CN105140508A - Method for preparing anode material Fe3O4/multi-wall carbon nanotube (MCNT) of lithium ion battery by hydrothermal method - Google Patents

Method for preparing anode material Fe3O4/multi-wall carbon nanotube (MCNT) of lithium ion battery by hydrothermal method Download PDF

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Publication number
CN105140508A
CN105140508A CN201510452413.8A CN201510452413A CN105140508A CN 105140508 A CN105140508 A CN 105140508A CN 201510452413 A CN201510452413 A CN 201510452413A CN 105140508 A CN105140508 A CN 105140508A
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mcnt
lithium ion
ion battery
solution
battery negative
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钟燕
吴状春
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Nanjing University of Science and Technology
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Nanjing University of Science and 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
    • H01M4/48—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
    • H01M10/05—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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • 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 discloses a method for preparing an anode material Fe3O4/multi-wall carbon nanotube (MCNT) of a lithium ion battery by a hydrothermal method. The preparation method comprises the following steps of: firstly, carrying out ultrasonic dispersion of the MCNT in a ferric chloride solution; secondly, stirring the solution and a sodium hydroxide solution and reacting to generate a red brown solution, carrying out hydrothermal reaction, cooling, cleaning and carrying out vacuum drying to obtain powder; and finally, sintering the powder in mixed gas, cooling to a room temperature, and preparing the anode material of the battery. The method has the advantages of wide availability in raw material and low production cost, the Fe3O4 synthesized according to the method is small and uniform in grain size, is high in crystallinity and conductivity, and has a favorable reversible capacity and a long cycle life.

Description

A kind of hydro thermal method prepares lithium ion battery negative material Fe 3o 4the method of/MCNT
Technical field
A kind of hydro thermal method technology in battery material preparation field that the invention belongs to prepares lithium ion battery negative material Fe 3o 4the method of/MCNT.
Background technology
Along with the exhaustion gradually of the main natural resources such as coal, oil, energy crisis has become one of key subjects that human future must solve.At present, the novel high-energy chemical power source of green non-pollution has become the focus competitively developed countries in the world.Theory and practice proves, lithium ion battery has the incomparable advantage of other secondary cells, with the characteristic such as its high voltage, high-energy-density, long-life, memory-less effect, self discharge be little, is widely used in the fields such as photoelectricity, information, traffic, national defense and military.Particularly along with the fast development of electric automobile and hybrid-electric car, people have higher requirement to lithium ion battery.
The negative pole mainly various material with carbon element of the lithium ion battery of industrialization at present, but it is low that material with carbon element also exists specific capacity, efficiency for charge-discharge is low, and organic solvent embeds deficiency altogether, therefore people also start the exploitation of the non-carbon material to other height ratio capacities while research material with carbon element, wherein Fe 3o 4due to its height ratio capacity and aboundresources, the characteristic of environmental protection, is considered to the very promising electrode material of one.
But Fe 3o 4the shortcoming existed as electrode material is that first Zhou Fang electricity has larger irreversible capacity, and coulombic efficiency is very low, and cycle performance is poor, and General Life is within 30 times.Current main research is the various nanometer Fe with special appearance of synthesis 3o 4and to Fe 3o 4carry out doping vario-property, be exactly and the compound of material with carbon element such as Graphene and carbon nano-tube etc. mainly.Zhou etc. are by the Fe of a kind of Graphene thin plate decoration of in-situ reactive synthesis 3o 4particle, after lower 30 circulations of 35mA/g, reversible capacity reaches 1026mAh/g, and under 700mA/g, after 100 circulations, reversible capacity has 580mAh/g (GuangminZhou, Da-WeiWang, FengLi, etal.Graphene-wrappedFe 3o 4anodematerialwithimprovedreversiblecapacityandcyclicstab ilityforlithiumionbatteries [J], Chemistyofmaterials, 22,2010,5306 – 5313).But the method complex steps, and Graphene belongs to two-dimensional structure, does not have the with the obvious advantage of carbon nano-tube.Wu etc. adopt water heat transfer FeOOH presoma, by itself and carbon nano-tube ULTRASONIC COMPLEX, do not add conductive agent and bonding agent, directly filter, make electrode.This electrode material is under 1C multiplying power, and after 50 circulations, reversible capacity is still at 1000mAh .g -1above.(ChunmeiBan, ZhuangchunWu, DaneT.Gillaspie, etal.NanostructuredFe 3o 4/ SWNTelectrode:binder-freeandhigh-rateli-ionanode [J], AdvancedMaterials, 22,2010, E145 – E149) but Single Walled Carbon Nanotube cost intensive, and filter method prepare film forming and be not suitable for large batch of industrial production, and very high to material morphology requirement, limit its practical application.
Current domestic relevant synthesis Fe 3o 4/ MCNT (multi-walled carbon nano-tubes) the patent being applied to lithium ion battery negative material also do not have, but about synthesis Fe 3o 4/ MCNT composite material, the patent being applied to catalysis and magnetic action has as follows, Chinese patent CN201210034375.0 discloses a kind of with multi-walled carbon nano-tubes, iron ammonium sulfate, iron chloride and NaOH are raw material, polyvinyl alcohol is as surfactant, reverse coprecipitation is adopted to obtain the method for ferroferric oxide/carbon nanotube magnetic nano composite material, but the method needs the translation of logical protection gas agitating, step is complicated, higher to equipment requirement, Chinese patent CN200810035150.0 discloses a kind of with MWCNTs, ethylene glycol, high iron chloride and sodium acetate are initiation material, cationic surfactant polymine is adopted to carry out surface modification to MWCNTs, add dispersant polyethylene glycol and polyvinylpyrrolidone again, the hot method of alcohol is adopted to prepare Fe 3o 4the method of/MWCNTs magnetic nanometer composite material, but the method applies a large amount of organic solution and surfactant, is unfavorable for biological environment and raw material comparatively complex and expensive.
Summary of the invention
A kind of hydro thermal method is the object of the present invention is to provide to prepare lithium ion battery negative material Fe 3o 4the method of/MCNT.
The invention provides a kind of hydro thermal method technology and prepare lithium ion battery negative material Fe 3o 4the method of/MCNT, comprises following implementation step:
(1) by MCNT ultrasonic disperse in ferric chloride solution;
(2) step (1) solution and sodium hydroxide solution are generated red tan solution under stirring reaction;
(3) by red tan solution hydro-thermal reaction 20-24h at 160-190 DEG C, after cooling, cleaning, vacuumize obtain powder;
(4) powder is sintered 1-2h in 350-380 DEG C under gaseous mixture, naturally cool to room temperature, obtain described Fe 3o 4/ MCNT cell negative electrode material.
Wherein, in step (1), ferric chloride solution concentration is the mass ratio of 0.1M, MCNT and iron chloride is 1.5%.
In step (2), described concentration of sodium hydroxide solution is 0.3M, and the mol ratio of NaOH and iron chloride is 20:3, and the stirring reaction time is not less than 1h.
In step (3), vacuumize temperature is not higher than 100 DEG C.
In step (4), described mist is Ar/H 2gaseous mixture, wherein H 2volume accounts for 5%.
In step (4), heating rate is 5-10 DEG C/min.
The present invention, compared with its prior art, has following remarkable advantage feature: (1) adopts hydro thermal method, and the material granule size tunable obtained, better crystallinity degree, consistency is high.(2) add multi-walled carbon nano-tubes at presoma, simplify synthesis step, and carbon nano-tube is combined closely with tri-iron tetroxide, increased substantially the electric conductivity of material; (3) this method raw material is simple, and preparation technology, equipment needed thereby are comparatively simple, and the time needed for synthesis is short, and manufacturing cycle is short, and cost is low, is conducive to large-scale industrial production.(4) Fe synthesized by the method 3o 4/ MCNT combination electrode material charge/discharge capacity is high, and cycle performance and high rate performance are all very outstanding, and under 0.1C multiplying power, electric discharge can reach 1711mAh/g first, and charging can reach 1209mAh/g, and coulombic efficiency is high.
Accompanying drawing explanation
Fig. 1 is the Fe of gained in the embodiment of the present invention 1 3o 4the XRD figure of/MCNT.
Fig. 2 is the Fe of gained in the embodiment of the present invention 1 3o 4the first charge-discharge figure of/MCNT.
Fig. 3 is the Fe of gained in the embodiment of the present invention 1 3o 4the high rate performance figure of/MCNT.
Fig. 4 is the Fe of gained in the embodiment of the present invention 1 3o 4the SEM figure of/MCNT.
Fig. 5 is the Fe of gained in the embodiment of the present invention 2 3o 4the high rate performance figure of/MCNT.
Fig. 6 is the Fe of gained in the embodiment of the present invention 3 3o 4the high rate performance figure of/MCNT.
Embodiment
The present invention is that hydro thermal method technology prepares lithium ion battery negative material Fe 3o 4the method of/MCNT, specifically comprises following implementation step:
Example 1
(1) by MCNT ultrasonic disperse in ferric chloride solution: take MCNT11mg, ferric chloride hexahydrate 1.215g, be dissolved in 40ml water, under condition of ice bath, use cell pulverization instrument to carry out ultrasonic to it, power is 40%, effective time is 30min, excusing from death 2s, rest 2s, MCNT quality accounts for 1.5% of iron chloride quality.
(2) step (1) solution, under magnetic agitation effect, is dropwise joined 0.3M, in the sodium hydroxide solution of 100ml, at room temperature stir and be no less than 1h, generate uniform red tan solution.
(3) by red tan solution hydro-thermal reaction 24h at 160 DEG C in hydrothermal reaction kettle, cool rear deionization and alcohol cleans three times in centrifuges respectively, at 80 DEG C, vacuum, dry 12h obtains powder;
(4) by powder (Ar/H under gaseous mixture protection 2gaseous mixture, wherein H 2volume accounts for 5%) in 350 DEG C of sintering 1.5h, naturally cool to room temperature, obtain described Fe 3o 4/ MCNT cell negative electrode material.
Fig. 1 is Fe obtained under example 1 condition 3o 4the XRD figure of/MCNT, contrasts PDF card known from Fig. 1, and Fe 3o 4peak position is coincide, and is Fe 3o 4phase, and the MCNT added is not because amount very little, has carbon cutting edge of a knife or a sword to occur.
Fig. 2 is Fe obtained under example 1 condition 3o 4the first charge-discharge figure of/MCNT, first charge-discharge specific capacity can reach 1711 and 1209mAh/g respectively as can be known from Fig. 2, and coulombic efficiency is high, and chemical property is good.
Fig. 3 is Fe obtained under example 1 condition 3o 4the high rate performance figure of/MCNT, under 1C multiplying power, capacity still has about 900mAh/g, and high rate performance is good.
Fig. 4 is Fe obtained under example 1 condition 3o 4the SEM figure of/MCNT, as can be seen from Figure 4 bar-shaped in rule of particle, particle is tiny, is evenly distributed, MCNT be wound around and rod between rod, combine well.
Example 2
According to the lithium ion battery negative material Fe described in embodiment 1 3o 4the preparation method of/MCNT, takes MCNT3.7mg, and ferric chloride hexahydrate 1.215g, MCNT quality accounts for 0.5% of iron chloride quality.
Fig. 5 is Fe obtained under example 2 condition 3o 4the high rate performance figure of/MCNT.As can be seen from Figure 5 electric discharge only has 1100mAh/g first, and under 1C multiplying power, capacity only reaches 600mAh/g, far below the capacity of products therefrom in example 1.This is because the MCNT added is very few, electrode material electric conductivity is poor.
Example 3
According to the lithium ion battery negative material Fe described in embodiment 1 3o 4the preparation method of/MCNT, takes MCNT18.3mg, and ferric chloride hexahydrate 1.215g, MCNT quality accounts for 2.5% of iron chloride quality.
Fig. 6 is Fe obtained under example 3 condition 3o 4the high rate performance figure of/MCNT.As can be seen from Figure 6 electric discharge only has 1250mAh/g first, and under 1C multiplying power, capacity only reaches 500mAh/g, far below the capacity of products therefrom in example 1.This is because the MCNT added is too much, cause active material quality relatively to reduce, capacity reduces, and MCNT excessive easily causing is wound around connection, the transfer rate of the electronics that slows down, thus conductivity is deteriorated.

Claims (6)

1. a hydro thermal method prepares lithium ion battery negative material Fe 3o 4the method of/MCNT, is characterized in that, comprises the steps:
(1) by MCNT ultrasonic disperse in ferric chloride solution;
(2) step (1) solution and sodium hydroxide solution are generated red tan solution under stirring reaction;
(3) by red tan solution hydro-thermal reaction 20-24h at 160 DEG C-190 DEG C, after cooling, cleaning, vacuumize obtain powder;
(4) powder is sintered 1-2h in 350 DEG C-380 DEG C under gaseous mixture, naturally cool to room temperature, obtain described Fe 3o 4/ MCNT cell negative electrode material.
2. a kind of hydro thermal method according to claim 1 prepares lithium ion battery negative material Fe 3o 4the method of/MCNT, is characterized in that: in step (1), and described MCNT and the mass ratio of iron chloride are 0.5%-2.5%.
3. a kind of hydro thermal method according to claim 1 prepares lithium ion battery negative material Fe 3o 4the method of/MCNT, is characterized in that: in step (1), and described MCNT and the mass ratio of iron chloride are 1.5%.
4. a kind of hydro thermal method according to claim 1 prepares lithium ion battery negative material Fe 3o 4the method of/MCNT, is characterized in that: in step (2), and the mol ratio of NaOH and iron chloride is 20:3, and the stirring reaction time is no less than 1 hour.
5. a kind of hydro thermal method according to claim 1 prepares lithium ion battery negative material Fe 3o 4the method of/MCNT, is characterized in that: in step (3), and described bake out temperature is not higher than 100 DEG C.
6. a kind of hydro thermal method according to claim 1 prepares lithium ion battery negative material Fe 3o 4the method of/MCNT, is characterized in that: in step (4), and heating rate is 5 DEG C-10 DEG C/min; Described mist is Ar/H 2gaseous mixture, wherein, H 2volume accounts for 5%.
CN201510452413.8A 2015-07-28 2015-07-28 Method for preparing anode material Fe3O4/multi-wall carbon nanotube (MCNT) of lithium ion battery by hydrothermal method Pending CN105140508A (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109088060A (en) * 2018-08-01 2018-12-25 武汉理工大学 A kind of lithium ion battery negative material preparation method based on ionic bond
CN110492080A (en) * 2019-08-27 2019-11-22 天津大学 Carbon/di-iron trioxide/multi-wall carbon nano-tube composite material and preparation method for negative electrode of lithium ion battery
CN111318257A (en) * 2020-03-12 2020-06-23 广州大学 Modified carbon nano-film and preparation method thereof
CN114639815A (en) * 2022-04-08 2022-06-17 东莞市沃泰通新能源有限公司 Preparation method of sodium ion battery negative electrode material, negative electrode sheet and sodium ion battery

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CN103531789A (en) * 2012-12-27 2014-01-22 中国矿业大学 Iron oxide-carbon nanotube ternary composite material and preparation method thereof

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CN103531789A (en) * 2012-12-27 2014-01-22 中国矿业大学 Iron oxide-carbon nanotube ternary composite material and preparation method thereof

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XIAOYU LI等: "Multi-walled carbon nanotubes composited with nanomagnetite for anodes in lithium ion batteries", 《ROYAL SOCIETY OF CHEMISTRY》 *
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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109088060A (en) * 2018-08-01 2018-12-25 武汉理工大学 A kind of lithium ion battery negative material preparation method based on ionic bond
CN109088060B (en) * 2018-08-01 2021-07-20 武汉理工大学 Preparation method of lithium ion battery cathode material based on ionic bond
CN110492080A (en) * 2019-08-27 2019-11-22 天津大学 Carbon/di-iron trioxide/multi-wall carbon nano-tube composite material and preparation method for negative electrode of lithium ion battery
CN110492080B (en) * 2019-08-27 2022-03-11 天津大学 Carbon/ferric oxide/multi-walled carbon nanotube composite material for lithium ion battery cathode and preparation method thereof
CN111318257A (en) * 2020-03-12 2020-06-23 广州大学 Modified carbon nano-film and preparation method thereof
CN111318257B (en) * 2020-03-12 2021-11-19 广州大学 Modified carbon nano-film and preparation method thereof
CN114639815A (en) * 2022-04-08 2022-06-17 东莞市沃泰通新能源有限公司 Preparation method of sodium ion battery negative electrode material, negative electrode sheet and sodium ion battery

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