CN102820465A - 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 PDFInfo
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- CN102820465A CN102820465A CN2012102052529A CN201210205252A CN102820465A CN 102820465 A CN102820465 A CN 102820465A CN 2012102052529 A CN2012102052529 A CN 2012102052529A CN 201210205252 A CN201210205252 A CN 201210205252A CN 102820465 A CN102820465 A CN 102820465A
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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
Technical field:
The invention belongs to the lithium ion battery negative material preparing technical field, particularly the application process of polyacrylic acid on the preparation lithium ion battery negative material.
Technical background:
Lithium ion battery is the new generation of green environment-friendly battery of putting on market after the nineties, and it is because operating voltage is high, specific energy is big, have extended cycle life, self discharge power is little, memory-less effect, advantage such as pollution-free and be widely used in portable electronics and the 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 adopted the earliest nearly all is carbon/graphite material; But because the current potential of the electrode potential of carbon and lithium is very approaching; When battery overcharge, have the part lithium ion and deposit in carbon electrodes, form Li dendrite and cause safety issue.On the other hand; Because when carbon/graphite discharges and recharges for the first time; Can form the middle phase of solid electrolyte (Solid Electrolyte Interface Film is called for short the SEI film) at carbon surface, cause bigger irreversible capacity loss; And the generation of SEI film has increased the electrode/electrolyte interface impedance, is unfavorable for Li
+Reversible embedding and deviate from.Yet existing commercial negative material has reached the limit of performance, and existing carbon negative pole material exists shortcoming and defect, and the breakthrough of new material technology becomes the urgent task of lithium ion battery development of new generation.Seek the novel negative material that security performance is better, specific capacity is higher, cycle life is longer, become the focus of Study on Li-ion batteries using.At present in the commodity battery actual specific capacity of the main graphite cathode material that adopts near the theoretical specific capacity limit (372mAhg of graphite
-1), the oxide of iron such 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,, be more potential transition metal oxide negative material all far above graphite.But it is too late material with carbon element aspect cyclical stability, and high rate performance is low.In order to improve the lithium ion battery negative specific capacity, improve the cyclical stability and the high rate performance of metal oxide negative pole, having proposed with iron powder and polyacrylic acid is the feedstock production presoma, prepares ferriferous oxide through firing method, and it is carried out modification.
The transition metal of research preparation both at home and abroad nano-oxide is a lot of as the scientific worker of lithium ion battery negative material, and what still major part adopted is hydro thermal method or solvent-thermal method.Hydro thermal method generally adopts the mixed solution of iron chloride and organic carbon source (glucose, CNT, Graphene etc.) to react down at autoclave 140-200 ℃ and obtained the FeOOH that carbon coats in 4-20 hour, calcines the oxide that obtains iron again; Solvent-thermal method generally adopts under the mixed solution of iron chloride or ferric nitrate and organic solvent and dispersant and carries out the water under high pressure thermal response.But these two kinds of methods are difficult to commercial production.
Since Poizot in 2000 etc. have studied the application of transition metal oxide in lithium ion battery, various metal oxides such as Co
3O
4, NiO, Cu
2The lithium electrical property research of O receives much concern.Transition metal oxide, shape such as MO (M=Fe, Co, Cu) etc.The mechanism of they and lithium reaction is, metal oxide MO is reduced to nano level metal M particle during discharge, and M is oxidized to the MO metal oxide again during charging, and the Li that is accompanied by
2O generates and decomposes.That the metal oxide charge and discharge process takes place is conversion reaction (MO
x+ 2xLi++2xe=M+xLi
2O), the slotting embedding theory that is different from traditional lithium ion battery material.Because every mole of corresponding 2-6 electron transfer of active material in the conversion reaction is so have the graphite cathode material (372mAhg than present commercial usefulness
-1) higher theoretical specific capacity.The oxide of iron is owing to having high theoretical specific capacity, like di-iron trioxide (1005mAhg
-1), tri-iron tetroxide (924mAhg
-1), cheap, nontoxic, advantage such as pollution-free has very big application prospect aspect lithium ion battery negative material.Fe
3O
4Embedding lithium current potential be about 0.8V, can form voltage with the 4V positive electrode be the lithium ion battery of 3 ~ 3.5V.Nano material generally has big specific area, lithium ion embedding and takes off characteristics such as the little and stroke of the degree of depth is short, makes nano-electrode have characteristics such as the degree of polarization that under big electric current, discharges and recharges is little, reversible capacity is high, have extended cycle life.Big specific area also helps cushioning simultaneously the variation of volume in the charge and discharge process, and its skin effect also helps more lithium and embeds.The carbon-coated nano ferriferous oxide can utilize the flexible nature of carbon to suppress and cushion the violent change in volume of iron in the charge and discharge process, and stops iron oxide particle to take off the reunion in the process in the lithium ion embedding.Carbon-coating can provide electron tunnel for material on the other hand, and the conductivity of reinforcing material increases specific area, and material is fully contacted with electrolyte.The change in volume of ferriferous oxide in charge and discharge process for a change, lot of domestic and international scientific worker has launched a series of research.The Cheng Feng of Central South University etc. utilizes the surfactant carbonizatin method to synthesize Fe
3O
4/ C composite material, and with commercial Fe
3O
4Contrast, this material has 691.7mAhg after 80 circulations under 0.2C
-1Specific capacity; Under 2C, has 520mAhg after 20 circulations
-1Specific capacity.Excellent cycle performance and high rate performance are given the credit to the triple role of carbon-coating: prevent particle accumulation as barrier layer; Improve conductivity; Stop the formation of thicker SEI film, stablize the SEI film simultaneously.This shows that the performance that carbon coats the ferriferous oxide negative material has significant effects.Doctor Yu Yan finds in transition metal oxide, to add Li
2The violent problem of available buffer transition metal oxide change in volume behind the O can reduce enclosed pasture loss first simultaneously.Yue Guoqiang obtains having the netted sheet Li-Fe composite oxides of porousness, the about 300-500nm of lamellar spacing with self-catalysis reverse atom transfer radical polymerization method is synthetic.The first discharge specific capacity of synthetic nanometer Li-Fe composite oxides is 1391mAhg
-1, specific discharge capacity is 1059mAhg for the second time
-1, after 100 times, specific discharge capacity still can reach 1249mAhg
-1
Summary of the invention:
Technical problem to be solved by this invention provides the application process of polyacrylic acid at preparation lithium ion battery negative material nano-iron oxide/carbon composite; These method raw material sources are extensive; The range of choice of source of iron is extensive; Technological process is simply quick, need not complex apparatus, the characteristics that cost is low.
Granularity pattern by the prepared composite products that goes out of method of the present invention is good, the controlled composite material of preparing, and chemical property is excellent.
Polyacrylic acid is characterized in that, with source of iron stirring reaction in deionized water and polyacrylic mixed solution, the iron-containing liquor of the clarification that obtains in the application of preparation lithium ion battery negative material nano-iron oxide/carbon composite; After iron-containing liquor is evaporated to gel, obtain presoma through 200-400 ℃ of precalcining; The presoma that obtains is obtained nano-iron oxide/carbon composite 400-800 ℃ 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 ℃.
Evaporating temperature is 60-100 ℃.
Described presoma is at air, and oxygen is calcined under the atmosphere of one or more in nitrogen and the argon gas.
The concrete preparation method of the present invention comprises:
(1) various sources of iron and deionized water and polyacrylic mixed solution are carried out stirring reaction, the stirring reaction temperature is 25-100 ℃, obtains clear solutions behind the 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) the above-mentioned iron-containing liquor that obtains is stirred evaporation in stirred reactor, bath temperature is 60-100 ℃ in the stirred reactor, is evaporated to solution and is gel;
(3) gel that step (2) is obtained carries out precalcining in Muffle furnace, calcining heat is 200-400 ℃, and the time is 1-10h, obtains presoma;
(4) presoma that step (3) is obtained is calcined under different atmosphere, and calcining heat is 400-800 ℃, 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 is included as iron powder, ferric trichloride, frerrous chloride, inorganic source of iron and organoiron compounds (like ferrocene or ferric acetyl acetonade etc.) such as ferric nitrate ferrous nitrate; Said inorganic source of iron can be technical grade, chemical pure or analyzes the pure iron source.
The present invention has overcome in the past that prepared lithium ion battery negative material nano-iron oxide/carbon composite flow process is complicated, preparation cost is high, the defective of the hydro-thermal reaction that complicated autoclave equipment and cycle are very long.Earlier above-mentioned source of iron is dissolved in the polyacrylic acid solution, obtains iron-containing liquor behind the stirring reaction certain hour.Stir evaporation toward this solution and obtain gel, gel is carried out precalcining obtain presoma in Muffle furnace.At last this presoma is calcined under different calcination atmosphere and obtained 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, also be fit to the production of other field nanostructure ferriferous oxide simultaneously.
The present invention compares with the method that other prepares lithium ion battery negative material nano-iron oxide and carbon composite thereof, and its advantage shows in the following areas:
1) the polyacrylic acid adaptability to raw material that the present invention adopted is strong, can with various source of iron solubilizing reactions;
2) technology equipment needed thereby of the present invention is simple, need not complex apparatus, like autoclave; Reaction time is short, need not long hydro-thermal reaction;
3) method of this invention more preferably is fit to inorganic source of iron iron powder, compares the very big advantage of existence with other inorganic molysites, has avoided anion to effect of material performance, and anion decomposes the pollution of corrosion on Equipment and atmosphere in calcination process etc.;
4) reaction of the present invention is fairly simple, thereby can obtain the nano-iron oxide material of different structure through the atmosphere of control iron and polyacrylic mass ratio and calcining fully;
5) the negative material ferriferous oxide granularity prepared of the present invention is little, pattern good, purity is high and specific area is big, and the chemical property of material is superior.
In sum; The present invention is well-designed through above technological process; Played the simplification industrial flow to greatest extent; Reduce cost, 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 stable, that cost is low a kind of method for preparing lithium ion battery negative material nano-iron oxide and carbon composite thereof.
Description of drawings:
Fig. 1 is lithium ion battery negative material Fe among the embodiment 1
2O
3Sem photograph;
Fig. 2 is lithium ion battery negative material Fe among the embodiment 1
2O
3XRD figure spectrum;
Fig. 3 is lithium ion battery negative material Fe among the embodiment 1
2O
3Charging and discharging curve under the 0.05C multiplying power;
Fig. 4 is lithium ion battery negative material Fe among the embodiment 2
2O
3XRD figure spectrum.
Embodiment:
Following examples are intended to explain the present invention rather than to further qualification of the present invention.
Embodiment 1:
Source of iron is chemical pure iron powder 5 grams; Be dissolved in deionized water and polyacrylic mixed solution (wherein polyacrylic content is 10% mass percent, and following examples together), iron and polyacrylic mass ratio are 1:8; In 60 ℃ water-bath, stir the solution that the 2h dissolving obtains iron content; Iron-containing liquor is positioned in the constant temperature oscillator evaporates, bath temperature is 80 ℃, evaporates to obtain gel after 6 hours; With gel 300 ℃ of following precalcinings 3 hours in Muffle furnace, take out and grind, again in the Muffle furnace air atmosphere following 450 ℃ down calcining obtained the lithium ion battery negative material nanometer Fe in 5 hours
2O
3/ C composite material.
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 25 ℃ water-bath, stir the solution that the 20min dissolving obtains iron content, iron-containing liquor is positioned in the constant temperature oscillator evaporates; Bath temperature is 90 ℃, evaporates to obtain gel after 5 hours; With gel and 400 ℃ of following precalcinings of Muffle furnace 3 hours, take out and grind, again in the tube furnace oxygen atmosphere following 500 ℃ down calcining obtained the lithium ion battery negative material nanometer Fe in 6 hours
2O
3/ C composite material.
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 60 ℃ water-bath, stir the solution that the 3h dissolving obtains iron content, iron-containing liquor is positioned in the constant temperature oscillator evaporates; Bath temperature is 90 ℃, evaporates to obtain gel after 4 hours; With gel and 400 ℃ of following precalcinings of Muffle furnace 3 hours, take out and grind, again in the tube furnace argon gas atmosphere following 500 ℃ down calcining obtained the lithium ion battery negative material nanometer Fe in 5 hours
3O
4/ C composite material.
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 60 ℃ water-bath, stir the solution that the 10min dissolving obtains iron content, iron-containing liquor is positioned in the constant temperature oscillator evaporates; Bath temperature is 80 ℃, evaporates to obtain gel after 6 hours; With gel and 350 ℃ of following precalcinings of Muffle furnace 3 hours, take out and grind, again in the tube furnace nitrogen atmosphere following 400 ℃ down calcining obtained the lithium ion battery negative material nanometer Fe in 5 hours
2O
3/ C composite material.
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 60 ℃ water-bath, stir the solution that the 10min dissolving obtains iron content, iron-containing liquor is positioned in the constant temperature oscillator evaporates; Bath temperature is 70 ℃, evaporates to obtain gel after 12 hours; With gel and 300 ℃ of following precalcinings of Muffle furnace 6 hours, take out and grind, again in the tube furnace nitrogen atmosphere following 600 ℃ down calcining obtained the lithium ion battery negative material nanometer Fe in 5 hours
3O
4/ C composite material.
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 changed or improve by multiple alternate manner, and does not break away from spirit and the scope of illustrating in the claim of the present invention.
Claims (6)
1. polyacrylic acid is characterized in that, with source of iron stirring reaction in deionized water and polyacrylic mixed solution, the iron-containing liquor of the clarification that obtains in the application of preparation lithium ion battery negative material nano-iron oxide/carbon composite; After iron-containing liquor is evaporated to gel, obtain presoma through 200-400 ℃ of precalcining; The presoma that obtains is obtained nano-iron oxide/carbon composite 400-800 ℃ of calcining.
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 ℃.
3. application according to claim 1 is characterized in that, evaporating temperature is 60-100 ℃.
4. application according to claim 1 is characterized in that, described presoma is at air, and oxygen is calcined under the atmosphere of one or more in nitrogen and the argon gas.
5. application according to claim 1 is characterized in that said source of iron is included as iron powder, ferric trichloride, frerrous chloride, ferric nitrate, ferrous nitrate, ferrocene or ferric acetyl acetonade.
6. according to each described application of claim 1-5, it is characterized in that may further comprise the steps:
(1) source of iron and deionized water and polyacrylic mixed solution are carried out stirring reaction, the stirring reaction temperature is 25-100 ℃, obtains clear solutions behind the 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) the above-mentioned iron-containing liquor that obtains is stirred evaporation in stirred reactor, the stirred reactor bath temperature is 60-100 ℃, and evaporation obtains gel;
(3) gel that step (2) is obtained carries out precalcining in Muffle furnace, calcining heat is 200-400 ℃, and the time is 1-10h, obtains presoma;
(4) presoma that step (3) is obtained is through calcining, and calcining heat is 400-800 ℃, and the time is 1-10h, obtains lithium ion battery negative material ferriferous oxide/carbon composite.
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Cited By (10)
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|---|---|---|---|---|
| CN103280577A (en) * | 2013-05-17 | 2013-09-04 | 上海交通大学 | Magnetic carbon-based iron oxide compound material and preparation method thereof |
| CN107768645A (en) * | 2017-11-28 | 2018-03-06 | 吉林大学 | A kind of porous nitrogen-doped carbon nanometer sheet composite negative pole material and preparation method thereof |
| CN111710839A (en) * | 2020-05-29 | 2020-09-25 | 桂林理工大学 | Fe3O4-MoO2Preparation method of @ SFAC lithium ion battery anode material |
| CN111769280A (en) * | 2020-05-25 | 2020-10-13 | 武汉船用电力推进装置研究所（中国船舶重工集团公司第七一二研究所） | Carbon-coated high-nickel-base quaternary positive electrode material and preparation method thereof |
| CN112072102A (en) * | 2020-07-30 | 2020-12-11 | 绍兴市卓诚新材料有限公司 | Fe2O3Loaded carbon coated nano Co3O4Lithium ion battery cathode material and preparation method thereof |
| CN112786869A (en) * | 2021-02-09 | 2021-05-11 | 四川轻化工大学 | Preparation method of ferric oxide/spiral carbon nanofiber composite anode material |
| CN114758904A (en) * | 2022-04-27 | 2022-07-15 | 深圳大学 | Composite material, preparation method thereof and super capacitor |
| CN114843475A (en) * | 2022-05-19 | 2022-08-02 | 西北工业大学深圳研究院 | Iron carbide-based composite material and preparation method thereof |
| CN115652329A (en) * | 2022-11-16 | 2023-01-31 | 电子科技大学长三角研究院(湖州) | Iron oxide-based oxygen evolution electrocatalyst and preparation method thereof |
| CN115652329B (en) * | 2022-11-16 | 2024-04-12 | 电子科技大学长三角研究院(湖州) | Iron oxide-based oxygen evolution electrocatalyst and preparation method thereof |
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| CN103280577B (en) * | 2013-05-17 | 2015-08-19 | 上海交通大学 | Magnetic carbon back silicon/iron oxide composite material and preparation method thereof |
| CN103280577A (en) * | 2013-05-17 | 2013-09-04 | 上海交通大学 | Magnetic carbon-based iron oxide compound material and preparation method thereof |
| CN107768645A (en) * | 2017-11-28 | 2018-03-06 | 吉林大学 | A kind of porous nitrogen-doped carbon nanometer sheet composite negative pole material and preparation method thereof |
| CN107768645B (en) * | 2017-11-28 | 2020-07-14 | 吉林大学 | Porous nitrogen-doped carbon nanosheet composite negative electrode material and preparation method thereof |
| CN111769280A (en) * | 2020-05-25 | 2020-10-13 | 武汉船用电力推进装置研究所（中国船舶重工集团公司第七一二研究所） | Carbon-coated high-nickel-base quaternary positive electrode material and preparation method thereof |
| CN111710839B (en) * | 2020-05-29 | 2021-07-20 | 桂林理工大学 | Fe3O4-MoO2Preparation method of @ SFAC lithium ion battery anode material |
| CN111710839A (en) * | 2020-05-29 | 2020-09-25 | 桂林理工大学 | Fe3O4-MoO2Preparation method of @ SFAC lithium ion battery anode material |
| CN112072102A (en) * | 2020-07-30 | 2020-12-11 | 绍兴市卓诚新材料有限公司 | Fe2O3Loaded carbon coated nano Co3O4Lithium ion battery cathode material and preparation method thereof |
| CN112072102B (en) * | 2020-07-30 | 2022-03-29 | 湖南博邦山河新材料有限公司 | Fe2O3Loaded carbon coated nano Co3O4Lithium ion battery cathode material and preparation method thereof |
| CN112786869A (en) * | 2021-02-09 | 2021-05-11 | 四川轻化工大学 | Preparation method of ferric oxide/spiral carbon nanofiber composite anode material |
| CN114758904A (en) * | 2022-04-27 | 2022-07-15 | 深圳大学 | Composite material, preparation method thereof and super capacitor |
| CN114843475A (en) * | 2022-05-19 | 2022-08-02 | 西北工业大学深圳研究院 | Iron carbide-based composite material and preparation method thereof |
| CN114843475B (en) * | 2022-05-19 | 2024-01-19 | 西北工业大学深圳研究院 | Iron carbide-based composite material and preparation method thereof |
| CN115652329A (en) * | 2022-11-16 | 2023-01-31 | 电子科技大学长三角研究院(湖州) | Iron oxide-based oxygen evolution electrocatalyst and preparation method thereof |
| CN115652329B (en) * | 2022-11-16 | 2024-04-12 | 电子科技大学长三角研究院(湖州) | Iron oxide-based oxygen evolution electrocatalyst and preparation method thereof |
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