CN102779994A - Iron-based complex oxide/graphene composite and preparation method and application thereof - Google Patents

Iron-based complex oxide/graphene composite and preparation method and application thereof Download PDF

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CN102779994A
CN102779994A CN2012102545102A CN201210254510A CN102779994A CN 102779994 A CN102779994 A CN 102779994A CN 2012102545102 A CN2012102545102 A CN 2012102545102A CN 201210254510 A CN201210254510 A CN 201210254510A CN 102779994 A CN102779994 A CN 102779994A
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iron
complex oxide
based complex
graphene
composite material
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谢健
刘双宇
郑云肖
宋文涛
朱铁军
曹高劭
赵新兵
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Zhejiang University ZJU
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Abstract

The invention discloses an iron-based complex oxide/graphene composite in a layer structure. The iron-based complex oxide/graphene composite is composed of a nanoscale iron-based complex oxide and graphene, wherein the general formula of the iron-based complex oxide is MFe2O4, and M refers to Mn, Co, Cu or Ni. The iron-based complex oxide in the composite can be uniformly distributed for forming the layer structure and is small in granularity due to scattering and bearing actions of the graphene, stability during charging and discharging of the iron-based complex oxide and cycling stability can be effectively improved, and the iron-based complex oxide/graphene composite can be used as a cathode material of lithium ion batteries. The invention further discloses a one-step lower-temperature preparation method of the composite. The iron-based complex oxide/graphene composite and the preparation method thereof have the advantages of simple process, low cost, short period, low energy consumption and the like and are suitable for mass industrial production.

Description

Iron-based complex oxide/graphene composite material
Technical field
The present invention relates to lithium ion battery and use field of compound material, be specifically related to a kind of iron-based complex oxide/graphene composite material.
Background technology
Lithium ion battery has advantages such as operating voltage height, energy density is big, security performance is good; Therefore in portable type electronic products such as digital camera, mobile phone and notebook computer, be used widely, also have application prospect for electric bicycle and electric automobile.Present commercial lithium ion battery generally adopts the carbon back negative material, and like graphite, though this material stability is higher, theoretical capacity only has 372mAhg -1
Compare with material with carbon element, some transition metal oxide has the high theoretical capacity, like Fe 2O 3Theoretical capacity up to 1000mAhg -1This type transition metal oxide has a general character: reversible reaction can take place with lithium metal in contained oxygen, and this reaction provides reversible capacity, and the transition metal discord lithium generation alloying of embedding lithium formation first/taking off alloying reaction, its process is:
M’ xO y+2y?Li→x?M’+y?Li 2O
Though this reaction can provide higher capacity,, cause the rapid decay of capacity because change in volume is bigger in the removal lithium embedded process.At present, effectively slow down capacity fast the method for decay generally be transition metal oxide and other basis material to be carried out compound, comparatively ideal basis material is a material with carbon element.In various material with carbon elements, Graphene is very desirable basis material because of its high conductivity, high mechanical strength, big specific area agent and porosity.
Existing a lot of as the report that basis material prepares composite material in the prior art with Graphene; As disclosing a kind of transition metal oxide/graphene composite material among the one Chinese patent application CN201110083375.5; Be made up of nano grade transition metal oxide and Graphene, described transition metal oxide is MnO, Fe 2O 3, Cr 2O 3, Cu 2O, CuO or V 2O 5Transition metal oxide in this composite material is because the dispersion of Graphene and the carrying effect can evenly distribute and granularity is little can effectively improve stability and the cyclical stability of transition metal oxide in charge and discharge process.A kind of lithium battery is disclosed among the one Chinese patent application CN201010237027.4 with transition metal oxide/graphene nano combination electrode material and preparation method thereof; It is the transition metal oxide of Graphene or graphene oxide modification; Mode with physics parcel or chemical bonding between transition metal oxide and Graphene or the graphene oxide is connected; Adopt a kind of in the following method: 1. will prepare the required precursor of transition metal oxide and Graphene (or graphene oxide) by weight being to 50: 100 in solvent evenly to mix at 0.01: 100, reaction obtains nanometer combined electrode material under uniform temperature, pressure; With Graphene (or graphene oxide) and transition metal oxide by weight being to 50: 100 in solvent fully to mix at 0.01: 100, obtain nanometer combined electrode material through drying; The preparation method is easy, easy to operate, is applicable to large-scale production, and the electrode material that makes has the conductivity of higher lithium ion and electronics, and the lithium battery specific capacity of being assembled is high, good cycle, is suitable for electrode material of lithium battery.Therefore, exploitation transition metal oxide/graphene composite material has broad application prospects.
Summary of the invention
The invention provides the iron-based complex oxide/graphene composite material of the good layer structure of a kind of electrochemical stability and cyclical stability.
The present invention also provides a kind of preparation method of iron-based complex oxide/graphene composite material of layer structure, and this method technology is simple, and energy consumption is low, cost is low, is suitable for large-scale industrial production.
The present invention finds iron-based complex oxide and Graphene is compound, can be used to improve the chemical property, particularly cyclical stability of iron-based complex oxide.
A kind of iron-based complex oxide/graphene composite material is layer structure, forms the formula M Fe of described iron-based complex oxide by nanoscale iron-based complex oxide and Graphene (G) 2O 4, wherein M is Mn, Co, Cu or Ni.
Described nanoscale iron-based complex oxide Dispersion of Particles in the Graphene lamella, each Graphene lamella cambium layer shape structure; Preferably, nanoscale iron-based complex oxide uniform particles is scattered in the Graphene lamella in the described composite material, each Graphene lamella cambium layer shape structure.
In order further to improve the application performance of composite material, the weight percentage of Graphene is preferably 0.4%～14% in the described composite material, further is preferably 2%～12%.
The particle diameter of iron-based complex oxide is more little; Easy more covering is stated from the Graphene, and the electrochemical stability performance of composite material is good more, so the present invention selects nanoscale iron-based complex oxide for use; Preferably, the particle diameter of described nanoscale iron-based complex oxide is 5 nanometers～15 nanometers.
The preparation method of described iron-based complex oxide/graphene composite material may further comprise the steps:
1) trivalent Fe salt and divalence M salt are pressed Fe 3+And M 2+Mol ratio is to be dissolved in deionized water or organic solvent at 2: 1, obtains Fe 3+And M 2+Total concentration is the solution of 0.015mol/L～0.15mol/L, adds graphene oxide (GO) again, obtains mixed solution through ultrasonic dispersion;
The addition of described GO is iron-based complex oxide MFe 2O 41%～35% of theoretical weight further is preferably 5%～30%;
Wherein M=Mn, Co, Cu or Ni;
2) with adding alkaline conditioner in the mixed solution of step 1) the pH value is transferred to 8～9.5; Sealing is warming up to 190 ℃～280 ℃ then; React cooling after 22 hours～48 hours, collect solid product, through deionized water and the washing of absolute ethyl alcohol alternate repetition; Drying obtains iron-based complex oxide/graphene composite material.
Need not use reducing agent in this method, under alkali condition, graphene oxide can be reduced into Graphene through solvent thermal.
Described trivalent Fe salt can be selected the fluoride of trivalent Fe, the chloride of trivalent Fe, the nitrate of trivalent Fe, the sulfate of trivalent Fe, the oxalates of trivalent Fe, the acetate of trivalent Fe or the hydrate of said any one salt for use.
Described divalence M salt can be selected the fluoride of divalence M, the chloride of divalence M, the nitrate of divalence M, the sulfate of divalence M, the oxalates of divalence M, the acetate of divalence M or the hydrate of said any one salt for use.
Described organic solvent is glycerine, methyl alcohol, ethylene glycol, 1-butanols, N, dinethylformamide, pyridine, ethylenediamine, benzene or toluene.
Described alkaline conditioner mainly is used for regulating pH value to 8～9.5, and addition is looked required pH and decided, and concentration does not have strict the qualification, and effect has two aspects: (1) promotes the hydrolysis of metal ion and the formation of complex oxide; (2) reduction of accelerating oxidation Graphene can be selected ammoniacal liquor, the monoethanolamine aqueous solution, sodium hydrate aqueous solution or potassium hydroxide aqueous solution for use.
Step 2) in, further preferably in 190 ℃～240 ℃ reactions cooling after 24 hours～32 hours; Reaction temperature is high, and the time is long, and the iron-based complex oxide is prone to form, and graphene oxide is prone to be reduced into Graphene, but little to the particle size influence.
The qualification that the temperature of described cooling is not strict is operating as the master with suitable, generally can be cooled to 15 ℃～30 ℃ ambient temperature.
Described iron-based complex oxide/graphene composite material can be used as lithium ion battery negative material.
Compared with prior art, the present invention has following advantage:
1, the present invention adopts one-step method to prepare iron-based complex oxide/graphene composite material at low temperature, has that technology is simple, cost is low, the cycle is short, energy consumption is low and is fit to advantage such as suitability for industrialized production.
2, owing to the dispersion and the carrying effect of Graphene, iron-based complex oxide granularity is little in the composite material of the present invention, and diameter is about 5 nanometers～15 nanometers, and it is more even to distribute.
3, iron-based oxidase complex composition granule is arranged in the Graphene lamella, each Graphene lamella cambium layer shape structure, and this structure helps the raising of chemical property.
Description of drawings
Fig. 1 is embodiment 1 gained CoFe 2O 4The X ray diffracting spectrum of/graphene composite material.
Fig. 2 is embodiment 1 gained CoFe 2O 4The transmission electron microscope photo of/graphene composite material.
Fig. 3 is embodiment 1 gained CoFe 2O 4The stereoscan photograph of/graphene composite material.
Fig. 4 is embodiment 1 gained CoFe 2O 4/ G composite material and pure CoFe 2O 4Chemical property figure.
Embodiment
Embodiment 1
With mol ratio 2: 1 FeCl 36H 2O and CoCl 26H 2O is dissolved in deionized water, is mixed with 80 milliliters of Co 2+And Fe 3+Total concentration is the solution of 0.015mol/L, adds 28 milligrams of GO again and makes mixed solution; It is that the KOH aqueous solution with 4mol/L transfers to 9.5 with the pH value again in 100 milliliters the autoclave (compactedness 80%, percent by volume) that mixed solution is placed capacity, then with the agitated reactor sealing, 190 ℃ of reactions 32 hours down, naturally cools to room temperature; Collect solid reaction product, through deionized water and the washing of absolute ethyl alcohol alternate repetition, drying obtains 0.105gCoFe with product 2O 4/ graphene composite material, wherein, the weight percentage of Graphene is 12%.
The X ray diffracting spectrum of the composite material of gained, transmission electron microscope photo and stereoscan photograph are respectively like Fig. 1, Fig. 2 and Fig. 3, and the diffraction maximum of X ray all can be summed up as CoFe among Fig. 1 2O 4, can not find out the diffraction maximum of Graphene from X ray diffracting spectrum, explain that Graphene is by CoFe 2O 4Dispersion of Particles.Can be clear that from Fig. 1 and Fig. 2 the composite material of gained is CoFe 2O 4/ graphene composite material, wherein CoFe 2O 4Particle size is nanoscale, and diameter is 5 nanometers～15 nanometers, and it is more even to distribute.Can find out that from stereoscan photograph composite material presents layer structure, i.e. CoFe 2O 4Nano particle is dispersed in each layer graphene lamella.
Respectively with gained CoFe 2O 4/ G composite material and pure nano Co Fe 2O 4(its particle diameter is 5 nanometers～15 nanometers; Pure nano Co Fe 2O 4Promptly the material of graphitiferous alkene not adopts CoFe 2O 4/ G prepares with quadrat method, and difference is not add graphene oxide in the building-up process, and other conditions are identical) carry out electrochemical property test (constant current charge-discharge in the certain voltage scope), gained CoFe as lithium ion battery negative material 2O 4/ G composite material and pure nano Co Fe 2O 4Chemical property figure such as Fig. 4, constant current charge-discharge (current density 50mAg -1, voltage range 0.05～3V) test shows, cycle-index are 1 o'clock, CoFe 2O 4The capacity of/G composite material is 880mAhg -1, cycle-index is 22 o'clock, CoFe 2O 4The capacity of/G composite material only is reduced to 730mAhg -1And cycle-index is 1 o'clock, pure nano Co Fe 2O 4Capacity be 800mAhg -1, cycle-index is 22 o'clock, pure nano Co Fe 2O 4Capacity reduce rapidly and be merely 150mAhg -1It is thus clear that with pure nano Co Fe 2O 4Compare CoFe 2O 4The cyclical stability of/G composite material obviously improves, and electrochemical stability is good.
Embodiment 2
With mol ratio 2: 1 Fe (NO 3) 39H 2O and MnC 2O 42H 2O is dissolved in the ethylene glycol, is mixed with 80 milliliters of Mn 2+And Fe 3+Total concentration is the solution of 0.03mol/L, adds 37 milligrams of GO again and makes mixed solution; It is in 100 milliliters the autoclave (compactedness 80%, percent by volume) that mixed solution is placed capacity, with 25wt% ammoniacal liquor the pH value is transferred to 8, then with the agitated reactor sealing, 200 ℃ of reactions 28 hours down, naturally cools to room temperature; Collect solid reaction product, through deionized water and the washing of absolute ethyl alcohol alternate repetition, drying obtains 0.195g MnFe with product 2O 4/ graphene composite material, wherein, the weight percentage of Graphene is 7.4%.
Can find out that from X ray diffracting spectrum, transmission electron microscope photo and the stereoscan photograph of the composite material of gained the composite material of gained is MnFe 2O 4/ graphene composite material, wherein MnFe 2O 4Particle size is nanoscale, and diameter is 5 nanometers～15 nanometers, and it is more even to distribute.Can find out that from stereoscan photograph composite material presents layer structure, i.e. MnFe 2O 4Nano particle is dispersed in each layer graphene lamella.
Respectively with gained MnFe 2O 4/ G composite material and pure nanometer MnFe 2O 4(its particle diameter is 5 nanometers～15 nanometers; Pure nanometer MnFe 2O 4Promptly the material of graphitiferous alkene not adopts MnFe 2O 4/ G prepares with quadrat method, and difference is not add graphene oxide in the building-up process, and other conditions are identical) carry out electrochemical property test as lithium ion battery negative material, method of testing is with embodiment 1, constant current charge-discharge (current density 50mAg -1, voltage range 0.05～3V) test shows, cycle-index are 1 o'clock, MnFe 2O 4The capacity of/G composite material is 915mAhg -1, cycle-index is 22 o'clock, MnFe 2O 4The capacity of/G composite material only is reduced to 850mAhg -1And cycle-index is 1 o'clock, pure nanometer MnFe 2O 4Capacity be 812mAhg -1, cycle-index is 22 o'clock, pure nanometer MnFe 2O 4Capacity reduce rapidly and be merely 255mAhg -1It is thus clear that with pure nanometer MnFe 2O 4Compare MnFe 2O 4The cyclical stability of/G composite material obviously improves, and electrochemical stability is good.
Embodiment 3
With mol ratio 1: 1 Fe 2(SO 4) 3And NiSO 46H 2O is dissolved in methyl alcohol, is mixed with 80 milliliters of Ni 2+And Fe 3+Total concentration is the solution of 0.09mol/L, adds 56 milligrams of GO again and makes mixed solution; It is in 100 milliliters the autoclave (compactedness 80%, percent by volume) that mixed solution is placed capacity, with the NaOH aqueous solution of 4mol/L the pH value is transferred to 9, then with the agitated reactor sealing, 220 ℃ of reactions 24 hours down, naturally cools to room temperature; Collect solid reaction product, through deionized water and the washing of absolute ethyl alcohol alternate repetition, drying obtains 0.59g NiFe with product 2O 4/ graphene composite material, wherein, the weight percentage of Graphene is 5%.
Can find out that from X ray diffracting spectrum, transmission electron microscope photo and the stereoscan photograph of the composite material of gained the composite material of gained is NiFe 2O 4/ graphene composite material, wherein NiFe 2O 4Particle size is nanoscale, and diameter is 5 nanometers～15 nanometers, and it is more even to distribute.Can find out that from stereoscan photograph composite material presents layer structure, i.e. NiFe 2O 4Nano particle is dispersed in each layer graphene lamella.
Respectively with gained NiFe 2O 4/ G composite material and pure nano-Ni/Fe 2O 4(its particle diameter is 5 nanometers～15 nanometers; Pure nano-Ni/Fe 2O 4Promptly the material of graphitiferous alkene not adopts NiFe 2O 4/ G prepares with quadrat method, and difference is not add graphene oxide in the building-up process, and other conditions are identical) carry out electrochemical property test as lithium ion battery negative material, method of testing is with embodiment 1, constant current charge-discharge (current density 50mAg -1, voltage range 0.05～3V) test shows, cycle-index are 1 o'clock, NiFe 2O 4The capacity of/G composite material is 895mAhg -1, cycle-index is 22 o'clock, NiFe 2O 4The capacity of/G composite material only is reduced to 827mAhg -1And cycle-index is 1 o'clock, pure nano-Ni/Fe 2O 4Capacity be 815mAhg -1, cycle-index is 22 o'clock, pure nano-Ni/Fe 2O 4Capacity reduce rapidly and be merely 191mAhg -1It is thus clear that with pure nano-Ni/Fe 2O 4Compare NiFe 2O 4The cyclical stability of/G composite material obviously improves, and electrochemical stability is good.
Embodiment 4
With mol ratio 2: 1 FeCl 36H 2O and Cu (CH 3COO) 2H 2O is dissolved in toluene, is mixed with 80 milliliters of Cu 2+And Fe 3+Total concentration is the solution of 0.15mol/L, adds 48 milligrams of GO again and makes mixed solution; It is in 100 milliliters the autoclave (compactedness 80%, percent by volume) that mixed solution is placed capacity, with the 25wt% monoethanolamine aqueous solution pH value is transferred to 8.5, then with the agitated reactor sealing, 240 ℃ of reactions 22 hours down, naturally cools to room temperature then; Collect solid reaction product, through deionized water and the washing of absolute ethyl alcohol alternate repetition, drying obtains 0.97gCuFe with product 2O 4/ graphene composite material, wherein, the weight percentage of Graphene is 2%.
Can find out that from X ray diffracting spectrum, transmission electron microscope photo and the stereoscan photograph of the composite material of gained the composite material of gained is CuFe 2O 4/ graphene composite material, wherein CuFe 2O 4Particle size is nanoscale, and diameter is 5 nanometers～15 nanometers, and it is more even to distribute.Can find out that from stereoscan photograph composite material presents layer structure, i.e. CuFe 2O 4Nano particle is dispersed in each layer graphene lamella.
Respectively with gained CuFe 2O 4/ G composite material and pure nanometer CuFe 2O 4(its particle diameter is 5 nanometers～15 nanometers; Pure nanometer CuFe 2O 4Promptly the material of graphitiferous alkene not adopts CuFe 2O 4/ G prepares with quadrat method, and difference is not add graphene oxide in the building-up process, and other conditions are identical) carry out electrochemical property test as lithium ion battery negative material, method of testing is with embodiment 1, constant current charge-discharge (current density 50mAg -1, voltage range 0.05～3V) test shows, cycle-index are 1 o'clock, CuFe 2O 4The capacity of/G composite material is 901mAhg -1, cycle-index is 22 o'clock, CuFe 2O 4The capacity of/G composite material only is reduced to 868mAhg -1And cycle-index is 1 o'clock, pure nanometer CuFe 2O 4Capacity be 784mAhg -1, cycle-index is 22 o'clock, pure nanometer CuFe 2O 4Capacity reduce rapidly and be merely 145mAhg -1It is thus clear that with pure nanometer CuFe 2O 4Compare CuFe 2O 4The cyclical stability of/G composite material obviously improves, and electrochemical stability is good.

Claims (10)

1. an iron-based complex oxide/graphene composite material is characterized in that, is layer structure, is made up of nanoscale iron-based complex oxide and Graphene, and the general formula of iron-based complex oxide is MFe 2O 4, wherein M is Mn, Co, Cu or Ni.
2. iron-based complex oxide/graphene composite material according to claim 1 is characterized in that, the weight percentage of Graphene is 0.4%～14% in the described composite material.
3. iron-based complex oxide/graphene composite material according to claim 1 is characterized in that, the particle diameter of described nanoscale iron-based complex oxide is 5 nanometers～15 nanometers.
4. iron-based complex oxide/graphene composite material according to claim 1 is characterized in that, described nanoscale iron-based complex oxide Dispersion of Particles in the Graphene lamella, each Graphene lamella cambium layer shape structure.
5. iron-based complex oxide/graphene composite material according to claim 4 is characterized in that, nanoscale iron-based complex oxide uniform particles is scattered in the Graphene lamella in the described composite material, each Graphene lamella cambium layer shape structure.
6. according to the preparation method of each described iron-based complex oxide/graphene composite material of claim 1～5, may further comprise the steps:
1) trivalent Fe salt and divalence M salt are pressed Fe 3+And M 2+Mol ratio is to be dissolved in deionized water or organic solvent at 2: 1, obtains Fe 3+And M 2+Total concentration is the solution of 0.015mol/L～0.15mol/L, adds GO again, obtains mixed solution through ultrasonic dispersion;
The addition of described GO is iron-based complex oxide MFe 2O 41%～35% of theoretical weight;
Wherein M=Mn, Co, Cu or Ni;
2) with adding alkaline conditioner in the mixed solution of step 1) the pH value is transferred to 8～9.5; Sealing is warming up to 190 ℃～280 ℃ then; React cooling after 22 hours～48 hours, collect solid product, through deionized water and the washing of absolute ethyl alcohol alternate repetition; Drying obtains the iron-based complex oxide/graphene composite material of layer structure.
7. preparation method according to claim 6; It is characterized in that the nitrate of the fluoride that described trivalent Fe salt is trivalent Fe, the chloride of trivalent Fe, trivalent Fe, the sulfate of trivalent Fe, the oxalates of trivalent Fe, the acetate of trivalent Fe or the hydrate of said any one salt;
The nitrate of the fluoride that described divalence M salt is divalence M, the chloride of divalence M, divalence M, the sulfate of divalence M, the oxalates of divalence M, the acetate of divalence M or the hydrate of said any one salt.
8. preparation method according to claim 6 is characterized in that, described organic solvent is glycerine, methyl alcohol, ethylene glycol, 1-butanols, N, dinethylformamide, pyridine, ethylenediamine, benzene or toluene.
9. preparation method according to claim 6 is characterized in that, described alkaline conditioner is ammoniacal liquor, the monoethanolamine aqueous solution, sodium hydrate aqueous solution or potassium hydroxide aqueous solution.
According to claim 1,2,3,4 or 5 described iron-based complex oxide/graphene composite materials as the application in the lithium ion battery negative material.
CN2012102545102A 2012-07-23 2012-07-23 Iron-based complex oxide/graphene composite and preparation method and application thereof Pending CN102779994A (en)

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CN105932231A (en) * 2016-04-29 2016-09-07 华南理工大学 Graphene-based core-shell structure MnO @ MnFe 2O 4 nano material and preparation and application thereof
CN105895885A (en) * 2016-06-17 2016-08-24 上海应用技术学院 Method for preparing cobalt ferrite-graphene lithium ion battery by using steel rolling oil sludge
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CN107516735B (en) * 2017-08-21 2019-08-23 湖南科技大学 A kind of secondary iron base composite material-iron copper cyanider battery and its manufacturing method
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CN108511733A (en) * 2018-05-16 2018-09-07 中国科学院金属研究所 A kind of MXene/ bimetallic oxides composite material and preparation method and lithium ion battery negative material
CN114423541A (en) * 2019-09-17 2022-04-29 石墨烯材料科技公司 Composite powder having iron-based particles coated with graphene material
CN110828788A (en) * 2019-10-09 2020-02-21 中国科学院福建物质结构研究所 Porous NiFe2O4Graphene composite material and preparation method and application thereof
CN111362310A (en) * 2020-02-21 2020-07-03 深圳大学 Multi-element heterostructure nanocomposite, controllable preparation method and lithium ion battery

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