CN102983313A - Silicon-carbon composite material and preparation method thereof, and lithium ion battery - Google Patents
Silicon-carbon composite material and preparation method thereof, and lithium ion battery Download PDFInfo
- Publication number
- CN102983313A CN102983313A CN2012105159706A CN201210515970A CN102983313A CN 102983313 A CN102983313 A CN 102983313A CN 2012105159706 A CN2012105159706 A CN 2012105159706A CN 201210515970 A CN201210515970 A CN 201210515970A CN 102983313 A CN102983313 A CN 102983313A
- Authority
- CN
- China
- Prior art keywords
- composite material
- preparation
- silicon
- metal
- quality
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000002153 silicon-carbon composite material Substances 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title claims abstract description 45
- 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 66
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 23
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 22
- 229910052751 metal Inorganic materials 0.000 claims abstract description 22
- 239000002184 metal Substances 0.000 claims abstract description 22
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 20
- 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
- 238000006722 reduction reaction Methods 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 45
- 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
- 239000002131 composite material Substances 0.000 claims description 20
- 229910052799 carbon Inorganic materials 0.000 claims description 19
- 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
- 239000008187 granular material Substances 0.000 claims description 15
- 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
- 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
- 239000000203 mixture Substances 0.000 claims description 10
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 9
- 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
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-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
- 229910052700 potassium Inorganic materials 0.000 claims description 5
- 239000011591 potassium Substances 0.000 claims description 5
- 239000010936 titanium Substances 0.000 claims description 5
- 229910052719 titanium Inorganic materials 0.000 claims description 5
- 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
- 230000035484 reaction time Effects 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- 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 2
- 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
- 239000011777 magnesium Substances 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 229910052708 sodium Inorganic materials 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 8
- 239000000843 powder Substances 0.000 abstract description 8
- 150000001875 compounds Chemical class 0.000 abstract 1
- 238000005562 fading Methods 0.000 abstract 1
- 238000011056 performance test Methods 0.000 description 17
- 239000002245 particle Substances 0.000 description 13
- 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
- 239000000126 substance Substances 0.000 description 7
- 229910000831 Steel Inorganic materials 0.000 description 6
- 230000004087 circulation Effects 0.000 description 6
- 239000010959 steel Substances 0.000 description 6
- 238000003756 stirring Methods 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
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 3
- 239000010405 anode material Substances 0.000 description 3
- 235000013339 cereals Nutrition 0.000 description 3
- 235000013312 flour Nutrition 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-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
- 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
- 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
- 238000012423 maintenance Methods 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
Images
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 silicon-carbon composite material and a preparation method thereof, and a lithium ion battery containing the material, 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-carbon composite material and the lithium ion battery prepared by using the silicon-carbon composite material in the charge and discharge processes. The preparation method of the silicon-carbon composite material, disclosed by the invention, comprises the steps of: mixing silicon dioxide, a conductive carbon material and metal to obtain compound powder, carrying out reduction reaction, and pickling to remove metal oxide. The silicon-carbon composite material with an excellent cycle performance is obtained by selecting proper technological parameters, and the lithium ion battery containing the silicon-carbon composite material is prepared.
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, 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 said method employing is business-like nano silica fume 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 Si-C 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 Si-C 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 Si-C composite material, and comprising: step 1) obtains composite granule with silicon dioxide, conductive carbon material and metal batch mixing;
Step 2) composite granule is carried out reduction reaction, obtain the mixture of silicon and metal oxide;
Step 3) is removed metal oxide with pickling.
The present invention is by obtaining composite granule with silicon dioxide, conductive carbon material and metal batch mixing, carry out afterwards reduction reaction, silica dioxide granule generation reduction reaction, original position generates silicon nanoparticle, because silicon grain wherein is generated in-situ, so its size little (nanometer scale), and Direct Uniform be dispersed in the carbon back skeleton that carbon granule consists of, can not produce reunion.Wherein silicon nanoparticle is embedding lithium active particle, and the carbon back skeleton 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 the carbon back skeleton 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, the mass ratio of described silicon dioxide and conductive carbon material is 1/9-9;
The quality of described metal is for just in time reducing the 50%-120% of whole silicon dioxide to the required theoretical metal quality of silicon;
The quality of described acid is for just in time removing the 120%-500% of the required theoretical acid quality of whole metal oxides.
Preferably, described silicon dioxide is one or more in Bio-sil, mesoporous silicon oxide, aerosil, crystalline silica and the 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 the acetylene black;
Described metal is one or more in lithium, sodium, potassium, calcium, magnesium, aluminium, the titanium;
Described acid is one or more in acetic acid, hydrochloric acid, sulfuric acid and the 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 ℃-1000 ℃, and the reaction time is 0.5h-24h.
Further preferably, described reaction temperature is 300 ℃-800 ℃, 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 the 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 the ether.
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 Si-C composite material.
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, and it is the said method preparation.
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 silicon nanoparticle and make this silicon nanoparticle be dispersed in the preparation method of the Si-C composite material in the 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 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 3.
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 Si-C composite material, comprising:
(1) silicon dioxide, conductive carbon material and metal batch mixing
To treat ball milling material aerosil (particle diameter 30nm), 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, and the quality of calcium metal particle is that the reducing gases aerosil is to 70% of the required theoretical calcium metal granular mass of silicon; Then add in the ball grinder toluene as the alkane dispersant (because of its not with metal reaction), wherein the quality of toluene is to treat 70% of ball milling quality of material; 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 composite granule.
(2) reduction reaction
Getting dry composite powder that above-mentioned (1) make packs in the crucible; 5 ℃/minute are warmed up to 120 ℃ under argon shield; be incubated 2 hours; evaporate alkane dispersant toluene; continuation is warmed up to 300 ℃ with 5 ℃/minute; 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
The product that above-mentioned (2) make is put into container, and adding amount of substance concentration is the hydrochloric acid solution of 2M, and wherein the quality of hydrochloric acid solution stirs 4h for removing 500% of the required theoretical hydrochloric acid quality of calcium oxide, obtains Si-C composite material.
(4) 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 LiPF of 1mol/L
6Solution, 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 2003mAh/g, after 100 circulations, capacity is about 957mAh/g.
Embodiment 2
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 treat ball milling material Bio-sil, 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, and the quality of sodium metal particle is for reducing Bio-sil to 50% of the required theoretical sodium metal granular mass of silicon; Then add the ether as the alkane dispersant in the ball grinder, wherein the quality of ether is to treat 50% of ball milling quality of material; 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 composite granule.
(2) reduction reaction
Getting dry composite powder that above-mentioned (1) make packs in the crucible; 5 ℃/minute are warmed up to 50 ℃ under argon shield; be incubated 2 hours; evaporate alkane dispersant ether; continuation is warmed up to 800 ℃ with 5 ℃/minute; 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
The product that above-mentioned (2) make is put into container, and adding amount of substance concentration is the ethanol acetate solution of 2M, and wherein the quality of ethanol acetate solution stirs 4h for removing 200% of the required theoretical acetic acid quality of sodium oxide molybdena, obtains Si-C composite material.
(4) 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 812mAh/g, after 100 circulations, capacity is about 423mAh/g.
Embodiment 3
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 treat ball milling material mesoporous silicon oxide, 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, and the quality of metallic potassium particle is for reducing mesoporous silicon oxide to 100% of the required theoretical metallic potassium granular mass of silicon; Then add the cyclohexane as the alkane dispersant in the ball grinder, wherein the quality of cyclohexane is to treat 150% of ball milling quality of material; 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 composite granule.
(2) reduction reaction
Getting dry composite powder that above-mentioned (1) make packs in the crucible; 5 ℃/minute are warmed up to 80 ℃ under argon gas and hydrogen shield; be incubated 2 hours; evaporate alkane dispersant cyclohexane; continuation is warmed up to 400 ℃ with 5 ℃/minute; 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
The product that above-mentioned (2) make is put into container, and adding amount of substance concentration is the sulfuric acid solution of 2M, and wherein the quality of sulfuric acid solution stirs 4h for removing 120% of the required theoretical sulfuric acid quality of potassium oxide, obtains Si-C composite material.
(4) 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 1969mAh/g, after 100 circulations, capacity is about 1013mAh/g.
As shown in Figure 1.The Si-C composite material discharge cycles of present embodiment preparation is functional.
Embodiment 4
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 treat ball milling material amorphous silica (300 order), 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, and the quality of calcium metal particle is for reducing amorphous silica to 120% of the required theoretical calcium metal granular mass of silicon; Then add the cyclohexane as the alkane dispersant in the ball grinder, wherein the quality of cyclohexane is to treat 200% of ball milling quality of material; 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 composite granule.
(2) reduction reaction
Getting dry composite powder that above-mentioned (1) make packs in the crucible; 5 ℃/minute are warmed up to 70 ℃ under argon shield; be incubated 2 hours; evaporate alkane dispersant cyclohexane; continuation is warmed up to 1000 ℃ with 5 ℃/minute; 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
The product that above-mentioned (2) make is put into container, and adding amount of substance concentration is the hydrofluoric acid solution of 2M, and wherein the quality of hydrofluoric acid solution stirs 4h for removing 150% of the required theoretical hydrogen fluoric acid quality of calcium oxide, obtains Si-C composite material.
(4) 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 2048mAh/g, after 100 circulations, capacity is about 853mAh/g.
Embodiment 5
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 treat ball milling material crystalline silica (300 order), 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, and the quality of magnesium metal particle is for reducing crystalline silica to 90% of the required theoretical magnesium metal granular mass of silicon; 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 composite granule.
(2) reduction reaction
Get dry composite powder that above-mentioned (1) make and pack in the crucible, 5 ℃/minute are warmed up to 600 ℃ under argon shield, are incubated 3 hours, generate the silicon nanoparticle and the magnesian mixture that are dispersed in the carbon back skeleton.
(3) acid-washed metal oxide
The product that above-mentioned (2) make is put into container, and adding amount of substance concentration is the hydrochloric acid solution of 2M, and wherein the quality of hydrochloric acid solution stirs 4h for removing 300% of the required theoretical hydrochloric acid quality of magnesium oxide, obtains Si-C composite material.
(4) 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 3117mAh/g, after 100 circulations, capacity is about 627mAh/g.
Embodiment 6
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 treat ball milling material aerosil (particle diameter 30nm), as carbon nano-tube (nanometer port, Shenzhen Co., Ltd of conductive carbon material, L-MWNT-2040, external diameter 20-40nm, length 5-15 μ m) 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, and the quality of Titanium particle is that the reducing gases aerosil is to 80% of the required theoretical Titanium granular mass of silicon; Then add the toluene as the alkane dispersant in the ball grinder, wherein the quality of toluene is to treat 120% of ball milling quality of material; 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 composite granule.
(2) reduction reaction
Getting dry composite powder that above-mentioned (1) make packs in the crucible; 5 ℃/minute are warmed up to 80 ℃ under argon shield; be incubated 2 hours; evaporate alkane dispersant toluene; continuation is warmed up to 500 ℃ with 5 ℃/minute; 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
The product that above-mentioned (2) make is put into container, and adding amount of substance concentration is the ethanol acetate solution of 2M, and wherein the quality of ethanol acetate solution stirs 4h for removing 400% of the required theoretical acetic acid quality of titanium oxide, obtains Si-C composite material.
(4) 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 1307mAh/g, after 100 circulations, capacity is about 895mAh/g.
Embodiment 7
Present embodiment provides a kind of Si-C composite material by the said method preparation.
Embodiment 8
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 (10)
1. the preparation method of a Si-C composite material is characterized in that, comprising:
Step 1) is carried out batch mixing with silicon dioxide, conductive carbon material and metal and is obtained composite granule;
Step 2) composite granule is carried out reduction reaction, obtain the mixture of silicon and metal oxide;
Step 3) is removed metal oxide with pickling.
2. the preparation method of Si-C composite material as claimed in claim 1 is characterized in that, the mass ratio of described silicon dioxide and conductive carbon material is 1/9-9;
The quality of described metal is for just in time reducing the 50%-120% of whole silicon dioxide to the required theoretical metal quality of silicon;
The quality of described acid is for just in time removing the 120%-500% of the required theoretical acid quality of whole metal oxides.
3. the preparation method of Si-C composite material as claimed in claim 1 is characterized in that, described silicon dioxide is one or more in Bio-sil, mesoporous silicon oxide, aerosil, crystalline silica and the 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 the acetylene black;
Described metal is one or more in lithium, sodium, potassium, calcium, magnesium, aluminium, the titanium;
Described acid is one or more in acetic acid, hydrochloric acid, sulfuric acid and the hydrofluoric acid.
4. the preparation method of Si-C composite material as claimed in claim 1 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 ℃-1000 ℃, and the reaction time is 0.5h-24h.
5. the preparation method of Si-C composite material as claimed in claim 4 is characterized in that, described reaction temperature is 300 ℃-800 ℃, and the reaction time is 1h-6h.
6. such as the preparation method of the arbitrary described Si-C composite material of claim 1-5, it is characterized in that described batch mixing is dry ball milling, 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 is characterized in that, described Ball-milling Time is 2-8h.
8. such as the preparation method of the arbitrary described Si-C composite material of claim 1-5, it is characterized in that, described batch mixing is wet ball grinding, wherein adopt the 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 the ether.
9. a Si-C composite material is characterised in that, this Si-C composite material is by the described method preparation of any one among the claim 1-8.
10. a lithium ion battery is characterized in that, its negative pole contains Si-C composite material claimed in claim 9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210515970.6A CN102983313B (en) | 2012-12-05 | 2012-12-05 | Si-C composite material and preparation method thereof, lithium ion battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210515970.6A CN102983313B (en) | 2012-12-05 | 2012-12-05 | Si-C composite material and preparation method thereof, lithium ion battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102983313A true CN102983313A (en) | 2013-03-20 |
| CN102983313B CN102983313B (en) | 2016-01-27 |
Family
ID=47857154
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210515970.6A Active CN102983313B (en) | 2012-12-05 | 2012-12-05 | Si-C composite material and preparation method thereof, lithium ion battery |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102983313B (en) |
Cited By (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103367726A (en) * | 2013-07-10 | 2013-10-23 | 奇瑞汽车股份有限公司 | Silicon-carbon composite material and preparation method thereof as well as lithium ion battery |
| CN103579596A (en) * | 2013-11-08 | 2014-02-12 | 合肥国轩高科动力能源股份公司 | Preparation method of lithium ion battery cathode material |
| CN103633305A (en) * | 2013-12-10 | 2014-03-12 | 苏州宇豪纳米材料有限公司 | Silicon composite anode material of lithium ion battery and preparation method of silicon composite anode material |
| CN105981204A (en) * | 2014-02-07 | 2016-09-28 | 信越化学工业株式会社 | 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 |
| CN107359306A (en) * | 2017-05-23 | 2017-11-17 | 中国第汽车股份有限公司 | A kind of preparation method of the compound silicon-carbon cathode material of organic carbon |
| CN107359317A (en) * | 2017-05-23 | 2017-11-17 | 中国第汽车股份有限公司 | Preparation method using Ludox as the compound silicon-carbon cathode of the organic carbon of silicon source |
| CN107369809A (en) * | 2017-05-23 | 2017-11-21 | 中国第汽车股份有限公司 | A kind of preparation method of lithium ion battery silicon-carbon cathode material |
| CN107394121A (en) * | 2017-05-23 | 2017-11-24 | 中国第汽车股份有限公司 | A kind of preparation method using Ludox as the silicon-carbon composite cathode material of silicon source |
| 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 |
| 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 |
| CN107768608A (en) * | 2016-08-15 | 2018-03-06 | 福建新峰二维材料科技有限公司 | The effectively preparation method of the lithium ion battery negative material of buffering silicon bulk effect |
| TWI627785B (en) * | 2013-10-31 | 2018-06-21 | Ｌｇ化學股份有限公司 | Anode active material for lithium secondary battery and method of preparing the same |
| CN109216683A (en) * | 2018-09-20 | 2019-01-15 | 天津师范大学 | A kind of synthetic method of lithium ion battery high-capacity cathode material |
| CN111384253A (en) * | 2018-12-27 | 2020-07-07 | Tcl集团股份有限公司 | Quantum dot light-emitting diode and preparation method thereof |
| CN112289997A (en) * | 2020-10-30 | 2021-01-29 | 中国科学院长春应用化学研究所 | Silicon dioxide-based composite negative electrode material for lithium ion battery and preparation method thereof |
| CN113013385A (en) * | 2019-12-19 | 2021-06-22 | 山西沃特海默新材料科技股份有限公司 | Coating agent, silicon-carbon material and preparation process |
| WO2021141013A1 (en) * | 2020-01-07 | 2021-07-15 | 積水化学工業株式会社 | Method for producing particles |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20090029256A1 (en) * | 2007-07-27 | 2009-01-29 | Samsung Sdi Co., Ltd. | Si/c composite, anode active materials, and lithium battery including the same |
| CN101604753A (en) * | 2009-07-24 | 2009-12-16 | 成都中科来方能源科技有限公司 | Carbon-silicon composite material and its production and use |
| CN102522534A (en) * | 2012-01-09 | 2012-06-27 | 奇瑞汽车股份有限公司 | Silicon-carbon composite material with high specific capacity, preparation method of silicon-carbon composite material, lithium ion battery anode material and lithium ion battery |
| CN102569759A (en) * | 2012-01-05 | 2012-07-11 | 北京理工大学 | Process for preparing materials of silicon-porous carbon negative electrodes of lithium-ion batteries |
| CN102593418A (en) * | 2012-02-24 | 2012-07-18 | 奇瑞汽车股份有限公司 | Carbon-silicon composite material, preparation method thereof, and lithium ion battery containing carbon-silicon composite material |
| CN102694156A (en) * | 2012-06-15 | 2012-09-26 | 东莞市迈科新能源有限公司 | Silicon-carbon composite negative pole material, preparation method thereof and lithium ion battery using foamed metal as negative pole current collector |
-
2012
- 2012-12-05 CN CN201210515970.6A patent/CN102983313B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20090029256A1 (en) * | 2007-07-27 | 2009-01-29 | Samsung Sdi Co., Ltd. | Si/c composite, anode active materials, and lithium battery including the same |
| CN101604753A (en) * | 2009-07-24 | 2009-12-16 | 成都中科来方能源科技有限公司 | Carbon-silicon composite material and its production and use |
| CN102569759A (en) * | 2012-01-05 | 2012-07-11 | 北京理工大学 | Process for preparing materials of silicon-porous carbon negative electrodes of lithium-ion batteries |
| CN102522534A (en) * | 2012-01-09 | 2012-06-27 | 奇瑞汽车股份有限公司 | Silicon-carbon composite material with high specific capacity, preparation method of silicon-carbon composite material, lithium ion battery anode material and lithium ion battery |
| CN102593418A (en) * | 2012-02-24 | 2012-07-18 | 奇瑞汽车股份有限公司 | Carbon-silicon composite material, preparation method thereof, and lithium ion battery containing carbon-silicon composite material |
| CN102694156A (en) * | 2012-06-15 | 2012-09-26 | 东莞市迈科新能源有限公司 | Silicon-carbon composite negative pole material, preparation method thereof and lithium ion battery using foamed metal as negative pole current collector |
Cited By (24)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103367726A (en) * | 2013-07-10 | 2013-10-23 | 奇瑞汽车股份有限公司 | Silicon-carbon composite material and preparation method thereof as well as lithium ion battery |
| CN103367726B (en) * | 2013-07-10 | 2016-12-28 | 奇瑞汽车股份有限公司 | Si-C composite material and preparation method thereof, lithium ion battery |
| US10355272B2 (en) | 2013-10-31 | 2019-07-16 | Lg Chem, Ltd. | Anode active material for lithium secondary battery and method of preparing the same |
| TWI627785B (en) * | 2013-10-31 | 2018-06-21 | Ｌｇ化學股份有限公司 | Anode active material for lithium secondary battery and method of preparing the same |
| CN103579596B (en) * | 2013-11-08 | 2016-09-14 | 合肥国轩高科动力能源有限公司 | The preparation method of lithium ion battery negative material |
| CN103579596A (en) * | 2013-11-08 | 2014-02-12 | 合肥国轩高科动力能源股份公司 | Preparation method of lithium ion battery cathode material |
| 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 |
| CN103633305A (en) * | 2013-12-10 | 2014-03-12 | 苏州宇豪纳米材料有限公司 | Silicon composite anode material of lithium ion battery and preparation method of silicon composite anode material |
| CN105981204A (en) * | 2014-02-07 | 2016-09-28 | 信越化学工业株式会社 | 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 |
| US10388950B2 (en) | 2014-02-07 | 2019-08-20 | Shin-Etsu Chemical Co., Ltd. | 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 |
| CN107768608B (en) * | 2016-08-15 | 2020-10-16 | 福建新峰二维材料科技有限公司 | Preparation method of lithium ion battery cathode material capable of effectively buffering silicon volume effect |
| CN107768608A (en) * | 2016-08-15 | 2018-03-06 | 福建新峰二维材料科技有限公司 | The effectively preparation method of the lithium ion battery negative material of buffering silicon bulk effect |
| CN107359306A (en) * | 2017-05-23 | 2017-11-17 | 中国第汽车股份有限公司 | A kind of preparation method of the compound silicon-carbon cathode material of organic carbon |
| CN107359317A (en) * | 2017-05-23 | 2017-11-17 | 中国第汽车股份有限公司 | Preparation method using Ludox as the compound silicon-carbon cathode of the organic carbon of silicon source |
| CN107369809A (en) * | 2017-05-23 | 2017-11-21 | 中国第汽车股份有限公司 | A kind of preparation method of lithium ion battery silicon-carbon cathode material |
| CN107394121A (en) * | 2017-05-23 | 2017-11-24 | 中国第汽车股份有限公司 | A kind of preparation method using Ludox as the silicon-carbon composite cathode material of silicon source |
| 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 |
| CN109216683A (en) * | 2018-09-20 | 2019-01-15 | 天津师范大学 | A kind of synthetic method of lithium ion battery high-capacity cathode material |
| CN111384253A (en) * | 2018-12-27 | 2020-07-07 | Tcl集团股份有限公司 | Quantum dot light-emitting diode and preparation method thereof |
| CN111384253B (en) * | 2018-12-27 | 2021-05-28 | Tcl科技集团股份有限公司 | Quantum dot light-emitting diode and preparation method thereof |
| CN113013385A (en) * | 2019-12-19 | 2021-06-22 | 山西沃特海默新材料科技股份有限公司 | Coating agent, silicon-carbon material and preparation process |
| WO2021141013A1 (en) * | 2020-01-07 | 2021-07-15 | 積水化学工業株式会社 | Method for producing particles |
| CN112289997A (en) * | 2020-10-30 | 2021-01-29 | 中国科学院长春应用化学研究所 | Silicon dioxide-based composite negative electrode material for lithium ion battery and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102983313B (en) | 2016-01-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102983313B (en) | Si-C composite material and preparation method thereof, lithium ion battery | |
| CN102306759B (en) | Silicon monoxide composite cathode material for lithium ion battery, and preparation method thereof | |
| CN110212183B (en) | Powder pre-lithiation silicon-based negative electrode material and preparation method and application thereof | |
| CN107275606B (en) | Carbon-coated spinel lithium manganate nanocomposite and preparation method and application thereof | |
| CN102237519B (en) | Fluorine-free preparation method for three-dimensional porous silica powder anode material of lithium ion battery | |
| CN103346324B (en) | Lithium ion battery cathode material and its preparation method | |
| CN100401559C (en) | Preparation method for composite negative electrode material of lithium ion battery | |
| CN104009210B (en) | A kind of porous silicon/carbon composite material, Preparation method and use | |
| CN102983317A (en) | Silicon-based composite material and preparation method thereof, silicon-carbon composite material and lithium ion battery | |
| CN102800851A (en) | Silicon carbon composite material and preparation method thereof, lithium ion battery containing same | |
| CN102340001A (en) | Method for preparing high-specific-capacity silicon carbon and tin carbon composite anode material | |
| CN111048770B (en) | Ternary doped silicon-based composite material and preparation method and application thereof | |
| CN102509778A (en) | Lithium ion battery cathode material and preparation method thereof | |
| CN102522534A (en) | Silicon-carbon composite material with high specific capacity, preparation method of silicon-carbon composite material, lithium ion battery anode material and lithium ion battery | |
| CN109449379B (en) | Nitrogen-doped carbon composite SnFe2O4Lithium ion battery cathode material and preparation method and application thereof | |
| CN103367726A (en) | Silicon-carbon composite material and preparation method thereof as well as lithium ion battery | |
| CN102881870A (en) | Lithium ion battery silicon substrate lithium salt composite negative electrode material and preparation method and application thereof | |
| CN106960954A (en) | A kind of preparation method and application of Prussian blue/graphene/sulphur composite | |
| CN105226285A (en) | A kind of porous silicon carbon composite and preparation method thereof | |
| CN107732203B (en) | Preparation method of nano cerium dioxide/graphene/sulfur composite material | |
| CN105655589A (en) | Graphene composite material and preparation method thereof | |
| CN108666560A (en) | Lithium ion battery, nano silicon material and preparation method thereof | |
| CN103259001A (en) | Silica composite material as well as preparation method thereof and lithium ion battery | |
| CN104332621A (en) | Method for preparing hollow nano silicon microsphere through metal thermal reduction and lithium ion battery | |
| CN109273700A (en) | A kind of silicon based composite material and its preparation method and application |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |