CN110137465A - A kind of carbon@Fe2O3@carbosphere composite material and its application - Google Patents
A kind of carbon@Fe2O3@carbosphere composite material and its application Download PDFInfo
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- CN110137465A CN110137465A CN201910394308.1A CN201910394308A CN110137465A CN 110137465 A CN110137465 A CN 110137465A CN 201910394308 A CN201910394308 A CN 201910394308A CN 110137465 A CN110137465 A CN 110137465A
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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
- H01M4/364—Composites as mixtures
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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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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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
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- 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 present invention relates to a kind of carbon@Fe2O3@carbosphere composite material and its application, the carbon@Fe2O3@carbosphere composite material is prepared by tetraethyl orthosilicate, ammonium hydroxide, resorcinol, formaldehyde, molysite and dopamine, and the carbon Fe2O3 carbosphere diameter prepared is 200~300 nm, and thickness of the shell is about 15~30nm in the microballoon carbon, the Fe2O3Intermediate layer thickness be 30~60nm, the carbon shell with a thickness of 3~7nm；The carbon@Fe2O3@carbosphere nanocomposite is used as the negative electrode material of lithium ion battery.The present invention has the advantages that carbon@Fe of the invention2O3@carbosphere material is applied to lithium ion battery, greatly improves lithium battery and obtains capacity retention ratio, and simple process, favorable reproducibility, easy to implement.
Description
Technical field
The invention belongs to technical field of lithium ion battery negative, in particular to a kind of carbon@Fe2O3@carbosphere composite wood
Material and its application.
Background technique
Lithium ion battery has high voltage, high capacity, small in size, light weight, memory-less effect, self discharge small and the circulation longevity
The advantages that long is ordered, the mechanism of new electrochemical power sources of 21 century great potential is become.Negative electrode material stone in commercialization lithium battery at present
The theoretical capacity of ink only has 372 mAh/g, is not able to satisfy the application demand of heavy-duty battery.Therefore, exploitation have higher capacity,
The negative electrode material of long circulation life and high rate capability becomes the target that domestic and international researcher is chased.
In order to improve Fe2O3 Chemical property, mainly account for from the following aspect: (1) preparing nanoscale Fe2O3It is empty
On the one hand heart nano material, the presence of hollow structure are conducive to the infiltration of electrolyte and the transmission of lithium ion, on the other hand can be with
Alleviate the variation of the material volume in charge and discharge process；(2) by Fe2O3 Compound with carbon progress, the presence of carbon can not only improve
The intrinsic low conductivity characteristic of iron oxide also can alleviate Fe as buffer layer2O3 Volume change in charge and discharge process
Generated stress；Chemical property of the di-iron trioxide as negative electrode material, this hair can be significantly improved in conjunction with above-mentioned design
It is bright to be prepared for carbon Fe using the processing methods such as simple low-temperature inorganic precipitating and subsequent calcination annealing2O3@carbosphere composite material.
This classification composite construction has its unique structural advantage, on the one hand its have the big hollow structure that is formed by internal carbon ball with
Small hollow structure inside iron oxide can significantly increase the material for the tolerances of volume change stress；On the other hand, interior
In the presence of the volume change that can not only preferably alleviate iron oxide as buffer layer while outer carbon-coating, can greatly also increase
The conductivity of the electrode material, to increase its high rate performance.Carbon@Fe2O3@carbosphere negative electrode material is applied to lithium battery, energy
The cycle life for significantly improving lithium battery (after recycling 100 times under the current density of 0.2 C, achieves about 1163 mAh/g's
Charging capacity, and coulombic efficiency is 98.06 %), which yet there are no relevant report both at home and abroad.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of carbon@Fe2O3@carbosphere composite material
And its application, it is asked using solving existing di-iron trioxide as the technology of lithium ion battery negative material cycle life difference
Topic.
In order to solve the above technical problems, the technical solution of the present invention is as follows: a kind of carbon@Fe2O3@carbosphere composite material, wound
New point is: the carbon@Fe2O3@carbosphere composite material is by tetraethyl orthosilicate, ammonium hydroxide, resorcinol, formaldehyde, molysite and more
Bar amine is prepared, and the carbon Fe2O3 carbosphere diameter prepared is 200~300 nm, and thickness of the shell is about in the microballoon carbon
15~30nm, the Fe2O3 Intermediate layer thickness be 30~60nm, the carbon shell with a thickness of 3~7nm；
The carbon@Fe2O3@carbosphere composite material, is prepared particular by following steps:
Step 1: the preparation of silica@phenolic resin microspheres: tetraethyl orthosilicate and ammonium hydroxide are added in ethanol/water solution,
Resorcinol and formaldehyde are added after 1~2h of stirring and continues 12~24 h of stirring；In the ethanol/water solution system, ethyl alcohol
Volume fraction be 72~85 %, containing TEOs be 50~80 ml in every liter of reaction solution, ammonia concn is 120~180 ml,
12~18 g of benzenediol, 18~25 ml of formaldehyde；Reaction solution is then moved into autoclave and 12~24 h of hydro-thermal reaction；
After naturally cooling to room temperature, centrifuge washing collects product, obtains silica@phenolic resin microspheres；
Step 2: the preparation of the hollow carbon balls of function dough: silica phenolic resin is placed in tube furnace, in nitrogen or argon
Be warming up to 400~500 DEG C under the argon-mixed atmosphere of nitrogen of gas or any ratio with the rate of 4~6 DEG C/min, then with 1~
The rate of 2.5 DEG C/min is warming up to 550~750 DEG C to prevent material structure broken, and is kept for 2~4 hours, makes phenolic resin
Sufficiently carbonization, cooled to room temperature, obtains SiO later2@carbosphere material；Again by SiO2@carbosphere is placed in 15~25 wt%
Hydrofluoric acid solution in impregnate 12~24 h, be then centrifuged for separating, be cleaned with deionized water, obtain hollow carbon balls；Then by institute
It obtains hollow carbon balls and is initially positioned at 25~35 DEG C, 2 h are stirred in the concentrated nitric acid that mass fraction is 60~70 % infiltrates it sufficiently simultaneously just
Step functionalization, temperature then rises to 50~80 DEG C and continues 8~10h of stirring be functionalized；Then it washes, it is dry, it obtains
The hollow carbon balls of function dough；
Step 3: carbon@Fe2O3The preparation of micro-sphere material: the hollow carbon balls of the resulting function dough of step 2 are added to deionization
In water, hollow carbon balls dispersion liquid is obtained；Then molysite is added into hollow carbon balls dispersion liquid again, under the conditions of 60~80 DEG C with
The speed of 600~900 rpm/min stirs 4~6 h, obtains carbon@FeOOH；The hollow carbon balls dispersion liquid concentration be 0.5~
1 g/L, the concentration of the molysite are 0.2~1 mol/L；By the way that product is collected by centrifugation, and it is washed with deionized 2~3 times,
Obtain the hollow carbosphere composite material carbon FeOOH of FeOOH package；Then carbon@FeOOH is placed in tube furnace,
350~450 DEG C are warming up to the rate of 1~6 DEG C/min under the argon-mixed atmosphere of nitrogen of nitrogen or argon gas or any ratio and are protected
2~6 h are held, later cooled to room temperature, obtains carbon@Fe2O3Microsphere nano material；
Step 4: by the carbon@Fe in step 32O3Microsphere nano material is scattered in tris solution, and is added
4~6 h are stirred after dopamine at normal temperature；The carbon@Fe2O3 The dispersion concentration of microsphere nano material is 0.5~1 g/L；
The dopamine concentration is 0.4~1 g/L；The concentration of the trishydroxymethylaminomethane is 1~1.2 g/L；It has reacted
Product is washed 2~3 times by the way that product is collected by centrifugation, and with deionized water at rear；Product after drying is placed in tube furnace,
250~300 DEG C are warming up to simultaneously under the argon-mixed atmosphere of nitrogen of nitrogen or argon gas or any ratio with the rate of 2~4 DEG C/min
0.5~1 h is kept, is then warming up to 350~450 DEG C with the rate of 0.5~1 DEG C/min with stabilizing material structure, and keep 2
~4 h Carbidopa amine layer, then cooled to room temperature, obtains carbon@Fe2O3@carbosphere composite material.
Further, the molysite is any one in iron chloride, ferric nitrate or ferric sulfate.
A kind of above-mentioned carbon@Fe2O3The application of@carbosphere composite material, innovative point are: the carbon@Fe2O3@carbon is micro-
Ball nanocomposite is used as the negative electrode material of lithium ion battery.
Further, the carbon@Fe2O3@carbosphere nanocomposite applications are in CR2032 fastening lithium ionic cell, tool
Steps are as follows for body:
Step A: according to the mass ratio of 70:20:10 by carbon@Fe2O3@carbosphere nanocomposite: conductive agent Super P: viscous
It ties agent carboxymethyl sodium cellulosate to be uniformly mixed, obtains solid mixture；
Step B: the solid mixture that step A is obtained is mixed with ultrapure water according to mass ratio for 18:82~25:75, is stirred
It mixes uniformly, slurry is made；
Step C: the slurry that step B is obtained is coated on copper foil, and the lithium with a thickness of 13~23 μm is made after drying, roll-in
Ion battery electrode piece；
Step D: the lithium ion cell electrode piece that step C is obtained uses microporous polypropylene membrane for diaphragm as battery cathode sheet,
Using 1 mol/L LiPF of solvent6For electrolyte, solvent is isometric dimethyl carbonate and dipropyl carbonate, is being full of argon gas
Glove box in be assembled into CR2032 fastening lithium ionic cell.
The present invention has the advantages that
(1) carbon@Fe of the present invention2O3On the one hand the presence of@carbosphere composite material, the classification hollow structure can alleviate three oxidations
Volume change of two iron in charge and discharge process, on the other hand also helps the infiltration of electrolyte and the transmission of lithium ion, in this way
Its cycle life can be significantly improved；And on the one hand the presence of carbon-coating can improve the characteristic of the low conductivity of di-iron trioxide,
The variation of its volume in charge and discharge process can be alleviated as a buffer layer simultaneously, to be effectively improved its stable circulation
Property；
(2) carbon@Fe of the present invention2O3The preparation method of@carbosphere composite material, wherein heated up using stage gradient to SiO2@phenol
Urea formaldehyde is carbonized, the functionalization stage of subsequent hollow carbon balls it is carried out using concentrated nitric acid infiltrating in advance and etc. both keep
The integrality of material structure also achieves ideal functionalization effect；Then by inorganic precipitation → annealing phase transition → poly-
The series of steps such as object package → step-up temperature carbonization are closed, finally having synthesized structure completely has the carbon of classification hollow structure
Fe2O3@carbosphere material；
(3) carbon@Fe of the present invention2O3@carbosphere composite material, can be used as the lithium ion battery negative material of function admirable, capacity
High and its cycle life that can be obviously improved lithium battery, (after recycling 100 times under 0.2 C, achieves the charging of 1163 mAh/g
Capacity, discharge capacity is still up to 758.8 mAh/g after recycling 1000 times under 1 C), and simple process, favorable reproducibility, it is easy to real
It applies, is suitble to large-scale production.
Detailed description of the invention
The present invention will be further described in detail below with reference to the accompanying drawings and specific embodiments.
Fig. 1 is hollow carbon balls scanning electron microscope (SEM) photograph prepared by the embodiment of the present invention 1.
Fig. 2 is carbon@Fe prepared by the embodiment of the present invention 12O3The X-ray diffraction result figure of@carbosphere.
Fig. 3 is carbon@Fe prepared by the embodiment of the present invention 12O3@carbosphere TEM figure.
Fig. 4 is carbon@Fe prepared by the embodiment of the present invention 12O3@carbosphere high power TEM figure.
Fig. 5 is carbon@Fe prepared by the embodiment of the present invention 12O3@carbosphere as negative electrode material lithium ion battery in 0.2 C
Under cycle performance curve.
Fig. 6 is carbon@Fe prepared by the embodiment of the present invention 12O3@carbosphere as negative electrode material lithium ion battery at 1C
Cycle performance curve.
Specific embodiment
The following examples can make professional and technical personnel that the present invention be more fully understood, but therefore not send out this
It is bright to be limited among the embodiment described range.
Embodiment 1
(1) by 1.7 ml TEOS, 4 ml ammonium hydroxide are added in the mixed solution being made of 15 ml ethyl alcohol and 6 ml water simultaneously and stir 1
h.0.4 g resorcinol and 0.56 ml formaldehyde is then added, continues to stir 24 h.Then by reaction solution in 100 DEG C of hydro-thermals
24 h are reacted, product are collected by centrifugation and with ethanol washing 4 times.Obtain SiO2@phenolic resin.
(2) SiO by step (1) after dry2@phenolic resin is placed in tube furnace, is passed through with the air inflow of 0.5 L/min
Nitrogen protection gas is first warming up to 400 DEG C with the rate of 6 DEG C/min and is kept for half an hour, then with the rate of 1 DEG C/min
It is warming up to 700 DEG C and is kept for 2 hours, obtain SiO2@carbosphere, then by SiO2@carbon, which is placed in 15 wt% hydrofluoric acid solutions, to be impregnated
Product is collected by centrifugation after 12 h, and is washed with water to neutrality, obtains hollow carbon balls.
(3) by the hollow carbon balls ultrasonic disperse of 300 mg in 20 ml concentrated nitric acids (68 wt%), after 1h is stirred at room temperature
80 DEG C and 10 h of return stirring are warming up to, product is collected by centrifugation with the revolving speed of 8000 r/min after the reaction was completed and uses ultrapure water
Washing 5 times, is functionalized to obtain hollow carbon balls.
(4) by hollow carbon balls 40 min of ultrasound of 50 mg, it is dispersed in it in 100 ml deionized waters, and be added
0.541 g ferric chloride hexahydrate, 5 h of stirring in water bath at 75 DEG C are centrifuged with the revolving speed of 8000 r/min receive after the reaction was completed
Collect product and with milli-Q water 4 times, obtains carbon@FeOOH.
(5) the carbon@FeOOH of step (4) after dry is placed in tube furnace, nitrogen is passed through with the air inflow of 0.5 L/min
Gas, heating rate are 2 DEG C/min, are warming up to 350 DEG C and calcine cooled to room temperature after 2 h, obtain carbon@Fe2O3 It is micro-
Ball nanocomposite.
(6) by the carbon@Fe of 150 mg2O3 20 min of microballoon compound material ultrasound, make its be dispersed in 250 ml go from
In sub- water, and 0.1 g dopamine and 1 g trishydroxymethylaminomethane is added.4 h are stirred at room temperature.After the reaction was completed with 5000
The revolving speed of r/min is collected by centrifugation product and with milli-Q water 4 time, by gained sample in 60 DEG C of dryings overnight；After drying
Sample is placed in tube furnace, is warming up to 300 DEG C with the rate of 4 DEG C/min and is kept 0.5 h, then with the rate of 1 DEG C/min
It is warming up to 450 DEG C and keeps the thorough Carbidopa amine layer of 2 h, finally obtain carbon@Fe2O3@carbosphere nanocomposite.
(7) assembling and performance test of lithium ion battery: according to mass ratio 70:20:10 by carbon@Fe2O3@carbosphere is led
Electric agent Super P and binder sodium carboxymethylcellulose are uniformly mixed；According still further to mass ratio 20:80 by solid after mixing
Mixture and ultrapure water are mixed and stirred for that slurry is uniformly made；Slurry is coated on copper foil later, after drying, roll-in
Lithium ion cell electrode piece is made.Then using lithium piece as electrode anode piece, microporous polypropylene membrane is diaphragm, 1 mol/L
LiPF6 (solvent is isometric dimethyl carbonate and dipropyl carbonate) is electrolyte, with this electrode slice in the hand for being full of argon gas
CR2032 fastening lithium ionic cell is assembled into casing.After lithium ion battery is stood 24 hours, respectively in 0.2C and 1C electric current
Charge-discharge test is carried out under density, charge and discharge voltage is between 0.01~3.0 V.
The result of the present embodiment is as shown in Figures 1 to 5；As seen from Figure 1, with uniform spherical morphology, from a
Other breakage can be seen that it with hollow structure, and diameter is about 220 nm；As seen from Figure 2, peak respectively corresponds
In the peak of di-iron trioxide (JCPDS card: 33-0664), wherein the broad peak near 22 ° is attributed to the peak of carbon in material；By
Fig. 3 can be seen that carbon@Fe2O3@carbosphere has uniform topographic profile, Fe2O3It is wrapped with carbon-coating, thickness is about 5 nm,
Furthermore Fe2O3Nanometer rods also have hollow structure；As seen from Figure 4, Fe2O3It is wrapped with carbon-coating, thickness is about 5 nm；
Fe2O3It presents rodlike and there is hollow structure.
Embodiment 2
(1) by 2.2 ml TEOS, 4 ml ammonium hydroxide are added in the mixed solution being made of 19 ml ethyl alcohol and 8 ml water simultaneously and stir 1
h.0.4 g resorcinol and 0.56 ml formaldehyde is then added, continues to stir 24 h.Then by reaction solution in 100 DEG C of hydro-thermals
24 h are reacted, product are collected by centrifugation and with ethanol washing 4 times.Obtain SiO2@phenolic resin.
(2) SiO by step (1) after dry2@phenolic resin is placed in tube furnace, is passed through with the air inflow of 0.5 L/min
Nitrogen protection gas is first warming up to 400 DEG C with the rate of 6 DEG C/min and is kept for half an hour, then with the rate of 1 DEG C/min
It is warming up to 700 DEG C and is kept for 2 hours, obtain SiO2@carbosphere, then by SiO2@carbon, which is placed in 15 wt% hydrofluoric acid solutions, to be impregnated
Product is collected by centrifugation after 12 h, and is washed with water to neutrality, obtains hollow carbon balls.
(3) by the hollow carbon balls ultrasonic disperse of 300 mg in 20 ml concentrated nitric acids (68 wt%), after 1h is stirred at room temperature
80 DEG C and 10 h of return stirring are warming up to, product is collected by centrifugation with the revolving speed of 8000 r/min after the reaction was completed and uses ultrapure water
Washing 5 times, is functionalized to obtain hollow carbon balls.
(4) by hollow carbon balls 40 min of ultrasound of 100 mg, it is dispersed in it in 100 ml deionized waters, and be added
Product is collected by centrifugation simultaneously with the revolving speed of 8000 r/min after the reaction was completed in 75 DEG C of 5 h of stirring in water bath in 0.829 g ferric nitrate
With milli-Q water 4 times, carbon@FeOOH is obtained.
Other steps are same as Example 1.
Embodiment 3
(1) by 1.3 ml TEOS, 4 ml ammonium hydroxide are added in the mixed solution being made of 12 ml ethyl alcohol and 4 ml water simultaneously and stir 1
h.0.4 g resorcinol and 0.56 ml formaldehyde is then added, continues to stir 24 h.Then by reaction solution in 100 DEG C of hydro-thermals
24 h are reacted, product are collected by centrifugation and with ethanol washing 4 times.Obtain SiO2@phenolic resin.
(2) SiO by step (1) after dry2@phenolic resin is placed in tube furnace, is passed through with the air inflow of 0.5 L/min
Nitrogen protection gas is first warming up to 400 DEG C with the rate of 6 DEG C/min and is kept for half an hour, then with the rate of 1 DEG C/min
It is warming up to 700 DEG C and is kept for 2 hours, obtain SiO2@carbosphere, then by SiO2@carbon, which is placed in 15 wt% hydrofluoric acid solutions, to be impregnated
Product is collected by centrifugation after 12 h, and is washed with water to neutrality, obtains hollow carbon balls.
(3) by the hollow carbon balls ultrasonic disperse of 300 mg in 20 ml concentrated nitric acids (68 wt%), after 1h is stirred at room temperature
80 DEG C and 10 h of return stirring are warming up to, product is collected by centrifugation with the revolving speed of 8000 r/min after the reaction was completed and uses ultrapure water
Washing 5 times, is functionalized to obtain hollow carbon balls.
(4) by hollow carbon balls 40 min of ultrasound of 100 mg, it is dispersed in it in 100 ml deionized waters, and be added
Product is collected by centrifugation simultaneously with the revolving speed of 8000 r/min after the reaction was completed in 75 DEG C of 5 h of stirring in water bath in 1.021 g ferric sulfate
With milli-Q water 4 times, carbon@FeOOH is obtained.
Other steps are same as Example 1.
The lithium electrical property result of embodiment 1-3 is as shown in Table 1 and Table 2.
Table 1 is that the lithium ion battery of Examples 1 to 3 carries out charge-discharge test first lap and the 100th circle under 0.2C electric current
Capacity obtained.
Table 1
As it can be seen from table 1 using carbon@Fe of the invention2O3@carbosphere is applied to lithium ion battery as electrode material,
Charging capacity has good cycle performance in 70 % or more in 1000 mAh/g or more, capacity retention ratio after 100 circle of circulation,
Still it is much higher than the graphite cathode material of Current commercial.
Table 2 carries out charge-discharge test first lap and the 1000th circle institute for the lithium ion battery of Examples 1 to 3 under 1C electric current
The capacity of acquisition.
Table 2
From table 2 it can be seen that using carbon@Fe of the invention2O3@carbon microballoons are applied to lithium ion battery as electrode material,
Charging capacity has good cyclicity in 64.8 % or more in 723 mAh/g or more, capacity retention ratio after the circle of circulation 1000
Can, still it is much higher than the graphite cathode material of Current commercial.
Basic principles and main features and advantages of the present invention of the invention have been shown and described above.The skill of the industry
Art personnel it should be appreciated that the present invention is not limited to the above embodiments, the above embodiments and description only describe
The principle of the present invention, without departing from the spirit and scope of the present invention, various changes and improvements may be made to the invention, these
Changes and improvements all fall within the protetion scope of the claimed invention.The claimed scope of the invention by appended claims and
Its equivalent thereof.
Claims (4)
1. a kind of carbon@Fe2O3@carbosphere composite material, it is characterised in that: the carbon@Fe2O3@carbosphere composite material is by positive silicon
Sour tetra-ethyl ester, ammonium hydroxide, resorcinol, formaldehyde, molysite and dopamine are prepared, the carbon@Fe2O3@carbosphere diameter prepared
For 200~300 nm, thickness of the shell is about 15~30nm in the microballoon carbon, the Fe2O3 Intermediate layer thickness is 30~60nm,
The carbon shell with a thickness of 3~7nm；
The carbon@Fe2O3@carbosphere composite material, is prepared particular by following steps:
Step 1: the preparation of silica@phenolic resin microspheres: tetraethyl orthosilicate and ammonium hydroxide are added in ethanol/water solution,
Resorcinol and formaldehyde are added after 1~2h of stirring and continues 12~24 h of stirring；In the ethanol/water solution system, ethyl alcohol
Volume fraction be 72~85 %, containing TEOs be 50~80 ml in every liter of reaction solution, ammonia concn is 120~180 ml,
12~18 g of benzenediol, 18~25 ml of formaldehyde；Reaction solution is then moved into autoclave and 12~24 h of hydro-thermal reaction；
After naturally cooling to room temperature, centrifuge washing collects product, obtains silica@phenolic resin microspheres；
Step 2: the preparation of the hollow carbon balls of function dough: silica phenolic resin is placed in tube furnace, in nitrogen or argon
Be warming up to 400~500 DEG C under the argon-mixed atmosphere of nitrogen of gas or any ratio with the rate of 4~6 DEG C/min, then with 1~
The rate of 2.5 DEG C/min is warming up to 550~750 DEG C to prevent material structure broken, and is kept for 2~4 hours, makes phenolic resin
Sufficiently carbonization, cooled to room temperature, obtains SiO later2@carbosphere material；Again by SiO2@carbosphere is placed in 15~25 wt%
Hydrofluoric acid solution in impregnate 12~24 h, be then centrifuged for separating, be cleaned with deionized water, obtain hollow carbon balls；Then by institute
It obtains hollow carbon balls and is initially positioned at 25~35 DEG C, 2 h are stirred in the concentrated nitric acid that mass fraction is 60~70 % infiltrates it sufficiently simultaneously just
Step functionalization, temperature then rises to 50~80 DEG C and continues 8~10h of stirring be functionalized；Then it washes, it is dry, it obtains
The hollow carbon balls of function dough；
Step 3: carbon@Fe2O3The preparation of micro-sphere material: the hollow carbon balls of the resulting function dough of step 2 are added to deionization
In water, hollow carbon balls dispersion liquid is obtained；Then molysite is added into hollow carbon balls dispersion liquid again, under the conditions of 60~80 DEG C with
The speed of 600~900 rpm/min stirs 4~6 h, obtains carbon@FeOOH；The hollow carbon balls dispersion liquid concentration be 0.5~
1 g/L, the concentration of the molysite are 0.2~1 mol/L；By the way that product is collected by centrifugation, and it is washed with deionized 2~3 times,
Obtain the hollow carbosphere composite material carbon FeOOH of FeOOH package；Then carbon@FeOOH is placed in tube furnace,
350~450 DEG C are warming up to the rate of 1~6 DEG C/min under the argon-mixed atmosphere of nitrogen of nitrogen or argon gas or any ratio and are protected
2~6 h are held, later cooled to room temperature, obtains carbon@Fe2O3Microsphere nano material；
Step 4: by the carbon@Fe in step 32O3Microsphere nano material is scattered in tris solution, and is added
4~6 h are stirred after dopamine at normal temperature；The carbon@Fe2O3 The dispersion concentration of microsphere nano material is 0.5~1 g/L；
The dopamine concentration is 0.4~1 g/L；The concentration of the trishydroxymethylaminomethane is 1~1.2 g/L；It has reacted
Product is washed 2~3 times by the way that product is collected by centrifugation, and with deionized water at rear；Product after drying is placed in tube furnace,
250~300 DEG C are warming up to simultaneously under the argon-mixed atmosphere of nitrogen of nitrogen or argon gas or any ratio with the rate of 2~4 DEG C/min
0.5~1 h is kept, is then warming up to 350~450 DEG C with the rate of 0.5~1 DEG C/min with stabilizing material structure, and keep 2
~4 h Carbidopa amine layer, then cooled to room temperature, obtains carbon@Fe2O3@carbosphere composite material.
2. carbon@Fe according to claim 12O3@carbosphere composite material, it is characterised in that: the molysite be iron chloride,
Any one in ferric nitrate or ferric sulfate.
3. a kind of carbon@Fe described in claim 12O3The application of@carbosphere composite material, it is characterised in that: the carbon@Fe2O3@
Carbosphere nanocomposite is used as the negative electrode material of lithium ion battery.
4. carbon@Fe according to claim 32O3The application of@carbosphere composite material, it is characterised in that: the carbon@Fe2O3@
Carbosphere nanocomposite applications are in CR2032 fastening lithium ionic cell, the specific steps are as follows:
Step A: according to the mass ratio of 70:20:10 by carbon@Fe2O3@carbosphere nanocomposite: conductive agent Super P: bonding
Agent carboxymethyl sodium cellulosate is uniformly mixed, and obtains solid mixture；
Step B: the solid mixture that step A is obtained is mixed with ultrapure water according to mass ratio for 18:82~25:75, is stirred
It mixes uniformly, slurry is made；
Step C: the slurry that step B is obtained is coated on copper foil, and the lithium with a thickness of 13~23 μm is made after drying, roll-in
Ion battery electrode piece；
Step D: the lithium ion cell electrode piece that step C is obtained uses microporous polypropylene membrane for diaphragm as battery cathode sheet,
Using 1 mol/L LiPF of solvent6For electrolyte, solvent is isometric dimethyl carbonate and dipropyl carbonate, is being full of argon gas
Glove box in be assembled into CR2032 fastening lithium ionic cell.
Priority Applications (1)
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| CN110756132A (en) * | 2019-10-31 | 2020-02-07 | 大连理工大学 | Preparation method of core-shell magnetic microspheres |
| CN110993367A (en) * | 2019-12-18 | 2020-04-10 | 上海应用技术大学 | Spherical carbon @ manganese oxide @ carbon @ iron oxide composite material and preparation and application thereof |
| CN111048229A (en) * | 2019-12-18 | 2020-04-21 | 上海应用技术大学 | Manganese/iron/carbon nano composite material and preparation and application thereof |
| CN111313044A (en) * | 2020-02-27 | 2020-06-19 | 电子科技大学 | Bimetallic atom hollow carbon nanosphere catalyst and preparation method thereof |
| WO2023071393A1 (en) * | 2021-10-28 | 2023-05-04 | 广东邦普循环科技有限公司 | Hollow-spherical-particle negative electrode material with openings, and preparation method therefor and use thereof |
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| CN110993367A (en) * | 2019-12-18 | 2020-04-10 | 上海应用技术大学 | Spherical carbon @ manganese oxide @ carbon @ iron oxide composite material and preparation and application thereof |
| CN111048229A (en) * | 2019-12-18 | 2020-04-21 | 上海应用技术大学 | Manganese/iron/carbon nano composite material and preparation and application thereof |
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| CN111313044B (en) * | 2020-02-27 | 2022-07-26 | 电子科技大学 | Bimetallic atom hollow carbon nanosphere catalyst and preparation method thereof |
| WO2023071393A1 (en) * | 2021-10-28 | 2023-05-04 | 广东邦普循环科技有限公司 | Hollow-spherical-particle negative electrode material with openings, and preparation method therefor and use thereof |
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