CN102983313B - Si-C composite material and preparation method thereof, lithium ion battery - Google Patents
Si-C composite material and preparation method thereof, lithium ion battery Download PDFInfo
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- 239000002153 silicon-carbon composite material Substances 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title claims abstract description 39
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 19
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 18
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 68
- 229910052751 metal Inorganic materials 0.000 claims abstract description 26
- 239000002184 metal Substances 0.000 claims abstract description 26
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 24
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 22
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 22
- 239000002131 composite material Substances 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 20
- 239000008187 granular material Substances 0.000 claims abstract description 17
- 238000006722 reduction reaction Methods 0.000 claims abstract description 17
- 238000002156 mixing Methods 0.000 claims abstract description 14
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 13
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 13
- 238000005554 pickling Methods 0.000 claims abstract description 3
- 238000000498 ball milling Methods 0.000 claims description 47
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 44
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 24
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 22
- 229910052799 carbon Inorganic materials 0.000 claims description 18
- 239000010703 silicon Substances 0.000 claims description 18
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 17
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 16
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 16
- 239000002270 dispersing agent Substances 0.000 claims description 16
- 229910052710 silicon Inorganic materials 0.000 claims description 16
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 12
- 229910002804 graphite Inorganic materials 0.000 claims description 12
- 239000010439 graphite Substances 0.000 claims description 12
- 229910052786 argon Inorganic materials 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 11
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 10
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 9
- 229910052744 lithium Inorganic materials 0.000 claims description 9
- 229910002012 Aerosil® Inorganic materials 0.000 claims description 8
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 8
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 8
- 239000011575 calcium Substances 0.000 claims description 8
- 229910052791 calcium Inorganic materials 0.000 claims description 8
- 239000007789 gas Substances 0.000 claims description 8
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 6
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 5
- 239000006230 acetylene black Substances 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 229910002026 crystalline silica Inorganic materials 0.000 claims description 5
- IJKVHSBPTUYDLN-UHFFFAOYSA-N dihydroxy(oxo)silane Chemical compound O[Si](O)=O IJKVHSBPTUYDLN-UHFFFAOYSA-N 0.000 claims description 5
- 229910021389 graphene Inorganic materials 0.000 claims description 5
- 239000010936 titanium Substances 0.000 claims description 5
- 229910052719 titanium Inorganic materials 0.000 claims description 5
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 4
- 239000002041 carbon nanotube Substances 0.000 claims description 4
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 4
- 239000000835 fiber Substances 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 229910052700 potassium Inorganic materials 0.000 claims description 4
- 239000011591 potassium Substances 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- 239000011777 magnesium Substances 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 239000004411 aluminium Substances 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 238000000227 grinding Methods 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 33
- 230000008569 process Effects 0.000 abstract description 12
- 230000000694 effects Effects 0.000 abstract description 7
- 238000011056 performance test Methods 0.000 description 17
- 239000002245 particle Substances 0.000 description 14
- 239000005543 nano-size silicon particle Substances 0.000 description 12
- 238000012360 testing method Methods 0.000 description 12
- 239000002923 metal particle Substances 0.000 description 8
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 7
- 239000000843 powder Substances 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 229910000831 Steel Inorganic materials 0.000 description 6
- 239000010959 steel Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 208000011580 syndromic disease Diseases 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 4
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 4
- 239000000292 calcium oxide Substances 0.000 description 4
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 4
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 4
- 229960002050 hydrofluoric acid Drugs 0.000 description 4
- 230000009467 reduction Effects 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
- 238000011065 in-situ storage Methods 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 230000015572 biosynthetic process 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
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 2
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 description 2
- 229910001950 potassium oxide Inorganic materials 0.000 description 2
- 229910021487 silica fume Inorganic materials 0.000 description 2
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 2
- 229910001948 sodium oxide Inorganic materials 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 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
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 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
- 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
- 150000002431 hydrogen Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 239000011159 matrix material 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
- 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
- 238000003786 synthesis reaction Methods 0.000 description 1
Classifications
-
- 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 kind of Si-C composite material and preparation method thereof, lithium ion battery containing this material, belong to technical field of lithium ion, it can solve bulk effect in charge and discharge process of existing Si-C composite material and lithium ion battery prepared therefrom and the problem of the capacity attenuation caused.The preparation method of Si-C composite material of the present invention comprises silicon dioxide, conductive carbon material and metal batch mixing and obtains composite granule, carry out reduction reaction afterwards, and the step of metal oxide is removed in pickling.The present invention obtains the excellent Si-C composite material of cycle performance by choosing suitable technological parameter, and has prepared the lithium ion battery containing Si-C composite 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 containing Si-C composite material.
Background technology
At present, the lithium ion battery of production and application mainly adopts graphite negative electrodes material, but the embedding lithium capacity of the theory of graphite is 372mAh/g, and reality reaches 370mAh/g, therefore, 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 becomes study hotspot due to its high specific discharge capacity (theoretical specific capacity of silicon is 4200mAh/g), but this material in doff lithium process along with serious volumetric expansion and contraction, cause the electroactive material powder of detached on electrode, finally cause capacity attenuation.In order to overcome the special capacity fade of silicon based anode material, generally that silicon and other inactive metals (as Fe, Al, Cu etc.) are formed alloy, as Chinese Patent Application No. CN03116070.0 discloses silicon aluminium alloy/carbon composite material used for lithium ion battery negative electrode and preparation method thereof; Or homogenize material is distributed in other active or non-active materials and forms composite material (as Si-C, Si-TiN etc.), as Chinese Patent Application No. CN02112180.X discloses Si-C composite material and the preparation method of used as negative electrode of Li-ion battery height ratio capacity.
Although said method alleviates the capacity attenuation of silicon based anode material to a certain extent, but due to said method employing is business-like nano silica fume even micron silica flour, silica flour is difficult to reach nano level in the base and is uniformly dispersed, so fundamentally can not suppress the bulk effect in charge and discharge process, capacity still can be decayed along with the increase of cycle-index quickly.The people such as WuJishan (HongfaXiang, KaiZhang, GeJi, JimYangLee, ChangjiZou, XiaodongChen, JishanWu, CARBON49 (2011) 1787-1796) report Graphene with nano silica fume directly mix synthesis composite negative pole material method, resulting materials shows good cycle performance, 30 specific capacities that circulate can also keep 1600mAh/g, but still there is the problem of slow-decay.Therefore, make silica flour reach nano level being uniformly dispersed in the base, thus effectively suppress the bulk effect of 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 object of the invention is to solve bulk effect in charge and discharge process of the Si-C composite material that obtains of art methods and lithium ion battery prepared therefrom and the problem of capacity attenuation that causes, the preparation method of the Si-C composite material providing a kind of cycle performance excellent.
The technical scheme that solution the technology of the present invention problem adopts is a kind of preparation method of Si-C composite material, comprising: silicon dioxide, conductive carbon material and metal batch mixing are obtained composite granule by step 1);
Step 2) composite granule is carried out reduction reaction, obtain the mixture of silicon and metal oxide;
Metal oxide is removed in step 3) pickling.
The present invention is by obtaining composite granule by silicon dioxide, conductive carbon material and metal batch mixing, carry out reduction reaction afterwards, silica dioxide granule generation reduction reaction, in-situ preparation silicon nanoparticle, because silicon grain is wherein generated in-situ, therefore its size little (nanometer scale), and Direct Uniform be dispersed in carbon granule form carbon back skeleton in, can not reunion be produced.Wherein silicon nanoparticle is embedding lithium active particle, and carbon back skeleton mainly plays peptizaiton, stops silicon nanoparticle in repetition doff lithium process, " electrochemistry sintering " occur and be agglomerated into bulky grain; On the other hand due to carbon back skeleton in doff lithium process without change in volume, so the bulk effect of whole particle also greatly reduces, form good electrical contact between the conductivity skeleton that nano silicon particles and carbon granule are connected into and keep always, thus effectively slow down the speed of capacity attenuation.
Preferably, described silicon dioxide and the mass ratio of conductive carbon material are 1/9-9;
The quality of described metal is for just in time reducing the 50%-120% of the theoretical metal quality needed for whole silicon dioxide to silicon;
The quality of described acid is for just in time removing the 120%-500% of the theoretical acid quality needed for whole metal oxide.
Preferably, described silicon dioxide is one or more in Bio-sil, mesoporous silicon oxide, aerosil, crystalline silica and amorphous silica
Described conductive carbon material is one or more in Graphene, carbon nano-tube, gas-phase growth of carbon fibre, graphite, expanded graphite and acetylene black;
Described metal is one or more in lithium, sodium, potassium, calcium, magnesium, aluminium, titanium;
Described acid is one or more in acetic acid, hydrochloric acid, sulfuric acid and hydrofluoric acid.
Preferably, described reduction reaction conditions is: atmosphere is the mixed atmosphere of argon gas or argon gas and hydrogen, and reaction temperature is 300 DEG C-1000 DEG C, and the reaction time is 0.5h-24h.
Further preferably, described reaction temperature is 300 DEG C-800 DEG C, and the reaction time is 1h-6h.
Preferably, described batch mixing is dry ball milling, and its rotational speed of ball-mill is 300-500 rev/min, and Ball-milling Time is 2-12h.
Further preferably, described Ball-milling Time is 2-8h.
Preferably, described batch mixing is wet ball grinding, wherein adopt alkane dispersant, the quality of described alkane dispersant is the 50%-200% of silicon dioxide, conductive carbon material and total metal mass, and described alkane dispersant is one or more in atoleine, cyclohexane, toluene and ether.
Due to high conductivity carbon granule add formation conducting matrix grain, be convenient to electric transmission, simultaneously as graphite itself also has certain doff lithium capacity, the specific capacity of increase Si-C composite material further.
Technical problem to be solved by this invention also comprises, and for bulk effect in charge and discharge process of Si-C composite material and lithium ion battery prepared therefrom and the problem of the capacity attenuation caused, provides the Si-C composite material that a kind of cycle performance is excellent.
The technical scheme that solution the technology of the present invention problem adopts is a kind of Si-C composite material, and it is prepared by said method.
Because Si-C composite material of the present invention is prepared by said method, its cycle performance is excellent.
Technical problem to be solved by this invention also comprises, and for the bulk effect of the existing lithium ion battery prepared by Si-C composite material in charge and discharge process and the problem of the capacity attenuation caused, provides the lithium ion battery that a kind of cycle performance is excellent.
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 silicon nanoparticle and make this silicon nanoparticle be dispersed in the preparation method of the Si-C composite material in carbon back skeleton at nanoscale.Raw material of the present invention is cheap and easy to get, preparation technology is simple, flow process is short, process easily controls, easily realize suitability for industrialized production, and resulting materials has excellent cycle performance.
Accompanying drawing explanation
The cycle performance figure of the Si-C composite material of Fig. 1 prepared by the embodiment of the present invention 3.
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, comprising:
(1) silicon dioxide, conductive carbon material and metal batch mixing
To ball milling material aerosil (particle diameter 30nm) be treated, add in the ball grinder of planetary ball mill as the graphite (150 order) of conductive carbon material and calcium metal particle (particle diameter 1mm), wherein, the mass ratio of aerosil and graphite is 1/9,70% of the theoretical metal calcium granular mass of quality needed for reducing gases aerosil to silicon of calcium metal particle; Then add in ball grinder as alkane dispersant toluene (because of its not with metal reaction), wherein the quality of toluene is treat ball milling quality of material 70%; The steel ball of ball milling pearl to be diameter be 20mm and 60mm, wherein ball milling pearl treats that the mass ratio of ball milling material is 6; The rotating speed of ball milling is 400 revs/min, ball milling 4h, obtains composite granule.
(2) reduction reaction
Getting above-mentioned (1) obtained dry composite powder loads in crucible; under argon shield, 5 DEG C/min are warmed up to 120 DEG C; be incubated 2 hours; evaporate alkane dispersant toluene; continue to be warmed up to 300 DEG C with 5 DEG C/min; be incubated 24 hours, generate and be dispersed in the silicon nanoparticle of carbon back skeleton and the mixture of calcium oxide.
(3) acid-washed metal oxide
Product obtained to above-mentioned (2) is put into container, adds the hydrochloric acid solution that substance withdrawl syndrome is 2M, wherein the quality of hydrochloric acid solution is for removing 500% of theoretical hydrochloric acid quality needed for calcium oxide, stirs 4h, obtains Si-C composite material.
(4) cycle performance test
With prepared Si-C composite material preparation experiment battery pole piece and test battery.
The process of preparation experiment battery pole piece is: 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, 100 DEG C of vacuumize 24 hours, taking-up is washed into pole piece, vacuumize 12h at 85 DEG C, carry out compressing tablet, vacuumize 12h at 85 DEG C, obtained experimental cell pole piece obtains experimental cell pole piece.
The process preparing test battery is: with the pole piece of above-mentioned preparation for negative pole, is to electrode with lithium sheet, the LiPF of electrolyte to be concentration be 1mol/L
6solution, its solvent is EC(ethyl carbonate ester)+DMC(dimethyl carbonate), wherein EC(ethyl carbonate ester) and DMC(dimethyl carbonate) volume ratio be 1 ︰ 1, barrier film is celgard2400 film, is assembled into CR2025 type button cell in the glove box being full 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 2003mAh/g, 100 times circulation after, capacity is about 957mAh/g.
Embodiment 2
The present embodiment provides a kind of preparation method of Si-C composite material, comprising:
(1) silicon dioxide, conductive carbon material and metal batch mixing
To ball milling material Bio-sil be treated, add in the ball grinder of planetary ball mill as the acetylene black of conductive carbon material and sodium metal particle (particle diameter 1mm), wherein, the mass ratio of Bio-sil and acetylene black is 0.5,50% of the quality of the sodium metal particle theoretical metal sodium granular mass needed for reduction Bio-sil to silicon; Then in ball grinder, add the ether as alkane dispersant, wherein the quality of ether is treat ball milling quality of material 50%; The steel ball of ball milling pearl to be diameter be 20mm and 60mm, wherein ball milling pearl treats that the mass ratio of ball milling material is 6; The rotating speed of ball milling is 300 revs/min, ball milling 2h, obtains composite granule.
(2) reduction reaction
Getting above-mentioned (1) obtained dry composite powder loads in crucible; under argon shield, 5 DEG C/min are warmed up to 50 DEG C; be incubated 2 hours; evaporate alkane dispersant ether; continue to be warmed up to 800 DEG C with 5 DEG C/min; be incubated 6 hours, generate and be dispersed in the silicon nanoparticle of carbon back skeleton and the mixture of sodium oxide molybdena.
(3) acid-washed metal oxide
Product obtained to above-mentioned (2) is put into container, adds the ethanol acetate solution that substance withdrawl syndrome is 2M, wherein the quality of ethanol acetate solution is for removing 200% of theoretical acetic acid quality needed for sodium oxide molybdena, stirs 4h, obtains Si-C composite material.
(4) cycle performance test
The experimental cell pole piece of cycle performance test is identical with the preparation method of test battery with the experimental cell pole piece in embodiment 1 with the preparation method of test battery.
At constant current 0.1C(1C=220mA/g) condition under carry out cycle performance test, this material first discharge specific capacity is 812mAh/g, 100 times circulation after, capacity is about 423mAh/g.
Embodiment 3
The present embodiment provides a kind of preparation method of Si-C composite material, comprising:
(1) silicon dioxide, conductive carbon material and metal batch mixing
To ball milling material mesoporous silicon oxide be treated, add in the ball grinder of planetary ball mill as the gas-phase growth of carbon fibre of conductive carbon material and metallic potassium particle (particle diameter 1mm), wherein, the mass ratio of mesoporous silicon oxide and gas-phase growth of carbon fibre is 9,100% of the quality of the metallic potassium particle theoretical metal k particle quality needed for reduction mesoporous silicon oxide to silicon; Then in ball grinder, add the cyclohexane as alkane dispersant, the quality of its cyclohexane is treat ball milling quality of material 150%; The steel ball of ball milling pearl to be diameter be 20mm and 60mm, wherein ball milling pearl treats that the mass ratio of ball milling material is 6; The rotating speed of ball milling is 500 revs/min, ball milling 8h, obtains composite granule.
(2) reduction reaction
Getting above-mentioned (1) obtained dry composite powder loads in crucible; under argon gas and hydrogen shield, 5 DEG C/min are warmed up to 80 DEG C; be incubated 2 hours; evaporate alkane dispersant cyclohexane; continue to be warmed up to 400 DEG C with 5 DEG C/min; be incubated 0.5 hour, generate and be dispersed in the silicon nanoparticle of carbon back skeleton and the mixture of potassium oxide.
(3) acid-washed metal oxide
Product obtained to above-mentioned (2) is put into container, adds the sulfuric acid solution that substance withdrawl syndrome is 2M, wherein the quality of sulfuric acid solution is for removing 120% of theoretical sulfuric acid quality needed for potassium oxide, stirs 4h, obtains Si-C composite material.
(4) cycle performance test
The experimental cell pole piece of cycle performance test is identical with the preparation method of test battery with the experimental cell pole piece in embodiment 1 with the preparation method of test battery.
At constant current 0.1C(1C=220mA/g) condition under carry out cycle performance test, this material first discharge specific capacity is 1969mAh/g, 100 times circulation after, capacity is about 1013mAh/g.
As shown in Figure 1.Si-C composite material discharge cycles prepared by the present embodiment is functional.
Embodiment 4
The present embodiment provides a kind of preparation method of Si-C composite material, comprising:
(1) silicon dioxide, conductive carbon material and metal batch mixing
To ball milling material amorphous silica (300 order) be treated, add in the ball grinder of planetary ball mill as the expanded graphite (150 order) of conductive carbon material and calcium metal particle (particle diameter 1mm), wherein, the mass ratio of amorphous silica and expanded graphite is 3,120% of the quality of the calcium metal particle theoretical metal calcium granular mass needed for reduction amorphous silica to silicon; Then in ball grinder, add the cyclohexane as alkane dispersant, the quality of its cyclohexane is treat ball milling quality of material 200%; The steel ball of ball milling pearl to be diameter be 20mm and 60mm, wherein ball milling pearl treats that the mass ratio of ball milling material is 6; The rotating speed of ball milling is 350 revs/min, ball milling 12h, obtains composite granule.
(2) reduction reaction
Getting above-mentioned (1) obtained dry composite powder loads in crucible; under argon shield, 5 DEG C/min are warmed up to 70 DEG C; be incubated 2 hours; evaporate alkane dispersant cyclohexane; continue to be warmed up to 1000 DEG C with 5 DEG C/min; be incubated 1 hour, generate and be dispersed in the silicon nanoparticle of carbon back skeleton and the mixture of calcium oxide.
(3) acid-washed metal oxide
Product obtained to above-mentioned (2) is put into container, adds the hydrofluoric acid solution that substance withdrawl syndrome is 2M, wherein the quality of hydrofluoric acid solution is for removing 150% of theoretical hydrogen fluoric acid quality needed for calcium oxide, stirs 4h, obtains Si-C composite material.
(4) cycle performance test
The experimental cell pole piece of cycle performance test is identical with the preparation method of test battery with the experimental cell pole piece in embodiment 1 with the preparation method of test battery.
At constant current 0.1C(1C=220mA/g) condition under carry out cycle performance test, this material first discharge specific capacity is 2048mAh/g, 100 times circulation after, capacity is about 853mAh/g.
Embodiment 5
The present embodiment provides a kind of preparation method of Si-C composite material, comprising:
(1) silicon dioxide, conductive carbon material and metal batch mixing
To ball milling material crystalline silica (300 order) be treated, add in the ball grinder of planetary ball mill as the Graphene (150 order) of conductive carbon material and magnesium metal particle (150 order), wherein, the mass ratio of crystalline silica and Graphene is 0.9,90% of the quality of the magnesium metal particle theoretical metal magnesium granules quality needed for reduction crystalline silica to silicon; The steel ball of ball milling pearl to be diameter be 20mm and 60mm, wherein ball milling pearl treats that the mass ratio of ball milling material is 6; The rotating speed of ball milling is 450 revs/min, ball milling 10h, obtains composite granule.
(2) reduction reaction
Get above-mentioned (1) obtained dry composite powder to load in crucible, under argon shield, 5 DEG C/min are warmed up to 600 DEG C, are incubated 3 hours, generate and are dispersed in the silicon nanoparticle of carbon back skeleton and magnesian mixture.
(3) acid-washed metal oxide
Product obtained to above-mentioned (2) is put into container, adds the hydrochloric acid solution that substance withdrawl syndrome is 2M, wherein the quality of hydrochloric acid solution is for removing 300% of theoretical hydrochloric acid quality needed for magnesium oxide, stirs 4h, obtains Si-C composite material.
(4) cycle performance test
The experimental cell pole piece of cycle performance test is identical with the preparation method of test battery with the experimental cell pole piece in embodiment 1 with the preparation method of test battery.
At constant current 0.1C(1C=220mA/g) condition under carry out cycle performance test, this material first discharge specific capacity is 3117mAh/g, 100 times circulation after, capacity is about 627mAh/g.
Embodiment 6
The present embodiment provides a kind of preparation method of Si-C composite material, comprising:
(1) silicon dioxide, conductive carbon material and metal batch mixing
Ball milling material aerosil (particle diameter 30nm), carbon nano-tube (nanometer port, Shenzhen Co., Ltd as conductive carbon material will be treated, L-MWNT-2040, external diameter 20-40nm, length 5-15 μm) and Titanium particle (particle diameter 1mm) add in the ball grinder of planetary ball mill, wherein, the mass ratio of aerosil and carbon nano-tube is 6,80% of the theoretical metal titanium granular mass of quality needed for reducing gases aerosil to silicon of Titanium particle; Then in ball grinder, add the toluene as alkane dispersant, wherein the quality of toluene is treat ball milling quality of material 120%; The steel ball of ball milling pearl to be diameter be 20mm and 60mm, wherein ball milling pearl treats that the mass ratio of ball milling material is 6; The rotating speed of ball milling is 400 revs/min, ball milling 6h, obtains composite granule.
(2) reduction reaction
Getting above-mentioned (1) obtained dry composite powder loads in crucible; under argon shield, 5 DEG C/min are warmed up to 80 DEG C; be incubated 2 hours; evaporate alkane dispersant toluene; continue to be warmed up to 500 DEG C with 5 DEG C/min; be incubated 18 hours, generate and be dispersed in the silicon nanoparticle of carbon back skeleton and the mixture of titanium oxide.
(3) acid-washed metal oxide
Product obtained to above-mentioned (2) is put into container, adds the ethanol acetate solution that substance withdrawl syndrome is 2M, wherein the quality of ethanol acetate solution is for removing 400% of theoretical acetic acid quality needed for titanium oxide, stirs 4h, obtains Si-C composite material.
(4) cycle performance test
The experimental cell pole piece of cycle performance test is identical with the preparation method of test battery with the experimental cell pole piece in embodiment 1 with the preparation method of test battery.
At constant current 0.1C(1C=220mA/g) condition under carry out cycle performance test, this material first discharge specific capacity is 1307mAh/g, 100 times circulation after, capacity is about 895mAh/g.
Embodiment 7
The present embodiment provides a kind of Si-C composite material prepared by said method.
Embodiment 8
The present embodiment provides a kind of negative pole to contain the lithium ion battery of above-mentioned Si-C composite material, and this lithium ion battery also comprises the assembly of other necessity such as certainly, and positive pole, barrier film, electrolyte and shell etc., repeat no more here.
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 (10)
1. a preparation method for Si-C composite material, is characterized in that, comprising:
Step 1) silicon dioxide, conductive carbon material and metal are carried out batch mixing acquisition composite granule; The quality of described metal is for just in time reducing the 50%-90% of the theoretical metal quality needed for whole silicon dioxide to silicon;
Step 2) composite granule is carried out reduction reaction, obtain the mixture of silicon and metal oxide;
Step 3) remove metal oxide with pickling, described acid is one or more in acetic acid, hydrochloric acid, sulfuric acid, and the Si-C composite material obtained is the silicon-silica-carbon compound containing silicon dioxide.
2. the preparation method of Si-C composite material as claimed in claim 1, it is characterized in that, described silicon dioxide and the mass ratio of conductive carbon material are 1/9-9;
The quality of described acid is for just in time removing the 120%-500% of the theoretical acid quality needed for whole metal oxide.
3. the preparation method of Si-C composite material as claimed in claim 1, it is characterized in that, described silicon dioxide is one or more in Bio-sil, mesoporous silicon oxide, aerosil, crystalline silica and amorphous silica;
Described conductive carbon material is one or more in Graphene, carbon nano-tube, gas-phase growth of carbon fibre, graphite, expanded graphite and acetylene black;
Described metal is one or more in lithium, sodium, potassium, calcium, magnesium, aluminium, titanium.
4. the preparation method of Si-C composite material as claimed in claim 1, it is characterized in that, described reduction reaction conditions is: atmosphere is the mixed atmosphere of argon gas or argon gas and hydrogen, and reaction temperature is 300 DEG C-1000 DEG C, and the reaction time is 0.5h-24h.
5. the preparation method of Si-C composite material as claimed in claim 4, it is characterized in that, described reaction temperature is 300 DEG C-800 DEG C, and the reaction time is 1h-6h.
6. the preparation method of the Si-C composite material as described in as arbitrary in claim 1-5, it is characterized in that, described batch mixing is dry ball milling, and its rotational speed of ball-mill is 300-500 rev/min, and Ball-milling Time is 2-12h.
7. the preparation method of Si-C composite material as claimed in claim 6, it is characterized in that, described Ball-milling Time is 2-8h.
8. the preparation method of the Si-C composite material as described in as arbitrary in claim 1-5, it is characterized in that, described batch mixing is wet ball grinding, wherein adopt alkane dispersant, the quality of described alkane dispersant is the 50%-200% of silicon dioxide, conductive carbon material and total metal mass, and described alkane dispersant is one or more in atoleine, cyclohexane, toluene and ether.
9. a Si-C composite material, is characterised in that, this Si-C composite material is prepared by the method in claim 1-8 described in any one.
10. a lithium ion battery, is characterized in that, its negative pole contains Si-C composite material according to claim 9.
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| JP6177345B2 (en) * | 2013-10-31 | 2017-08-09 | エルジー・ケム・リミテッド | Negative electrode active material for lithium secondary battery and method for producing the same |
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| CN103633305B (en) * | 2013-12-10 | 2015-09-23 | 苏州宇豪纳米材料有限公司 | Lithium ion battery silicon composite cathode material and preparation method thereof |
| JP6082355B2 (en) * | 2014-02-07 | 2017-02-15 | 信越化学工業株式会社 | Negative electrode active material for negative electrode material of non-aqueous electrolyte secondary battery, negative electrode for non-aqueous electrolyte secondary battery, and non-aqueous electrolyte secondary battery |
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| CN107528055A (en) * | 2017-08-25 | 2017-12-29 | 南陵县生产力促进中心 | A kind of porous silicon carbon material and preparation method for cathode of lithium battery |
| CN107492649A (en) * | 2017-08-25 | 2017-12-19 | 南陵县生产力促进中心 | A kind of silicon carbon material for cathode of lithium battery and preparation method thereof |
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