CN101439972A - Silicon-carbon composite material, preparation thereof, battery cathode and lithium ionic cell - Google Patents
Silicon-carbon composite material, preparation thereof, battery cathode and lithium ionic cell Download PDFInfo
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- CN101439972A CN101439972A CNA2007101871828A CN200710187182A CN101439972A CN 101439972 A CN101439972 A CN 101439972A CN A2007101871828 A CNA2007101871828 A CN A2007101871828A CN 200710187182 A CN200710187182 A CN 200710187182A CN 101439972 A CN101439972 A CN 101439972A
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Abstract
The invention relates to a silicon-carbon composite material, which contains nano-silicon/carbon nanotube composite particles and amorphous carbon, wherein the amorphous carbon is coated on the surfaces of the composite particles. A method for preparing the material comprises the following steps: dispersing the nano-silicon and the carbon nanotubes in a dispersant, and removing the dispersant to obtain the nano-silicon/carbon nanotube composite particles; and contacting the nano-silicon/carbon nanotube composite particles with an amorphous carbon precursor solution, and removing a solvent to carbonize the amorphous carbon precursor. The invention also provides a negative pole of a lithium ion cell made from the composite material. The method for preparing the composite material is simple, the process is easy to control, and a cell made of the negative pole made from the composite material has a lower first irreversible specific capacity, higher specific capacity and excellent cycling performance.
Description
Technical field
The present invention relates to a kind of Si-C composite material and preparation method thereof, and the battery cathode and the lithium ion battery that use this material to make.
Background technology
Development along with electronics and information industry, the miniaturization of electronics and high performance high speed development improve constantly the cell container density requirements, add since the capacity of carbon back negative material almost near the theoretical value of 372mAh/g, people sight invested silicon, tin, aluminium and antimony etc. can with the lithium electrochemical alloyed metal (AM).Wherein, silicon is the most attractive a kind of, and its theoretical capacity is up to 4200mAh/g.But they embed and deviate from the process volume at lithium ion and expand and shrink, the variation that electrically contacts that causes active material and collector, and then causing the capacity and the cycle performance variation of material, the battery life of making is very short, has hindered the practicability of these materials.In order to address the above problem, people have researched and developed the negative pole that the matrix material of silicon and carbon is made, as disclosed nano-sized carbon silicon composite among the CN1903793A, but though this material is very big owing to specific surface area, loading capacity is higher, but the lithium consumption of the solid electrolyte interface film (SEI film) that the surface forms is serious, the first charge-discharge irreversible capacity is higher, and accelerates in the decay of the rear electrode capacity that repeatedly circulates, and also has a segment distance from practicability.In the prior art, be difficult to make the recursive nature of silicon/carbon composite to obtain effect preferably.
Summary of the invention
The objective of the invention is to provides a kind of lithium ion battery negative active material with higher capacity and excellent cycle performance and preparation method thereof in order to overcome the shortcoming of the lithium ion battery negative cycle performance difference that Si-C composite material is made in the prior art.
Another object of the present invention is to provide a kind of lithium ion battery negative that uses negative material of the present invention to make.
The 3rd purpose of the present invention is to provide a kind of lithium ion battery that uses negative pole of the present invention to make.
The invention provides a kind of Si-C composite material, this matrix material contains nano-silicon/carbon nanotube composite particles and decolorizing carbon, and described decolorizing carbon is coated on described composite particles surface.
The invention provides a kind of preparation method of Si-C composite material, this method comprises nano-silicon and carbon nanotube is dispersed in the dispersion agent, removes dispersion agent, obtains nano-silicon/carbon nanotube composite particles; Nano-silicon/carbon nanotube composite particles is contacted with the decolorizing carbon precursor solution, remove and desolvate, and make the charing of decolorizing carbon presoma.
The present invention also provides a kind of silicon-carbon composite lithium ion battery cathode, and this negative pole comprises negative current collector and the negative material that is coated on the collector, wherein, and the active substance of described negative material matrix material provided by the invention.
The present invention also provides a kind of lithium ion battery, and this battery comprises battery container, electrode group and electrolytic solution, and electrode group and electrolytic solution are sealed in the battery container, and the electrode group comprises positive pole, barrier film and negative pole, and wherein, described negative pole is a negative pole of the present invention.
Carbon nanotube has good electricity, mechanical property, the structure high resilience.Carbon nanotube and nano-silicon are compound can to form many nano level spaces, and these spaces can become the expansible space of silicon, thereby slows down the influence of the expansion of silicon to coating layer; Carbon nanotube itself also has big lithium storage content; Simultaneously, surperficial amorphous carbon layer can be alleviated the influence of the height storage lithium situation of electrolytic solution and electrode surface SEI film in use of nano-silicon/carbon nano tube compound material, reduces battery round-robin irreversible capacity first.Its preparation method is simple, and process is controlled easily, and the battery made from the negative pole of this material preparation has lower irreversible capacity first, higher specific storage and excellent cycle performance.
Embodiment
Si-C composite material provided by the invention contains nano-silicon/carbon nanotube composite particles and decolorizing carbon, and described decolorizing carbon is coated on described composite particles surface.
The particle diameter of described nano-silicon is the 20-100 nanometer; The diameter of described carbon nanotube is the 20-100 nanometer, and length is the 0.5-2 micron.Nano-silicon with 100 weight parts is a benchmark, and the content of carbon nanotube can be the 1-50 weight part, is preferably the 1-25 weight part; The content of decolorizing carbon can be the 30-200 weight part, is preferably the 40-150 weight part.
The preparation method of Si-C composite material provided by the invention comprises nano-silicon and carbon nanotube is dispersed in the dispersion agent, removes dispersion agent, obtains nano-silicon/carbon nanotube composite particles; Nano-silicon/carbon nanotube composite particles is contacted with the decolorizing carbon precursor solution, remove and desolvate, and make the charing of decolorizing carbon presoma.
The particle diameter of described nano-silicon is the 20-100 nanometer; The diameter of described carbon nanotube is the 20-100 nanometer, and length is the 0.5-2 micron.
The dispersion agent that is used for dispersing nanometer silicon and carbon nanotube can make nano-silicon and carbon nanotube dispersive liquid for various, for example, can be water, ethanol, propyl alcohol, propylene glycol or their mixture.The consumption of described dispersion agent is that per 100 gram nano-silicons adding 1-15 rise dispersion agent.
The consumption of described nano-silicon, carbon nanotube and decolorizing carbon presoma makes in the matrix material that obtains, and is benchmark with the nano-silicon of 100 weight parts, and the content of carbon nanotube is the 1-50 weight part, is preferably the 1-25 weight part; The content of decolorizing carbon is the 30-200 weight part, is preferably the 40-150 weight part.
Described decolorizing carbon precursor solution is dissolved in the solvent by the decolorizing carbon presoma and forms.Described decolorizing carbon presoma can be preferably in resin, pitch, glucose, sucrose, starch, asccharin, benzene, naphthalene and the benzene naphthalene copolymer one or more for forming the organism of decolorizing carbon after any thermo-cracking; Solvent for use can make selected presoma dissolved common solvent for any, for example can be in acetone, dehydrated alcohol, N-Methyl pyrrolidone, chloroform, the hexanaphthene one or more.Decolorizing carbon presoma with 100 grams is a benchmark, and the add-on of solvent is the 150-3000 milliliter.
Described remove desolvated and carbonization process is vaporization at high temperature solvent and charing under the protection of inert gas.The method of described solvent flashing for the nano-silicon/carbon nanotube composite particles that will be coated with the decolorizing carbon presoma under protection of inert gas, be warmed up to 200-400 ℃ with 0.5-10 ℃/minute speed, be incubated 2-10 hour; The method of described charing for will except that the product after desolvating under protection of inert gas, be heated to 850-1200 ℃ with 1-10 ℃/minute speed, be incubated 2-8 hour.At last, naturally cool to normal temperature.Used rare gas element can be in nitrogen and the neutral element gas one or more.
Desolventize finish with charing after, it can also be ground, sieves.
Under the preferable case, the preparation method of Si-C composite material provided by the invention comprises the steps:
(1) preparation of nano-silicon/carbon nanotube composite particles
With deionized water and ethanol volume ratio is 2-9:1 configuration solution.With the total solution weight is benchmark, adds the tensio-active agent of 0.2-0.6 weight %, stirs for some time, is mixed with solution.Put into nano-silicon and carbon nanotube then, continue to stir 20-60 minute.Filtration, 60-80 ℃ oven dry obtain nano-silicon/carbon nanotube composite particles.
(2) composite particles is contacted with the decolorizing carbon precursor solution
Preparation decolorizing carbon precursor solution is preferably resin/ethanolic soln and/or pitch/tetrahydrofuran solution, is benchmark with the 100 decolorizing carbon presomas that restrain, and the add-on of solvent is the 300-1000 milliliter.Stir and add the nano-silicon/carbon nanotube composite particles that makes in the step (1) down, continuation stirring 20-60 minute.Filter, obtain the nano-silicon/carbon nanotube combination product of coated with carbon presoma.
(3) desolventize and charing
The combination product that step (2) obtains is put in the High Temperature Furnaces Heating Apparatus that is connected with rare gas element, be heated to 200-400 ℃, be incubated 2-10 hour with 0.5-10 ℃ of/minute intensification; Be heated to 800-1200 ℃ of insulation 2-8 hour with 1-10 ℃/minute again.Naturally cool to normal temperature.Take out material, the soft grinding sieved, and promptly obtains product.
Silicon-carbon composite lithium ion battery cathode provided by the invention comprises negative current collector and the negative material that is coated on the collector, and wherein, the active substance of described negative material is a matrix material provided by the invention.
Described negative current collector can be for negative pole conducting base conventional in the lithium ion battery, as stamped metal, and tinsel, net metal, foamed metal uses Copper Foil as negative current collector in specific embodiments of the present invention.
Described negative material comprises negative electrode active material and tackiness agent.Described negative electrode active material is a matrix material provided by the invention; The kind of described tackiness agent and content are conventionally known to one of skill in the art, for example one or more in fluorine resin and polyolefin compound such as poly(vinylidene fluoride) (PVDF), polytetrafluoroethylene (PTFE), styrene-butadiene rubber(SBR) (SBR), Vltra tears, Xylo-Mucine, Natvosol, the polyvinyl alcohol; In general, according to the difference of adhesive therefor kind, be benchmark with the weight of negative electrode active material, the content of tackiness agent is 0.01-10 weight %, is preferably 0.02-5 weight %.
Lithium ion battery provided by the present invention comprises electrode group and electrolytic solution, and described electrode group and electrolytic solution are sealed in the battery container, and described electrode group comprises positive pole, barrier film and negative pole.Except described negative pole adopts negative pole provided by the invention, can use conventional positive pole, barrier film and electrolytic solution.
Described positive pole comprises plus plate current-collecting body and the positive electrode active materials that is coated on the plus plate current-collecting body.
Described positive electrode active materials is not particularly limited, and can be the positive electrode active materials of the embedded removal lithium embedded of this area routine, a kind of or its mixture: the Li in the preferred following material
xNi
1-yCoO
2(wherein, 0.9≤x≤1.1,0≤y≤1.0), Li
1+aM
bMn
2-bO
4(wherein ,-0.1≤a≤0.2,0≤b≤1.0, M is a kind of in lithium, boron, magnesium, aluminium, titanium, chromium, iron, cobalt, nickel, copper, zinc, gallium, yttrium, fluorine, iodine, the element sulphur), Li
mMn
2-nB
nO
2(wherein, B is a transition metal, 0.9≤m≤1.1,0≤n≤1.0).
Described plus plate current-collecting body is conventionally known to one of skill in the art, for example can be selected from aluminium foil, Copper Foil or various Punching steel strip.
According to lithium ion battery provided by the invention, membrane layer is arranged between positive pole and the negative pole, has electrical insulation capability and liquid retainability energy.Described membrane layer can be selected from and well known to a person skilled in the art various membrane layers used in the lithium ion battery, for example polyolefin micro porous polyolefin membrane, polyethylene felt, glass mat or beta glass fibre paper.
Described electrolytic solution can be the electrolytic solution of various routines, for example nonaqueous electrolytic solution.Described nonaqueous electrolytic solution is the solution that electrolyte lithium salt forms in non-aqueous solvent.Can be selected from lithium hexafluoro phosphate (LiPF such as electrolyte lithium salt
6), lithium perchlorate (LiClO
4), LiBF4 (LiBF
4), hexafluoroarsenate lithium (LiAsF
6), hexafluorosilicic acid lithium (LiSiF
6), tetraphenyl lithium tetraborate (LiB (C
6H
5)
4), lithium chloride (LiCl), lithiumbromide (LiBr), chlorine lithium aluminate (LiAlCl
4) and fluorocarbon based sulfonic acid lithium (LiC (SO
2CF
3)
3), LiCH
3SO
3, LiN (SO
2CF
3)
2In one or more.Non-aqueous solvent can be selected from chain acid esters and ring-type acid esters mixing solutions, wherein the chain acid esters can be fluorine-containing for methylcarbonate (DMC), diethyl carbonate (DEC), Methyl ethyl carbonate (EMC), carbonic acid first propyl ester (MPC), dipropyl carbonate (DPC) and other, sulfur-bearing or contain in the chain organosilane ester of unsaturated link(age) one or more.The ring-type acid esters can (γ-BL), sultone and other be fluorine-containing, sulfur-bearing or contain in the ring-type organosilane ester of unsaturated link(age) one or more for NSC 11801 (EC), propylene carbonate (PC), vinylene carbonate (VC), gamma-butyrolactone.
According to lithium ion battery provided by the invention, the preparation method of this battery is as well known to those skilled in the art, and in general, the preparation method of this battery comprises the electrode group is inserted in the battery case, adds electrolytic solution, and sealing obtains lithium ion battery then.Wherein, the method for sealing, the consumption of electrolytic solution is conventionally known to one of skill in the art.
The following examples will the invention will be further described.
Embodiment 1
Present embodiment is used to illustrate the preparation of used as negative electrode of Li-ion battery matrix material provided by the invention.
(1) preparation of nano-silicon/carbon nanotube composite particles
In 1500 ml beakers, successively add 600 ml deionized water and 150 milliliters of ethanol and 20 gram polyvinyl alcohol, stir after 30 minutes, slowly add the mixture that contains 10 gram nano-silicons and 0.6 gram carbon nanotube under the agitation condition, the nano-silicon particle diameter is the 20-50 nanometer, carbon nanotube diameter 20-50 nanometer, length 1-2 micron stirs after 40 minutes, filter 80 ℃ of oven dry.
(2) composite particles is contacted with the decolorizing carbon precursor solution
Nano-silicon/carbon nanotube composite particles that step (1) is obtained joins containing in 15 gram Resins, epoxy and the 400 milliliters of alcoholic acid solution of stirring in advance, stirs after 40 minutes filtration.
(3) desolventize and charing
Step (2) is filtered the solid product obtain at N
2Protection is warming up to 400 ℃ with 5 ℃/minute down in High Temperature Furnaces Heating Apparatus, be incubated 1 hour, is warming up to 900 ℃ with 5 ℃/minute again, is incubated 3 hours, is cooled to naturally then below 100 ℃, takes out from High Temperature Furnaces Heating Apparatus.Pulverize, behind 200 mesh sieves, promptly obtain 17.5 gram products excessively, note is made E1.
Embodiment 2
Present embodiment is used to illustrate the preparation of used as negative electrode of Li-ion battery matrix material provided by the invention.
(1) preparation of nano-silicon/carbon nanotube composite particles
With with the identical method of embodiment step (1), different is that the ethanol of adding is 80 milliliters; Replace 20 gram polyvinyl alcohol with 20 gram polyvinylpyrrolidones; And the consumption of carbon nanotube changes 2 grams into.
(2) composite particles is contacted with the decolorizing carbon precursor solution
With with the identical method of embodiment step (2), different is replaces containing 15 gram Resins, epoxy and 400 milliliters of alcoholic acid solution with 1000 milliliters of tetrahydrofuran solutions that contain 24 gram pitch prills.
(3) desolventize and charing
With with the identical method of embodiment step (3), product 34 gram, note is made E2.
Embodiment 3
Present embodiment is used to illustrate the preparation of used as negative electrode of Li-ion battery matrix material provided by the invention.
(1) preparation of nano-silicon/carbon nanotube composite particles
With with the identical method of embodiment step (1), the consumption of different is carbon nanotube changes 1 gram into.
(2) composite particles is contacted with the decolorizing carbon precursor solution
With with the identical method of embodiment step (2), different is, the Resins, epoxy of adding is 20 grams.
(3) desolventize and charing
With with the identical method of embodiment step (3), product 23.2 gram, note is made E3.
Comparative Examples 1
This Comparative Examples is used to illustrate the preparation of prior art used as negative electrode of Li-ion battery Si-C composite material.
Take by weighing 0.001 gram iron powder and 10 gram silicon grains (median size is 5 microns), mixed grinding was placed in the graphite boat after 5 hours, in the tube furnace of packing into, charged into argon gas.After the temperature programming to 800 ℃, gas is converted to the gas mixture of methane and hydrogen, volume ratio is 1:20, and flow is 300sccm, and constant temperature carried out chemical vapour deposition in 20 minutes.Then gas is converted to argon gas, naturally cools to room temperature and promptly obtain silicon/carbon nano tube compound material, product 11.2 grams, note is made C1.
Embodiment 4-6
Embodiment 4-6 is used to prepare lithium ion battery of the present invention.
The preparation of negative pole
The negative electrode active material that embodiment 1-3 is made, SBR, CMC and water mix with the weight ratio of 100:2.5:1.5:120 respectively, make cathode size, and cathode size is uniformly coated on the copper foil surface that thickness is 10 μ m, and the calendering of dry back obtains negative plate.
The anodal preparation
LiCoO with 100 grams
2Powder and as acetylene black 3 gram of conductive agent is blended in the 50 gram nmp solutions that contain 2 gram PVDF binding agents, is modulated into the anode mixture soup compound.Above-mentioned anode mixture soup compound is coated on the aluminium foil as current collector, rolls after dry.
The preparation of electrolytic solution
NSC 11801 and diethyl carbonate are mixed as solvent with the 3:7 volume ratio, with respect to this solvent with 1 mol with LiPF
6Electrolytic solution is made in dissolving.With respect to these electrolytic solution 100 weight parts, mix the vinylene carbonate of 5 weight parts, the electrolytic solution of using as battery.
The preparation of battery
The above negative pole that makes, positive pole, electrolytic solution and aluminium lamination shell are prepared into 053450 rectangular cell, and note is made A1, A2 and A3, and the active substance of used negative pole is respectively the matrix material that embodiment 1,2 and 3 makes.
Comparative Examples 2
Make battery B1 according to the method identical with embodiment 4-6, different is that the matrix material that use Comparative Examples 1 is made is as negative active core-shell material.
Performance test
Measure irreversible first specific storage, specific storage and the cycle performance of lithium ion battery A1, A2, A3 and B1 in accordance with the following methods.
Irreversible first specific storage: under 25 ℃ with battery with 1C electric current constant current charge to 3.8V, then change constant voltage charging, cut-off current 0.05C; Then, again with battery with 1C electric current constant-current discharge to 2.75V, the promptly irreversible first specific storage of the difference of its initial charge specific storage and first discharge specific capacity.
Specific storage: under 25 ℃ with battery with 1C electric current constant current charge to 3.8V, then change constant voltage charging, cut-off current 0.05C; Then, again with battery with 1C electric current constant-current discharge to 2.75V, obtain the specific storage of battery normal temperature 1C current discharge to 2.75V.
Cycle performance: under the room temperature, with battery with 1C electric current constant current charge to 3.8V, then change constant voltage charging, cut-off current 0.05C; Then, again with battery with 1C electric current constant-current discharge to 2.75V.Repeat above step 100 time, obtain the capacity of 100 circulation backs of battery normal temperature 1C current discharge, cell container sustainment rate after the computation cycles to 2.75V.
Measurement result is as shown in table 1.
Table 1
| Numbering | Irreversible first specific storage/mAh/g | Specific storage/mAh/g | Capability retention (%) |
| A1 | 700 | 1000 | 40 |
| A2 | 700 | 1080 | 60 |
| A3 | 550 | 850 | 55 |
| B1 | 2534 | 829 | 5 |
By table 1 as can be seen, the battery made from the negative pole of Composite Preparation provided by the invention has lower irreversible first specific storage, higher specific storage and excellent cycle performance.
Claims (12)
1, a kind of Si-C composite material is characterized in that, this matrix material contains nano-silicon/carbon nanotube composite particles and decolorizing carbon, and described decolorizing carbon is coated on described composite particles surface.
2, matrix material according to claim 1, wherein, the particle diameter of described nano-silicon is the 20-100 nanometer; The diameter of described carbon nanotube is the 20-100 nanometer, and length is the 0.5-2 micron.
3, matrix material according to claim 1 wherein, is a benchmark with the nano-silicon of 100 weight parts, and the content of carbon nanotube is the 1-25 weight part, and the content of decolorizing carbon is the 40-150 weight part.
4, the preparation method of the described matrix material of claim 1 is characterized in that, this method comprises nano-silicon and carbon nanotube are dispersed in the dispersion agent, removes dispersion agent, obtains nano-silicon/carbon nanotube composite particles; Nano-silicon/carbon nanotube composite particles is contacted with the decolorizing carbon precursor solution, remove and desolvate, and make the charing of decolorizing carbon presoma.
5, method according to claim 4, wherein, described decolorizing carbon precursor solution is dissolved in the solvent by the decolorizing carbon presoma and forms; Described decolorizing carbon presoma is selected from one or more in resin, pitch, glucose, sucrose, starch, asccharin, benzene, naphthalene and the benzene naphthalene copolymer; The used solvent of decolorizing carbon precursor solution is one or more in acetone, dehydrated alcohol, N-Methyl pyrrolidone, chloroform and the hexanaphthene; Decolorizing carbon presoma with 100 grams is a benchmark, and the add-on of solvent is the 150-3000 milliliter.
6, method according to claim 4, wherein, the described method of desolvating of removing is dried under protection of inert gas for the nano-silicon/carbon nanotube composite particles that will be coated with the decolorizing carbon precursor solution, and bake out temperature is 200-400 ℃; The method of described charing will be for keeping 2-8 hour down at 850-1200 ℃ under protection of inert gas except that the product after desolvating.
7, method according to claim 6, wherein, described rare gas element is selected from one or more in nitrogen and the neutral element gas.
8, method according to claim 4, wherein, described dispersion agent is selected from one or more in water, ethanol, propyl alcohol, the propylene glycol; The consumption of described dispersion agent is that per 100 gram nano-silicons adding 1-15 rise dispersion agent.
9, method according to claim 4, wherein, the consumption of described nano-silicon, carbon nanotube and decolorizing carbon presoma makes in the matrix material that obtains, and is benchmark with the nano-silicon of 100 weight parts, the content of carbon nanotube is the 1-25 weight part, and the content of decolorizing carbon is the 40-150 weight part.
10, according to claim 4 or 9 described methods, wherein, the particle diameter of described nano-silicon is the 20-100 nanometer; The diameter of described carbon nanotube is the 20-100 nanometer, and length is the 0.5-2 micron.
11, a kind of lithium ion battery negative, this negative pole comprise negative current collector and the negative material that is coated on the collector, it is characterized in that the active substance of described negative material is any described matrix material among the claim 1-3.
12, a kind of lithium ion battery, this battery comprises battery container, electrode group and electrolytic solution, and electrode group and electrolytic solution are sealed in the battery container, and the electrode group comprises positive pole, barrier film and negative pole, it is characterized in that, and described negative pole is the negative pole described in the claim 11.
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| CN1315207C (en) * | 2005-06-22 | 2007-05-09 | 浙江大学 | Composite negative pole material of Li-ion battery and its preparing process |
| CN1913200B (en) * | 2006-08-22 | 2010-05-26 | 深圳市贝特瑞电子材料有限公司 | Silicon carbone compound negative polar material of lithium ion battery and its preparation method |
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