CN101740764B - Tin-graphite composite cathode material for lithium ion battery and preparation method thereof - Google Patents
Tin-graphite composite cathode material for lithium ion battery and preparation method thereof Download PDFInfo
- Publication number
- CN101740764B CN101740764B CN2008102032321A CN200810203232A CN101740764B CN 101740764 B CN101740764 B CN 101740764B CN 2008102032321 A CN2008102032321 A CN 2008102032321A CN 200810203232 A CN200810203232 A CN 200810203232A CN 101740764 B CN101740764 B CN 101740764B
- Authority
- CN
- China
- Prior art keywords
- solution
- graphite
- tin
- obtains
- lithium ion
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- 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
Landscapes
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a tin-graphite composite cathode material for lithium ion battery and a preparation method thereof. The composite material comprises a core-shell structure which is composed of an internal core and an external shell, wherein the internal core is graphite and the external shell is a uniform compound of metal tin and amorphous carbon. In the invention, an organic solvent system, not a common aqueous solution system, is adopted, graphite, metal tin and organic high polymer form a uniform sol-gel system, which does not generate deposit all the time in the material preparation process, thus finally obtaining cathode composite material of lithium ion battery with special core-shell structure. In the composite material, metal Sn in the C material is highly uniformly dispersed, micro-particles of Sn are not easy to agglomerate, the material structure is stable, and the characteristics of high capacity of metal tin good stability of graphite material are composited, thus efficiently improving charging and discharging performances of the composite material.
Description
Technical field
Lithium ion battery negative material of the present invention, particularly compound negative material of a kind of tin-graphite of lithium ion battery and preparation method thereof.
Background technology
High-performance electrode is the core component of secondary lithium battery, and it is the key component of lightweight, large capacity, high reliability lithium ion battery.At present outer commercial negative material mainly is native graphite, Delanium or its all kinds of modified graphites.Graphite passes through LiC
6The reversible storage of compound Li
+Mechanism, its theoretical reversible capacity 372mAh/g, actual commercialization graphite material capacity is generally at 320～360mAh/g, graphite material has stable performance, voltage platform is low, the characteristics such as cyclicity is good because capacity relative is lower, are difficult to satisfy such as notebook computer, mobile phone and portable digital product etc. constantly to the requirement of ultralight ultra-thin, high energy density cells.Compare with graphite cathode material, tin base cathode material has higher specific capacity, and metallic tin passes through
(0≤x≤4.4) alloy mechanism storage lithium, theoretical capacity reaches 994mAh/g.Yet because metallic tin produces 3 times change in volume in charge and discharge process, cause easily that electrode peels off, efflorescence and cause capacity seriously to be decayed, cycle performance is poor.Therefore the general and graphite of metallic tin is made composite material, utilizes the stable and good characteristics of cyclicity of graphite material, in conjunction with the advantage of the high power capacity of tin, is expected to prepare and has preferably Sn/C composite negative pole material of capacity height, stability and cyclicity.But the tin microparticle is reunited easily, and in the tin-graphite composite material that generally makes, tin disperses inhomogeneous, and this has affected the performance of tin-graphite composite material as lithium ion battery negative material greatly.
Summary of the invention
Therefore, the technical problem to be solved in the present invention is exactly to disperse the irregular capacity of lithium ion battery that causes less for the tin that the compound negative material of the tin-graphite of existing lithium ion battery exists, the defective that cycle performance is relatively poor, a kind of compound negative material of tin-graphite of lithium ion battery is provided, the capacity of lithium ion battery that this negative material is made is high, stable performance.
The present invention solves the problems of the technologies described above one of technical scheme of adopting: the negative material that a kind of tin-graphite of lithium ion battery is compound, this composite material has nucleocapsid structure, nucleocapsid structure is comprised of kernel and shell, described kernel is graphite, and described shell is the even complex of metallic tin and amorphous carbon.
According to the present invention, the particle diameter of described graphite be preferably 6～25 μ m, maximum preferably is no more than 30 μ m, minimum is generally 5 μ m.Described graphite is better is selected from natural spherical plumbago, natural flake graphite and all kinds of Delanium.Described graphite account for the quality percentage composition of described anode material better be 65～85%.Described metallic tin account for the quality percentage composition of described anode material better be 5%～30%.Described amorphous carbon account for the quality percentage composition of described anode material better be 5%～15%.
The present invention solves the problems of the technologies described above two of the technical scheme that adopts: a kind of preparation method of anode material of aforesaid lithium ion battery with nucleocapsid structure may further comprise the steps:
1) with SnCl
4Or tin alkoxide Sn (OR)
4Be dissolved in normal propyl alcohol or the n-butanol, the solution A that obtains, wherein R is the hydrocarbyl chain of 2～4 carbon;
2) organic high molecular polymer is dissolved in n-butanol, normal propyl alcohol or the toluene, obtains solution B;
3) solution A and solution B are mixed obtain solution C;
4) graphite is added strong agitation evenly obtains solidliquid mixture slurry D in the solution C;
5) ammoniacal liquor or urea are dissolved in the mixture of ethanol or second alcohol and water, obtain solution E;
6) heating mixture paste D to 70～100 ℃ under intensively stirred condition, and in this mixture paste, drip solution E, in the process that drips, the solution compound becomes the colloidal sol compound, the viscosity of whole system constantly increases, solution E drops to whole system and becomes till the gel, obtains gel/graphite mixed system F;
7) this gel/graphite mixed system F is changed in the vacuum drying chamber, under 100 ℃～120 ℃ conditions of temperature, carry out drying, after equal solvent is got rid of fully, under this temperature, be incubated 1～3 hour again, then temperature is risen to 180～220 ℃ and be incubated 3～5 hours, at last naturally be cooled to 15～40 ℃, obtain dried material G;
8) with dried material G through grind and-300 orders～-150 mesh sieve divisional processing after, under nitrogen or inert gas atmosphere protection, in 800～1200 ℃ of heat treatments 6～10 hours, and get final product.
According to the present invention, step 1) be with SnCl
4Or tin alkoxide Sn (OR)
4Be dissolved in normal propyl alcohol or the n-butanol, obtain solution A, wherein R is the hydrocarbyl chain of 2～4 carbon.Wherein, described SnCl
4Or tin alkoxide is the presoma of the metallic tin in the nucleocapsid structure of lithium ion anode material.Anhydrous SnCl
4Or the solubility of tin alkoxide in normal propyl alcohol or n-butanol is better, and the solute effect of other pink salt in organic solvent is undesirable, and other organic solvent is to SnCl
4Or tin alkoxide Sn (OR)
4Solute effect also bad.That the concentration of described solution A is better is 9wt%～45wt%.
According to the present invention, step 2) be that organic high molecular polymer is dissolved in n-butanol, normal propyl alcohol or the toluene, obtain solution B.Wherein, described organic high molecular polymer is as presoma, can be the various soluble resins such as phenolic resins, furane resins, or all kinds of low softening point asphalt matter, such as coal tar pitch, petroleum asphalt etc.Better, described organic high molecular polymer is selected from phenolic resins, furane resins and petroleum asphalt.Described organic high molecular polymer is dissolved in n-butanol, normal propyl alcohol or the toluene, and the selection prerequisite of solvent is will get well the solute dissolubility, preferably selects to use the solvent identical with step 1.Better, also add curing agent in the described solution B.When being phenolic resins such as presoma, add hexa as curing agent, need to be dissolved in hexa in the ethanol and re-use, it is better generally to be mixed with 0.1g/ml.That the concentration of described solution B is better is 5wt%～15wt%.
According to the present invention, step 4) be graphite to be added strong agitation evenly obtains solidliquid mixture slurry D in the solution C.Wherein, described graphite is the inner nuclear material in the nucleocapsid structure of lithium ion anode material, better natural spherical plumbago, natural flake graphite and all kinds of Delanium of being selected from.The graphite particle size range is better is controlled at 6～25 μ m.Intensively stirred speed of agitator is better 〉=450r/min, can sedimentation and agglomeration is arranged otherwise graphite occurs easily, and can not be dispersed in well in the solution, can not get uniform sizing material.
According to the present invention, step 5) be that ammoniacal liquor or urea are dissolved in the mixture of ethanol or second alcohol and water, obtain solution E.Wherein, described ammoniacal liquor or urea (urea) can be dissolved in ethanol as alkaline matter, their ethanolic solution can with step 4 in organic system mix, and other alkaline matters such as NaOH etc. all are insoluble to alcohols, therefore solvent is selected the mixture of ethanol or second alcohol and water, and ammoniacal liquor or the urea solubility in other alcohols is very low, is not suitable for the present invention.That the concentration of described solution E is better is 5wt%～20wt%.
According to the present invention, step 6) is heating mixture paste D to 70 under intensively stirred condition～100 ℃, and in this mixture paste, drip solution E, in the process that drips, the solution compound becomes the colloidal sol compound, the viscosity of whole system constantly increases, and solution E drops to whole system and becomes till the gel, obtains gel/graphite mixed system F.Under 70～100 ℃ temperature, chemical reaction has occured in this system, and organic high molecular polymer begins slowly to solidify such as phenolic resins, on the other hand SnCl on the one hand
4Or hydrolysis has occured in tin alkoxide and condensation reaction becomes colloidal sol (rather than precipitation), and system shows as thick mixed liquor, and namely the viscosity of system constantly increases, and becomes at last gel solidification on the graphite nodule surface.System to colloidal sol, arrives gel by mixed liquor at last, until solidify fully, the viscosity of system is by the very little infinity that progressively changes to.
According to the present invention, step 7) be that this gel/graphite mixed system F is changed in the vacuum drying chamber, under 100 ℃～120 ℃ conditions of temperature, carry out drying, after equal solvent is got rid of fully, under this temperature, be incubated 1～3 hour again, then temperature is risen to 180～220 ℃ and be incubated 3～5 hours, naturally be cooled to-10～40 ℃ at last and obtain dried material G.Wherein, the drying in 100～120 ℃ of stages mainly is to remove solvent, and 180～220 ℃ of phase process mainly are to allow organic polymer solidify more fully.
According to the present invention; step 8) be with dried material G through grind and-300 orders～-150 mesh sieve divisional processing after; under nitrogen or inert gas atmosphere protection, in 800～1200 ℃ of heat treatments 6～10 hours, namely obtain above-mentioned anode material with lithium ion battery of nucleocapsid structure.Wherein, under 800～1200 ℃ of heat treatments, the organic high molecular polymers such as phenolic resins occur to decompose emits H
2, CO, CO
2, CH
4Deng gas, and produce carbonization, form amorphous carbon; Under such high temperature, the compound of tin and carbon and these reducibility gas generation reduction reactions are reduced into metal Sn.This reaction better in step carries out in can be in graphite crucible.
The raw material that the present invention is used or reagent except specifying, equal commercially available getting.
Than prior art, beneficial effect of the present invention is as follows: the present invention adopts organic solvent system, but not general water solution system, make graphite, metallic tin and organic high molecular polymer form a kind of uniform collosol-gelatum system, in the material preparation process, do not precipitate from start to finish, thereby finally obtained having the anode material of the lithium ion battery of special nucleocapsid structure.In this composite material, the height Uniform Dispersion of metal Sn in the C material, Sn microparticle are difficult for reuniting, and material structure is stable, combine the high and stable good characteristics of graphite material of capacity of metallic tin, the charge-discharge performance of Effective Raise composite material.It is simple that the present invention has technological process, with low cost, is easy to realize suitability for industrialized production, has great application prospect.
Description of drawings
Below in conjunction with description of drawings feature of the present invention and beneficial effect.
Fig. 1 is scanning electron microscopy (SEM) photo of the compound negative material of the tin-graphite of lithium ion battery of the present invention.A) raw material graphite nodule, multiplication factor: 5000 times; B) the compound negative material of the tin-graphite of lithium ion battery, multiplication factor: 5000 times.The SEM photo show negative material that tin-graphite of the present invention is compound surface ratio raw material graphite nodule smooth, illustrate at the raw material graphite nodule to have coated one deck shell.
Fig. 2 is the XRD collection of illustrative plates of the compound negative material of the tin-graphite of lithium ion battery of the present invention.
Embodiment
The below further specifies the present invention with embodiment, but the present invention is not limited.The experimental technique of unreceipted actual conditions in the following example, usually according to normal condition, or the condition of advising according to manufacturer.Among the present invention, the temperature when described room temperature is operation in the laboratory is generally 20～25 ℃.
Embodiment 1
Take by weighing 45g SnCl
4Be dissolved in the 200ml n-butanol and obtain solution A.Taking by weighing 20g phenolic resins is dissolved in the 200g n-butanol and obtains solution B.Solution A and solution B mixed obtain solution C.The natural spherical plumbago powder 70g that takes by weighing the about 15 μ m of particle diameter adds that strong agitation evenly obtains solidliquid mixture slurry D in the solution C.The 20ml ammonia solvent is obtained solution E in 90ml ethanol.The heating mixture paste is D to 100 ℃ under intensively stirred condition, and drips solution E in this mixture paste, and in the process that drips, the viscosity of mixture paste system constantly increases, and obtains at last gel/graphite mixed system F.This gel/graphite mixed system F is changed in the vacuum drying chamber, under 120 ℃ of conditions of temperature, carry out drying, after evaporating, solvent under this temperature, kept 2 hours again, then temperature is risen to 200 ℃ and be incubated 4 hours after, cool the temperature to room temperature and obtain dried material G, this material G is placed obtain powder below being ground to-200 orders in the agate ball grinding machine.This powder is placed in the graphite crucible, at N
2Namely obtain Sn/C lithium ion battery negative material sample after 8 hours in 1000 ℃ of heat treatments under the atmosphere protection.
In this negative material sample, content of graphite is 70wt%, and metallic tin content is 20wt%, and agraphitic carbon content is 10wt%.
Get wherein sample segment and carry out scanning electron microscopy and take a picture, gained SEM photo is seen Fig. 1.Wherein, figure is the raw material graphite nodule in a), multiplication factor: 5000 times; Figure b) be the compound negative material of tin-graphite of lithium ion battery in, multiplication factor: 5000 times.The SEM photo show negative material that tin-graphite of the present invention is compound surface ratio raw material graphite nodule smooth, illustrate at the raw material graphite nodule to have coated one deck shell.Fig. 2 is X-ray diffraction analysis (XRD) collection of illustrative plates of this sample.
Take by weighing a certain amount of sample, mix with the mass ratio of 1:0.2:0.02 by sample powder, conductive carbon black, PVDF (Kynoar), be pressed into electrode slice, as anodal, as negative pole, electrolyte is 1M LiPF with the pure metal lithium sheet after vacuumize
6DMC+EMC+EC (volume ratio 1:1:1), recording current density is 0.7mA/cm
2Specific discharge capacity be 480mAh/g.
Embodiment 2
Take by weighing 45g SnCl
4Be dissolved in the 200ml n-butanol and obtain solution A.Take by weighing 12g phenolic resins and be dissolved in the butanol solution that obtains phenolic resins in the 200g n-butanol, then adding concentration is the hexa ethanolic solution 30ml of 0.1g/ml, obtains solution B after stirring.Solution A and solution B mixed obtain solution C.Take by weighing natural flake graphite powder 75g that particle diameter is about 18 μ m and add that strong agitation evenly obtains solidliquid mixture slurry D in the solution C.The 20g urea is dissolved in the mixed liquor of 90ml ethanol and 30ml deionized water and obtains solution E.Then heat mixture paste D to temperature 70 C under intensively stirred condition, and add solution E in this mixture paste, As time goes on, the viscosity of mixture paste system constantly increases, and obtains at last gel/graphite mixed system F.This gel/graphite mixed system F is changed in the vacuum drying chamber, under the about 120 ℃ of conditions of temperature, carry out drying, after evaporating, solvent under this temperature, kept 2 hours again, again temperature is risen to 200 ℃ and be incubated 4 hours after naturally be cooled to room temperature and obtain dried material F, then material F is placed to obtain powder below being ground to-200 orders in the agate ball grinding machine.This powder is placed in the graphite crucible, at N
2Namely obtained Sn/C lithium ion battery negative material sample in 8 hours in 1000 ℃ of heat treatments under the atmosphere protection.
In this negative material sample, content of graphite is 75wt%, and metallic tin content is 20wt%, and agraphitic carbon content is 5wt%.Take by weighing a certain amount of sample, mix with the mass ratio of 1:0.2:0.02 by sample powder, conductive carbon black, PVDF, be pressed into electrode slice, as anodal, as negative pole, electrolyte is 1M LiPF with the pure metal lithium sheet after vacuumize
6DMC+EMC+EC (volume ratio 1:1:1), recording current density is 0.7mA/cm
2Specific discharge capacity be 476mAh/g.
Taking by weighing 90g n-butanol tin is dissolved in the 200ml n-butanol and obtains solution A.Taking by weighing 20g phenolic resins is dissolved in the 200g n-butanol and obtains B.Solution A and solution B mixed obtain solution C.Take by weighing graphous graphite powder 70g that particle diameter is about 20 μ m and add that strong agitation evenly obtains solidliquid mixture slurry D in the solution C.12ml deionized water and 90ml ethanol are mixed to get solution E.Then at room temperature, under intensively stirred condition, slowly drip solution E in this mixture paste, As time goes on, the viscosity of mixture paste system constantly increases, and obtains at last gel/graphite mixed system F.This gel/graphite mixed system F is changed in the vacuum drying chamber, under the about 120 ℃ of conditions of temperature, carry out drying, after evaporating, solvent under this temperature, kept 2 hours again, again temperature is risen to 200 ℃ and be incubated 4 hours after naturally be cooled to room temperature and obtain dried material G, then material G is placed to obtain powder below being ground to-200 orders in the agate ball grinding machine.This powder is placed in the graphite crucible, at N
2Namely obtained Sn/C lithium ion battery negative material sample in 8 hours in 1000 ℃ of heat treatments under the atmosphere protection.
In this negative material sample, content of graphite is 65wt%, and metallic tin content is 30wt%, and agraphitic carbon content is 5wt%.Take by weighing a certain amount of sample, mix with the mass ratio of 1:0.2:0.02 by sample powder, conductive carbon black, PVDF, be pressed into electrode slice, as anodal, as negative pole, electrolyte is 1M LiPF with the pure metal lithium sheet after vacuumize
6DMC+EMC+EC (volume ratio 1:1:1), recording current density is 0.7mA/cm
2Specific discharge capacity be 511mAh/g.
Take by weighing 45g SnCl
4Be dissolved in the 200ml n-butanol and obtain solution A.Taking by weighing 20g petroleum asphalt is dissolved in the 200g toluene and obtains solution B.Solution A and solution B mixed obtain solution C.The natural spherical plumbago powder 70g that takes by weighing the about 15 μ m of particle diameter adds that strong agitation evenly obtains solidliquid mixture slurry D in the solution C.The 20ml ammonia solvent is obtained solution E in 90ml ethanol.The heating mixture paste is D to 90 ℃ under intensively stirred condition, and drips solution E in this mixture paste, and in the process that drips, the viscosity of mixture paste system constantly increases, and obtains at last gel/graphite mixed system F.This gel/graphite mixed system F is changed in the vacuum drying chamber, under 120 ℃ of conditions of temperature, carry out drying, after evaporating, solvent under this temperature, kept 2 hours again, then temperature is risen to 200 ℃ and be incubated 4 hours after, cool the temperature to room temperature and obtain dried material G, this material G is placed obtain powder below being ground to-200 orders in the agate ball grinding machine.This powder is placed in the graphite crucible, at N
2Namely obtain Sn/C lithium ion battery negative material sample after 8 hours in 1200 ℃ of heat treatments under the atmosphere protection.
In this negative material sample, content of graphite is 65wt%, and metallic tin content is 20wt%, and agraphitic carbon content is 15wt%.Take by weighing a certain amount of sample, mix with the mass ratio of 1:0.2:0.02 by sample powder, conductive carbon black, PVDF, be pressed into electrode slice, as anodal, as negative pole, electrolyte is 1M LiPF with the pure metal lithium sheet after vacuumize
6DMC+EMC+EC (volume ratio 1:1:1), recording current density is 0.7mA/cm
2Specific discharge capacity be 464mAh/g.
Embodiment 5
Taking by weighing 40g n-butanol tin is dissolved in the 200ml n-butanol and obtains solution A.Taking by weighing the 20g furane resins is dissolved in the 200g n-butanol and obtains B.Solution A and solution B mixed obtain solution C.Take by weighing natural spherical plumbago powder 60g 85g that particle diameter is about 25 μ m and add that strong agitation evenly obtains solidliquid mixture slurry D in the solution C.12ml ammoniacal liquor and 90ml ethanol are mixed to get solution E.Then at room temperature, under intensively stirred condition, slowly drip solution E in this mixture paste, As time goes on, the viscosity of mixture paste system constantly increases, and obtains at last gel/graphite mixed system F.This gel/graphite mixed system F is changed in the vacuum drying chamber, under the about 120 ℃ of conditions of temperature, carry out drying, after solvent evaporates, under this temperature, kept 2 hours again, again temperature is risen to 200 ℃ and be incubated 4 hours after naturally be cooled to room temperature and obtain dried material G.Then material G is placed and obtain powder below being ground to-200 orders in the agate ball grinding machine.Powder F is placed in the graphite crucible, at N
2Namely obtained Sn/C lithium ion battery negative material sample in 8 hours in 800 ℃ of heat treatments under the atmosphere protection.
In this negative material sample, content of graphite is 85wt%, and metallic tin content is 10wt%, and agraphitic carbon content is 5wt%.Take by weighing a certain amount of sample, mix with the mass ratio of 1:0.2:0.02 by sample powder, conductive carbon black, PVDF, be pressed into electrode slice, as anodal, as negative pole, electrolyte is 1M LiPF with the pure metal lithium sheet after vacuumize
6DMC+EMC+EC (volume ratio 1:1:1), recording current density is 0.7mA/cm
2Specific discharge capacity be 442mAh/g.
Embodiment 6
Taking by weighing 75g ethanol tin is dissolved in the 200ml normal propyl alcohol and obtains solution A.Taking by weighing 10g phenolic resins is dissolved in the 200g normal propyl alcohol and obtains solution B.Solution A and solution B mixed obtain solution C.The natural spherical plumbago powder 65g that takes by weighing the about 6 μ m of particle diameter adds that strong agitation evenly obtains solidliquid mixture slurry D in the solution C.The 5ml ammonia solvent is obtained solution E in 90ml ethanol.The heating mixture paste is D to 100 ℃ under intensively stirred condition, and drips solution E in this mixture paste, and in the process that drips, the viscosity of mixture paste system constantly increases, and obtains at last gel/graphite mixed system F.This gel/graphite mixed system F is changed in the vacuum drying chamber, under 100 ℃ of conditions of temperature, carry out drying, after evaporating, solvent under this temperature, kept 1 hour again, then temperature is risen to 200 ℃ and be incubated 3 hours after, cool the temperature to 40 ℃ and obtain dried material G, this material G is placed obtain powder below being ground to-300 orders in the agate ball grinding machine.This powder is placed in the graphite crucible, at N
2Namely obtain Sn/C lithium ion battery negative material sample after 6 hours in 1200 ℃ of heat treatments under the atmosphere protection.
In this negative material sample, content of graphite is 65wt%, and metallic tin content is 30wt%, and agraphitic carbon content is 5wt%.Take by weighing a certain amount of sample, mix with the mass ratio of 1:0.2:0.02 by sample powder, conductive carbon black, PVDF, be pressed into electrode slice, as anodal, as negative pole, electrolyte is 1M LiPF with the pure metal lithium sheet after vacuumize
6DMC+EMC+EC (volume ratio 1:1:1), recording current density is 0.7mA/cm
2Specific discharge capacity be 503mAh/g.
Embodiment 7
Taking by weighing 18g isopropyl alcohol tin is dissolved in the 200ml normal propyl alcohol and obtains solution A.Taking by weighing 30g phenolic resins is dissolved in the 200g toluene and obtains solution B.Solution A and solution B mixed obtain solution C.The natural spherical plumbago powder 80g that takes by weighing the about 6 μ m of particle diameter adds that strong agitation evenly obtains solidliquid mixture slurry D in the solution C.The 20ml ammonia solvent is obtained solution E in 90ml ethanol.The heating mixture paste is D to 70 ℃ under intensively stirred condition, and drips solution E in this mixture paste, and in the process that drips, the viscosity of mixture paste system constantly increases, and obtains at last gel/graphite mixed system F.This gel/graphite mixed system F is changed in the vacuum drying chamber, under 110 ℃ of conditions of temperature, carry out drying, after evaporating, solvent under this temperature, kept 3 hours again, then temperature is risen to 180 ℃ and be incubated 5 hours after, cool the temperature to 10 ℃ and obtain dried material G, this material G is placed obtain powder below being ground to-150 orders in the agate ball grinding machine.This powder is placed in the graphite crucible, under the argon atmospher protection, namely obtain Sn/C lithium ion battery negative material sample after 10 hours in 800 ℃ of heat treatments.
In this negative material sample, content of graphite is 80wt%, and metallic tin content is 5wt%, and agraphitic carbon content is 15wt%.Take by weighing a certain amount of sample, mix with the mass ratio of 1:0.2:0.02 by sample powder, conductive carbon black, PVDF, be pressed into electrode slice, as anodal, as negative pole, electrolyte is 1M LiPF with the pure metal lithium sheet after vacuumize
6DMC+EMC+EC (volume ratio 1:1:1), recording current density is 0.7mA/cm
2Specific discharge capacity be 407mAh/g.
Claims (12)
1. the compound negative material of the tin-graphite of a lithium ion battery is characterized in that, this composite material has nucleocapsid structure, and nucleocapsid structure is comprised of kernel and shell, and described kernel is graphite, and described shell is the even complex of metallic tin and amorphous carbon;
The compound negative material of the tin-graphite of described lithium ion battery is made by following preparation method:
1) with SnCl
4Or tin alkoxide Sn (OR)
4Be dissolved in normal propyl alcohol or the n-butanol, the solution A that obtains, wherein R is the hydrocarbyl chain of 2～4 carbon;
2) organic high molecular polymer is dissolved in n-butanol, normal propyl alcohol or the toluene, obtains solution B;
3) solution A and solution B are mixed obtain solution C;
4) graphite is added strong agitation evenly obtains solidliquid mixture slurry D in the solution C;
5) ammoniacal liquor or urea are dissolved in the mixture of ethanol or second alcohol and water, obtain solution E;
6) heating mixture paste D to 70～100 ℃ under intensively stirred condition, and in this mixture paste, drip solution E, in the process that drips, the solution compound becomes the colloidal sol compound, the viscosity of whole system constantly increases, solution E drops to whole system and becomes till the gel, obtains gel/graphite mixed system F;
7) this gel/graphite mixed system F is changed in the vacuum drying chamber, under 100 ℃～120 ℃ conditions of temperature, carry out drying, after equal solvent is got rid of fully, under this temperature, be incubated 1～3 hour again, then temperature is risen to 180～220 ℃ and be incubated 3～5 hours, naturally be cooled to 10～40 ℃ at last and obtain dried material G;
8) with dried material G through grind and-300 orders～-150 mesh sieve divisional processing after, under nitrogen or inert gas atmosphere protection, in 800～1200 ℃ of heat treatments 6～10 hours, and get final product.
2. negative material as claimed in claim 1 is characterized in that, the particle diameter of described graphite is 6～25 μ m.
3. negative material as claimed in claim 1 is characterized in that, described graphite is selected from natural spherical plumbago, natural flake graphite and all kinds of Delanium.
4. negative material as claimed in claim 1 is characterized in that, the quality percentage composition that described graphite accounts for described anode material is 65～85%.
5. negative material as claimed in claim 1 is characterized in that, the quality percentage composition that described metallic tin accounts for described anode material is 5%～30%.
6. negative material as claimed in claim 1 is characterized in that, the quality percentage composition that described amorphous carbon accounts for described anode material is 5%～15%.
7. the preparation method of the anode material of the lithium ion battery with nucleocapsid structure as claimed in claim 1 is characterized in that, may further comprise the steps:
1) with SnCl
4Or tin alkoxide Sn (OR)
4Be dissolved in normal propyl alcohol or the n-butanol, the solution A that obtains, wherein R is the hydrocarbyl chain of 2～4 carbon;
2) organic high molecular polymer is dissolved in n-butanol, normal propyl alcohol or the toluene, obtains solution B;
3) solution A and solution B are mixed obtain solution C;
4) graphite is added strong agitation evenly obtains solidliquid mixture slurry D in the solution C;
5) ammoniacal liquor or urea are dissolved in the mixture of ethanol or second alcohol and water, obtain solution E;
6) heating mixture paste D to 70～100 ℃ under intensively stirred condition, and in this mixture paste, drip solution E, in the process that drips, the solution compound becomes the colloidal sol compound, the viscosity of whole system constantly increases, solution E drops to whole system and becomes till the gel, obtains gel/graphite mixed system F;
7) this gel/graphite mixed system F is changed in the vacuum drying chamber, under 100 ℃～120 ℃ conditions of temperature, carry out drying, after equal solvent is got rid of fully, under this temperature, be incubated 1～3 hour again, then temperature is risen to 180～220 ℃ and be incubated 3～5 hours, naturally be cooled to 10～40 ℃ at last and obtain dried material G;
8) with dried material G through grind and-300 orders～-150 mesh sieve divisional processing after, under nitrogen or inert gas atmosphere protection, in 800～1200 ℃ of heat treatments 6～10 hours, and get final product.
8. preparation method as claimed in claim 7 is characterized in that, the concentration of the described solution A of step 1) is 9wt%～45wt%.
9. preparation method as claimed in claim 7 is characterized in that step 2) described organic high molecular polymer is selected from phenolic resins, furane resins and petroleum asphalt.
10. preparation method as claimed in claim 7 is characterized in that step 2) also add curing agent in the described solution B.
11. preparation method as claimed in claim 7 is characterized in that step 2) concentration of described solution B is 5wt%～15wt%.
12. preparation method as claimed in claim 7 is characterized in that, the concentration of the described solution E of step 5) is 5wt%～20wt%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008102032321A CN101740764B (en) | 2008-11-24 | 2008-11-24 | Tin-graphite composite cathode material for lithium ion battery and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008102032321A CN101740764B (en) | 2008-11-24 | 2008-11-24 | Tin-graphite composite cathode material for lithium ion battery and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101740764A CN101740764A (en) | 2010-06-16 |
| CN101740764B true CN101740764B (en) | 2013-10-23 |
Family
ID=42463871
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2008102032321A Active CN101740764B (en) | 2008-11-24 | 2008-11-24 | Tin-graphite composite cathode material for lithium ion battery and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101740764B (en) |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102376941B (en) * | 2010-08-19 | 2014-04-02 | 比亚迪股份有限公司 | Preparation method of negative active material, negative active material and lithium ion battery |
| CN102544444B (en) * | 2010-12-29 | 2015-01-14 | 比亚迪股份有限公司 | Preparation method for lithium ion battery anode active material |
| CN102694152B (en) * | 2011-03-25 | 2015-08-26 | 比亚迪股份有限公司 | A kind of negative active core-shell material and preparation method thereof and a kind of lithium ion battery |
| CN103022432B (en) * | 2011-09-26 | 2015-08-26 | 比亚迪股份有限公司 | A kind of negative active core-shell material and preparation method thereof and a kind of lithium ion battery |
| CN102891294A (en) * | 2012-09-24 | 2013-01-23 | 上海锦众信息科技有限公司 | Method for manufacturing tin-carbon anode composite material of lithium battery |
| CN103050671A (en) * | 2012-11-30 | 2013-04-17 | 东莞市翔丰华电池材料有限公司 | Preparation method of tin carbon composition material for lithium ion battery negative pole |
| CN105529436A (en) * | 2014-09-29 | 2016-04-27 | 深圳市比克电池有限公司 | Preparation method for carbon-tin composite negative electrode material |
| CN105680026B (en) * | 2016-04-21 | 2019-07-09 | 苏州协鑫集成科技工业应用研究院有限公司 | Carbon composite and preparation method thereof and battery |
| CN113451576B (en) * | 2020-03-26 | 2022-07-01 | 贝特瑞(江苏)新能源材料有限公司 | Graphite composite material, preparation method thereof and lithium ion battery |
| CN117239127B (en) * | 2022-07-14 | 2024-06-28 | 四川金汇能新材料股份有限公司 | Lithium ion battery negative electrode material and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1254961A (en) * | 1998-11-25 | 2000-05-31 | 三星电管株式会社 | Active material of negative electrode for lithium accumulator, its preparing process and lithium accumulator containg said material |
| CN1581544A (en) * | 2003-08-16 | 2005-02-16 | 比亚迪股份有限公司 | Modified graphite and its preparing method |
| CN1996645A (en) * | 2006-01-04 | 2007-07-11 | Ls电线有限公司 | Carbonaceous electrode material for secondary battery, process for producing the same, and secondary batteries using the same |
-
2008
- 2008-11-24 CN CN2008102032321A patent/CN101740764B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1254961A (en) * | 1998-11-25 | 2000-05-31 | 三星电管株式会社 | Active material of negative electrode for lithium accumulator, its preparing process and lithium accumulator containg said material |
| CN1581544A (en) * | 2003-08-16 | 2005-02-16 | 比亚迪股份有限公司 | Modified graphite and its preparing method |
| CN1996645A (en) * | 2006-01-04 | 2007-07-11 | Ls电线有限公司 | Carbonaceous electrode material for secondary battery, process for producing the same, and secondary batteries using the same |
Non-Patent Citations (2)
| Title |
|---|
| Basker Veeraraghavan, et al..Study of Sn-Coated Graphite as Anode Material for Secondary Lithium-Ion Batteries.《Journal of The Electrochemical Society》.2002,第149卷(第6期),第A675页摘要，引用，实验. |
| Study of Sn-Coated Graphite as Anode Material for Secondary Lithium-Ion Batteries;Basker Veeraraghavan, et al.;《Journal of The Electrochemical Society》;20020412;第149卷(第6期);第A675页摘要，引言，实验 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101740764A (en) | 2010-06-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101740764B (en) | Tin-graphite composite cathode material for lithium ion battery and preparation method thereof | |
| CN101800304B (en) | Different-orientation spherical natural graphite negative electrode material and preparation method thereof | |
| CN102050437B (en) | Carbon composite material, preparation method and application thereof | |
| CN112652770A (en) | Silicon-carbon negative electrode material with low specific surface area and preparation method thereof | |
| CN103325997B (en) | For the material with carbon element and preparation method thereof of lithium ion power cell cathode | |
| US20210391569A1 (en) | Core-shell composite negative electrode material, preparation method therefor and use thereof | |
| CN105000545A (en) | Method for preparing lithium ion battery artificial graphite/coke anode material | |
| CN116799210A (en) | Composite lithium supplementing material and preparation method thereof, lithium supplementing coating and preparation method thereof, and lithium battery | |
| CN115036505A (en) | Carbon-coated germanium composite negative electrode material for lithium ion battery and preparation method and application thereof | |
| CN105576221A (en) | Lithium ion battery negative active material precursor, lithium ion battery negative active material and preparation method thereof | |
| CN116435590A (en) | Solid electrolyte with modification layer, solid lithium metal battery and preparation method | |
| CN112072113A (en) | Electrode thickener and negative electrode slurry using same | |
| CN115275207A (en) | Biomass carbon-coated sodium iron phosphate composite material and preparation method and application thereof | |
| CN115249799A (en) | Rosin-based nitrogen-doped coated hard carbon negative electrode material of sodium ion battery and preparation method of rosin-based nitrogen-doped coated hard carbon negative electrode material | |
| CN107317019B (en) | Ferrous carbonate/graphene composite material for sodium ion battery cathode and preparation method and application thereof | |
| CN113571686A (en) | Preparation method of core-shell carbon-silicon negative electrode material | |
| CN115893503B (en) | Preparation method and application of carbon-coated lithium ferrite | |
| CN110620218A (en) | Lithium ion battery cathode material and preparation method and application thereof | |
| CN114709389B (en) | Pre-lithiation negative electrode material and preparation method and application thereof | |
| CN116885312A (en) | Composite lithium supplementing agent, preparation method, pole piece containing composite lithium supplementing agent and preparation method | |
| CN114203978B (en) | High-capacity graphite anode material and preparation method and application thereof | |
| CN1803631A (en) | Preparation method of multi-element nanometer sulfur anode material for lithium ion battery | |
| CN206210928U (en) | A kind of production system of Si C composite lithium ion battery cathode materials | |
| CN110212170B (en) | Silicon-based negative electrode material prepared by solid-phase hot pressing and preparation method thereof | |
| CN110212172B (en) | Carbon material in-situ deposition nano-lead crystal grain/lead oxide composite material and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20191218 Address after: 352000 Dajia village, Dajia Town, Gutian County, Ningde, Fujian province (Tenth phase 1 of Dajia industrial concentrated area) Patentee after: Fujian Shanshan Science & Technology Co Ltd Address before: 201209 No. 3158 Golden Sea Road, Shanghai, Pudong New Area Co-patentee before: Ningbo Shanshan New Materila Technology Co., Ltd. Patentee before: Shanshan Science and Technology Co., Ltd., Shanghai |