CN103337613B - A kind of Si-C composite material and preparation method thereof, lithium ion battery - Google Patents
A kind of Si-C composite material and preparation method thereof, lithium ion battery Download PDFInfo
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Abstract
The invention discloses a kind of Si-C composite material and preparation method thereof, lithium ion battery, the method comprises the following steps: (1) arranges transition zone on silica-base material, obtains the silica-base material that transition zone is coated; (2) at the silica-base material outer cladding carbon that transition zone is coated, carbon-transition zone-silicon based composite material is obtained; (3) remove transition zone, obtain Si-C composite material.Above-mentioned preparation method by arranging transition zone outside silica-base material, then at transition zone outer cladding carbon, then removes between the silica-based and carbon in Si-C composite material that the transition zone between silica-base material and carbon obtains and has certain hole.According to silica-base material microvolume expanded size of theory when embedding lithium, the thickness of transition zone is set, accurately can control the pore size between silica-based and carbon, thus effectively decrease the bulk effect of Si-C composite material, further increase the cycle performance of lithium ion battery.Carbon in this Si-C composite material improves conductivity and the high rate performance of this material.
Description
Technical field
The invention belongs to technical field of lithium ion, be specifically related to a kind of Si-C composite material and preparation method thereof, lithium ion battery.
Background technology
At present, the lithium ion battery of commercial applications extensively adopts graphite or modified graphite as negative material.Lithium ion battery is in charge and discharge process, above-mentioned negative material volumetric expansion when embedding lithium less (embedding lithium coefficient of cubical expansion <9%), show higher coulombic efficiency and good cyclical stability, but its theoretical maximum specific capacity only has 372mAh/g, thus limit the further raising of the specific energy of lithium ion battery.
The lithium ion battery negative material of height ratio capacity has become the key improving battery performance, because silica-base material has higher specific capacity (silicon theoretical specific capacity is 4200mAh/g), therefore silica-base material is considered to the most promising negative material of one, and causes the extensive concern of battery material circle.But silica-base material has very large bulk effect (embedding lithium cubical expansivity >300%) in the process of doff lithium, cause the efflorescence of silica-base material in charging and discharging lithium battery process, obscission seriously, cycle performance of battery is sharply declined.
In prior art, the process preparing silicon/carbon/composite cathode material of silicon/carbon/graphite in CN100379059C is: be dispersed in after silica flour and graphite mixing in organic substance, then carry out high temperature cabonization process, form silicon/carbon/graphite composite material; The process preparing Si-C composite material in CN02112180.X is: high temperature sintering after being mixed with silica flour by pitch, obtains Si-C composite material.Although silicon/carbon/composite cathode material of silicon/carbon/graphite that said method prepares or Si-C composite material improve the cyclical stability of lithium ion battery to a certain extent, still there is efflorescence, obscission.Use above-mentioned material as the lithium ion battery of negative material after repeatedly charge and discharge cycles, capacity starts rapid decay, does not fundamentally solve the bulk effect in silicon based anode material charge and discharge process.
Summary of the invention
Technical problem to be solved by this invention is for above shortcomings in prior art, provides a kind of Si-C composite material and preparation method thereof, lithium ion battery.Between silica-based and carbon in the Si-C composite material that this preparation method obtains, there is certain hole, decrease the bulk effect of Si-C composite material.
The technical scheme that solution the technology of the present invention problem adopts is to provide a kind of preparation method of Si-C composite material, comprises the following steps:
(1) transition zone is set on silica-base material, obtains the silica-base material that described transition zone is coated;
(2) at the silica-base material outer cladding carbon that described transition zone is coated, carbon-transition zone-silicon based composite material is obtained;
(3) remove described transition zone, obtain Si-C composite material.
Preferably, described step is specially:
(1) on silica-base material, precipitate metal carbonate transition zone, obtain the silica-base material that this metal carbonate is coated;
(2) at the silica-base material outer cladding carbon that described transition metal carbonate is coated, obtain carbon-metal carbonate-silicon based composite material, wherein, the heat decomposition temperature of described transition metal carbonate is higher than the temperature in the process of the described silica-base material outer cladding carbon coated at described metal carbonate;
(3) use acid solution to erode described metal carbonate, obtain Si-C composite material.
Preferably, the mass ratio of described silica-base material and described metal carbonate is (1: 9) ~ (2: 3).
Preferably, the mass ratio of described silica-base material and described metal carbonate is (1: 6.5) ~ (1: 3.2).
Preferably, the described carbon in described Si-C composite material and the mass ratio of described silica-base material are (1: 19) ~ (9: 1).
Preferably, the described carbon in described Si-C composite material and the mass ratio of described silica-base material are (3: 17) ~ (3: 2).
Preferably, described carbonate comprises any one or a few in magnesium carbonate, calcium carbonate, strontium carbonate, brium carbonate, zinc carbonate, ceruse.
Preferably, described silica-base material comprises any one or a few in silicon, silicon monoxide, silicon alloy.
Preferably, described silicon alloy is silicon silver alloy, silicon copper, any one or a few in silicon nickel alloy.
Preferably, described step (2) is specially: after being mixed with carbon source by silica-base material coated for described metal carbonate, under nonoxidizing atmosphere, carry out calcination, and described calcination temperature is 250 DEG C ~ 800 DEG C, be incubated 1 ~ 8 hour, obtain described carbon-metal carbonate-silicon based composite material.
Preferably, described carbon source is any one or a few in polyvinyl alcohol, sucrose, glucose, polyacrylonitrile, phenolic resins, polyvinyl chloride, pitch.
Preferably, described step (1) is specially: by the aqueous solution of described silica-base material and slaine, then add carbonate deposition agent, obtain the silica-base material that described metal carbonate is coated.
Preferably, described slaine is one or more in calcium nitrate, barium nitrate, calcium acetate, calcium chloride, barium acetate, barium chloride, strontium chloride, strontium nitrate, strontium acetate, magnesium chloride, magnesium nitrate, magnesium acetate, zinc chloride, zinc nitrate, plumbi nitras, zinc sulfate, lead acetate.
Preferably, described carbonate deposition agent is any one or a few in sodium carbonate, potash, ammonium carbonate.
The present invention also provides a kind of Si-C composite material, and it is prepared by above-mentioned preparation method.
The present invention also provides a kind of lithium ion battery, and its negative pole contains above-mentioned Si-C composite material.
The preparation method of the Si-C composite material in the present invention, by arranging transition zone outside silica-base material, then at transition zone outer cladding carbon, then removes between the silica-based and carbon in Si-C composite material that the transition zone between silica-base material and carbon obtains and has certain hole.According to silica-base material microvolume expanded size of theory when embedding lithium, the thickness of transition zone is set, accurately can control the pore size between silica-based and carbon, thus effectively decrease the bulk effect of Si-C composite material, further increase the cycle performance of lithium ion battery.Carbon in this Si-C composite material improves conductivity and the high rate performance of this material.Carbon in this Si-C composite material improves Si-C composite material conductivity, improves the high rate performance of Si-C composite material.
Accompanying drawing explanation
Fig. 1 is the schematic diagram preparing the structural change of Si-C composite material process in which materials in the embodiment of the present invention 2;
Fig. 2 is the charge-discharge performance resolution chart of the lithium ion battery that the Si-C composite material of the embodiment of the present invention 2 preparation is made;
Fig. 3 is the high rate performance resolution chart of the lithium ion battery that the Si-C composite material of the embodiment of the present invention 2 preparation is made.
In figure: 1-silica-base material; 2-calcium carbonate; 3-carbon; 4-hole.
Embodiment
For making those skilled in the art understand technical scheme of the present invention better, below in conjunction with the drawings and specific embodiments, the present invention is described in further detail.
Embodiment 1
The present embodiment provides a kind of preparation method of Si-C composite material, comprises the following steps:
(1) transition zone is set on silica-base material, obtains the silica-base material that described transition zone is coated;
(2) at the silica-base material outer cladding carbon that described transition zone is coated, carbon-transition zone-silicon based composite material is obtained;
(3) remove described transition zone, obtain Si-C composite material.
Above-mentioned preparation method by arranging transition zone outside silica-base material, then at transition zone outer cladding carbon, then removes between the silica-based and carbon in Si-C composite material that the transition zone between silica-base material and carbon obtains and has certain hole.According to silica-base material microvolume expanded size of theory when embedding lithium, the thickness of transition zone is set, accurately can control the pore size between silica-based and carbon, thus effectively decrease the bulk effect of Si-C composite material, further increase the cycle performance of lithium ion battery.Carbon in this Si-C composite material improves conductivity and the high rate performance of this material.Carbon in this Si-C composite material improves Si-C composite material conductivity, improves the high rate performance of Si-C composite material.
The present embodiment prepares a kind of Si-C composite material by above-mentioned preparation method.
The present embodiment also provides a kind of lithium ion battery, and its negative pole contains above-mentioned Si-C composite material.
Embodiment 2
The present embodiment provides a kind of preparation method of Si-C composite material, comprises the following steps:
(1) prepare the aqueous solution of calcium chloride, then add silica flour, stir and silica flour is uniformly dispersed in the aqueous solution of calcium chloride.Under stirring, the aqueous solution of sodium carbonate is dripped in said mixture, winnofil on silica flour, and the aqueous solution of the sodium carbonate added excessive 2% is to ensure that calcium ions precipitate in the aqueous solution is complete, leaves standstill after 2 hours, suction filtration or centrifugal, washing 3 times, after super-dry, obtain the silica-base material that calcium carbonate is coated, wherein, the mass ratio of silica-base material and calcium carbonate is 1: 3.34.
(2) add in planetary ball mill by silica-base material coated for calcium carbonate and sucrose, with the rotating speed ball milling 5h of 280r/min, after mixing, now sucrose is coated on outside the coated silica-base material of calcium carbonate.And then sinter under putting into nitrogen atmosphere, 500 DEG C are heated to the heating rate of 4 DEG C/min, be incubated 4 hours, thus make sucrose carbonization become carbon, now at the silica-base material outer cladding carbon that calcium carbonate is coated, obtain carbon-to-carbon acid calcium-silicon based composite material, wherein, the heat decomposition temperature of calcium carbonate is 825 DEG C.
(3) carbon-to-carbon acid calcium-silicon based composite material is added in distilled water, after dispersed with stirring is even, again under stirring, drip dilute hydrochloric acid solution wherein to corrode calcium carbonate, and the dilute hydrochloric acid solution added excessive 2% is to ensure that calcium carbonate dissolves completely, then carry out centrifugal, washing 3 times, after super-dry, obtain Si-C composite material, wherein, the carbon in this Si-C composite material and the mass ratio of silica-base material are 3: 1.
As shown in Figure 1, the preparation process of Si-C composite material: step (1), at the outer winnofil 2 of silica-base material 1 silica flour, obtains the coated silica-base material of calcium carbonate 21; Step (2) at the coated silica-base material 1 outer cladding carbon 3 of calcium carbonate 2, Formed-calcium carbonate-silicon based composite material; Calcium carbonate 2 in carbon-to-carbon acid calcium-silicon based composite material is eroded by dilute hydrochloric acid solution by step (3), obtains Si-C composite material.The Si-C composite material obtained by this preparation method has nucleocapsid structure, wherein, carbon 3 is in the outside of silica-base material 1, and silica-base material 1 is the core of this nucleocapsid structure, carbon 3 is the shell of this nucleocapsid mechanism, the silica-base material 1 in this nucleocapsid structure and be the hole 4 of hollow between carbon 3.Shell in Si-C composite material and the hole between core 4 are the hole 4 between carbon 3 and silica-base material 1, this hole 4 accurately can be controlled by above-mentioned preparation process, the thickness being carried out the calcium carbonate 2 of precipitation on silica-base material 1 in rate-determining steps (1) by silica-base material 1 microvolume expanded size of theory when embedding lithium is controlled, this mainly controls the volume of calcium carbonate 2 by the quality controlling the calcium carbonate 2 be deposited on silica-base material 1, such as: the quality being deposited in the calcium carbonate 2 on silica-base material 1 in step (1) is larger, the thickness being namely deposited in the calcium carbonate 2 on silica-base material 1 is thicker, hole 4 between the carbon 3 of the Si-C composite material so finally obtained and silica-base material 1 is also larger.At the silica-base material 1 outer cladding sucrose that calcium carbonate 2 is coated in step (2), and then high temperature cabonization in a nitrogen atmosphere, the temperature of this carbonisation is mainly 500 DEG C, and the heat decomposition temperature of calcium carbonate 2 is 825 DEG C, so in sucrose carbonisation, calcium carbonate 2 still stable existence and can not thermal decomposition, carbon-to-carbon acid calcium-silicon composite is obtained by this step, in this material, silica-base material 1 is at innermost layer, calcium carbonate 2 is at the skin of silica-base material 1, carbon 3 is at the skin of calcium carbonate 2, and namely calcium carbonate 2 is between silica-base material 1 and carbon 3.Calcium carbonate 2 is eroded by watery hydrochloric acid in (3) by step, after eroding calcium carbonate 2 like this, just between silica-base material 1 and carbon 3, forms certain hole 4.Carbon 3 is not only comprised in this Si-C composite material, but also comprise silica-base material 1, because the volumetric expansion of carbon 3 is less, the specific capacity of silica-base material 1 is high, the advantage specific capacity that such Si-C composite material has silica-base material 1 is high, and the advantage volumetric expansion also while of this Si-C composite material with carbon 3 is less.This Si-C composite material volumetric expansion is little, be on the one hand because this Si-C composite material comprises carbon 3, so the advantage that the volumetric expansion with carbon 3 is little, on the other hand owing to there is certain hole 4, so make the bulk effect of Si-C composite material reduce between the silica-base material 1 of Si-C composite material and carbon 3.
Simple in the method for the outer winnofil 2 of silica-base material 1 silica flour in above-mentioned steps (1), calcium chloride water and aqueous sodium carbonate is used all to belong to the little solution of corrosivity, and aqueous sodium carbonate makes the reaction of calcium chloride precipitation be very easy to operate, cost is low, this step reaction efficiency is very high, to the waste of raw material less, waste reaction solution is few, makes the preparation method of whole Si-C composite material be convenient to large-scale industrial production.In step (1), the amount of winnofil 2 is very easy to control, thus makes the hole 4 between the silica-base material 1 of final obtained Si-C composite material and carbon 3 also be very easy to control.Silica-base material 1 in the Si-C composite material obtained by said method and between carbon 3, there is certain hole 4, so use the lithium ion battery of this Si-C composite material in charge and discharge process, effectively reduce the bulk effect of Si-C composite material, avoid powder of detached phenomenon, this Si-C composite material has higher specific energy.According to silica-base material microvolume expanded size when embedding lithium, the space size of the volumetric expansion of the silica-base material 1 in reserved this Si-C composite material corresponding in this Si-C composite material can be determined, thus effectively can alleviate volumetric expansion; Meanwhile, the housing in Si-C composite material is carbon 3, and this carbon 3 improves the conductivity of composite material, improves high rate performance and the cycle life of material; The kernel of this Si-C composite material is silica-base material 1, and this silica-base material 1 improves the specific capacity of composite material; Namely the Si-C composite material with nucleocapsid structure prepared in the present embodiment has the advantage of the chemical property of silica-base material 1 and carbon 3 simultaneously.
The present embodiment prepares a kind of Si-C composite material by above-mentioned preparation method.
The present embodiment also provides a kind of lithium ion battery, and its negative pole contains above-mentioned Si-C composite material.
The preparation method of battery pole piece is as follows:
By gained Si-C composite material respectively with conductive agent acetylene black, binding agent PVDF(Kynoar) mix according to mass ratio 8:1:1, use NMP(1-N-methyl-2-2-pyrrolidone N-) this mixture is modulated into slurry, evenly be coated on Copper Foil, put into baking oven, at 80 DEG C ~ 120 DEG C, dry 1h, take out and be washed into pole piece, 85 DEG C of vacuumize 12 hours, carry out compressing tablet, 85 DEG C of vacuumize 12 hours, obtained experimental cell pole piece.Be to electrode with lithium sheet, electrolyte is the LiPF of 1.2mol/L
6eC(ethyl carbonate ester)+DMC(dimethyl carbonate) (volume ratio 1:1) solution, barrier film is celgard2400 film, is assembled into CR2025 type button cell in the glove box being full of argon gas atmosphere.
As shown in Figure 2, charge-discharge performance test is carried out to this button cell: discharge and recharge by voltage be 0.01 ~ 1.5V, (wherein 1C=700mA/g be the condition of 0.1C at charging and discharging currents under, according to the test program of the Theoretical Design capacity setting battery of battery in the present embodiment, the value of material 1C is obtained again) by first charge-discharge test result, first discharge specific capacity is 839.78mAh/g, the specific discharge capacity after 100 times that circulates still remains on more than 647.09mAh/g, and the cyclical stability of battery is better.
As shown in Figure 3, high rate performance test is carried out to this button cell: discharge and recharge is 0.01 ~ 1.5V by voltage, and charging and discharging currents is respectively 0.1C, 0.2C, 0.5C, 1C, each circulation 10 times, wherein, 1C=700mA/g.High rate performance test result shows, 0.1C specific discharge capacity is about 710.96mAh/g, and 1C specific discharge capacity is still at more than 525mAh/g, and the high rate performance of battery is better.
Embodiment 3
The present embodiment provides a kind of preparation method of Si-C composite material, comprises the following steps:
(1) prepare the aqueous solution of barium nitrate, then add silicon monoxide (theoretical specific capacity of a silication silicon is about 1200mAh/g), stir and silicon monoxide is uniformly dispersed in the aqueous solution of barium nitrate.Under stirring, the aqueous solution of sodium carbonate is dripped in said mixture, barium carbonate on silicon monoxide, and the aqueous solution of the sodium carbonate added excessive 2% is to ensure that barium ions precipitation in the aqueous solution is completely, leaves standstill after 2 hours, suction filtration or centrifugal, washing 3 times, after super-dry, obtain the silicon monoxide material that brium carbonate is coated, wherein, the mass ratio of silicon monoxide and brium carbonate is 1: 6.5.
(2) by silicon monoxide material coated for brium carbonate and polyacrylonitrile manually ground and mixed evenly after, now polyacrylonitrile is coated on outside the coated silicon monoxide material of brium carbonate.And then sinter under putting into argon gas atmosphere, 800 DEG C are heated to the heating rate of 5 DEG C/min, be incubated 2 hours, thus make polyacrylonitrile carbonization become carbon, now at the silicon monoxide material outer cladding carbon that brium carbonate is coated, obtain carbon-to-carbon acid barium-silicon monoxide composite material, wherein, the heat decomposition temperature of brium carbonate is 1300 DEG C.
(3) carbon-to-carbon acid barium-silicon monoxide composite material is added in distilled water, after dispersed with stirring is even, again under stirring, drip dilute hydrochloric acid solution wherein to corrode brium carbonate, and the dilute hydrochloric acid solution added excessive 2% is to ensure that brium carbonate dissolves completely, then carry out centrifugal, washing 3 times, after super-dry, obtain Si-C composite material, wherein, the carbon in this Si-C composite material and the mass ratio of silicon monoxide are 1: 1.
The present embodiment prepares a kind of Si-C composite material by above-mentioned preparation method.
The present embodiment also provides a kind of lithium ion battery, and its negative pole contains above-mentioned Si-C composite material.
According to the method preparing button cell in embodiment 2, the obtained Si-C composite material of this comparative example is used to make button cell as negative material, and charge-discharge performance test is carried out to this battery: first discharge specific capacity reaches 998.651mAh/g, still more than 756.2mAh/g is remained on, the good cycling stability of this battery after 100 circulations.
Embodiment 4
The present embodiment provides a kind of preparation method of Si-C composite material, comprises the following steps:
(1) prepare the aqueous solution of strontium chloride, then add silicon copper, stir and silicon copper is uniformly dispersed in the aqueous solution of strontium chloride.Under stirring, the aqueous solution of potash is dripped in said mixture, silicon copper precipitates strontium carbonate, and the aqueous solution of the potash added excessive 2% is to ensure that strontium ion precipitation in the aqueous solution is completely, leaves standstill after 2 hours, suction filtration or centrifugal, washing 3 times, after super-dry, obtain the Si-Cu alloy material that strontium carbonate is coated, wherein, the mass ratio of silicon copper and strontium carbonate is 1: 4.5.
(2) Si-Cu alloy material coated for strontium carbonate, phenolic resins and sucrose are added magnetic agitation in ethanol, after mixing, dry, now phenolic resins and sucrose are coated on outside the coated Si-Cu alloy material of strontium carbonate jointly.And then sinter under putting into hydrogen atmosphere, 600 DEG C are heated to the heating rate of 3 DEG C/min, be incubated 5 hours, thus make the equal carbonization of phenolic resins and sucrose become carbon, now at the Si-Cu alloy material outer cladding carbon that strontium carbonate is coated, obtain carbon-to-carbon acid strontium-silicon copper composite material, wherein, the heat decomposition temperature of strontium carbonate is 1100 DEG C.
(3) carbon-to-carbon acid strontium-silicon copper composite material is added in distilled water, after dispersed with stirring is even, again under stirring, drip dilute hydrochloric acid solution wherein to corrode strontium carbonate, and the dilute hydrochloric acid solution added excessive 2% is to ensure that strontium carbonate dissolves completely, then carry out centrifugal, washing 3 times, after super-dry, obtain Si-C composite material, wherein, the carbon in this Si-C composite material and the mass ratio of silicon copper are 3: 17.
Silicon copper in this Si-C composite material is alloy due to it, this silicon copper is equivalent to copper facing on silicon, so silicon copper has good conductivity, and the theoretical specific capacity of silicon copper is about 4200mAh/g, therefore the Si-C composite material including this silicon copper has good conductivity, and then makes the lithium ion battery using this Si-C composite material have extraordinary cyclical stability (namely the life-span is long) and high rate capability.
The present embodiment prepares a kind of Si-C composite material by above-mentioned preparation method.
The present embodiment also provides a kind of lithium ion battery, and its negative pole contains above-mentioned Si-C composite material.
According to the method preparing button cell in embodiment 2, the obtained Si-C composite material of this comparative example is used to make button cell as negative material, and charge-discharge performance test is carried out to this battery: first discharge specific capacity reaches 2765.65mAh/g, still more than 1852.986mAh/g is remained on, the good cycling stability of this battery after 100 circulations.
Embodiment 5
The present embodiment provides a kind of preparation method of Si-C composite material, comprises the following steps:
(1) prepare the aqueous solution of magnesium nitrate, then add the mixture (wherein, the mass ratio of silica flour and silicon monoxide is 1: 1) of silica flour and silicon monoxide, stir and silica flour and silicon monoxide are all uniformly dispersed in the aqueous solution of magnesium nitrate.Under stirring, drip the aqueous solution of ammonium carbonate more wherein, equal precipitated magnesium carbonate on silica flour and silicon monoxide, and the aqueous solution of the ammonium carbonate added excessive 2% is to ensure that magnesium ion precipitation in the aqueous solution is completely, leaves standstill after 2 hours, suction filtration or centrifugal, washing 3 times, after super-dry, obtain the coated silicon materials of magnesium carbonate and the coated silicon monoxide material of magnesium carbonate, wherein, the quality of silicon and silicon monoxide and be 1: 2.2 with the mass ratio of magnesium carbonate.
(2) silicon materials coated for magnesium carbonate and polyvinyl alcohol are added in planetary ball mill, with the rotating speed ball milling 6h of 300r/min, after mixing, now, polyvinyl alcohol is coated on outside the coated silicon materials of magnesium carbonate, and polyvinyl alcohol is coated on outside the coated silicon monoxide material of magnesium carbonate.And then sinter under putting into nitrogen atmosphere, 300 DEG C are heated to the heating rate of 3 DEG C/min, be incubated 2 hours, thus make polyvinyl alcohol carbonization become carbon, now at the coated silicon materials outer cladding carbon of magnesium carbonate and at the coated silicon monoxide material outer cladding carbon of magnesium carbonate, obtain the mixture of carbon-to-carbon acid magnesium-silicon composite material and carbon-to-carbon acid magnesium-silicon monoxide composite material, wherein, the heat decomposition temperature of magnesium carbonate is 350 DEG C.
(3) mixture of carbon-to-carbon acid magnesium-silicon composite material and carbon-to-carbon acid magnesium-silicon monoxide composite material is added in distilled water, after dispersed with stirring is even, again under stirring, drip dilute hydrochloric acid solution wherein to corrode magnesium carbonate, and the dilute hydrochloric acid solution added excessive 2% is to ensure that magnesium carbonate dissolves completely, then carry out centrifugal, washing 3 times, after super-dry, obtain Si-C composite material, wherein, the carbon in this Si-C composite material and the quality of silicon and silicon monoxide and mass ratio be 1: 19.
The present embodiment prepares a kind of Si-C composite material by above-mentioned preparation method.
The present embodiment also provides a kind of lithium ion battery, and its negative pole contains above-mentioned Si-C composite material.
According to the method preparing button cell in embodiment 2, the obtained Si-C composite material of this comparative example is used to make button cell as negative material, and charge-discharge performance test is carried out to this battery: first discharge specific capacity reaches 1006.365mAh/g, still more than 805.6mAh/g is remained on, the good cycling stability of this battery after 100 circulations.
Embodiment 6
The present embodiment provides a kind of preparation method of Si-C composite material, comprises the following steps:
(1) prepare the aqueous solution of calcium acetate, then add silicon silver alloy, stir and silicon silver alloy is uniformly dispersed in the aqueous solution of calcium acetate.Under stirring, the aqueous solution of potash is dripped in said mixture, winnofil on silicon silver alloy, and the aqueous solution of the potash added excessive 2% is to ensure that calcium ions precipitate in the aqueous solution is complete, leaves standstill after 2 hours, suction filtration or centrifugal, washing 3 times, after super-dry, obtain the silicon silver alloy that calcium carbonate is coated, wherein, the mass ratio of silicon silver alloy and calcium carbonate is 2: 3.
(2) add in planetary ball mill by silicon silver alloy coated for calcium carbonate and pitch, with the rotating speed ball milling 5h of 320r/min, after mixing, now pitch-coating is outside the silicon silver alloy that calcium carbonate is coated.And then sinter under putting into argon gas atmosphere, 550 DEG C are heated to the heating rate of 4 DEG C/min, be incubated 8 hours, thus make bitumencarb change into carbon, now at the silicon silver alloy outer cladding carbon that calcium carbonate is coated, obtain carbon-to-carbon acid calcium-silicon silver alloy composite material, wherein, the heat decomposition temperature of calcium carbonate is 825 DEG C.
(3) carbon-to-carbon acid calcium-silicon silver alloy composite material is added in distilled water, after dispersed with stirring is even, again under stirring, drip dilute hydrochloric acid solution wherein to corrode calcium carbonate, and the dilute hydrochloric acid solution added excessive 2% is to ensure that calcium carbonate dissolves completely, then carry out centrifugal, washing 3 times, after super-dry, obtain Si-C composite material, wherein, the carbon in this Si-C composite material and the mass ratio of silicon silver alloy are 9: 1.
The present embodiment prepares a kind of Si-C composite material by above-mentioned preparation method.
The present embodiment also provides a kind of lithium ion battery, and its negative pole contains above-mentioned Si-C composite material.
According to the method preparing button cell in embodiment 2, the obtained Si-C composite material of this comparative example is used to make button cell as negative material, and charge-discharge performance test is carried out to this battery: first discharge specific capacity reaches 635.852mAh/g, still more than 552.56mAh/g is remained on, the good cycling stability of this battery after 100 circulations.
Embodiment 7
The present embodiment provides a kind of preparation method of Si-C composite material, comprises the following steps:
(1) prepare the aqueous solution of strontium chloride, then add silicon nickel alloy, stir and silicon nickel alloy is uniformly dispersed in the aqueous solution of strontium chloride.Under stirring, the aqueous solution of ammonium carbonate is dripped in said mixture, silicon nickel alloy precipitates strontium carbonate, and the aqueous solution of the ammonium carbonate added excessive 2% is to ensure that strontium ion precipitation in the aqueous solution is completely, leaves standstill after 2 hours, suction filtration or centrifugal, washing 3 times, after super-dry, obtain the silicon nickel alloy material that strontium carbonate is coated, wherein, the mass ratio of silicon nickel alloy and strontium carbonate is 1: 9.
(2) add in planetary ball mill by silicon nickel alloy material coated for strontium carbonate and polyvinyl chloride, with the rotating speed ball milling 5h of 280r/min, after mixing, now polyvinyl chloride is coated on outside the coated silicon nickel alloy material of strontium carbonate.And then sinter under putting into nitrogen atmosphere, 650 DEG C are heated to the heating rate of 4 DEG C/min, be incubated 1 hour, thus make polyvinyl chloride carbonization become carbon, now at the silicon nickel alloy material outer cladding carbon that strontium carbonate is coated, obtain carbon-to-carbon acid strontium-silicon nickel alloy composite material, wherein, the heat decomposition temperature of strontium carbonate is 1100 DEG C.
(3) carbon-to-carbon acid strontium-silicon nickel alloy composite material is added in distilled water, after dispersed with stirring is even, again under stirring, drip dilute hydrochloric acid solution wherein to corrode strontium carbonate, because the nickel in silicon nickel alloy also reacts with watery hydrochloric acid, so the dilute hydrochloric acid solution added excessive 2% is to ensure that strontium carbonate and nickel dissolve all completely, carry out again centrifugal, washing 3 times, after super-dry, obtain Si-C composite material, wherein, the carbon in this Si-C composite material and the mass ratio of silicon are 2: 3.
The present embodiment prepares a kind of Si-C composite material by above-mentioned preparation method.
The present embodiment also provides a kind of lithium ion battery, and its negative pole contains above-mentioned Si-C composite material.
Embodiment 8
The present embodiment provides a kind of preparation method of Si-C composite material, comprises the following steps:
(1) prepare the mixed aqueous solution of zinc nitrate and plumbi nitras, then add silica flour, stir and silica flour is uniformly dispersed in the mixed aqueous solution of zinc nitrate and plumbi nitras.Under stirring, the aqueous solution of sodium carbonate is dripped in said mixture, now zinc nitrate and plumbi nitras generation coprecipitation reaction, silica flour precipitates zinc carbonate and ceruse simultaneously, and the aqueous solution of the sodium carbonate added excessive 2% is to ensure that zinc ion in the aqueous solution and lead ion all precipitate completely, leave standstill after 2 hours, suction filtration or centrifugal, washing 3 times, after super-dry, obtain zinc carbonate and the jointly coated silicon materials of ceruse, wherein, silicon and zinc carbonate and ceruse quality and mass ratio be 1: 3.2.
(2) add in planetary ball mill by zinc carbonate and the jointly coated silicon materials of ceruse, glucose, with the rotating speed ball milling 5h of 280r/min, after mixing, now glucose is coated on outside zinc carbonate and the jointly coated silicon materials of ceruse.And then sinter under putting into nitrogen atmosphere, 250 DEG C are heated to the heating rate of 4 DEG C/min, be incubated 4 hours, thus make the equal carbonization of glucose become carbon, now at zinc carbonate and the jointly coated silicon materials outer cladding carbon of ceruse, obtain carbon-to-carbon acid zinc/ceruse-silicon composite, wherein, the heat decomposition temperature of zinc carbonate is 300 DEG C, and the heat decomposition temperature of ceruse is 315 DEG C.
(3) carbon-to-carbon acid zinc/ceruse-silicon composite is added in distilled water, after dispersed with stirring is even, again under stirring, drip dilute nitric acid solution wherein to corrode zinc carbonate, ceruse, and the dilute nitric acid solution added excessive 2% is to ensure that zinc carbonate and ceruse dissolve all completely, then carry out centrifugal, washing 3 times, after super-dry, obtain Si-C composite material, wherein, the carbon in this Si-C composite material and the mass ratio of silicon are 3: 2.
The present embodiment prepares a kind of Si-C composite material by above-mentioned preparation method.
The present embodiment also provides a kind of lithium ion battery, and its negative pole contains above-mentioned Si-C composite material.
Be understandable that, the illustrative embodiments that above execution mode is only used to principle of the present invention is described and adopts, but the present invention is not limited thereto.For those skilled in the art, without departing from the spirit and substance in the present invention, can make various modification and improvement, these modification and improvement are also considered as protection scope of the present invention.
Claims (13)
1. a preparation method for Si-C composite material, is characterized in that, comprises the following steps:
(1) transition zone is set on silica-base material, obtains the silica-base material that described transition zone is coated;
(2) at the silica-base material outer cladding carbon that described transition zone is coated, carbon-transition zone-silicon based composite material is obtained;
(3) remove described transition zone, obtain Si-C composite material;
Described step is specially:
(1) on described silica-base material, precipitate metal carbonate transition zone, obtain the silica-base material that this metal carbonate is coated;
(2) carbon described in the coated silica-base material outer cladding of described transition metal carbonate, obtain carbon-metal carbonate-silicon based composite material, wherein, the heat decomposition temperature of described transition metal carbonate is higher than the temperature in the process of the described silica-base material outer cladding carbon coated at described metal carbonate;
(3) use acid solution to erode described metal carbonate, obtain described Si-C composite material.
2. the preparation method of Si-C composite material according to claim 1, is characterized in that, the mass ratio of described silica-base material and described metal carbonate is (1: 9) ~ (2: 3).
3. the preparation method of Si-C composite material according to claim 2, is characterized in that, the mass ratio of described silica-base material and described metal carbonate is (1: 6.5) ~ (1: 3.2).
4. the preparation method of Si-C composite material according to claim 1, is characterized in that, the described carbon in described Si-C composite material and the mass ratio of described silica-base material are (1: 19) ~ (9: 1).
5. the preparation method of Si-C composite material according to claim 4, is characterized in that, the described carbon in described Si-C composite material and the mass ratio of described silica-base material are (3: 17) ~ (3: 2).
6. the preparation method of Si-C composite material according to claim 1, is characterized in that, described carbonate comprise in magnesium carbonate, calcium carbonate, strontium carbonate, brium carbonate, zinc carbonate, ceruse any one or a few.
7. the preparation method of Si-C composite material according to claim 1, is characterized in that, described silica-base material comprise in silicon, silicon monoxide, silicon alloy any one or a few.
8. the preparation method of Si-C composite material according to claim 7, is characterized in that, described silicon alloy is silicon silver alloy, silicon copper, any one or a few in silicon nickel alloy.
9. the preparation method of Si-C composite material according to claim 1, it is characterized in that, described step (2) is specially: after being mixed with carbon source by silica-base material coated for described metal carbonate, calcination is carried out under nonoxidizing atmosphere, described calcination temperature is 250 DEG C ~ 800 DEG C, obtains described carbon-metal carbonate-silicon based composite material.
10. the preparation method of Si-C composite material according to claim 9, is characterized in that, described carbon source is any one or a few in polyvinyl alcohol, sucrose, glucose, polyacrylonitrile, phenolic resins, polyvinyl chloride, pitch.
The preparation method of 11. Si-C composite materials according to claim 1, it is characterized in that, described step (1) is specially: by the aqueous solution of described silica-base material and slaine, then add carbonate deposition agent, obtain the silica-base material that described metal carbonate is coated.
12. 1 kinds of Si-C composite materials, is characterized in that, it is prepared by the preparation method described in claim 1 ~ 11 any one.
13. 1 kinds of lithium ion batteries, is characterized in that, its negative pole contains Si-C composite material according to claim 12.
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