CN106025243A - Silicon negative electrode composite material for lithium-ion battery and preparation method thereof - Google Patents
Silicon negative electrode composite material for lithium-ion battery and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a silicon negative electrode composite material for a lithium-ion battery. The silicon negative electrode composite material is of a double-shell-layer structure; a core layer is a composite nano silicon material with a cavity structure and an inner shell layer is a carbon material cladding layer; and an outer shell layer is a conductive polymer thin film. The invention further discloses a preparation method of the silicon negative electrode composite material for the lithium-ion battery. The preparation method comprises the following steps: firstly, mixing nano silicon and nano F23O4 micro-spheres and carrying out carbon cladding; cladding one layer of the conductive polymer thin film on the outer surface to form the double-shell-layer structure; taking the nano F23O4 micro-spheres as a sacrificial template and sacrificing the F23O4 micro-spheres through an acid etching agent to enable the core layer to form a composite nano silicon material with a cavity structure, so as to effectively buffer volume expansion of the nano silicon material. The silicon negative electrode composite material has the advantages of high specific capacity, good circulating performance and rate performance, high tap density and the like.
Description
Technical field
The present invention relates to ion cathode material lithium technical field, be specifically related to a kind of lithium ion battery silicon anode material and preparation method thereof.
Background technology
Lithium ion primary cell, owing to having the features such as volume is little, energy density is big, is widely used as main flow power supply at electronic products such as mobile communication equipment, digital camera, notebook computers and is used.But along with electronic apparatus miniaturization, energetic, the growth requirement of portability and the development of electric automobile and exploitation, the performance of lithium ion battery there is is higher requirement.And the improvement of performance of lithium ion battery depends primarily on embedding lithium electrode material energy densities and the raising of cycle life, the theoretical lithium storage content of the graphite-like carbon negative pole material that lithium ion battery is widely used is relatively low at present, obviously the most not adapting to the demand of development, exploitation novel high-performance negative material has become the task of top priority.Research finds that silica-base material is had high specific capacity, and theoretical capacity can reach 4200mAh/g, therefore be received more and more attention as lithium ion battery negative material by silica-base material.
But, silica-base material can produce huge change in volume before and after removal lithium embedded, causes broken, the efflorescence of silicon materials to cause the forfeiture of removal lithium embedded ability, silicium cathode material is made to depart from conductive network, internal resistance increases, and causes reversible capacity to be decayed rapidly, and lithium battery cycle performance significantly declines.For the problems referred to above, researchers try to explore the method improving silicium cathode material circulation performance, as reduced silicon materials grain diameter, poromerics, silicon nanowires, thin-film material, composite etc..The most relatively effective method is to prepare silicon composite pin to the volumetric expansion alleviating in battery charge and discharge process, in oneself study on the modification through being widely used in lithium ion battery negative material of the method.
China Patent Publication No. CN180094A discloses the preparation method of a kind of silicon/carbon nuclear-shell structured nano-composite material, by carbon is coated on silicon grain, suppress the efflorescence of silicon grain, and avoid the reunion of silicon grain possible in charge and discharge process, thus extend its cycle life.
China Patent Publication No. CN 105024076A discloses a kind of lithium ion battery negative material and its preparation method and application, including carbon core layer and silicon clad, silicon clad carbon coated core layer forms silicon/carbon composite, silicon/carbon composite external sheath layer of metal oxide cladding layers, solves the problem that siliceous negative material easily expands the battery capacity rapid decay caused.
China Patent Publication No. CN104916826A discloses a kind of graphene coated silicium cathode material and preparation method thereof, electrostatic self-assembled legal system is used to obtain graphene coated silicium cathode material, the expansion of silicon electrode can be buffered, Graphene has more excellent electric conductivity to strengthen electronics transmission efficiency in graphene coated silicon, is conducive to improving storage lithium specific capacity and the cycle performance of graphene coated silicon.
At present, research shows that silicon composite all can be effectively reduced in charge and discharge process due to the silicon volumetric expansion impact on battery performance, mainly improving its chemical property by the change of appearance structure, doping and carbon cladding etc., the most common silicon based composite material includes silicon-metal alloy, silicon nonmetallic compound.But, due to silicon when discharge and recharge cubical expansivity up to 400%, by conventional technique means as with the mixing of carbon, the cladding of surface carbon, or by adding conducting metal, conducting polymer, not can effectively solve the problem that the problem causing cycle performance of battery to decline due to the expansion of silicon.Therefore, it is necessary to research and develop the high lithium battery silicium cathode composite with good cycling stability of a kind of specific capacity, the deficiencies in the prior art are solved.
Summary of the invention
The present invention is directed to the deficiencies in the prior art, propose a kind of lithium ion battery silicon anode material, the problem that the cycle performance of battery caused to solve siliceous negative material in prior art easily to expand declines.Another object of the present invention is to provide the preparation method of a kind of lithium ion battery silicon anode material, to realize the industrialized production with the lithium ion battery of the excellent properties such as height ratio capacity, long circulation life.
For solve the problems referred to above, the present invention by the following technical solutions:
A kind of lithium ion battery silicon anode material, it is characterised in that described silicium cathode composite has bivalve Rotating fields, and stratum nucleare is the composite Nano silicon materials with cavity structure, and hypostracum is material with carbon element clad, and outer shell is conducting polymer thin film layer；Wherein said material with carbon element is porous filamentous nanocarbon and Graphene is 1 ~ 3:1 composition in mass ratio.
The thickness of the hypostracum of double-shell structure described above is between 20～50nm, and the thickness of outer shell is between 20nm～100nm.
The composite Nano silicon materials of cavity structure described above are with nanometer Fe3O4Microsphere is to sacrifice template to prepare, it is preferable that described nanometer Fe3O4Microsphere be particle diameter be 200～500nm, the thickness of shell is the Fe of 20～50nm3O4Tiny balloon.
Preferably, described conducting polymer thin film is any one in film of poly pyrrole, polythiophene film.
Preferably, described porous filamentous nanocarbon is diameter 100 ~ 300nm, aperture is contained about in inside
The multi-cellular structure of 1 ~ 20nm；Described Graphene is the graphene oxide that the number of plies is less than 10 layers.
The preparation method of a kind of lithium ion battery silicon anode material, comprises the following steps:
(1) by nanometer Fe3O4Microsphere is dispersed in the aqueous solution containing polyvinyl alcohol, ultrasonic makes Fe3O4Microsphere is uniformly dispersed, and adds the silicon nanoparticle modified through coupling agent surface, continues ultrasonic disperse, obtains mixing suspension；
(2) material with carbon element is dispersed in surfactant solution, forms finely dispersed suspension, add the mixing suspension that step (1) obtains, ultrasonic disperse, be centrifuged, filter, wash, obtain mixture；Mixture is enclosed lower high-temperature process 2 ~ 4 hours at nitrogen protective atmosphere, and reaction temperature is 400 ~ 700 DEG C, obtains composite Nano silicon materials；
(3) the composite Nano silicon materials obtained dissolving is dispersed in ethanol water, add etching agent and be uniformly mixing to obtain mixed liquor, under agitation polymer monomer is joined in above-mentioned mixed liquor, reaction 40 ~ 90min is stirred under room temperature, adding azo initiator, azo initiator concentration in mixed solution is 1～5mM/L；Then it is stirred reacting 2 ~ 5 hours at temperature is 50 DEG C～70 DEG C, obtains the composite Nano silicon emulsion containing conducting polymer shell structurre；
(4) emulsion obtained in step (3) is centrifugally separating to obtain precipitation, washing of precipitate is removed impurity, vacuum drying, obtain lithium ion battery silicon anode material.
Preferably, Fe in the mixing suspension described in above-mentioned steps (1)3O4Concentration be 10～20 mM/L, the mass concentration of poly-vinyl alcohol solution is 2%～8%, Fe3O4Microsphere is 1:10 ~ 20 with the mass ratio of silicon nanoparticle, and the described ultrasonic disperse time is 30 ~ 60min.
Preferably, surfactant described in above-mentioned steps (2) is any one in hexadecyltrimethylammonium chloride, sodium lauryl sulphate, the basic sodium sulfonate of dodecane, the concentration of surfactant solution is 8 ~ 15 mM/L, and the described ultrasonic disperse time is 20 ~ 40min.
Preferably, the etching agent described in above-mentioned steps (3) is semi-annular jade pendant base salicylic acid, and the concentration of etching agent is 1～5 mM/L.
One lithium ion battery silicon anode material of the present invention and preparation method thereof, compared with prior art, its prominent feature and excellent effect are:
1, the silicium cathode composite structure prepared by the present invention is novel, has bivalve Rotating fields, and forms cavity on the basis of traditional core shell structure, solves nano-silicon as volumetric expansion problem during lithium ion battery negative material.
2, the present invention utilizes porous carbon fiber and Graphene mixing material as carbon covering, netted cushion is formed on nano silicon material surface, the volumetric expansion of buffering nano silicon material, and loose structure can accelerate the diffusion velocity of lithium ion, be conducive to improving storage lithium specific capacity and the cycle performance of silicium cathode material.
3, the present invention utilizes nanometer Fe3O4Tiny balloon, as sacrificing template, utilizes etching agent to form cavity in nanometer silicon composite material stratum nucleare structure while carrying out conducting polymer cladding, and cavity can suppress the bulk effect of silicon nanoparticle, improves the cycle performance of lithium battery.
4, the inventive method is simple, and degree of being practical is high, and the silicon composite of preparation has that reversible capacity is big, cycle performance and large current discharging capability is good, tap density advantages of higher.
Detailed description of the invention
Below in conjunction with detailed description of the invention, the present invention is explained in detail, is not restricted to the present invention.In the case of without departing from said method thought of the present invention, the various replacements made according to ordinary skill knowledge and customary means or improvement, should be included within the scope of the present invention.
Embodiment
1
(1) being 200nm by particle diameter, the thickness of shell is the nanometer Fe of 20nm3O4Tiny balloon is dispersed in the aqueous solution containing polyvinyl alcohol, ultrasonic disperse 60min, makes Fe3O4Microsphere is uniformly dispersed, and adds the silicon nanoparticle modified through coupling agent surface, continues ultrasonic disperse 40min, obtains mixing suspension；Wherein Fe in mixing suspension3O4Concentration be 10 mM/L, the mass concentration of poly-vinyl alcohol solution is 2%, Fe3O4Microsphere is 1:10 with the mass ratio of silicon nanoparticle；
(2) porous filamentous nanocarbon diameter 300nm, inside being contained aperture about 100nm and graphene oxide mass ratio are that 3:1 forms material with carbon element, material with carbon element is dispersed in the hexadecyltrimethylammonium chloride surfactant solution that concentration is 15 mM/L, form finely dispersed suspension, add the mixing suspension that step (1) obtains, ultrasonic disperse, it is centrifuged, filters, washs, obtain mixture；Mixture is enclosed lower high-temperature process 4 hours at nitrogen protective atmosphere, and reaction temperature is 500 DEG C, obtains composite Nano silicon materials；
(3) the composite Nano silicon materials obtained dissolving is dispersed in ethanol water, add the semi-annular jade pendant base salicylic acid that concentration is 1 mM/L and be uniformly mixing to obtain mixed liquor, under agitation polymer monomer is joined in above-mentioned mixed liquor, stirring reaction 40min under room temperature, adding azo initiator, azo initiator concentration in mixed solution is 1mM/L；Then it is stirred reacting at temperature is 70 DEG C 5 hours, obtains the composite Nano silicon emulsion containing conducting polymer shell structurre；
(4) emulsion obtained in step (3) is centrifugally separating to obtain precipitation, washing of precipitate is removed impurity, vacuum drying, obtain lithium ion battery silicon anode material.
The lithium ion battery silicon anode material of above-mentioned gained has bivalve Rotating fields, and the thickness of hypostracum is at 20nm, and the thickness of outer shell is at 100nm.The chemical property of silicium cathode composite is shown in Table 1.
Embodiment
2
(1) being 300nm by particle diameter, the thickness of shell is the nanometer Fe of 30nm3O4Tiny balloon is dispersed in the aqueous solution containing polyvinyl alcohol, ultrasonic disperse 50min, makes Fe3O4Microsphere is uniformly dispersed, and adds the silicon nanoparticle modified through coupling agent surface, continues ultrasonic disperse 30min, obtains mixing suspension；Wherein Fe in mixing suspension3O4Concentration be 15 mM/L, the mass concentration of poly-vinyl alcohol solution is 4%, Fe3O4Microsphere is 1:15 with the mass ratio of silicon nanoparticle；
(2) porous filamentous nanocarbon diameter 200nm, inside being contained aperture about 5nm and graphene oxide mass ratio are that 2:1 forms material with carbon element, material with carbon element is dispersed in the lauryl sodium sulfate surfactant solution that concentration is 10mM/L, form finely dispersed suspension, add the mixing suspension that step (1) obtains, ultrasonic disperse, it is centrifuged, filters, washs, obtain mixture；Mixture is enclosed lower high-temperature process 3 hours at nitrogen protective atmosphere, and reaction temperature is 600 DEG C, obtains composite Nano silicon materials；
(3) the composite Nano silicon materials obtained dissolving is dispersed in ethanol water, add the semi-annular jade pendant base salicylic acid that concentration is 2mM/L and be uniformly mixing to obtain mixed liquor, under agitation polymer monomer is joined in above-mentioned mixed liquor, stirring reaction 60min under room temperature, adding azo initiator, azo initiator concentration in mixed solution is 2mM/L；Then it is stirred reacting at temperature is 50 DEG C 5 hours, obtains the composite Nano silicon emulsion containing conducting polymer shell structurre；
(4) emulsion obtained in step (3) is centrifugally separating to obtain precipitation, washing of precipitate is removed impurity, vacuum drying, obtain lithium ion battery silicon anode material.
The lithium ion battery silicon anode material of above-mentioned gained has bivalve Rotating fields, and the thickness of hypostracum is at 30nm, and the thickness of outer shell is at 80nm.The chemical property of silicium cathode composite is shown in Table 1.
Embodiment
3
(1) being 400nm by particle diameter, the thickness of shell is the nanometer Fe of 40nm3O4Tiny balloon is dispersed in the aqueous solution containing polyvinyl alcohol, ultrasonic disperse 30min, makes Fe3O4Microsphere is uniformly dispersed, and adds the silicon nanoparticle modified through coupling agent surface, continues ultrasonic disperse 60min, obtains mixing suspension；Wherein Fe in mixing suspension3O4Concentration be 20 mM/L, the mass concentration of poly-vinyl alcohol solution is 6%, Fe3O4Microsphere is 1:20 with the mass ratio of silicon nanoparticle；
(2) porous filamentous nanocarbon diameter 300nm, inside being contained aperture about 10nm and graphene oxide mass ratio are that 1:1 forms material with carbon element, material with carbon element is dispersed in the basic sulfonate surfactants solution of dodecane that concentration is 12 mM/L, form finely dispersed suspension, add the mixing suspension that step (1) obtains, ultrasonic disperse, it is centrifuged, filters, washs, obtain mixture；Mixture is enclosed lower high-temperature process 3 hours at nitrogen protective atmosphere, and reaction temperature is 500 DEG C, obtains composite Nano silicon materials；
(3) the composite Nano silicon materials obtained dissolving is dispersed in ethanol water, add the semi-annular jade pendant base salicylic acid that concentration is 4 mM/L and be uniformly mixing to obtain mixed liquor, under agitation polymer monomer is joined in above-mentioned mixed liquor, stirring reaction 80min under room temperature, adding azo initiator, azo initiator concentration in mixed solution is 4mM/L；Then it is stirred reacting at temperature is 60 DEG C 3 hours, obtains the composite Nano silicon emulsion containing conducting polymer shell structurre；
(4) emulsion obtained in step (3) is centrifugally separating to obtain precipitation, washing of precipitate is removed impurity, vacuum drying, obtain lithium ion battery silicon anode material.
The lithium ion battery silicon anode material of above-mentioned gained has bivalve Rotating fields, and the thickness of hypostracum is at 40nm, and the thickness of outer shell is at 90nm.The chemical property of silicium cathode composite is shown in Table 1.
Embodiment
4
(1) being 500nm by particle diameter, the thickness of shell is the nanometer Fe of 50nm3O4Tiny balloon is dispersed in the aqueous solution containing polyvinyl alcohol, ultrasonic disperse 50min, makes Fe3O4Microsphere is uniformly dispersed, and adds the silicon nanoparticle modified through coupling agent surface, continues ultrasonic disperse 30min, obtains mixing suspension；Wherein Fe in mixing suspension3O4Concentration be 20 mM/L, the mass concentration of poly-vinyl alcohol solution is 8%, Fe3O4Microsphere is 1:15 with the mass ratio of silicon nanoparticle；
(2) porous filamentous nanocarbon diameter 100nm, inside being contained aperture about 1nm and graphene oxide mass ratio are that 3:1 forms material with carbon element, material with carbon element is dispersed in the hexadecyltrimethylammonium chloride surfactant solution that concentration is 15 mM/L, form finely dispersed suspension, add the mixing suspension that step (1) obtains, ultrasonic disperse, it is centrifuged, filters, washs, obtain mixture；Mixture is enclosed lower high-temperature process 2 hours at nitrogen protective atmosphere, and reaction temperature is 700 DEG C, obtains composite Nano silicon materials；
(3) the composite Nano silicon materials obtained dissolving is dispersed in ethanol water, add the semi-annular jade pendant base salicylic acid that concentration is 5 mM/L and be uniformly mixing to obtain mixed liquor, under agitation polymer monomer is joined in above-mentioned mixed liquor, stirring reaction 40min under room temperature, adding azo initiator, azo initiator concentration in mixed solution is 5mM/L；Then it is stirred reacting at temperature is 65 DEG C 5 hours, obtains the composite Nano silicon emulsion containing conducting polymer shell structurre；
(4) emulsion obtained in step (3) is centrifugally separating to obtain precipitation, washing of precipitate is removed impurity, vacuum drying, obtain lithium ion battery silicon anode material.
The lithium ion battery silicon anode material of above-mentioned gained has bivalve Rotating fields, and the thickness of hypostracum is at 50nm, and the thickness of outer shell is at 100nm.The chemical property of silicium cathode composite is shown in Table 1.
The charge-discharge performance of silicium cathode composite in table 1. embodiment
| Embodiment | 1 | 2 | 3 | 4 |
| Initial charge specific capacity/mAh/g | 1548.2 | 1158.1 | 485.2 | 658.2 |
| First discharge specific capacity/mAh/g | 1791.9 | 1323.4 | 531.8 | 734.4 |
| Efficiency/% first | 86.4 | 87.5 | 91.2 | 89.6 |
| 500 circulation volume conservation rate/% | 88.8 | 89.3 | 92.2 | 90.6 |
Note: first charge-discharge electric current density: 50mA/g；Voltage range: 0 ~ 2V
We can see that from upper table, the silicium cathode composite of the present invention has higher specific capacity and preferable cycle characteristics relative to the silicium cathode material of prior art, after circulating 500 times, capability retention is about 90%, solve the cycle performance of existing silicium cathode material, meet the demand of existing heavy-duty battery further.
Claims (9)
1. a lithium ion battery silicon anode material, it is characterised in that described silicium cathode composite has bivalve Rotating fields, stratum nucleare is the composite Nano silicon materials with cavity structure, and hypostracum is material with carbon element clad, and outer shell is conducting polymer thin film layer；Wherein said material with carbon element is porous filamentous nanocarbon and Graphene is 1 ~ 3:1 composition in mass ratio；The composite Nano silicon materials of described cavity structure are with nanometer Fe3O4Microsphere is to sacrifice template to prepare.
Lithium ion battery silicon anode material the most according to claim 1, it is characterised in that the thickness of the hypostracum of described bivalve Rotating fields is between 20～50nm, and the thickness of outer shell is between 20nm～100nm.
Lithium ion battery silicon anode material the most according to claim 1, it is characterised in that described nanometer Fe3O4Microsphere be particle diameter be 200～500nm, the thickness of shell is the Fe of 20～50nm3O4Tiny balloon.
Lithium ion battery silicon anode material the most according to claim 1, it is characterised in that described conducting polymer thin film is any one in film of poly pyrrole, polythiophene film.
Lithium ion battery silicon anode material the most according to claim 1, it is characterised in that described porous filamentous nanocarbon is diameter
100 ~ 300nm, the internal multi-cellular structure containing aperture 1 ~ 20nm；Described Graphene is the graphene oxide that the number of plies is less than 10 layers.
6. the method preparing lithium ion battery silicon anode material according to any one of claim 1-5, comprises the following steps:
(1) by nanometer Fe3O4Microsphere is dispersed in the aqueous solution containing polyvinyl alcohol, ultrasonic makes Fe3O4Microsphere is uniformly dispersed, and adds the silicon nanoparticle modified through coupling agent surface, continues ultrasonic disperse, obtains mixing suspension；
(2) material with carbon element is dispersed in surfactant solution, forms finely dispersed suspension, add the mixing suspension that step (1) obtains, ultrasonic disperse, be centrifuged, filter, wash, obtain mixture；Mixture is enclosed lower high-temperature process 2 ~ 4 hours at nitrogen protective atmosphere, and reaction temperature is 400 ~ 700 DEG C, obtains composite Nano silicon materials；
(3) the composite Nano silicon materials obtained dissolving is dispersed in ethanol water, add etching agent and be uniformly mixing to obtain mixed liquor, under agitation polymer monomer is joined in above-mentioned mixed liquor, reaction 40 ~ 90min is stirred under room temperature, adding azo initiator, azo initiator concentration in mixed solution is 1～5mM/L；Then it is stirred reacting 2 ~ 5 hours at temperature is 50 DEG C～70 DEG C, obtains the composite Nano silicon emulsion containing conducting polymer shell structurre；
(4) emulsion obtained in step (3) is centrifugally separating to obtain precipitation, washing of precipitate is removed impurity, vacuum drying, obtain lithium ion battery silicon anode material.
The preparation method of lithium ion battery silicon anode material the most according to claim 6, it is characterised in that Fe in the mixing suspension described in step (1)3O4Concentration be 10～20 mM/L, the mass concentration of poly-vinyl alcohol solution is 2%～8%, Fe3O4Microsphere is 1:10 ~ 20 with the mass ratio of silicon nanoparticle, and the described ultrasonic disperse time is 30 ~ 60min.
The preparation method of lithium ion battery silicon anode material the most according to claim 6, it is characterized in that, surfactant described in step (2) is any one in hexadecyltrimethylammonium chloride, sodium lauryl sulphate, the basic sodium sulfonate of dodecane, the concentration of surfactant solution is 8 ~ 15 mM/L, and the described ultrasonic disperse time is 20 ~ 40min.
The preparation method of lithium ion battery silicon anode material the most according to claim 6, it is characterised in that the etching agent described in step (3) is semi-annular jade pendant base salicylic acid, the concentration of etching agent is 1～5 mM/L.
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