CN104466169A - Method for preparing ferrum electrode material of ferro-nickel rechargeable secondary battery - Google Patents

Method for preparing ferrum electrode material of ferro-nickel rechargeable secondary battery Download PDF

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Publication number
CN104466169A
CN104466169A CN201410815743.4A CN201410815743A CN104466169A CN 104466169 A CN104466169 A CN 104466169A CN 201410815743 A CN201410815743 A CN 201410815743A CN 104466169 A CN104466169 A CN 104466169A
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electrode material
iron
ferronickel
secondary cell
iron electrode
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CN104466169B (en
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刘洪涛
洪诗雨
唐有根
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Central South University
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Central South University
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • 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
    • H01M10/24—Alkaline accumulators
    • H01M10/30—Nickel accumulators
    • 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

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Inorganic Chemistry (AREA)
  • Carbon And Carbon Compounds (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The invention provides a method for preparing a ferrum electrode material of a ferro-nickel rechargeable secondary battery. The method comprises the following steps: dissolving ferric salt and oleate according to a substance ratio of (1:1)-(1:10) in a mixed solvent of absolute ethyl alcohol, deionized water and aliphatic hydrocarbon, thereby obtaining an oleic acid iron-based compound; dispersing expanded graphite carbon powder in a mixed solvent of oleylamine and aromatic hydrocarbon according to a volume ratio of (1:1)-(1:10), thereby obtaining oleylamine modified nano graphene sheets; dissolving the compound and the nano graphene sheets in the aromatic hydrocarbon, and drying after treatment, thereby obtaining a ferrum electrode precursor compound containing the graphene sheets; heating in a tubular furnace at a rate of 1 to 20 DEG C per minute under the inert gas or nitrogen protection, and performing heat treatment; and naturally cooling to room temperature, thereby obtaining the graphene sheet modified iron electrode material for the ferro-nickel rechargeable secondary battery. According to the method disclosed by the invention, the ferrum electrode of the ferro-nickel rechargeable secondary battery has excellent quick charge and discharge performance, the operation process is simple, the repeatability is high, the material test effect is obvious, and the commercial popularization and application are promoted.

Description

A kind of preparation method that can fill secondary cell iron electrode material for ferronickel
Technical field
The invention belongs to electrode material field, particularly a kind of preparation method filling graphene modified iron electrode material.
Background technology
Nickel iron cell had just invented before a century, and traditional nickel iron cell is typically used as reserve cell.Its main feature can work under very rugged environment, and battery has very long useful life.But because iron electrode generates fine and close passivating film when discharging, making nickel iron cell charge difficulty, can only recycle under small area analysis condition, when adding charging, liberation of hydrogen is serious, makes the efficiency for charge-discharge of iron electrode extremely low.Therefore, the interface charge transmission performance improving iron electrode just becomes the key that lifting ferronickel can fill secondary cell competitiveness.
Patent (CN102616864A) discloses a kind of manufacture method of ferroferric oxide for iron electrode, the method take ferrous salt as source of iron, through heating, alkalization, oxidation, filtration washing, drying, pulverize and sieve, a series of operation such as reduction obtains tri-iron tetroxide electrode material.Although this electrode material iron electrode material charge/discharge capacity more obtained than conventional method (Acetylene Reduction di-iron trioxide) increases, but still the interface charge that high resistance passivating film causes cannot be overcome transmit slow problem.Document (Chem. Commun., 2011,47,12473 – 12475) report one and can fill iron electrode material, directly grow on carbon nano-fiber by α-di-iron trioxide by hydro thermal method, the Quick conductive ability by carbon fiber improves the charge transport properties of iron electrode.The method is with strong points, principle is simple, but the electro-chemical activity of di-iron trioxide itself is poor, and therefore prepared iron electrode whole volume is lower.
summary of the invention:
The present invention aims to provide and a kind ofly realizes the iron electrode material preparation method that ferronickel can fill secondary cell fast charging and discharging.Mainly through the graphene film self assembly that formation of iron based nanoparticles and the oleyl amine of oleic acid protection are modified, form orderly composite structure framework, the graphene film after heat treatment obtaining having rapid electric charge transmittability modifies iron electrode material.
For realizing technical scheme of the present invention, mainly should following steps be comprised:
1. molysite and oleate are dissolved in absolute ethyl alcohol, deionized water and aliphatic hydrocarbon mixed solvent by amount of substance than 1:1 ~ 1:10, volume ratio 1:1:1 ~ the 1:10:10 of absolute ethyl alcohol, deionized water and aliphatic hydrocarbon in mixed solvent, stirring reaction 0.5 ~ 6h at 40 ~ 100 DEG C, leave standstill, upper strata is the iron-based composite of oleic acid modified.
2. expanded graphite carbon dust is scattered in ultrasonic process 0.5 ~ 24h in the oleyl amine that volume ratio is 1:1 ~ 1:10 and aromatic hydrocarbon mixed solvent, removing insoluble matter, by mixed liquor 5000-10000 turn/min condition under centrifugal obtain oleyl amine modify nano-graphene sheet.
3. the nano-graphene sheet that oleyl amine in the iron oleate base complex and 2 obtained in 1 is modified is dissolved in aromatic hydrocarbon, stir 0 ~ 30min under 10 ~ 90 DEG C of water-baths after, proceeds to reactor, at 150 ~ 250 DEG C, react 0.5 ~ 12h.Product, through alcohol wash and washing, obtains the iron electrode precursor complex of graphene-containing sheet after drying.
4. the precursor complex that obtains in 3 to be heated up 400 ~ 1000 DEG C of heat treatment 0.5 ~ 12h with 1 ~ 20 DEG C/min under inert gas or nitrogen protection in tube furnace.Naturally cool to room temperature, the graphene film obtaining can filling for ferronickel secondary cell modifies iron electrode material.
Preferably, described molysite is the chloride of water-soluble iron, sulfate or nitrate.
Preferably, described oleate is enuatrol or potassium oleate.
Preferably, described aliphatic hydrocarbon to be carbon number be 5 ~ 8 saturated or unsaturation fat alkane.
Preferably, described aromatic hydrocarbon is the substituted benzene that carbon number is greater than 6.
Compared with prior art, the invention has the beneficial effects as follows:
1. iron-based nano active particle is fixed on the avtive spot of graphene film, inhibits the unordered reunion of nano particle and grows up, and the effective rate of utilization of active material is improved greatly.
2. nanometer electric active particle couples together by the Graphene network of high connductivity, significantly enhances the fast transport ability of iron electrode interface charge.
3. the technology of the present invention gained iron electrode material is applied to ferronickel secondary cell, and its high-rate charge-discharge capability is better.
accompanying drawing illustrates:
The scanning electron microscope (SEM) photograph that can fill secondary cell iron electrode material for ferronickel that Fig. 1 provides for embodiment 1.
embodiment:
Following examples are intended to further illustrate the present invention, and the correlated condition of employing does not limit the present invention.
embodiment 1
Take 9.6g FeCl 36H 2o and 23.9g enuatrol, is dissolved in 20ml absolute ethyl alcohol, in the mixed solvent of 40ml deionized water and 50ml n-hexane composition, and water bath with thermostatic control 2h at 85 DEG C.Leave standstill, get upper strata bronzing iron-based oleate with separatory funnel.Separately get 20mg thermal expansion graphene film, add in the mixed solvent be made up of 15ml oleyl amine and 20ml toluene, ultrasonic 12h.By mixed liquor centrifugal nano-graphene sheet obtaining oleyl amine and modify under 5000rpm condition.The nano-graphene sheet that 2g iron-based oleate and 20mg oleyl amine are modified is dissolved in 50ml dimethylbenzene, at 80 DEG C, proceeds to reactor after heating water bath 15min, at 150 DEG C, react 10h.Product, through alcohol wash and washing, obtains the iron electrode precursor complex of graphene film after drying, it is warming up to 300 DEG C of heat treatment 6h with 10 DEG C/min under inert gas shielding in tube furnace.Naturally cool to room temperature, the graphene film obtaining can filling for ferronickel secondary cell modifies iron electrode material.
embodiment 2
Take 8.7g FeCl 36H 2o and 55.6g enuatrol, is dissolved in 30ml absolute ethyl alcohol, in the mixed solvent of 60ml deionized water and 100ml n-hexane composition, and water bath with thermostatic control 2h at 85 DEG C.Leave standstill, get upper strata bronzing iron-based oleate with separatory funnel.Separately get 10mg thermal expansion graphene film, add in the mixed solvent be made up of 10ml oleyl amine and 20ml toluene, ultrasonic 12h.By mixed liquor centrifugal nano-graphene sheet obtaining oleyl amine and modify under 5000rpm condition.The nano-graphene sheet that 2g iron-based oleate and 10mg oleyl amine are modified is dissolved in 50ml dimethylbenzene, at 80 DEG C, proceeds to reactor after heating water bath 15min, at 150 DEG C, react 10h.Product, through alcohol wash and washing, obtains the iron electrode compound without heat treated graphene film after drying.
embodiment 3
Take 9.6g FeCl 36H 2o and 24.8g potassium oleate, is dissolved in 20ml absolute ethyl alcohol, in the mixed solvent of 40ml deionized water and 50ml n-hexane composition, and water bath with thermostatic control 4h at 75 DEG C.Leave standstill, get upper strata bronzing iron-based oleate with separatory funnel.Separately get 20mg thermal expansion graphene film, add in the mixed solvent be made up of 15ml oleyl amine and 20ml toluene, ultrasonic 12h.By mixed liquor centrifugal nano-graphene sheet obtaining oleyl amine and modify under 5000rpm condition.Take 1g iron-based oleate to mix with 100ml dimethylbenzene with 20mg thermal expansion graphene film, at 80 DEG C, proceed to reactor after heating water bath 15min, at 150 DEG C, react 12h.Product, through alcohol wash and washing, obtains the iron electrode precursor complex of graphene film after drying, it is warming up to 300 DEG C of heat treatment 6h with 10 DEG C/min under inert gas shielding in tube furnace.Naturally cool to room temperature, the graphene film obtaining can filling for ferronickel secondary cell modifies iron electrode material.
embodiment 4
Take 13.3g Fe 2(SO 4) 3with 70.5g enuatrol, be dissolved in 20ml absolute ethyl alcohol, in the mixed solvent of 50ml deionized water and 50ml n-hexane composition, water bath with thermostatic control 4h at 75 DEG C.Leave standstill, get upper strata bronzing iron-based oleate with separatory funnel.Separately get 10mg thermal expansion graphene film, add in the mixed solvent be made up of 15ml oleyl amine and 20ml toluene, ultrasonic 12h.By mixed liquor centrifugal nano-graphene sheet obtaining oleyl amine and modify under 8000rpm condition.Take 2g iron-based oleate to mix with 50ml dimethylbenzene with 5mg thermal expansion graphene film, at 80 DEG C, proceed to reactor after heating water bath 15min, at 180 DEG C, react 10h.Product, through alcohol wash and washing, obtains the iron electrode precursor complex of graphene film after drying, it is warming up to 400 DEG C of heat treatment 4h with 10 DEG C/min under inert gas shielding in tube furnace.Naturally cool to room temperature, the graphene film obtaining can filling for ferronickel secondary cell modifies iron electrode material.
embodiment 5
Take 12.1g Fe (NO 3) 3with 46.7g enuatrol, be dissolved in 20ml absolute ethyl alcohol, in the mixed solvent of 20ml deionized water and 50ml n-hexane composition, water bath with thermostatic control 2h at 85 DEG C.Leave standstill, get upper strata bronzing iron-based oleate with separatory funnel.Separately get 20mg thermal expansion graphene film, add in the mixed solvent be made up of 15ml oleyl amine and 20ml toluene, ultrasonic 12h.By mixed liquor centrifugal nano-graphene sheet obtaining oleyl amine and modify under 8000rpm condition.Take 2g iron-based oleate to mix with 50ml dimethylbenzene with 5mg thermal expansion graphene film, at 80 DEG C, proceed to reactor after heating water bath 15min, at 150 DEG C, react 10h.Product, through alcohol wash and washing, obtains the iron electrode precursor complex of graphene film after drying, it is warming up to 400 DEG C of heat treatment 4h with 20 DEG C/min under inert gas shielding in tube furnace.Naturally cool to room temperature, the graphene film obtaining can filling for ferronickel secondary cell modifies iron electrode material.
Table 1 is assembled into discharge capacity (mAh/g) contrast of nickel iron cell the 200th discharge and recharge under different electric current for iron electrode material that each embodiment provides.
Table 1
Iron electrode material discharge capacity 1A·g -1 2.5A·g -1 5A·g -1 7.5A·g -1 8.5A·g -1 10A·g -1
Embodiment 1 124 206 259 277 358 409
Embodiment 2 117 200 234 260 351 396
Embodiment 3 121 199 231 277 355 402
Embodiment 4 115 190 225 249 349 392
Embodiment 5 107 187 224 251 347 389

Claims (6)

1. can fill a preparation method for secondary cell iron electrode material for ferronickel, comprise the following steps:
Molysite and oleate are dissolved in absolute ethyl alcohol, deionized water and aliphatic hydrocarbon mixed solvent by amount of substance than 1:1 ~ 1:10, volume ratio 1:1:1 ~ the 1:10:10 of absolute ethyl alcohol, deionized water and aliphatic hydrocarbon in mixed solvent, stirring reaction 0.5 ~ 6h at 40 ~ 100 DEG C, leave standstill, upper strata is the iron-based composite of oleic acid modified;
Expanded graphite carbon dust is scattered in ultrasonic process 0.5 ~ 24h in the oleyl amine that volume ratio is 1:1 ~ 1:10 and aromatic hydrocarbon mixed solvent, removing insoluble matter, by mixed liquor 5000-10000 turn/min condition under centrifugal obtain oleyl amine modify nano-graphene sheet;
The nano-graphene sheet that the iron oleate base complex obtained in (1) and oleyl amine in (2) are modified is dissolved in aromatic hydrocarbon, stir 0 ~ 30min under 10 ~ 90 DEG C of water-baths after, proceeds to reactor, at 150 ~ 250 DEG C, react 0.5 ~ 12h; Product, through alcohol wash and washing, obtains the iron electrode precursor complex of graphene-containing sheet after drying;
The precursor complex obtained in (3) is warming up to 400 ~ 1000 DEG C of heat treatment 0.5 ~ 12h with 1 ~ 20 DEG C/min under inert gas or nitrogen protection in tube furnace; Naturally cool to room temperature, the graphene film obtaining can filling for ferronickel secondary cell modifies iron electrode material.
2. the preparation method that can fill secondary cell iron electrode material for ferronickel as described in claim 1, is characterized in that: the molysite described in step (1) is the chloride of water-soluble iron, sulfate or nitrate.
3. the preparation method that can fill secondary cell iron electrode material for ferronickel as described in claim 1, is characterized in that: the oleate described in step (1) is enuatrol or potassium oleate.
4. the preparation method that can fill secondary cell iron electrode material for ferronickel as described in claim 1, is characterized in that: the aliphatic hydrocarbon described in step (1) to be carbon number be 5 ~ 8 saturated or unsaturation fat alkane.
5. the preparation method that can fill secondary cell iron electrode material for ferronickel as described in claim 1, it is characterized in that: the expanded graphite carbon described in step (2) is natural flaky graphite, compact massive graphite or the artificial high purity graphite of chemistry or heat or microwave expansion.
6. the preparation method that can fill secondary cell iron electrode material for ferronickel as described in claim 1, is characterized in that: step (2) and the aromatic hydrocarbon described in (3) are the substituted benzene that carbon number is greater than 6.
CN201410815743.4A 2014-12-23 2014-12-23 A kind of preparation method that can fill secondary cell iron electrode material for ferronickel Expired - Fee Related CN104466169B (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105428626A (en) * 2015-12-18 2016-03-23 电子科技大学 Alkaline capacitor battery iron electrode and preparation method thereof
CN105552325A (en) * 2015-12-18 2016-05-04 电子科技大学 Iron electrode composite material and preparation method therefor
CN107335416A (en) * 2017-06-08 2017-11-10 浙江工业大学 A kind of catalyst nanoparticles dispersion liquid and preparation method and application
CN108615582A (en) * 2018-04-04 2018-10-02 苏州尤林斯新材料科技有限公司 A kind of preparation method based on nano silver wire, graphene composite and flexible transparent conductive film

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105428626A (en) * 2015-12-18 2016-03-23 电子科技大学 Alkaline capacitor battery iron electrode and preparation method thereof
CN105552325A (en) * 2015-12-18 2016-05-04 电子科技大学 Iron electrode composite material and preparation method therefor
CN105552325B (en) * 2015-12-18 2018-10-02 电子科技大学 Iron electrode composite material and preparation method
CN105428626B (en) * 2015-12-18 2018-10-02 电子科技大学 Alkaline capacitor batteries iron electrode and preparation method thereof
CN107335416A (en) * 2017-06-08 2017-11-10 浙江工业大学 A kind of catalyst nanoparticles dispersion liquid and preparation method and application
CN108615582A (en) * 2018-04-04 2018-10-02 苏州尤林斯新材料科技有限公司 A kind of preparation method based on nano silver wire, graphene composite and flexible transparent conductive film

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