CN102623693B - 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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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 for lithium ion battery with high energy density negative pole; Belong to preparation and the lithium ion battery applications field of nano material.
Background technology
One of key of exploitation lithium ion battery is to find suitable electrode material, make battery there is sufficiently high lithium embedded quantity and good lithium deintercalation invertibity, to ensure large capacity and the long circulation life of lithium ion battery, thereby promote the application of lithium ion battery at the aspect such as electric motor car, intelligent grid.
As far back as late nineteen eighties in last century, metal oxide is TiO such as
2, W
2o
3, SnO
2deng being proved to be the performance with reversible lithium storage.French Tarascon (the Nature of group afterwards, 2000,407,496.) find nano-structural transition metal oxide MOx (M=Co, Fe, Ni etc.) can react and there is electro-chemical activity with lithium, and then reversible storage lithium, its capacity is approximately 500～1000mAh/g, higher than commercial carbon negative pole material, this has important Practical significance for development high capacity lithium ion battery of new generation, and transition metal oxide negative material has caused numerous scholars' interest subsequently.But, find this type of oxide cathode material lower (Energy Environ.Sci. of coulomb efficiency first in charge and discharge process through research, 2011,4,2682-2699), capacitance loss is higher, and part is up to 40%, and cycle performance is poor, become current main task so improve first coulomb efficiency and improve cyclical stability.
In the last few years, Fe
3o
4be widely used in every field, such as information storage, Magnetic Isolation, magnetic resonance imaging etc., in addition due to Fe
3o
4there is higher 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 first a kind of desirable lithium ion battery negative material by French Tarascon group (Nature, 2000,407,496.), and cause gradually people's concern.The people such as Taberna (Nat.Mater., 2006,5,567) have reported the Fe being distributed in Cu nanometer stick array structure
3o
4as the negative material of lithium ion battery, the specific capacity when the C/32 reaches 800mAh/g to electrode, and has good high rate performance, but its manufacture craft more complicated.Due to the electrode change in volume that transition metal oxide causes in the time that lithium ion embeds and deviates from, cause its large-scale application aspect lithium ion battery to be hindered.In order to overcome these shortcomings, need under normal circumstances preparation to there is the metal oxide of special nanostructure, or metal oxide is coated with compound to the volumetric expansion of electrode in buffer cycles process.LouX.W. (J.Phys.Chem.C, 2011,115,9814-9820) utilizes hydro thermal method first to synthesize the coated bar-shaped FeOOH of glucose, then it calcined and obtains Fe in inert atmosphere
3o
4/ C composite material, can keep the capacity of 800mAh/g, but coulombic efficiency is lower first for it after 100 circulations, and cyclical stability neither be fine.Wang G.X. (Chem.Eur.J., 2012,18,488-497) is by the synthetic polyhedron Fe of low temperature
3o
4although discharge capacity is up to 2600mAh/g first, reversible charging capacity only has 1300mAh/g first, and coulomb efficiency only has 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 by chemical precipitation method, Hydrolyze method, hydro thermal method, sol-gal process etc.
3o
4.According to application demand, people generally wish to obtain controllable grain size, technique is simple, cost is low Fe
3o
4material.But,, in existing synthetic method, first by the pattern of regulation and control presoma, then passed through the method that carbon thermal reduction obtains the fusiformis tri-iron tetroxide/carbon nano-composite material of similar pattern and be have not been reported through retrieval.
Summary of the invention
For the deficiencies in the prior art, the invention provides a kind of reasonable in design, technique is simple, pattern is controlled, even size distribution and the preparation method of coulomb efficiency and the higher tri-iron tetroxide/carbon nano-composite material of specific capacity first, utilizes the method can obtain a kind of height ratio capacity fusiformis tri-iron tetroxide/carbon nano-composite material for lithium ion battery negative.
Technical scheme of the present invention is to have designed a kind of easy carbothermic method, first taking the mixed liquor of glycerol and distilled water as solvent, soluble ferric iron salt is raw material, iron oxide hydroxide (FeOOH) presoma of synthetic fusiformis, then passed through carbon thermal reduction and obtain fusiformis Fe
3o
4/ C compound.Then by the Fe of preparation
3o
4/ C mixes and makes electrode slice with acetylene black and binding agent (Kynoar+1-METHYLPYRROLIDONE); Electrode slice is formed in glove box to button cell, at room temperature measure its discharge capacity and reversible charging capacity first, to check Fe
3o
4/ C nano composite material is as the chemical property of lithium ion battery negative material.
Height ratio capacity fusiformis tri-iron tetroxide/carbon (Fe for lithium ion battery negative of the present invention
3o
4/ C) nano composite material, it is characterized in that, described fusiformis tri-iron tetroxide/carbon nano-composite material makes by the following method:
(1) ratio that is 1: 1～1: 19 by volume using glycerol and distilled water is mixed as solvent, in solvent, add soluble ferric iron salt with the proportional quantities of 2～15mmol: 40mL by soluble ferric iron salt and solvent, magnetic agitation 10～30min, dissolves molysite completely;
(2) solution step (1) being made is transferred to in teflon-lined reactor, and the baking oven that is placed in 100～180 DEG C reacts 5～30h;
(3) reactor is naturally cooled to room temperature, then suction filtration is isolated product, wash 3～5 times with distilled water, absolute ethyl alcohol respectively, put in the baking oven of 100 ± 10 DEG C dryly, 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 the ratio of 1: 1～10: 1, take respectively the iron oxide hydroxide making in glucose and step (3), ultrasonic 20～30min is dispersed in distilled water it, then be transferred to hydrothermal reaction kettle, the baking oven that is placed in 180 ± 10 DEG C reacts 4～5h, then reactor is naturally cooled to room temperature, centrifugation goes out product, puts in the baking oven of 100 ± 10 DEG C dry;
(5) product step (4) being made is placed in the blanket of nitrogen of 300～650 DEG C, 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 preferably 1: 3～1: 8 of the described glycerol of step (1) and distilled water.
Wherein, the preferred FeCl of the described soluble ferric iron salt of step (1)
3or Fe (NO
3)
3.
Wherein, the described 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, preferably 120～160 DEG C of the described temperature of step (2), the reaction time is 5～15h preferably.
Wherein, the mass ratio of the described glucose of step (4) and iron oxide hydroxide be preferably 4: 1～10: 1.
Wherein, the preferred 450-600 DEG C of the described calcining heat of step (5), calcination time is 3～6h preferably.
Height ratio capacity fusiformis tri-iron tetroxide/carbon (Fe for lithium ion battery negative of the present invention
3o
4/ C) nano composite material is in the application of preparing in lithium ion battery with high energy density.
Further, the method for described application is: the ratio that (1) is 7: 2: 1 according to mass ratio takes fusiformis tri-iron tetroxide/carbon (Fe
3o
4/ C) nano composite material, acetylene black, Kynoar, put into crucible and grind 10min, then add 1-METHYLPYRROLIDONE and continue to grind 20～30min, make mixture in the pasty state, then it is applied on Copper Foil uniformly, under 100 ± 10 DEG C of conditions, dry 12～20h, rolls this Copper Foil afterwards, be cut into the certain disk of diameter, make electrode slice; (2), in the glove box that is full of argon gas, with conventional method, electrode slice, barrier film, lithium sheet and nickel foam are assembled into button cell.
At room temperature measure discharge capacity first and the reversible charging capacity of the button cell made from test method, the coulombic efficiency first while 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 charging capacity is 1094.5mAh/g first, so coulomb efficiency reaches 80% first.
First the present invention utilizes simple solvent-thermal method to prepare the iron oxide hydroxide of fusiformis (FeOOH) presoma, then by the carbon thermal reduction of presoma process, has improved the crystallinity of product, carbon is coated on to Fe simultaneously
3o
4surface, made fusiformis tri-iron tetroxide/carbon composite, and studied its chemical property as lithium ion battery negative material, comprise first charge-discharge capacity and coulomb efficiency first.The charge/discharge capacity that it is higher and first coulombic efficiency have overcome the shortcoming of conventional transition metal oxide negative material, make it in lithium ion battery field, have potential application.
The preparation method of fusiformis tri-iron tetroxide/carbon nano-composite material of the present invention, easy to operation, raw materials used low price, be easy to large-scale production, tri-iron tetroxide/the carbon nano-composite material of the fusiformis of synthesized has overcome traditional negative material shortcoming that coulomb efficiency is low first, specific capacity is low, is suitable as lithium ion battery negative material large-scale application.
Brief description of the drawings
Fig. 1 XRD figure; Wherein: the XRD figure of prepared iron oxide hydroxide (FeOOH) presoma of a; The Fe that b is prepared
3o
4the XRD figure of/C nano composite material.
The TEM picture of prepared iron oxide hydroxide (FeOOH) presoma of Fig. 2.
Fig. 3 Fe
3o
4for the first time and for the second time charging and discharging curve figure of/C.
Embodiment
Embodiment 1:
(1) ratio that is 1: 4 by volume using glycerol and distilled water is mixed as solvent, adds soluble ferric iron salt by soluble ferric iron salt and solvent with the proportional quantities of 3mmol: 40mL in solvent, and magnetic agitation 25min, dissolves molysite completely;
(2) solution step (1) being made is transferred to in teflon-lined reactor, and the baking oven that is placed in 120 DEG C reacts 12h;
(3) reactor is naturally cooled to room temperature, then suction filtration is isolated product, wash 5 times with distilled water, absolute ethyl alcohol respectively, put in the baking oven of 100 DEG C dryly, obtaining orange-yellow iron oxide hydroxide (FeOOH) solid is fusiformis iron oxide hydroxide presoma;
(4) ratio that is 5: 1 in the mass ratio of glucose and iron oxide hydroxide, take respectively the iron oxide hydroxide making in glucose and step (3), ultrasonic 30min is dispersed in distilled water it, then be transferred to hydrothermal reaction kettle, the baking oven that is placed in 180 DEG C reacts 5h, then reactor is naturally cooled to room temperature, centrifugation goes out product, puts in the baking oven of 100 DEG C dry;
(5) product step (4) being made is placed in the blanket of nitrogen of 450 DEG C, 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 0.07g tri-iron tetroxide/carbon, 0.02g acetylene black, 0.01g Kynoar and in crucible, grind 10min, then adding 1-METHYLPYRROLIDONE to continue to grind 20min must be by the mixture of pasty state, it is applied on Copper Foil uniformly, dry 12h under 100 DEG C of conditions, afterwards this Copper Foil is rolled, be cut into the disk that diameter is 12mm, make electrode slice; In the glove box that is full of argon gas, with conventional method, electrode slice, barrier film, lithium sheet and nickel foam are assembled into button cell.Speed with 200mA/g is carried out electrochemical property test in constant current charge-discharge system.
Embodiment 2:
(1) ratio that is 1: 3 by volume using glycerol and distilled water is mixed as solvent, adds soluble ferric iron salt by soluble ferric iron salt and solvent with the proportional quantities of 7mmol: 40mL in solvent, and magnetic agitation 25min, dissolves molysite completely;
(2) solution step (1) being made is transferred to in teflon-lined reactor, and the baking oven that is placed in 160 DEG C reacts 12h;
(3) reactor is naturally cooled to room temperature, then suction filtration is isolated product, wash 5 times with distilled water, absolute ethyl alcohol respectively, put in the baking oven of 100 DEG C dryly, obtaining orange-yellow iron oxide hydroxide (FeOOH) solid is fusiformis iron oxide hydroxide presoma;
(4) ratio that is 7: 1 in the mass ratio of glucose and iron oxide hydroxide, take respectively the iron oxide hydroxide making in glucose and step (3), ultrasonic 30min is dispersed in distilled water it, then be transferred to hydrothermal reaction kettle, the baking oven that is placed in 180 DEG C reacts 5h, then reactor is naturally cooled to room temperature, centrifugation goes out product, puts in the baking oven of 100 DEG C dry;
(5) product step (4) being made is placed in the blanket of nitrogen of 600 DEG C, 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 0.07g tri-iron tetroxide/carbon, 0.02g acetylene black, 0.01g Kynoar and in crucible, grind 10min, then adding 1-METHYLPYRROLIDONE to continue to grind 20min must be by the mixture of pasty state, it is applied on Copper Foil uniformly, dry 12h under 100 DEG C of conditions, afterwards this Copper Foil is rolled, be cut into the disk that diameter is 12mm, make electrode slice; In the glove box that is full of argon gas, with conventional method, electrode slice, barrier film, lithium sheet and nickel foam are assembled into button cell.Speed with 200mA/g is carried out electrochemical property test in constant current charge-discharge system.
Embodiment 3:
(1) ratio that is 1: 5 by volume using glycerol and distilled water is mixed as solvent, adds soluble ferric iron salt by soluble ferric iron salt and solvent with the proportional quantities of 5mmol: 40mL in solvent, and magnetic agitation 25min, dissolves molysite completely;
(2) solution step (1) being made is transferred to in teflon-lined reactor, and the baking oven that is placed in 150 DEG C reacts 15h;
(3) reactor is naturally cooled to room temperature, then suction filtration is isolated product, wash 5 times with distilled water, absolute ethyl alcohol respectively, put in the baking oven of 100 DEG C dryly, obtaining orange-yellow iron oxide hydroxide (FeOOH) solid is fusiformis iron oxide hydroxide presoma;
(4) ratio that is 8: 1 in the mass ratio of glucose and iron oxide hydroxide, take respectively the iron oxide hydroxide making in glucose and step (3), ultrasonic 30min is dispersed in distilled water it, then be transferred to hydrothermal reaction kettle,, the baking oven that is placed in 180 DEG C reacts 5h, then reactor is naturally cooled to room temperature, centrifugation goes out product, puts in the baking oven of 100 DEG C dry;
(5) product step (4) being made is placed in the blanket of nitrogen of 500 DEG C, 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 0.07g tri-iron tetroxide/carbon, 0.02g acetylene black, 0.01g Kynoar and in crucible, grind 10min, then adding 1-METHYLPYRROLIDONE to continue to grind 20min must be by the mixture of pasty state, it is applied on Copper Foil uniformly, dry 12h under 100 DEG C of conditions, afterwards this Copper Foil is rolled, be cut into the disk that diameter is 12mm, make electrode slice; In the glove box that is full of argon gas, with conventional method, electrode slice, barrier film, lithium sheet and nickel foam are assembled into button cell.Speed with 200mA/g is carried out electrochemical property test in constant current charge-discharge system.
Claims (1)
1. for a preparation method for the height ratio capacity fusiformis tri-iron tetroxide/carbon nano-composite material of lithium ion battery negative, step is:
(1) alcoholic solvent is mixed as solvent with distilled water, in solvent, add soluble ferric iron salt FeCl with the proportional quantities of 2～15mmol:40mL by soluble ferric iron salt and solvent
3or Fe (NO
3)
3, magnetic agitation 10～30min, dissolves molysite completely;
(2) solution step (1) being made is transferred to in teflon-lined reactor, and the baking oven that is placed in 100～180 DEG C reacts 5～30h;
(3) reactor is naturally cooled to room temperature, then suction filtration is isolated product, wash 3～5 times with distilled water, absolute ethyl alcohol respectively, put in the baking oven of 100 ± 10 DEG C dryly, obtaining orange-yellow iron oxide hydroxide (FeOOH) solid is fusiformis iron oxide hydroxide presoma;
(4) ratio that is 1:1～10:1 in the mass ratio of glucose and iron oxide hydroxide, take respectively the iron oxide hydroxide making in glucose and step (3), ultrasonic 20～30min is dispersed in distilled water it, then be transferred to hydrothermal reaction kettle, the baking oven that is placed in 180 ± 10 DEG C reacts 4～5h, then reactor is naturally cooled to room temperature, centrifugation goes out product, puts in the baking oven of 100 ± 10 DEG C dry;
(5) product step (4) being made is placed in the blanket of nitrogen of 300～650 DEG C, 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;
It is characterized in that:
The described alcoholic solvent of step (1) is glycerol, and the volume ratio of glycerol and distilled water is 1:3～1:8.
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