CN102820465B - Application of polyacrylic acid in preparation of lithium ion battery anode material nano-sized iron oxide/carbon composite material - Google Patents

Application of polyacrylic acid in preparation of lithium ion battery anode material nano-sized iron oxide/carbon composite material Download PDF

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Publication number
CN102820465B
CN102820465B CN201210205252.9A CN201210205252A CN102820465B CN 102820465 B CN102820465 B CN 102820465B CN 201210205252 A CN201210205252 A CN 201210205252A CN 102820465 B CN102820465 B CN 102820465B
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iron
lithium ion
ion battery
carbon composite
polyacrylic
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CN102820465A (en
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王志兴
吴飞翔
郭华军
肖玮
李新海
吴秀锋
范玉磊
赵前进
颜志梁
彭文杰
胡启阳
张云河
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Central South University
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Central South University
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    • 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 an application of polyacrylic acid in the preparation of a lithium ion battery anode material, namely a nano-sized iron oxide/carbon composite material, comprising the following steps of: adding an iron source into a mixed solution of deionized water and polyacrylic acid for stirred reaction so as to obtain a clear iron-containing solution; evaporating the iron-containing solution until it is gel-like, and carrying out precalcination at the temperature of 200-400 DEG C to obtain a precursor; and calcining the obtained precursor at the temperature of 400-800 DEG C to obtain the nano-sized iron oxide/carbon composite material. The preparation method of the nano-sized iron oxide/carbon composite material provided by the invention has characteristics of wide raw material range, simple process flow, little energy consumption and low cost. The obtained product has good particle morphology and excellent electrochemical performance.

Description

The application of lithium ion battery negative material nano-iron oxide/carbon composite prepared by polyacrylic acid
Technical field:
The invention belongs to lithium ion battery negative material preparing technical field, particularly the application process on lithium ion battery negative material prepared by polyacrylic acid.
Technical background:
Lithium ion battery is the new generation of green environment-friendly battery of putting on market after the nineties, it because high, the specific energy of operating voltage large, have extended cycle life, self discharge power is little, memory-less effect, the advantage such as pollution-free and be widely used in portable electronics and electric motor car.And lithium ion battery negative material is one of key factor of its overall performance of restriction.The negative material that commercial lithium ion battery adopts the earliest is nearly all carbon/graphite material, but due to the electrode potential of carbon and the current potential of lithium very close, when the battery is overcharged, have part lithium ion and deposit in carbon electrodes, form Li dendrite and cause safety issue.On the other hand, during due to carbon/graphite first time discharge and recharge, solid-electrolyte interphace (Solid ElectrolyteInterface Film can be formed at carbon surface, be called for short SEI film), cause larger irreversible capacity loss, and the generation of SEI film adds electrode/electrolyte interface impedance, is unfavorable for Li +reversible embedding and deviate from.But existing business negative material has reached the limit of performance, and existing carbon negative pole material also exists shortcoming and defect, and the breakthrough of new material technology becomes the urgent task of lithium ion battery of new generation development.Find the Novel anode material that security performance is better, specific capacity is higher, cycle life is longer, become the focus of Study on Li-ion batteries.The actual specific capacity of the graphite cathode material mainly adopted in commercial batteries is at present close to the theoretical specific capacity limit (372mAhg of graphite -1), the oxide of iron is as di-iron trioxide (Fe 2o 3) theoretical specific capacity reaches 1005mAhg -1, tri-iron tetroxide (Fe 3o 4) theoretical specific capacity reach 924mAhg -1, all far above graphite, be more potential transition metal oxide negative material.But it is not as good as material with carbon element in cyclical stability, and high rate performance is low.In order to improve lithium ion battery negative specific capacity, improving cyclical stability and the high rate performance of metal oxide negative pole, to propose with iron powder and polyacrylic acid as presoma prepared by raw material, preparing ferriferous oxide by combustion method, and modification is carried out to it.
It is a lot of as the scientific worker of lithium ion battery negative material that transition metal nano-oxide is prepared in domestic and international research, but major part employing is hydro thermal method or solvent-thermal method.Hydro thermal method generally adopts the mixed solution of iron chloride and organic carbon source (glucose, carbon nano-tube, Graphene etc.) to react at autoclave 140-200 DEG C and within 4-20 hour, obtains the coated FeOOH of carbon, then carries out calcining the oxide obtaining iron; Solvent-thermal method carries out water under high pressure thermal response under generally adopting the mixed solution of iron chloride or ferric nitrate and organic solvent and dispersant.But these two kinds of methods are difficult to industrial production.
Since Poizot in 2000 etc. have studied the application of transition metal oxide in lithium ion battery, various metal oxide is as Co 3o 4, NiO, Cu 2the lithium electrical property research of O receives much concern.Transition metal oxide, shape is as MO (M=Fe, Co, Cu) etc.The mechanism that they and lithium react is, during electric discharge, metal oxide MO is reduced to nano level metal M particle, and during charging, M is oxidized to again MO metal oxide, and along with Li 2o generates Sum decomposition.That metal oxide charge and discharge process occurs is conversion reaction (MO x+ 2xLi++2xe=M+xLi 2o), the slotting embedding theory of conventional lithium ion battery material is different from.Because corresponding 2-6 the electro transfer of every moles of active species in conversion reaction, so have the graphite cathode material (372mAhg than present business -1) higher theoretical specific capacity.The oxide of iron owing to having high theoretical specific capacity, as di-iron trioxide (1005mAhg -1), tri-iron tetroxide (924mAhg -1), cheap, nontoxic, the advantage such as pollution-free, has very large application prospect in lithium ion battery negative material.Fe 3o 4intercalation potential be about 0.8V, can form with 4V positive electrode the lithium ion battery that voltage is 3 ~ 3.5V.Nano material generally has the characteristics such as the little and stroke of large specific area, the embedding de-degree of depth of lithium ion is short, nano-electrode the is had feature such as the degree of polarization of discharge and recharge under big current is little, reversible capacity is high, have extended cycle life.Large specific area is also conducive to the change cushioning volume in charge and discharge process simultaneously, and its skin effect is also conducive to more lithium and embeds.Carbon-coated nano ferriferous oxide can utilize the flexible nature of carbon to suppress and cushion the violent change in volume of iron in charge and discharge process, and stops the reunion of iron oxide particle in the embedding de-process of lithium ion.Carbon-coating can provide electron tunnel for material, the conductivity of reinforcing material on the other hand, increases specific area, material is fully contacted with electrolyte.The for a change change in volume of ferriferous oxide in charge and discharge process, lot of domestic and international scientific worker expands a series of research.Central South University Cheng Feng etc. utilizes surfactant carbonizatin method to synthesize Fe 3o 4/ C composite, and with business Fe 3o 4contrast, this material has 691.7mAhg after 80 circulations under 0.2C -1specific capacity; Under 2C, after 20 circulations, there is 520mAhg -1specific capacity.Good cycle performance and high rate performance give the credit to the triple role of carbon-coating: prevent particle from assembling as barrier layer; Improve conductivity; Stop the formation of thicker SEI film, Simultaneous Stabilization SEI film.As can be seen here, the coated performance on ferriferous oxide negative material of carbon has important impact.Doctor Yu Yan finds to add Li in transition metal oxide 2the problem that after O, available buffer transition metal oxide change in volume is violent, can reduce coulomb loss first simultaneously.The synthesis of Yue Guoqiang self-catalysis reverse atom transfer radical polymerization method obtains with the netted sheet Li-Fe composite oxides of porousness, and lamellar spacing is about 300-500nm.The first discharge specific capacity of the nanometer Li-Fe composite oxides of synthesis is 1391mAhg -1, second time specific discharge capacity is 1059mAhg -1, after 100 times, specific discharge capacity still can reach 1249mAhg -1.
Summary of the invention:
Technical problem to be solved by this invention is to provide polyacrylic acid at the application process preparing lithium ion battery negative material nano-iron oxide/carbon composite, the method raw material sources are extensive, the range of choice of source of iron is extensive, technological process is simple and quick, without the need to the equipment of complexity, the feature that cost is low.
The granularity pattern of the composite products prepared by method of the present invention is good, and controlled synthesis goes out composite material, and electrochemical performance.
Polyacrylic acid, preparing the application of lithium ion battery negative material nano-iron oxide/carbon composite, is characterized in that, by source of iron stirring reaction in deionized water and polyacrylic mixed solution, and the iron-containing liquor of the clarification obtained; After iron-containing liquor is evaporated to gel, obtain presoma through 200-400 DEG C of precalcining; The presoma obtained is obtained nano-iron oxide/carbon composite 400-800 DEG C of calcining.
Polyacrylic acid preferred molecular weight of the present invention is 2000-5000.
The temperature of source of iron stirring reaction in deionized water and polyacrylic mixed solution is 25-100 DEG C.
Evaporating temperature is 60-100 DEG C.
Described presoma is at air, and oxygen, calcines under the atmosphere of one or more in nitrogen and argon gas.
The concrete preparation method of the present invention comprises:
(1) various source of iron and deionized water and polyacrylic mixed solution are carried out stirring reaction, stirring reaction temperature is 25-100 DEG C, obtains the solution clarified after stirring reaction 5-720min; Wherein iron and polyacrylic mass ratio are 1:1 ~ 1:100, and deionized water and polyacrylic mass ratio are 1:1 ~ 100:1;
(2) iron-containing liquor obtained above is carried out in stirred reactor stirring evaporation, in stirred reactor, bath temperature is 60-100 DEG C, and being evaporated to solution is gel;
(3) gel that step (2) obtains is carried out precalcining in Muffle furnace, calcining heat is 200-400 DEG C, and the time is 1-10h, obtains presoma;
(4) calcined under different atmosphere by the presoma that step (3) obtains, calcining heat is 400-800 DEG C, and the time is 1-10h, obtains lithium ion battery negative material iron oxide or iron oxide/carbon composite.
Source of iron of the present invention comprises for iron powder, ferric trichloride, frerrous chloride, inorganic source of iron and the organoiron compounds (as ferrocene or ferric acetyl acetonade etc.) such as ferric nitrate ferrous nitrate; Described inorganic source of iron can be technical grade, chemical pure or analyzes pure iron source.
Instant invention overcomes technique in the past and prepare that lithium ion battery negative material nano-iron oxide/carbon composite flow process is complicated, preparation cost is high, the defect of complicated autoclave equipment and cycle very long hydro-thermal reaction.First above-mentioned source of iron is dissolved in polyacrylic acid solution, after stirring reaction certain hour, obtains iron-containing liquor.Carry out stirring evaporation toward this solution and obtain gel, gel is carried out in Muffle furnace precalcining and obtain presoma.Finally this presoma is calcined under different calcination atmosphere and obtain lithium ion battery negative material nano-iron oxide and carbon composite thereof.Raw material sources of the present invention are wide, technological process is simple, energy consumption is little, cost is low, equipment is simple, reaction time is short, product purity is high, granularity is little, pattern is good, be particularly suitable for the production of the ferriferous oxide of lithium ion battery negative material nanostructure, be also applicable to the production of other field nanostructure ferriferous oxide simultaneously.
The present invention is compared with other method preparing lithium ion battery negative material nano-iron oxide and carbon composite thereof, and its advantage shows in the following areas:
1) polyacrylic acid adaptability to raw material of the present invention is strong, can with various source of iron solubilizing reaction;
2) technique equipment needed thereby of the present invention is simple, without the need to the equipment of complexity, as autoclave; Reaction time is short, without the need to long hydro-thermal reaction;
3) method of this invention is more preferably applicable to inorganic source of iron iron powder, and the advantage that existence is very large compared with other inorganic molysites, avoids the impact of anion on material property, and anion decomposes the pollution etc. of corrosion to equipment and air in calcination process;
4) reaction of the present invention is fairly simple, completely can by controlling the atmosphere of iron and polyacrylic mass ratio and calcining thus obtaining the nano-iron oxide material of different structure;
5) the negative material ferriferous oxide granularity prepared of the present invention is little, pattern good, purity is high and specific area is large, and the chemical property of material is superior.
In sum, the present invention is well-designed by above technological process, serve simplification industrial flow to greatest extent, reduce costs, the effect of production cycle, is that a kind of raw material sources are wide, technological process is simple, energy consumption is little, reaction time is short, good product quality and a kind of stable, cost is low method preparing lithium ion battery negative material nano-iron oxide and carbon composite thereof.
Accompanying drawing illustrates:
Fig. 1 is lithium ion battery negative material Fe in embodiment 1 2o 3scanning electron microscope (SEM) photograph;
Fig. 2 is lithium ion battery negative material Fe in embodiment 1 2o 3xRD collection of illustrative plates;
Fig. 3 is lithium ion battery negative material Fe in embodiment 1 2o 3charging and discharging curve under 0.05C multiplying power;
Fig. 4 is lithium ion battery negative material Fe in embodiment 2 2o 3xRD collection of illustrative plates.
Embodiment:
Following examples are intended to the present invention instead of limitation of the invention further are described.
Embodiment 1:
Source of iron is chemical pure iron powder 5 grams, (wherein polyacrylic content is 10% mass percent to be dissolved in deionized water and polyacrylic mixed solution, following examples are same), iron and polyacrylic mass ratio are 1:8, in the water-bath of 60 DEG C, carry out stirring 2h dissolve the solution obtaining iron content, be positioned in constant temperature oscillator by iron-containing liquor and evaporate, bath temperature is 80 DEG C, evaporates and obtains gel after 6 hours; By gel precalcining 3 hours at 300 DEG C in Muffle furnace, take out grinding, then calcining obtains lithium ion battery negative material nanometer Fe in 5 hours at lower 450 DEG C of Muffle furnace air atmosphere 2o 3/ C composite.
Embodiment 2:
Source of iron is chemical pure ferric nitrate 10 grams, be dissolved in deionized water and polyacrylic mixed solution (wherein polyacrylic content is 5%), iron and polyacrylic mass ratio are 1:2, in the water-bath of 25 DEG C, carry out stirring 20min dissolve the solution obtaining iron content, iron-containing liquor is positioned in constant temperature oscillator and evaporates, bath temperature is 90 DEG C, evaporates and obtains gel after 5 hours; By precalcining at gel and Muffle furnace 400 DEG C 3 hours, take out grinding, then calcining obtains lithium ion battery negative material nanometer Fe in 6 hours at lower 500 DEG C of tube furnace oxygen atmosphere 2o 3/ C composite.
Embodiment 3:
Source of iron is chemical pure iron powder 5 grams, be dissolved in deionized water and polyacrylic mixed solution (wherein polyacrylic content is 10%), iron and polyacrylic mass ratio are 1:7, in the water-bath of 60 DEG C, carry out stirring 3h dissolve the solution obtaining iron content, iron-containing liquor is positioned in constant temperature oscillator and evaporates, bath temperature is 90 DEG C, evaporates and obtains gel after 4 hours; By precalcining at gel and Muffle furnace 400 DEG C 3 hours, take out grinding, then calcining obtains lithium ion battery negative material nanometer Fe in 5 hours at lower 500 DEG C of tube furnace argon gas atmosphere 3o 4/ C composite.
Embodiment 4:
Source of iron is chemical pure frerrous chloride 10 grams, be dissolved in deionized water and polyacrylic mixed solution (wherein polyacrylic content is 10%), iron and polyacrylic mass ratio are 1:1, in the water-bath of 60 DEG C, carry out stirring 10min dissolve the solution obtaining iron content, iron-containing liquor is positioned in constant temperature oscillator and evaporates, bath temperature is 80 DEG C, evaporates and obtains gel after 6 hours; By precalcining at gel and Muffle furnace 350 DEG C 3 hours, take out grinding, then calcining obtains lithium ion battery negative material nanometer Fe in 5 hours at lower 400 DEG C of tube furnace nitrogen atmosphere 2o 3/ C composite.
Embodiment 5:
Source of iron is for analyzing pure ferrocene (Fe (C 5h 5) 2) 30 grams, be dissolved in deionized water and polyacrylic mixed solution (wherein polyacrylic content is 3%), iron and polyacrylic mass ratio are 1:10, in the water-bath of 60 DEG C, carry out stirring 10min dissolve the solution obtaining iron content, iron-containing liquor is positioned in constant temperature oscillator and evaporates, bath temperature is 70 DEG C, evaporates and obtains gel after 12 hours; By precalcining at gel and Muffle furnace 300 DEG C 6 hours, take out grinding, then calcining obtains lithium ion battery negative material nanometer Fe in 5 hours at lower 600 DEG C of tube furnace nitrogen atmosphere 3o 4/ C composite.
Although the present invention is described in each preferred embodiment, but the easy cleavage the present invention of those skilled in the art is not limited to foregoing description, it can be undertaken changing or improving by multiple alternate manner, and does not depart from the spirit and scope illustrated in the claims in the present invention.

Claims (5)

1. polyacrylic acid is preparing the application of lithium ion battery negative material nano-iron oxide/carbon composite, it is characterized in that, by source of iron stirring reaction in deionized water and polyacrylic mixed solution, obtains the iron-containing liquor clarified; After iron-containing liquor is evaporated to gel, obtain presoma through 200-400 DEG C of precalcining; The presoma obtained is obtained nano-iron oxide/carbon composite 400-800 DEG C of calcining; Described source of iron is iron powder, ferric trichloride, frerrous chloride, ferric nitrate, ferrous nitrate, ferrocene or ferric acetyl acetonade.
2. application according to claim 1, is characterized in that, the temperature of source of iron stirring reaction in deionized water and polyacrylic mixed solution is 25-100 DEG C.
3. application according to claim 1, is characterized in that, evaporating temperature is 60-100 DEG C.
4. application according to claim 1, is characterized in that, described presoma is at air, and oxygen, calcines under the atmosphere of one or more in nitrogen and argon gas.
5. the application according to any one of claim 1-4, is characterized in that comprising the following steps:
(1) source of iron and deionized water and polyacrylic mixed solution are carried out stirring reaction, stirring reaction temperature is 25-100 DEG C, obtains the iron-containing liquor clarified after stirring reaction 5-720min; Wherein ferro element and polyacrylic mass ratio are 1:1 ~ 1:100, and deionized water and polyacrylic mass ratio are 1:1 ~ 100:1;
(2) iron-containing liquor obtained above is carried out in stirred reactor stirring evaporation, stirred reactor bath temperature is 60-100 DEG C, and evaporation obtains gel;
(3) gel that step (2) obtains is carried out precalcining in Muffle furnace, calcining heat is 200-400 DEG C, and the time is 1-10h, obtains presoma;
(4) presoma step (3) obtained is through calcining, and calcining heat is 400-800 DEG C, and the time is 1-10h, obtains lithium ion battery negative material nano-iron oxide/carbon composite.
CN201210205252.9A 2012-06-20 2012-06-20 Application of polyacrylic acid in preparation of lithium ion battery anode material nano-sized iron oxide/carbon composite material Expired - Fee Related CN102820465B (en)

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