CN101159323A - Electric pole material of natural modified spherical mineral carbon load nano particle and preparation method thereof - Google Patents

Electric pole material of natural modified spherical mineral carbon load nano particle and preparation method thereof Download PDF

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Publication number
CN101159323A
CN101159323A CNA2007100461756A CN200710046175A CN101159323A CN 101159323 A CN101159323 A CN 101159323A CN A2007100461756 A CNA2007100461756 A CN A2007100461756A CN 200710046175 A CN200710046175 A CN 200710046175A CN 101159323 A CN101159323 A CN 101159323A
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electrode material
capacity
msg
load
preparation
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夏永姚
李峰
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Fudan University
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Fudan 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

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Abstract

The invention relates to a composite electrode material of natural modified spherical graphite (MSG)-loading nano-Cu6Sn5 and a fabrication method thereof. The main body of the electrode material is natural modified spherical graphite (MSG), and the particle surface of the main body material loads Cu6Sn5 alloy particles in the scale of nanometer. In the structure of the composite material, Cu6Sn5 nanoparticles are fixedly loaded on the surface of graphite, which buffers the volume expansion as well as ensures the conductivity in the process of recirculation, and the surface of graphite has Cu6Sn5 nanoparticles of high specific capacity, which enhances the capacity of entire electrode materials. By using the present composite material as negative materials of Li-ion batteries, the negative materials of Li-ion batteries can be obtained with high-capacity Li-storage, excellent security and good circulation.

Description

Electrode material of natural modified spherical mineral carbon load nano particle and preparation method thereof
Technical field
The invention belongs to the electrochemical material technical field, be specifically related to a kind of natural modified spherical mineral carbon load nanometer Cu 6Sn 5Particle combination electrode material and preparation method thereof.
Background technology
Along with economy constantly develops, must cause increasing the weight of of depletion of natural resources, environmental pollution and global greenhouse effects such as oil, coal.The human equilibrium relation that must hold between economic growth, environmental protection and the energy resource supply this Trinitarian " three E ".Now the consumption figure in energy every year is converted to oil and is about 8,000,000,000 tons in the world, and wherein 90% is fossil fuel.By present consumption speed, greatly just can be exhausted after 100 years to 200 years.The comprehensive high-efficiency development and utilization of new forms of energy, power-saving technology and green technology has become very urgent subject.Lithium ion battery applies in the middle of the daily life widely as a kind of newer secondary energy sources.But along with science and technology development, people have higher requirement to present business-like lithium ion battery, and hope can further improve its power density and energy density.Concerning present business-like graphite material, its theoretical capacity has only 372mAh/g, more and more is difficult to satisfy the demand along with the perfect day by day various electronic products of scientific and technological progress.Therefore, a kind of negative material with suitable potential and high power capacity will bring revolutionary development to the lithium ion battery industry.
In recent years, discover that many metals (Sn, Zn, Al, Si etc.) can form alloy with it by the embedding lithium, and its theoretical embedding lithium capacity is higher than graphite material far away.Yet these materials are embedding/are deviating from and having serious volumetric expansion and contraction in the lithium process, cause the avalanche of material structure and efflorescence, the peeling phenomenon of electrode material easily, and this just makes material and collector body loose contact, and the cycle performance of electrode sharply descends.1999, Kepler people such as (Electrochem.Solid State Lett.2 (7) (1999) 307) found Cu 6Sn 5Alloy material can embed the Li ion and form Li xCu 6Sn 5Alloy, the theoretical capacity of embedding lithium can reach 650mAh/g, is far longer than the theoretical capacity of graphite, and its energy density per unit volume metric density is bigger several times than graphite simultaneously, is a kind of up-and-coming high-energy-density lithium ion battery negative material.At Cu 6Sn 5In the alloy structure.Inactive Cu plays the buffer medium effect that disperses in lattice, reduce that lithium embeds and the volumetric expansion when deviating from.However, common synthetic Cu 6Sn 5Alloy material is owing to the volumetric expansion problem in the embedding lithium process, and performance still can't reach business-like requirement.Discover, prepare nano level alloy material and can reduce its absolute volume variation in charge and discharge process better cycle ability is arranged than common alloy material.Nano level then alloy material, the volumetric expansion in cyclic process also can cause the secondary agglomeration of nano particle, thereby after particle is grown up gradually the performance that the efflorescence peeling phenomenon has reduced electrode material take place again.
Summary of the invention
In order to address the above problem, the present invention proposes a kind of natural modified graphite MSG loaded with nano Cu 6Sn 5Electrode material of particle and preparation method thereof is to satisfy the application requirements of high-energy-density lithium ion battery negative material.Its preparation method is to use the nanometer Cu of liquid phase reduction with preparation 6Sn 5Particle load is on native graphite MSG surface.This nano level alloy particle adhere to the capacity that has not only improved the overall electrode material, simultaneously because the existence of graphite base has effectively suppressed Cu 6Sn 5The reunion of nano particle and volumetric expansion are greatly increased whole cycle performance.
The electrode material of the natural modified mineral carbon load nano particle that the present invention proposes is by nano particle Cu 6Sn 5Load on natural spherical plumbago MSG surface composition uniformly, Cu 6Sn 5The load quality ratio from 10wt% to 40wt%, preferred load quality is than being 15%--20%.If the load quality ratio is lower than 10wt%, then because Cu 6Sn 5Content cross the low specific capacity that can't improve the overall electrode material effectively; If the load quality ratio is greater than 40wt%, then because Cu 6Sn 5Can't be distributed to the serious reunion that graphite surface causes nano particle effectively thereby content is excessive, reduce the cycle performance of electrode material to a great extent.
Among the present invention, be carried on the Cu of graphite surface 6Sn 5Be nano particle, its preparation method is to pass through NaBH 4Or KBH 4Also to contain molar ratio be 6: 5 the copper and the salting liquid of tin for original reagent reduction, adds citric acid or oleic acid etc. as complexing agent, obtained nano level alloy particle thereby suppress growing up of particle effectively.Compare with using the synthetic alloy method of high-temperature calcination in the conventional method, this method is simple to operate, and synthetic particle particle is little, has also avoided the secondary agglomeration phenomenon of particle in the high-temperature calcination process to take place.
Among the present invention, employed preparation method is as follows: natural modified spherical mineral carbon MSG is added in the mixed solution of entry and ethanol, ultrasonic dispersion adds the powerful stirring of reducing agent and complexing agent.To contain molar ratio is that 6: 5 the copper and the salting liquid of tin slowly splash in the solution, is added dropwise to complete the back and continues to stir a period of time, and resulting product is filtered, washs and vacuumize, promptly obtains natural modified graphite MSG loaded with nano Cu 6Sn 5Particle composite material.
With natural modified graphite MSG loaded with nano Cu of the present invention 6Sn 5Particle composite material is as lithium ion battery negative, and its specific capacity also has excellent cycle performance simultaneously apparently higher than traditional graphite cathode material.
Specific implementation method
The embodiment of the following stated understands the present invention in detail.
Embodiment 1:
With natural modified spherical mineral carbon MSG as negative material, its electrode preparation method is as follows: with conductive agent: binding agent: (conductive agent adopts acetylene black or carbon black to the mixed slurry of graphite (MSG)=5: 10: 85 here, binding agent adopts polyvinylidene fluoride (pvdf)), control certain thickness and evenly be coated on the Copper Foil collector.Cut out suitable big or small electrode slice, in vacuum, behind 80 ℃ of baking 12h, in glove box, put into the test of row single electrode according to the der group of positive pole/barrier film/negative pole.The single electrode test is a negative pole with the lithium sheet, 1M LiPF 6-EC/DMC (volume ratio is 1: 1) is an electrolyte, and barrier film adopts the commercial Li-ion batteries barrier film, is assembled into button cell (CR2016).Battery operated interval is 0-2.0V, charging and discharging currents is 100mA/g, recording its initial discharge capacity is 397mAh/g, the second circle discharge capacity is 315mAh/g, the first circle irreversible capacity is 82mAh/g, discharge platform still maintains 290mAh/g through 30 circulation back capacity between 0.2V-0.05V, shown its excellent cycle performance (seeing table 1 for details).
Embodiment 2:
With 1.3g citric acid and 5g NaBH 4Or KBH 4Powerful stirring and dissolving in the mixed solution of adding 200ml ethanol and 600ml deionized water, other takes by weighing 1.05g CuCl 2With 1.800g SnCl 4In the dissolving and the 20ml aqueous solution, stir and slowly splash into NaBH down 4In the solution, dropwise the back and continue to stir 10min, obtain nanometer Cu after filtration, washing and the vacuumize 6Sn 5Material, its granular size is between 20-50nm.With nanometer Cu 6Sn 5As negative material, according to embodiment 1 described method assembled battery.This alloy material discharge capacity first can reach 792mAh/g, but first circle irreversible capacity big (350mAh/g), and its cycle performance is relatively poor, and 30 times circulation back capacity only is 223mAh/g.MSG compares with native graphite, nanometer Cu 6Sn 5Do not have tangible discharge platform, charging and discharging curve all is the curve (seeing table 1 for details) that tilts between 0-2V.
Embodiment 3:
The natural modified graphite MSG of 9.0g is added in the mixed solution of 200ml ethanol and 600ml deionized water, and ultrasonic dispersion 30min adds 1.3g citric acid and 5g NaBH 4Or KBH 4Powerful stirring and dissolving in solution, other takes by weighing 1.05g CuCl 2With 1.80g SnCl 4In the dissolving and the 20ml aqueous solution, stir and slowly splash into MSG and NaBH down 4In the mixed solution, dropwise the back and continue to stir 10min, obtain natural modified graphite MSG loaded with nano Cu after filtration, washing and the vacuumize 6Sn 5Particle composite material, its load capacity are 10wt%, the Cu of load 6Sn 5Particle size is between 10-30nm.With this composite material as negative material, according to embodiment 1 described method assembled battery.This composite material discharge capacity first can reach 526mAh/g, and the second circle discharge capacity is 404mAh/g, and the first circle irreversible capacity is 122mAh/g.30 times circulation back capacity also has 324mAh/g.MSG compares with native graphite, 10wt%Cu 6Sn 5Discharge capacity after the composite material of the load capacity 30 times circulation is big 34mAh/g, and show reasonable cycle performance (seeing table 1 for details).
Embodiment 4:
The natural modified graphite MSG of 4.0g is added in the mixed solution of 200ml ethanol and 600ml deionized water, and ultrasonic dispersion 30min adds 1.3g citric acid and 5g NaBH 4Or KBH 4Powerful stirring and dissolving in solution, other takes by weighing 1.05g CuCl 2With 1.80g SnCl 4In the dissolving and the 20ml aqueous solution, stir and slowly splash into MSG and NaBH down 4In the mixed solution, dropwise the back and continue to stir 10min, obtain natural modified graphite MSG loaded with nano Cu after filtration, washing and the vacuumize 6Sn 5Particle composite material, its load capacity are 20wt%.With this composite material as negative material, according to embodiment 1 described method assembled battery.This composite material discharge capacity first can reach 619mAh/g, and the second circle discharge capacity is 457mAh/g, and the first circle irreversible capacity is 162mAh/g.30 times circulation back capacity also has 357mAh/g.MSG compares with native graphite, and its charging and discharging curve is different with native graphite, and after the platform of 0.2V-0.05V, charging and discharging curve all comparatively tilts, and this has represented Cu 6Sn 5Capacity.Because Cu 6Sn 5Capacity bigger, improved the specific capacity of composite material on the whole, simultaneously because graphite base has good electrical conductivity, make whole cycle performance also better (seeing table 1 for details).
Embodiment 5:
The natural modified graphite MSG of 2.3g is added in the mixed solution of 200ml ethanol and 600ml deionized water, and ultrasonic dispersion 30min adds 1.3g citric acid and 5g NaBH 4Or KBH 4Powerful stirring and dissolving in solution, other takes by weighing 1.05g CuCl 2With 1.80g SnCl 4In the dissolving and the 20ml aqueous solution, stir and slowly splash into MSG and NaBH down 4In the mixed solution, dropwise the back and continue to stir 10min, obtain natural modified graphite MSG loaded with nano Cu after filtration, washing and the vacuumize 6Sn 5Particle composite material, its load capacity are 30wt%.With this composite material as negative material, according to embodiment 1 described method assembled battery.This composite material discharge capacity first can reach 678mAh/g, but the second circle discharge capacity only is 428mAh/g, and the first circle irreversible capacity is 250mAh/g.30 times circulation back capacity also has 284mAh/g.Find out from data, though load 30wt%Cu 6Sn 5The composite material of particle has very big discharge capacity first, but because Cu 6Sn 5Load capacity is too big, can't be distributed to graphite surface effectively, thereby causes particle self to reunite, therefore capacity attenuation rapid (seeing table 1 for details) in charge and discharge process.
Embodiment 6:
The natural modified graphite MSG of 1.5g is added in the mixed solution of 200ml ethanol and 600ml deionized water, and ultrasonic dispersion 30min adds 1.3g citric acid and 5g NaBH 4Or KBH 4Powerful stirring and dissolving in solution, other takes by weighing 1.05g CuCl 2With 1.80g SnCl 4In the dissolving and the 20ml aqueous solution, stir and slowly splash into MSG and NaBH down 4In the mixed solution, dropwise the back and continue to stir 10min, obtain natural modified graphite MSG loaded with nano Cu after filtration, washing and the vacuumize 6Sn 5Particle composite material, its load capacity are 40wt%.With this composite material as negative material, according to embodiment 1 described method assembled battery.Its first discharge capacity can reach 716mAh/g, but capacity attenuation is rapid, 30 only surplus 254mAh/g of circulation back capacity.The capacity that composite material is described is along with Cu 6Sn 5Load capacity increase and increase, but cycle performance is along with Cu 6Sn 5Load capacity increase and reduce.Relatively comprehensive, the Cu of load 20wt% 6Sn 5Composite material higher specific capacity and better cycle performance (seeing table 1 for details) are arranged.
Embodiment 7:
The natural modified graphite MSG of 4.0g is added in the 800ml ethanolic solution, and ultrasonic dispersion 30min adds 1.80g oleic acid and 5g NaBH 4Or KBH 4Powerful stirring and dissolving in solution, other takes by weighing 1.05g CuCl 2With 1.80g SnCl 4In the dissolving and the 20ml aqueous solution, stir and slowly splash into MSG and NaBH down 4In the mixed solution, dropwise the back and continue to stir 10min, obtain natural modified graphite MSG load 20wt% Cu after filtration, washing and the vacuumize 6Sn 5Nano composition.With the Cu that uses citric acid to synthesize as complexing agent 6Sn 5Nano particle is identical substantially, and granular size is between 10-30nm.With this composite material as negative material, according to embodiment 1 described method assembled battery.This composite material discharge capacity first can reach 602mAh/g, and the second circle discharge capacity is 449mAh/g, and the first circle irreversible capacity is 153mAh/g.30 times circulation back capacity also has 345mAh/g (seeing table 1 for details).
Table .1 different content Cu 6Sn 5The MSG chemical property of nanometer particle load relatively
Discharge capacity mAh/g first Coulombic efficiency first 30 circulation back capacity mAh/g 30 circulation back capability retentions
Embodiment 1 (natural modified spherical mineral carbon MSG) 397 78％ 290 73％
Embodiment 2 (nanometer Cu 6Sn 5) 792 56％ 223 28％
Embodiment 3 (MSG load 10 wt%Cu 6Sn 5Composite material) 526 76％ 324 61％
Embodiment 4 (MSG load 20 wt%Cu 6Sn 5Composite material) 619 73％ 357 58％
Embodiment 5 (MSG load 30 wt%Cu 6Sn 5Composite material) 678 61％ 284 42％
Embodiment 6 (MSG load 40 wt%Cu 6Sn 5Composite material) 716 58％ 254 35％
Embodiment 7 (MSG load 20 wt%Cu 6Sn 5Composite material is made complexing agent with oleic acid) 602 74％ 345 57％

Claims (6)

1. the electrode material of a natural modified spherical mineral carbon load nano particle is characterized in that by nano particle Cu 6Sn 5The particle uniform load is in natural spherical plumbago MSG surface composition, Cu 6Sn 5The quality of particle load is 10%--40%.
2. electrode material according to claim 2 is characterized in that Cu 6Sn 5The load quality ratio be 15%--20%.
3. the preparation method of an electrode material as claimed in claim 1, it is characterized in that concrete steps are: natural modified spherical mineral carbon is added in the mixed solution of second alcohol and water, ultrasonic dispersion, add reducing agent and complexing agent, and stir, will contain mol ratio is that 6: 5 the copper and the salting liquid of tin are added drop-wise in the above-mentioned solution, continue to stir, reaction finishes the back filters, and washing, vacuumize promptly obtain described electrode material.
4. the preparation method of electrode material according to claim 3 is characterized in that described reducing agent is NaBH 4Or KBH 4
5. according to the preparation method of any one described electrode material in claim 3 or 4, it is characterized in that described complexing agent is citric acid or oleic acid.
6. electrode material according to claim 1 and 2 is used for lithium ion battery negative.
CNA2007100461756A 2007-09-20 2007-09-20 Electric pole material of natural modified spherical mineral carbon load nano particle and preparation method thereof Pending CN101159323A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20140065488A1 (en) * 2012-08-28 2014-03-06 Knu-Industry Cooperation Foundation Method of preparing negative active material for rechargeable lithium battery, and negative active material and rechargeable lithium battery prepared from the same
US9368792B2 (en) 2012-08-28 2016-06-14 Kangwon National University University-Industry Cooperation Foundation Negative active material for rechargeable lithium battery, method of preparing the same, and rechargeable lithium battery including the same
CN112041266A (en) * 2018-04-25 2020-12-04 格亚诺马特有限公司 Method for obtaining nano material composed of carbon-containing material and metal oxide

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20140065488A1 (en) * 2012-08-28 2014-03-06 Knu-Industry Cooperation Foundation Method of preparing negative active material for rechargeable lithium battery, and negative active material and rechargeable lithium battery prepared from the same
US9368792B2 (en) 2012-08-28 2016-06-14 Kangwon National University University-Industry Cooperation Foundation Negative active material for rechargeable lithium battery, method of preparing the same, and rechargeable lithium battery including the same
US9580322B2 (en) * 2012-08-28 2017-02-28 Knu-Industry Cooperation Foundation Method of preparing negative active material for rechargeable lithium battery, and negative active material and rechargeable lithium battery prepared from the same
CN112041266A (en) * 2018-04-25 2020-12-04 格亚诺马特有限公司 Method for obtaining nano material composed of carbon-containing material and metal oxide

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