CN101582495B - Anode composite material of lithium ion battery and preparation method thereof - Google Patents

Anode composite material of lithium ion battery and preparation method thereof Download PDF

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Publication number
CN101582495B
CN101582495B CN2009103040298A CN200910304029A CN101582495B CN 101582495 B CN101582495 B CN 101582495B CN 2009103040298 A CN2009103040298 A CN 2009103040298A CN 200910304029 A CN200910304029 A CN 200910304029A CN 101582495 B CN101582495 B CN 101582495B
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composite material
ion battery
anode composite
lithium
lithium ion
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CN101582495A (en
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彭忠东
曹雁冰
胡国荣
杜柯
蒋庆来
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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 provides an anode composite material of a lithium ion battery and a preparation method thereof. The anode composite material of the lithium ion battery has a molecular formula of Li2FeSio4/C. According to mass percentage, the content of silicate is 95%-80%, and the content of compounded carbon is 5%-20%. The preparation method of the anode composite material comprises the following steps: (1) ferrite and the silicate are evenly mixed by a ball mill according to a stoichiometric proportion, thereby obtaining a mixture; the mixture is fully washed with deionized water and then dried, thereby obtaining a precursor; and (2) the precursor, lithium salt and organic carbon source undergo mixing, ball milling, tabletting and microwave treatment under inert gas shielding, thereby obtaining the Li2FeSio4/C anode composite material of the lithium ion battery. The invention can obtain the carbon-coated anode composite material which has good crystals, thin and uniform crystal grains and high purity, and can improve the electrochemical properties of a Li2FeSio4 anode material.

Description

A kind of anode composite material of lithium ion battery and preparation method thereof
Technical field
The invention belongs to the anode material for lithium-ion batteries preparing technical field, related to a kind of anode composite material of lithium ion battery (Li 2FeSiO 4/ C) and preparation method thereof.
Background technology
The world today, petroleum resources are day by day nervous, and environmental pollution is on the rise, and people are to being that the secondary energy sources of power are more and more paid attention to green secondary cell.Lithium ion battery is most active green energy resource through the development of more than ten years on present secondary cell market, is expected to become the desirable energy storage device of electric motor car and hybrid vehicle.The high-performance electrokinetic cell that can be used for field such as hybrid-electric car is in industrialization and is about to stage of breaking through, and positive electrode is the key component of power-type lithium ion battery, and the raising of its performance and the reduction of cost directly influence the whole power battery industry.Therefore it is most important to motive force of development battery industry to seek cheapness, stable performance, safety, eco-friendly cell positive material.The appearance of polyanion type positive electrode, particularly LiFePO in recent years 4Advantages such as, safety cheap, stable circulation and become the research focus of lithium ion power battery cathode material with it.In all polyanion type compounds, Li 2FeSiO 4Because of having the LiFePO of ratio 4The abundanter characteristic more friendly with environment of raw material reserves caused the great interest in lithium ion battery material field.Anton Nyte ' n etc. utilized solid phase method successfully to synthesize Li in 2005 2FeSiO 4[Nyte ' n A, Abouimrane A, Armand M, et al.Electrochemicalperformance of Li 2FeSiO 4As a new Li-battery cathodematerial[J] .Electrochemistry Communications, 2005,7:156-160.] according to existing document, adopt the ferrous lithium of high temperature solid-state method synthetic silicic acid mostly, also have by softening methods such as sol-gal process and hydro thermal methods and come the ferrous lithium of synthetic silicic acid [R.Dominko, D.E.Conte, D.Hanzel et al.Impact of synthesisconditions on the structure and performance of Li 2FeSiO 4[J] .Journal of PowerSources, 2008,178 (2): 842-847.].Though the synthetic method of solid phase method is simple, it is exactly that material grains after synthetic is big that this method has common shortcoming, skewness.The synthetic advantage of sol-gal process is that the material granule that obtains has good uniformity, but this method complex process is wayward and the reaction time is longer.The technology that adopts all needs the very long processing time at present, and energy consumption is excessive, and prepared material contains dephasign in most of research, and purity is not enough.
Summary of the invention
The purpose of this invention is to provide a kind of anode composite material of lithium ion battery and preparation method thereof, with obtain advantages of good crystallization, crystal grain tiny evenly, have highly purified carbon and coat composite positive pole, realize Li 2FeSiO 4The improvement of positive electrode chemical property.
For achieving the above object, technical scheme of the present invention is:
A kind of anode composite material of lithium ion battery is characterized in that, the molecular formula of this anode composite material of lithium ion battery is Li 2FeSiO 4/ C, by mass percentage, the content of silicate is 95%～80%, the content of compound carbon be 5%～20%.
A kind of preparation method of anode composite material of lithium ion battery is characterized in that, may further comprise the steps:
1) be that 1: 1 ferrous salt and silicate makes its even mixing by ball milling with mol ratio, mixture; Fully wash this mixture with deionized water, obtain presoma in 50 ~ 120 ℃ of oven dry;
2) again presoma and lithium salts and organic carbon source are carried out mixing and ball milling; in the lithium salts in Li element and the presoma mol ratio of Fe element be 2: 1; the addition of organic carbon source is: by quality than presoma: organic carbon source=1: 0.2～0.5; presoma and lithium salts and organic carbon source mix the back compressing tablet; microwave thermal is handled under inert gas shielding; the microwave thermal treatment temperature is 600～800 ℃, makes Li 2FeSiO 4/ C anode composite material of lithium ion battery, by mass percentage, the content of silicate is 95%～80%, the content of compound carbon be 5%～20%.
The time that ferrous salt and silicate ball milling mix is 30 ~ 60min, and the time that presoma and lithium salts and organic carbon source carry out mixing and ball milling is 2～6h, and the microwave heat treatment period is 5～20min.
Molysite is selected from least a in frerrous chloride, the ferrous sulfate; Silicate is selected from least a in sodium metasilicate, the potassium metasilicate; Step 2) in, described lithium salts is selected from least a in lithium acetate, lithium carbonate, the lithium hydroxide; Described organic carbon source is selected from least a in starch, glucose, sucrose, the polyvinyl alcohol.
Positive electrode of the present invention is made into CR2025 type button cell and carries out the charge and discharge cycles test.Adopt coating method to prepare electrode, with N2 N-methyl-2-2-pyrrolidone N-(NMP) is solvent, respectively takes by weighing active material, acetylene black and PVDF at 75: 15: 10 by mass ratio, after mixing, be coated on the pretreated aluminium foil, put into vacuum drying chamber and obtain positive plate 120 ℃ of dryings.In being full of the glove box of argon gas, be negative pole with the metal lithium sheet, 0.8MLiBOB/EC+PC+EMC (1: 1: 3 volume ratio) is an electrolyte, the Celgard2400 porous polyethylene membrane is a barrier film, the assembling button cell.Carry out the constant current charge-discharge performance test with the LAND battery test system.Voltage range: 2.0～4.0V, probe temperature are 60 ℃.
Advantage of the present invention and effect:
The present invention adopts the auxiliary microwave process for synthesizing of low fever solid phase reaction to prepare Li 2FeSiO 4Abundant mixing and finely dispersed FeOOH/ amorphous Si O under the effect of mechanical force, have been obtained 2Presoma.And the refinement of low fever solid phase reaction process crystal grain, greatly improve the precursor powder reactivity, improve even particle distribution.The control of synthesis conditions such as selection that can be by the differential responses objects system and mechanical force time, particle size is little, specific area big and the presoma of regular morphology to obtain, and reaches the improvement to anodal material microstructure.The presoma technology of preparing is handled advantage in conjunction with microwave thermal, make reaction system obtain quick integral and heat equably, strengthened solid ionic diffusivity in the reaction, accelerate reaction rate, shorten the generated time of material greatly, help the acquisition of pure phase material and the formation of small grains.Adopting the carbon organic precursor simultaneously is that carbon source can be mixed with reactant more equably, and the carbon of organic substance cracking in microwave thermal is handled is except serving as reducing agent, remaining carbon can also stop the reunion of product particle, is evenly dispersed between the anodal particle, and carbon coats and Li 2FeSiO 4Crystal growth was finished in a step, had realized that original position carbon coats; The excessive grain growth of material also forms the conductive network that is interconnected in having suppressed to react, and improves conductivity of electrolyte materials, has improved the electrode reaction dynamic performance.
The present invention prepares Li with the auxiliary microwave carbothermic method of low fever solid phase reaction 2FeSiO 4/ C composite material is beneficial to the synthetic and synchronous with it particle surface carbon of realizing ferric reduction, ferric metasilicate lithium and coats,, technology is simple, and generated time is short, and power consumption is few, and process is controlled, and prepared material has specific discharge capacity and cycle performance preferably.In the ferrous lithium of in the technology of the present invention technical background, mentioning of softening method synthetic silicic acid, though obtained Li 2FeSiO 4/ C composite material, but contain more impurity (Fe 2O 3, SiO 2And Li 2SiO 3), at C/20 (8.5mAg -1) current density under specific discharge capacity be approximately 100mAhg -1The material that the method that the present invention adopts makes has higher purity and better electrochemical performance.To contain the Li of 10%w C 2FeSiO 4/ C composite material is an example, and the XRD analysis result does not see Li 2SiO 3Exist Deng dephasign, have higher phase purity, at 10mAg -1And 30mAg -1Under the current density condition specific discharge capacity be respectively 119.6,103.7mAhg -1
Description of drawings
Fig. 1 is Li 2FeSiO 4The x-ray diffraction pattern of/C composite sample.(a, embodiment 1; B, embodiment 2; C, embodiment 3).
Fig. 2 is the Li that embodiment 4 obtains 2FeSiO 4/ C composite sample SEM figure.(a, 20000 times of multiplication factors; B, multiplication factor is 3000 times).
Fig. 3 is preceding 2 charging and discharging curve figure of battery among the embodiment 1, and current density is 10mAg -1, a charges and discharge curve first; B charges and discharge curve for the second time.
Fig. 4 is the first charge-discharge curve chart of battery among the embodiment 2, and current density is a, 10mAg -1B, 30mAg -1
Fig. 5 is the 2nd, 3 charging and discharging curve figure of battery among the embodiment 3, and current density is 10mAg -1(a, the 2nd time; B the 3rd time).
Fig. 6 is the 2nd charging and discharging curve of battery among the embodiment 4, and current density is a, 10mAg -1B, 30mAg -1
Fig. 7 is the cycle performance figure of battery among the embodiment 4, and current density is 15mAg -1
Fig. 8 is the cycle performance figure of battery among the embodiment 5, and current density is 10mAg -1
Embodiment
Embodiment 1
With 19.88gFeCl 24H 2O and 28.42g Na 2SiO 39H 2The O ball milling evenly mixes 60min, with three said mixtures of deionized water wash, filters, in 80 ℃ of oven dry.To obtain the precursor powder again with 7.4g Li 2CO 3With 5.5g starch ball milling 5h, mix the back compressing tablet, microwave heating is handled 8min for 750 ℃ under argon shield, promptly obtains described composite material.In this composite material, 95%w Li 2FeSiO 4, 5%w C.Do not see Fe in the XRD figure 2O 3, SiO 2, Li 2SiO 3Exist Deng dephasign, this composite material has higher phase purity and good crystal property.This composite positive pole is 10mAg in current density -1Under the condition preceding 2 specific discharge capacities be respectively 109.9,110mAhg -1
Embodiment 2
With 9.94gFeCl 24H 2O and 8.62g K 2SiO 3H 2The O ball milling evenly mixes 40min, with three said mixtures of deionized water wash, filters, in 60 ℃ of oven dry.To obtain the precursor powder again with 4.42g LiOHH 2O and 6g glucose ball milling 4h mix the back compressing tablet, and microwave heating is handled 10min for 650 ℃ under argon shield, promptly obtains described composite material.In this composite material, 90%w Li 2FeSiO 4, 10%w C.This composite positive pole is at 10mAg -1And 30mAg -1Under the current density condition first discharge specific capacity be respectively 119.6,103.7mAhg -1
Embodiment 3
With 6.95gFeSO 47H 2O and 7.11g Na 2SiO 39H 2The O ball milling evenly mixes 30min, with three said mixtures of deionized water wash, filters 70 ℃ of oven dry.To obtain the precursor powder again with 5.1g LiAc2H 2O and 4.5g sucrose ball milling 3h mix the back compressing tablet, and microwave heating is handled 15min for 600 ℃ under argon shield, promptly obtains described composite material.In this composite material, 85%w Li 2FeSiO 4, 15%w C.Do not see Fe in the XRD figure 3O 4, SiO 2, Li 2SiO 3Exist Deng dephasign, this composite material has higher phase purity.This composite positive pole is at 10mAg -1Under the current density condition the 2nd, 3 specific discharge capacity be respectively 120.9,121.7mAhg -1
Embodiment 4
With 19.88gFeCl 24H 2O and 28.42g Na 2SiO 39H 2The O ball milling evenly mixes 50min, with three said mixtures of deionized water wash, filters, in 90 ℃ of oven dry.To obtain the precursor powder again with 8.84g LiOHH 2O and 5g polyvinyl alcohol ball milling 6h mix the back compressing tablet, and microwave heating is handled 12min for 650 ℃ under argon shield, promptly obtains described composite material.In this composite material, 88%w Li 2FeSiO 4, 12%w C.The less particle mean size of this composite positive pole product particle size is about 200 ~ 300nm among the SEM figure, and is evenly distributed, and carbon is dispersed in particle surface well.This composite positive pole is at 10mAg -1And 30mAg -1Under the current density condition the 2nd specific discharge capacity be respectively 120,104.3mAhg -1In current density is 15mAg -1Under the condition, 60 specific discharge capacities that circulate are from 116.7mAhg -1Remain 112.9mAhg -1
Embodiment 5
With 27.8gFeSO 47H 2O and 17.23g K 2SiO 3H 2The O ball milling evenly mixes 60min, with three said mixtures of deionized water wash, filters, in 50 ℃ of oven dry.To obtain the precursor powder again with 7.4g Li 2CO 3With 4g polyvinyl alcohol ball milling 6h, mix the back compressing tablet, microwave heating is handled 10min for 700 ℃ under argon shield, promptly obtains described composite material.In this composite material, 91%w Li 2FeSiO 4, 9%w C.This composite positive pole is at 10mAg -130 specific discharge capacities of circulation are from 118.5mAhg under the current density condition -1Remain 116.2mAhg -1

Claims (3)

1. the preparation method of an anode composite material of lithium ion battery is characterized in that, may further comprise the steps:
1) be that 1: 1 ferrous salt and silicate makes its even mixing by ball milling with mol ratio, mixture; Fully wash this mixture with deionized water, obtain presoma in 50～120 ℃ of oven dry;
2) again presoma and lithium salts and organic carbon source are carried out mixing and ball milling; in the lithium salts in Li element and the presoma mol ratio of Fe element be 2: 1; the addition of organic carbon source is: by quality than presoma: organic carbon source=1: 0.2～0.5; presoma and lithium salts and organic carbon source mix the back compressing tablet; microwave thermal is handled under inert gas shielding; the microwave thermal treatment temperature is 600～800 ℃, makes Li 2FeSiO 4/ C anode composite material of lithium ion battery, by mass percentage, the content of silicate is 95%～80%, the content of compound carbon be 5%～20%.
2. the preparation method of anode composite material of lithium ion battery according to claim 1, it is characterized in that, the time that ferrous salt and silicate ball milling mix is 30～60min, the time that presoma and lithium salts and organic carbon source carry out mixing and ball milling is 2～6h, and the microwave heat treatment period is 5～20min.
3. the preparation method of anode composite material of lithium ion battery according to claim 1 and 2 is characterized in that, molysite is selected from least a in frerrous chloride, the ferrous sulfate; Silicate is selected from least a in sodium metasilicate, the potassium metasilicate; Step 2) in, described lithium salts is selected from least a in lithium acetate, lithium carbonate, the lithium hydroxide; Described organic carbon source is selected from least a in starch, glucose, sucrose, the polyvinyl alcohol.
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