preparation is slowly added to, after magnetic agitation 20 hours, through deionized water centrifuge washing 3 times and in 60 DEG C
Lower drying, obtaining powder is a kind of carbon coating Na0.55Mn2O4 .1.5H2O nanocomposite.
Embodiment 7
1) 0.3 g manganese dioxide is weighed（MnO2）Nanometer rods measure the oxalic acid of 200 μ L, are separately added into 50 mL deionizations
It is through deionized water centrifuge washing 3 times and dry at 80 DEG C after being ultrasonically treated 30 minutes with ultrasonic cleaner in water；It will be upper
It states powder and is scattered in 90 mL ethylene glycol solutions（Alcohol water ratio is 1:4）In, the ammonia spirit and 0.6 mL for being separately added into 1 mL are just
Tetraethyl orthosilicate, it is through deionized water centrifuge washing 3 times and dry at 80 DEG C after magnetic agitation 3 hours, obtain core-shell structure
Coated with silica manganese dioxide nano-rod；
2) 30 mL ethylene glycol solutions are added in the sucrose of 0.3 g（Alcohol water ratio is 1:4）In, then weigh the step of 120 mg
Suddenly（1）The powder-like of middle preparation is scattered in the solution, and after being ultrasonically treated 30 minutes with ultrasonic cleaner, magnetic agitation 24 is small
When, it is through deionized water centrifuge washing 3 times and dry at 80 DEG C；Gained compound is placed in the tube furnace full of nitrogen, with
The heating rate of 10 DEG C/min keeps the temperature 10 hours at 450 DEG C, to tube furnace natural cooling, obtains black powder；
3) by the sodium hydroxide of 0.3 g（NaOH）It is added in 20 mL deionized waters, heating water bath is to after 90 DEG C, by step
（2）The black powder of middle preparation is slowly added to, after magnetic agitation 22 hours, through deionized water centrifuge washing 3 times and at 80 DEG C
Dry, obtaining powder is a kind of carbon coating Na0.55Mn2O4 .1.5H2O nanocomposite.
Embodiment 8
1) 0.3 g manganese dioxide is weighed（MnO2）Nanometer rods measure the sulfuric acid of 900 μ L, are separately added into 50 mL deionizations
It is after ten minutes with ultrasonic cleaner ultrasonic treatment, through deionized water centrifuge washing 3 times and dry at 60 DEG C in water；It will be upper
It states powder and is scattered in 100 mL glycerin solutions（Alcohol water ratio is 1:2）In, it is separately added into the ammonia spirit and 0.2 mL of 1 mL
Tetraethyl orthosilicate, it is through deionized water centrifuge washing 3 times and dry at 60 DEG C after magnetic agitation 4 hours, obtain nucleocapsid knot
Structure coated with silica manganese dioxide nano-rod；
2) 30 mL glycerin solutions are added in the chitosan of 0.4 g（Alcohol water ratio is 1:2）In, then weigh 120 mg's
Step（1）The powder-like of middle preparation is scattered in the solution, and after ten minutes with ultrasonic cleaner ultrasonic treatment, magnetic agitation 12 is small
When, it is through deionized water centrifuge washing 3 times and dry at 60 DEG C；Gained compound is placed in the tube furnace full of argon gas, with
The heating rate of 5 DEG C/min keeps the temperature 8 hours at 750 DEG C, to tube furnace natural cooling, obtains black powder；
3) by the sodium hydroxide of 0.5 g（NaOH）It is added in 40 mL deionized waters, heating water bath is to after 40 DEG C, by step
（2）The black powder of middle preparation is slowly added to, after magnetic agitation 20 hours, through deionized water centrifuge washing 3 times and at 60 DEG C
Dry, obtaining powder is a kind of carbon coating Na0.55Mn2O4 .1.5H2O nanocomposite.
Embodiment 9
1) 0.435 g manganese dioxide is weighed（MnO2）Nanometer rods, measure 900 μ L oxalic acid, be separately added into 50 mL go from
It is after twenty minutes with ultrasonic cleaner ultrasonic treatment, through deionized water centrifuge washing 3 times and dry at 70 DEG C in sub- water；It will
Above-mentioned powder is scattered in 90 mL ethyl alcohol and isopropyl alcohol mixture（Ratio is 1:1）In, be separately added into 1 mL ammonia spirit and
The tetraethyl orthosilicate of 0.8 mL, it is through deionized water centrifuge washing 3 times and dry at 70 DEG C after magnetic agitation 5 hours, it obtains
To core-shell structure coated with silica manganese dioxide nano-rod；
2) by the citric acid of 0.5 g（CA）10 mL ethyl alcohol and isopropyl alcohol mixture is added（Ratio is 1:1）In, then
The step of weighing 160 mg（1）The powder-like of middle preparation is scattered in the solution, after twenty minutes with ultrasonic cleaner ultrasonic treatment,
It is magnetic agitation 16 hours, through deionized water centrifuge washing 3 times and dry at 70 DEG C；Gained compound is placed in full of hydrogen
Tube furnace in, with the heating rate of 10 DEG C/min, keep the temperature 8 hours at 750 DEG C, to tube furnace natural cooling, obtain black
Color powder；
3) by the sodium hydroxide of 0.8 g（NaOH）It is added in 30 mL deionized waters, heating water bath is to after 40 DEG C, by step
（2）The black powder of middle preparation is slowly added to, after magnetic agitation 22 hours, through deionized water centrifuge washing 3 times and at 70 DEG C
Dry, obtaining powder is a kind of carbon coating Na0.55Mn2O4 .1.5H2O nanocomposite.
Embodiment 10
1) 0.435 g manganese dioxide is weighed（MnO2）Nanometer rods measure the hydrochloric acid of 900 μ L（HCl）, it is separately added into 50 mL
In deionized water, after being ultrasonically treated 30 minutes with ultrasonic cleaner, done through deionized water centrifuge washing 3 times and at 60 DEG C
It is dry；80 mL isopropanols and ethylene glycol mixed solution are dispersed by above-mentioned powder（Alcohol water ratio is 3:1）In, it is separately added into 1 mL's
The tetraethyl orthosilicate of ammonia spirit and 0.8 mL, after magnetic agitation 3 hours, through deionized water centrifuge washing 3 times and in 60 DEG C
Lower drying obtains core-shell structure coated with silica manganese dioxide nano-rod；
2) 30 mL isopropanols and ethylene glycol mixed solution are added in the chitosan of 0.5 g（Alcohol water ratio is 3:1）In, then
The step of weighing 160 mg（1）The powder-like of middle preparation is scattered in the solution, after being ultrasonically treated 30 minutes with ultrasonic cleaner,
It is magnetic agitation 18 hours, through deionized water centrifuge washing 3 times and dry at 60 DEG C；Gained compound is placed in full of nitrogen
Tube furnace in, with the heating rate of 15 DEG C/min, keep the temperature 5 hours at 550 DEG C, to tube furnace natural cooling, obtain black
Color powder；
3) by the sodium hydroxide of 0.8 g（NaOH）It is added in 40 mL deionized waters, heating water bath is to after 90 DEG C, by step
（2）The black powder of middle preparation is slowly added to, after magnetic agitation 20 hours, through deionized water centrifuge washing 3 times and at 60 DEG C
Dry, obtaining powder is a kind of carbon coating Na0.55Mn2O4 .1.5H2O nanocomposite.
Claims (10)
1. carbon coating Na0.55Mn2O4·1.5H2O nanocomposite, it is characterised in that：Na0.55Mn2O4·1.5H2O is by nanometer
The spherical structure of stick composition, and be uniformly wrapped in amorphous carbon layer, it is by coated with silica manganese dioxide nano
Stick obtains carbon-coated core-shell structure coated with silica manganese dioxide nano-rod by carbon coating, and excessive heat is then added
It is stirred to react in sodium hydroxide solution.
2. carbon coating Na described in claim 10.55Mn2O4·1.5H2The preparation method of O nanocomposite, it is characterised in that：
Include the following steps：
(1) it disperses the manganese dioxide nano-rod after sour surface modification in alcohol or alcohol-water mixture, positive silicic acid is added
Tetra-ethyl ester and tetraethyl orthosilicate hydrolytic accelerating agent, stirring, the coated with silica for keeping surface negatively charged are positively charged to surface
On the manganese dioxide nano-rod of lotus, then through deionized water centrifuge washing and drying, obtains coated with silica manganese dioxide and receive
Rice stick；
(2) carbon coating is carried out to the sample that step (1) obtains：Carbon source is added in alcohol or alcohol-water mixture, then by step (1)
Middle gained nucleocapsid coated with silica manganese dioxide nano-rod is scattered in the solution, ultrasound, after stirring a period of time, through deionization
Water centrifuge washing is dry；Then gained compound is subjected to high-temperature heat treatment under reproducibility or inert atmosphere, natural cooling obtains
Composite material after to carbonization；
(3) carbon coating Na0.55Mn2O4·1.5H2The preparation of O nanocomposite：By the composite material after the carbonization in step (2)
Powder-like is slowly added in the sodium hydroxide solution of excessive heat, is stirred to react, most dry through deionized water centrifuge washing afterwards, is obtained
Carbon coating Na0.55Mn2O4·1.5H2O nanocomposite.
3. carbon coating Na according to claim 20.55Mn2O4·1.5H2The preparation method of O nanocomposite, feature
It is：Mixing time in step (1) is 3-5h；The mixing time of step (2) is 12-24h；The mixing time of step (3) is
18-24h。
4. carbon coating Na according to claim 20.55Mn2O4·1.5H2The preparation method of O nanocomposite, feature
It is：Surface described in step (1) is modified as：Manganese dioxide nano-rod is added in the solution containing acid, ultrasound makes its dispersion,
Then dry through deionized water centrifuge washing；The acid is inorganic acid hydrochloric acid, sulfuric acid, perchloric acid, nitric acid and organic acid 12
Any one of alkyl sulfonic acid, phytic acid, oxalic acid, citric acid, dodecyl benzene sulfonic acid, camphorsulfonic acid and naphthalene sulfonic acids；Step (1) institute
The volume for the acid stated and the amount ratio of manganese dioxide nano-rod are 200~900 μ L：0.087~0.435g.
5. carbon coating Na according to claim 20.55Mn2O4·1.5H2The preparation method of O nanocomposite, feature
It is：The amount ratio of tetraethyl orthosilicate described in step (1) and manganese dioxide nano-rod is 0.1868-0.7472g：0.087
~0.435g；
The amount ratio of carbon source and nucleocapsid coated with silica manganese dioxide powder is in step (2)：0.1~0.5g:40~
160mg；
Hydrolytic accelerating agent described in step (1) is ammonium hydroxide, and the volume of ammonium hydroxide and the amount ratio of tetraethyl orthosilicate are 1ml：
0.1868-0.7472g。
6. carbon coating Na according to claim 20.55Mn2O4·1.5H2The preparation method of O nanocomposite, feature
It is：Alcohol described in step (1) is ethyl alcohol, ethylene glycol, isopropanol, any one or more than one combination in polyalcohol；
Alcohol-water mixture be ethyl alcohol, ethylene glycol, isopropanol, any one or more than one combination and deionized water in polyalcohol with
Volume ratio is 1:4~4:1 mixing.
7. carbon coating Na according to claim 20.55Mn2O4·1.5H2The preparation method of O nanocomposite, feature
It is：Carbon source described in step (2) is one of citric acid, sucrose, chitosan.
8. carbon coating Na according to claim 20.55Mn2O4·1.5H2The preparation method of O nanocomposite, feature
It is：Reducing atmosphere described in step (2) is the mixed gas for being nitrogen containing 5% hydrogen, remaining gas, and inert atmosphere is nitrogen
Gas, argon atmosphere.
9. carbon coating Na according to claim 20.55Mn2O4·1.5H2The preparation method of O nanocomposite, feature
It is：High-temperature heat treatment described in step (2) refers to full of containing 5% hydrogen, the mixed gas or nitrogen that remaining gas is nitrogen
In the tube furnace of gas or argon gas, with 5~15 DEG C/min heating rate, heat preservation 5~10 is small after being raised to 450~750 DEG C of target temperatures
When.
10. carbon coating Na according to claim 20.55Mn2O4·1.5H2The preparation method of O nanocomposite, feature
It is：The temperature of the sodium hydroxide solution of heat described in step (3) is 40~90 DEG C.
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| CN108448051B (en) * | 2018-04-11 | 2020-11-03 | 深圳市源驰科技有限公司 | Aqueous sodium ion battery Na0.58Mn2O4·1.38H2O material, preparation method and application thereof, and electrode |
| CN108987683B (en) * | 2018-05-30 | 2020-09-01 | 天能帅福得能源股份有限公司 | Preparation method of carbon-coated ternary cathode material |
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