CN101867038B - Method for preparing anode composite material for lithium sulfur secondary batteries - Google Patents

Method for preparing anode composite material for lithium sulfur secondary batteries Download PDF

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CN101867038B
CN101867038B CN2010101938694A CN201010193869A CN101867038B CN 101867038 B CN101867038 B CN 101867038B CN 2010101938694 A CN2010101938694 A CN 2010101938694A CN 201010193869 A CN201010193869 A CN 201010193869A CN 101867038 B CN101867038 B CN 101867038B
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composite material
preparation
lithium
anode composite
rechargeable battery
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CN101867038A (en
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魏进平
靳佳
周震
秦杏
邢丽英
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Nankai University
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    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
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    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries

Abstract

The invention discloses a method for preparing an anode composite material for lithium sulfur secondary batteries, which comprises the following steps: 1) hydrolyzing ethyl orthosilicate to obtain nano SiO2 spheres; 2) mixing solution of a carbon source with the nano SiO2 spheres and heating the mixture to react the solution of the carbon source with the nano SiO2 spheres; 3) cooling, centrifuging, drying, calcining and carbonizing the product obtained by the previous step to obtain a SiO2-C core-shell structure material; 4) etching the SiO2-C core-shell structure material by using solution of HF, NaOH or KOH to obtain a hollow carbon sphere material; and 5) grinding and mixing sulfur and the hollow carbon sphere material, placing the mixture in a sealed container filled with an Ar gas, heating the mixture and casting the melt to obtain a S-C composite material. The method has the advantages that: 1) the process is simple; 2) the raw material is cheap and readily available and the production cost is low; and 3) the composite material has a special core-shell structure and therefore inhibits the loss of active materials, improves the conductive performance of the material and obviously improves the electrochemical performance of electrodes.

Description

A kind of preparation method who is used for the lithium-sulfur rechargeable battery anode composite material
Technical field
The present invention relates to the preparation of Li-S secondary battery electrode material, particularly a kind of preparation method who is used for the lithium-sulfur rechargeable battery anode composite material.
Background technology
Present commercial lithium ion secondary battery anode material has LiCoO 2, LiMn 2O 4And LiFePO 4Deng.But LiCoO 2Exist safety problem and cost higher, LiMn 2O 4The Reversible Cycle poor performance, LiFePO 4Theoretical specific capacity not high, be merely 170mAh/g, thereby limited its application aspect hybrid vehicle and large-scale redundant electrical power.Li-S secondary cell with high-energy-density has caused people's attention in recent years again.Elemental sulfur not only nature reserves is abundant, and is cheap, and theoretical specific capacity is 1672mAh/g, and the battery system theoretical energy density that constitutes with lithium metal will reach 2600Wh/kg, have the energy density that other positive electrodes are difficult to match in excellence or beauty.But the preparation of efficient S positive electrode is difficulty relatively; Because the polysulfide poorly conductive that generates in elemental sulfur and the charge and discharge process; And be soluble in organic electrolyte and make the sulfur electrode active material run off; The electrode cycle performance is poor, and the preparation of sulfur-bearing positive electrode is the key factor that restriction Li-S secondary cell further develops.
The S-C composite material becomes the focus of research in recent years.People [Electrochim.Acta 54 (2009) 3708] such as people such as Lai [J.Phys.Chem.C 113 (2009) 4712] and Zhang have synthesized the porous carbon-S composite material of high-specific surface area, and the electrochemistry capacitance and the cyclical stability of composite material are significantly improved.People such as Liang [Chem.Mater.21 (2009) 4724] have reported a kind of high-specific surface area and have had the S-C nano composite material of hierarchy that distillation S passes through CS 2The solvent osmosis gets in the bimodulus porous carbon materials, has improved the utilance of S, has improved the cycle performance of S.People such as Han Zhicheng make an addition to surfactant in active material S or the S based compound in [Chinese patent CN1467865A], not only prevented the formation of agglomerate but also increased ionic conductivity, thereby improved the energy density and the cycle life of battery.People such as Huang Dezhe are coated on positive active material S based compound on the collector in [Chinese patent CN1495937A]; Then the collector that is coated with is immersed in and forms polymeric layer in the polymer solution; This battery has improved the electrochemical reaction of electrode, shows high electrochemistry capacitance.People such as Nazar [Nat.Mater.8 (2009) 500] have prepared a kind of nanometer S-C composite material of height rule, and the S-C closeness of contact is very high.Highly the porous carbon CMK-3 of rule not only can arrive the S of insulation by the conducting electronics; And its structure can limit the sulphur nanofiber and in its duct, grows; The more important thing is many lithium sulfides that can be captured in the redox reaction in addition, active material is run off significantly reduce.That but people such as Nazar at first utilize is a kind of SiO of consisting of 2Hard template SBA-15 synthesize CMK-3, and the preparation complicacy of SBA-15 is loaded down with trivial details in the experiment.
Summary of the invention
The objective of the invention is to above-mentioned existing problems; A kind of preparation method who is used for the lithium-sulfur rechargeable battery anode composite material is provided; Simple, easy and simple to handle, the low in raw material cost of this method preparation technology; The composite material that makes have the S-C nucleocapsid structure and particle diameter little, its nucleocapsid structure has suppressed the loss of active material and has improved the electric conductivity of material, has significantly improved the chemical property of electrode.
Technical scheme of the present invention:
A kind of preparation method who is used for the lithium-sulfur rechargeable battery anode composite material comprises the steps:
1) ethyl orthosilicate is obtained nanometer SiO through method for hydrolysis 2Ball;
2) with carbon source solution and nanometer SiO 2Ball carries out reacting by heating after mixing;
3) with the above-mentioned product that makes through the cooling, centrifugal and the oven dry after calcine carbonization, make SiO 2-C nucleocapsid structure material;
4) with HF, NaOH or KOH solution etching SiO 2-C nucleocapsid structure material can obtain the hollow carbon sphere material;
5) with sulphur and hollow carbon sphere material ground and mixed, put into the airtight container that is full of Ar gas, promptly get the S-C composite material after the heating and melting perfusion.
The method for hydrolysis of said ethyl orthosilicate is: in the 500ml absolute ethyl alcohol, add (10~40) ml deionized water and (10~40) ml ammoniacal liquor; The mass percent concentration of ammoniacal liquor is (18~30) %; Back adding (20~60) ml ethyl orthosilicate stirs; Continue to stir 24~72 hours, promptly get SiO through centrifugal, oven dry then 2Ball.
Said carbon source is the combination of a kind of, two or more arbitrary proportion in glucose, sucrose, citric acid and the acetylene black, and the carbon source solution concentration is (0.1~5) mol/L water; Carbon source total amount and SiO 2The mass ratio that mixes is 1~3.
The temperature of said reacting by heating is (120~210) ℃, and the reaction time is 3~20 hours.
Said calcining carburizing temperature is (550~950) ℃, and the calcining carbonization time is 3~10 hours.
The mass percent concentration of said HF solution is (2~20) %, and etch period is 5~72 hours.
The concentration of said NaOH or KOH solution is (3~15) mol/L, and etch period is 5~80 hours, and temperature is (20~85) ℃.
The mass ratio of said sulphur and hollow carbon sphere material ground and mixed is 1~3, and the fusion filling temperature is (130-200) ℃, and the fusion infusion time is 5~40 hours.
Good effect of the present invention is: 1) this method technology is simple; 2) prices of raw and semifnished materials cheap, be easy to get, production cost is low; 3) the distinctive nucleocapsid structure of composite material has suppressed the loss of active material and has improved the electric conductivity of material, has significantly improved the chemical property of electrode.
Description of drawings
Fig. 1 is nanometer SiO 2The SEM figure of ball.
Fig. 2 is 850 ℃ of SiO after the calcining 2The SEM figure of-C composite material of core-shell structure.
Fig. 3 is the TEM figure of hollow material with carbon element.
Fig. 4 is the TEM figure of S-C composite material of core-shell structure.
Fig. 5 is the first charge-discharge figure of bright sulfur and S-C composite material of core-shell structure.
Fig. 6 is the charge and discharge circulation life figure of bright sulfur and S-C composite material of core-shell structure.
Embodiment
Embodiment 1:
1) nanometer SiO 2The preparation of ball
In the 500ml absolute ethyl alcohol, add 20ml deionized water and 20ml ammoniacal liquor, the mass percent concentration of ammoniacal liquor is 25%, and the back that stirs adds the 40ml ethyl orthosilicate, continues to stir 48 hours, promptly gets SiO through centrifugal, oven dry then 2Ball.SiO 2The pattern of ball is seen Fig. 1.
2) SiO 2The preparation of-C composite material of core-shell structure
With etc. the glucose and the nanometer SiO of quality 2Ball is at 30ml deionized water for stirring mixing, and 180 ℃ of reactions are after 10 hours, and product is earlier through cooling, and is centrifugal, and oven dry promptly got SiO in 5 hours through 850 ℃ of calcinings again 2-C composite material of core-shell structure.SiO 2The pattern of-C composite material of core-shell structure is seen Fig. 2.
3) preparation of hollow material with carbon element
With SiO 2-C composite material of core-shell structure uses mass percent concentration to be 8%HF solution etching 24 hours, promptly gets hollow material with carbon element, and the transmission electron microscope picture of hollow material with carbon element is seen Fig. 3.
4) preparation of S-C composite material of core-shell structure
Sulphur and hollow material with carbon element ground and mixed is even, put into the sealed reactor that is full of Ar gas, then sealed reactor is put into 155 ℃ of fusion perfusions of baking oven and promptly got in 24 hours.The transmission electron microscope picture of S-C composite material of core-shell structure is seen Fig. 4.
S-C composite material of core-shell structure, conductive agent, binding agent (PTFE) are pressed mass ratio to be mixed at 70: 20: 10; Being pressed into diameter is the circular electrode sheet of 8mm; Form battery with lithium electrode and compare test, charging and discharging currents density is 40mA/g, and voltage range is 1.5~3V.
Fig. 5 is the first charge-discharge figure of bright sulfur and S-C composite material of core-shell structure.Visible from figure, the discharge capacity in first week of S-C composite material is 465.3mAh/g, and the discharge capacity first of bright sulfur is merely 130mAh/g, and this shows that the chemical property of S-C composite material has had significant improvement.
Fig. 6 is the charge and discharge circulation life figure of bright sulfur and S-C composite material of core-shell structure.Discharge capacity is 293.5mAh/g after 26 weeks of S-C composite material circulation, and bright sulfur only has 98.7mAh/g, shows that the cycle performance of S-C composite material has bigger improvement.
Embodiment 2:
1) nanometer SiO 2The preparation of ball
In the 500ml absolute ethyl alcohol, add 15ml deionized water and 15ml ammoniacal liquor, the mass percent concentration of ammoniacal liquor is 20%, stirs the back and adds the 30ml ethyl orthosilicate, stirs 36 hours after centrifugal again, and oven dry promptly gets SiO 2Ball.The SiO that obtains 2The pattern of ball is similar with Fig. 1.
2) SiO 2The preparation of-C composite material of core-shell structure
With etc. the sucrose and the nanometer SiO of quality 2Ball is at 30ml deionized water for stirring mixing, and 170 ℃ of reactions are after 10 hours, and product is earlier through cooling, and is centrifugal, and oven dry promptly got SiO in 5 hours through 800 ℃ of calcinings again 2-C composite material of core-shell structure.The SiO of preparation 2The pattern of-C composite material of core-shell structure is similar with Fig. 2.
3) preparation of hollow material with carbon element
With SiO 2-C composite material of core-shell structure 60 ℃ of following etchings 40 hours, can make hollow material with carbon element with the KOH solution of mass percent concentration 10mol/L.The pattern of this hollow material with carbon element with see that Fig. 3 is similar.
4) preparation of S-C composite material of core-shell structure
It is 1~3 to mix that sulphur and hollow material with carbon element are ground by mass ratio, puts into the sealed reactor that is full of Ar gas, then sealed reactor is put into 160 ℃ of fusions perfusions of baking oven and promptly gets in 20 hours.
S-C composite material of core-shell structure, conductive agent, binding agent (PTFE) are pressed mass ratio to be mixed at 70: 20: 10; Being pressed into diameter is the circular electrode sheet of 8mm; Form battery with lithium electrode and compare test, charging and discharging currents density is 40mA/g, and voltage range is 1.5~3V.The discharge capacity in first week of S-C composite material is 440mAh/g, and the discharge capacity first of bright sulfur is merely 130mAh/g, and this shows that the chemical property of S-C composite material has had significant improvement.

Claims (8)

1. a preparation method who is used for the lithium-sulfur rechargeable battery anode composite material is characterized in that comprising the steps:
1) ethyl orthosilicate is obtained nanometer SiO2 ball through method for hydrolysis;
2) with carbon source solution with carry out reacting by heating after nanometer SiO2 ball mixes;
3) with the above-mentioned product that makes through the cooling, centrifugal and the oven dry after calcine carbonization, make SiO2-C nucleocapsid structure material;
4) can obtain the hollow carbon sphere material with HF, NaOH or KOH solution etching SiO2-C nucleocapsid structure material;
5) with sulphur and hollow carbon sphere material ground and mixed, put into the airtight container that is full of Ar gas, promptly get the S-C composite material after the heating and melting perfusion;
Described carbon source is one or more in glucose, sucrose or the citric acid.
2. the preparation method who is used for the lithium-sulfur rechargeable battery anode composite material according to claim 1; It is characterized in that: the method for hydrolysis of said ethyl orthosilicate is: in the 500ml absolute ethyl alcohol, add 10~40ml deionized water and 10~40ml ammoniacal liquor; The mass percent concentration of ammoniacal liquor is 18~30%; Add 20~60ml ethyl orthosilicate after stirring, continue to stir 24~72 hours, promptly get the SiO2 ball through centrifugal, oven dry then.
3. the preparation method who is used for the lithium-sulfur rechargeable battery anode composite material according to claim 1 is characterized in that: the concentration of said carbon source solution is 0.1~5mol/L water; The mass ratio that the carbon source total amount is mixed with SiO2 is 1~3.
4. the preparation method who is used for the lithium-sulfur rechargeable battery anode composite material according to claim 1 is characterized in that: the temperature of said reacting by heating is 120~210 ℃, and the reaction time is 3~20 hours.
5. the preparation method who is used for the lithium-sulfur rechargeable battery anode composite material according to claim 1 is characterized in that: said calcining carburizing temperature is 550~950 ℃, and the calcining carbonization time is 3~10 hours.
6. the preparation method who is used for the lithium-sulfur rechargeable battery anode composite material according to claim 1 is characterized in that: the mass percent concentration of said HF solution is 2~20%, and etch period is 5~72 hours.
7. the preparation method who is used for the lithium-sulfur rechargeable battery anode composite material according to claim 1 is characterized in that: the concentration of said NaOH or KOH solution is 3~15mol/L, and etch period is 5~80 hours, and temperature is 20~85 ℃.
8. the preparation method who is used for the lithium-sulfur rechargeable battery anode composite material according to claim 1; It is characterized in that: the mass ratio of said sulphur and hollow carbon sphere material ground and mixed is 1~3; The fusion filling temperature is 130~200 ℃, and the fusion infusion time is 5~40 hours.
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CN102097622B (en) * 2011-01-18 2013-03-20 中国人民解放军国防科学技术大学 Sulfur-containing composite anode material, anode plate and Li-S (lithium-sulfur) secondary battery and preparation method thereof
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CN104393266B (en) * 2014-12-08 2016-10-05 北京化工大学 A kind of silico-carbo combination electrode material of nucleocapsid structure and preparation method thereof
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CN104900845B (en) * 2015-05-14 2017-04-05 中国矿业大学 The preparation method of the sulfur meso-porous titanium dioxide silicon composite of nano-valve encapsulation
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