CN101210112A - Silicon-containing composite material and its preparation method and application - Google Patents
Silicon-containing composite material and its preparation method and application Download PDFInfo
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Abstract
The invention provides a siliceous composite material, comprising silicon particles, graphite particles and conducting polymer, wherein, the conducting polymer is wrapped on the surface of the graphite particles; at least part of the silicon particles is adhered to the surface of the conducting polymer. The siliceous composite material provided by the invention takes the conducting polymer as a clad material; the polymer does not need to be transformed further into 'hard carbon' and the siliceous composite material is guaranteed to have excellent conductivity; meanwhile, the aggregation between silicon particles can be avoided. When the composite material is taken as negative active material of a lithium iron battery, the lithium iron battery is guaranteed to have high reversible capacity and good cycle performance. Therefore, the invention can be used as the negative active material of the lithium iron battery. As the polymer does not need to be transformed further into the 'hard carbon' and the siliceous composite material has good conductivity in the preparation of the siliceous composite material provided by the invention, the manufacturing technique is simplified and the problem of huge energy consumption caused by the high temperature carbonization process in the prior art is solved.
Description
Technical field
The invention relates to a kind of silicon composite and its production and use 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 carbon class 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 electromobile demand to large vol, superpower 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 storage 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 volume effect in silicon in the process of removal lithium embedded, and the cyclical stability of the battery that causes using silicon to do negative active core-shell material is poor, thereby has hindered the industrial applications of silicon.
For this reason, present many investigators are devoted to the modification and the optimization design of high lithium storage materials, and have obtained certain progress.The volume 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 scale operation, and when the thickness of silicon film surpasses 1 micron, the diffusion length of lithium ion increases, and resistance increases.The 2nd, prepare siliceous matrix material, modal is silicon/carbon composite.Though the affiliation that adds of carbon causes the specific storage of matrix material to descend to some extent, the specific storage after reducing still is much higher than the specific storage of carbon itself, therefore still can be used as the desirable surrogate of carbon class negative active core-shell material.Present silicon/carbon composite mainly is " cake type " structure, is about to silicon grain and at first is dispersed in (mainly being pitch, resin etc.) in the organic precursor, organism is carried out high temperature carbonization again and handles, and obtains silicon/carbon composite.This silicon/carbon composite need be handled (generally at 900-1200 ℃) by high temperature carbonization and just can obtain; carbonization process also needs inert atmosphere protection; higher temperature and protection of inert gas bring great inconvenience to industrial production, and have increased production cost greatly.In addition, need to destroy the clad structure of product after the said products is handled through high temperature carbonization, thereby influence the chemical property of matrix material through break process.
Summary of the invention
The objective of the invention is to overcome the preparation method who contains silicon composite of the prior art and need under inert atmosphere protection, carry out the shortcoming that high temperature carbonization is handled, provide a kind of and need not inert atmosphere protection and need not to carry out that high temperature carbonization handles contains silicon composite and its production and use.
The silicon composite that contains provided by the invention contains silicon particle, graphite particle and conductive polymers, and described conductive polymers is coated on the surface of graphite particle, described silicon particle to small part attached on the conductive polymers surface.
The preparation method who contains silicon composite provided by the invention is included in the silicon particle and graphite particle exists down, under polymeric reaction condition, make conductive polymers presoma polymerization reaction take place, obtain containing the silicon composite that contains of silicon particle, graphite particle and conductive polymers, described conductive polymers is coated on the surface of graphite particle, described silicon particle to small part attached on the conductive polymers surface.
Provided by the inventionly contain the application of silicon composite in negative electrode of lithium ionic secondary battery.
According to the silicon composite that contains provided by the invention, because what be coated on the graphite particle surface is conductive polymers, thereby need not polymkeric substance further is transformed into " hard carbon " and can make this contain silicon composite to have excellent electroconductibility, can also act synergistically with graphite simultaneously, avoid the reunion between the silicon particle, can make lithium ion battery have high reversible capacity and excellent cycle performance during as the lithium ion battery negative active material, thereby can be used as the lithium ion battery negative active material.The preparation method who contains silicon composite provided by the invention carries out polymerization by selecting the material that can form conductive polymers for use at silicon particle and graphite particle surface, obtain electric conductive polymer, thereby need not that polymkeric substance further is transformed into " hard carbon " can make this contain the electroconductibility that silicon composite has excellence, simplified production technique thus, also solved by high temperature carbonization of the prior art and handled the huge energy consumption problem that brings.
Specifically, the preparation method who contains silicon composite provided by the present invention has the following advantages:
(1) adopt the in-situ polymerization method for coating, simple for process;
(2) reaction is carried out at normal temperatures, does not need heating and high temperature carbonization to handle, and energy consumption is low;
(3) reaction is without any need for shielding gas;
(4) reaction can be carried out in the water system environment, do not use any organic solvent, so environmental pollution is little;
(5) siliceous composite products even structure, do not lump, do not need break process, thereby can obtain having the composite material granular of complete nucleocapsid structure;
(6) replace carbon as coating material with polymkeric substance, the chemical property of matrix material is good.
Description of drawings
The scanning electron photomicrograph that contain silicon composite (SEM) of Fig. 1 for making by the embodiment of the invention 1;
Fig. 2 is the scanning electron photomicrograph (SEM) of the matrix material that is formed by graphite and conductive polymers that made by Comparative Examples 1;
The scanning electron photomicrograph that contains silicon composite (SEM) that Fig. 3 makes for Comparative Examples 2.
Embodiment
According to the silicon composite that contains provided by the invention, wherein, described conductive polymers can be in the prior art various specific conductivity greater than the conductive polymers of 0.1S/cm such as 1-100S/cm.This conductive polymers generally contains organic polymer and inorganic doping agent composition, and described inorganic doping agent is for can make organic polymer have the material of electroconductibility.Described organic polymer is the various macromolecular compounds that can form electrical conductor with inorganic doping agent effect, for example is in polyaniline, polypyrrole, Polythiophene, poly-Ursol D, poly-fourth thiophene, the polyparaphenylene one or more.Because polyaniline has synthetic easy, premium propertiess such as high thermal resistance good, good in oxidation resistance and high conductance, so the preferred described conductive polymers of the present invention is a polyaniline.Described inorganic doping agent can be hydrochloric acid, Hydrogen bromide, hydroiodic acid HI, sulfuric acid, perchloric acid, iron trichloride, iodine, fluoridize in arsenic, lithium chloride, lithiumbromide, the lithium iodide one or more.With the total amount that contains silicon composite is benchmark, and the content of conductive polymers can be 2-30 weight %, is preferably 5-20 weight %.Further under the preferable case, the content of described conductive polymers is 1-3 times of described silicon particle content.
Well known to a person skilled in the art and be, above-mentioned organic polymer and inorganic doping agent interaction energy access specific conductivity greater than the 0.1S/cm conductive polymers of 1-100S/cm for example, the size of specific conductivity depends primarily on the kind and the doping content of inorganic doping agent, it is less influenced by the polymerization degree of organic polymer, thereby need not among the present invention the polymerization degree of conductive polymers is limited especially.The weight ratio of organic polymer and inorganic doping agent makes the specific conductivity of conductive polymers greater than 0.1S/cm in the described conductive polymers.Those skilled in the art are easy to draw the content of inorganic doping agent in the conductive polymers according to description of the invention.
Among the present invention, described silicon particle can be the technical grade nano-silicon, also can be HIGH-PURITY SILICON.Say from cost, be preferably the technical grade nano-silicon.Use nano level silicon particle can slow down the variation of silicon components volume in the charge and discharge process, prevent the efflorescence of negative pole, improve the cycle performance of secondary cell, so the preferred described silicon particle of the present invention is the nano-silicon particle.The diameter of described nano-silicon particle is preferably 20-500 nanometer, more preferably 20-200 nanometer.The shape of described silicon particle can be one or more in spherical, bar-shaped, wire, the tubulose, is preferably spherical.
But the lithium storage content that contains silicon composite provided by the invention is a specific storage can be regulated by regulating this content that contains silicon particle in the silicon composite.The content of silicon particle is low excessively, and the specific storage that contains silicon composite is close with the specific storage of simple graphite, can not satisfy the battery needs.The content of silicon particle is high more, under the identical situation of other conditionally complete, this specific storage that contains silicon composite is also high more, but simultaneously by the silicon particle bring also severe more because of discharging and recharging the volumetric expansion that causes, thereby cause using the cycle performance of this battery that contains silicon composite also poor more.Comprehensive above-mentioned two aspects consider that the present invention is described containing in the silicon composite preferably, is benchmark with the total amount that contains silicon composite, and the content of silicon particle is 3-20 weight %, is preferably 5-15 weight %.
Described graphite can be the graphite of lithium ion battery field routine, for example can be natural graphite and/or synthetic graphite, and its shape can sphere, in the elliposoidal, flakey one or more, preferred sphere and/or elliposoidal.Under the preferable case, described graphite is average particle diameter D
50Be the 1-100 micron, be preferably the 5-50 micron, more preferably the 10-30 micron.With the total amount that contains silicon composite is benchmark, and the content of graphite particle is 50-95 weight %, is preferably 70-90 weight %.
According to the preparation method who contains silicon composite provided by the invention, in order to make more homogeneous and conductive polymers is coated on the graphite particle surface more equably of polyreaction, described polyreaction, mix and preferably in the solution of conductive polymers presoma, carry out.The solution of described conductive polymers presoma contains organic polymer precursor body, inorganic doping agent and solvent, and the concentration of organic polymer precursor body can be 0.1-10 weight % in the solution, is preferably 1-5 weight %.Described organic polymer precursor body is the monomeric substance that can form conductive polymers after the polymerization with inorganic doping agent effect.Described organic polymer precursor style is as being in aniline, pyrroles, thiophene, Ursol D, 3-butyl thiophene, the benzene one or more.Because the aniline raw material is cheap and easy to get, synthesis condition is simple, product yield is high, the preferred described material that can form conductive polymers of the present invention is an aniline.The weight ratio of described organic polymer precursor body and silicon particle can be 0.1-10: 1, be preferably 1-3: 1.Can control the specific conductivity of the conductive polymers that obtains by the add-on of controlled doping agent.According to the present invention, the weight ratio of organic polymer and inorganic doping agent makes the specific conductivity of conductive polymers greater than 0.1S/cm in the described conductive polymers.Those skilled in the art are easy to draw the add-on of inorganic doping agent in the conductive polymers according to description of the invention, for example can be 1-20 times of organic polymer precursor body weight.Described doping agent can be that the solution form of 0.1-5 mol adds with concentration.For different conductive polymerss, the concentration of described doping agent may be different, and for example when preparing polyaniline with hydrochloric acid as doping agent, the concentration of hydrochloric acid can be the 0.1-5 mol, is preferably the 0.5-2 mol.
For silicon fully being disperseed and being contained silicon composite uniformly, under the preferable case, also contain tensio-active agent in the described polybenzazole precursor liquid solution, described tensio-active agent is one or more in polyvinylpyrrolidone, polyvinyl alcohol, polyvinyl alcohol, polyacrylamide, the poly-methyl acrylate.Based on every gram silicon particle, the consumption of tensio-active agent can restrain for 0.1-5, is preferably the 0.2-2.5 gram, more preferably the 0.5-1.5 gram.
Described polyreaction, adulterated condition have been conventionally known to one of skill in the art, for example, carry out in the presence of initiator.Described initiator can be the various initiators that can cause above-mentioned organic polymer monomer polymerization reaction take place, is preferably to cause above-mentioned organic polymer precursor body polymeric initiator down and/or to cause above-mentioned organic polymer precursor height in the short time fast in as 30 minutes lower temperature such as 5-50 ℃ to imitate the polymeric initiator.For different organic polymer precursor bodies, initiator that can use or preferred initiator may be different, for example, and for aniline, initiator can be one or more in ammonium persulphate, iron trichloride, heavy cadmium acid potassium, hydrogen peroxide, Potassium Iodate, the potassium permanganate, initiator system of ammonium persulfate.For the material of determining that can form conductive polymers, those skilled in the art are easy to instruction according to the present invention and select suitable initiator.Initiator amount can be the consumption of initiator in the conventional polyreaction, and for example for 1 mole of aniline, the consumption of ammonium persulphate can be the 0.5-1.5 mole, is preferably the 0.8-1.2 mole.Described initiator preferably contacts with the material that can form conductive polymers in the mode that drips, and the dropping time of initiator can be 1 minute to 5 hours, is preferably 30 minutes to 1.5 hours.
Other condition of polyreaction comprises that temperature can be 5-100 ℃, be preferably 5-50 ℃, reaction times is preferably and adds the back that finishes at initiator and continued 1 minute to 10 hours, so that the abundant polymerization of organic polymer precursor body, obtains being coated on the conductive polymer coating on graphite particle surface.
According to one embodiment of the present invention, the preparation method who contains silicon composite provided by the invention can finish by following step:
(1) tensio-active agent, silicon particle, graphite, organic polymer precursor body and inorganic doping agent dispersed with stirring in solvent is even, the time of dispersed with stirring can be 1 minute to 5 hours, is preferably 30 minutes to 1.5 hours;
(2) initiator or its solution are slowly joined above-mentioned steps (1) dispersions obtained in, and constantly mix liquid, cause organic polymer precursor body polymerization reaction take place; The time that drips can be 1 minute to 5 hours;
(3) above-mentioned steps (2) gained reaction system is continued to stir 1 minute to 10 hours, make the abundant polymerization of organic polymer precursor body;
(4) above-mentioned steps (3) products therefrom filtered, wash after drying, promptly get the silicon composite that contains of the present invention.Described drying can be carried out under 0-300 ℃ of temperature, can be forced air drying or vacuum-drying.
Can silicon particle and graphite particle fully be disperseed by modes such as ultra-sonic dispersion, stirrings.
Contain silicon composite by what above-mentioned preparation method made, do not need break process, can have complete nucleocapsid structure.
" containing silicon composite " of the present invention is meant in in-situ polymerization process of the present invention, the silicon particle is attached on the graphite particle surface after being coated by conductive polymers, perhaps coated by conductive polymers once more, form the superpacket coating of silicon and conductive polymers then on the graphite granule surface.The silicon composite that contains of the present invention is used for lithium ion battery negative, and in the embedding of lithium ion with when taking off embedding, conductive polymers can be protected the nano-silicon particle, avoids the reunion of nanoparticle.The matrix material of this kind structure has high reversible capacity and excellent cycle performance.
The following examples will the present invention is further illustrated.
Embodiment 1
This embodiment is used to illustrate the silicon composite and preparation method thereof that contains provided by the invention.
0.5 gram nano-silicon (particle dia is the 20-50 nanometer) and 0.5 gram polyvinylpyrrolidone are added in the hydrochloric acid soln that 100 ml concns are 1 mol, and magnetic agitation is uniformly dispersed nano-silicon.Add 9.5 gram synthetic graphite (average particle diameter D again
50=20.75 microns, microcrystalline coating spacing d
002Be 0.33688 nanometer), stir.Add 0.7 gram aniline then, the continuation magnetic agitation will contain 1.84 gram ammonium persulphates after 30 minutes 1 mol hydrochloric acid solns are added drop-wise in the mixed solution for 50 milliliters, cause the aniline monomer polymerization, are added dropwise to complete in 1 hour.After dropwising, continue to stir after 3 hours mixed solution is filtered, dry under the washing, 80 ℃ of temperature, obtain black-and-blue micro mist, promptly electrically conductive polyaniline coats contains silicon composite S1.Record average particle diameter D with the X100 particle-size analyzer
50It is 22.83 microns.Calculating the content that contains silicon in the silicon composite is 4.69 weight %, and the content of graphite is 89.19 weight %, and the content of conductive polymers is 6.12 weight %.This is contained silicon composite be pressed into sheet, recording the product specific conductivity with four probe method is 2.73S/cm.
Comparative Examples 1
This Comparative Examples is used to illustrate not siliceous graphite composite material and preparation method thereof.
Prepare graphite composite material according to embodiment 1 described method, different is not add the silicon particle, thereby make graphite composite material CS1.
Comparative Examples 2
This Comparative Examples is used to illustrate the existing silicon composite and preparation method thereof that contains.
2.0 gram Resins, epoxy are dissolved in the tetrahydrofuran solvent, and the back that stirs slowly adds 9.5 gram synthetic graphite particle (average particle diameter D
50=20.75 microns, microcrystalline coating spacing d
002Be 0.33688 nanometer), add 0.5 gram silicon particle (particle dia D after stirring again
50Be the 20-50 nanometer), and stir.Behind the heating evaporation solvent; mixture is moved into the crucible that places in the resistance furnace; feed rare gas element Ar protection; slowly be warming up to 480 ℃, be incubated after 2 hours, continue to be warming up to about 1000 ℃; temperature rise rate is less than 10 ℃/minute; after insulation was fired 4 hours, sample cooled to room temperature with the furnace, and inert atmosphere protection is arranged in the whole process always.Post reaction mixture obtains reference and contains silicon composite CS2 through grinding break process, crossing 200 mesh sieves.Record average particle diameter D with the X100 particle-size analyzer
50It is 23.94 microns.Calculating the content that contains silicon in the silicon composite is 4.53 weight %, and the content of graphite is 86.07 weight %, and the content of agraphitic carbon coating layer is 9.40 weight %.This is contained silicon composite be pressed into sheet, recording the product specific conductivity with four probe method is 2.98S/cm.
Embodiment 2
This embodiment is used to illustrate the silicon composite and preparation method thereof that contains provided by the invention.
0.8 gram nano-silicon (particle dia is the 20-50 nanometer) and 0.8 gram polyvinylpyrrolidone are added in the lithium chloride solution that 100 ml concns are 1 mol, and magnetic agitation is uniformly dispersed nano-silicon.Add 9.2 gram synthetic graphite (average particle diameter D again
50=20.75 microns, microcrystalline coating spacing d
002Be 0.33688 nanometer), stir.Add 1.4 gram aniline then, the continuation magnetic agitation will contain 3.68 gram ammonium persulphates after 30 minutes 1 mol lithium chloride solutions are added drop-wise in the mixed solution for 50 milliliters, cause the aniline monomer polymerization, are added dropwise to complete in 1 hour.After dropwising, continue to stir after 3 hours mixed solution is filtered, dry under the washing, 80 ℃ of temperature, obtain black-and-blue micro mist, promptly electrically conductive polyaniline coats contains silicon composite S2.Record average particle diameter D with the X100 particle-size analyzer
50It is 26.06 microns.Calculating the content that contains silicon in the silicon composite is 7.08 weight %, and the content of graphite is 81.40 weight %, and the content of conductive polymers is 11.52 weight %.This is contained silicon composite be pressed into sheet, recording the product specific conductivity with four probe method is 2.15S/cm.
Embodiment 3
This embodiment is used to illustrate the silicon composite and preparation method thereof that contains provided by the invention.
With 1.0 gram silicon particle (average particle diameter D
50Be 0.21 micron) and 1.5 the gram polyvinylpyrrolidones add in the hydrochloric acid soln that 100 ml concns are 1 mol, magnetic agitation is uniformly dispersed nano-silicon.Add 9.0 gram synthetic graphite (average particle diameter D again
50=20.75 microns, microcrystalline coating spacing d
002Be 0.33688 nanometer), stir.Add 2.0 gram aniline then, the continuation magnetic agitation will contain 7.5 gram iron(ic) chloride after 30 minutes 1 mol lithium chloride solutions are added drop-wise in the mixed solution for 50 milliliters, cause the aniline monomer polymerization, are added dropwise to complete in 1 hour.After dropwising, continue to stir after 3 hours mixed solution is filtered, dry under the washing, 80 ℃ of temperature, obtain black-and-blue micro mist, promptly electrically conductive polyaniline coats contains silicon composite S3.Record average particle diameter D with the X100 particle-size analyzer
50It is 27.32 microns.Calculating the content that contains silicon in the silicon composite is 9.09 weight %, and the content of graphite is 81.81 weight %, and the content of conductive polymers is 9.1 weight %.This is contained silicon composite be pressed into sheet, recording the product specific conductivity with four probe method is 1.85S/cm.
Embodiment 4
This embodiment is used to illustrate the silicon composite and preparation method thereof that contains provided by the invention.
With 1.0 gram nano-silicon (average particle diameter D
50Be 0.45 micron) and 1.5 the gram polyvinyl alcohol add in the hydrochloric acid soln that 100 ml concns are 1 mol, magnetic agitation is uniformly dispersed nano-silicon.Add 9.0 gram synthetic graphite (average particle diameter D again
50=20.75 microns, microcrystalline coating spacing d
002Be 0.33688 nanometer), stir.Add 1.4 gram benzene and 5.0 gram AlCl then
36H
2O continued magnetic agitation 30 minutes.Contain 4.0 gram CuCl with 50 milliliters then
22H
2The 1 mol hydrochloric acid of O is added drop-wise in the mixed solution, causes the benzene monomer polymerization, is added dropwise to complete in 1 hour.After dropwising, continue to stir after 3 hours mixed solution is filtered, dry under the washing, 80 ℃ of temperature, obtain the black micro mist, promptly polyparaphenylene coats contains silicon composite S4.Record average particle diameter D with the X100 particle-size analyzer
50It is 27.76 microns.Calculating the content that contains silicon in the silicon composite is 8.93 weight %, and the content of graphite is 80.37 weight %, and the content of conductive polymers is 10.7 weight %.This is contained silicon composite be pressed into sheet, recording the product specific conductivity with four probe method is 0.63S/cm.
Embodiment 5
This embodiment is used to the pattern that contains silicon composite that illustrates that the present invention obtains.
With the pattern that contains silicon composite S1 that KYKY2800 type sem observation is made by embodiment 1, the result as shown in Figure 1.As can be seen from Figure 1, this contains the uniform particles of silicon composite, the coating layer structural integrity.
Comparative Examples 3-4
Following Comparative Examples is used to illustrate the pattern of the matrix material that is obtained by Comparative Examples 1-2.
Observe the pattern that contains silicon composite CS1 and CS2 that is made by Comparative Examples 1 and Comparative Examples 2 respectively with KYKY2800 type scanning electronic microscope, the result is respectively as Fig. 2, shown in Figure 3.As can be seen from Figure 2, the smooth surface of the graphite composite material of siliceous particle is not smooth, and is similar with the smooth surface of graphite itself, is difficult to observe conductive polymers.As can be seen from Figure 3, it is inhomogeneous that reference contains the particle of silicon composite CS1, has a large amount of fragments.
By Fig. 1 and Fig. 2 are contrasted as can be seen, only the surface of the graphite particle that is coated by conductive polymers is more similar to the surface of graphite particle itself, surfacing is smooth, be difficult to observe conductive polymers, and the silicon composite that contains of the present invention is because of also containing the silicon particle, the surface is very rough, a lot of small-particles are arranged attached on the cover surface, and the particulate size is much smaller than the size of graphite particle, should be especially nano-silicon particle of silicon particle, this shows, of the present invention containing in the silicon composite, the silicon particle forms coating layer attached to wrapping up on the conductive polymers or by conductive polymers, and then be wrapped in the graphite particle surface, form typical " nuclear-shell " structure.
Embodiment 6-9
Following embodiment is used to illustrate siliceous performance of composites provided by the invention.
1, the electrochemical specific capacity that contains silicon composite.The electrochemical specific capacity that contains silicon composite respectively according to following step test:
With diameter is that 16 millimeters, weight are that the metal lithium sheet of 0.34 gram is a negative electrode active material, is barrier film with the modified polypropene barrier film, with the LiPF of 1 mol
6(solvent is 1: 1 EC of volume ratio: the DMC mixed solvent) be electrolytic solution, the silicon composite S1-S4 that contains that is made by the foregoing description 1-4 with 0.05 gram is a positive active material to solution respectively, makes 2016 type button cells.
Respectively 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 standard capacity (MAH)=charging current (milliampere) * duration of charging of button cell (hour) calculate the standard capacity of button cell, standard capacity promptly gets the button cell positive active material electrochemical specific capacity of (containing silicon composite) divided by the weight of the positive active material (containing silicon composite) of button cell, and the result is as shown in table 1.
2, the cycle life that contains silicon composite.The cycle life that contains silicon composite respectively according to following step test:
With 6.39 gram LiCoO
2Being positive active material, is barrier film with the modified polypropene barrier film, with the LiPF of 1 mol
6(solvent is 1: 1 EC of volume ratio to solution: the DMC mixed solvent) be electrolytic solution, the silicon composite S1-S4 that contains that is made by the foregoing description 1-4 with 1.0 grams is a negative electrode active material respectively, makes 043450A type (the design cell container is 800 MAHs) secondary lithium battery.
The cycle life that contains silicon composite respectively according to 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 above-mentioned steps 20 times, record the surplus capacity after the circulation 20 times, calculate the capability retention after the circulation 20 times according to the capability retention after time circulation of surplus capacity/electrochemical specific capacity=20 after 20 circulations, the result is as shown in table 1.
Comparative Examples 5
Following Comparative Examples is used to illustrate existing siliceous performance of composites.
Measure the performance that contains silicon composite CS2 for preparing by Comparative Examples 2 according to the method for embodiment 6-9.The result is as shown in table 1.
Table 1
| The embodiment numbering | Contain the silicon composite numbering | Initial charge specific storage (MAH/gram) | First charge-discharge efficiency (%) | Capability retention (%) after 20 circulations |
| Embodiment 6 | S1 | 420 | 82 | 78 |
| Embodiment 7 | S2 | 487 | 79 | 76 |
| Embodiment 8 | S3 | 533 | 76 | 69 |
| Embodiment 9 | S4 | 501 | 67 | 52 |
| Comparative Examples 5 | CS2 | 395 | 78 | 81 |
From the result of last table 1 as can be seen, the silicon composite that contains provided by the invention also has good charge ratio capacity and cycle performance when having than height ratio capacity, specific storage adopts the silicon composite that contains of high temperature carbonization methods preparation apparently higher than Comparative Examples 2, and charge ratio capacity and cycle performance and employing high temperature carbonization method prepare to contain silicon composite suitable.
Claims (12)
1. one kind contains silicon composite, and this material contains the silicon particle, it is characterized in that, this material also contains graphite particle and conductive polymers, and described conductive polymers is coated on the surface of graphite particle, described silicon particle to small part attached on the conductive polymers surface.
2. the silicon composite that contains according to claim 1 wherein, is a benchmark with the total amount that contains silicon composite, and the content of silicon particle is 3-20 weight %, and the content of graphite particle is 50-95 weight %, and the content of conductive polymers is 2-30 weight %.
3. the silicon composite that contains according to claim 1, wherein, the specific conductivity of described conductive polymers is greater than 0.1S/cm.
4. the silicon composite that contains according to claim 3, wherein, the specific conductivity of described conductive polymers is 1-100S/cm.
5. the silicon composite that contains according to claim 1, wherein, described conductive polymers contains organic polymer and inorganic doping agent, described organic polymer is the macromolecular compound that can form electrical conductor with inorganic doping agent effect, and described inorganic doping agent is to make organic polymer have the material of electroconductibility.
6. the silicon composite that contains according to claim 5, wherein, described polymkeric substance is one or more in polyaniline, poly-Ursol D, polypyrrole, Polythiophene, poly-fourth thiophene, the polyparaphenylene, and described inorganic doping agent is hydrochloric acid, Hydrogen bromide, hydroiodic acid HI, sulfuric acid, perchloric acid, iron trichloride, iodine, fluoridize in arsenic, lithium chloride, lithiumbromide, the lithium iodide one or more.
7. the silicon composite that contains according to claim 1, wherein, the diameter of silicon particle is the 20-500 nanometer, the average particle diameter D of graphite particle
50Be the 1-100 micron.
8. preparation method who contains silicon composite, this method is included in the silicon particle and graphite particle exists down, under polymeric reaction condition, make conductive polymers presoma polymerization reaction take place, obtain containing the silicon composite that closes of silicon particle, graphite particle and conductive polymers, described conductive polymers is coated on the surface of graphite particle, described silicon particle to small part attached on the conductive polymers surface.
9. method according to claim 8, wherein, described polyreaction is carried out in the conductive polymers precursor solution, described conductive polymers precursor solution contains inorganic doping agent and organic polymer precursor body, the concentration of polymer precursor is 0.1-10 weight % in the described conductive polymers precursor solution, and described organic polymer precursor body can form the monomeric substance of conductive polymers during for polymerization with inorganic doping agent effect.
10. method according to claim 9, wherein, described organic polymer precursor body is one or more in aniline, pyrroles, thiophene, Ursol D, 3-butyl thiophene, the benzene, and described inorganic doping agent is hydrochloric acid, Hydrogen bromide, hydroiodic acid HI, sulfuric acid, perchloric acid, iron trichloride, iodine, fluoridize in arsenic, lithium chloride, lithiumbromide, the lithium iodide one or more.
11. method according to claim 9, wherein, also contain tensio-active agent in the described polybenzazole precursor liquid solution, described tensio-active agent is one or more in polyvinylpyrrolidone, polyvinyl alcohol, polyvinyl alcohol, polyacrylamide, the poly-methyl acrylate, based on every gram silicon particle, the consumption of tensio-active agent is the 0.1-5 gram.
12. any one describedly contains the application of silicon composite in negative electrode of lithium ionic secondary battery among the claim 1-7.
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