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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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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)

1.一种铁基复杂氧化物/石墨烯复合材料，其特征在于，为层状结构，由纳米级铁基复杂氧化物和石墨烯组成，铁基复杂氧化物的通式为MFe2O4，其中M为Mn、Co、Cu或Ni。1. An iron-based complex oxide/graphene composite material is characterized in that it is a layered structure consisting of nanoscale iron-based complex oxides and graphene, and the general formula of the iron-based complex oxide is MFe 2 O 4 , wherein M is Mn, Co, Cu or Ni. 2.根据权利要求1所述的铁基复杂氧化物/石墨烯复合材料，其特征在于，所述的复合材料中石墨烯的重量百分含量为0.4％～14％。2. The iron-based complex oxide/graphene composite material according to claim 1, characterized in that the weight percentage of graphene in the composite material is 0.4% to 14%. 3.根据权利要求1所述的铁基复杂氧化物/石墨烯复合材料，其特征在于，所述的纳米级铁基复杂氧化物的颗粒直径为5纳米～15纳米。3. The iron-based complex oxide/graphene composite material according to claim 1, characterized in that, the particle diameter of the nanoscale iron-based complex oxide is 5 nm to 15 nm. 4.根据权利要求1所述的铁基复杂氧化物/石墨烯复合材料，其特征在于，所述的纳米级铁基复杂氧化物颗粒分散于石墨烯片层中，各石墨烯片层形成层状结构。4. iron-based complex oxide/graphene composite material according to claim 1, is characterized in that, described nanoscale iron-based complex oxide particle is dispersed in graphene sheet, and each graphene sheet forms layer shape structure. 5.根据权利要求4所述的铁基复杂氧化物/石墨烯复合材料，其特征在于，所述的复合材料中纳米级铁基复杂氧化物颗粒均匀分散于石墨烯片层中，各石墨烯片层形成层状结构。5. iron-based complex oxide/graphene composite material according to claim 4, is characterized in that, nanoscale iron-based complex oxide particles are evenly dispersed in graphene sheets in the composite material, and each graphene The sheets form a layered structure. 6.根据权利要求1～5任一项所述的铁基复杂氧化物/石墨烯复合材料的制备方法，包括以下步骤：6. according to the preparation method of the iron-based complex oxide/graphene composite material described in any one of claim 1～5, comprise the following steps: 1)将三价Fe盐与二价M盐按Fe3+和M2+摩尔比为2∶1溶于去离子水或有机溶剂中，得到Fe3+和M2+总浓度为0.015mol/L～0.15mol/L的溶液，再加入GO，经超声分散得到混合溶液；1) The trivalent Fe salt and the divalent M salt are dissolved in deionized water or an organic solvent at a molar ratio of Fe 3+ and M 2+ of 2:1 to obtain a total concentration of Fe 3+ and M 2+ of 0.015mol/ L ~ 0.15mol/L solution, then add GO, and obtain a mixed solution by ultrasonic dispersion; 所述的GO的加入量为铁基复杂氧化物MFe2O4理论重量的1％～35％；The amount of GO added is 1% to 35% of the theoretical weight of the iron-based complex oxide MFe2O4 ; 其中M＝Mn、Co、Cu或Ni；Wherein M=Mn, Co, Cu or Ni; 2)将步骤1)的混合溶液中加入碱性调节剂将pH值调至8～9.5，然后密封升温至190℃～280℃，反应22小时～48小时后冷却，收集固体产物，经去离子水和无水乙醇交替反复洗涤，干燥，得到层状结构的铁基复杂氧化物/石墨烯复合材料。2) Add an alkaline regulator to the mixed solution in step 1) to adjust the pH value to 8-9.5, then seal and heat up to 190°C-280°C, react for 22 hours to 48 hours, cool down, collect the solid product, and deionize Water and absolute ethanol are alternately washed repeatedly, and dried to obtain a layered iron-based complex oxide/graphene composite. 7.根据权利要求6所述的制备方法，其特征在于，所述的三价Fe盐为三价Fe的氟化物、三价Fe的氯化物、三价Fe的硝酸盐、三价Fe的硫酸盐、三价Fe的草酸盐、三价Fe的醋酸盐或所述任意一种盐的水合物；7. preparation method according to claim 6 is characterized in that, described trivalent Fe salt is the fluoride of trivalent Fe, the chloride of trivalent Fe, the nitrate of trivalent Fe, the sulfuric acid of trivalent Fe salt, trivalent Fe oxalate, trivalent Fe acetate, or a hydrate of any of said salts; 所述的二价M盐为二价M的氟化物、二价M的氯化物、二价M的硝酸盐、二价M的硫酸盐、二价M的草酸盐、二价M的醋酸盐或所述任意一种盐的水合物。The divalent M salt is divalent M fluoride, divalent M chloride, divalent M nitrate, divalent M sulfate, divalent M oxalate, divalent M acetic acid salt or a hydrate of any one of the salts. 8.根据权利要求6所述的制备方法，其特征在于，所述的有机溶剂是丙三醇、甲醇、乙二醇、1-丁醇、N，N-二甲基甲酰胺、吡啶、乙二胺、苯或甲苯。8. preparation method according to claim 6 is characterized in that, described organic solvent is glycerol, methyl alcohol, ethylene glycol, 1-butanol, N, N-dimethylformamide, pyridine, ethyl alcohol Diamine, benzene or toluene. 9.根据权利要求6所述的制备方法，其特征在于，所述的碱性调节剂是氨水、乙醇胺水溶液、氢氧化钠水溶液或氢氧化钾水溶液。9. The preparation method according to claim 6, characterized in that, the alkaline regulator is ammonia water, ethanolamine aqueous solution, sodium hydroxide aqueous solution or potassium hydroxide aqueous solution. 10.根据权利要求1、2、3、4或5所述的铁基复杂氧化物/石墨烯复合材料在作为锂离子电池负极材料中的应用。10. The application of the iron-based complex oxide/graphene composite material according to claim 1, 2, 3, 4 or 5 as a negative electrode material for lithium ion batteries.
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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Cited By (16)

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CN103077834A (en) * 2013-01-18 2013-05-01 南京理工大学 Water system neutral electrolyte-based asymmetric supercapacitor and preparation method thereof
CN104332625A (en) * 2014-08-27 2015-02-04 山东大学 Cobalt ferrite-nitrogen doped carbon composite negative electrode material for dynamic lithium battery and preparation method thereof
CN104709902A (en) * 2015-02-12 2015-06-17 宁波市疾病预防控制中心 Preparation method of magnetic graphene ternary composite material based on click chemistry
CN105176628A (en) * 2015-10-20 2015-12-23 唐山建华科技发展有限责任公司 Preparation method for lubricating oil of graphene loaded nanometer oxides
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
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
CN106115796A (en) * 2016-06-29 2016-11-16 广西桂柳化工有限责任公司 Preparation method of graphene-manganese dioxide nano material containing magnetic iron
CN106531967A (en) * 2016-12-16 2017-03-22 黑龙江大学 A kind of preparation method of lithium battery negative electrode material of cobalt ferrite-carbon cloth
CN107516735A (en) * 2017-08-21 2017-12-26 湖南科技大学 A kind of secondary iron-based composite material-copper ferricyanide battery and its manufacturing method
CN107591255A (en) * 2017-09-08 2018-01-16 南陵县生产力促进中心 A kind of ultracapacitor graphene/CuFe2O4Composite nano materials and preparation method thereof
CN107946089A (en) * 2017-11-17 2018-04-20 常州大学 A kind of MnFe2O4The preparation method of/rGO composite materials and its application as electrode material for super capacitor
CN108264041A (en) * 2016-12-31 2018-07-10 哈尔滨工业大学 Graphene oxide/copper oxide composite powder and preparation method thereof, microcosmic stratiform structure graphite alkene/method of manufacturing carbon/carbon-copper composite material
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
CN110828788A (en) * 2019-10-09 2020-02-21 中国科学院福建物质结构研究所 A kind of porous NiFe2O4 graphene composite material and its preparation method and application
CN111362310A (en) * 2020-02-21 2020-07-03 深圳大学 Multi-element heterostructure nanocomposite, controllable preparation method and lithium ion battery
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

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Cited By (23)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103077834A (en) * 2013-01-18 2013-05-01 南京理工大学 Water system neutral electrolyte-based asymmetric supercapacitor and preparation method thereof
CN104332625A (en) * 2014-08-27 2015-02-04 山东大学 Cobalt ferrite-nitrogen doped carbon composite negative electrode material for dynamic lithium battery and preparation method thereof
CN104709902A (en) * 2015-02-12 2015-06-17 宁波市疾病预防控制中心 Preparation method of magnetic graphene ternary composite material based on click chemistry
CN105176628B (en) * 2015-10-20 2018-02-13 唐山市烯润科技发展有限公司 The preparation method of the lubricating oil of graphene-supported nano-oxide
CN105176628A (en) * 2015-10-20 2015-12-23 唐山建华科技发展有限责任公司 Preparation method for lubricating oil of graphene loaded nanometer oxides
CN105932231B (en) * 2016-04-29 2018-06-29 华南理工大学 Graphene-based core-shell structure MnO @ MnFe2O4Nano material and preparation and application thereof
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
CN105895885B (en) * 2016-06-17 2018-05-15 上海应用技术学院 A kind of method that cobalt ferrite-graphene lithium ion battery is prepared using steel rolling greasy filth
CN106115796B (en) * 2016-06-29 2017-12-08 广西桂柳化工有限责任公司 Preparation method of graphene-manganese dioxide nano material containing magnetic iron
CN106115796A (en) * 2016-06-29 2016-11-16 广西桂柳化工有限责任公司 Preparation method of graphene-manganese dioxide nano material containing magnetic iron
CN106531967A (en) * 2016-12-16 2017-03-22 黑龙江大学 A kind of preparation method of lithium battery negative electrode material of cobalt ferrite-carbon cloth
CN106531967B (en) * 2016-12-16 2017-12-12 黑龙江大学 Preparation method of lithium battery negative electrode material of cobalt tetraoxide ferrate-carbon cloth
CN108264041B (en) * 2016-12-31 2019-12-24 哈尔滨工业大学 Graphene oxide/copper oxide composite powder and preparation method thereof, preparation method of microscopic layered structure graphene/copper composite material
CN108264041A (en) * 2016-12-31 2018-07-10 哈尔滨工业大学 Graphene oxide/copper oxide composite powder and preparation method thereof, microcosmic stratiform structure graphite alkene/method of manufacturing carbon/carbon-copper composite material
CN107516735A (en) * 2017-08-21 2017-12-26 湖南科技大学 A kind of secondary iron-based composite material-copper ferricyanide battery and its manufacturing method
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
CN107591255A (en) * 2017-09-08 2018-01-16 南陵县生产力促进中心 A kind of ultracapacitor graphene/CuFe2O4Composite nano materials and preparation method thereof
CN107946089A (en) * 2017-11-17 2018-04-20 常州大学 A kind of MnFe2O4The preparation method of/rGO composite materials and its application as electrode material for super capacitor
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 A kind of porous NiFe2O4 graphene composite material and its preparation method and application
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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