CN101202341B - Carbon cladding alloy nanometer particle material for lithium ion battery and method for making same - Google Patents

Carbon cladding alloy nanometer particle material for lithium ion battery and method for making same Download PDF

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CN101202341B
CN101202341B CN2007101721784A CN200710172178A CN101202341B CN 101202341 B CN101202341 B CN 101202341B CN 2007101721784 A CN2007101721784 A CN 2007101721784A CN 200710172178 A CN200710172178 A CN 200710172178A CN 101202341 B CN101202341 B CN 101202341B
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CN101202341A (en
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夏永姚
李峰
罗加严
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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
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    • Y02E60/10—Energy storage using batteries

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Abstract

The invention belongs to the electrochemical technical field, in particular to a carbon-coated alloy nano-particle electrode material and a preparation method which are used for li-ion batteries. The electrode material body is nano-alloy material; phenolic resins are uniformly coated on the alloy nano-particle to form a core-shell structure by a method of emulsion polymerization, and at last the alloy nano-particle which is coated by the carbon is obtained by high-temperature calcination and carbonization in inertia gas environment. In the structure of the composite material, the nano-alloy particle is uniformly and firmly covered by the carbon which has excellent conductivity and certain expansion contractibility, thereby damping the volume expansion and ensuring the conductivity of the integrated electrode at the same time in the circulation process. By taking the composite material as the material for a cathode material of the li-ion battery, the cathode material of the li-ion battery with high li-content capability, excellent safety and excellent circulation performance can be obtained.

Description

Carbon cladding alloy nanometer particle material for lithium ion battery and preparation method thereof
Technical field
The invention belongs to technical field of electrochemistry, be specifically related to a kind of lithium ion battery carbon clad alloy nano particle 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 loose contact, and the cycle performance of electrode sharply descends.Along with development of scientific research, the alloy material that it is found that some binary also can the embedding lithium, and its chemical property is better than the alloy material of monobasic.1999, American Studies personnel people 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.Calendar year 2001, the researcher of Korea S has studied by the synthetic Mg of mechanical ball milling method 2The chemical property of Sn alloy and removal lithium embedded mechanism.The result shows that its reversible capacity reaches 400mAh/g, and circulating still has big reversible capacity for 20 times.In the binary system alloy, (such as Mg, Ni Cu) plays the buffer medium effect that disperses to inactive metal in lattice, reduces that lithium embeds and the volumetric expansion when deviating from, so the cycle performance of bianry alloy is higher than the monobasic alloy.However, common synthetic bianry alloy material is owing to still exist the pulverizing problem of volumetric expansion and electrode material in the embedding lithium process, and its performance 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 the performance that the efflorescence peeling phenomenon reduces electrode material takes place again after particle is grown up gradually.
Summary of the invention
In order to address the above problem, the present invention proposes a kind of carbon clad alloy nano particle combination electrode material and preparation method thereof, to satisfy the application requirements of high-energy-density lithium ion battery negative material.
Preparation method of the present invention is, at first uses liquid phase reduction to prepare the Nanoalloy particle, and particle size is greatly about the 10-50nm scope.Use hydrophobization reagent (hexadecyl mercaptan, lauryl mercaptan be one or more mixed solution wherein for ethyl thioglycolate, ethyl mercaptan) to handle alloy particle then, make its hydrophobization; Use microemulsion polymerization method to make the even clad nano alloy particle of phenolic resins; The clad material that obtains high-temperature calcination carbonization under inert atmosphere obtains the alloy nano particle that carbon coats.
The combination electrode material of the conductive carbon clad nano alloy that the present invention proposes, it is not simply to be mixed with alloy particle by material with carbon element to form, but carbon and bulk material clad structure that the alloy particle carburizing reagent at high temperature that is evenly coated by phenolic resins forms, its carbon coating layer combines closely with the alloy material of body, be difficult for peeling off, and certain expansion shrinkage and good electron conductive capability are arranged.
The body of above-mentioned electrode composite material is an alloy nano particle, for embedding and deviate from the Cu of lithium ion 6Sn 5, Mg 2Sn, CoSn, Ni 3Sn 4, CeSn 3, Ni 3Sn 2Deng one or more mixtures of material in the alloy.Carbon coating layer is evenly intactly to be coated on the alloy nanoparticle sub-surface, and the carbon content of its coating accounts for the 10%-30% of composite material gross mass.If the carbon coated amount is less than 10%, then because carbon content is low excessively, the carbon-coating of coating is too thin or can't coat fully, thereby the alloy that causes dissolving in the high-temperature calcination process forms huge alloying pellet from inner outflow of carbon shell; If covering amount greater than 30%, then because the capacity of this part material with carbon element itself is lower, thereby reduces the capacity of whole composite material to a great extent.
Among the present invention, the body of composite material is an alloy nano particle, and its preparation method is by NaBH 4Or KBH 4Also the original reagent reduction contains corresponding mol ratio example salting liquid, adds citric acid as complexing agent, has 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.
The combination electrode material of the conductive carbon clad nano alloy that proposes among the present invention is with the complete clad alloy equably of phenolic resins nano particle outside by microemulsion polymerization method.The Nanoalloy particle, initator, resorcinol and the formaldehyde that in the aqueous solution, add surfactant, hydrophobization, the temperature that stirs polymerization reaction is 60 ℃-90 ℃, the time of reaction is 8h-24h; Wherein, the surfactant that uses is wherein a kind of of lauryl sodium sulfate, cetyl ammonium bromide, polyvinylpyrrolidone, and initator is a sodium carbonate.Its principle is that certain density surfactant forms micella in aqueous solution dissolving, and the alloy nano particle of hydrophobization and resorcinol are by the hydrophobic micella parcel of surfactant, and formaldehyde and initator dissolve at aqueous phase.During initiated polymerization, initator is crossed over water/oily interface by warm-up movement, has caused the resorcinol in the oil phase and the polymerization of formaldehyde, and the phenolic resins of generation therefore can the complete nano particle of clad alloy equably outside.
Among the preparation method of the present invention, high-temperature calcination need be controlled at 600 ℃-900 ℃ under the inert atmosphere.If calcining heat is lower than 600 ℃, then the carbon-coating electric conductivity of the combination electrode material of final gained is not good; If temperature of plate is high 900 ℃, and the electric conductivity of carbon-coating tangible raising can not take place, and only can cause the energy resource consumption that there is no need.
Adopt carbon clad alloy nano particle combination electrode material of the present invention to be used for lithium ion battery negative, its specific capacity is apparently higher than traditional graphite cathode material, and cycle performance also is better than common alloy material greatly.
Specific implementation method
The embodiment of the following stated understands the present invention in detail.
Embodiment 1:
With 1.3g citric acid and 5g NaBH 4Or KBH 4Add powerful stirring and dissolving in the 600ml deionized water, other takes by weighing 1.05g CuCl 2With 1.8g SnCl 4In the dissolving and the 20ml aqueous solution, stirring slowly splashes in the previous solution down, dropwises the back and continues stirring 10min, obtains nanometer Cu after filtration, washing and the vacuumize 6Sn 5Material, its granular size is between 10-50nm.Remaining alloy nano particle CoSn, Ni 3Sn 4, wait by identical method synthetic.With the Nanoalloy material 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 alloy=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, and charging and discharging currents is 100mA/g.Record and find that all alloy materials discharge first and shown bigger capacity and lower coulombic efficiency first, and there is not tangible discharge platform, this is because nano level alloy particle has bigger specific surface and more surface group, in discharge process first lithium ion can and surface group react, form the SEI film at particle surface simultaneously, therefore cause bigger discharge capacity first and lower coulombic efficiency first.Because Nanoalloy particle crystalline form is very poor, therefore in discharge process, do not show tangible discharge platform simultaneously.The relatively poor cycle performance that shows of all alloy nano particles is found in test in addition, though this is because be nano level alloy, but the expansion and the contraction of alloy particle generation volume in charge and discharge process, the secondary agglomeration that causes nano particle, the efflorescence peeling phenomenon of common alloying pellet can take place again after particle is grown up gradually, thereby has reduced the performance of electrode material.Cu wherein 6Sn 5Discharge capacity first can reach 792mAh/g, but capacity attenuation is very fast, 30 times circulation back capacity is 223mAh/g (seeing table 1 for details).
Embodiment 2:
Take by weighing 2.0g nanometer Cu 6Sn 5Particle is put into the ethanolic solution of certain volume, and adds 1ml lauryl mercaptan sonicated half an hour.Cu with hydrophobization 6Sn 5Alloy particle filters the back and adds in the 100ml aqueous solution, adds 50ml formaldehyde, 0.5g resorcinol and 80mg lauryl sodium sulfate again, then with the ultrasonic dispersion of mixed solution half an hour.Afterwards mixed solution is added 0.16g sodium carbonate under 70 ℃ of constant temperature stir, and keep stirring polymerization reaction 12h, at last the composite material that filters out is calcined 2h for following 600 ℃ in inert atmosphere, obtain the Cu6 that carbon coats Sn 5Composite material, wherein the content of carbon accounts for 23% of gross mass.Remaining carbon clad alloy nano composition CoSn, Ni 3Sn 4Deng synthetic by identical method.The alloy material that coats with carbon is as negative material, according to embodiment 1 described method assembled battery and test.Can find that discharge capacity has had certain reducing first, but coulombic efficiency is greatly improved first, and cycle performance is greatly improved.This can be owing to the existence of the carbon-coating that evenly coats, because carbon-coating has certain expansion shrinkage and good electron conductivity, can cushion the volumetric expansion that alloy particle causes in charge and discharge process, avoid the efflorescence and the secondary agglomeration of particle, thereby improve the performance of electrode material.With Cu 6Sn 5Be example, the discharge capacity first after carbon coats drops to 704mAh/g, and coulombic efficiency first rises to 65%, and the capacity after 30 circulations still has 421mAh/g (seeing table 1 for details).
Embodiment 3:
Take by weighing 2.0g nanometer Cu 6Sn 5Particle is put into the ethanolic solution of certain volume, and adds 1ml lauryl mercaptan sonicated half an hour.Cu with hydrophobization 6Sn 5Alloy particle filters the back and adds in the 100ml aqueous solution, adds 50ml formaldehyde, 0.3g resorcinol and 80mg lauryl sodium sulfate again, then with the ultrasonic dispersion of mixed solution half an hour.Afterwards mixed solution is added 0.16g sodium carbonate under 70 ℃ of constant temperature stir, and keep stirring polymerization reaction 12h, at last the composite material that filters out is calcined 2h for following 600 ℃ in inert atmosphere, obtain the Cu that carbon coats 6Sn 5Composite material, wherein the content of carbon accounts for 17% of gross mass.Cu with this carbon coating 6Sn 5Composite material is as negative material, according to embodiment 1 described method assembled battery and test.Cu with embodiment 2 6Sn 5Composite material is compared, because Cu 6Sn 5Relative amount increase, cause first that discharge capacity also increases to some extent, reach 731mAh/g, but capability retention behind coulombic efficiency and 30 circles and the Cu of embodiment 2 6Sn 5Composite material is close, reduces although the content of carbon is described, still clad alloy particle (seeing table 1 for details) intactly.
Embodiment 4:
Take by weighing 2.0g nanometer Cu 6Sn 5Particle is put into the ethanolic solution of certain volume, and adds 1ml lauryl mercaptan sonicated half an hour.Cu with hydrophobization 6Sn 5Alloy particle filters the back and adds in the 100ml aqueous solution, adds 50ml formaldehyde, 0.3g resorcinol and 80mg lauryl sodium sulfate again, then with the ultrasonic dispersion of mixed solution half an hour.Afterwards mixed solution is added 0.16g sodium carbonate under 70 ℃ of constant temperature stir, and keep stirring polymerization reaction 12h, at last the composite material that filters out is calcined 2h for following 900 ℃ in inert atmosphere, obtain the Cu that carbon coats 6Sn 5Composite material, wherein the content of carbon accounts for 15% of gross mass.Cu with this carbon coating 6Sn 5Composite material is as negative material, according to embodiment 1 described method assembled battery and test.Can find that the discharge capacity first of this composite material decreases than the composite material among the embodiment 3, reaches 724mAh/g, but the capability retention after coulombic efficiency and 30 encloses first improves a lot than the composite material among the embodiment 3 all.This is that the while has been reduced the group content of carbon surface again because carbon through high-temperature calcination, has improved electric conductivity, so has reduced irreversible capacity first and improved cycle performance (seeing table 1 for details).
The chemical property of the carbon clad alloy nano particle that different carbon contents of table .1 and calcining heat are handled relatively
Discharge capacity mAh/g first Initial charge capacity mAh/g Coulombic efficiency first 30 circulation back capacity mAh/g 30 circulation back capability retentions
Embodiment 1 (nanometer Cu 6Sn 5) 792 443 56％ 223 28％
Embodiment 1 (nano Co Sn) 728 350 48％ 182 25％
Embodiment 1 (nanometer Ni 3Sn 4) 852 434 51％ 175 21％
(carbon coats Cu to embodiment 2 6Sn 5, phosphorus content 23%) 704 457 65％ 421 60％
Embodiment 2 (carbon coats CoSn, phosphorus content 23%) 657 402 61％ 379 58％
(carbon coats Ni to embodiment 2 3Sn 4, phosphorus content 23%) 742 489 66％ 427 57％
(carbon coats Cu to embodiment 3 6Sn 5, phosphorus content 17%) 731 479 65％ 434 59％
(carbon coats Cu to embodiment 4 6Sn 5, phosphorus content 15%) 724 498 69％ 477 66％

Claims (4)

1. the preparation method of a carbon cladding alloy nanometer particle material for lithium ion battery, it is characterized in that concrete steps are as follows: at first prepare the Nanoalloy particle with liquid phase reduction, the particle diameter of particle is 10-50nm; Use hydrophobization agent treatment alloy particle then, make its hydrophobization; The Nanoalloy particle, initator, resorcinol and the formaldehyde that in the aqueous solution, add surfactant, hydrophobization,
Re-use microemulsion polymerization method and make the even clad alloy nano particle of phenolic resins; The high-temperature calcination carbonization obtains the alloy nano particle that carbon coats under inert atmosphere at last; Wherein:
Described Nanoalloy particle be can the embedding lithium bianry alloy material C u 6Sn 5, Mg 2Sn, CoSn, Ni 3Sn 4, CeSn 3Or Ni 3Sn 2In one or more mixtures of material;
Used hydrophobization reagent is one or more mixed solution in ethyl thioglycolate, ethyl mercaptan, hexadecyl mercaptan, the lauryl mercaptan;
Described high-temperature calcination temperature is 600 ℃-900 ℃, and the content of carbon accounts for the 10%-30% of composite material gross mass in the carbon clad alloy nano particle that obtains at last.
2. according to the preparation method described in the claim 1, the step that it is characterized in that described micro-emulsion polymerization thing method is as follows: the Nanoalloy particle, initator, resorcinol and the formaldehyde that add surfactant, hydrophobization in the aqueous solution, carry out polymerization reaction under stirring, reaction temperature is 60 ℃-90 ℃, and the reaction time is 8h-24h; Wherein, the surfactant that uses is wherein a kind of of lauryl sodium sulfate, cetyl ammonium bromide, polyvinylpyrrolidone, and initator is a sodium carbonate.
3. preparation method according to claim 1, it is characterized in that described use liquid phase reduction prepares the Nanoalloy particle, the steps include: at first to add in the aqueous solution strong reductant and complexing agent and powerful stirring and dissolving, salting liquid is added drop-wise in the above-mentioned solution afterwards, fully reaction, obtain the Nanoalloy particle after the vacuumize, used strong reductant is NaBH 4Or KBH 4In one or both mix reagent, used complexing agent is a citric acid.
4. according to the carbon cladding alloy nanometer particle material of the described preparation method of one of claim 1-3 preparation.
CN2007101721784A 2007-12-13 2007-12-13 Carbon cladding alloy nanometer particle material for lithium ion battery and method for making same Expired - Fee Related CN101202341B (en)

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