CN104617290B - Homogenous precipitation method for preparing Fe2O3 nanobelt and Fe2O3 nanobelt-carbon composite material - Google Patents
Homogenous precipitation method for preparing Fe2O3 nanobelt and Fe2O3 nanobelt-carbon composite material Download PDFInfo
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- H—ELECTRICITY
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- B—PERFORMING OPERATIONS; TRANSPORTING
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Abstract
A homogenous precipitation method for preparing a Fe2O3 nanobelt and a Fe2O3 nanobelt-carbon composite material comprises the following steps: reacting a complexing agent C2O4＜2-＞ with Fe＜3+＞ in a solution to generate a soluble [Fe(C2O4)3]＜3+＞ complex, reducing Fe (III) to Fe (II) by using a reducing agent, and reacting Fe (II) with C2O4＜2-＞ in the above solution to generate a FeC2O4 precipitate or to generate the FeC2O4 precipitate homogenously precipitated on a carbon material in order to obtain FeC2O4 or a FeC2O4/carbon composite material precursor; and carrying out calcining treatment at a certain temperature to prepare the Fe2O3 nanobelt or the Fe2O3 nanobelt/carbon composite material. The Fe2O3 nanobelt/carbon has excellent electrochemical performances as a lithium ion battery negative material. The carbon material can effectively buffer the volume change of Fe2O3 in the charge and discharge process to improve the cycle stability of the composite material, and also can form an effective conductive network in order to facilitate rapid transfer of electrons and improve the rate performance of the composite material. The above preparation method has the advantages of low device requirements, mild preparation conditions, simple process, short period, low cost, and suitableness for large scale production.
Description
Technical field
The invention belongs to new energy materialses and electrochemical field are and in particular to one kind prepares Fe2O3Nano belt and its with carbon
The homogeneous precipitation method of composite.
Background technology
Lithium ion battery has that running voltage is high, specific energy is big, memory-less effect, pollution-free, self-discharge rate is low and uses
The advantages of life-span length, be the best secondary cell system of current combination property.It is widely used to mobile phone, notebook computer, number
The portable consumer electronics such as code-phase machine field, and gradually extend to the field such as electric automobile and energy-storage battery.
Negative material is one of crucial composition of lithium ion battery, is the key determining lithium ion battery whole synthesis performance
Factor.In business-like lithium ion battery, negative material is mainly graphitic carbon material at present, and its theoretical specific capacity is 372mAh
g-1, can not meet the demand of height ratio capacity lithium ion battery of new generation, for this reason, the new negative pole of research and development height ratio capacity
Material becomes one of focus of Study on Li-ion batteries.In the research of height ratio capacity novel anode material, silica-base material, tinbase
Material, transition metal oxide（As Fe2O3、Fe3O4、NiO、Co3O4）Deng the very big concern all receiving people.Wherein, Fe2O3
Because having height ratio capacity（Theoretical capacity is 1007mAh g-1）, low cost, environmental friendliness and seen the advantages of abundant raw materials
Doing is a kind of very promising lithium ion battery negative material.However, Fe2O3It is accompanied by larger volume during Li insertion extraction
Change, material is incidental to reunite and efflorescence, leads to capacity rapid decaying cycle stability poor；Fe simultaneously2O3It is quasiconductor,
Electric conductivity is poor, leads to its high rate performance also not ideal.Therefore, how to improve Fe2O3The cyclical stability of negative material and carrying
High rate capability becomes premise and key for realizing its practical application.For solving the above problems, researcher is to Fe2O3Carry out
Substantial amounts of modified work.Modified measures numerous at present can be divided into design preparation to have the Fe of nanostructured2O3With structure Fe2O3
Composite two big class.Design preparation has the Fe of nanostructured2O3The transfer distance of electronics or ion can be reduced, improve electricity
Chemical reactivity, simultaneously nanostructured can effectively alleviate its bulk effect in charge and discharge process, and then improve it
Chemical property.Build Fe2O3Composite is another kind of conventional and effective method of modifying, by Fe2O3With good conductivity, body
The little activity of long-pending effect or inert matter are combined, and on the one hand these materials can effectively buffer Fe2O3In charge and discharge process
Change in volume, on the other hand can provide effective electronics to spread out of passage, thus effectively improving the chemical property of material.
Build Fe2O3- carbon composite is Fe2O3The Typical Representative of based composites.
Representative Fe in document and patent2O3Base negative material includes：
The microemulsion that Wang etc. is formed in water with glycerol steeps as template, is prepared for diameter using hydro-thermal method and is about 1 μm
Fe2O3Hollow ball, is used as showing good cyclical stability during negative material, with 200mA g-1Electric current density fill
Electric discharge, after 100 circulations, its reversible capacity may remain in 710mAh g-1Hence it is evident that better than solid Fe2O3Granule
（J.Am.Chem.Soc.,2011,133(43),17146-17148）.Liu etc. is prepared for diameter using hydro-thermal method and is about 60-
80nm Fe2O3Nanometer rods, under the multiplying power of 0.1C during discharge and recharge, its first discharge capacity be 1332mAh g-1, 30 circulations
Capacity is 763mAh g afterwards-1, far above commercialization micro-meter scale Fe2O3112mAh g-1.（Electrochimica
Acta,2009,54(6),1733-1736）.Gao etc. has synthesized, using microemulsion method, the Fe that width is about 20-40nm2O3Nano belt,
It is used as during lithium ion battery negative material, showing higher embedding, de- lithium activity, it is put first, charging capacity is respectively
1068 and 701mAh g-1, but cyclical stability is poor.（CrystEngComm,2011,13(20),6045-6049）.Yu etc. adopts
It is the CNTs that template is prepared for that internal diameter is about 55nm with the method for chemical vapor deposition using AAO, then using dipping-calcining
Method by Fe2O3It is filled in CNTs, after removing AAO template, be prepared for Fe2O3- CNTs composite.This composite with
35mA·g-1Electric current density charge and discharge cycles 40 times circulation after its reversible capacity be 768mAh g-1（Chem.Commun,
2010,46(45),8576-8578）.In patent CN102427129A, Pan Hongge etc. is with business-like Fe2O3Powder body and carbon materials
Material carries out ball-milling treatment and is prepared for ferrous oxide/carbon composite with reference to Technology for Heating Processing, and this material is used for lithium ion battery
There is during negative pole preferable cyclical stability, but specific capacity is relatively low.In patent CN103227324A, Zhao Hailei etc. adopts
Sol-gal process is prepared for the ferrum oxide presoma with aerogel structure, is prepared for iron oxides/carbon after further heat treatment
Composite, this material is used as there is higher initial reversible capacity during negative pole, but cyclical stability is undesirable.
In sum, in document and patent report for iron oxide material as lithium ion battery negative material research,
How oxidation iron-based negative material is prepared using template, hydro-thermal method, microemulsion method and sol-gel process.These method majority works
Skill process is complex, high cost, and homogeneity of product is poor.
The present invention is reduced to ferrous ion with ferric ion in simple reduction reaction modulation solution first, promotes all
Even precipitation occurs, and generates Ferrox. precipitation or makes Ferrox. precipitate uniform deposition on carbonaceous material, prepares grass
Acid ferrous iron or Ferrox ./carbon composite；Fe is obtained after uniform temperature calcination processing again2O3Nano belt or Fe2O3Nanometer
Band/carbon composite.The method technical process is simple, and preparation condition is gentle, low cost, reproducible and be easy to scale metaplasia
Produce.The material of synthesis has good microcosmic composite construction, uses it for showing during lithium ion battery negative material excellent
Chemical property.
Content of the invention
The purpose of the present invention is for current Fe2O3Negative material cycle performance difference and the shortcoming of high rate performance difference, there is provided
One kind prepares Fe2O3Nano belt and its homogeneous precipitation method with the composite of carbon.
The invention provides one kind prepares Fe2O3Nano belt and its homogeneous precipitation method with the composite of carbon, using network
Mixture C2O4 2-With the Fe in solution3+Reaction generates solvable [Fe (C2O4)3]3+Complex, recycles reducing agent reduction Fe（III）
For Fe（II）, Fe（II）With the C in solution2O4 2-Reaction generates FeC2O4Precipitation or uniform deposition FeC on the carbonaceous material2O4
Precipitation, obtains FeC2O4Or FeC2O4/ carbon composite presoma；Fe is obtained after uniform temperature calcination processing again2O3Nanometer
Band or Fe2O3Nano belt/carbon composite；Comprise the following steps that：
1）Dispersion carbonaceous material：Weigh required quality carbonaceous material and be dispersed in formation suspension in solvent；
Wherein, the dispersing mode of carbonaceous material is one of ultrasonic disperse, dispersed with stirring or two kinds；
2）Prepare reaction solution：Trivalent inorganic iron salt and chelating agent are dissolved in solvent, or are dissolved in containing material with carbon element
Suspension in；Again reducing agent is added thereto, and continuous stirring reaction, it is precipitated product；
3）By step 2）The precipitated product centrifugation obtaining or filtration separation, washing, and be vacuum dried in 40～85 DEG C, obtain
FeC2O4Or FeC2O4/ carbon composite；
4）By step 3）The FeC obtaining2O4Or FeC2O4/ carbon composite is in protective atmosphere at 250～900 DEG C
Calcining 0.5～24h, prepared Fe2O3Nano belt or Fe2O3Nano belt/carbon composite.
The preparation Fe that the present invention provides2O3Nano belt and its homogeneous precipitation method with the composite of carbon, step 1）Middle institute
The carbonaceous material stated is CNT, carbon aerogels, mesoporous carbon, expanded graphite, Graphene, conductive carbon black, Cabot superconduct
One of carbon black BP2000, activated carbon or two or more；The electrical conductivity of carbonaceous material is more than or equal to 0.1S cm-1, compare table
Area is more than or equal to 50m2·g-1, pore volume is more than or equal to 0.2cm3·g-1.
The preparation Fe that the present invention provides2O3Nano belt and its homogeneous precipitation method with the composite of carbon, step 1）Middle institute
The ultrasonic disperse stated is that ultrasonic power is 25～1000W, when ultrasonic using ultrasonic washing unit or cell disruptor ultrasonic disperse
Between be 0.1～3h；Described dispersed with stirring is magnetic agitation or mechanical agitation, and the speed of stirring is 400～1000rmp, stirring
Time is 0.1～3h.
The preparation Fe that the present invention provides2O3Nano belt and its homogeneous precipitation method with the composite of carbon, step 1）And step
Rapid 2）Described in solvent be deionized water, methanol, ethanol, propanol, isopropanol, ethylene glycol one or more.
The preparation Fe that the present invention provides2O3Nano belt and its homogeneous precipitation method with the composite of carbon, step 2）Middle institute
The trivalent inorganic iron salt stated be ferric nitrate, iron chloride, iron sulfate one or more；Wherein, iron ion and carbonaceous material
Mol ratio be 1:1.5～100.
The preparation Fe that the present invention provides2O3Nano belt and its homogeneous precipitation method with the composite of carbon, step 2）Middle institute
The chelating agent stated be potassium oxalate, Disodium oxalate., lithium oxalate, ammonium oxalate, oxalic acid one or more；Wherein, trivalent inorganic ferrum
Iron ion in salt is 1 with the mol ratio of chelating agent oxalate ion:0.5～6.
The preparation Fe that the present invention provides2O3Nano belt and its homogeneous precipitation method with the composite of carbon, step 2）Middle institute
The reducing agent stated is one of sodium borohydride, potassium borohydride, hydrazine hydrate, sodium hypophosphite, ascorbic acid or two or more；Its
In, the iron ion in trivalent inorganic iron salt is 1 with the mol ratio of reducing agent:0.5～3.
The preparation Fe that the present invention provides2O3Nano belt and its homogeneous precipitation method with the composite of carbon, step 2）In plus
After entering reducing agent, mixing speed is 400～1000rmp, and reaction temperature is 0～90 DEG C, and the response time is 0.1～3h.
The preparation Fe that the present invention provides2O3Nano belt and its homogeneous precipitation method with the composite of carbon, step 4）In
Described calcining heat is 300～700 DEG C.
The preparation Fe that the present invention provides2O3Nano belt and its homogeneous precipitation method with the composite of carbon, step 4）Middle institute
The protective atmosphere stated be air, oxygen, argon, nitrogen one or more.
The preparation Fe that the present invention provides2O3Nano belt and its homogeneous precipitation method with the composite of carbon, described preparation
Fe2O3Nano belt and its with the composite of carbon in Fe2O3Mass fraction is 5%～98%, preferably 25%～90%.
The Fe of the method for the invention preparation2O3Nano belt and its composite with carbon are applied to lithium ion battery or non-
Negative material in the electrochemical energy storage device of symmetric form ultracapacitor.
The device have the advantages that being：
First, chelating agent C2O4 2-With the reactant Fe in solution3+There is complex reaction, when addition reducing agent in phase solution
When, Fe（III）It is reduced into Fe（II）, and rapid and surrounding C2O4 2-There is combination reaction, generate FeC2O4Precipitation.Due to
Fe2+Ion, from the internal output of solution, can be prevented effectively from the excessive phenomenon of local concentration, therefore, Fe2+In ion and solution
C2O4 2-Reaction equably generates FeC2O4Precipitation, or FeC2O4Precipitation uniform deposition on the carbonaceous material, synthesizes
FeC2O4/ carbon composite.Secondly, C2O4 2-Also act as the effect of directed agents, promote the generation of nano strip material.Institute of the present invention
The FeC of preparation2O4Or FeC2O4In/carbon composite, FeC2O4, all in nanobelt shape structure, has been obtained Fe after calcination processing2O3
Or Fe2O3/ carbon composite.In Fe2O3And Fe2O3Fe in/carbon composite2O3Maintain receiving of its presoma Ferrox.
Rice banded structure, and be uniformly distributed in material with carbon element on, define good composite construction.3rd, Fe2O3Nano belt/carbon is used as
During lithium ion battery negative material, show excellent chemical property.On the one hand, with micron-sized commodity Fe2O3Compare,
Fe2O3Nano belt has higher electro-chemical activity and has excellent structural stability；On the other hand, in the composite, carbon
Material can effectively buffer Fe2O3Change in volume in charge and discharge process, improves the electric conductivity of material simultaneously, thus entering
One step improves cycle performance and the high rate performance of material.Finally, production equipment needed for the preparation method of the present invention is simple, preparation
Mild condition, process is simple, cycle is short, low cost, suitable large-scale production.
Brief description
The Fe that Fig. 1 obtains for embodiment 22O3Nano belt/carbon X-ray diffractogram；
The Fe that Fig. 2 obtains for embodiment 32O3The TEM figure of nano belt/carbon；
The Fe that Fig. 3 obtains for embodiment 42O3The charging and discharging curve of nano belt/carbon；
The Fe that Fig. 4 obtains for embodiment 62O3The cycle performance curve of nano belt/carbon；
The Fe that Fig. 5 obtains for embodiment 82O3The high rate performance curve of nano belt/carbon.
Specific embodiment
The following examples will be further described to the present invention, but not thereby limiting the invention.
Embodiment 1
First, take 0.5g FeCl respectively3·6H2O and 0.134g Disodium oxalate. is dissolved in 200mL deionized water successively.Take
0.20g ascorbic acid is dissolved in about 5mL deionized water, and then aqueous ascorbic acid is dropwise added drop-wise to stirring above-mentioned
In solution, after completion of dropping, continue stirring reaction about 3h.Product is washed three times using deionized water, then puts by centrifugation
It is dried in 85 DEG C of vacuum drying ovens and yellow product is obtained.Obtained yellow product is placed in porcelain boat, 700 in air atmosphere
DEG C heat treatment 3h, is obtained final product Fe2O3Nano belt.
Embodiment 2
First, take 25.0mg CNT（CNTs）, add it in 200mL deionized water, ultrasonic agitation 3h.So
Afterwards, take 6.06g Fe (NO respectively3)3·9H2O and 6.6g ammonium oxalate is added sequentially in the dispersion liquid of above-mentioned CNTs, and stirring makes
Its dissolving.Take 3.52g sodium hypophosphite to be dissolved in about 10mL deionized water, then ortho phosphorous acid sodium water solution is dropwise added drop-wise to
Fe (the NO stirring3)3, oxalic acid ammonia and CNTs mixed liquor in, continue stirring reaction about 0.5h after completion of dropping.Centrifugation point
From, using ethanol by product wash three times, be subsequently placed in 85 DEG C of vacuum drying ovens be dried be obtained black product.Will be obtained black
Color product is placed in porcelain boat, 250 DEG C of heat treatment 3h in air atmosphere, and final product Fe is obtained2O3- CNTs composite.
Fig. 1 is the Fe preparing2O3The XRD figure of/carbon, from the figure, it can be seen that sample is in the diffraction maximum pair of 2 θ=26.2 °
Should be in CNTs in crystal face（002）Diffraction maximum, and occur in that and significantly correspond to α-Fe2O3The diffraction maximum of phase, explanation prepares
Sample be Fe2O3With CNTs composite.
Embodiment 3
First, take 100mg CNTs, add it in 200mL deionized water, and utilize ultrasonic wave added dispersed with stirring
0.5h.Then, take 0.5g FeCl respectively3·6H2O and 0.134g Disodium oxalate. is added sequentially in the dispersion liquid of above-mentioned CNTs, stirs
Mix and so that it is dissolved.Take 0.20g ascorbic acid to be dissolved in about 5mL deionized water, then aqueous ascorbic acid is dropwise added drop-wise to
The FeCl stirring3, Disodium oxalate. and CNTs mixed liquor in, continue stirring reaction about 3h after completion of dropping.Centrifugation, profit
With ethanol, product is washed three times, be subsequently placed in 85 DEG C of vacuum drying ovens and prepared black product is dried.Obtained black is produced
Thing is placed in porcelain boat, 300 DEG C of heat treatment 0.5h in air atmosphere, after under argon or nitrogen atmosphere in 700 DEG C of heat treatment 3h,
Final product Fe is obtained2O3- CNTs composite.
Fig. 2 is the Fe preparing2O3The TEM figure of nano belt/carbon, from the figure, it can be seen that Fe2O3Become nano strip knot
Structure, and be laid on CNTs, define good microcosmic composite construction.
Embodiment 4
First, take 75mg Graphene（GO）, add it in 200mL deionized water and ethanol mixing, and using ultrasonic
Auxiliary dispersed with stirring 2h.Then, take 0.80g Fe respectively2(SO4)3·9H2O and 0.70g oxalic acid is added sequentially to dividing of above-mentioned GO
In dispersion liquid, stirring makes it dissolve.Take 0.20g sodium borohydride to be dissolved in about 5mL deionized water, then by sodium borohydride aqueous solution by
It is added drop-wise to the Fe stirring2(SO4)3, oxalic acid and GO mixed liquor in, continue stirring reaction about 1h after completion of dropping.Centrifugation
Separate, using ethanol, product is washed three times, be subsequently placed in 60 DEG C of vacuum drying ovens and prepared black product is dried.Will be obtained
Black product is placed in porcelain boat, 300 DEG C of heat treatment 1h in air atmosphere, and final product Fe is obtained2O3- GO composite.
Fe by preparation2O3/ GO composite is used as lithium ion battery negative material, with acetylene black, PVDF according to mass ratio
80:10:10 ratio is mixed to get slurry.Slurry is coated uniformly on Copper Foil and obtains working electrode, be to electrode with lithium piece,
Celgard2325 polypropylene screen is barrier film, 1MLiPF6/EC+DMC(EC:DMC=1:1) it is electrolyte, in the glove full of argon
It is assembled into button cell in case.
Above-mentioned battery is carried out charge-discharge test on Land discharge and recharge instrument.Charging/discharging voltage scope 0.005～3.0V.With
100mA·g-1Constant current charge-discharge, it first can inverse put, charge specific capacity respectively 1347.8 and 1033.9mAh g-1.Fig. 3 is
Prepared Fe2O3The charging and discharging curve figure circulating twice before-GO composite.
Embodiment 5
First, take 200mg mesoporous carbon, add it in 200mL deionized water and alcohol mixeding liquid, and using ultrasonic auxiliary
Help dispersed with stirring 1h.Then, take 52.5mg Fe (NO respectively3)3·9H2O and 55mg oxalic acid is added sequentially to above-mentioned mesoporous carbon
In dispersion liquid, stirring makes it dissolve.0.30mL hydrazine hydrate solution is taken dropwise to be added drop-wise to the Fe (NO stirring3)3, oxalic acid and Jie
In the mixed liquor of hole carbon, after completion of dropping, continue stirring reaction about 1h.Centrifugation, using ethanol by product wash three times, so
After be placed in 85 DEG C of vacuum drying ovens be dried be obtained black product.Obtained black product is placed in porcelain boat, in air atmosphere
In 300 DEG C of heat treatment 1h, final product Fe is obtained2O3- mesoporous carbon composite material.
Embodiment 6
First, take 50mg carbon aerogels, add it in 200mL deionized water, and utilize ultrasonic wave added dispersed with stirring
3h.Then, take 0.60g Fe (NO respectively3)3·9H2O and 0.70g potassium oxalate is added sequentially to the dispersion liquid of above-mentioned carbon aerogels
In, stirring makes it dissolve.Take 0.40g ascorbic acid to be dissolved in about 5mL deionized water, then aqueous ascorbic acid is dropwise dripped
It is added to the Fe (NO stirring3)3, oxalic acid and carbon aerogels mixed liquor in, continue stirring reaction about 3h after completion of dropping.From
The heart separates, and is washed product three times using ethanol, is subsequently placed in 85 DEG C of vacuum drying ovens and prepared black product is dried.Will be obtained
Black product be placed in porcelain boat, in 250 heat treatment 3h in air atmosphere, after be placed in 500 DEG C of heat treatment 1h, be obtained final
Product Fe2O3- carbon aerogel composite material.
Fe by preparation2O3/ carbon aerogels material is used as lithium ion battery negative material, with acetylene black, PVDF according to quality
Ratio 80:10:10 ratio is mixed to get slurry.Slurry is coated uniformly on Copper Foil and obtains working electrode, be to electricity with lithium piece
Pole, Celgard2325 polypropylene screen is barrier film, 1MLiPF6/EC+DMC(EC:DMC=1:1) it is electrolyte, full of argon
It is assembled into button cell in glove box.
Above-mentioned battery is carried out charge-discharge test on Land discharge and recharge instrument.Charging/discharging voltage scope 0.005～3.0V, electricity
Current density is 100mA g-1.Fig. 4 is prepared Fe2O3The cycle performance curve chart of-carbon aerogel composite material.
Embodiment 7
First, take 100mg commercialization BP2000, add it in 200mL ethanol, and utilize ultrasonic wave added dispersed with stirring
3h.Then, take 0.60g FeCl respectively3·9H2O and 0.70g oxalic acid is added sequentially in the dispersion liquid of above-mentioned BP2000, stirring
So that it is dissolved.0.4mL hydrazine hydrate solution is taken dropwise to be added drop-wise to the FeCl stirring3, oxalic acid and BP2000 mixed liquor in, drip
Add and after finishing, continue stirring reaction about 3h.Product is washed three times using ethanol, is subsequently placed in 60 DEG C of vacuum drying ovens by centrifugation
Middle drying is obtained black product.Obtained black product is placed in porcelain boat, 400 DEG C of heat treatment 1h in air atmosphere, system
Obtain product Fe finally2O3- BP2000 composite.
Embodiment 8
First, take 100mg conductive carbon black, add it in 200mL deionized water and alcohol mixeding liquid, and using ultrasonic
Auxiliary dispersed with stirring 1h.Then, take 0.80g Fe (NO respectively3)3·9H2O and 0.90g oxalic acid is added sequentially to above-mentioned mesoporous carbon
Dispersion liquid in, stirring so that it is dissolved.Take 0.5g potassium borohydride to be dissolved in about 5mL deionized water, and it is just dropwise added drop-wise to
Fe (NO in stirring3)3, oxalic acid and mesoporous carbon mixed liquor in, continue stirring reaction about 1h after completion of dropping.Centrifugation, profit
With ethanol, product is washed three times, be subsequently placed in 85 DEG C of vacuum drying ovens and prepared black product is dried.Obtained black is produced
Thing is placed in porcelain boat, 300 DEG C of heat treatment 1h in air atmosphere, and final product Fe is obtained2O3- carbon composite.
Fe by preparation2O3/ conductive carbon black composite be used as lithium ion battery negative material, with acetylene black, PVDF according to
Mass ratio 80:10:10 ratio is mixed to get slurry.Slurry is coated uniformly on Copper Foil and obtains working electrode, with lithium piece be
To electrode, Celgard2325 polypropylene screen is barrier film, 1MLiPF6/EC+DMC(EC:DMC=1:1) it is electrolyte, full of argon
It is assembled into button cell in the glove box of gas.
Above-mentioned battery is carried out charge-discharge test on Land discharge and recharge instrument.Charging/discharging voltage scope 0.005～3.0V.Figure
5 is prepared Fe2O3The high rate performance curve chart of-mesoporous carbon composite material.
Claims (13)
1. one kind prepares Fe2O3Nano belt and its with the homogeneous precipitation method of the composite of carbon it is characterised in that：
Using chelating agent C2O4 2-With the Fe in solution3+Reaction generates [Fe (C2O4)3]3+Complex, recycles reducing agent reduction Fe
（III）For Fe（II）, Fe（II）With the C in solution2O4 2-Reaction generates FeC2O4Precipitate, or generation is uniformly deposited on carbonaceous material
FeC on material2O4Precipitation, obtains Ferrox. or Ferrox ./carbon composite；It is obtained after uniform temperature calcination processing again
Fe2O3Nano belt or Fe2O3Nano belt/carbon composite；Comprise the following steps that：
1）Dispersion carbonaceous material：Weigh required quality carbonaceous material and be dispersed in formation suspension in solvent；
Wherein, the dispersing mode of carbonaceous material is one of ultrasonic disperse, dispersed with stirring or two kinds；
2）Prepare reaction solution：Trivalent inorganic iron salt and chelating agent are dissolved in solvent, then reducing agent is added thereto, not
Disconnected stirring reaction, is precipitated product；
Or trivalent inorganic iron salt and chelating agent are dissolved in the suspension containing material with carbon element, then reducing agent are added thereto,
And continuous stirring reaction, it is precipitated product；
3）By step 2）The precipitated product centrifugation obtaining or filtration separation, washing, and be vacuum dried in 40～85 DEG C, obtain
FeC2O4Or FeC2O4/ carbon composite；
4）By step 3）The FeC obtaining2O4Or FeC2O4/ carbon composite is calcined in protective atmosphere at 250～900 DEG C
0.5～24h, prepared Fe2O3Nano belt or Fe2O3Nano belt/carbon composite.
2. according to preparation Fe described in claim 12O3Nano belt and its homogeneous precipitation method with the composite of carbon, its feature
It is：Step 1）Described in carbonaceous material be CNT, carbon aerogels, mesoporous carbon, expanded graphite, Graphene, conductive carbon
Black, one of Cabot Super-conductive carbon BP2000, activated carbon or two or more；
The electrical conductivity of carbonaceous material is more than or equal to 0.1S cm-1, specific surface area is more than or equal to 50m2·g-1, pore volume is more than
Or it is equal to 0.2cm3·g-1.
3. according to preparation Fe described in claim 12O3Nano belt and its homogeneous precipitation method with the composite of carbon, its feature
It is：Step 1）Described in ultrasonic disperse be using ultrasonic washing unit or cell disruptor ultrasonic disperse, ultrasonic power is
25～1000W, ultrasonic time is 0.1～3h；
Described dispersed with stirring is magnetic agitation or mechanical agitation, and the speed of stirring is 400～1000rmp, and mixing time is 0.1
～3h.
4. according to preparation Fe described in claim 12O3Nano belt and its homogeneous precipitation method with the composite of carbon, its feature
It is：Step 1）With step 2）Described in solvent be deionized water, methanol, ethanol, propanol, isopropanol, one kind of ethylene glycol
Or it is two or more.
5. according to preparation Fe described in claim 12O3Nano belt and its homogeneous precipitation method with the composite of carbon, its feature
It is：Step 2）Described in trivalent inorganic iron salt be ferric nitrate, iron chloride, iron sulfate one or more；
Wherein, iron ion and the mol ratio of carbonaceous material are 1:1.5～100.
6. according to preparation Fe described in claim 12O3Nano belt and its homogeneous precipitation method with the composite of carbon, its feature
It is：Step 2）Described in chelating agent be potassium oxalate, Disodium oxalate., lithium oxalate, ammonium oxalate, oxalic acid one or more；
Wherein, the iron ion in trivalent inorganic iron salt and the mol ratio of chelating agent oxalate ion are 1:0.5～6.
7. according to preparation Fe described in claim 12O3Nano belt and its homogeneous precipitation method with the composite of carbon, its feature
It is：Step 2）Described in reducing agent be sodium borohydride, potassium borohydride, hydrazine hydrate, sodium hypophosphite, in ascorbic acid one
Plant or two or more；
Wherein, the iron ion in trivalent inorganic iron salt and the mol ratio of reducing agent are 1:0.5～3.
8. according to preparation Fe described in claim 12O3Nano belt and its homogeneous precipitation method with the composite of carbon, its feature
It is：Step 2）After middle addition reducing agent, mixing speed is 400～1000rmp, and reaction temperature is 0～90 DEG C, and the response time is
0.1～3h.
9. according to preparation Fe described in claim 12O3Nano belt and its homogeneous precipitation method with the composite of carbon, its feature
It is：Step 4）Described in calcining heat be 300～700 DEG C.
10. according to preparation Fe described in claim 12O3Nano belt and its homogeneous precipitation method with the composite of carbon, its feature
It is：Step 4）Described in protective atmosphere be air, oxygen, argon, nitrogen one or more.
11. according to preparation Fe described in claim 12O3Nano belt and its homogeneous precipitation method with the composite of carbon, its feature
It is：The Fe of described preparation2O3Nano belt and its with the composite of carbon in Fe2O3Mass fraction is 5%～98%.
12. according to preparation Fe described in claim 112O3Nano belt and its homogeneous precipitation method with the composite of carbon, it is special
Levy and be：The Fe of described preparation2O3Nano belt and its with the composite of carbon in Fe2O3Mass fraction is 25%～90%.
The Fe of 13. claim 1 methods described preparations2O3Nano belt and its composite with carbon be applied to lithium ion battery or
Negative material in the electrochemical energy storage device of asymmetric type supercapacitor.
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| CN107195891A (en) * | 2017-06-30 | 2017-09-22 | 绍兴文理学院 | A kind of preparation method of lithium battery graphene composite negative pole |
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| CN101085732A (en) * | 2007-07-12 | 2007-12-12 | 中国铝业股份有限公司 | Method for producing ferrous oxalate from hematite |
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