CN105140494A - Biomimetic synthesis method of Fe3O4/Fe/C nano composite battery electrode material - Google Patents

Biomimetic synthesis method of Fe3O4/Fe/C nano composite battery electrode material Download PDF

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CN105140494A
CN105140494A CN201510378518.3A CN201510378518A CN105140494A CN 105140494 A CN105140494 A CN 105140494A CN 201510378518 A CN201510378518 A CN 201510378518A CN 105140494 A CN105140494 A CN 105140494A
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cellulose
synthesis method
electrode material
battery electrode
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CN105140494B (en
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何文
张旭东
张书振
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Qilu University of Technology
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/523—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron for non-aqueous cells
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention relates to a biomimetic synthesis method of an Fe3O4/Fe/C nano composite battery electrode material. The method comprises the following steps: firstly, preparing active nano cellulose from cheap natural cellulose cotton as a template and a carbon source, and then mixing the active nano cellulose with a FeCl3.6H2O water solution; adding ammonium hydroxide to generate sediments, and carrying out hydro-thermal treatment to form a mixture of a precursor Fe3O4 and the cellulose; and carrying out thermal treatment on the mixture in nitrogen atmosphere, so as to obtain the Fe3O4/Fe/C nano composite material. The composite material prepared by the method can be used for preparing a power lithium-ion battery as a lithium battery anode material.

Description

A kind of Fe 3o 4the biomimetic synthesis method of the nano combined battery electrode material of/Fe/C
Technical field
The present invention relates to a kind of iron oxide/iron/carbon (Fe with good electrical chemical property 3o 4/ Fe/C) biomimetic synthesis method of nano combined battery electrode material, belong to lithium ion battery material technical field.
Background technology
Transition metal oxide, particularly nanocrystalline transition metal oxide, because having, raw material sources enriches, cost is lower, the size of metal oxide particle (from nanometer to micron) is easy to shape and location advantages such as adjusting, theoretical energy density is high, and becomes important lithium ion battery negative material.
In transition metal oxide, iron oxide because theoretical specific capacity is high, nature rich reserves, the advantage such as nontoxic, causing domestic and international people pays close attention to greatly, is considered to the lithium ion battery negative material having application potential.But iron oxide change in volume in charge and discharge process is larger, and along with larger change in volume, easily cause the efflorescence of electrode material, cause the rapid decay of capacity, especially under high current density, decay rapidly, far can not meet current commercial li-ion battery for the large multiplying power of electrode material, long-life demand.
Relevant synthetic iron oxide material also has some bibliographical informations at present, such as, Chinese patent literature CN103022422A discloses a kind of method that solid phase method prepares active carbon nanotube/ferric oxide lithium ion battery electrode material, the method utilizes phase oxidative agent to modify original carbon nanotubes surface texture, while significantly improving specific surface area of carbon nanotube, iron nano-particle is direct oxidation into iron oxide.But the shortcoming such as the method carbon nano-tube used exists that cost is high, preparation method is complicated and material source is non-renewable.
Chinese patent literature CN104157832A discloses a kind of preparation method of ferroferric oxide/carbon composite lithium ion battery material.First bombax cotton after purified treatment is immersed certain density Fe (NO by the method 3) 3in solution, become taking-up after uniform yellow until bombax cotton and drain.Utilize ammonia to spread the presoma obtaining iron hydroxide/carbon, after heat treatment, namely obtain Fe 3o 4/ C composite.But ammonia diffusion process is higher to requirement for experiment condition, in prepared presoma, iron hydroxide degree of crystallinity is poor, and final calcining produces Fe 3o 4grain structure breaks, and easily reunites.
There is the problems such as agents useful for same is poisonous, dangerous, synthesis technique is complicated, the difficult control of cost intensive, building-up process in the existing modification for transition metal oxide.According to the market demand and the energy-conserving and environment-protective requirement of lithium ion battery, be badly in need of the negative material that research and development are new, improve its chemical property further, reduce synthesis cost, reduce environmental pollution and reproducible utilization, thus meet the needs of new energy field to lithium ion battery material.
Summary of the invention
The deficiency of the cycle performance existed for existing iron oxide material and high rate performance difference, the invention provides a kind of Fe 3o 4the biomimetic synthesis method of the nano combined battery electrode material of/Fe/C.Biotechnology combines with chemical synthesis process by the present invention, and obtained material can be used as lithium ion battery negative material.
Term explanation
Bio-mimetic syntheses: the reaction in mimic biology body and natural goods structure carry out the process of synthesizing.
Technical scheme of the present invention is as follows:
A kind of Fe 3o 4the biomimetic synthesis method of the nano combined battery electrode material of/Fe/C, comprises step as follows:
(1) preparation of nano-cellulose biological template
Be soaked in the sulfuric acid solution of thing mass concentration (10 ~ 15) mol/L after native cellulose is shredded, in 30 DEG C ~ 60 DEG C insulations 30 ~ 60 minutes, Separation of Solid and Liquid, solid water is washed till neutrality, obtained active nano cellulose after drying, active nano cellulose uses as biological template;
(2)) the preparation of composite material precursor
The active nano cellulose that step (1) is obtained is dipped in the FeCl that thing mass concentration is (0.06 ~ 0.069) mol/L 36H 2in the O aqueous solution, active nano cellulose and FeCl 36H 2the mass volume ratio of the O aqueous solution is: 1:(60 ~ 80), unit g/ml; Stirred at ambient temperature 1-3h, then regulates pH=8, forms Fe (OH) 3with cellulosic mixed sediment, regulate the mixed liquor after pH in 160 DEG C ~ 200 DEG C hydrothermal treatment consists 2h ~ 6h, Separation of Solid and Liquid, washing, obtains presoma Fe after drying 3o 4with cellulosic mixture;
(3) heat treatment of composite material precursor
The presoma Fe obtained by step (2) 3o 4with cellulosic mixture under inert gas shielding, be warming up to 600 DEG C ~ 800 DEG C and heat-treat 3 ~ 5 hours, naturally after cooling, obtained Fe 3o 4/ Fe/C nano composite material.
Preferred according to the present invention, described native cellulose is cotton, fiber crops or silk flosssilk wadding, highly preferred, and described native cellulose is cotton, native cellulose is cut into the chip of length 3 ~ 6mm.
Preferred according to the present invention, in step (1), the mass volume ratio of native cellulose and sulfuric acid solution is: 1:(10 ~ 15), unit g/ml, the thing mass concentration of sulfuric acid solution is preferably 15mol/L.
Preferred according to the present invention, in step (1), reaction temperature is 40 DEG C ~ 50 DEG C, and the reaction time is 30 ~ 50 minutes, and preferably, reaction temperature is 45 DEG C, and the reaction time is 40 minutes.
Preferred according to the present invention, in step (1), bake out temperature is 50 DEG C ~ 60 DEG C.
Preferred according to the present invention, in step (2), active nano cellulose and FeCl 36H 2the mass volume ratio of the O aqueous solution is: 1:80, unit g/ml, FeCl 36H 2the thing mass concentration of the O aqueous solution is 0.069mol/L.
Preferred according to the present invention, in step (2), hydrothermal treatment consists temperature is 170 DEG C ~ 190 DEG C, and the hydro-thermal time is 3 ~ 5h, and preferably, hydrothermal treatment consists temperature is 180 DEG C, and the hydro-thermal time is 4h.
Preferred according to the present invention, in step (2), baking temperature is 70 DEG C ~ 80 DEG C.
Preferred according to the present invention, in step (2), add ammonia spirit regulating system pH=8, the mass concentration of ammonia spirit is 25 ~ 35wt%.
Preferred according to the present invention, in step (3), heat treatment temperature is 650 DEG C ~ 800 DEG C, heat treatment time 4 ~ 5 hours, and preferably, heat treatment temperature is 700 DEG C, and heat treatment time is 4h.
Preferred according to the present invention, in step (3), inert gas is nitrogen.
According to the present invention, preferably, in step (3), synthetic method of the present invention is combined with chemical synthesis at biotechnology, by positively charged Fe 3+mix with electronegative cellulose solution, under the active force attracted each other between positive and negative charge, iron ion is more easily adsorbed and deposits on cellulosic green alga sphaerocyst.After heat treatment, the Fe of 20 ~ 100nm is formed on the surface at cellulose template 3o 4nano particle, thus the bio-mimetic syntheses realizing nano-sized iron oxide.In bio-mimetic syntheses process, cellulose not only serves the effect of stay in place form, and is preparation Fe 3o 4/ Fe/C nano composite material provides conduction carbon source and nanoparticle binder, thus improves Fe 3o 4the bulk density of/Fe/C nano composite material, conductivity and specific capacity.
The present invention is preferred, above-mentioned Fe 3o 4the application of/Fe/C nano composite material, described Fe 3o 4/ Fe/C nano composite material is as the negative material of lithium ion battery.
Concrete application process is as follows:
(1) by Fe 3o 4after/Fe/C nano composite material and conductive agent and the abundant ground and mixed of binding agent, add 1-METHYLPYRROLIDONE solvent, obtain precoating after stirring and refine slurries;
(2) slurries being refined in above-mentioned precoating coats on Copper Foil, and then namely obtain lithium ion battery negative electrode slice by after electrode slice drying process, gained lithium ion battery negative electrode slice is used for button-type battery or soft-package battery lithium ion battery.
Fe prepared by the inventive method 3o 4/ Fe/C nano composite material, the first charge-discharge specific capacity under charging/discharging voltage is 0 ~ 3.0V and 1A/g high current density reaches 596.8mAh/g and 903.8mAh/g respectively; The specific discharge capacity after 60 times that circulates still can reach 524.6mAh/g.
The present invention compared with the prior art, it is advantageous that and utilize native cellulose cotton for stay in place form and conduction carbon source and nanoparticle binder, adopt simple preparation technology, and bio-mimetic syntheses has the Fe of good circulation performance and high rate performance 3o 4/ Fe/C nano composite anode material, the reagent of use is nontoxic, synthesis technique simple, cost is lower, can be used as negative material for the preparation of power lithium-ion battery.
Accompanying drawing explanation
Fig. 1 is the presoma Fe that the embodiment of the present invention 1 obtains 3o 4with cellulosic mixture, Fe 3o 4the XRD figure of/Fe/C nano composite material, wherein left ordinate is intensity, and abscissa is angle of diffraction (2 θ).
Fig. 2 is the Fe that the embodiment of the present invention 1 obtains 3o 4the SEM figure of/Fe/C nano composite material;
Fig. 3 is the Fe that the embodiment of the present invention 1 obtains 3o 4/ Fe/C nano composite material electrochemistry cycle performance curve chart.
Embodiment
Below in conjunction with embodiment, the present invention will be further described, but be not limited thereto.
Embodiment 1
A kind of Fe 3o 4the biomimetic synthesis method of the nano combined battery electrode material of/Fe/C, preparation process is as follows:
(1) 3g cotton being cut into length is that to be soaked in 45mL thing mass concentration be in the sulfuric acid solution of 15mol/L for the chip of 5mm, through 45 DEG C of insulations 40 minutes, Separation of Solid and Liquid, dry under 60 DEG C of conditions after solid water is washed till neutrality, obtain active nano cellulose, active nano cellulose uses as biological template.
(2)) the active nano cellulose lg that step (1) is obtained is dipped in the FeCl that 80ml concentration is 0.069mol/L 36H 2in the O aqueous solution, stirred at ambient temperature 2h, then adds mass concentration 25wt% ammonia spirit and regulates pH=8, form Fe (OH) 3with cellulosic mixed sediment, by the mixed liquor after adjustment pH in 180 DEG C of hydrothermal treatment consists 4h, Separation of Solid and Liquid, 4 washings, obtain presoma Fe after 80 DEG C of dryings 3o 4with cellulosic mixture;
The presoma Fe that this step obtains 3o 4scheme as shown in Figure 1 with the XRD of cellulosic mixture.
(3) again by obtained presoma Fe 3o 4with cellulosic mixture in a nitrogen atmosphere, be warming up to 700 DEG C and heat-treat 4 hours, naturally after cooling, obtained Fe 3o 4/ Fe/C nano composite material.
The Fe that the present embodiment obtains 3o 4as shown in Figure 1, SEM figure as shown in Figure 2 for the XRD of/Fe/C nano composite material.
Electrochemical property test
By Fe prepared by this embodiment 3o 4/ Fe/C nano composite material is used as lithium ion battery negative material, adopts rubbing method to prepare electrode.By Fe 3o 4/ Fe/C nano composite material, acetylene black and Kynoar (PVDF) by the abundant ground and mixed of the mass ratio of 80:10:10, add 1-METHYLPYRROLIDONE stirring solvent evenly after obtain precoating and refine slurries; Slurries are refined in above-mentioned precoating coat respectively on Copper Foil, through 60 DEG C of dry 6h or 20 DEG C vacuumize 12h, naturally utilize sheet-punching machine to be cut into the disk of diameter 15cm after cooling, namely make lithium ion battery negative electrode slice.
Assemble successively according to the order of anode cover-electrode slice-electrolyte-barrier film-electrolyte-lithium sheet-pad-spring leaf-negative electrode casing, recycling sealing machine, by cell sealing, can obtain CR2032 type button half-cell.
Finally at A713-2008S-3TGF-A type high accuracy discharge and recharge instrument, constant current charge-discharge test is carried out to battery.Discharge and recharge condition: the first discharge specific capacity in 0 ~ 3.0V voltage range and under 1A/g current density is 903.8mAh/g, the specific discharge capacity after 60 circulations still can reach 524.6mAh/g, and test result as shown in Figure 3.
Embodiment 2
A kind of Fe 3o 4the biomimetic synthesis method of the nano combined battery electrode material of/Fe/C, preparation process is as follows:
(1) 3g cotton being cut into length is that to be soaked in 45mL thing mass concentration be in the sulfuric acid solution of 15mol/L for the chip of 5mm, through 30 DEG C of insulations 60 minutes, Separation of Solid and Liquid, dry under 60 DEG C of conditions after solid water is washed till neutrality, obtain active nano cellulose, active nano cellulose uses as biological template.
(2)) the active nano cellulose lg that step (1) is obtained is dipped in the FeCl that 80ml concentration is 0.069mol/L 36H 2in the O aqueous solution, stirred at ambient temperature 2h, then adds mass concentration 25wt% ammonia spirit and regulates pH=8, form Fe (OH) 3with cellulosic mixed sediment, by the mixed liquor after adjustment pH in 160 DEG C of hydrothermal treatment consists 6h, Separation of Solid and Liquid, 4 washings, obtain presoma Fe after 80 DEG C of dryings 3o 4with cellulosic mixture;
(3) again by obtained presoma Fe 3o 4with cellulosic mixture in a nitrogen atmosphere, be warming up to 600 DEG C and heat-treat 5 hours, naturally after cooling, obtained Fe 3o 4/ Fe/C nano composite material.
By this composite material composition lithium sheet to the half-cell of electrode, the first discharge specific capacity under charging/discharging voltage is 0 ~ 3.0V and 1A/g current density is 453.6mAh/g, and the discharge capacity after 50 charge and discharge cycles is 102.3mAh/g.
Embodiment 3
A kind of Fe 3o 4the biomimetic synthesis method of the nano combined battery electrode material of/Fe/C, preparation process is as follows:
(1) 3g cotton being cut into length is that to be soaked in 45mL thing mass concentration be in the sulfuric acid solution of 15mol/L for the chip of 5mm, through 60 DEG C of insulations 30 minutes, Separation of Solid and Liquid, dry under 60 DEG C of conditions after solid water is washed till neutrality, obtain active nano cellulose, active nano cellulose uses as biological template.
(2)) the active nano cellulose lg that step (1) is obtained is dipped in the FeCl that 80ml concentration is 0.069mol/L 36H 2in the O aqueous solution, stirred at ambient temperature 2h, then adds mass concentration 25wt% ammonia spirit and regulates pH=8, form Fe (OH) 3with cellulosic mixed sediment, by the mixed liquor after adjustment pH in 200 DEG C of hydrothermal treatment consists 2h, Separation of Solid and Liquid, 5 washings, obtain presoma Fe after 80 DEG C of dryings 3o 4with cellulosic mixture;
(3) again by obtained presoma Fe 3o 4with cellulosic mixture in a nitrogen atmosphere, be warming up to 800 DEG C and heat-treat 3 hours, naturally after cooling, obtained Fe 3o 4/ Fe/C nano composite material.
By this composite material composition lithium sheet to the half-cell of electrode, the first discharge specific capacity under charging/discharging voltage is 0 ~ 3.0V and 1A/g current density is 750mAh/g, and the discharge capacity after 10 charge and discharge cycles is 206mAh/g.

Claims (10)

1. a Fe 3o 4the biomimetic synthesis method of the nano combined battery electrode material of/Fe/C, comprises step as follows:
(1) preparation of nano-cellulose biological template
Be soaked in the sulfuric acid solution of thing mass concentration (10 ~ 15) mol/L after native cellulose is shredded, in 30 DEG C ~ 60 DEG C insulations 30 ~ 60 minutes, Separation of Solid and Liquid, solid water is washed till neutrality, obtained active nano cellulose after drying, active nano cellulose uses as biological template;
(2) preparation of composite material precursor
The active nano cellulose that step (1) is obtained is dipped in the FeCl that thing mass concentration is (0.06 ~ 0.069) mol/L 36H 2in the O aqueous solution, active nano cellulose and FeCl 36H 2the mass volume ratio of the O aqueous solution is: 1:(60 ~ 80), unit g/ml; Stirred at ambient temperature 1-3h, then regulates pH=8, forms Fe (OH) 3with cellulosic mixed sediment, regulate the mixed liquor after pH in 160 DEG C ~ 200 DEG C hydrothermal treatment consists 2h ~ 6h, Separation of Solid and Liquid, washing, obtains presoma Fe after drying 3o 4with cellulosic mixture;
(3) heat treatment of composite material precursor
The presoma Fe obtained by step (2) 3o 4with cellulosic mixture under inert gas shielding, be warming up to 600 DEG C ~ 800 DEG C and heat-treat 3 ~ 5 hours, naturally after cooling, obtained Fe 3o 4/ Fe/C nano composite material.
2. Fe according to claim 1 3o 4the biomimetic synthesis method of the nano combined battery electrode material of/Fe/C, is characterized in that, described native cellulose is cotton, fiber crops or silk flosssilk wadding, and preferably, described native cellulose is cotton; Native cellulose is cut into the chip of length 3 ~ 6mm.
3. Fe according to claim 1 3o 4the biomimetic synthesis method of the nano combined battery electrode material of/Fe/C, it is characterized in that, in step (1), the mass volume ratio of native cellulose and sulfuric acid solution is: 1:(10 ~ 15), unit g/ml, the thing mass concentration of sulfuric acid solution is preferably 15mol/L.
4. Fe according to claim 1 3o 4the biomimetic synthesis method of the nano combined battery electrode material of/Fe/C, is characterized in that, in step (1), reaction temperature is 40 DEG C ~ 50 DEG C, and the reaction time is 30 ~ 50 minutes; Preferably, reaction temperature is 45 DEG C, and the reaction time is 40 minutes.
5. Fe according to claim 1 3o 4the biomimetic synthesis method of the nano combined battery electrode material of/Fe/C, is characterized in that, in step (1), bake out temperature is 50 DEG C ~ 60 DEG C.
6. Fe according to claim 1 3o 4the biomimetic synthesis method of the nano combined battery electrode material of/Fe/C, is characterized in that, in step (2), and active nano cellulose and FeCl 36H 2the mass volume ratio of the O aqueous solution is: 1:80, unit g/ml, FeCl 36H 2the thing mass concentration of the O aqueous solution is 0.069mol/L.
7. Fe according to claim 1 3o 4the biomimetic synthesis method of the nano combined battery electrode material of/Fe/C, is characterized in that, in step (2), hydrothermal treatment consists temperature is 170 DEG C ~ 190 DEG C, and the hydro-thermal time is 3 ~ 5h; Preferably, hydrothermal treatment consists temperature is 180 DEG C, and the hydro-thermal time is 4h; Baking temperature is 70 DEG C ~ 80 DEG C.
8. Fe according to claim 1 3o 4the biomimetic synthesis method of the nano combined battery electrode material of/Fe/C, is characterized in that, in step (2), adds ammonia spirit regulating system pH=8, and the mass concentration of ammonia spirit is 25 ~ 35wt%.
9. Fe according to claim 1 3o 4the biomimetic synthesis method of the nano combined battery electrode material of/Fe/C, is characterized in that, in step (3), heat treatment temperature is 650 DEG C ~ 800 DEG C, heat treatment time 4 ~ 5 hours; Preferably, heat treatment temperature is 700 DEG C, and heat treatment time is 4h; The inert gas used is nitrogen.
10. Fe according to claim 1 3o 4the Fe that the biomimetic synthesis method of the nano combined battery electrode material of/Fe/C is obtained 3o 4the application of/Fe/C nano composite material, described Fe 3o 4/ Fe/C nano composite material as the negative material of lithium ion battery,
Concrete application process is as follows:
(1) by Fe 3o 4after/Fe/C nano composite material and conductive agent and the abundant ground and mixed of binding agent, add 1-METHYLPYRROLIDONE solvent, obtain precoating after stirring and refine slurries;
(2) slurries are refined in above-mentioned precoating to coat respectively on Copper Foil, then namely obtain lithium ion battery negative electrode slice by after electrode slice drying process, gained lithium ion battery negative electrode slice is used for button-type battery or soft-package battery lithium ion battery.
CN201510378518.3A 2015-07-01 2015-07-01 A kind of Fe3O4The biomimetic synthesis method of the nano combined battery electrode materials of/Fe/C Expired - Fee Related CN105140494B (en)

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CN105609753A (en) * 2015-12-14 2016-05-25 青岛大学 Preparation method for one-dimensional multi-layer porous fibrous positive electrode material of lithium ion battery
CN105609753B (en) * 2015-12-14 2019-04-30 青岛大学 The preparation method of one-dimensional multi-layer porous fibrous anode material for lithium-ion batteries
CN105645477A (en) * 2016-03-21 2016-06-08 黄山学院 Preparation method of ferroferric oxide
CN107681137A (en) * 2017-09-20 2018-02-09 齐鲁工业大学 A kind of sodium-ion battery C/C70/ CaS composite negative pole materials and preparation method thereof
CN108333237A (en) * 2017-12-31 2018-07-27 苏州南尔材料科技有限公司 A kind of preparation method of nano-cellulose sensor electrode material
CN109807350A (en) * 2019-03-06 2019-05-28 浙江工业大学 A kind of preparation method of 3-D ordered multiporous copper current collector
CN109807350B (en) * 2019-03-06 2022-04-05 浙江工业大学 Preparation method of three-dimensional ordered porous copper current collector
CN111180686A (en) * 2019-12-29 2020-05-19 华东理工大学 Preparation method of flexible self-supporting silicon-based lithium ion battery cathode material
CN111769263A (en) * 2020-06-18 2020-10-13 合肥国轩高科动力能源有限公司 Three-dimensional C/Fe3O4Lithium ion battery cathode material and preparation method thereof
CN111769263B (en) * 2020-06-18 2022-06-07 合肥国轩高科动力能源有限公司 Three-dimensional C/Fe3O4Lithium ion battery cathode material and preparation method thereof

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