CN107946590A - A kind of pomegranate type structure di-iron trioxide and preparation method thereof and the application as lithium-ion negative pole active material - Google Patents
A kind of pomegranate type structure di-iron trioxide and preparation method thereof and the application as lithium-ion negative pole active material Download PDFInfo
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- CN107946590A CN107946590A CN201711095375.0A CN201711095375A CN107946590A CN 107946590 A CN107946590 A CN 107946590A CN 201711095375 A CN201711095375 A CN 201711095375A CN 107946590 A CN107946590 A CN 107946590A
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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
- H01M4/523—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron for non-aqueous cells
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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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- 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
Application the invention discloses a kind of pomegranate type structure di-iron trioxide and preparation method thereof and as lithium-ion negative pole active material, pomegranate type structure di-iron trioxide is made of micron order di-iron trioxide shell parcel nanoscale di-iron trioxide bead, its preparation process is to be thermally decomposed bodied ferric sulfate, up to pomegranate type structure di-iron trioxide, the preparation method is simple, efficient, low cost, the pomegranate type structure di-iron trioxide of preparation shows excellent capacity, multiplying power and cycle performance as lithium ion battery negative material.
Description
Technical field
The present invention relates to a kind of di-iron trioxide material, and more particularly to one kind is directly pyrolyzed preparation by bodied ferric sulfate has
The method of the di-iron trioxide of special pomegranate type structure, and its as negative active core-shell material high power capacity, high rate capability lithium from
Application in sub- battery；Belong to lithium ion battery material technical field.
Background technology
In recent years, diversified portable electric appts are higher and higher to battery request, and lithium ion battery relies on its work
Make that voltage is high, specific capacity is big, have extended cycle life, self discharge is few, operation interval scope is wide, memory-less effect and non-environmental-pollution etc.
Advantage is used widely.Di-iron trioxide is as a kind of new lithium ion battery negative material, in theory with Fabrication of High Specific Capacitance
Measure (1005mAhg-1), far above commercial graphite cathode material (372mAhg-1), while it is with suitable operating voltage, thus
It is considered as one of most potential high-capacity cathode material.
In the prior art, synthesize di-iron trioxide method generally use ferrous ion or ferric ion as iron
Source, a nanometer di-iron trioxide, but three oxidations two prepared by these methods are synthesized by hydrolysis or using the method for template reagent
Iron as lithium ion battery negative material also there are some urgent problems to be solved, such as：In the charge and discharge process of lithium ion battery
In, di-iron trioxide and lithium ion combine the iron lithium compound generated and can cause negative material volumetric expansion, destroy electrode structure,
The reversibility of negative material is set to be deteriorated, cycle performance declines, and battery capacity decay is violent, which seriously limits three oxidations
Scale application of two iron as lithium ion battery negative material.Chinese patent (Publication No. CN106025263A) discloses one
Kind ferric oxide nano-material and preparation method thereof, negative electrode of lithium ion battery and lithium ion battery, by di-iron trioxide nanometer
Piece is assembled into nanotube, improves the chemical property of di-iron trioxide material to a certain extent, but di-iron trioxide material
Without referring to, overall chemical property needs to be further improved high rate performance.
Di-iron trioxide material of the prior art, existing research report are mostly focused on nano-scale di-iron trioxide
Negative material, although nanometer size effect can make ferric oxide particle, the volumetric expansion in battery charging and discharging cyclic process has
Largely alleviate, but be easy to reunite from the angle of industrialization practical application, the di-iron trioxide of nano-scale, processing performance
Difference, it is difficult to mass produce, and big there are specific surface area, the problem such as cause coulombic efficiency low that side reaction is more.Chinese patent
(Publication No. CN 106129377A) discloses a kind of preparation method of sesquioxide/graphene composite material, three oxidations two
Iron is supported in three-dimensional grapheme surface and pore passage structure, and battery capacity is carried when being applied to negative electrode of lithium ion battery
Height, but its preparation method is cumbersome, is not easy to carry out industrial operation.
The content of the invention
There are volumetric expansion during being used for existing di-iron trioxide material as lithium ion battery negative material to lead
The problem of cause cyclical stability is poor, poorly conductive, the purpose of the present invention, which aims to provide one kind, has special pomegranate type structure, and has
There is the di-iron trioxide of micro-nano size, which is not easy to reunite, and processing performance is more preferable, and is used as ion cathode material lithium
The volume change of di-iron trioxide negative material in charge and discharge process can effectively be alleviated during use, improve leading for negative material
Electrically.
Second object of the present invention is to provide the preparation pomegranate type that a kind of flow is short, operation is simple, efficient, inexpensive
The method of structure di-iron trioxide material, this method are conducive to mass produce.
Third object of the present invention is in providing the application of the di-iron trioxide material in lithium ion battery, by it
Negative electrode of lithium ion battery is prepared as negative active core-shell material, capacity, multiplying power and the cycle performance of battery can be significantly improved.
To realize above-mentioned technical purpose, the present invention provides a kind of pomegranate type structure di-iron trioxide, by three oxygen of micron order
Change two iron shells parcel nanoscale di-iron trioxide bead to form.
The di-iron trioxide of the present invention has special pomegranate type structure, and pomegranate type structure refers to its X rays topographs pomegranate,
Including micron-size spherical appearance, peel off spherical shell layer and can see many nano level di-iron trioxide beads, this structure image
Ground is described as pomegranate type structure.This pomegranate type structure can alleviate di-iron trioxide negative active core-shell material body in charge and discharge process
The adverse effect that product expansion is brought, helps further to improve the chemical property of negative material.
Preferable scheme, the size of the micron order di-iron trioxide shell is 50~150 μm；The nanoscale three aoxidizes
The size of two iron beads is 50~300nm.Pomegranate type structure di-iron trioxide with micro-nano size is received with most of reports
Rice di-iron trioxide or nanometer di-iron trioxide carbon composite are compared, and the di-iron trioxide of micro-nano size is not easy to reunite, and has
More preferably processing performance, as cell negative electrode material in use, the specific surface area of micro-nano di-iron trioxide is often below nanometer three
Two iron materials are aoxidized, electrode side reaction is less, and coulombic efficiency is higher.
Preferable scheme, the micron order di-iron trioxide shell are formed by nanoscale ferric oxide particle is intensive.
More preferably scheme, the nanoscale ferric oxide particle particle diameter are 50~300nm.
Present invention also offers a kind of preparation method of pomegranate type structure di-iron trioxide, this method is by bodied ferric sulfate
Thermally decomposed, up to pomegranate type structure di-iron trioxide.
Technical scheme brings it about the reaction of a series of complex, such as by being heated to bodied ferric sulfate
Condensation dehydration, make sulfate ion by reactions such as thermal decomposition volatilizations, the final special pomegranate type structure that has for obtaining high-purity
Di-iron trioxide material.This method step is simple, only needs step high temperature thermal decomposition reaction to realize that raw material is simple, is cheap city
Sell bodied ferric sulfate.
Preferable scheme, bodied ferric sulfate is placed in air atmosphere, is warming up to the heating rate of 5~15 DEG C/min
650~850 DEG C, keep the temperature 2~4h.Temperature is less than 650 DEG C, and there are part polyiron sulfate to decompose not exclusively, and temperature is excessive, is higher than
850 DEG C, then the pomegranate type structure generated is easily broken, it is difficult to obtains stable pomegranate type structure di-iron trioxide.
Present invention also offers a kind of application of pomegranate type structure di-iron trioxide, lives as negative electrode of lithium ion battery
Property materials application.
Preferable scheme, after pomegranate type structure di-iron trioxide, conductive carbon black and Kynoar solution mixed grinding,
Coated on copper foil, tabletting, is made lithium-ion negative pole.
The di-iron trioxide material of the present invention is adopted with conductive agent and binding agent etc. as lithium ion battery negative pole active materials
Negative electrode of lithium ion battery electrode is prepared with existing negative electrode of lithium ion battery electrode fabrication.Conductive agent, the binding agent of use
For existing conventional material, such as：Conductive black, Kynoar.It is dispersed in by binding agent of Kynoar in electrode slice, by institute
State micro-nano structure di-iron trioxide material to add to polyvinylidene fluoride aqueous solution, stir 0.5~1h at room temperature, add conductive charcoal
It is black to stir 0.5~1h at room temperature；Gained slurry is coated on copper foil, is obtained in 60 DEG C of vacuum drying chambers after dry 24h
The anode of di-iron trioxide material.
Technical scheme directly prepares di-iron trioxide using commercially available cheap bodied ferric sulfate as thermal decomposition
Raw material.And bodied ferric sulfate is used as flocculant under normal circumstances in the prior art, technical solution of the present invention is first
Used as the source of iron for preparing lithium ion battery anode active material, greatly promote its use value.
The technology of the present invention prepares the single table with micro-nano size by temperature control using bodied ferric sulfate as raw material
Face pattern is the di-iron trioxide (Fig. 3) of pomegranate type structure.
The bodied ferric sulfate used in technical scheme is to be bonded by multiple ferric iron cations by hydroxyl
The polymer of the nano-scale of formation.
The micro-nano size di-iron trioxide microsphere average grain diameter prepared in technical scheme is at 100 μm or so.
Compared with the prior art, the beneficial effect that technical scheme is brought is：
1st, the di-iron trioxide material prepared in technical scheme is with cheap and easy to get, structure-controllable polymerised sulphur
Sour iron is raw material, and the lower cost for material, easily realize industrialized production.
2nd, the di-iron trioxide material prepared in technical scheme is directly to be thermally decomposed by bodied ferric sulfate
It is made, without the use of organic formwork, preparation method is simple, efficient.
3rd, di-iron trioxide material of the invention is pomegranate type structure, which can buffer in charge and discharge cycles inside particle
Volumetric expansion, di-iron trioxide negative material is shown preferably chemical property, applied in lithium ion battery, have
The characteristics of capacity is high, high rate performance is excellent.
4th, di-iron trioxide material of the invention is micro-nano size, which has the group of being not easy
It is poly-, the good advantage of processing performance, and as cell negative electrode material in use, less with electrode side reaction, coulombic efficiency is higher
The features such as.
5th, di-iron trioxide material of the invention prepares lithium ion battery as negative active core-shell material, shows excellent electricity
Chemical property, as 0.1C current density under, first discharge specific capacity 887mAh g-1；Capacity is 887mAh g-1, with electric current
Density increases to 0.2,0.5C, and specific discharge capacity maintains 491,436mAh g respectively-1；Cycle performance is shown in the electric current of 0.1C
First discharge specific capacity is 887mAh g under density-1, 381mAh g are maintained after 30 circulations-1, capacity retention ratio 43%；30
340mAh g are maintained after secondary circulation-1, capacity retention ratio 38%, does not continue to decay；Show higher capacity, multiplying power and circulation
Performance preferably feature, has commercialized application prospect.
Brief description of the drawings
【Fig. 1】For polymerizable raw material ferric sulfate scanning of materials Electronic Speculum (SEM) figure；
【Fig. 2】For polymerizable raw material sulfuric acid iron material high magnification scanning electron microscope (SEM) figure；
【Fig. 3】For di-iron trioxide material X-ray diffraction (XRD) figure prepared by embodiment 1；
【Fig. 4】For di-iron trioxide scanning of materials Electronic Speculum (SEM) figure prepared by embodiment 1；
【Fig. 5】For di-iron trioxide material high magnification scanning electron microscope (SEM) figure prepared by embodiment 1；
【Fig. 6】For the di-iron trioxide material high rate performance figure prepared by embodiment 1；
【Fig. 7】For the di-iron trioxide material circulation performance map prepared by embodiment 1；
【Fig. 8】For di-iron trioxide scanning of materials Electronic Speculum (SEM) figure prepared by embodiment 2；
【Fig. 9】For di-iron trioxide material high magnification scanning electron microscope (SEM) figure prepared by embodiment 2；
【Figure 10】For di-iron trioxide scanning of materials Electronic Speculum (SEM) figure prepared by embodiment 3；
【Figure 11】For di-iron trioxide material high magnification scanning electron microscope (SEM) figure prepared by embodiment 3；
【Figure 12】For di-iron trioxide scanning of materials Electronic Speculum (SEM) figure prepared by comparative example 1；
【Figure 13】For di-iron trioxide material high magnification scanning electron microscope (SEM) figure prepared by comparative example 1；
【Figure 14】For the di-iron trioxide material high rate performance figure prepared by comparative example 1；
【Figure 15】For the di-iron trioxide material circulation performance map prepared by comparative example 1；
【Figure 16】For the di-iron trioxide material high rate performance figure prepared by comparative example 2；
【Figure 17】For the di-iron trioxide material circulation performance map prepared by comparative example 2.
Embodiment
In order to make the technical means, the creative features, the aims and the efficiencies achieved by the present invention easy to understand, tie below
Specific embodiment is closed, content that the present invention is further explained, mainly explanation temperature prepares three oxygen to embodiment 1~3 to bodied ferric sulfate
Change the influence of two iron, and its typical micro-nano size pomegranate type structure is characterized.Comparative example 1 and 2 is using template
Di-iron trioxide is prepared using other iron presomas, the chemical property of obtained di-iron trioxide material is poor.
Embodiment 1
1. taking 4.005g bodied ferric sulfates to be put into heat safe porcelain boat, porcelain boat is put into Muffle furnace.
2. Muffle furnace programming rate is arranged to 10 DEG C/min, the heating-up time is arranged to 80min, and soaking time is arranged to
220min, can obtain di-iron trioxide 1.388g.
3. taking 70mg di-iron trioxides that 0.5-1h is stirred at room temperature after mixing with 20mg conductive black powder mulls, then add
Enter 10mg Kynoar 0.5-1h is stirred at room temperature to obtain cathode size, be coated on prepared cathode size using film applicator
On copper foil, in 60 DEG C of vacuum drying chambers after dry 24h, section obtains di-iron trioxide anode.
4. will 3. it be matched with lithium metal gained di-iron trioxide anode, with 1mol L-1LiPF6EC/DMC (volume ratios 1:
1) solution is electrolyte, and assembling CR2016 lithium ions button battery carries out multiplying power, cycle performance test.
Embodiment 2
1. taking 4.007g bodied ferric sulfates to be put into heat safe porcelain boat, porcelain boat is put into Muffle furnace.
2. Muffle furnace programming rate is arranged to 10 DEG C/min, the heating-up time is arranged to 60min, and soaking time is arranged to
220min, can obtain di-iron trioxide 2.359g.
3. taking 70mg di-iron trioxides that 0.5-1h is stirred at room temperature after mixing with 20mg conductive black powder mulls, then add
Enter 10mg Kynoar 0.5-1h is stirred at room temperature to obtain cathode size, be coated on prepared cathode size using film applicator
On copper foil, in 60 DEG C of vacuum drying chambers after dry 24h, section obtains di-iron trioxide anode.
Embodiment 3
1. taking 4.003g bodied ferric sulfates to be put into heat safe porcelain boat, porcelain boat is put into Muffle furnace.
2. Muffle furnace programming rate is arranged to 10 DEG C/min, the heating-up time is arranged to 90min, and soaking time is arranged to
220min, can obtain di-iron trioxide 1.438g.
3. taking 70mg di-iron trioxides that 0.5-1h is stirred at room temperature after mixing with 20mg conductive black powder mulls, then add
Enter 10mg Kynoar 0.5-1h is stirred at room temperature to obtain cathode size, be coated on prepared cathode size using film applicator
On copper foil, in 60 DEG C of vacuum drying chambers after dry 24h, section obtains di-iron trioxide anode.
In order to verify the present invention more preferably scheme raw material selection bodied ferric sulfate and be without the use of template in experimentation
Advantage, carried out the reality of similarity condition using template using other two kinds common iron presoma ironic citrates and ferrite
Test, see comparative example 1 and 2.
Comparative example 1 (ironic citrate prepares di-iron trioxide)
1. 1.5g polyvinylpyrrolidones and 0.06g potassium persulfates is taken to add into double-neck flask.The bottleneck of center
Condenser pipe is inserted into, connecing sebific duct at the top of condenser pipe leads to N2, the mouth insertion separatory funnel of bottle side, separatory funnel top rubber stopper is close
Envelope.Vacuumized from conduit and lead to N2It is repeated several times.
2. 50mL distilled water and 10mL styrene are injected from separatory funnel mouth with syringe.
3. reaction bulb is transferred on magnetic stirring apparatus, 70 DEG C of oil bath temperature is set, stirs 24h.
4. solution, white particle made from taking-up are evaporated at 110rpm, 60 DEG C with revolving instrument.
5. taking the bodied ferric sulfate mixing of the trisodium citrate and 4.0g of 0.01mol to be dissolved in 40mL distilled water, 24h is stood.
6. will 4. in obtained white particle add in 5. solution, remove unnecessary solution after infiltrating 24h at room temperature.
7. will 6. in obtained solid be dried at room temperature for 24h.
8. will 7. in obtained solid be put into Muffle furnace, set 5 DEG C/min of heating rate, keep the temperature 5h when rising to 500 DEG C.
9. take 8. obtained 70mg di-iron trioxides be stirred at room temperature after mixing with 20mg conductive blacks powder mull
0.5-1h, adds 10mg Kynoar 0.5-1h is stirred at room temperature and obtain cathode size, using film applicator by prepared anode
Slurry is coated on copper foil, and in 66 DEG C of vacuum drying chambers after dry 24h, section obtains di-iron trioxide anode.
10. will 9. it be matched with lithium metal gained di-iron trioxide anode, with 1mol L-1LiPF6EC/DMC (volume ratios 1:
1) solution is electrolyte, and assembling CR2016 lithium ions button battery carries out multiplying power, cycle performance test.
Comparative example 2 (ferrite prepares di-iron trioxide)
1. 1.5g polyvinylpyrrolidones and 0.06g potassium persulfates is taken to add into double-neck flask.The bottleneck of center
Condenser pipe is inserted into, connecing sebific duct at the top of condenser pipe leads to N2, the mouth insertion separatory funnel of bottle side, separatory funnel top rubber stopper is close
Envelope.Vacuumized from conduit and lead to N2It is repeated several times.
2. 50mL distilled water and 10mL styrene are injected from separatory funnel mouth with syringe.
3. reaction bulb is transferred on magnetic stirring apparatus, 70 DEG C of oil bath temperature is set, stirs 24h.
4. solution, white particle made from taking-up are evaporated at 110rpm, 60 DEG C with revolving instrument.
5. 30mol ethylene glycol solutions and 20mol methanol solutions is taken to add into reaction bulb.
6. taking 4g bodied ferric sulfates to add in 5. solution, more colloid substances are removed after standing 24h.
7. will 4. in obtained white particle add in 6. solution, remove unnecessary solution after infiltrating 24h at room temperature.
8. will 7. in obtained solid be put into chamber type electric resistance furnace, 500 DEG C of the in-furnace temperature of resistance furnace, heating-up time are set
100min, soaking time 5h.
9. take 8. obtained 70mg di-iron trioxides be stirred at room temperature after mixing with 20mg conductive blacks powder mull
0.5-1h, adds 10mg Kynoar 0.5-1h is stirred at room temperature and obtain cathode size, using film applicator by prepared anode
Slurry is coated on copper foil, and in 66 DEG C of vacuum drying chambers after dry 24h, section obtains di-iron trioxide anode.
10. will 9. it be matched with lithium metal gained di-iron trioxide anode, with 1mol L-1LiPF6EC/DMC (volume ratios 1:
1) solution is electrolyte, and assembling CR2016 lithium ions button battery carries out multiplying power, cycle performance test.
Fig. 1 is the scanning electron microscope (SEM) photograph of polymerizable raw material sulfuric acid iron material, and it is micrometre hollow sphere shell to show polyaluminum sulfate iron material
Structure, Average Particle Diameters are about 100 μm.
Fig. 2 is polymerizable raw material sulfuric acid iron material high magnification scanning electron microscope (SEM) photograph, and the spherical shell for showing polyaluminum sulfate iron material is cause
Close structure.
Fig. 3 is the X-ray diffractogram of 1 gained di-iron trioxide material of embodiment, 2 θ=24.06 in XRD diffraction datas,
33.08,35.52,40.76,49.36,53.98,57.50,62.34,63.88 correspond to Fe respectively2O3(012), (104),
(110), the crystal faces such as (113), (024), (116), (018), (214), (300).With<01-089-0507>Hematite-Fe2O3
Collection of illustrative plates meets, and impurity peaks are almost invisible, that is, what is obtained is the di-iron trioxide of high-purity.
Fig. 4 is the scanning electron microscope (SEM) photograph of 1 gained di-iron trioxide material of embodiment, and it is micro-nano ruler to show di-iron trioxide material
Very little, its spherical structure and size are roughly the same with bodied ferric sulfate.
Fig. 5 is the high magnification scanning electron microscope (SEM) photograph of 1 gained di-iron trioxide material of embodiment, is shown in di-iron trioxide material
The spherical shell of broken microballoon is made of the densely arranged nano particle of multilayer, these nano particle sizes are about 200nm, in spherical shell
A nanometer di-iron trioxide bead is contained, particle diameter is about 150nm.
Fig. 6,7 for embodiment 1 battery performance test as a result, by bodied ferric sulfate prepare di-iron trioxide material have
Outstanding chemical property, high rate performance show that first discharge specific capacity is 887mAh g under the current density of 0.1C-1, with
Current density increases to 0.2,0.5C, and specific discharge capacity maintains 491,436mAh g respectively-1；Cycle performance is shown in 0.1C
Current density under first discharge specific capacity be 887mAh g-1, 381mAh g are maintained after 30 circulations-1, capacity retention ratio
43%；340mAh g are maintained after 30 circulations-1, capacity retention ratio 38%, does not continue to decay.
Fig. 8 and Figure 10 is respectively embodiment 2, the scanning electron microscope (SEM) photograph of 3 gained di-iron trioxide materials, shows di-iron trioxide
Material is also micro-nano size, but 2 decomposition temperature of embodiment is relatively low there are undecomposed bodied ferric sulfate hollow ball shell, and is implemented
Decomposed in example 3 generation di-iron trioxide microballoon crush it is more serious.
Fig. 9 and Figure 11 is respectively embodiment 2, the high magnification scanning electron microscope (SEM) photograph of 3 gained di-iron trioxide materials, shows three oxygen
To change in the microballoon that two iron materials crush, spherical shell is also to be made of the densely arranged nanometer bead of multilayer, but under different experimental conditions,
The generating state of nanometer bead is different, and nanometer bead generation particle is smaller in embodiment 2, nanometer bead generation in embodiment 3
Grain is larger.
Figure 12 is the di-iron trioxide scanning of materials electron microscope prepared by comparative example 1, shows to be prepared by ironic citrate
Di-iron trioxide material surface it is coarse, resulting materials Particle Breakage is serious, it is difficult to obtains prepared by technical solution of the present invention
Micro-nano size di-iron trioxide material.
Figure 13 is the di-iron trioxide material high magnification scanning electron microscope (SEM) photograph prepared by comparative example 1, it can be seen that is not adopted
Di-iron trioxide mainly exists in the form of irregular aggregate prepared by technical solution of the present invention, its grain diameter size
About 200nm.
Figure 14,15,16,17 are respectively the di-iron trioxide that the gained of comparative example 1,2 is prepared by ironic citrate, ferrite
Although the battery performance test of material is results, it can be seen that the di-iron trioxide material and sheet that are prepared by ironic citrate, ferrite
Di-iron trioxide material prepared by invention has similar micron-scale structure, but the di-iron trioxide material prepared by ironic citrate
Material, increase current density cause charging and discharging capacity very big influence, and the specific capacity of 0.2C only has the 67% of 0.1C, shows
The high rate performance of the di-iron trioxide material prepared by ironic citrate is general；The di-iron trioxide material prepared by ferrite, its
It is 304mAh g to circulate specific capacity first-1, well below expected specific capacity, and after cycling special capacity fade also quickly,
Show that the cycle performance of the di-iron trioxide material by ferrite preparation is general.
The pomegranate type structure di-iron trioxide that the present invention is prepared micro-nano size by bodied ferric sulfate has been shown and described above
The main method feature and advantage of material.It should be understood by those skilled in the art that the present invention is not limited to the above embodiments,
The above embodiments and description only illustrate the principle of the present invention and procedure, do not depart from spirit of the invention and
On the premise of scope, various changes and modifications of the present invention are possible, these changes and improvements both fall within claimed invention
In the range of.The scope of the present invention is defined by the appended claims and its equivalents.
Claims (8)
- A kind of 1. pomegranate type structure di-iron trioxide, it is characterised in that：Nanoscale three is wrapped up by micron order di-iron trioxide shell Aoxidize two iron beads composition.
- A kind of 2. pomegranate type structure di-iron trioxide according to claim 1, it is characterised in that：The micron order three aoxidizes The size of two iron shells is 50~150 μm；The size of the nanoscale di-iron trioxide bead is 50~300nm.
- A kind of 3. pomegranate type structure di-iron trioxide according to claim 1 or 2, it is characterised in that：The micron order three Two iron shells are aoxidized to be formed by nanoscale ferric oxide particle is intensive.
- A kind of 4. pomegranate type structure di-iron trioxide according to claim 3, it is characterised in that：The nanoscale three aoxidizes Two iron particle particle diameters are 50~300nm.
- A kind of 5. preparation method of pomegranate type structure di-iron trioxide of Claims 1 to 4 any one of them, it is characterised in that： Bodied ferric sulfate is thermally decomposed, to obtain the final product.
- A kind of 6. preparation method of pomegranate type structure di-iron trioxide according to claim 5, it is characterised in that：Will polymerization Ferric sulfate is placed in air atmosphere, is warming up to 650~850 DEG C with the heating rate of 5~15 DEG C/min, is kept the temperature 2~4h.
- 7. according to the application of Claims 1 to 4 any one of them pomegranate type structure di-iron trioxide, it is characterised in that：As Lithium ion battery anode active material application.
- 8. the application of pomegranate type structure di-iron trioxide according to claim 7, it is characterised in that：By pomegranate type structure three After aoxidizing two iron, conductive carbon black and Kynoar solution mixed grinding, coated on copper foil, tabletting, obtained lithium ion is born Pole.
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| CN201711095375.0A CN107946590B (en) | 2017-11-09 | 2017-11-09 | Pomegranate-type structure ferric oxide, preparation method thereof and application of pomegranate-type structure ferric oxide as lithium ion negative electrode active material |
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| CN201711095375.0A CN107946590B (en) | 2017-11-09 | 2017-11-09 | Pomegranate-type structure ferric oxide, preparation method thereof and application of pomegranate-type structure ferric oxide as lithium ion negative electrode active material |
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| CN101453017A (en) * | 2008-12-12 | 2009-06-10 | 中国科学院化学研究所 | Lithium cell negative pole material and preparation thereof |
| CN102659188A (en) * | 2012-05-22 | 2012-09-12 | 中北大学 | Magnetic ferric oxide micrometer flower material with multi-stage structure and preparation method thereof |
| CN104003448A (en) * | 2014-05-20 | 2014-08-27 | 江苏大学 | [Alpha]-phase ferric oxide porous core-shell microspheres and controllable synthetic preparation method thereof |
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| CN101453017A (en) * | 2008-12-12 | 2009-06-10 | 中国科学院化学研究所 | Lithium cell negative pole material and preparation thereof |
| CN102659188A (en) * | 2012-05-22 | 2012-09-12 | 中北大学 | Magnetic ferric oxide micrometer flower material with multi-stage structure and preparation method thereof |
| CN104003448A (en) * | 2014-05-20 | 2014-08-27 | 江苏大学 | [Alpha]-phase ferric oxide porous core-shell microspheres and controllable synthetic preparation method thereof |
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