CN1242502C - Silicon aluminium alloy/carbon composite material used for lithium ion battery negative electrode and its preparation method - Google Patents
Silicon aluminium alloy/carbon composite material used for lithium ion battery negative electrode and its preparation method Download PDFInfo
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Abstract
The present invention relates to silicon aluminium alloy/carbon composite material used for the negative electrode of a lithium ion battery, and a preparation method thereof, which is characterized in that the proportion of silicon to aluminium is from 1 to 5: 1 in the silicon aluminium alloy, and the content of silicon aluminium active material in the composite material is from 10 wt% to 50 wt% after a high temperature solid state reaction. Carbon and graphite powder of a scattered carrier is scattered in a carbon basal body formed by cracked carbon; the mass ratio of the graphite powder to silicon aluminium alloy powder is 2 to 3. The present invention has the preparation method that a two-step sintering process is adopted, and the aluminium silicon alloy is prepared first; then, organic polymers are cracked, the graphite powder is added in the organic polymer; afterwards, the reacting aluminium silicon alloy is added in the organic polymer to form slurry; finally, the slurry has a heating reaction in a sealed system, the temperature is from 600 DEG C to 1000 DEG C, and the reaction time is from 60 minutes to 300 minutes. The first reversible capacity of the prepared composite material can exceed 700 mAh/g to the greatest extent, and the capacity still keeps more than 90% after 25 times of circulation.
Description
Technical field
The present invention relates to a kind of as lithium ion battery cathode material and its preparation method.Be specifically related to a kind of can be used as lithium ion battery negative material have height ratio capacity, silicon-aluminum/carbon composite that cycle performance is good and preparation method thereof.Belong to the lithium ion battery field.
Background technology
Present commercial lithium ion battery adopts lithium transition-metal oxide/graphite system mostly, though the chemical property excellence of this class system, but because itself storage lithium ability lower (the theory storage lithium amount as graphite is 372mAh/g), be difficult to adapt to the miniaturization development of present various portable electric appts and electric automobile widespread demand to the large-capacity high-power chemical power source.Therefore at present very active to the research of the novel positive and negative utmost point material of the lower lithium transition-metal oxide/graphite system of alternative existing storage lithium ability.The promptly pre-novel electrode material system of developing as European Danionics company that adopts of the 5th generation lithium ion battery.
Studies show that non-carbon negative pole material of present report, many materials with high storage lithium performance, as Al, Sn, Sb etc. can with Li alloyed metal (AM) and alloy type material thereof, its reversible lithium storage capacity is far longer than graphite-like negative pole (D.Fauteux and R.Koksbang, J.Appl.Electrochem.Soc, 1993,23:1-6), but these materials take off at lithium and all have serious bulk effect in the embedding process, this is to cause the cyclical stability of material poor, hinders a key factor of its practicability.Unformed glassy state tin oxide reversible capacity (Yoshio Idota more than 600mAh/g that employing high temperature sintering methods such as Yoshio Idota are prepared, et al., Science, 1997,276:30), but the irreversible capacity first of this material is bigger, and the tin active body has agglomeration in charge and discharge process.In the intercalation materials of li ions known today, pure silicon is because of having the highest theoretical lithium storage content (3800mAh/g), relatively low embedding lithium current potential, be difficult in the charge and discharge process reuniting, have characteristics such as higher physical stability and chemical stability than other metal_based materials, just becoming the research focus in ion cathode material lithium field at present.But it is the same with other metals and alloy type material, the stress that produces owing to bulk effect in degree of depth removal lithium embedded process causes silicon lattice structure avalanche and material efflorescence easily, cause active material to break away from electrode system and lose activity, so have very poor cyclical stability.Present many researchers are devoted to the modification and the optimal design of this high lithium storage materials, and have obtained certain progress.As adopt ductility such as Ni, Fe good metal material and Si compound, formation is the activated centre with Si, with the inert metal is the activity/inertia compound system of dispersible carrier, when having improved the electric conductivity of material, improved the cycle performance (J.-H.Ahn of material, G.X.Wang, et al., J.Metastable and Nanocrystalline Material).But this material easily generates the MSi of inertia under hot conditions
2Phase (M is Ni, Fe etc.), so the general ball grinding method that adopts synthetic more, this method length consuming time (generally more than 150～200h), and the molal weight of Ni, Fe itself is big, belong to non-intercalation materials of li ions, therefore weakened the high advantage of silica-base material specific capacity to a certain extent.In addition, Ni, Fe material itself belong to electronic conductor, do not have ionic conductivity, therefore are easy to generate " screen effect ", make electrolyte solution be difficult to enter the zone of Ni, the coating of Fe matrix, thereby make this part active material lose the effect of embedding lithium.
Summary of the invention
The object of the present invention is to provide the silicon-aluminum/carbon composite that is used for lithium ion battery negative and the preparation method of a kind of height ratio capacity, stable cycle performance.The serious bulk effect that when the electrochemical lithium embedding is taken off, produces at silicon, select for use the aluminium that has embedding lithium activity equally as alloying element, form the silicon-aluminum system, utilization is as Si, the Al embedding lithium effect under different potentials in activated centre, the volumetric expansion of material is occurred under the different potentials, can alleviate consequent internal stress.On the other hand, because Al itself has embedding lithium performance, and its molal weight is suitable with silicon, for the specific capacity of system very big contribution is arranged.With the carbon parent (by graphite powder and Pintsch process carbon jointly form) of sial active body high degree of dispersion in bulk effect very little (＜9%), the height ratio capacity characteristic that has kept sial, improved the energy density of lithium ion battery negative material, make the change in volume of overall electrode be controlled at reasonable level simultaneously, increased its cyclical stability.Graphite in the carbon parent has improved the voltage characteristic of composite material, and Pintsch process carbon has then kept the mechanical performance of material.The result shows that this negative material has higher power characteristic than carbon class negative material commonly used in the present commercial lithium ion battery.
The feature that can be used for the sial/carbon composite of lithium ion battery negative material provided by the invention comprises:
(1) alloy part of Si, Al formation is scattered in the carbon carrier as the height ratio capacity activated centre of composite material;
(2) carbon as dispersible carrier is the mixed conductor of ion and electronics, has excellent cycle performance and lower bulk effect;
(3) the stored up lithium of combination electrode specific capacity is regulated by the content of silicon-aluminum in system;
(4) composite material discharge and recharge feature possess carrier carbon material and silica-alumina material separately discharge and recharge feature, and composite attribute, promptly composite material possesses the high lithium storage content characteristic of silica-alumina material and the high cyclical stability of carbon class material simultaneously.
Described electrode active material mainly is the alloy part that sial forms.This alloy is synthetic by high temperature solid state reaction, and silicon, aluminium combine by the diffusion under the high temperature; Because the temperature of process control is more than the fusing point of aluminium, therefore the time of high temperature solid state reaction can directly influence performance of composites, overlong time, the aluminium bead contacts with each other, reunites, form big bead, the time is too short, and the diffusion on the sial interface is incomplete, mechanical performance is bad, so the time of silicon, aluminium high-temperature process should be controlled between 30min～120min; Because aluminium belongs to embedding lithium active material, and has good ductility and electronic transmission performance, with alloying with silicon, forms stable interface, can obviously improve the mechanical property and the electric conductivity of silicon active body, improve the electrical contact performance of silicon in charge and discharge process; Because the theoretical capacity of aluminium is far below silicon, and it is as the reactive metal material, the same with other metal displacer lithium materials, in charge and discharge process, be easy to generate agglomeration, thereby influence the cycle performance of material,, promptly bring into play the high capacity characteristics of silicon and the good electrical properties of aluminium so can give play to good synergistic for making between component, the ratio of silicon/aluminium should be between 1: 1～5: 1, and the sial ratio directly influences the capacity and the cyclical stability of composite material;
Described is to be made of cracking carbon that obtains by Pintsch process and graphite powder as dispersible carrier, and wherein the graphite powder is scattered in the cracking carbon.The pre-reaction material of this cracking carbon is organic polymers such as pitch, polyvinyl chloride (PVC), phenolic resins, Pintsch process by routine, dehydrogenation reaction takes place, form after the carbonization and have certain lithium storage content, reversible doff lithium performance, the dispersible carrier that electric conductivity is good, suppressing the reunion of activated centre body, and alleviated the change in volume of electrode material.The graphite powder is scattered in the cracking carbon, has improved the stable circulation performance of material.In addition, the adding of graphite powder has also reduced the voltage difference that discharges and recharges, has improved the voltage characteristic of battery; But the graphite powder be added in the mechanical stability that can reduce composite material to a certain extent, addition is answered the quality of the cracking carbon in the composite material of Xiao Yu preparation;
But the lithium storage content of described composite material is regulated by the content of sial active material in composite material.Refer to by active material and carrier pre-reaction material ratio before the control cracking reaction, final lithium storage content and the good composite material of cycle performance of after reaction, obtaining, the content of reaction back sial active material in composite material can be in 10%～50wt% scope;
Described composite material possesses the high lithium storage content characteristic of silicon, aluminium and the high cyclical stability of carbon class material simultaneously, refers to that this composite material can obtain to be better than the cyclical stability of silicon/carbon composite.
Described lithium ion battery is as follows with the preparation process of alusil alloy/carbon anode material:
(1) the initial aluminium powder of electrode active material and silica flour adopt method such as ball milling to mix;
(2) with homogeneous mixture of forming in (1) under inert atmosphere protection, through high-temperature process, powder is fully spread and alloying, form the active body predecessor;
(3), be dissolved in the organic solvent as the organic polymer of one of dispersible carrier predecessor;
(4) will add in (3) as the graphite powder of one of dispersible carrier predecessor, be uniformly dispersed;
(5) mixed powder that makes in (2) is got in an amount of adding (4), be uniformly dispersed, form slurry;
(6) slurry that forms in (5) is at room temperature volatilized behind the organic solvent, the mixture that obtains moves in the sealed reaction system, and there is protective atmosphere sealed reaction system inside;
(7) the sealed reaction system begins to carry out temperature reaction, sets heating rate, and controlling reaction time;
(8) after reaction finished, under protective atmosphere, system naturally cooled to room temperature.
The former powder of described electrode active material is meant main silica flour and aluminium powder to have electro-chemical activity, and the particle diameter of used powder can be micron, sub-micron and nanoscale;
Described ball grinding method is meant the ball milling that carries out under inert atmosphere such as Ar gas shiled, ball milling mixes silica flour, aluminium powder;
Described high-temperature process is meant the High temperature diffusion reaction of carrying out under protective atmosphere, the time of reaction can be between 60min～300min, and reaction temperature can be between 600 ℃～1000 ℃;
Described dispersible carrier predecessor is made up of two parts, and a part is the graphite powder that itself has embedding lithium activity; Another part is organic polymer such as pitch, the PVC etc. of cracking at high temperature, dehydrogenation carbonization.The dispersible carrier predecessor is through high-temperature process, and the dispersible carrier that obtains is made up of graphite and cracking carbon, has certain lithium storage content, and the stable performance of reversible doff lithium; The mass ratio of graphite powder and alusil alloy is 2: 3.
Described organic solvent can be organic polymer can be dissolved, and at room temperature has good volatile organic solvent, as acetone, oxolane, expoxy propane etc.;
Described protective atmosphere can be the mist of inert gas or inert gas and reducibility gas, as adding 5.5vol%H in the Ar gas
2
Described reaction temperature is between 600 ℃～1300 ℃, and described heating rate can be 0～30 ℃/min, and the described reaction time can be between 30min～300min.
The present invention adopts the advantage of the synthetic silicon-aluminum/carbon anode material of high temperature solid state reaction to be:
(1) obviously strengthens the mechanical stability of material, improved the cyclical stability of material; (2) improved the electron conduction of silicon class material.
The present invention adopts high temperature solid state reaction, adopts the two-step sintering method to prepare the sial/carbon composite of high power capacity; This negative material is the activated centre with the silicon-aluminum, obviously improved since the characteristic of semiconductor of silicon bring electrically contact problem; The volumetric expansion in the charge and discharge process has effectively been alleviated in the removal lithium embedded behavior under different potentials of silicon, aluminium, and aluminium mix the mechanical property of having improved material, improved the cyclical stability of material; Dispersible carrier carbon makes the reunion of metal active center aluminium obtain effective inhibition, and the graphite powder in the carrier is filled in the cracking carbon parent, has reduced the share of cracking material with carbon element in complex and the irreversible capacity that causes thus; The specific capacity of the composite negative pole material of preparing is much higher than the carbonaceous mesophase spherules (CMS or MCMB) that present lithium ion battery generally uses, and the silicon monomer that cycle life then is better than one-size is the Si-C composite material in activated centre.
Description of drawings
Fig. 1 is the cycle performance curve of the SiAl/C composite material of embodiment one preparation.Abscissa is a cycle-index; Ordinate is a specific discharge capacity, the mAhg of unit
-1
Fig. 2 is that the sial/carbon composite of embodiment three preparations and the 10th charging and discharging curve of carbonaceous mesophase spherules CMS of commercial production compare.Abscissa is a specific discharge capacity, the mAhg of unit
-1Ordinate is a voltage, the unit volt; 1 is charging curve, and 2 is discharge curve.
The specific embodiment mode
Embodiment one
Granularity is the silica flour (purity is 99%) of 5 μ m and pure aluminium powder with mass ratio is 3: 1 ratio, is sealed in the agate jar in being full of the glove box of argon gas, and ball milling mixes under the condition of 400 commentaries on classics/min.With the powder of mixing at Ar and H
2Mist (H
2Shared volume ratio is 5.5%) protect in 900 ℃ of heat treatment 90min, make aluminum silicon powder body portion alloying.Take by weighing an amount of pitch and be dissolved in the oxolane organic solvent, stir; With granularity is that the graphite powder of 1～2 μ m slowly adds, and stirs gently and suitably grinds; Silicon after the aforesaid heat treatment/aluminium powder body is added in the cold primer-oil, and stir; After at room temperature treating solvent evaporates, mixture is moved into sealed silica envelope, place heating furnace, feed inert gas Ar protection, slowly be warming up to about 1000 ℃, heating rate is less than 20 ℃/min, about reaction time 150min.Reacted sample naturally cools to room temperature, and inert atmosphere protection is arranged in the whole process always.Post reaction mixture, preparation technology makes electrode slice according to pole piece, does that with metal Li electrode is made button cell, and electrolyte is LiPF
6/ EC:DMC (1: 1, Vol).Test charging and discharging currents density is 0.2mA/cm
2, by charging/discharging voltage 0.02V～1.50V.The composite negative pole material of preparation reversible capacity first reaches 600mAh/g, and first charge-discharge efficiency is more than 85%, and 25 times circulation back capacity still keeps more than 90%.
Embodiment two
Silica flour (granularity＜1 μ m, purity is 99%) and pure aluminium powder are 4: 1 ratio with mass ratio, are sealed in the agate jar in being full of the glove box of argon gas, after ball milling mixes under the condition of 450 commentaries on classics/min.Other are with embodiment one.Test charging and discharging currents density is 0.2mA/cm
2, by charging/discharging voltage 0.02V～1.50V.The preparation composite material first reversible capacity more than 700mAh/g.
Embodiment three
Granularity is the silica flour (purity is 99%) of 5 μ m and pure aluminium powder with mass ratio is 3: 1 ratio, is sealed in the agate jar in being full of the glove box of argon gas, and ball milling mixes under the condition of 400 commentaries on classics/min.With the powder of mixing at Ar and H
2Mist (H
2Shared volume ratio is 5.5%) protect in 900 ℃ of heat treatment 120min, make aluminum silicon powder body portion alloying.Take by weighing an amount of PVC and be dissolved in the expoxy propane organic solvent, stir; With granularity is that the graphite powder of 1～2 μ m slowly adds, and stirs gently and suitably grinds, and the graphite powder of adding and the mass ratio of aforesaid silicon-aluminum powder are 2: 3; Sial powder after the aforementioned hot processing is added in the cold primer-oil, and stir; After at room temperature treating solvent evaporates, mixture is moved into sealed silica envelope, place heating furnace, feed inert gas Ar protection, slowly be warming up to about 1000 ℃, heating rate is less than 20 ℃/min, about reaction time 150min.Other are with embodiment one.The preparation material first reversible capacity more than 600mAh/g.
Claims (6)
1, a kind of used as negative electrode of Li-ion battery silicon-aluminum/carbon composite is characterized in that silicon/al proportion is between 1: 1～5: 1 in silicon, the aluminium alloy, and the content of sial active material in composite material is 10～50wt% behind the high temperature solid state reaction; Dispersible carrier is made of cracking carbon that obtains by Pintsch process and graphite powder, and wherein the graphite powder is scattered in the cracking carbon.
2, by the described used as negative electrode of Li-ion battery silicon-aluminum/carbon composite of claim 1, the mass ratio that it is characterized in that described graphite powder and silicon-aluminum powder is 2: 3.
3, the method for preparation used as negative electrode of Li-ion battery silicon-aluminum/carbon composite as claimed in claim 1 is characterized in that adopting two-step sintering to prepare composite material, and concrete steps are:
(1) it is evenly mixed that electrode active material aluminium powder and silica flour adopt the ball milling method under protective atmosphere; Silicon/al proportion is between 1: 1～5: 1, and the particle diameter of aluminium powder, silica flour is micron order, submicron order or nanoscale;
(2) with mixture 600～1000 ℃ of high-temperature process 30-120min under inert atmosphere protection of silica flour in the step (1) and aluminium powder, form the active body predecessor;
(3) be a kind of in pitch, polyvinyl chloride or the phenolic resins as the organic polymer of dispersible carrier predecessor, be dissolved in and be cracked into carbon in the organic solvent; Described organic solvent is a kind of in acetone, oxolane or the expoxy propane;
(4) graphite powder adds in the carbon of (3) cracking, and is uniformly dispersed;
(5) (2) active body predecessor is joined in (4), the formation slurry is uniformly dispersed;
(6) slurry that forms in (5) is at room temperature volatilized move into the sealed reaction system behind the organic solvent, temperature reaction under inert gas or inert gas are protected with reducibility gas, reaction temperature is at 600～1000 ℃, reaction time 60～300min.
4, by the preparation method of the described used as negative electrode of Li-ion battery silicon-aluminum/carbon composite of claim 3, it is characterized in that described rotational speed of ball-mill is 400～450 commentaries on classics/min.
5, by the preparation method of the described used as negative electrode of Li-ion battery silicon-aluminum/carbon composite of claim 3, the temperature reaction that it is characterized in that the sealed reaction system is to add 5.5vol%H in inert gas Ar or inert gas Ar
2
6,, it is characterized in that the heating rate 10～30min of sealed reaction system by the preparation method of the described used as negative electrode of Li-ion battery silicon-aluminum/carbon composite of claim 3.
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| CN100352084C (en) * | 2004-05-31 | 2007-11-28 | 潘树明 | Method for making negative electrode material of lithium ion cell |
| CN1315207C (en) * | 2005-06-22 | 2007-05-09 | 浙江大学 | Composite negative pole material of Li-ion battery and its preparing process |
| CN100386905C (en) * | 2006-05-26 | 2008-05-07 | 清华大学 | Metal particle-cladded active carbon microsphere cathode composite materials and method for preparing same |
| CN101210112B (en) * | 2006-12-29 | 2010-12-08 | 比亚迪股份有限公司 | Silicon-containing composite material and its preparation method and application |
| CN101969111B (en) * | 2010-09-30 | 2013-09-04 | 湛江市聚鑫新能源有限公司 | Silicon-carbon alloy cathode material for lithium ion batteries and preparation method thereof |
| TWI407620B (en) | 2010-12-24 | 2013-09-01 | Ind Tech Res Inst | Energy storage composite particle, battery anode material and battery |
| US20130099159A1 (en) * | 2011-10-25 | 2013-04-25 | GM Global Technology Operations LLC | Production of metal or metalloid nanoparticles |
| CN102361073B (en) * | 2011-11-02 | 2013-08-07 | 北京科技大学 | Preparation method of lithium ion battery silicon aluminium carbon composite cathode material |
| CN104157864B (en) * | 2014-07-14 | 2016-07-06 | 浙江大学 | The preparation method of type lithium ion perfluorinated sulfonic resin cladding aluminium lithium alloy material |
| CN105789560B (en) * | 2016-05-02 | 2018-02-09 | 北京工业大学 | A kind of method that alloy is welded and taken off using laser melting coating composite diffusion and prepares lithium ion battery silicium cathode |
| KR102272893B1 (en) * | 2016-11-07 | 2021-07-05 | 쥐알에스티 인터내셔널 리미티드 | Method for preparing anode slurry for batteries |
| CN106848199B (en) * | 2017-02-24 | 2020-02-14 | 中南大学 | Nano-silicon/porous carbon composite anode material of lithium ion battery and preparation method and application thereof |
| CN107623119B (en) * | 2017-10-12 | 2020-09-11 | 合肥国轩高科动力能源有限公司 | Lithium ion battery cathode material and preparation method thereof |
| CN109755483A (en) * | 2017-11-03 | 2019-05-14 | 北京万源工业有限公司 | A kind of preparation method and application of lithium ion battery silicon-carbon cathode material |
| CN109686964A (en) * | 2018-12-20 | 2019-04-26 | 国联汽车动力电池研究院有限责任公司 | A kind of silicon particle material and its purposes for preparing lithium ion battery negative material |
| CN112652744A (en) * | 2019-10-12 | 2021-04-13 | 江苏天奈科技股份有限公司 | Preparation method of high-capacity high-cycle lithium battery negative electrode material and lithium battery |
| CN117790764A (en) * | 2024-02-28 | 2024-03-29 | 赣州市瑞富特科技有限公司 | Preparation process of high-circularity lithium ion battery anode material |
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