CN102623693A - High specific capacity spindle-shaped ferroferric oxide/carbon nano composite material for negative electrode of lithium ion battery - Google Patents
High specific capacity spindle-shaped ferroferric oxide/carbon nano composite material for negative electrode of lithium ion battery Download PDFInfo
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- CN102623693A CN102623693A CN2012101091244A CN201210109124A CN102623693A CN 102623693 A CN102623693 A CN 102623693A CN 2012101091244 A CN2012101091244 A CN 2012101091244A CN 201210109124 A CN201210109124 A CN 201210109124A CN 102623693 A CN102623693 A CN 102623693A
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Abstract
The invention discloses a high specific capacity spindle-shaped ferroferric oxide/carbon nano composite material for a negative electrode of a lithium ion battery. A raw material, namely soluble ferric salt is solved in a mixed solvent of glycerol and distilled water; after low-temperature treatment, precipitates are collected, and a spindle-shaped iron oxide hydroxide (FeOOH) precursor is obtained; and after the precursor is subject to carbothermal reduction, the ferroferric oxide/carbon nano composite material with the same appearance is obtained. The invention discloses a preparation method of the spindle-shaped ferroferric oxide/carbon, which has the advantages that the operation is simple, convenient and simple to do, the used raw material has a cheap price, mass production is facilitated, and the synthetized spindle-shaped ferroferric oxide/carbon nano composite material shows high first time coulomb efficiency and high specific capacity when being used as the negative electrode of the lithium ion battery, and is a promising negative electrode material of the lithium ion battery.
Description
Technical field
The present invention relates to a kind of fusiformis tri-iron tetroxide/carbon composite that is used for the high energy density lithium ion GND; The preparation and the lithium ion battery applications field that belong to nano material.
Background technology
One of key of exploitation lithium ion battery is to seek suitable electrode material; Make battery have sufficiently high lithium embedded quantity and take off the embedding invertibity with good lithium; With the big capacity and the long circulation life of assurance lithium ion battery, thereby promote the application of lithium ion battery at aspects such as electric motor car, intelligent grids.
As far back as the late nineteen eighties in last century, metal oxide is TiO for example
2, W
2O
3, SnO
2Deng being proved to be performance with reversible lithium storage.French afterwards Tarascon group (Nature, 2000,407; 496.) find that nano-structural transition metal oxide MOx (M=Co, Fe, Ni etc.) can have electro-chemical activity with the lithium reaction; And then reversible storage lithium, its capacity is approximately 500～1000mAh/g, is higher than commercial carbon negative pole material; This has important Practical significance for development high capacity lithium ion battery of new generation, and the transition metal oxide negative material has caused numerous scholars' interest subsequently.But, through discovering this type of oxide cathode material enclosed pasture efficient lower (Energy Environ.Sci., 2011 first in charge and discharge process; 4; 2682-2699), capacitance loss is higher, and part is up to 40%; And cycle performance is poor, so improve first enclosed pasture efficient and improve cyclical stability and become current main task.
In the last few years, Fe
3O
4Be widely used in every field, such as information storage, Magnetic Isolation, nulcear magnetic resonance (NMR) video picture etc., in addition because Fe
3O
4Have high theoretical capacity (924mAh/g), higher electron conductivity (2 * 10
4S m
-1) advantage such as aboundresources, safety non-toxic and proposed can be used as a kind of desirable lithium ion battery negative material first by French Tarascon group (Nature, 2000,407,496.), and cause people's attention gradually.People such as Taberna (Nat.Mater., 2006,5,567) have reported the Fe that is distributed in the Cu nanometer stick array structure
3O
4Electrode reaches 800mAh/g as the negative material of the lithium ion battery specific capacity when the C/32, and has good high rate performance, but its manufacture craft more complicated.Because the electrode change in volume that transition metal oxide causes when lithium ion embeds and deviates from has caused its large-scale application aspect lithium ion battery to be hindered.In order to overcome these shortcomings, generally need prepare metal oxide with special nanostructure, perhaps metal oxide is coated with compound the volumetric expansion of electrode in the buffer cycles process.LouX.W. (J.Phys.Chem.C, 2011,115,9814-9820) utilize hydro thermal method at first to synthesize the bar-shaped FeOOH that glucose coats, it is calcined in inert atmosphere obtain Fe then
3O
4/ C composite material after 100 circulations, can keep the capacity of 800mAh/g, but coulombic efficiency is lower first for it, and cyclical stability neither be fine.Wang G.X. (Chem.Eur.J., 2012,18,488-497) through the synthetic polyhedron Fe of low temperature
3O
4Though discharge capacity is up to 2600mAh/g first, reversible first charging capacity has only 1300mAh/g, and enclosed pasture efficient has only 50% first, and irreversible capacity loss is more serious.Remain current main task so improve the coulombic efficiency first of lithium ion battery negative material.
Lot of domestic and international scholar is devoted to Fe
3O
4Preparation method's research, people have prepared the Fe of various patterns through chemical precipitation method, Hydrolyze method, hydro thermal method, sol-gal process etc.
3O
4According to application demand, people generally hope to obtain controllable grain size, technology is simple, cost is low Fe
3O
4Material.Yet, in existing synthetic method, at first, again it is not also appeared in the newspapers through the method that carbon thermal reduction obtains the fusiformis tri-iron tetroxide/carbon nano-composite material of similar pattern through the pattern of regulation and control presoma through retrieval.
Summary of the invention
Deficiency to prior art; The invention provides a kind of reasonable in design, technology is simple, pattern is controlled, even size distribution and the preparation method of the higher tri-iron tetroxide/carbon nano-composite material of enclosed pasture efficient and specific capacity first, utilizes this method can obtain a kind of height ratio capacity fusiformis tri-iron tetroxide/carbon nano-composite material that is used for lithium ion battery negative.
Technical scheme of the present invention is to have designed a kind of easy carbothermic method, and at first the mixed liquor with glycerine and distilled water is a solvent, and soluble ferric iron salt is a raw material, and iron oxide hydroxide (FeOOH) presoma of synthetic fusiformis obtains fusiformis Fe with it through carbon thermal reduction again
3O
4/ C compound.Then with the Fe for preparing
3O
4/ C and acetylene black and binding agent (Kynoar+N-methyl pyrrolidone) mix and process electrode slice; Electrode slice is formed button cell in glove box, at room temperature measure its discharge capacity and reversible charging capacity first, with check Fe
3O
4/ C nano composite material is as the chemical property of lithium ion battery negative material.
The height ratio capacity fusiformis tri-iron tetroxide/carbon (Fe that is used for lithium ion battery negative of the present invention
3O
4/ C) nano composite material is characterized in that said fusiformis tri-iron tetroxide/carbon nano-composite material is made by following method:
(1) be that 1: 1～1: 19 mixed is as solvent by volume with glycerine and distilled water; In solvent, add soluble ferric iron salt by soluble ferric iron salt and solvent with the proportional quantities of 2～15mmol: 40mL; Magnetic agitation 10～30min makes molysite dissolve fully;
(2) solution that step (1) is made is transferred to and is had in the teflon-lined agitated reactor, places 100～180 ℃ baking oven to react 5～30h;
(3) agitated reactor is naturally cooled to room temperature, suction filtration is isolated product then, washes 3～5 times with distilled water, absolute ethyl alcohol respectively, puts in 100 ± 10 ℃ the baking oven dryly, and obtaining orange-yellow iron oxide hydroxide (FeOOH) solid is fusiformis iron oxide hydroxide presoma;
(4) in the mass ratio of glucose and iron oxide hydroxide be 1: 1～10: 1 ratio; Take by weighing the iron oxide hydroxide that makes in glucose and the step (3) respectively, ultrasonic 20～30min is dispersed in the distilled water it, is transferred to hydrothermal reaction kettle then; Place 180 ± 10 ℃ baking oven to react 4～5h; Then agitated reactor is naturally cooled to room temperature, centrifugalize out product, put in 100 ± 10 ℃ the baking oven dry;
(5) product that step (4) is made places 300～650 ℃ blanket of nitrogen, calcines 2～10h, obtains the lithium ion battery negative material of height ratio capacity, i.e. fusiformis tri-iron tetroxide/carbon (Fe
3O
4/ C) nano composite material.
Wherein, the volume ratio of said glycerine of step (1) and distilled water is preferred 1: 3～1: 8.
Wherein, the preferred FeCl of the said soluble ferric iron salt of step (1)
3Or Fe (NO
3)
3
Wherein, said soluble ferric iron salt of step (1) and solvent are preferably with 2～8mmol: the proportional quantities of 40mL adds soluble ferric iron salt in solvent.
Wherein, preferred 120～160 ℃ of the said temperature of step (2), preferred 5～15h of reaction time.
Wherein, the mass ratio of said glucose of step (4) and iron oxide hydroxide be preferably 4: 1～10: 1.
Wherein, preferred 450-600 ℃ of the said calcining heat of step (5), the preferred 3～6h of calcination time.
The height ratio capacity fusiformis tri-iron tetroxide/carbon (Fe that is used for lithium ion battery negative according to the invention
3O
4/ C) the application of nano composite material in preparation high energy density lithium ion battery.
Further, the method for said application is: (1) is that 7: 2: 1 ratio takes by weighing fusiformis tri-iron tetroxide/carbon (Fe according to mass ratio
3O
4/ C) nano composite material, acetylene black, Kynoar put into crucible and ground 10min, adds the N-methyl pyrrolidone then and continues to grind 20～30min; Make mixture in the pasty state; Then it is applied on the Copper Foil uniformly, dry 12～20h rolls this Copper Foil afterwards under 100 ± 10 ℃ of conditions; Be cut into the certain disk of diameter, process electrode slice; (2) in being full of the glove box of argon gas, electrode slice, barrier film, lithium sheet and nickel foam are assembled into button cell with conventional method.
At room temperature measure the discharge capacity first and the reversible charging capacity of the button cell of processing with test method, the coulombic efficiency first when checking fusiformis tri-iron tetroxide/carbon nano-composite material as lithium ion battery negative.
Result of the test: under the speed of 200mA/g, discharge capacity is 1367.8mAh/g first, and reversible first charging capacity is 1094.5mAh/g, so enclosed pasture efficient reaches 80% first.
The present invention at first utilizes simple solvent-thermal method to prepare iron oxide hydroxide (FeOOH) presoma of fusiformis, then with the carbon thermal reduction of presoma process, has improved the crystallinity of product, simultaneously carbon is coated on Fe
3O
4The surface, made fusiformis tri-iron tetroxide/carbon composite, and studied its chemical property as lithium ion battery negative material, comprise the first charge-discharge capacity and first the enclosed pasture efficient.The charge/discharge capacity that it is higher and first coulombic efficiency overcome the shortcoming of conventional transition metal oxide negative material, make it that potential application arranged in the lithium ion battery field.
The preparation method of fusiformis tri-iron tetroxide/carbon nano-composite material according to the invention; Easy to operation; Raw materials used low price; Be easy to large-scale production, the tri-iron tetroxide/carbon nano-composite material of the fusiformis of being synthesized has overcome traditional negative material enclosed pasture shortcoming that efficient is low, specific capacity is low first, is suitable as lithium ion battery negative material and large-scale application.
Description of drawings
Fig. 1 XRD figure; Wherein: the XRD figure of iron oxide hydroxide (FeOOH) presoma that a is prepared; The Fe that b is prepared
3O
4The XRD figure of/C nano composite material.
The TEM picture of iron oxide hydroxide (FeOOH) presoma that Fig. 2 is prepared.
Fig. 3 Fe
3O
4The first time of/C and the charging and discharging curve figure second time.
Embodiment
Embodiment 1:
(1) with glycerine and distilled water be by volume 1: 4 mixed as solvent, in solvent, add soluble ferric iron salt by soluble ferric iron salt and solvent with the proportional quantities of 3mmol: 40mL, magnetic agitation 25min makes molysite dissolve fully;
(2) solution that step (1) is made is transferred to and is had in the teflon-lined agitated reactor, places 120 ℃ baking oven to react 12h;
(3) agitated reactor is naturally cooled to room temperature, suction filtration is isolated product then, washes 5 times with distilled water, absolute ethyl alcohol respectively, puts in 100 ℃ the baking oven dryly, and obtaining orange-yellow iron oxide hydroxide (FeOOH) solid is fusiformis iron oxide hydroxide presoma;
(4) in the mass ratio of glucose and iron oxide hydroxide be 5: 1 ratio; Take by weighing the iron oxide hydroxide that makes in glucose and the step (3) respectively, ultrasonic 30min is dispersed in the distilled water it, is transferred to hydrothermal reaction kettle then; Place 180 ℃ baking oven to react 5h; Then agitated reactor is naturally cooled to room temperature, centrifugalize out product, put in 100 ℃ the baking oven dry;
(5) product that step (4) is made places 450 ℃ blanket of nitrogen, calcines 3h, obtains the lithium ion battery negative material of height ratio capacity, i.e. fusiformis tri-iron tetroxide/carbon (Fe
3O
4/ C) nano composite material.
(6) take by weighing 0.07g tri-iron tetroxide/carbon, 0.02g acetylene black, 0.01g Kynoar and in crucible, grind 10min; Adding N-methyl pyrrolidone continuation grinding 20min then must be with the mixture of pasty state; It is applied on the Copper Foil uniformly, and dry 12h under 100 ℃ of conditions rolls this Copper Foil afterwards; Be cut into the disk that diameter is 12mm, process electrode slice; In being full of the glove box of argon gas, electrode slice, barrier film, lithium sheet and nickel foam are assembled into button cell with conventional method.Speed with 200mA/g is carried out electrochemical property test in the constant current charge-discharge system.
Embodiment 2:
(1) with glycerine and distilled water be by volume 1: 3 mixed as solvent, in solvent, add soluble ferric iron salt by soluble ferric iron salt and solvent with the proportional quantities of 7mmol: 40mL, magnetic agitation 25min makes molysite dissolve fully;
(2) solution that step (1) is made is transferred to and is had in the teflon-lined agitated reactor, places 160 ℃ baking oven to react 12h;
(3) agitated reactor is naturally cooled to room temperature, suction filtration is isolated product then, washes 5 times with distilled water, absolute ethyl alcohol respectively, puts in 100 ℃ the baking oven dryly, and obtaining orange-yellow iron oxide hydroxide (FeOOH) solid is fusiformis iron oxide hydroxide presoma;
(4) in the mass ratio of glucose and iron oxide hydroxide be 7: 1 ratio; Take by weighing the iron oxide hydroxide that makes in glucose and the step (3) respectively, ultrasonic 30min is dispersed in the distilled water it, is transferred to hydrothermal reaction kettle then; Place 180 ℃ baking oven to react 5h; Then agitated reactor is naturally cooled to room temperature, centrifugalize out product, put in 100 ℃ the baking oven dry;
(5) product that step (4) is made places 600 ℃ blanket of nitrogen, calcines 6h, obtains the lithium ion battery negative material of height ratio capacity, i.e. fusiformis tri-iron tetroxide/carbon (Fe
3O
4/ C) nano composite material.
(6) take by weighing 0.07g tri-iron tetroxide/carbon, 0.02g acetylene black, 0.01g Kynoar and in crucible, grind 10min; Adding N-methyl pyrrolidone continuation grinding 20min then must be with the mixture of pasty state; It is applied on the Copper Foil uniformly, and dry 12h under 100 ℃ of conditions rolls this Copper Foil afterwards; Be cut into the disk that diameter is 12mm, process electrode slice; In being full of the glove box of argon gas, electrode slice, barrier film, lithium sheet and nickel foam are assembled into button cell with conventional method.Speed with 200mA/g is carried out electrochemical property test in the constant current charge-discharge system.
Embodiment 3:
(1) with glycerine and distilled water be by volume 1: 5 mixed as solvent, in solvent, add soluble ferric iron salt by soluble ferric iron salt and solvent with the proportional quantities of 5mmol: 40mL, magnetic agitation 25min makes molysite dissolve fully;
(2) solution that step (1) is made is transferred to and is had in the teflon-lined agitated reactor, places 150 ℃ baking oven to react 15h;
(3) agitated reactor is naturally cooled to room temperature, suction filtration is isolated product then, washes 5 times with distilled water, absolute ethyl alcohol respectively, puts in 100 ℃ the baking oven dryly, and obtaining orange-yellow iron oxide hydroxide (FeOOH) solid is fusiformis iron oxide hydroxide presoma;
(4) in the mass ratio of glucose and iron oxide hydroxide be 8: 1 ratio, take by weighing the iron oxide hydroxide that makes in glucose and the step (3) respectively, ultrasonic 30min is dispersed in the distilled water it; Be transferred to hydrothermal reaction kettle then;, place 180 ℃ baking oven to react 5h, then agitated reactor is naturally cooled to room temperature; Centrifugalize out product, put in 100 ℃ the baking oven dry;
(5) product that step (4) is made places 500 ℃ blanket of nitrogen, calcines 5h, obtains the lithium ion battery negative material of height ratio capacity, i.e. fusiformis tri-iron tetroxide/carbon (Fe
3O
4/ C) nano composite material.
(6) take by weighing 0.07g tri-iron tetroxide/carbon, 0.02g acetylene black, 0.01g Kynoar and in crucible, grind 10min; Adding N-methyl pyrrolidone continuation grinding 20min then must be with the mixture of pasty state; It is applied on the Copper Foil uniformly, and dry 12h under 100 ℃ of conditions rolls this Copper Foil afterwards; Be cut into the disk that diameter is 12mm, process electrode slice; In being full of the glove box of argon gas, electrode slice, barrier film, lithium sheet and nickel foam are assembled into button cell with conventional method.Speed with 200mA/g is carried out electrochemical property test in the constant current charge-discharge system.
Claims (9)
1. height ratio capacity fusiformis tri-iron tetroxide/carbon nano-composite material that is used for lithium ion battery negative is characterized in that said fusiformis tri-iron tetroxide/carbon nano-composite material is made by following method:
(1) be that 1: 1～1: 19 mixed is as solvent by volume with glycerine and distilled water; In solvent, add soluble ferric iron salt by soluble ferric iron salt and solvent with the proportional quantities of 2～15mmol: 40mL; Magnetic agitation 10～30min makes molysite dissolve fully;
(2) solution that step (1) is made is transferred to and is had in the teflon-lined agitated reactor, places 100～180 ℃ baking oven to react 5～30h;
(3) agitated reactor is naturally cooled to room temperature, suction filtration is isolated product then, washes 3～5 times with distilled water, absolute ethyl alcohol respectively, puts in 100 ± 10 ℃ the baking oven dryly, and obtaining orange-yellow iron oxide hydroxide (FeOOH) solid is fusiformis iron oxide hydroxide presoma;
(4) in the mass ratio of glucose and iron oxide hydroxide be 1: 1～10: 1 ratio; Take by weighing the iron oxide hydroxide that makes in glucose and the step (3) respectively, ultrasonic 20～30min is dispersed in the distilled water it, is transferred to hydrothermal reaction kettle then; Place 180 ± 10 ℃ baking oven to react 4～5h; Then agitated reactor is naturally cooled to room temperature, centrifugalize out product, put in 100 ± 10 ℃ the baking oven dry;
(5) product that step (4) is made places 300～650 ℃ blanket of nitrogen, calcines 2～10h, obtains the lithium ion battery negative material of height ratio capacity, i.e. fusiformis tri-iron tetroxide/carbon (Fe
3O
4/ C) nano composite material.
2. be used for the height ratio capacity fusiformis tri-iron tetroxide/carbon nano-composite material of lithium ion battery negative according to claim 1, it is characterized in that, the volume ratio of said glycerine of step (1) and distilled water is 1: 3～1: 8.
3. be used for the height ratio capacity fusiformis tri-iron tetroxide/carbon nano-composite material of lithium ion battery negative according to claim 1, it is characterized in that, the said soluble ferric iron salt of step (1) is FeCl
3Or Fe (NO
3)
3
4. the height ratio capacity fusiformis tri-iron tetroxide/carbon nano-composite material that is used for lithium ion battery negative according to claim 1; It is characterized in that said soluble ferric iron salt of step (1) and solvent add soluble ferric iron salt with the proportional quantities of 2～8mmol: 40mL in solvent.
5. be used for the height ratio capacity fusiformis tri-iron tetroxide/carbon nano-composite material of lithium ion battery negative according to claim 1, it is characterized in that, the said temperature of step (2) is 120～160 ℃, and the reaction time is 5～15h.
6. be used for the height ratio capacity fusiformis tri-iron tetroxide/carbon nano-composite material of lithium ion battery negative according to claim 1, it is characterized in that, the mass ratio of said glucose of step (4) and iron oxide hydroxide is 4: 1～10: 1.
7. be used for the height ratio capacity fusiformis tri-iron tetroxide/carbon nano-composite material of lithium ion battery negative according to claim 1, it is characterized in that, the said calcining heat of step (5) is 450～600 ℃, and calcination time is 3～6h.
8. be used for of the application of the height ratio capacity fusiformis tri-iron tetroxide/carbon nano-composite material of lithium ion battery negative according to claim 1 at preparation high energy density lithium ion battery.
9. application as claimed in claim 8 is characterized in that: the method for said application is: (1) is that 7: 2: 1 ratio takes by weighing fusiformis tri-iron tetroxide/carbon (Fe according to mass ratio
3O
4/ C) nano composite material, acetylene black, Kynoar put into crucible and ground 10min, adds the N-methyl pyrrolidone then and continues to grind 20～30min; Make mixture in the pasty state; Then it is applied on the Copper Foil uniformly, dry 12～20h rolls this Copper Foil afterwards under 100 ± 10 ℃ of conditions; Be cut into the certain disk of diameter, process electrode slice; (2) in being full of the glove box of argon gas, electrode slice, barrier film, lithium sheet and nickel foam are assembled into button cell with conventional method.
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| CN103219510A (en) * | 2013-03-21 | 2013-07-24 | 华中科技大学 | Lithium battery negative electrode material preparation method and its product |
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101492576A (en) * | 2008-01-22 | 2009-07-29 | 中国科学院化学研究所 | Carbon nano-complex particle, preparation and uses thereof |
-
2012
- 2012-04-13 CN CN201210109124.4A patent/CN102623693B/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101492576A (en) * | 2008-01-22 | 2009-07-29 | 中国科学院化学研究所 | Carbon nano-complex particle, preparation and uses thereof |
Non-Patent Citations (5)
| Title |
|---|
| 《无机化学学报》 20091231 郭培志等 纺锤形beta-FeOOH纳米结构和alpha-氧化铁亚微米/微米粒子的合成与转变 第25卷, 第4期 * |
| TING ZHU，ETAL: "Glusoce-Assisted one-pot synthesis of FeOOHnanorods and their transformation to Fe3O4/Carbon nanorods for applications in lithium ion batteries", 《JOURNAL OF PHYSICAL CHEMISTRY C》 * |
| WEI MING ZHANG，ETAL: "carbon coated Fe3O4 nanospindles as a superior anode material for lithium-ion batteries", 《ADVANCED FUNCTIONAL MATERIALS》 * |
| 郭培志等: "纺锤形β-FeOOH纳米结构和α-氧化铁亚微米/微米粒子的合成与转变", 《无机化学学报》 * |
| 钭启升等: "氧化铁和羟基氧化铁纳米结构的水热法制备及其表征", 《无机材料学报 》 * |
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