CN102637872A - High-capacity silicon-carbon composited anode material, preparation method and application thereof - Google Patents
High-capacity silicon-carbon composited anode material, preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to a high-capacity silicon-carbon composited anode material, a preparation method and application thereof, wherein the silicon-carbon composited anode material comprises the following compositions in parts by weight: 1-30 parts of silicon materials, 30-120 parts of carbon materials, and 10-80 parts of pyrolytic carbon. The silicon materials in the silicon-carbon composited anode material disclosed by the invention are uniformly adhered to the surfaces of carbon material particles, and then the outer layers of the carbon material particles are wrapped with the pyrolytic carbon, therefore, the silicon-carbon composited anode material disclosed by the invention has the advantages of lower first irreversible specific capacity, higher specific capacity, excellent cycle performance, low preparation cost and the like; and the first discharge capacity of the silicon-carbon composited anode material is greater than 450 mAh.g<-1> under a 0.2 C discharge ratio, and the retention rate of capacity after 50 cycles is more than 80%.
Description
Technical field
The invention belongs to the lithium ion battery material field, be specifically related to a kind of high power capacity Si-C composite material and preparation method thereof and its application.
Background technology
The graphite-like negative material has high cycle efficieny and excellent cycle performance, has been widely used in preparing lithium ion battery negative material.But the graphite-like negative material exists lithium storage content lower, and theoretical specific capacity only has 372mAhg
-1Etc. defective.For this reason, need the development of new negative material to improve the chemical property of lithium ion battery.
At present, and the research of high power capacity composite negative pole material (Wang Baofeng, Yang Jun et al. lithium ion battery be with silicon/carbon compound cathode materials [J], ACTA CHIMICA SINICA, and 2003,61 (10): (theoretical capacity is 4200mAhg 1572-1576) mainly to concentrate on silicon
-1), Sn (theoretical capacity 990mAhg
-1), Sb (theoretical capacity 536mAhg
-1), Al (theoretical capacity 400mAhg
-1) wait the metallic composite or the nonmetallic composite of reversible removal lithium embedded; The reversible lithium embedding lithium capacity that takes off of these composite negative pole materials is far longer than graphite; But its at the embedding lithium, take off and need experience serious volumetric expansion and contraction in the cyclic process of lithium, cause the electrically contacting property variation of active material and collector, and then cause the capacity and the cycle performance variation of material; The battery life of processing is shorter, thereby has hindered the practicability of these composite materials.For this reason, the researcher adopts some to improve one's methods to improve the capacity of composite negative pole material and improve cyclical stability, for example; Wang Baofeng, (lithium ion battery is with silicon/carbon compound cathode materials [J], ACTA CHIMICA SINICA for Yang Jun etc.; 2003; 61 (10): 1572-1576) disclose a kind of method that reduces the alloying pellet particle diameter for preparing, this method is controlled to be submicron order or nanoscale with the particle size range of alloying pellet, to reduce the relative volume effect of alloy; CN1402366A discloses a kind of composite material, comprises multiple components such as SiOx, Si-Ag, Si-Al, Sn-Cu in the said composite material, wherein, 0＜x＜2, the method that the heterogeneous doped and compounded of this composite material by adopting, substep are accomplished doff lithium prepares; Yoshio, people such as M. (Electrochem.Soc, 2002,149 (A1598.)) adopt the coated with carbon of vapour deposition process at silicon, to improve the conductivity and the cycle performance of composite material; But this method exists the having relatively high expectations of equipment, and is difficult to obtain the product of performance homogeneous, large-scale production defective such as have difficulties.CN101439972A discloses a kind of Si-C composite material that contains nano-silicon/CNT composite particles and amorphous carbon; Said amorphous carbon is coated on the composite particles surface; The battery that the negative pole of this Composite Preparation is processed has lower irreversible first specific capacity, higher specific capacity and excellent cycle performance; But defective such as there is shortage of resources in its material carbon nanotube, cost an arm and a leg, the manufacturing cost that causes composite material is too high and influence its practicality and industrialization.CN101153358A discloses a kind of preparation method of lithium ion battery silicon-carbon cathode material; Comprise the steps; 1) adopts high molecular polymer that nano level silica flour is handled, form one deck conducting film on the surface of nano silica fume with conductivity and electro-chemical activity; 2) binder pitch is dissolved in the organic solvent, the nano silica fume that is coated with conducting film that again itself and step 1) is made stirs, and adds spherical graphite again, boils off solvent after stirring, and forms siliceous coating layer on the spherical graphite surface; 3) under the protection of inert gas, to step 2) material that makes carries out carbonization treatment, in the siliceous coating layer of graphite surface, produces closed pore; 4) pitch is dissolved in the organic solvent, slowly adds the material that step 3) makes, boil off solvent after stirring, coat pitch again in silicon coating layer outside; 5) under the protection of inert gas, the material that step 4) is made carries out carbonization treatment, promptly gets.The Si-C composite material that this method makes has higher capacity and better cycle performance, but its preparation process is comparatively complicated.For this reason, need research to have excellent removal lithium embedded performance, have composite material of improvement cycle performance and stability and preparation method thereof.
Summary of the invention
The object of the present invention is to provide a kind of Si-C composite material, it is characterized in that, in the weight portion of each composition in the Si-C composite material, silicon materials are 1-30 part, and material with carbon element is 30-120 part, and RESEARCH OF PYROCARBON is 10-80 part.
In the optimal technical scheme of the present invention, in the weight portion of each composition in the Si-C composite material, silicon materials are 5-15 part, and material with carbon element is 60-80 part, and RESEARCH OF PYROCARBON is 15-25 part.
In the optimal technical scheme of the present invention, said silicon materials are nano-silicon, are preferably nano simple substance silicon.
In the optimal technical scheme of the present invention, the particle diameter of said silicon materials is 20-100nm, is preferably 30-80nm.
In the optimal technical scheme of the present invention, described material with carbon element is selected from any or its combination of native graphite, Delanium, is preferably Delanium, more preferably MCMB.
In the optimal technical scheme of the present invention, the meta particle diameter (D of said material with carbon element
50) be 1-100 μ m, be preferably 10-40 μ m, more preferably 10-20 μ m.
In the optimal technical scheme of the present invention, the fixed carbon content in the said material with carbon element is not less than 99.0%, is preferably 99.0-99.9%.
In the optimal technical scheme of the present invention, described " RESEARCH OF PYROCARBON " is meant that RESEARCH OF PYROCARBON precursor organic substance (claiming " RESEARCH OF PYROCARBON precursor " again) is through the later amorphous carbon of roasting charing.
In the optimal technical scheme of the present invention; Described RESEARCH OF PYROCARBON precursor organic substance is selected from any or its combination of pitch, coal tar, polyvinyl alcohol, butadiene-styrene rubber, carboxymethyl cellulose, polystyrene, polyvinyl chloride, polyacrylonitrile, phenolic resins, furfural resin, epoxy resin, glucose, sucrose, fructose, citric acid, cellulose, starch, is preferably any or its combination of phenolic resins, furfural resin, epoxy resin, sucrose, citric acid.
In the optimal technical scheme of the present invention, said pitch is selected from any or its combination of mid temperature pitch, hard pitch, secondary coal tar pitch, petroleum asphalt.
In the optimal technical scheme of the present invention, the discharge capacity first of said Si-C composite material is not less than 450mAhg
-1
In the optimal technical scheme of the present invention, 50 circulation back capability retentions of said Si-C composite material are not less than 80%.
Silicon in the Si-C composite material of the present invention is evenly attached to the graphite granule surface; Skin evenly coats for RESEARCH OF PYROCARBON; Problems such as the removal lithium embedded capacity that has overcome Si-C composite material is low, cycle performance is poor, manufacturing cost height, the made battery of the negative pole of this Composite Preparation have advantages such as lower irreversible first specific capacity, higher specific capacity, excellent cycle performance, low preparation cost.
Another object of the present invention is to provide a kind of preparation method of Si-C composite material, wherein, in the weight portion of each composition in the Si-C composite material; Silicon materials are 1-30 part; Material with carbon element is 30-120 part, and RESEARCH OF PYROCARBON is 10-80 part, and described preparation method comprises the steps:
1) silicon materials and material with carbon element are placed dispersant, stir or sonic oscillation,, remove dispersant, make silicon/material with carbon element composite particles to being uniformly dispersed;
2) under stirring condition, silicon/material with carbon element composite particles that step 1) is made joins in the RESEARCH OF PYROCARBON precursor solution, and dispersing and mixing is removed and desolvated, and under inert gas shielding, the roasting charing promptly gets the Si-C composite material that RESEARCH OF PYROCARBON coats.
In the optimal technical scheme of the present invention, in the weight portion of each composition in the Si-C composite material, silicon materials are 5-15 part, and material with carbon element is 60-80 part, and RESEARCH OF PYROCARBON is 15-25 part.
In the optimal technical scheme of the present invention, said silicon materials are nano-silicon, are preferably nano simple substance silicon.
In the optimal technical scheme of the present invention, the particle diameter of said silicon materials is 20-100nm, is preferably 30-80nm.
In the optimal technical scheme of the present invention, said material with carbon element is selected from any or its combination of native graphite, Delanium, is preferably Delanium, more preferably MCMB.
In the optimal technical scheme of the present invention, the meta particle diameter (D of said material with carbon element
50) be 1-100 μ m, be preferably 10-40 μ m, more preferably 10-20 μ m.
In the optimal technical scheme of the present invention, the carbon content in the said material with carbon element is not less than 99.0%, is preferably 99.0-99.9%.
In the optimal technical scheme of the present invention, described dispersant is selected from any or its combination of water, methyl alcohol, ethanol, propyl alcohol, isopropyl alcohol, propane diols, butanols, butanediol, acetone, is preferably any or its combination of water, methyl alcohol, ethanol.
In the optimal technical scheme of the present invention, described " RESEARCH OF PYROCARBON " is meant that RESEARCH OF PYROCARBON precursor organic substance is through the later amorphous carbon of roasting charing.
In the optimal technical scheme of the present invention; Described RESEARCH OF PYROCARBON precursor organic substance is selected from any or its combination of pitch, coal tar, polyvinyl alcohol, butadiene-styrene rubber, carboxymethyl cellulose, polystyrene, polyvinyl chloride, polyacrylonitrile, phenolic resins, furfural resin, epoxy resin, glucose, sucrose, fructose, citric acid, cellulose, starch, is preferably any or its combination of phenolic resins, furfural resin, epoxy resin, sucrose, citric acid.
In the optimal technical scheme of the present invention, said pitch is selected from any or its combination of mid temperature pitch, hard pitch, secondary coal tar pitch, petroleum asphalt.
In the optimal technical scheme of the present invention; Described RESEARCH OF PYROCARBON precursor solution is the solution that RESEARCH OF PYROCARBON presoma organic substance of the present invention is dissolved in gained in the solvent; Wherein, Said solvent is selected from any or its combination of water, methyl alcohol, ethanol, butanols, acetone, ethyl acetate, oxolane, pyridine, N-methyl pyrrolidone, chloroform, cyclohexane, is preferably any or its combination of water, methyl alcohol, ethanol, butanols, ethyl acetate.
In the optimal technical scheme of the present invention, described method of removing dispersant or solvent is selected from filtration, centrifugal, dry any or its combination.
In the optimal technical scheme of the present invention, said inert gas is any or its combination of nitrogen, argon gas, hydrogen, helium.
In the optimal technical scheme of the present invention, described roasting carbonization condition does, is warming up to 200-500 ℃ with the heating rate of 1-5 ℃/min, constant temperature 1-8h, and the heating rate with 1-10 ℃/min is warming up to 500-1600 ℃ again, and constant temperature 2-24h is cooled to room temperature; Preferred roasting carbonization condition is warming up to 250-450 ℃ for the heating rate with 1-3 ℃/min, constant temperature 2-6h, and the heating rate with 2-8 ℃/min is warming up to 600-1200 ℃ again, and constant temperature 8-18h is cooled to room temperature.
In the optimal technical scheme of the present invention, the discharge capacity first of said Si-C composite material is not less than 450mAhg
-1
In the optimal technical scheme of the present invention, 50 circulation back capability retentions of said Si-C composite material are not less than 80%.
(wherein, said material with carbon element is preferably any or its combination of native graphite, Delanium with silicon materials (wherein, said silicon materials are preferably nano-silicon, more preferably nano simple substance silicon) and material with carbon element in the present invention; More preferably Delanium most preferably is MCMB) powder places dispersant, stirs or sonic oscillation; To being uniformly dispersed, remove dispersant, make silicon/material with carbon element composite particles; The silicon that makes/carbon composite particles is joined in the RESEARCH OF PYROCARBON precursor solution, dispersing and mixing is removed and is desolvated again; Under inert gas shielding, the roasting charing promptly gets the Si-C composite material that RESEARCH OF PYROCARBON coats.Silicon in the Si-C composite material of the present invention is evenly attached to the material with carbon element particle surface; The outer RESEARCH OF PYROCARBON that evenly coats; And having advantages such as lower irreversible first specific capacity, higher specific capacity, excellent cycle performance, preparation cost are low, the first discharge capacity of silicon-carbon composite cathode material under the 0.2C discharge-rate is greater than 450mAhg
-1, 50 circulation back capability retentions have cyclical stability preferably, defectives such as the specific discharge capacity that has overcome existing Si-C composite material is low, cycle performance is poor, manufacturing cost height more than 80%.Si-C composite material of the present invention is used to prepare lithium ion battery negative material; Add the specific capacity that Si has improved negative material in the composite material; And defectives such as the carbon negative pole material theoretical capacity is low have been overcome; And the even coating layer of RESEARCH OF PYROCARBON has retrained the bulk effect of silicon in charge and discharge process, has significantly improved the cycle performance and the stability of silicon carbon material.And it is simple that the preparation method of Si-C composite material of the present invention has technology, easy operating, and cost is low, and is pollution-free, is fit to advantages such as suitability for industrialized production.
The present invention also aims to provide a kind of Si-C composite material to be used for preparing the application of lithium ion battery negative material.
In order clearly to explain protection scope of the present invention, the present invention defines term as follows:
" silicon/carbon composite particles " of the present invention is meant the homogeneous mixture of silicon materials and material with carbon element; Its preparation method comprises the steps, takes by weighing the silicon material powder and the material with carbon element powder of aequum, and silicon material powder that takes by weighing and material with carbon element powder are placed dispersant; Stir or sonic oscillation; To its even dispersion, remove dispersant, obtain silicon/carbon composite particles.
" RESEARCH OF PYROCARBON " of the present invention is meant that RESEARCH OF PYROCARBON precursor organic substance (claiming " RESEARCH OF PYROCARBON precursor " again) is through the later amorphous carbon of roasting charing.
" RESEARCH OF PYROCARBON precursor solution " of the present invention is claimed " RESEARCH OF PYROCARBON organic substance precursor solution " again; Be the solution that RESEARCH OF PYROCARBON precursor organic substance of the present invention is dissolved in gained in the solvent of the present invention; Wherein, Described RESEARCH OF PYROCARBON precursor is selected from any or its combination of pitch, coal tar, polyvinyl alcohol, butadiene-styrene rubber, carboxymethyl cellulose, polystyrene, polyvinyl chloride, polyacrylonitrile, phenolic resins, furfural resin, epoxy resin, glucose, sucrose, fructose, citric acid, cellulose, starch, and said solvent is selected from any or its combination of water, methyl alcohol, ethanol, butanols, acetone, ethyl acetate, oxolane, pyridine, N-methyl pyrrolidone, chloroform, cyclohexane.
MCMB of the present invention is a kind of of Delanium; Described MCMB with mink cell focus, pitch (wherein; Said pitch comprises mid temperature pitch, hard pitch, secondary coal tar pitch, petroleum asphalt etc.), residual oil, coal tar, secondary petroleum heavy oil, carbolineum, polycyclic aromatic hydrocarbon etc. are the preparation raw material; Can adopt preparation method known in the art to prepare, as adopting too equality people (" material science and technology ", the grain size analysis of diauxic growth MCMB and structural research of Lee; 2007,15 (3)) disclosed method prepares.The disclosed content of these documents is all as the application's reference.Wherein, The preparation of MCMB has not only realized the efficient trans-utilization of these raw materials; And the MCMB particle size distribution that makes is even; Its particle is spherical in shape or type spherical, has advantages such as good electrical conductivity and chemical stability, high surface, low manufacturing cost, corrosion-resistant, electrochemically resistant burn into environmental protection.
The step that is mixed with of silicon of the present invention/material with carbon element composite particles and RESEARCH OF PYROCARBON precursor comprises; Silicon of the present invention/material with carbon element composite particles is joined in the RESEARCH OF PYROCARBON precursor solution; Evenly mix or ultrasonic dispersion; Obtain the RESEARCH OF PYROCARBON precursor solution of dispersed silicon/material with carbon element composite particles, remove and desolvate, make the homogeneous mixture of silicon/material with carbon element composite particles and RESEARCH OF PYROCARBON precursor.
Meta particle diameter (D of the present invention
50) be meant that the cumulative particle sizes percentile of sample reaches 50% o'clock pairing particle diameter.The present invention adopts laser method and selects for use MASTERSIZER 2000 analyzers to measure the D of material
50
Characteristics such as the surface topography of the Japanese JSM-6700F electronic scanner microscope observation sample of science of electronic scanner microscope of the present invention (SEM) test employing, granular size; Wherein, Emission voltage is 5KV; Powder surface is carried out vacuum metal spraying 2min; Through the high-power electron beam that gathering is obtained on sample, scan the physical signallings such as secondary electron, times scattered electron, transmitted electron, absorption electronics, visible light and X ray that inspired reception, amplify and be shown as picture and come analytical sample, obtain the various information of sample topography.
XRD figure spectrum of the present invention adopts the test of X-ray diffraction analysis method to obtain, and the Cu-Ka radiation source is used in this XRD test, and Guan Liuwei 40mA, pipe press and be 40KV, 12 °/min of sweep speed, and sweep limits 10-90 °, step-length is 0.020 °.
Charge-discharge performance test of the present invention adopts LAND CT2001A battery test system that simulated battery is carried out the constant current charge-discharge test, and the voltage tester scope is 0-1.8V.The making of simulated battery comprises the steps: according to Si-C composite material: conductive carbon black: the mass ratio of Kynoar (PVDF) is 85: 5: 10, takes by weighing required Si-C composite material, conductive carbon black and PVDF, and Si-C composite material and conductive carbon black are ground in mortar; It is mixed; Join in N-methyl pyrrolidone (NMP) solution of PVDF, stir, make slurry; Again slurry is coated on the Copper Foil, processes pole piece through oven dry, roll extrusion.Do electrode with metal lithium sheet, Celgard2400 is a barrier film, 1mol/L LiPF
6/ EC (ethylene carbonate)+DMC (dimethyl carbonate)+EMC (methyl ethyl carbonate fat) (volume ratio 1: 1: 1) is an electrolyte, in the glove box of logical argon gas, is assembled into simulated battery, tests after leaving standstill 12h.
Except as otherwise noted, when the present invention relates to the percentage between liquid and the liquid, described percentage is volume percentage; When the present invention relates to the percentage between liquid and the solid, said percentage is volume/weight percentage; When the present invention relates to the percentage between solid and the liquid, said percentage is weight/volume percent; All the other are weight/percentage by weight.
Compared with prior art, the present invention has following advantage:
1, the silicon in the Si-C composite material of the present invention is evenly attached to the material with carbon element particle surface; The outer RESEARCH OF PYROCARBON that evenly coats; Have advantages such as lower irreversible first specific capacity, higher specific capacity, excellent cycle performance, preparation cost are low, the first discharge capacity of silicon-carbon composite cathode material under the 0.2C discharge-rate is greater than 450mAhg
-1, 50 circulation back capability retentions have cyclical stability preferably, and have overcome low, the defectives such as cycle performance is poor, manufacturing cost height of specific discharge capacity of existing Si-C composite material more than 80%.
2, Si-C composite material of the present invention is used to prepare lithium ion battery negative material; Add the specific capacity that Si has improved negative material in the composite material; And defectives such as the carbon negative pole material theoretical capacity is low have been overcome; And the outer RESEARCH OF PYROCARBON that evenly coats has retrained the bulk effect of silicon in charge and discharge process, has improved the cycle performance and the stability of silicon carbon material.
3, the present invention adopts nano-silicon to make the silicon phase, evenly mixes in dispersant with the micron order graphite granule, and with thermal decomposition method RESEARCH OF PYROCARBON is coated on the Si-C composite material particle surface, has improved the specific discharge capacity of material with carbon element.
4, to have technology simple for the preparation method of Si-C composite material of the present invention, easy operating, and cost is low, and is pollution-free, is fit to advantages such as suitability for industrialized production.
Description of drawings
The section SEM figure (amplifying 5000 times) of the Si-C composite material of Fig. 1 embodiment 2 preparations.
The XRD figure spectrum of the Si-C composite material of Fig. 2 embodiment 2 preparations.
The section SEM figure (amplifying 5000 times) of the Si-C composite material of Fig. 3 embodiment 5 preparations.
The XRD figure spectrum of Si-C composite material, pure silicon and the native graphite of Fig. 4 embodiment 5 preparations.
Embodiment
Below will combine embodiment to specify the present invention, embodiments of the invention only are used to technical scheme of the present invention is described, and non-limiting essence of the present invention.
Embodiment 1The preparation of Si-C composite material of the present invention
(1) preparation of silicon/material with carbon element composite particles
Taking by weighing the 0.50g particle diameter is nano simple substance Si powder and the 10.00g D of 30-80nm
50Be the MCMB of 20 μ m, wherein, the fixed carbon content in the MCMB is 99.8%; It is the ethanol water of 33v/v% that the nano simple substance Si powder that is taken by weighing and MCMB are placed 60ml concentration; After stirring 30min, the ethanol water (suspension) with nano simple substance silicon that makes and MCMB places ultrasonator again, ultrasonic dispersion 2h; After nano-silicon and MCMB are evenly disperseed; Filter, 80 ℃ of oven dry obtain silicon/MCMB composite particles (being silicon/carbon composite particles).
(2) preparation of the mixture of silicon/material with carbon element composite particles and RESEARCH OF PYROCARBON precursor
Take by weighing 3.00g epoxy resin, it is dissolved in the 10ml ethyl acetate; Under stirring condition; The silicon that obtains in the step (1)/MCMB composite particles is joined in the epoxy resin ethyl acetate solution (promptly getting RESEARCH OF PYROCARBON precursor solution); Continue to stir 30min; Sonic oscillation carries out vacuumize at 80 ℃ after disperseing 2h, obtains the mixture (being RESEARCH OF PYROCARBON precursor mixture) of silicon/MCMB composite particles and epoxy resin.
(3) preparation of Si-C composite material
Silicon/MCMB the composite particles that step (2) is made and the mixture of epoxy resin are put into tube furnace, under argon shield, carry out the roasting charing; Wherein, Described roasting carbonization condition does, is warming up to 400 ℃, constant temperature 5h with the heating rate of 1 ℃/min; Heating rate with 2 ℃/min is warming up to 1200 ℃ again, and constant temperature 12h is cooled to room temperature, grinds, and crosses 300 mesh sieves, promptly gets.
According to detection method of the present invention, the 0.2C first discharge specific capacity (mAhg of the silicon/material with carbon element composite particulate material of test implementation example 1 preparation
-1) and 50 times circulation volume and capability retention, the result sees table 1.
Embodiment 2The preparation of Si-C composite material of the present invention
(1) preparation of silicon/material with carbon element composite particles
Taking by weighing the 0.50g particle diameter is nano simple substance Si powder and the 10.00g D of 30-80nm
50Be the MCMB of 20 μ m, wherein, the fixed carbon content in the MCMB is 99.8%; It is the methanol aqueous solution of 33v/v% that the nano simple substance Si powder that is taken by weighing and MCMB are placed 60ml concentration; After stirring 30min, the methanol aqueous solution (suspension) with nano simple substance silicon that makes and MCMB places ultrasonator again, ultrasonic dispersion 2h; After nano-silicon and MCMB are evenly disperseed; Filter, 80 ℃ of oven dry obtain silicon/MCMB composite particles (being silicon/material with carbon element composite particles).
(2) silicon/material with carbon element composite particles mixes with RESEARCH OF PYROCARBON precursor solution
Take by weighing the 5.00g citric acid, it is dissolved in the 50ml water; Under agitation; The silicon that obtains in the step (1)/MCMB composite particles is joined in the aqueous citric acid solution; Continue to stir 30min; Sonic oscillation disperses 2h again, carries out vacuumize at 80 ℃, obtains the mixture (being RESEARCH OF PYROCARBON precursor mixture) of silicon/MCMB composite particles and citric acid.
(3) preparation of Si-C composite material
Silicon/MCMB the composite particles that step (2) is made and the mixture of citric acid are put into tube furnace, under argon shield, carry out the roasting charing, and wherein, described roasting carbonization condition does, are warming up to 400 ℃, constant temperature 5h with the heating rate of 1 ℃/min; Heating rate with 2 ℃/min is warming up to 1200 ℃ again, and constant temperature 12h is cooled to room temperature, grinds, and crosses 300 mesh sieves, promptly gets.
According to detection method of the present invention, XRD, SEM, the 0.2C first discharge specific capacity (mAhg of the silicon/material with carbon element composite particulate material of test implementation example 2 preparations
-1) and 50 times circulation volume and capability retention, the result sees Fig. 1, Fig. 2 and table 1.
Visible by Fig. 2 (XRD figure), the diffraction maximum of Si is arranged in the composite material, explain that this material is a Si-C composite material; Visible by Fig. 1 (SEM figure), the centre of Si-C composite material is a graphite granule, and the granule of surface white is a silicon nanoparticle, silicon in the Si-C composite material that the present invention makes be described evenly attached to the material with carbon element particle surface, outer evenly coating RESEARCH OF PYROCARBON.
Embodiment 3The preparation of Si-C composite material of the present invention
(1) preparation of silicon/material with carbon element composite particles
Taking by weighing the 0.50g particle diameter is nano simple substance Si powder and the 10.00g D of 30-80nm
50Be the MCMB of 20 μ m, wherein, the fixed carbon content in the MCMB is 99.8%; It is the aqueous acetone solution of 33v/v% that the nano simple substance Si powder that is taken by weighing and MCMB are placed 60ml concentration; After stirring 30min, the aqueous acetone solution (suspension) with nano simple substance Si powder that makes and MCMB places ultrasonator again, ultrasonic dispersion 2h; After nano-silicon and MCMB are evenly disperseed; Filter, 80 ℃ of oven dry obtain silicon/MCMB composite particles (being silicon/material with carbon element composite particles).
(2) silicon/material with carbon element composite particles mixes with RESEARCH OF PYROCARBON precursor solution
Take by weighing 8.00g sucrose, it is dissolved in the 50ml water; Under agitation; The silicon that obtains in the step (1)/MCMB composite particles is joined in the aqueous sucrose solution; Continue to stir 30min; Sonic oscillation disperses 2h again, carries out vacuumize at 80 ℃, obtains the mixture (being RESEARCH OF PYROCARBON precursor mixture) of silicon/MCMB composite particles and sucrose.
(3) preparation of Si-C composite material
Silicon/material with carbon element the composite particles that step (2) is made and the mixture of sucrose are put into tube furnace, under argon shield, carry out the roasting charing, and wherein, described roasting carbonization condition does, are warming up to 400 ℃, constant temperature 5h with the heating rate of 1 ℃/min; Heating rate with 2 ℃/min is warming up to 1200 ℃ again, and constant temperature 12h is cooled to room temperature, grinds, and crosses 300 mesh sieves, promptly gets.
According to detection method of the present invention, the 0.2C first discharge specific capacity (mAhg of the silicon/material with carbon element composite particulate material of test implementation example 3 preparations
-1) and 50 times circulation volume and capability retention, the result sees table 1.
Embodiment 4The preparation of Si-C composite material of the present invention
Embodiment 4 is that with the difference of embodiment 1 consumption of nano simple substance silica flour is 1.00g, and used material with carbon element is D
50Be the native graphite of 20 μ m, wherein, the fixed carbon content of native graphite is 99.0%.
According to detection method of the present invention, the 0.2C first discharge specific capacity (mAhg of the silicon/material with carbon element composite particulate material of test implementation example 4 preparations
-1) and 50 times circulation volume and capability retention, the result sees table 1.
Embodiment 5The preparation of Si-C composite material of the present invention
Embodiment 5 is that with the difference of embodiment 2 consumption of nano simple substance silica flour is 1.00g, and used material with carbon element is D
50Be the native graphite of 20 μ m, wherein, the carbon content in the native graphite is 99.0%.
According to detection method of the present invention, XRD, SEM, the 0.2C first discharge specific capacity (mAhg of the silicon/carbon composite particulate material of test implementation example 5 preparations
-1) and 50 times circulation volume and capability retention, the result sees Fig. 3, Fig. 4 and table 1.
Visible by Fig. 4 (XRD figure), the diffraction maximum of Si is arranged in the composite material, explain that this material is a Si-C composite material; Visible by Fig. 3 (SEM figure), the centre of Si-C composite material is a graphite granule, and the granule of surface white is a silicon nanoparticle, silicon in the Si-C composite material that the present invention makes be described evenly attached to the material with carbon element particle surface, outer evenly coating RESEARCH OF PYROCARBON.
Embodiment 6The preparation of Si-C composite material of the present invention
Embodiment 6 is that with the difference of embodiment 3 consumption of nano simple substance silica flour is 1.00g, and used material with carbon element is D
50Be the native graphite of 20 μ m, wherein, the carbon content of native graphite is 99.0%.
According to detection method of the present invention, the 0.2C first discharge specific capacity (mAhg of the Si-C composite material of test implementation example 6 preparations
-1) and 50 times circulation volume and capability retention, the result sees table 1.
Comparative Examples 1
(1) mixture of material with carbon element and RESEARCH OF PYROCARBON preparation
3g epoxy resin is dissolved in the 10g ethyl acetate, under agitation, the 10g MCMB is joined in the ethyl acetate solution of epoxy resin; Continue to stir 30min; Sonic oscillation disperses 2h again, at 80 ℃ of vacuum dryings, obtains the mixture of MCMB and epoxy resin.
(2) preparation of carbon coated composite material
The MCMB that obtains in the step (1) and the mixture of epoxy resin are put into tube furnace, under argon shield, be warming up to 400 ℃, constant temperature 5h with the heating rate of 1 ℃/min; Heating rate with 2 ℃/min is warming up to 1200 ℃ again, and constant temperature 12h is cooled to room temperature, grinds, and crosses 300 mesh sieves, promptly gets.
According to detection method of the present invention, the 0.2C first discharge specific capacity (mAhg of the silicon/carbon composite particulate material of test comparison example 1 preparation
-1) and 50 times circulation volume and capability retention, the result sees table 1.
Comparative Examples 2
Prepare silicon-carbon cathode material according to CN101153358A embodiment 1 disclosed method, comprise the steps: D
50Be the silica flour ball milling 14 hours of 2 μ m, it added in N-methyl pyrrolidone (NMP) solution of polyaniline stir process 1 hour, low temperature drying.Get in the pyridine solution that 0.4 gram this kind silica flour adds binder pitch (1 gram binder pitch is dissolved in the 15ml pyridine solution), stirred 1 hour.In this system, slowly add 9.6 gram D
50Be the spherical graphite of 19 μ m, stirred 1 hour, oven dry.This material is positioned over carbonization in the tube furnace of nitrogen protection, 1000 ℃ of carburizing temperatures, carbonization time 2 hours.(1 gram dipping agent bitumen is dissolved in the 15ml nmp solution) stirred 2 hours in the nmp solution with the above-mentioned material adding dipping agent bitumen that makes, flung to solvent.This material is positioned over carbonization in the tube furnace of nitrogen protection, 1000 ℃ of carburizing temperatures, carbonization time 5 hours obtains Si-C composite material.
Embodiment 7Electro-chemical test
The composite material that embodiment 1-6 and Comparative Examples 1-2 are made is assembled into battery, carries out electro-chemical test.Wherein, Take by weighing composite material granular, conductive carbon black, the PVDF that makes at 85: 5: 10 by mass ratio, active material (composite material that embodiment 1-6 and Comparative Examples 1-2 make) and conductive carbon black are ground in mortar it is mixed, join in the nmp solution of PVDF; Stir; Make slurry, again the slurry that makes is coated on the Copper Foil, process pole piece through oven dry, roll extrusion.Do electrode with metal lithium sheet, Celgard2400 is a barrier film, 1mol/L LiPF
6/ EC+DMC+EMC (volume ratio 1: 1: 1) is an electrolyte, in the glove box of logical argon gas, is assembled into simulated battery, leaves standstill 12h.
At ambient temperature, under the 0.2C discharge-rate, carry out the constant current charge-discharge test, voltage range is 0-1.8V, and the result sees table 1.
Visible by table 1; Add the specific capacity that Si has improved negative material in the Si-C composite material of the present invention; Wherein, silicon is evenly attached to the material with carbon element particle surface, and the outer RESEARCH OF PYROCARBON that evenly coats; Retrained the bulk effect of silicon in charge and discharge process; Improved the cycle performance and the stability of silicon carbon material, and had advantages such as lower irreversible first specific capacity, higher specific capacity, excellent cycle performance, preparation cost are low, the first discharge capacity of silicon-carbon composite cathode material under the 0.2C discharge-rate is greater than 450mAhg
-1, 50 circulation back capability retentions have cyclical stability preferably, defectives such as the specific discharge capacity that has overcome existing Si-C composite material is low, cycle performance is poor, manufacturing cost height more than 80%.It is simple that the preparation method of Si-C composite material of the present invention has technology, easy operating, and cost is low, and is pollution-free, is fit to advantages such as suitability for industrialized production.
The test result of the Si-C composite material of table 1 Different Silicon content
Explain: do not do this detection in "--" expression list of references in the table 1, so there is not this testing result.
Claims (14)
1. the preparation method of a Si-C composite material, wherein, in the weight portion of each composition in the Si-C composite material, silicon materials are 1-30 part, and material with carbon element is 30-120 part, and RESEARCH OF PYROCARBON is 10-80 part, and described preparation method comprises the steps:
1) silicon materials and material with carbon element are placed dispersant, stir or sonic oscillation,, remove dispersant, make silicon/material with carbon element composite particles to being uniformly dispersed;
2) under stirring condition, silicon/material with carbon element composite particles that step 1) is made joins in the RESEARCH OF PYROCARBON precursor solution, and dispersing and mixing is removed and desolvated, and under inert gas shielding, the roasting charing promptly gets the Si-C composite material that RESEARCH OF PYROCARBON coats,
Wherein, in the optimal technical scheme of the present invention, in the weight portion of each composition in the Si-C composite material, silicon materials are 5-15 part, and material with carbon element is 60-80 part, and RESEARCH OF PYROCARBON is 15-25 part.
2. preparation method according to claim 1, said silicon materials are nano-silicon, are preferably nano simple substance silicon.
3. preparation method according to claim 1 and 2, the particle diameter of said silicon materials is 20-100nm, is preferably 30-80nm.
4. according to each described preparation method of claim 1-3, said material with carbon element is selected from any or its combination of native graphite, Delanium, is preferably Delanium, more preferably MCMB.
5. according to each described preparation method of claim 1-4, the meta particle diameter (D of said material with carbon element
50) be 1-100 μ m, be preferably 10-40 μ m, more preferably 10-20 μ m.
6. according to each described preparation method of claim 1-5, the carbon content in the said material with carbon element is not less than 99.0%, is preferably 99.0-99.9%.
7. according to each described preparation method of claim 1-6; Described dispersant is selected from any or its combination of water, methyl alcohol, ethanol, propyl alcohol, isopropyl alcohol, propane diols, butanols, butanediol, acetone, is preferably any or its combination of water, ethanol, methyl alcohol.
8. according to each described preparation method of claim 1-7; Described RESEARCH OF PYROCARBON is that RESEARCH OF PYROCARBON precursor organic substance is through the later amorphous carbon of roasting charing; Preferred described RESEARCH OF PYROCARBON precursor organic substance is selected from any or its combination of pitch (preferred said pitch is selected from any or its combination of mid temperature pitch, hard pitch, secondary coal tar pitch, petroleum asphalt), coal tar, polyvinyl alcohol, butadiene-styrene rubber, carboxymethyl cellulose, polystyrene, polyvinyl chloride, polyacrylonitrile, phenolic resins, furfural resin, epoxy resin, glucose, sucrose, fructose, citric acid, cellulose, starch, is preferably any or its combination of phenolic resins, furfural resin, epoxy resin, sucrose, citric acid.
9. according to each described preparation method of claim 1-8; Described RESEARCH OF PYROCARBON precursor solution is the solution that RESEARCH OF PYROCARBON presoma organic substance is dissolved in gained in the solvent; Wherein, Said solvent is selected from any or its combination of water, ethanol, methyl alcohol, butanols, acetone, ethyl acetate, oxolane, pyridine, N-methyl pyrrolidone, chloroform, cyclohexane, is preferably any or its combination of water, methyl alcohol, ethanol, butanols, ethyl acetate.
10. according to each described preparation method of claim 1-9, described method of removing dispersant or solvent is selected from filtration, centrifugal, dry any or its combination.
11. according to each described preparation method of claim 1-10, described roasting carbonization condition does, is warming up to 200-500 ℃ with the heating rate of 1-5 ℃/min; Constant temperature 1-8h, the heating rate with 1-10 ℃/min is warming up to 500-1600 ℃, constant temperature 2-24h again; Be cooled to room temperature, preferred roasting carbonization condition is warming up to 250-450 ℃, constant temperature 2-6h for the heating rate with 1-3 ℃/min; Heating rate with 2-8 ℃/min is warming up to 600-1200 ℃ again, and constant temperature 8-18h is cooled to room temperature.
12. according to each described preparation method of claim 1-11, the discharge capacity first of said Si-C composite material is not less than 450mAhg
-1, 50 circulation back capability retentions of preferred said Si-C composite material are not less than 80%.
13. a Si-C composite material is characterized in that, in the weight portion of each composition in the Si-C composite material; Silicon materials are 1-30 part, and material with carbon element is 30-120 part, and RESEARCH OF PYROCARBON is 10-80 part; Being preferably silicon materials is 5-15 part, and material with carbon element is 60-80 part, and RESEARCH OF PYROCARBON is 15-25 part; Perhaps described Si-C composite material is prepared by each preparation method of claim 1-12.
14. the application that the described Si-C composite material of claim 13 is used to prepare lithium ion battery negative material.
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Application publication date: 20120815 |