CN102983317A - Silicon-based composite material and preparation method thereof, silicon-carbon composite material and lithium ion battery - Google Patents
Silicon-based composite material and preparation method thereof, silicon-carbon composite material and lithium ion battery Download PDFInfo
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- CN102983317A CN102983317A CN2012105159871A CN201210515987A CN102983317A CN 102983317 A CN102983317 A CN 102983317A CN 2012105159871 A CN2012105159871 A CN 2012105159871A CN 201210515987 A CN201210515987 A CN 201210515987A CN 102983317 A CN102983317 A CN 102983317A
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- 239000002131 composite material Substances 0.000 title claims abstract description 73
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 62
- 239000010703 silicon Substances 0.000 title claims abstract description 62
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 61
- 238000002360 preparation method Methods 0.000 title claims abstract description 53
- 239000002153 silicon-carbon composite material Substances 0.000 title claims abstract description 40
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 21
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 20
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 70
- 239000000843 powder Substances 0.000 claims abstract description 39
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 31
- 238000000034 method Methods 0.000 claims abstract description 26
- 239000007833 carbon precursor Substances 0.000 claims abstract description 12
- 239000011248 coating agent Substances 0.000 claims abstract description 10
- 238000000576 coating method Methods 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 10
- 229910002804 graphite Inorganic materials 0.000 claims description 27
- 239000010439 graphite Substances 0.000 claims description 27
- 239000008187 granular material Substances 0.000 claims description 15
- 239000000725 suspension Substances 0.000 claims description 14
- 239000011159 matrix material Substances 0.000 claims description 13
- 238000005255 carburizing Methods 0.000 claims description 12
- 239000003153 chemical reaction reagent Substances 0.000 claims description 12
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 12
- 239000003575 carbonaceous material Substances 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 8
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 6
- 229930006000 Sucrose Natural products 0.000 claims description 6
- 239000005720 sucrose Substances 0.000 claims description 6
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 4
- 239000002202 Polyethylene glycol Substances 0.000 claims description 4
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 4
- 229920002125 Sokalan® Polymers 0.000 claims description 4
- 239000006230 acetylene black Substances 0.000 claims description 4
- 239000002041 carbon nanotube Substances 0.000 claims description 4
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 4
- 239000008103 glucose Substances 0.000 claims description 4
- 229910021389 graphene Inorganic materials 0.000 claims description 4
- 239000007770 graphite material Substances 0.000 claims description 4
- 239000004584 polyacrylic acid Substances 0.000 claims description 4
- 229920001223 polyethylene glycol Polymers 0.000 claims description 4
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 4
- 239000000835 fiber Substances 0.000 claims description 3
- 239000007921 spray Substances 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 47
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 16
- 150000001875 compounds Chemical class 0.000 abstract description 14
- 230000008569 process Effects 0.000 abstract description 13
- 239000000758 substrate Substances 0.000 abstract description 3
- 229910052814 silicon oxide Inorganic materials 0.000 abstract 2
- 238000003763 carbonization Methods 0.000 abstract 1
- 238000005562 fading Methods 0.000 abstract 1
- 238000000498 ball milling Methods 0.000 description 42
- 238000011056 performance test Methods 0.000 description 17
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 14
- 239000010406 cathode material Substances 0.000 description 12
- 238000012360 testing method Methods 0.000 description 12
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 7
- 229910052786 argon Inorganic materials 0.000 description 7
- 229910052744 lithium Inorganic materials 0.000 description 7
- 239000002243 precursor Substances 0.000 description 7
- 239000000377 silicon dioxide Substances 0.000 description 7
- 229910000831 Steel Inorganic materials 0.000 description 6
- 230000004087 circulation Effects 0.000 description 6
- 239000005543 nano-size silicon particle Substances 0.000 description 6
- 238000001694 spray drying Methods 0.000 description 6
- 239000010959 steel Substances 0.000 description 6
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 4
- 239000010405 anode material Substances 0.000 description 3
- 235000013339 cereals Nutrition 0.000 description 3
- 235000013312 flour Nutrition 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 230000004888 barrier function Effects 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- -1 ethyl carbonate ester Chemical class 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910021487 silica fume Inorganic materials 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 229910018540 Si C Inorganic materials 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 239000011263 electroactive material Substances 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 150000003376 silicon Chemical class 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention provides a silicon-based composite material and a preparation method thereof, a silicon-carbon composite material, and a lithium ion battery containing the materials, belongs to the technical field of lithium ion batteries, and can solve the problem of capacity fading caused by a volume effect of the existing silicon-based composite material and the lithium ion battery prepared by using the silicon-based composite material in the charge and discharge processes. The preparation method of the silicon-based composite material, disclosed by the invention, comprises the steps of: mixing SiOx (x is smaller than or equal to 1.5 and greater than or equal to 0.5) and a conductive carbon substrate to obtain compound powder of the SiOx ( the x is smaller than or equal to 1.5 and greater than or equal to 0.5); and coating the compound powder by a carbon precursor to obtain a coating and carrying out carbonization reaction on the coating. The silicon-based composite material and the silicon-carbon composite material with an excellent cycle performance are obtained by selecting proper technological parameters, and the lithium ion battery containing the materials is prepared. The composite materials disclosed by the invention are prepared by using the method, and the lithium ion battery disclosed by the invention contains the composite materials.
Description
Technical field
The invention belongs to technical field of lithium ion, be specifically related to a kind of silicon based composite material and preparation method thereof, Si-C composite material, contain the lithium ion battery of Si-C composite material.
Background technology
At present, the lithium ion battery of production and application mainly adopts the graphite negative electrodes material, but the theoretical embedding lithium capacity of graphite is 372mAh/g, and reality has reached 370mAh/g, therefore, the graphite negative electrodes material on capacity almost without room for promotion.
The nearly more than ten years, various novel high power capacity and high magnification negative material are developed, wherein silica-base material is owing to its high specific discharge capacity (theoretical specific capacity of silicon is 4200mAh/g) becomes study hotspot, yet this material is accompanied by serious volumetric expansion and contraction in the doff lithium process, cause the electroactive material powder of detached on the electrode, finally cause capacity attenuation.In order to overcome the special capacity fade of silicon based anode material, generally be that silicon and other inactive metals (such as Fe, Al, Cu etc.) are formed alloy, disclose silicon aluminium alloy/carbon composite material used for lithium ion battery negative electrode and preparation method thereof such as Chinese patent application CN03116070.0; Or material evenly spread to form composite material (such as Si-C, Si-TiN etc.) in other activity or the non-active material, Si-C composite material and the preparation method of used as negative electrode of Li-ion battery height ratio capacity disclosed such as Chinese patent application CN02112180.X.
Although said method has been alleviated the capacity attenuation of silicon based anode material to a certain extent, but because the business-like nano silica fume that said method adopts even micron silica flour, silica flour is difficult to reach nano level and is uniformly dispersed in matrix, so can not fundamentally suppress the bulk effect in the charge and discharge process, capacity still can the quickly decay along with the increase of cycle-index.People (the Hongfa Xiang such as Wu Jishan, Kai Zhang, Ge Ji, JimYang Lee, Changji Zou, Xiaodong Chen, Jishan Wu, CARBON 49 (2011) 1787-1796) reported the method that Graphene directly mixes synthetic composite negative pole material with nano silica fume, resulting materials shows preferably cycle performance, 30 specific capacities that circulate can also keep 1600mAh/g, but still have the problem of slow-decay.Therefore, make silica flour in matrix, reach nano level being uniformly dispersed, thereby the bulk effect of establishment silicon avoid capacity attenuation to become the research and development focus in high power capacity silicon based anode material field.
Summary of the invention
The objective of the invention is to solve silicon based composite material that art methods makes and lithium ion battery prepared therefrom in charge and discharge process bulk effect and the problem of the capacity attenuation that causes provides the preparation method of the good silicon based composite material of a kind of cycle performance.
The technical scheme that solution the technology of the present invention problem adopts is a kind of preparation method of silicon based composite material, comprising:
Step 1) is with SiO
x(0.5≤x≤1.5) powder and conductive carbon matrix batch mixing obtain SiO
xThe composite granule of (0.5≤x≤1.5)/C;
Step 2) with SiO
xThe composite granule of (0.5≤x≤1.5)/C coats with the carbon precursor and obtains coating;
Step 3) is carried out carburizing reagent with coating.
The present invention passes through SiO
x(0.5≤x≤1.5) powder and conductive carbon matrix batch mixing obtain SiO
xThe composite granule of (0.5≤x≤1.5)/C, and the carbon precursor is coated on SiO equably
xThe high temperature cabonization reaction is carried out, afterwards at SiO in the composite granule surface of (0.5≤x≤1.5)/C
xThe surface of the composite granule of (0.5≤x≤1.5)/C forms one deck conductive carbon layer, simultaneously SiO
x(0.5≤x≤1.5) particle generation disproportionated reaction, original position generates silicon nanoparticle and silicon dioxide, because silicon grain wherein is generated in-situ, so its size little (nanometer scale), and be dispersed in the silica substrate Direct Uniform, can not produce reunion.Wherein silicon nanoparticle is embedding lithium active particle, and silica substrate mainly plays peptizaiton, stops silicon nanoparticle " electrochemistry sintering " to occur and be agglomerated into bulky grain in repetition doff lithium process; On the other hand since silicon dioxide in the doff lithium process without change in volume, so the bulk effect of whole particle also greatly reduces, so that form good electrically contacting and always maintenance between the conductivity skeleton that nano silicon particles and carbon granule connect into, thereby the speed of effectively having slowed down capacity attenuation.
Preferably, described SiO
xX in the powder is 0.8-1.2;
Further preferably, described SiO
xThe mass ratio of (0.5≤x≤1.5) powder and conductive carbon material is 1/9-9;
Described conductive carbon material is one or more in Graphene, carbon nano-tube, gas-phase growth of carbon fibre, graphite, expanded graphite and the acetylene black.
Preferably, with SiO
xThe composite granule of (0.5≤x≤1.5)/C and carbon precursor are added to the water stirring and obtain suspension, and described spray dried is obtained coating;
Wherein, the quality of described water and SiO
xThe ratio of the composite granule of (0.5≤x≤1.5)/C and the gross mass of carbon precursor is 3-15; Described spray-dired inlet temperature is 250 ℃-350 ℃, and outlet temperature is 80 ℃-120 ℃.
Preferably, described carbon precursor and SiO
xSiO in the composite granule of (0.5≤x≤1.5)/C
xMass ratio be 0.2-5;
Described carbon precursor is one or more in polyethylene glycol, polyvinyl alcohol, polyacrylic acid, citric acid, sucrose and the glucose.
Preferably, the temperature of described carburizing reagent is 700 ℃-1200 ℃, and the carburizing reagent time is 0.5h-24h.
Because the adding of the carbon granule of high conductivity forms conducting matrix grain, is convenient to electric transmission, also have certain doff lithium capacity such as graphite itself simultaneously, further increase the specific capacity of silicon based composite material.
Technical problem to be solved by this invention also comprises, for silicon based composite material and lithium ion battery prepared therefrom in charge and discharge process bulk effect and the problem of the capacity attenuation that causes provides a kind of cycle performance good silicon based composite material.
The technical scheme that solution the technology of the present invention problem adopts is a kind of silicon based composite material, and it is the said method preparation.
Because silicon based composite material of the present invention is by the said method preparation, its cycle performance is good.
Technical problem to be solved by this invention also comprises, for Si-C composite material and lithium ion battery prepared therefrom in charge and discharge process bulk effect and the problem of the capacity attenuation that causes provides a kind of cycle performance good Si-C composite material.
The technical scheme that solution the technology of the present invention problem adopts is a kind of Si-C composite material, be that the silicon based composite material of 5%-30% and the graphite material of surplus form by mass fraction, wherein: described silicon based composite material is by the described method preparation of any one among the claim 1-7; The first efficient of described graphite material is greater than 95%.
Because Si-C composite material of the present invention is by the said method preparation, its cycle performance is good.
Technical problem to be solved by this invention also comprises, for existing lithium ion battery by the Si-C composite material preparation in charge and discharge process bulk effect and the problem of the capacity attenuation that causes provides a kind of cycle performance good lithium ion battery.
The technical scheme that solution the technology of the present invention problem adopts is a kind of lithium ion battery, and its negative pole contains above-mentioned Si-C composite material.
The invention provides a kind of generated in-situ nano-silicon and make this nano-silicon in the preparation method of the finely dispersed silicon based composite material of nanoscale, and with this silicon based composite material and graphite-made standby height ratio capacity (800mAh/g) Si-C composite material.Raw material of the present invention is cheap and easy to get, preparation technology is simple, flow process is short, process is controlled easily, realize that easily suitability for industrialized production, resulting materials have good cycle performance.
Description of drawings
Fig. 1 is the cycle performance figure of the prepared Si-C composite material of the embodiment of the invention 1.
Embodiment
For making those skilled in the art understand better technical scheme of the present invention, below in conjunction with the drawings and specific embodiments the present invention is described in further detail.
Embodiment 1
Present embodiment provides a kind of preparation method of silicon based composite material, comprising:
(1) SiO
x(0.5≤x≤1.5) powder and conductive carbon material batch mixing
To treat ball milling material SiO
0.9Powder (300 order) and adding as the graphite (150 order) of high conductivity material with carbon element in the ball grinder of planetary ball mill, wherein SiO
0.9With the mass ratio of graphite be 1/9; The ball milling pearl is that diameter is the steel ball of 20mm and 60mm, and wherein the ball milling pearl treats that the mass ratio of ball milling material is 6; The rotating speed of ball milling is 400 rev/mins, and ball milling 4h obtains compound.
(2) carbon coated presoma
Get above-mentioned compound, add entry, wherein the mass ratio of water and compound is 5; Adding is as polyvinyl alcohol and the sucrose of carbon matrix precursor, wherein carbon matrix precursor and SiO
0.9The mass ratio of powder is 5, and wherein the mass ratio of polyvinyl alcohol and sucrose is 1 ︰ 1; Above-mentioned material stirring evenly obtains suspension, and this suspension is carried out spray drying, and wherein air inlet temperature is 250 ℃, and air outlet temperature is 100 ℃, makes dry powder.
(3) carburizing reagent
Get above-mentioned dry powder and pack in the crucible, 5 ℃/minute are warmed up to 700 ℃ under argon shield, are incubated 24 hours, make silicon based composite material.
(4) preparation Si-C composite material
The above-mentioned silicon based composite material that makes and efficient first are mixed with Si-C composite material greater than 95% graphite cathode material (commercially available high-end graphite cathode material), and wherein silicon based composite material accounts for 5% at Si-C composite material.
(5) cycle performance test
With prepared Si-C composite material preparation experiment battery pole piece and test battery.
The preparation experiment battery with the process of pole piece is: with the gained Si-C composite material respectively with conductive agent acetylene black, binding agent PVDF(Kynoar) mix according to mass ratio 8 ︰ 1 ︰ 1, use the NMP(1-N-methyl-2-2-pyrrolidone N-) this mixture is modulated into slurry, evenly be coated on the Copper Foil, put into baking oven, 100 ℃ of vacuumize 24 hours, taking-up is washed into pole piece, at 85 ℃ of lower vacuumize 12h, carry out compressing tablet, at 85 ℃ of lower vacuumize 12h, make experimental cell and make the experimental cell pole piece with pole piece.
The process of preparation test battery is: take the pole piece of above-mentioned preparation as negative pole, take the lithium sheet as to electrode, electrolyte is that concentration is the solution of the LiPF6 of 1mol/L, its solvent is EC(ethyl carbonate ester)+the DMC(dimethyl carbonate), EC(ethyl carbonate ester wherein) and the DMC(dimethyl carbonate) volume ratio be 1 ︰ 1, barrier film is the celgard2400 film, is assembled into CR2025 type button cell in being full of the glove box of argon gas atmosphere.
At constant current 0.1C(1C=220mA/g) condition under carry out cycle performance test, this material first discharge specific capacity is 1192mAh/g, after 100 circulations, capacity is about 818mAh/g.
As shown in Figure 1.The Si-C composite material discharge cycles of present embodiment preparation is functional.
Embodiment 2
Present embodiment provides a kind of preparation method of silicon based composite material, comprising:
(1) SiO
x(0.5≤x≤1.5) powder and conductive carbon material batch mixing
To treat ball milling material SiO
1.5(300 order) and add as the carbon nano-tube (150 order) of high conductivity material with carbon element in the ball grinder of planetary ball mill, wherein SiO
1.5With the mass ratio of carbon nano-tube be 0.5; The ball milling pearl is that diameter is the steel ball of 20mm and 60mm, and wherein the ball milling pearl treats that the mass ratio of ball milling material is 6; The rotating speed of ball milling is 300 rev/mins, and ball milling 2h obtains compound.
(2) carbon coated presoma
Get above-mentioned compound, add entry, wherein the mass ratio of water and compound is 12; Adding is as the sucrose of carbon matrix precursor, wherein sucrose and SiO
1.5The mass ratio of powder is 3; Above-mentioned material stirring evenly obtains suspension, and this suspension is carried out spray drying, and wherein air inlet temperature is 350 ℃, and air outlet temperature is 120 ℃, makes dry powder.
(3) carburizing reagent
Get above-mentioned dry powder and pack in the crucible, 5 ℃/minute are warmed up to 900 ℃ under argon shield, are incubated 6 hours, make silicon based composite material.
(4) preparation Si-C composite material
The above-mentioned silicon based composite material that makes and efficient first are mixed with Si-C composite material greater than 95% graphite cathode material (commercially available high-end graphite cathode material), and wherein silicon based composite material accounts for 20% at Si-C composite material.
(5) cycle performance test
The experimental cell of cycle performance test usefulness uses the preparation method of pole piece and test battery identical with the preparation method of pole piece and test battery with the experimental cell among the embodiment 1.
At constant current 0.1C(1C=220mA/g) condition under carry out cycle performance test, this material first discharge specific capacity is 1205mAh/g, after 100 circulations, capacity is about 657mAh/g.
Embodiment 3
Present embodiment provides a kind of preparation method of silicon based composite material, comprising:
(1) SiO
x(0.5≤x≤1.5) powder and conductive carbon material batch mixing
To treat ball milling material SiO
0.5Powder (300 order) and adding as the expanded graphite (150 order) of high conductivity material with carbon element in the ball grinder of planetary ball mill, wherein SiO
0.5With the mass ratio of graphite be 9; The ball milling pearl is that diameter is the steel ball of 20mm and 60mm, and wherein the ball milling pearl treats that the mass ratio of ball milling material is 6; The rotating speed of ball milling is 500 rev/mins, and ball milling 8h obtains compound.
(2) carbon coated presoma
Get above-mentioned compound, add entry, wherein the mass ratio of water and compound is 7; Adding is as the glucose of carbon matrix precursor, wherein glucose and SiO
0.5The mass ratio of powder is 0.5; Above-mentioned material stirring evenly obtains suspension, and this suspension is carried out spray drying, and wherein air inlet temperature is 300 ℃, and air outlet temperature is 80 ℃, makes dry powder.
(3) carburizing reagent
Get above-mentioned dry powder and pack in the crucible, 5 ℃/minute are warmed up to 1200 ℃ under argon shield, are incubated 0.5 hour, make silicon based composite material.
(4) preparation Si-C composite material
The above-mentioned silicon based composite material that makes and efficient first are mixed with Si-C composite material greater than 95% graphite cathode material (commercially available high-end graphite cathode material), and wherein silicon based composite material accounts for 15% at Si-C composite material.
(5) cycle performance test
The experimental cell of cycle performance test usefulness uses the preparation method of pole piece and test battery identical with the preparation method of pole piece and test battery with the experimental cell among the embodiment 1.
At constant current 0.1C(1C=220mA/g) condition under carry out cycle performance test, this material first discharge specific capacity is 1152mAh/g, after 100 circulations, capacity is about 531mAh/g.
Embodiment 4
Present embodiment provides a kind of preparation method of silicon based composite material, comprising:
(1) SiO
x(0.5≤x≤1.5) powder and conductive carbon material batch mixing
To treat ball milling material SiO
1.2Powder (300 order) and adding as the acetylene black (150 order) of high conductivity material with carbon element in the ball grinder of planetary ball mill, wherein SiO
1.2With the mass ratio of graphite be 3; The ball milling pearl is that diameter is the steel ball of 20mm and 60mm, and wherein the ball milling pearl treats that the mass ratio of ball milling material is 6; The rotating speed of ball milling is 350 rev/mins, and ball milling 12h obtains compound.
(2) carbon coated presoma
Get above-mentioned compound, add entry, wherein the mass ratio of water and compound is 15; Adding is as the polyacrylic acid of carbon matrix precursor, wherein polyacrylic acid and SiO
1.2The mass ratio of powder is 0.8; Above-mentioned material stirring evenly obtains suspension, and this suspension is carried out spray drying, and wherein air inlet temperature is 280 ℃, and air outlet temperature is 90 ℃, makes dry powder.
(3) carburizing reagent
Get above-mentioned dry powder and pack in the crucible, 5 ℃/minute are warmed up to 1000 ℃ under argon shield, are incubated 1 hour, make silicon based composite material.
(4) preparation Si-C composite material
The above-mentioned silicon based composite material that makes and efficient first are mixed with Si-C composite material greater than 95% graphite cathode material (commercially available high-end graphite cathode material), and wherein silicon based composite material accounts for 25% at Si-C composite material.
(5) cycle performance test
The experimental cell of cycle performance test usefulness uses the preparation method of pole piece and test battery identical with the preparation method of pole piece and test battery with the experimental cell among the embodiment 1.
At constant current 0.1C(1C=220mA/g) condition under carry out cycle performance test, this material first discharge specific capacity is 1056mAh/g, after 100 circulations, capacity is about 637mAh/g.
Embodiment 5
Present embodiment provides a kind of preparation method of silicon based composite material, comprising:
(1) SiO
x(0.5≤x≤1.5) powder and conductive carbon material batch mixing
To treat ball milling material SiO
0.8Powder (300 order) and adding as the Graphene (150 order) of high conductivity material with carbon element in the ball grinder of planetary ball mill, wherein SiO
0.8With the mass ratio of graphite be 0.9; The ball milling pearl is that diameter is the steel ball of 20mm and 60mm, and wherein the ball milling pearl treats that the mass ratio of ball milling material is 6; The rotating speed of ball milling is 450 rev/mins, and ball milling 10h obtains the ball milling material.
(2) carbon coated presoma
Get above-mentioned ball milling material, add entry, wherein the mass ratio of water and ball milling material is 10; Adding is as the citric acid of carbon matrix precursor, wherein citric acid and SiO
0.8The mass ratio of powder is 1; Above-mentioned material stirring evenly obtains suspension, and this suspension is carried out spray drying, and wherein air inlet temperature is 320 ℃, and air outlet temperature is 110 ℃, makes dry powder.
(3) carburizing reagent
Get above-mentioned dry powder and pack in the crucible, 5 ℃/minute are warmed up to 800 ℃ under argon shield, are incubated 3 hours, make silicon based composite material.
(4) preparation Si-C composite material
The above-mentioned silicon based composite material that makes and efficient first are mixed with Si-C composite material greater than 95% graphite cathode material (commercially available high-end graphite cathode material), and wherein silicon based composite material accounts for 30% at Si-C composite material.
(5) cycle performance test
The experimental cell of cycle performance test usefulness uses the preparation method of pole piece and test battery identical with the preparation method of pole piece and test battery with the experimental cell among the embodiment 1.
At constant current 0.1C(1C=220mA/g) condition under carry out cycle performance test, this material first discharge specific capacity is 1171mAh/g, after 100 circulations, capacity is about 778mAh/g.
Embodiment 6
Present embodiment provides a kind of preparation method of silicon based composite material, comprising:
(1) SiO
x(0.5≤x≤1.5) powder and conductive carbon material batch mixing
To treat ball milling material SiO
1.0Powder (300 order) and adding as the gas-phase growth of carbon fibre (150 order) of high conductivity material with carbon element in the ball grinder of planetary ball mill, wherein SiO
1.0With the mass ratio of graphite be 6; The ball milling pearl is that diameter is the steel ball of 20mm and 60mm, and wherein the ball milling pearl treats that the mass ratio of ball milling material is 6; The rotating speed of ball milling is 400 rev/mins, and ball milling 6h obtains the ball milling material.
(2) carbon coated presoma
Get above-mentioned ball milling material, add entry, wherein the mass ratio of water and ball milling material is 4; Adding is as the polyethylene glycol of carbon matrix precursor, wherein polyethylene glycol and SiO
1.0The mass ratio of powder is 0.2; Above-mentioned material stirring evenly obtains suspension, and this suspension is carried out spray drying, and wherein air inlet temperature is 350 ℃, and air outlet temperature is 80 ℃, makes dry powder.
(3) carburizing reagent
Get above-mentioned dry powder and pack in the crucible, 5 ℃/minute are warmed up to 850 ℃ under argon shield, are incubated 18 hours, make silicon based composite material.
(4) preparation Si-C composite material
The above-mentioned silicon based composite material that makes and efficient first are mixed with Si-C composite material greater than 95% graphite cathode material (commercially available high-end graphite cathode material), and wherein silicon based composite material accounts for 10% at Si-C composite material.
(5) cycle performance test
The experimental cell of cycle performance test usefulness uses the preparation method of pole piece and test battery identical with the preparation method of pole piece and test battery with the experimental cell among the embodiment 1.
At constant current 0.1C(1C=220mA/g) condition under carry out cycle performance test, this material first discharge specific capacity is 1546mAh/g, after 100 circulations, capacity is about 712mAh/g.
Embodiment 7
Present embodiment provides a kind of silicon based composite material by the said method preparation.
Embodiment 8
Present embodiment provides a kind of Si-C composite material by the said method preparation.
Embodiment 9
The lithium ion battery that present embodiment provides a kind of negative pole to contain above-mentioned Si-C composite material, this lithium ion battery for example also comprises other necessary assembly certainly, positive pole, barrier film, electrolyte and shell etc. repeat no more here.
Be understandable that above execution mode only is the illustrative embodiments that adopts for principle of the present invention is described, yet 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 also are considered as protection scope of the present invention.
Claims (9)
1. the preparation method of a silicon based composite material is characterized in that, comprising:
Step 1) is with SiO
x(0.5≤x≤1.5) powder and conductive carbon matrix batch mixing obtain SiO
xThe composite granule of (0.5≤x≤1.5)/C;
Step 2) with SiO
xThe composite granule of (0.5≤x≤1.5)/C coats with the carbon precursor and obtains coating;
Step 3) is carried out carburizing reagent with coating.
2. the preparation method of silicon based composite material as claimed in claim 1 is characterized in that, described SiO
xX in the powder is 0.8-1.2.
3. the preparation method of silicon based composite material as claimed in claim 1 is characterized in that, described SiO
xThe mass ratio of (0.5≤x≤1.5) powder and conductive carbon material is 1/9-9;
Described conductive carbon material is one or more in Graphene, carbon nano-tube, gas-phase growth of carbon fibre, graphite, expanded graphite and the acetylene black.
4. such as the preparation method of the arbitrary described silicon based composite material of claim 1-3, it is characterized in that described coating comprises: with SiO
xThe composite granule of (0.5≤x≤1.5)/C and carbon precursor are added to the water stirring and obtain suspension, and described spray dried is obtained coating;
Wherein, the quality of described water and SiO
xThe ratio of the composite granule of (0.5≤x≤1.5)/C and the gross mass of carbon precursor is 3-15; Described spray-dired inlet temperature is 250 ℃-350 ℃, and outlet temperature is 80 ℃-120 ℃.
5. the preparation method of silicon based composite material as claimed in claim 4 is characterized in that, described carbon precursor and SiO
xSiO in the composite granule of (0.5≤x≤1.5)/C
xMass ratio be 0.2-5;
Described carbon precursor is one or more in polyethylene glycol, polyvinyl alcohol, polyacrylic acid, citric acid, sucrose and the glucose.
6. the preparation method of silicon based composite material as claimed in claim 1 is characterized in that, the temperature of described carburizing reagent is 700 ℃-1200 ℃, and the carburizing reagent time is 0.5h-24h.
7. a silicon based composite material is characterised in that, this based composites is by the described method preparation of any one among the claim 1-6.
8. a Si-C composite material is characterized in that, is that the silicon based composite material of 5%-30% and the graphite material of surplus form by mass fraction, wherein:
Described silicon based composite material is by the described method preparation of any one among the claim 1-7;
The first efficient of described graphite material is greater than 95%.
9. a lithium ion battery is characterized in that, its negative pole contains Si-C composite material claimed in claim 9.
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