CN100576610C - A kind of silicon composite and preparation method thereof that contains - Google Patents
A kind of silicon composite and preparation method thereof that contains Download PDFInfo
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- CN100576610C CN100576610C CN200610170615A CN200610170615A CN100576610C CN 100576610 C CN100576610 C CN 100576610C CN 200610170615 A CN200610170615 A CN 200610170615A CN 200610170615 A CN200610170615 A CN 200610170615A CN 100576610 C CN100576610 C CN 100576610C
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Abstract
A kind of silicon composite that contains, this material contains elemental silicon, graphite and agraphitic carbon, and wherein, this material also contains carbon nano-tube, and described elemental silicon is a nano simple substance silicon, is coated on elemental silicon, graphite and the carbon nano tube surface to the described agraphitic carbon of small part.Even under lower silicone content situation, also have higher specific capacity, but also can use this to contain silicon composite has excellence as the battery of negative electrode active material cyclical stability according to the silicon composite that contains provided by the invention.
Description
Technical field
The invention relates to a kind of silicon composite and preparation method thereof that contains.
Background technology
Present commercial lithium ion battery adopts lithium transition-metal oxide/graphite system as negative active core-shell material mostly, though the chemical property excellence of this class system, but it is lower itself to store up the lithium ability, particularly the theoretical capacity of graphite-like negative active core-shell material only is 372 MAH/grams, and so low capacity has been difficult to adapt to the miniaturization development of various portable electric appts and the electric automobile demand to big capacity, high power chemical power source at present.Therefore, studying at present a kind of new performance that the negative active core-shell material of height ratio capacity more improves lithium ion battery that has, meeting the need of market.
To studies show that of non-carbon negative active core-shell material, have the metal or alloy class material of many high storage lithium performances to use as negative active core-shell material, wherein silicon becomes the most attractive a kind of because of having embedding lithium specific capacity big (theoretical specific capacity can reach 4200 MAH/grams) and the low characteristics such as (less than 0.5 volts) of embedding lithium current potential.Yet, there is serious bulk effect in silicon in the process of removal lithium embedded, owing to volumetric expansion produces bigger mechanical stress, the cyclical stability of the battery that causes using silicon to do negative active core-shell material is poor in the charge and discharge process of battery, thereby has hindered the industrial applications of silicon.
For this reason, present many researchers are devoted to the modification and the optimal design of high lithium storage materials, and have obtained certain progress.The bulk effect problem that solves silicon materials has two kinds of methods usually: the one, and depositing silicon film on the collector of battery cathode, the advantage of this method is not need to add other component in the electrode, shortcoming is to be not suitable for large-scale production, and when the thickness of silicon thin film surpasses 1 micron, the diffusion length of lithium ion increases, and resistance increases.The 2nd, prepare siliceous composite material, modal is silicon/carbon composite.Though the affiliation that adds of carbon causes the specific capacity of composite material to descend to some extent, the specific capacity after reducing still is much higher than the specific capacity of carbon itself, therefore still can be used as the desirable substitute of carbon class negative active core-shell material.Silicon/carbon composite has two kinds of structures, and a kind of is " cake type " structure, is about to silicon grain and at first is dispersed in (mainly being pitch, resin etc.) in the organic precursor, organic substance is carried out high temperature carbonization again and handles, and obtains silicon/carbon composite.For example, CN 1218418C discloses the negative electrode active material that a kind of charging lithium accumulator is used, this negative electrode active material contain a kind of graphite particle, a kind of be combined in the lip-deep silicon micro particles of graphite particle and be coated in graphite particle and the silicon micro particles on carbon film, wherein, described carbon film is by polymeric material is coated on the graphite particle, and again with the calcined material that obtained and the amorphous carbon film for preparing, described silicon micro particles is to be combined in the lip-deep of graphite particle by this carbon film, and the content of this silicon micro particles is 3-10 weight %.When the content of silicon micro particles was 5 weight %, the specific capacity of this negative electrode active material was 447 MAH/grams.
CN 1790779A discloses a kind of negative electrode active material, and this anode active material comprises graphite core and be formed on first coating and second coating on graphite core surface, and wherein this first coating contains the silicon particle and second coating contains carbon fiber.The preparation method of this negative electrode active material comprises graphite powder, silica flour and polymeric material joined in the solvent, stirs dryly then, calcines dry thing to prepare first coating; With polymeric material, wherein form the graphite core of first coating and carbon fiber and add in the solvent, dry while stirring then, calcine dry thing to prepare second coating.Described polymeric material is preferably one or more in vinyl, celluosic resin, phenolic resins, pitch and the tar resin.When the content of silicon micro particles was 9 weight %, the specific capacity of this negative electrode active material reached as high as 632 MAH/grams, but the capability retention less than 70% behind the 0.2C cycle charge-discharge 50 times.
CN 1761089A discloses a kind of lithium ion battery silicon/carbon/composite cathode material of silicon/carbon/graphite, and this composite negative pole material is made up of the agraphitic carbon of 10-80 weight % elemental silicon, 10-60 weight % graphite granule and surplus.This composite material is by carrying out high-energy ball milling after silica flour and the graphite mixing, then the material behind the ball milling is joined in the carbohydrate saturated solution, the back baking of being uniformly dispersed makes in the saturated solution solvent evaporates complete, until forming slurry like material, in the slurry that forms, add the concentrated sulfuric acid again, stir, leave standstill dehydration carbonization 1-5 hour, add water suction filtration, washing, drying, pulverize, sieving gets final product.When the content of silica flour was 20 weight %, the specific capacity of this negative material was 847.1 MAH/grams.And it is serious to equipment corrosion on the one hand to use the concentrated sulfuric acid to carry out charing, also can cause the extremely strong spent acid of a large amount of corrosivity on the other hand.
Though when silicone content is higher, the above-mentioned specific capacity that contains silicon composite is higher, but still there is the problem that causes the cycle performance of battery difference when discharging and recharging because of the silicon volumetric expansion greatly when silicone content is higher, and silicone content is when low, then the specific capacity of composite material cycle performance low, battery is relatively poor, can not satisfy actual needs.
Summary of the invention
The objective of the invention is in order to overcome the existing shortcoming that the silicon composite specific capacity is low, cycle performance of battery is relatively poor that contains, provide a kind of specific capacity height, cycle performance of battery good contain silicon composite and preparation method thereof.
The silicon composite that contains provided by the invention contains elemental silicon, graphite and agraphitic carbon, and wherein, this material also contains carbon nano-tube, and described elemental silicon is a nano simple substance silicon, is coated on elemental silicon, graphite and the carbon nano tube surface to the described agraphitic carbon of small part.
The preparation method who contains silicon composite provided by the invention comprises and will contain elemental silicon; the composite particles of graphite and surfactant and carbon predecessor mix in solvent; obtain the elemental silicon that contains of coated with carbon predecessor; the composite particles of graphite and surfactant; be agraphitic carbon with carbon predecessor and surfactant charing then; wherein; the described elemental silicon that contains; the composite particles of graphite and surfactant also contains carbon nano-tube; described elemental silicon is a nano simple substance silicon, is coated on elemental silicon to the described agraphitic carbon of small part; on graphite and the carbon nano tube surface.
According to the silicon composite that contains provided by the invention, owing to increased carbon nano-tube and used nano simple substance silicon, therefore make elemental silicon in charge and discharge process, be alleviated, can also slow down the influence of the expansion of elemental silicon simultaneously the agraphitic carbon coating layer because of the mechanical stress that volumetric expansion produces.The most important thing is, because the synergy of elemental silicon, graphite and agraphitic carbon and carbon nano-tube, even make this material under lower silicone content situation, also have higher specific capacity, also make simultaneously and use this to contain silicon composite has excellence as the battery of negative electrode active material cyclical stability.For example, use contains the capability retention of silicon composite after as 50 circulations of the lithium rechargeable battery of negative electrode active material up to 90% by what embodiment 1 made, and prior art contain the capability retention less than 70% of silicon composite under the identical situation of other conditionally complete.
Embodiment
According to the silicon composite that contains provided by the invention, although a spot of carbon nano-tube can realize purpose of the present invention, preferable case, with respect to 100 weight portion graphite, the content of described carbon nano-tube is the 0.01-2 weight portion, is preferably the 0.1-0.7 weight portion; The content of described nano simple substance silicon is the 2-15 weight portion, is preferably the 3-10 weight portion; The content of described agraphitic carbon is the 5-20 weight portion, is preferably the 8-15 weight portion.
Although the carbon nano-tube of various different-diameters and draw ratio all can realize purpose of the present invention, under the preferable case, the diameter of described carbon nano-tube is the 1-200 nanometer, is preferably the 10-150 nanometer, more preferably the 60-100 nanometer; Length is preferably the 0.1-2 micron, more preferably the 0.5-1 micron.The carbon nano-tube that use has above-mentioned diameter and length can guarantee to form between the carbon nano-tube better conductive network, thereby further improve the conductivity of this composite material, and, the dispersiveness of carbon nano-tube in water with above-mentioned diameter and length is better, when the preparation anode sizing agent, be not easy to reunite, and have an imbibition ability preferably, lower resistivity.Carbon nano-tube with above-mentioned size can be commercially available, and also can obtain by the prepared in various methods of prior art.
Among the present invention, using the nano silicone particle is to increase and can be cushioned by the elasticity of carbon nano-tube in order to make by the silicon particle volume that produces that expands, thereby alleviates the mechanical stress that the silicon particle produces because of volumetric expansion in charge and discharge process.The nano-silicon particle that described silicon particle can be all size and shape.For example, can be that particle diameter is 1-500 nanometer, the nano-silicon particle of 5-200 nanometer more preferably.The shape of described silicon particle can be one or more in spherical, bar-shaped, wire, the tubulose, is preferably spherical.Purity to the silicon particle does not have special requirement, can be technical pure, analysis pure silicon particle or HIGH-PURITY SILICON particle.
Among the present invention, described graphite can be the graphite of lithium ion battery field routine, and under the preferable case, described graphite is mean particle diameter D
50Be the flaky graphite of 5-50 micron, be preferably mean particle diameter D
50Flaky graphite for the 15-25 micron.The microcrystalline coating spacing d of described graphite
002Be preferably the 0.335-0.338 nanometer.
Among the present invention, described agraphitic carbon can obtain by the charing of carbon predecessor and surfactant.Described carbon predecessor can be one or more in various vistanexes, celluosic resin, thermosetting phenolic resin, Lauxite, epoxy resin, pitch and the tar resin.Described pitch can be coal tar pitch and/or petroleum asphalt.The method of described charing can be a method well known in the art, also can be method disclosed by the invention.
According to the preparation method who contains silicon composite provided by the invention, the composite material granular that contains elemental silicon, graphite and surfactant can remove to desolvate and obtain by back that elemental silicon particle, graphite particle and carbon nano-tube are uniformly dispersed in containing the solution of surfactant.Described surfactant can be conventional various high molecular surfactants, for example can be in polyvinyl alcohol, polyvinylpyrrolidone, polyethylene glycol, polyacrylic acid, polytetrafluoroethylene, Kynoar, carboxymethyl cellulose, carboxyethyl cellulose, carboxymethyl methyl fiber, the polyacrylamide one or more.Above-mentioned high molecular surfactant obtains containing the composite material granular of elemental silicon, graphite and carbon nano-tube elemental silicon, graphite and carbon nano-tube particle being coated except that after desolvating.Because polyvinyl alcohol, polyvinylpyrrolidone, polyethylene glycol, polyacrylic acid, polyacrylamide can play the effect of dispersant simultaneously, prevent the nano-silicon particle aggregation, elemental silicon particle, graphite particle and carbon nano-tube are fully mixed, so the preferred described surfactant of the present invention is in polyvinyl alcohol, polyvinylpyrrolidone, polyethylene glycol, polyacrylic acid, the polyacrylamide one or more.The addition of described surfactant is preferably the 5-25 weight % of elemental silicon particle, graphite particle and carbon nano-tube total weight.
The solvent that forms solution can be variously surfactant fully can be dissolved various organic solvents and/or the inorganic solvent that obtains solution, can be water for example, have lower alcohol, acetone, a N of 1-4 carbon atom, one or more in dinethylformamide, methyl-sulfoxide, carbon tetrachloride, benzene,toluene,xylene, the chlorobenzene.For example can be water and pure mixed solvent with volume ratio 7-9: 1-3.
The concentration of described solution can make elemental silicon particle, graphite particle and carbon nano-tube fully mix required concentration therein for having, and for example can be 5-50 weight %, is preferably 15-25 weight %.Although rarer solution also can be realized the abundant mixing of elemental silicon particle, graphite particle and carbon nano-tube, but because solvent needs to remove after mixing, too big quantity of solvent has increased the removal amount of solvent undoubtedly and has caused cost to increase, therefore, as long as the concentration of solution can make surfactant fully dissolve, make elemental silicon particle, graphite particle and carbon nano-tube fully to mix.
Can elemental silicon particle, graphite particle and carbon nano-tube fully be mixed by modes such as ultrasonic dispersion, stirrings.
It is described that to remove the mode desolvate can be to make solvent evaporates under field conditions (factors), also can be under heating and/or reduced pressure, to make solvent evaporates, the preferred described mode of desolvating of removing of the present invention is to make solvent evaporates under vacuum heating conditions, like this can not only accelerated solvent remove, and can also make the structure of the compound particle that contains elemental silicon particle, graphite particle and carbon nano-tube more stable.
The mixing of described carbon predecessor and the composite material granular that contains elemental silicon, graphite and carbon nano-tube can and the dissolving of carbon predecessor be formed in all kinds of solvents of solution in the structure of not destroying the above-mentioned compound particle that contains elemental silicon particle, graphite particle and carbon nano-tube carries out, for example can carry out in the lower alcohol with 1-4 carbon atom, oxolane, benzene, toluene.The addition of described solvent is so that the carbon predecessor fully dissolves to form solution and this solution is fully mixed with the composite material granular that contains elemental silicon, graphite and carbon nano-tube is as the criterion, for example, the addition of described solvent is to contain the composite particles of elemental silicon, graphite and surfactant and 2-5 times of carbon predecessor total weight.
Described carbon predecessor makes with respect to 100 weight portion graphite with the addition that contains the composite particles of elemental silicon, graphite and surfactant, the content of agraphitic carbon is the 5-20 weight portion, the content of described carbon nano-tube is the 0.01-2 weight portion, and the content of described nano simple substance silicon is the 2-15 weight portion.For example, the addition of described carbon predecessor is the 7-20 weight % that contains the composite particles weight of elemental silicon, graphite and surfactant, and elemental silicon, graphite and carbon nano-tube are coated by agraphitic carbon fully.The inventor found through experiments, and under above-mentioned condition of the present invention, with respect to 100 weight portion graphite, total addition of carbon predecessor and surfactant can be the 25-45 weight portion.What obtain in the addition scope of above-mentioned carbon predecessor contains in the silicon composite, and the content of agraphitic carbon is the 5-20 weight portion.
Can the compound particle that contain elemental silicon particle, graphite particle, surfactant and carbon nano-tube fully be mixed with the carbon precursor solution by modes such as ultrasonic dispersion, stirrings.
Described charing can be carried out according to the method for well known to a person skilled in the art.For example, can be under inert gas shielding formerly in for example 100-500 ℃ preferred 200-400 ℃ heating 1-10 hour preferred 2-8 hour down, and then heat down at 600-1500 ℃ of preferred 800-1200 ℃ and to carry out in 1-8 hour preferred 2-6 hour.Described inert gas can be the gas of group 0 element in the nitrogen and the periodic table of elements, as in helium, neon, argon gas and the xenon one or more.Described heating is preferably with the heating of 0.5-10 ℃/minute speed.
The following examples will the present invention is described further.
Embodiment 1
This embodiment is used to illustrate the silicon composite and preparation method thereof that contains provided by the invention.
60 ml deionized water, 15 milliliters of ethanol and 2 gram polyvinyl alcohol are added in 100 ml beakers, stirs after 30 minutes, under stirring condition, slowly add 10 and restrain native graphite (mean particle diameter D
50=18 microns, microcrystalline coating spacing d
002Be 0.335 nanometer), continue to stir after 30 minutes, the 1 gram nano-silicon (particle diameter is the 20-50 nanometer) and 0.06 that contains that adds prior ultrasonic dispersion 30 minutes restrains carbon nano-tube (particle diameter is the 20-50 nanometer, length 1-2 micron) mixture, continue to stir after 40 minutes and filter, with joining after the solid vacuumize that obtains in the solution that contains 1.5 gram epoxy resin E-44s and 40 milliliters of ethanol that stirs in advance, continue to stir after 40 minutes and filter, the gained solid is dried.With the oven dry solid at N
2Protection down is warming up to 400 ℃ and insulation 1 hour under this temperature with 5 ℃/minute, is warming up to 900 ℃ and insulation 3 hours under this temperature with 5 ℃/minute then.Naturally be cooled to below 100 ℃, take out, sieve the soft back of pulverizing, and obtains 11.4 gram mean particle diameter D
50Be 20.41 microns provided by the invention siliceous composite sample S1.
Comparative Examples 1
What this Comparative Examples was used to illustrate prior art contains silicon composite and preparation method thereof.
Contain silicon composite according to the preparation of the method for embodiment 1, different is, does not add carbon nano-tube, obtains 11.5 gram mean particle diameter D
50Be 19.92 microns the siliceous composite sample CS1 of reference.
Comparative Examples 2
What this Comparative Examples was used to illustrate prior art contains silicon composite and preparation method thereof.
Method preparation according to embodiment 1 contains silicon composite, and different is that described 1 gram nano-silicon is the silicon particle replacement of 0.5-1 micron by 1 gram particle diameter, obtains 11.2 gram mean particle diameter D
50Be 20.76 microns the siliceous composite sample CS2 of reference.
Embodiment 2
This embodiment is used to illustrate the silicon composite and preparation method thereof that contains provided by the invention.
60 ml deionized water, 15 milliliters of ethanol and 2 gram polyvinylpyrrolidones are added in 100 ml beakers, stirs after 25 minutes, under stirring condition, slowly add 10 and restrain native graphite (mean particle diameter D
50=20 microns, microcrystalline coating spacing d
002Be 0.335 nanometer), continue to stir after 30 minutes, the 1 gram nano-silicon (particle diameter is the 20-50 nanometer) and 0.17 that contains that adds prior ultrasonic dispersion 30 minutes restrains carbon nano-tube (particle diameter is the 20-50 nanometer, length 0.5-1 micron) mixture, continue to stir after 40 minutes and filter, with joining after the solid vacuumize that obtains in the solution that contains 1.5 gram epoxy resin E-50 and 40 milliliters of ethanol that stirs in advance, continue to stir after 40 minutes and filter, the gained solid is dried.With the oven dry solid at N
2Protection down is warming up to 400 ℃ and insulation 1 hour under this temperature with 10 ℃/minute, is warming up to 900 ℃ and insulation 3 hours under this temperature with 10 ℃/minute then.Naturally be cooled to below 100 ℃, take out, sieve the soft back of pulverizing, and obtains 11.1 gram mean particle diameter D
50Be 20.52 microns provided by the invention siliceous composite sample S2.
Embodiment 3
This embodiment is used to illustrate the silicon composite and preparation method thereof that contains provided by the invention.
60 ml deionized water, 15 milliliters of ethanol and 0.6 gram polyacrylic acid are added in 100 ml beakers, stirs after 25 minutes, under stirring condition, slowly add 10 and restrain native graphite (mean particle diameter D
50=18 microns, microcrystalline coating spacing d
002Be 0.335 nanometer), continue to stir after 30 minutes, the 1 gram nano-silicon (particle diameter is the 50-100 nanometer) and 0.10 that contains that adds prior ultrasonic dispersion 30 minutes restrains carbon nano-tube (particle diameter is the 60-100 nanometer, length 1-2 micron) mixture, continue to stir after 40 minutes and filter, with joining after the solid vacuumize that obtains in the solution that contains 2.5 gram epoxy resin E-53 and 40 milliliters of oxolanes that stirs in advance, continue to stir after 40 minutes and filter, the gained solid is dried.With the oven dry solid at N
2Protection down is warming up to 300 ℃ and insulation 2 hours under this temperature with 5 ℃/minute, is warming up to 900 ℃ and insulation 3 hours under this temperature with 10 ℃/minute then.Naturally be cooled to below 100 ℃, take out, sieve the soft back of pulverizing, and obtains 11.3 gram mean particle diameter D
50Be 19.12 microns provided by the invention siliceous composite sample S3.
Embodiment 4
This embodiment is used to illustrate the silicon composite and preparation method thereof that contains provided by the invention.
60 ml deionized water, 15 milliliters of ethanol and 3.5 gram polyethylene glycol are added in 100 ml beakers, stirs after 30 minutes, under stirring condition, slowly add 10 and restrain native graphite (mean particle diameter D
50=18 microns, microcrystalline coating spacing d
002Be 0.335 nanometer), continue to stir after 30 minutes, the 0.2 gram nano-silicon (particle diameter is the 20-50 nanometer) and 0.07 that contains that adds prior ultrasonic dispersion 30 minutes restrains carbon nano-tube (particle diameter is the 20-50 nanometer, length 0.5-1 micron) mixture, continue to stir after 40 minutes and filter, with joining after the solid vacuumize that obtains in the solution that contains 1.0 gram coal tar pitch and 40 milliliters of oxolanes that stirs in advance, continue to stir after 40 minutes and filter, the gained solid is dried.With the oven dry solid at N
2Protection down is warming up to 350 ℃ and insulation 1 hour under this temperature with 5 ℃/minute, is warming up to 1000 ℃ and insulation 2.5 hours under this temperature with 5 ℃/minute then.Naturally be cooled to below 100 ℃, take out, sieve the soft back of pulverizing, and obtains 11.1 gram mean particle diameter D
50Be 20.15 microns provided by the invention siliceous composite sample S4.
Embodiment 5
This embodiment is used to illustrate the silicon composite and preparation method thereof that contains provided by the invention.
60 ml deionized water, 15 milliliters of ethanol and 2 gram polyacrylamides are added in 100 ml beakers, stirs after 30 minutes, under stirring condition, slowly add 10 and restrain Delanium (mean particle diameter D
50=18 microns, microcrystalline coating spacing d
002Be 0.337 nanometer), continue to stir after 25 minutes, the 1 gram nano-silicon (particle diameter is the 20-50 nanometer) and 0.06 that contains that adds prior ultrasonic dispersion 30 minutes restrains carbon nano-tube (particle diameter is the 20-50 nanometer, length 0.5-1 micron) mixture, continue to stir after 40 minutes and filter, with joining after the solid vacuumize that obtains in the solution that contains 1.5 gram Lauxites and 40 milliliters of ethanol that stirs in advance, continue to stir after 40 minutes and filter, the gained solid is dried.With the oven dry solid at N
2Protection down is warming up to 200 ℃ and insulation 3 hours under this temperature with 5 ℃/minute, is warming up to 1200 ℃ and insulation 2 hours under this temperature with 5 ℃/minute then.Naturally be cooled to below 100 ℃, take out, sieve the soft back of pulverizing, and obtains 11.4 gram mean particle diameter D
50Be 19.64 microns provided by the invention siliceous composite sample S5.
Embodiment 6
This embodiment is used to illustrate the silicon composite and preparation method thereof that contains provided by the invention.
60 ml deionized water, 15 milliliters of ethanol and 2 gram Kynoar are added in 100 ml beakers, stirs after 30 minutes, under stirring condition, slowly add 10 and restrain Delanium (mean particle diameter D
50=18 microns, microcrystalline coating spacing d
002Be 0.337 nanometer), continue to stir after 25 minutes, the 1.5 gram nano-silicons (particle diameter is the 20-50 nanometer) and 0.06 that contain that add prior ultrasonic dispersion 30 minutes restrain carbon nano-tube (particle diameter are the 20-50 nanometer, length 0.5-1 micron) mixture, continue to stir after 40 minutes and filter, with joining after the solid vacuumize that obtains in the solution that contains 1.5 gram thermosetting phenolic resins and 40 milliliters of ethanol that stirs in advance, continue to stir after 40 minutes and filter, the gained solid is dried.With the oven dry solid at N
2Protection down is warming up to 200 ℃ and insulation 3 hours under this temperature with 5 ℃/minute, is warming up to 1200 ℃ and insulation 2 hours under this temperature with 5 ℃/minute then.Naturally be cooled to below 100 ℃, take out, sieve the soft back of pulverizing, and obtains 11.8 gram mean particle diameter D
50Be 19.81 microns provided by the invention siliceous composite sample S6.
Embodiment 7
This embodiment is used to illustrate the chemical property of siliceous composite sample provided by the invention.
1, electrochemical specific capacity.Test the electrochemical specific capacity of the siliceous composite sample S1 that makes by the foregoing description 1 according to following step:
With thickness is that 0.06 millimeter, diameter are that 16 millimeters, weight are that the metal lithium sheet of 0.0064 gram is a negative electrode active material, is barrier film with the modified polypropene barrier film, with the LiPF of 1 mol
6Solution is electrolyte, and the siliceous composite sample S1, conductive carbon black and the Kynoar that are made by the foregoing description 1 with 0.125 gram are positive electrode with 40: 40: 20 mixture of weight ratio, make 2016 type button cells.
According to following step measurements electrochemical specific capacity: battery shelved change into to 0.2 volt of voltage with 0.2 milliampere of electric current after 60 minutes, then respectively with 1 milliampere, 0.8 milliampere, 0.7 milliampere, 0.6 milliampere constant current discharge to 0.005 volt, after shelving 30 minutes, again with 0.5 milliampere, 0.3 milliampere, 0.1 milliampere, 0.06 milliampere, 0.03 milliampere constant current discharge to 0.005 volt, shelve after 30 minutes with 0.3 milliampere of electric current constant current charge, record charges to cell voltage and reaches 2.5 volts time, according to normal capacity (MAH)=charging current (milliampere) * charging interval of button cell (hour) calculate the normal capacity of button cell, normal capacity promptly gets the electrochemical specific capacity of button cell positive active material (siliceous composite sample S 1) divided by the weight of the positive active material (siliceous composite sample S1) of button cell, and the result is as shown in table 1.
2, cycle performance.Test the cycle performance of siliceous composite sample S1 according to following step:
With 6.39 gram LiCoO
2Being positive active material, is barrier film with the modified polypropene barrier film, with the LiPF of 1 mol
6Solution is electrolyte, is negative electrode active material with siliceous composite sample S 1, conductive carbon black and the Kynoar that is made by the foregoing description 1 with 40: 40: 20 mixture of weight ratio with 2.00 grams, makes 043450A type (the design battery capacity is 800 MAHs) secondary lithium battery.
Cycle performance according to the siliceous composite sample S1 of following step measurements: with 80 milliamperes of (0.1C) constant current charges 960 minutes, deboost is 4.2 volts, shelved after the charging 15 minutes, with 160 milliamperes of (0.2C) constant current discharge to 3.0 volts, repeat the above-mentioned step 50 time of discharging and recharging, the discharge capacity after the record circulation 50 times is calculated this capacity and the ratio of discharge capacity first, be the capability retention of circulation after 50 times, the result is as shown in table 1.
Embodiment 8-12
Following embodiment is used to illustrate the chemical property of siliceous composite sample provided by the invention.
According to the method for embodiment 7 test the discharge first of siliceous composite sample must capacity and 50 circulations after capability retention, different is, the siliceous composite sample S1 that is made by the foregoing description 1 is replaced by the siliceous composite sample S2-S6 that embodiment 2-6 makes respectively, and the result is as shown in table 1.
Comparative Examples 3-4
This Comparative Examples is used to illustrate the chemical property of siliceous composite sample of the prior art.
According to the method for embodiment 7 test the discharge first of siliceous composite sample must capacity and 50 circulations after capability retention, different is, the siliceous composite sample S1 that is made by the foregoing description 1 is replaced by the siliceous composite sample CS1 of reference, the CS2 that Comparative Examples 1, Comparative Examples 2 make respectively, and the result is as shown in table 1.
Table 1
From the result of last table 1 as can be seen, the silicon composite that contains provided by the invention has superior comprehensive electrochemical, and the capability retention after first discharge specific capacity and 50 circulations all is significantly improved than the silicon composite that contains of prior art.
Claims (12)
1, a kind of silicon composite that contains, this material contains elemental silicon, graphite and agraphitic carbon, it is characterized in that, this material also contains carbon nano-tube, described elemental silicon is a nano simple substance silicon, be coated on elemental silicon, graphite and the carbon nano tube surface to the described agraphitic carbon of small part, and in this material, elemental silicon, graphite and even carbon nanotube are mixed.
2, material according to claim 1, wherein, with respect to 100 weight portion graphite, the content of described carbon nano-tube is the 0.01-2 weight portion, and the content of described nano simple substance silicon is the 2-15 weight portion, and the content of described agraphitic carbon is the 5-20 weight portion.
3, material according to claim 1, wherein, the particle diameter of described carbon nano-tube is the 20-100 nanometer, length is the 0.5-2 micron.
4, material according to claim 1, wherein, the particle diameter of described nano simple substance silicon is the 5-200 nanometer.
5, material according to claim 1, wherein, the particle diameter of described graphite is the 15-25 micron.
6; a kind of preparation method who contains silicon composite; this method comprises and will contain elemental silicon; the composite particles of graphite and surfactant and carbon predecessor mix in solvent; obtain the elemental silicon that contains of coated with carbon predecessor; the composite particles of graphite and surfactant; be agraphitic carbon with carbon predecessor and surfactant charing then; it is characterized in that; the described elemental silicon that contains; the composite particles of graphite and surfactant also contains carbon nano-tube; described elemental silicon is a nano simple substance silicon, is coated on elemental silicon to the described agraphitic carbon of small part; on graphite and the carbon nano tube surface.
7, method according to claim 6, wherein, described carbon predecessor makes with respect to 100 weight portion graphite with the addition that contains the composite particles of elemental silicon, graphite and surfactant, the content of agraphitic carbon is the 5-20 weight portion, the content of described carbon nano-tube is the 0.01-2 weight portion, and the content of described nano simple substance silicon is the 2-15 weight portion.
8, according to claim 6 or 7 described methods, wherein, the addition of described carbon predecessor is the 7-20 weight % that contains the composite particles weight of elemental silicon, graphite and surfactant.
9, method according to claim 6, wherein, the preparation method who contains the composite particles of elemental silicon, graphite and surfactant comprises elemental silicon, graphite and the carbon nano-tube back that is uniformly dispersed in containing the solution of surfactant is removed and desolvated.
10, method according to claim 9, wherein, described surfactant is one or more in polyvinyl alcohol, polyvinylpyrrolidone, polyethylene glycol, polyacrylic acid, the polyacrylamide, and the addition of described surfactant is the 5-25 weight % of elemental silicon, graphite and carbon nano-tube total weight.
11, method according to claim 6, wherein, the particle diameter of described carbon nano-tube is the 20-100 nanometer, length is the 0.5-2 micron, the particle diameter of described nano simple substance silicon is the 5-200 nanometer, the particle diameter of described graphite is the 15-25 micron, described carbon predecessor is a vistanex, celluosic resin, thermosetting phenolic resin, Lauxite, epoxy resin, in pitch and the tar resin one or more, described solvent are energy dissolved carbon predecessor but do not dissolve the described elemental silicon that contains, the composite particles of graphite and surfactant and not with carbon predecessor and the described elemental silicon that contains, the solvent of the composite particles reaction of graphite and surfactant.
12, method according to claim 6, wherein, the addition of described solvent is to contain the composite particles of elemental silicon, graphite and surfactant and 2-5 times of carbon predecessor total weight, the mode of described charing is that the composite particles that contains elemental silicon, graphite and surfactant of coated with carbon predecessor was heated 2-10 hour down at 200-400 ℃, heats 2-8 hour down at 800-1200 ℃ then.
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Assignee: Shenzhen BYD Lithium Battery Co., Ltd. Assignor: Biyadi Co., Ltd. Contract record no.: 2011440020249 Denomination of invention: Silicon-containing composite material and its preparation method and application Granted publication date: 20091230 License type: Exclusive License Open date: 20080625 Record date: 20110623 |