CN106848277A - A kind of magnesium iron oxygen/carbon composite and preparation method thereof - Google Patents
A kind of magnesium iron oxygen/carbon composite and preparation method thereof Download PDFInfo
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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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/46—Alloys based on magnesium or aluminium
- H01M4/466—Magnesium based
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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
- 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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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- 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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- 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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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
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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
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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Abstract
The present invention relates to a kind of magnesium iron oxygen/carbon composite and preparation method thereof, source of iron, magnesium powder, liquid carbon source are mixed, be transferred in closed reaction vessel, be sealed and placed in crucible furnace, 8 12h are reacted at 550 650 DEG C, so as to obtain combination product.Magnesium powder, liquid carbon source, molysite simultaneous reactions in the present invention, magnesia and the iron oxide of production form homogeneous phase magnesium iron oxygen, and the carbon-coating that liquid carbon source is formed is coated on particle surface just.In the process, the synchronized compound of magnesia and iron oxide, when binary oxide particle is generated, synchronous pyrolysis liquids carbon source obtains carbon coating layer, two kinds of materials are mutually depended under the atmosphere of chemical reaction, carbon coating layer forms preferable core shell structure with binary oxide particle, and a step builds carbon composite.
Description
Technical field
The application relate to it is a kind of can be used as the preparation method of the carbon composite of lithium ion battery negative material and its lithium
Electrical quality detection, particularly a kind of preparation method and applications of carbon composite magnesium ferrite material, it is used as lithium cell negative pole material table
The characteristics of revealing high magnification, stable circulation.
Background technology
Current metal oxide is that (its theoretical specific capacity is up to a research topic for hot topic as ion cathode material lithium
1000mAh/g, and conventional graphite class negative material, theoretical specific capacity is only 372mAh/g), but there is certain lacking in its own
Fall into so as to limit its application.
Oxide, as lithium cell negative pole material, is the equal of iron oxide and gold in cyclic process such as simple iron oxide
Discharge and recharge behavior between category iron particle, i.e. thing before and after battery one cycle mutually changes, and thus causes material structure to collapse
Collapse, cyclicity is progressively deteriorated.Current most efficient method is to coat one layer of conductive carbon on oxide particle top layer, and this carbon-coating can hinder
Aggregation between block compound, also can keep its microscopic appearance constant as the supporter of oxide；Again, carbon coating layer tool
There is fabulous electric conductivity, the high-rate charge-discharge capability of material can be improved, this improved route obtains the universal of researcher
Approval.
It is believed that cladding carbon material mainly change be material surface architectural feature, for cause material particle inside
Also similar improvement is obtained, researcher is had found using two kinds even synergy of various metals, can be with the work of improved materials
Property and structural stability.Such multivariant oxide, with the intercalation/deintercalation of lithium ion, produces corresponding oxygen in cyclic process
Compound.If copper ferrite material, original material are CuFe2O4 pure phases, battery discharges first, and following reaction (1-2) occurs；Fill first
, there is (3-4) reaction in electricity, the above terminates for first circulation.Battery is continued cycling through, then be the reaction of (3-4), i.e., follow-up anti-
Should be the mutual conversion of oxide and its respective metal.
CuFe2O4+nLi--ne-→LinCuFe2O4 (1)
LinCuFe2O4-(8-n)Li-+(8-n)e-→xCu0+(2-x)Fe0+FexCu1-x+4Li2O(0≤n.x≤1) (2)
At present ,/carbon coating structure, the experimental program that researcher typically takes are combined to obtain multivariant oxide and carbon
It is as follows：
A. solid-phase synthesis, such as CuFe2O4, first pass through ball milling mixing raw material, after need to be passed through inert gas：Such as nitrogen.
(bibliography：One-step solid state reaction to selectively fabricate cubic and
tetragonal CuFe2O4anode material for high power lithium ion batteries)。
B. sol-gel process, first prepares uniform solution, after forming gel through treatment, in the calcining of nitrogen high temperature
(Combustion synthesis of MgFe2O4graphene nanocomposite as a high-performance
negative for lithium ion batteries)。
C. solvent-thermal method, magnesium salts and molysite mix in EG, additionally add a small amount of additive, 200 degree of solvent thermal reactions.But
The cycle-index of report is only 70 (Hollow spheres of MgFe2O4as anode material for lithium-
ion batteries)。
D. sol-gel process：After ferric nitrate and magnesium nitrate and citric acid form gel, can just be obtained by the heat treatment of three steps
To product (MgFe2O4nanoparticles as anode materials for lithium-ion batteries)。
E. coprecipitation, first prepares binary presoma, and subsequent high-temperature calcination obtains product.Cladding carbon material, will need to produce again
Thing mixes with conventional solid carbon source, high temperature cabonization (Preparation of carbon-coated MgFe2O4with
excellent cycling and rate performance)。
F. microwave assisting method, is carbon material using graphene oxide.Graphene oxide is expensive, and the method reaction is complicated
(MgFe2O4reduced graphene oxide composites as high-performance anode materials
for sodium ion batteries；Microwave catalyst MgFe2O4-Fe2O3Microwave catalysis oxidation degraded crystal violet waste water _ height
Order flies).
It can be to improve material to lead that experiment flow more than can be seen that many research work at present to a certain degree
Electrically, the performance such as specific discharge capacity, but most experiments process is complex, it is sometimes desirable to and logical special gas, these can all increase
Adduction is into cost.Compound with carbon material, or even need more steps, this is resulted in, and materials synthesis route is complex, yield
Low, high cost situation.
The content of the invention
In order to overcome building-up process complexity, particularly carbon recombination process in the prior art, or even inert gas is needed to use,
Yield poorly, the problem of high cost, the present invention provides a kind of preparation method of magnesium iron oxygen/carbon composite, by source of iron, magnesium powder, liquid
Body carbon source mixes, and is transferred in closed reaction vessel, is sealed and placed in crucible furnace, and 8-12h is reacted at 550-650 DEG C, from
And obtain combination product.
Be mutually mixed using the salt of two kinds of metals in the prior art, then the mode that is processed is different, present invention profit
With the reproducibility of metal magnesium powder, Mg reacts in confined conditions with liquid carbon source such as ethanol, and Mg is converted into magnesium carbonate or magnesia,
Ethanol itself is partially converted into carbon material except discharging gas, and the ferric nitrate (molysite) in raw material, it is decomposed into iron oxide.
That is magnesium powder, ethanol, molysite simultaneous reactions, magnesia and the iron oxide of production form homogeneous phase magnesium iron oxygen, the carbon-coating that ethanol is formed
Just it is coated on particle surface.In the process, magnesia and the synchronized compound of iron oxide, are generating binary oxide particle
When, synchronous pyrolysis carbon source (ethanol) obtains carbon coating layer, and two kinds of materials are mutually depended under the atmosphere of chemical reaction, carbon coating layer
Preferable core shell structure is formed with binary oxide particle, a step builds carbon composite.
The equation of reaction is：
Mg+CH3CH2OH→2C+MgO+3H2↑
4Fe(NO3)3=2Fe2O3+l2NO2↑+3O2↑
MgO+Fe2O3=MgFe2O4
Overall reaction is：
2Mg+2CH3CH2OH+4Fe(NO3)3→2MgFe2O4/C+2C+6H2↑+l2NO2↑+3O2↑
Carbon recombination process is the critically important process in carbon composite synthesis.At present, the carbon recombination process of most reports
2 steps or multistep is needed to realize, such as (E and F in above-mentioned bibliography).Prepared compared to our step complicated a lot.
Many reports obtain carbon material at present, are required for being carried out under special inert atmosphere, this method power consumption, gas consumption, yield poorly, and must
To carbon material electric conductivity it is more much lower than the carbon material obtained in closed container.
The crystallinity of simultaneous oxidation thing is better, illustrates that its microcosmic crystal defect is few, also has actively impact to chemical property.
In terms of material crystalline degree is improved, having been reported that is：The poor oxide of the presoma or crystallinity of synthesis oxide first,
Annealed under high temperature, the purpose of crystallinity is improved so as to reach, such as (B and D in above-mentioned bibliography).And our work
It is that raw material is placed in reaction vessel, is disposably warmed up to fixed temperature, you can obtains the good oxide particle of crystallinity.
Material of the present invention synthesizes by needing single step reaction.Conventional carbon recombination process is the oxide particle that will obtain with
Carbon material mixes, and this belongs to simple mixing, is that surface contacts between oxide and carbon material.Carbon composite of the invention is
From the mixing of raw material angle, in a closed reaction vessel, the product that the intermolecular reaction that contacts with each other is obtained.Therefore, oxygen
Contact of the compound particle with carbon-coating evenly, by transmission electron microscope it can be seen that the top layer of all of magnesium iron oxygen particle is all uniformly covered
One layer of carbon film of lid, and thickness is uniform.Again, the oxide that general low temperature (200 degree or so) obtains is required for high temperature (generally higher than
500 degree) annealing process, this process not only removes a small amount of moisture inside oxide, can also improve its crystallinity.The present invention
In, controlling reaction temperature is directly increased to 600 degree from room temperature, directly obtains the fabulous oxide particle of crystallinity.Preparation method
Simply, it is only necessary to the sealing of attentive response container, the auxiliary of any special atmosphere is not required to, experimentation is easy, operability
By force, only a step is that can obtain product.
Preferably：Source of iron is selected from least one of the ferric iron sources such as ferric nitrate, iron chloride.
Preferably：Liquid carbon source is absolute ethyl alcohol, ether, acetone, at least one of ethylene glycol etc..
Preferably：The mol ratio of iron and magnesium is 2-2.5: 1-1.5.
Preferably：The volume of liquid carbon source and the molal quantity ratio of magnesium are 0.1-0.5mol/L.
Preferably：Source of iron, magnesium powder, liquid carbon source mixing condition are ultrasonic mixing 30min at room temperature.
Preferably：Heating rate in crucible furnace is 6-8 DEG C/min.
Preferably：After combination product is washed through the mixed solution of water and alcohol, 4-10h is dried at 60-80 DEG C.
The present invention also provides a kind of magnesium iron oxygen/carbon composite prepared using the above method, and the existence form of carbon includes
Carbon coating layer and carbon ball, carbon coating layer are connected to each other and 3 D stereo configuration are presented, and are evenly coated at magnesium iron oxide particle surface,
So that oxide particle is no longer grown up, the degree of particle size very little is maintained, it is rounded, relatively stablize.Oxide is very
Easy agglomeration, the particularly oxide of iron content, because with magnetic, product can grow to micron order, if without carbon-coating
Cladding, ferriferous oxide easily aggregation forms larger octahedra or random aggregation, and in the present invention, the cladding of carbon-coating can be with
Aggregation between isolation oxide particle quickly.
The a diameter of 30-80nm of magnesium iron oxide particle, a diameter of micron order of carbon ball, carbon coating layer thickness is 7-9nm, carbon bag
The mass ratio of coating and carbon ball is 1: 8-10.
Unlike the prior art, magnesium ferrite material of the invention produces MgO and iron oxide in cyclic process, wherein
Magnesia maintains the microscopic appearance of iron oxide mainly as the supporter of ferric oxide particles, is not involved in discharge and recharge behavior (magnesia
Not as lithium cell negative pole material, therefore it is not involved in discharge and recharge).Thus, the presence of magnesia is played surely from the inside of composite
The effect of fixed structure so that the cyclical stability of product is high.
Carbon material in the present invention is carbon-coating and carbon ball, and both of which plays a part of stabilizing material, but emphasis is different：
Carbon coating layer is relatively thin, and it can control the size of magnesium iron oxygen particle in experimental products generating process.If magnesium iron
The particle of oxygen is larger, and it is in the charge and discharge process of battery, and structure collapses are very serious, while being also unfavorable for the conveying of lithium ion.
Therefore the important role of carbon coating layer, nano level carbon coating layer can both limit magnesium iron oxygen granular size, and energy conduct is led
Electric material quickly transmits electronics, improves the specific discharge capacity and cycle life of material.
Carbon ball particle is larger, can prevent active particle from assembling, and itself also can provide capacity as material, and can be used as activity
The accole of particle, prevents active particle from caving in, and plays a part of rock-steady structure.Therefore, on the one hand carbon ball provides electric discharge in itself
Capacity, while also functioning to extend the effect in material circulation life-span.
When the presence of carbon coating magnesium iron oxygen and carbon ball causes the composite as lithium ion battery negative material, electric discharge is held
Amount and cycle life have significant increase.
Brief description of the drawings
Fig. 1 is the EDX figures of embodiment 1
Fig. 2 is the MgFe of embodiment 12O4@C product scanning electron microscope (SEM) photographs
Fig. 3 is the carbon coating layer scanning electron microscope (SEM) photograph of embodiment 1
Fig. 4 is the MgFe of embodiment 12O4@C product transmission electron microscope pictures
Fig. 5 is the carbon coating layer transmission electron microscope picture of embodiment 1
That Fig. 6-7 is embodiment 1 is MgFe2O4The high-resolution transmission plot of@C products
Fig. 8-9 be embodiment 1 and 6 thermogravimetric analysis figure (in Fig. 8 ethanol be 10ml, be the thermogravimetric of example 1；Ethanol in Fig. 9
Be 5ml, be the thermogravimetric of example 6) Figure 10 for embodiment 1-3 XRD diffraction patterns
Figure 11 is the XRD diffraction patterns of embodiment 4-5
Figure 12 is the XRD diffraction patterns of embodiment 3 and 6
Figure 13-16 is respectively the XRD diffraction patterns of embodiment 7-10
Figure 17-18 be embodiment 1 constant current charge-discharge circulation figure (Figure 17 for current ratio 100mA/g discharge and recharge specific volume
Amount, Figure 18 is change multiplying power, and multiplying power is followed successively by：0.1C-0.2C-0.5C-1C-1.5C-2C-2.5C-2C-1.5C-1C-0.5C-
0.C (1C=1000mA/g))
Figure 19-20 be embodiment 1 constant current charge-discharge circulation figure (Figure 19 for current ratio 1000mA/g discharge and recharge specific volume
Amount, Figure 20 is the charging and discharging capacity of 3000mA/g；Explanation：The theoretical capacity of conventional graphite：372mAh/g；Magnesium ferriferous oxide
Theoretical capacity：~1000mAh/g.)
Specific embodiment
Specific embodiment in the present invention is described in further detail below in conjunction with accompanying drawing.
Mg powder consumption is 0.02-0.056g, obtains pure phase product, can be matched just：PCPDF standard cards number：88-
1936。
Embodiment 1：Weigh a certain amount of 2.0130g Fe (NO3)3·9H2O and metal magnesium powder 0.0560g, pour into 10ml without
Water-ethanol.Ultrasound 30min, shifts and is sealed in the pyroreaction kettle that volume is 20ml at room temperature.Reactor is placed in crucible
In stove, 600 DEG C are raised to the heating rate of 6 DEG C/min, keep 10h, after waiting reactor natural cooling, collect product, and spend
The mixed solution of ionized water and absolute ethyl alcohol is washed 3 times, and 6h is dried in 70 DEG C of drying box, obtains black powder product
(MgFe2O4@C, XRD, Figure 10).
Embodiment 2：Weigh a certain amount of 2.0154g Fe (NO3)3·9H2O and metal magnesium powder 0.0325g, pour into 10ml without
Water-ethanol.Subsequent process obtains pure phase product, XRD with example 1.
Embodiment 3：Weigh a certain amount of 2.0155g Fe (NO3)3·9H2O and metal magnesium powder 0.0287g, pour into 10ml without
Water-ethanol.Subsequent process obtains pure phase product, XRD with example 1.
Mg powder consumption is more than 0.056g, and magnesium carbonate (MgCO is contained in the product for obtaining3) impurity, correspondence magnesium carbonate standard card
401 crystal faces in piece 08-0479.
Embodiment 4：Weigh a certain amount of 2.0558g Fe (NO3)3·9H2O and metal magnesium powder 0.1194g, pour into 10ml without
Water-ethanol.Subsequent process obtains the product containing carbonic acid magnesium addition with example 1, and XRD is confirmed, sees Figure 11.
Embodiment 5：Weigh a certain amount of 2.0023g Fe (NO3)3·9H2O and metal magnesium powder 0.0726g, pour into 10ml without
Water-ethanol.Subsequent process obtains the product containing carbonic acid magnesium addition with example 1, and XRD is confirmed, sees Figure 11.
Ethanol consumption scope：5-10ml, to product purity, magnesium iron oxygen particle size and carbon layers having thicknesses influence are little, right
Carbon content influences also smaller (see Fig. 8-9, thermogravimetric analysis carbon content) in product, compared with example 2.
Embodiment 6：Weigh a certain amount of 2.0141g Fe (NO3)3·9H2O and metal magnesium powder 0.0338g, pour into 5ml without
Water-ethanol.Subsequent process obtains pure phase product with example 1, and XRD is shown in Figure 12.
Embodiment 7：Source of iron is FeCl3·6H2O (1.330g, 4.92mmol), magnesium powder (0.0308g), ethanol 6ml (ethanol
Consumption influence is little, and the result of 10ml is basically identical with 6ml).With example 1, product is the magnesium iron oxygen of pure phase to subsequent process.
XRD is shown in Figure 13.
Embodiment 8：Source of iron is ferric nitrate (2.058g), magnesium powder (0.032g), ether 5ml (result of 10ml and the base of 5ml
This is consistent).Subsequent process contains a small amount of carbonic acid magnesium addition with example 1 in product, removed by the consumption for adjusting magnesium powder.XRD is shown in
Figure 14.
Embodiment 9：Source of iron is ferric nitrate (2.007g), magnesium powder (0.031g), acetone 5ml (result of 10ml and the base of 5ml
This is consistent).With example 1, product is the magnesium iron oxygen of pure phase to subsequent process.XRD is shown in Figure 15.
Embodiment 10：Source of iron is ferric nitrate (2.038g), magnesium powder (0.032g), the ethylene glycol 5ml (results and 5ml of 10ml
It is basically identical).With example 1, product is the magnesium iron oxygen of pure phase to subsequent process.XRD is shown in Figure 16.
The composite of the application combines advantage during any thing phase individualism, and avoids respective thing phase simultaneously
Shortcoming.Such as, carbon material is used as lithium cell negative pole material, the advantage with high conductance and stable circulation, but its electric discharge ratio
Capacity is relatively low (its theoretical specific capacity is limited, is 372mAh/g)；Magnesium ferrite material, with specific capacity (its theoretical specific volume higher
Amount：~1000mAh/g), but cycle performance is poor.The composite that we build finds by test, not only with higher
Specific discharge capacity, while after circulating thousands of times, capability retention is higher, is the high magnification of a class great potential, long-life lithium
Electric negative pole alternative materials.Material variety used in this application is few, with low cost and environmentally friendly；Product is easily prepared, and can be grasped
The property made is strong, it is easy to extensive into product.
Product is mixed with acetylene black, PVDF powder, cathode pole piece is fabricated to；Button lithium electricity electricity is assembled in glove box
Pond.Constant current charge-discharge performance testing is carried out, as shown in figures 17 to 20.
Figure 17 illustrates that charge-discharge performance of the material when current ratio is 100mA/g, capacity has what is be gradually increasing to become
Gesture (after circulation 60 times, specific discharge capacity is 941mAh/g, be theoretical specific capacity 94%) and rise steady, illustrate material structure
Gradually stablize.
Figure 18 illustrates that the structure of material is very stable, even across big multiplying power discharging (2.5C=2500mA/g) after, return to small
During multiplying power (0.1C), material is still close with initial discharge capacity (920mAh/g), and coulombic efficiency is almost 99.9%, is said
The stabilization of bright its structure.
Figure 19-20 is the cycle performance performance under battery more high current multiplying power.Figure 19 fills for current ratio 1000mA/g's
Specific discharge capacity, Figure 20 is the charging and discharging capacity of 3000mA/g.Under 2 kinds of high current multiplying powers, battery discharge specific capacity is put down
Slow stabilization, circulates 650 times and 1000 times respectively, and in 665mAh/g and 440mAh/g, its capacity is generally higher than at present capacity stabilization
Report；And cycle life is also unattenuated up to thousands of times.
Magnesium, iron, oxygen, four kinds of presence of element of carbon in product, can be schemed to illustrate, as shown in Figure 1 by EDX.
By ESEM and transmission electron microscope, COMPOSITE MATERIALS surface texture and core shell structure：
Fig. 2 has larger carbon ball (at black circles), and less carbon coating magnesium iron oxygen particle during product can be seen；Figure
3 wash off via hydrochloric acid for convenience of observation core shell structure, the magnesium iron oxygen particle in product.
As in Fig. 2, it can be seen that have larger carbon ball (at black circles), carbon ball in product：5-7μm；And less carbon
Cladding magnesium iron oxygen particle.For convenience of observation core shell structure, we wash away the magnesium iron oxygen particle in product, remaining carbon coating with hydrochloric acid
Layer and carbon ball, and by ultrasound, detection scanning.Wherein carbon coating layer can be seen thering is obvious cavitation, hollow position by Fig. 3
It is the magnesium iron oxygen particle of script, because after carbon composite oxides are via acid soak, magnesium iron oxygen can be with molten with acid reaction production
In the magnesium ion and iron ion of water, a residual carbon precipitation of material is got off, such as carbon-coating and carbon ball.
The carbon material that ethanol is produced has two kinds, and a kind of is big carbon ball, and another kind is exactly carbon-coating, and this carbon-coating can pass through
Transmission picture is visible in detail.Because in closed container, oxygen is limited, therefore, ethanol is not decomposed into gas all, and
It is that part is carbonized.Meanwhile, furnace temperature rises quickly, and the generation of oxide is almost same stepping with the decomposition of ethanol and carbonization
OK, thus magnesium iron oxygen particle is formed just, and carbon-coating also cover magnesium iron oxygen surface while, it is suppressed that the length of magnesium iron oxygen particle
Greatly, control is in 50nm or so.
Carbon material has two kinds of patterns：Carbon coating layer：7-9nm thickness, carbon coating magnesium iron oxygen particle mean size be 50nm (see
Transmission plot, Fig. 4-5, what Fig. 4 can be apparent from sees homogeneous carbon-coating；, for convenience of observing, magnesium iron oxygen particle is via hydrochloric acid for Fig. 5
Wash off, therefore carbon-coating is hollow-core construction in picture).Fig. 4 is MgFe2O4@C products, Fig. 5 is carbon coating layer, the microcosmic upper presentation of material
Three-dimensional carbon clad structure, wherein MgFe2O4Particle is uniformly embedded into the inside of carbon-coating, each other by carbon-coating connection (see Fig. 4).Fig. 6-7
It is MgFe2O4The high-resolution transmission picture of@C products, carbon layers having thicknesses are 7-9nm.
Carbon content is tested using thermogravimetry, ethanol is 10mL in Fig. 8, ethanol is 5mL, carbon percentage composition point in Fig. 9
Not Wei 56.94% and 53.27%, illustrate experiment in ethanol consumption be not very big for the influence of carbon content.
Claims (9)
1. a kind of magnesium iron oxygen/carbon composite, it is characterised in that：The existence form of carbon includes carbon coating layer and carbon ball, carbon coating
Layer is connected to each other and 3 D stereo configuration is presented, and is evenly coated at magnesium iron oxide particle surface, a diameter of micron order of carbon ball, carbon bag
Coating thickness is 7-9nm, a diameter of 30-80nm of magnesium iron oxide particle, and the mass ratio of carbon coating layer and carbon ball is 1: 8-10.
2. the method for preparing composite as claimed in claim 1, it is characterised in that：Source of iron, magnesium powder, liquid carbon source are mixed,
It is transferred in closed reaction vessel, is sealed and placed in crucible furnace, 8-12h is reacted at 550-650 DEG C, so as to obtains compound product
Thing.
3. method as claimed in claim 2, it is characterised in that：Source of iron is ferric iron source；It is preferred that ferric nitrate, iron chloride are at least
It is a kind of.
4. method as claimed in claim 2, it is characterised in that：Liquid carbon source is alcohols and ethers；It is preferred that absolute ethyl alcohol, second two
At least one of alcohol acetone, ether.
5. method as claimed in claim 2, it is characterised in that：The mol ratio of iron and magnesium is 2-2.5: 1-1.5.
6. method as claimed in claim 2, it is characterised in that：The volume of liquid carbon source and the molal quantity ratio of magnesium are 0.1-
0.5mol/L。
7. method as claimed in claim 2, it is characterised in that：Source of iron, magnesium powder, liquid carbon source mixing condition are ultrasonic at room temperature
Mixing 30min.
8. method as claimed in claim 2, it is characterised in that：Heating rate in crucible furnace is 6-8 DEG C/min.
9. method as claimed in claim 2, it is characterised in that：After combination product is washed through the mixed solution of water and alcohol, 60-80
4-10h is dried at DEG C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN201710045078.9A CN106848277B (en) | 2017-01-22 | 2017-01-22 | Magnesium-iron-oxygen/carbon composite material and preparation method thereof |
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| CN108091838A (en) * | 2017-11-24 | 2018-05-29 | 西安交通大学 | One step prepares nuclear shell structured nano α-Fe2O3The method of@C composites |
| CN111468117A (en) * | 2019-01-23 | 2020-07-31 | 中国石油化工股份有限公司 | Carbon-coated transition metal nanocomposite containing alkaline earth metal and preparation method and application thereof |
| CN113506865A (en) * | 2021-06-28 | 2021-10-15 | 山东玉皇新能源科技有限公司 | Battery negative electrode material and preparation method thereof |
| CN113506866A (en) * | 2021-06-28 | 2021-10-15 | 山东玉皇新能源科技有限公司 | Carbon-coated Fe2O3Hard carbon composite material and preparation method thereof |
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| CN108091838B (en) * | 2017-11-24 | 2020-06-26 | 西安交通大学 | Method for preparing core-shell structure nano α -Fe2O3@ C composite material in one step |
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| CN113506866A (en) * | 2021-06-28 | 2021-10-15 | 山东玉皇新能源科技有限公司 | Carbon-coated Fe2O3Hard carbon composite material and preparation method thereof |
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