CN104577066A - Silicon oxide composite negative pole material for lithium ion secondary battery and preparation method thereof - Google Patents
Silicon oxide composite negative pole material for lithium ion secondary battery and preparation method thereof Download PDFInfo
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- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention relates to a silicon oxide composite negative pole material for a lithium ion secondary battery and a preparation method thereof. The composite material consists of silicon oxide, graphite type carbon materials and amorphous carbon materials. The preparation method comprises the following steps: performing magnesiothermic reduction on silicon dioxide so as to generate the silicon oxide by using alkaline(soil) metal chloride as a heat absorbent; after performing acid corrosion, sucking filtration, washing and vacuum drying on the silicon oxide, performing pre-ball milling on the dried silicon oxide and graphite; then complementing an organic carbon source, performing secondary ball milling, and then performing high-temperature heat treatment so as to obtain the silicon oxide composite negative pole material. The oxygen content of the silicon oxide is controlled by regulating the proportion of the silicon dioxide to magnesium, and then the silicon oxide is uniformly mixed with the graphite type carbon materials and the organic carbon source. The silicon oxide composite negative pole material disclosed by the invention has the characteristics of a higher first-time Kulun efficiency, a high specific capacity, a better cycle performance and the like; the preparation method adopted by the invention is easy in operation, simple in technology, low in cost and suitable for the industrial mass production.
Description
Technical field
The present invention relates to ion secondary battery cathode material lithium and technology of preparing thereof, particularly a kind of Si oxide composite negative pole material and preparation method thereof of lithium rechargeable battery.
Background technology
Lithium rechargeable battery because its specific energy is large, have extended cycle life, the advantage such as low in the pollution of the environment, become primary study direction, countries in the world.At present, what the ion secondary battery cathode material lithium successfully realizing large-scale commercial mainly adopted is graphite is main carbon materials.But such material theoretical maximum specific capacity only has 372mAh/g, has been difficult to the requirement meeting high capacity power source.In non-carbon negative material, silicon has the highest theoretical specific capacity (about 3800mAh/g), close to 10 times of graphite theoretical capacity, but owing to inhaling, putting volumetric expansion (up to 300%) larger in lithium process and cause its cycle performance poor.In numerous silicon and compound thereof, the theoretical capacity of SiO is high (~ 2000mAh/g), the Li generated in first all courses of reaction
2o and Li
4siO
4cushioning effect is had, to the effect that cycle performance is improved to volumetric expansion.But SiO conductivity is poor, and generate in first charge-discharge process reduce first effect can not anti-phase Li
2o and Li
4siO
4, in order to improve the chemical property being oxidized sub-silicon, carry out RESEARCH OF PYROCARBON mainly through organic carbon source coated.In addition, industrial production SiO major part cools rapidly after (more than 1000 DEG C) silicon dioxide and elemental silicon effect under the high temperature conditions to prepare, and production cost is high is unfavorable for large-scale production.Therefore, the SiO production technology of developing low-cost is extremely urgent.Unbodied SiO in Si oxide
2being converted into completely in all embedding lithium processes of head can not anti-phase Li
2o and Li
4siO
4, usually serve as activated centre Si at the buffer matrix inhaling, put the volumetric expansion in lithium process, significantly can improve the cycle performance of material.
Chinese patent CN101752547B discloses nucleocapsid structure Si-SiO
2the preparation method of-C composite.The method selects the sub-silicon of oxidation, graphite, pitch as initial feed, prepares the Si-SiO with nucleocapsid structure
2-C negative material, this material has higher specific capacity and good cycle performance, but its first coulombic efficiency only have about 70%, cannot commercial applications be realized; Simultaneously in mechanical milling process with an organic solvent, easily cause environmental pollution in last handling process and cost is high.
A kind of lithium rechargeable battery composite negative pole material is disclosed in CN103441250A.It take oxide containing silicon as raw material, mixes with graphite and pitch ball milling, adds conductive metal salt, prepare through high-energy ball milling method and high-temperature heat treatment.Take silicon monoxide as the composite material that silicon source prepares in this patent of invention, although the doping of argent improves the conductivity of composite material, the problem of initial coulomb efficiency low (less than 70%) is not still resolved.
A kind of lithium ion battery silicon oxide composite negative pole material is disclosed in CN102306759A.The method will be oxidized sub-silicon high temperature sintering generation silicon nanoparticle and amorphous silica under an inert atmosphere, then be mixed to get final material with a certain amount of conductive agent ball milling.The Si oxide composite negative pole material prepared in this patent of invention, first three ten weeks capacity attenuation is very fast, although have good cycle performance after 30 weeks, recycle ratio capacity only has about 550mAh/g.
A kind of preparation method of tin Si oxide composite negative pole material is disclosed in CN103545496A.It is with SnCl
2powder, NaOH powder and NaCl powder are that nano SnO prepared by raw material, and wherein NaCl plays the effect of control SnO crystallite dimension as structure directing agent; Again with nano SnO, SiO and organic polymer for raw material, prepare tin Si oxide composite negative pole material.Although this invention has prepared nano level SnO, SnO, SiO and organic macromolecule liquid phase by NaCl as structure directing agent stir the Homogeneous phase mixing not realizing three, thus causes cyclical stability poor.
Summary of the invention
Si oxide composite negative pole material that the object of this invention is to provide a kind of lithium rechargeable battery and preparation method thereof, the defect of prior art can be overcome, achieve and reduce silicon monoxide production cost, and solve the technical problem of existing head effect, circulation and capacity etc.Silicon oxide composite material provided by the invention is made up of Si oxide and material with carbon element, wherein Si oxide is the mixture with alkali (soil) the metal chloride silicon monoxide that to be heat absorbent prepared by magnesium reduction process and silicon dioxide, simultaneously can by the oxygen content regulating the ratio of silicon dioxide and magnesium to control in Si oxide; Material with carbon element is the mixture of graphite-like material with carbon element and amorphous carbon material.The preparation method that the present invention adopts is easy to operation, technique is simple, cost is low, is suitable for industrialization large-scale production.Silicon oxide composite material provided by the invention has the features such as higher coulombic efficiency first, height ratio capacity and good cycle performance, is suitable as lithium ion battery negative material.
The Si oxide composite negative pole material of lithium rechargeable battery provided by the invention is with Si oxide, graphite-like material with carbon element and amorphous carbon material precursor for raw material, is 10: 1-10: 1-5 to be prepared from according to the mass ratio of Si oxide, graphite-like material with carbon element and amorphous carbon material precursor (organic carbon source); Concrete technology is: after SiO 2 powder, magnesium powder, alkali metal or alkaline earth metal chloride Homogeneous phase mixing, ball milling; 300-600 DEG C of high temperature magnesiothermic reduction reaction is carried out under the Buchholz protection of falling property; product hcl corrosion, dissolving, washing; obtain Si oxide; Si oxide again with the even once mixture of graphite-like material with carbon element ball milling; add organic carbon source ball milling again and be mixed to get secondary mixture, 500-1000 DEG C of high-temperature heat treatment, naturally cool.
Described Si oxide is made up of the mixture of silicon monoxide and silicon dioxide, and wherein the mass ratio of silicon monoxide and silicon dioxide is 10-2: 1.
Described graphite-like material with carbon element is the one in native graphite, Delanium and meso-phase graphite.
Described amorphous carbon material precursor is organic carbon source.The amorphous carbon material that organic carbon source high temperature pyrolysis prepares, wherein organic carbon source is at least one in glucose, sucrose, polyvinyl alcohol, citric acid, phenolic resins, pitch.
The preparation method of a kind of lithium rechargeable battery Si oxide composite negative pole material provided by the invention, specifically comprises the following steps:
1) by metering SiO 2 powder, magnesium powder, alkali metal chloride or and alkaline earth metal chloride powder ball milling mixing; magnesiothermic reduction reaction is carried out under argon gas atmosphere protection; the HCl of excessive 0.5mol/L is adopted to leave standstill corrosion after being down to normal temperature; filtering and washing; vacuumize, can obtain Si oxide.
2) above-mentioned Si oxide and graphite-like material with carbon element are mixed under argon gas atmosphere protection in planetary ball mill, obtain once mixture; Under argon gas atmosphere protection, then precursor organic carbon source is mended join ball milling in once mixture and be mixed to get secondary mixture.
3) under inert atmosphere protection, high-temperature heat treatment is carried out to secondary mixture, naturally cool to room temperature and namely obtain final composite negative pole material.
Step 1) described in alkali (soil) metal chloride be NaCl, MgCl
2, CaCl
2, at least one in LiCl;
Step 2) described in the mass ratio of Si oxide, graphite-like material with carbon element and organic carbon source be 10: 1-10: 1-5;
Step 1) and step 2) described in ball milling condition: rotating speed is 300-500rpm, and Ball-milling Time is 1h-30h, and ratio of grinding media to material is 5-20: 1;
Step 1) described in magnesiothermic reduction, reaction temperature is 300-600 DEG C, and temperature retention time is 2-6h, and heating rate is 3-20 DEG C/min;
Step 3) described high-temperature heat treatment temperature is 500-1000 DEG C, the processing time is 0.5-10h, and heating rate is 2-20 DEG C/min.
The Si oxide composite negative pole material of lithium rechargeable battery provided by the invention is for raw material with Si oxide, graphite-like material with carbon element and amorphous carbon material precursor, overcome the defect of prior art, achieve and reduce silicon monoxide production cost, and solve the technical problem of existing head effect, circulation and capacity etc.Silicon oxide composite material provided by the invention is made up of Si oxide and material with carbon element, wherein Si oxide is the mixture with alkali (soil) the metal chloride silicon monoxide that to be heat absorbent prepared by magnesium reduction process and silicon dioxide, the temperature adding reduction reaction system of heat absorbent or title grinding aid, prevent abrasive body from being sticked by material and impel material particles to disperse time, same attenuating material hardness can improve grinding efficiency, especially can by the oxygen content regulating the ratio of silicon dioxide and magnesium to control in Si oxide; Material with carbon element is the mixture of graphite-like material with carbon element and amorphous carbon material.The preparation method that the present invention adopts is easy to operation, technique is simple, cost is low, is suitable for industrialization large-scale production.Silicon oxide composite material provided by the invention has the features such as higher coulombic efficiency first, height ratio capacity and good cycle performance, is suitable as lithium ion battery negative material.
Accompanying drawing explanation
X-ray photoelectron spectroscopic analysis (XPS) spectrogram of Fig. 1 composite material prepared by the embodiment of the present invention 1.
X-ray diffraction (XRD) spectrogram of Fig. 2 composite material prepared by the embodiment of the present invention 1.
The electrochemistry cyclic curve of Fig. 3 composite material prepared by the embodiment of the present invention 1 and coulombic efficiency curve.
Embodiment
Further illustrate the present invention below in conjunction with embodiment, its objective is that can understand content of the present invention is better embody substantive distinguishing features of the present invention, therefore the cited case should not be considered as limiting the scope of the invention.Here also particularly point out specific experiment method and apparatus involved in embodiment if no special instructions, be conventional method or implement according to the condition of manufacturer's specification suggestion, involved reagent is commercially available without specified otherwise.
Embodiment 1:
The Si oxide composite negative pole material of a kind of lithium rechargeable battery of the present invention can be prepared by the following method:
1) by mass ratio be 1: 0.4: 10 SiO 2 powder, magnesium powder and NaCl powder ball milling mixing, ball milling condition is: rotating speed is 400rpm, and Ball-milling Time is 5h, and ratio of grinding media to material is 10: 1; Carry out magnesiothermic reduction reaction under argon gas atmosphere protection, be incubated 4h under 500 DEG C of conditions, heating rate is 5 DEG C/min, and adopt the HCl of excessive 0.5mol/L to leave standstill corrosion after being down to normal temperature, filtering and washing, vacuumize, can obtain Si oxide.
2) by the Si oxide of above-mentioned preparation and native graphite be in mass ratio 10: 2.5 argon gas atmosphere protection under mix in planetary ball mill, ball milling condition is: rotating speed is 400rpm, and Ball-milling Time is 20h, and ratio of grinding media to material is 10: 1, obtains once mixture.Then, under argon gas atmosphere protection, then be that 12.5: 5 ball millings are mixed to get secondary mixture in mass ratio by the once mixture of above-mentioned preparation and glucose.
3) under inert atmosphere protection, carry out high-temperature heat treatment to secondary mixture, be incubated 2h under 700 DEG C of conditions, heating rate is 10 DEG C/min, naturally cools to room temperature and namely obtains final composite negative pole material.
Fig. 1 is X-ray photoelectron spectroscopic analysis (XPS) spectrogram of the silicon oxide composite material stripping 5min of above-mentioned preparation.The Si2p spectrogram value list of the silicon oxide composite material of 5min peeled off by table 1
As can be seen from this figure, there is a broad peak in the composite material peeling off 5min, and through over-fitting, this peak belongs to the Si of+4 valencys and the Si of+divalent.Can learn from the data of table 1, the Si content of+divalent is higher, account for 78.0%, and the Si of+4 valencys accounts for 22.0%.This result shows, partly the Si of+4 valencys is reduced to+divalent, and wherein the mass ratio of silicon monoxide and silicon dioxide is 2.6: 1.
Fig. 2 is X-ray diffraction (XRD) spectrogram of the silicon oxide composite material of above-mentioned preparation.As can be seen from this figure, being 20 ° ~ 30 ° at 2 θ has individual broad peak, belongs to Si oxide; Be 26.5 ° at 2 θ and have a sharp-pointed strong diffraction maximum, belong to carbon.
With the silicon oxide composite material of above-mentioned preparation for active electrode material, test its cycle performance in 2032 type button cells.Electrode material consists of: active material: conductive agent: the mass ratio of PVdF is 8: 1: 1; Be lithium metal to electrode; Electrolyte is EC/DMC (volume ratio is 1: the 1) solution of 1mol/L LiPF6; Barrier film is Cellgard2400 barrier film.Fig. 3 is electrochemistry cyclic curve and the coulombic efficiency curve of the silicon oxide composite material electrode of above-mentioned preparation.As can be seen from the figure, discharge capacity is 1255.3mAh/g first, and charging capacity is 984.7mAh/g, and namely coulombic efficiency is 78.4% first, and after circulating 50 weeks, discharge capacity remains on 691.5mAh/g.This result shows, prepared silicon oxide composite material has higher coulombic efficiency first, higher specific capacity and good cyclical stability.
Embodiment 2:
1) by mass ratio be 1: 0.37: 8 SiO 2 powder, magnesium powder and MgCl
2powder ball milling mixes, and ball milling condition is: rotating speed is 500rpm, and Ball-milling Time is 1h, and ratio of grinding media to material is 5: 1; Carry out magnesiothermic reduction reaction under argon gas atmosphere protection, be incubated 2h under 600 DEG C of conditions, heating rate is 20 DEG C/min, and adopt the HCl of excessive 0.5mol/L to leave standstill corrosion after being down to normal temperature, filtering and washing, vacuumize, can obtain Si oxide.
2) by the Si oxide of above-mentioned preparation and native graphite be in mass ratio 10: 1 argon gas atmosphere protection under mix in planetary ball mill, ball milling condition is: rotating speed is 500rpm, and Ball-milling Time is 1h, and ratio of grinding media to material is 10: 1, obtains once mixture.Then, under argon gas atmosphere protection, then be that 11: 5 ball millings are mixed to get secondary mixture in mass ratio by the once mixture of above-mentioned preparation and polyvinyl alcohol.
3) under inert atmosphere protection, carry out high-temperature heat treatment to secondary mixture, be incubated 0.5h under 1000 DEG C of conditions, heating rate is 2 DEG C/min, naturally cools to room temperature and namely obtains final composite negative pole material.
The XPS spectrum figure that the Si2p spectrum peak after 5min peeled off by composite material obtained under above-mentioned condition is similar to Fig. 1 with Fig. 2 in embodiment 1 with XRD spectra, indicate prepared composite material to be made up of Si oxide and carbon, in this composite material, the mass ratio of silicon monoxide and silicon dioxide is 10: 1.
With the composite material of above-mentioned preparation for electrode active material, test loop performance in 2032 type button cells equally, test condition is identical with embodiment 1.This electrode first discharge capacity is 1189.8mAh/g, and coulombic efficiency is 78.9% first, and after circulating 50 weeks, electrode reversible capacity is 687.8mAh/g.
Embodiment 3:
1) by mass ratio be 1: 0.32: 1 SiO 2 powder, magnesium powder and CaCl
2powder ball milling mixes, and ball milling condition is: rotating speed is 300rpm, and Ball-milling Time is 30h, and ratio of grinding media to material is 20: 1; Carry out magnesiothermic reduction reaction under argon gas atmosphere protection, be incubated 5h under 400 DEG C of conditions, heating rate is 5 DEG C/min, and adopt the HCl of excessive 0.5mol/L to leave standstill corrosion after being down to normal temperature, filtering and washing, vacuumize, can obtain Si oxide.
2) by the Si oxide of above-mentioned preparation and meso-phase graphite be in mass ratio 10: 4 argon gas atmosphere protection under mix in planetary ball mill, ball milling condition is: rotating speed is 300rpm, and Ball-milling Time is 30h, and ratio of grinding media to material is 20: 1, obtains once mixture.Then, under argon gas atmosphere protection, then by the once mixture of above-mentioned preparation and phenolic resins in mass ratio for 14:1 ball milling is mixed to get secondary mixture.
3) under inert atmosphere protection, carry out high-temperature heat treatment to secondary mixture, be incubated 10h under 500 DEG C of conditions, heating rate is 5 DEG C/min, naturally cools to room temperature and namely obtains final composite negative pole material.
The XPS spectrum figure that the Si2p spectrum peak after 5min peeled off by composite material obtained under above-mentioned condition is similar to Fig. 1 with Fig. 2 in embodiment 1 with XRD spectra, indicate prepared composite material to be made up of Si oxide and carbon, in this composite material, the mass ratio of silicon monoxide and silicon dioxide is 3: 1.
With the composite material of above-mentioned preparation for electrode active material, test loop performance in 2032 type button cells equally, test condition is identical with embodiment 1.This electrode first discharge capacity is 1398.3mAh/g, and coulombic efficiency is 78.8% first, and after circulating 50 weeks, electrode reversible capacity is 677.2mAh/g.
Embodiment 4:
1) by mass ratio be 1: 0.5: 20 SiO 2 powder, magnesium powder and LiCl powder ball milling mixing, ball milling condition is: rotating speed is 400rpm, and Ball-milling Time is 15h, and ratio of grinding media to material is 5: 1; Carry out magnesiothermic reduction reaction under argon gas atmosphere protection, be incubated 6h under 300 DEG C of conditions, heating rate is 3 DEG C/min, and adopt the HCl of excessive 0.5mol/L to leave standstill corrosion after being down to normal temperature, filtering and washing, vacuumize, can obtain Si oxide.
2) by the Si oxide of above-mentioned preparation and Delanium be in mass ratio 10: 1 argon gas atmosphere protection under mix in planetary ball mill, ball milling condition is: rotating speed is 300rpm, and Ball-milling Time is 20h, and ratio of grinding media to material is 10: 1, obtains once mixture.Then, under argon gas atmosphere protection, then be that 11: 1 ball millings are mixed to get secondary mixture in mass ratio by the once mixture of above-mentioned preparation and sucrose.
3) under inert atmosphere protection, carry out high-temperature heat treatment to secondary mixture, be incubated 4h under 900 DEG C of conditions, heating rate is 8 DEG C/min, naturally cools to room temperature and namely obtains final composite negative pole material.
The XPS spectrum figure that the Si2p spectrum peak after 5min peeled off by composite material obtained under above-mentioned condition is similar to Fig. 1 with Fig. 2 in embodiment 1 with XRD spectra, indicate prepared composite material to be made up of Si oxide and carbon, in this composite material, the mass ratio of silicon monoxide and silicon dioxide is 2: 1.
With the composite material of above-mentioned preparation for electrode active material, test loop performance in 2032 type button cells equally, test condition is identical with embodiment 1.This electrode first discharge capacity is 979.5mAh/g, and coulombic efficiency is 80.4% first, and after circulating 50 weeks, electrode reversible capacity is 654.3mAh/g.
Embodiment 5:
1) by mass ratio be 1: 0.2: 10: 10 SiO 2 powder, magnesium powder, NaCl and LiCl powder ball milling mixing, ball milling condition is: rotating speed is 300rpm, and Ball-milling Time is 8h, and ratio of grinding media to material is 20: 1; Carry out magnesiothermic reduction reaction under argon gas atmosphere protection, be incubated 3h under 500 DEG C of conditions, heating rate is 15 DEG C/min, and adopt the HCl of excessive 0.5mol/L to leave standstill corrosion after being down to normal temperature, filtering and washing, vacuumize, can obtain Si oxide.
2) by the Si oxide of above-mentioned preparation and Delanium be in mass ratio 10: 7 argon gas atmosphere protection under mix in planetary ball mill, ball milling condition is: rotating speed is 400rpm, and Ball-milling Time is 10h, and ratio of grinding media to material is 10: 1, obtains once mixture.Then, under argon gas atmosphere protection, then be that 17: 4 ball millings are mixed to get secondary mixture in mass ratio by the once mixture of above-mentioned preparation and citric acid.
3) under inert atmosphere protection, carry out high-temperature heat treatment to secondary mixture, be incubated 2h under 600 DEG C of conditions, heating rate is 15 DEG C/min, naturally cools to room temperature and namely obtains final composite negative pole material.
The XPS spectrum figure that the Si2p spectrum peak after 5min peeled off by composite material obtained under above-mentioned condition is similar to Fig. 1 with Fig. 2 in embodiment 1 with XRD spectra, indicate prepared composite material to be made up of Si oxide and carbon, in this composite material, the mass ratio of silicon monoxide and silicon dioxide is 7: 1.
With the composite material of above-mentioned preparation for electrode active material, test loop performance in 2032 type button cells equally, test condition is identical with embodiment 1.This electrode first discharge capacity is 1037.4mAh/g, and coulombic efficiency is 79.1% first, and after circulating 50 weeks, electrode reversible capacity is 708.5mAh/g.
Embodiment 6:
1) by mass ratio be 1: 0.24: 6: 6: 6 SiO 2 powder, magnesium powder, NaCl, LiCl, MgCl
2powder ball milling mixes, and ball milling condition is: rotating speed is 300rpm, and Ball-milling Time is 4h, and ratio of grinding media to material is 15: 1; Carry out magnesiothermic reduction reaction under argon gas atmosphere protection, be incubated 3h under 500 DEG C of conditions, heating rate is 6 DEG C/min, and adopt the HCl of excessive 0.5mol/L to leave standstill corrosion after being down to normal temperature, filtering and washing, vacuumize, can obtain Si oxide.
2) by the Si oxide of above-mentioned preparation and Delanium be in mass ratio 10: 10 argon gas atmosphere protection under mix in planetary ball mill, ball milling condition is: rotating speed is 400rpm, and Ball-milling Time is 12h, and ratio of grinding media to material is 15: 1, obtains once mixture.Then, under argon gas atmosphere protection, then be that 20: 5 ball millings are mixed to get secondary mixture in mass ratio by the once mixture of above-mentioned preparation and pitch.
3) under inert atmosphere protection, carry out high-temperature heat treatment to secondary mixture, be incubated 2h under 700 DEG C of conditions, heating rate is 20 DEG C/min, naturally cools to room temperature and namely obtains final composite negative pole material.
The XPS spectrum figure that the Si2p spectrum peak after 5min peeled off by composite material obtained under above-mentioned condition is similar to Fig. 1 with Fig. 2 in embodiment 1 with XRD spectra, indicate prepared composite material to be made up of Si oxide and carbon, in this composite material, the mass ratio of silicon monoxide and silicon dioxide is 8: 1.
With the composite material of above-mentioned preparation for electrode active material, test loop performance in 2032 type button cells equally, test condition is identical with embodiment 1.This electrode first discharge capacity is 1156.2mAh/g, and coulombic efficiency is 74.4% first, and after circulating 50 weeks, electrode reversible capacity is 710.2mAh/g.
Embodiment 7:
1) by mass ratio be 1: 0.31: 2: 4: 6: 8 SiO 2 powder, magnesium powder, NaCl, LiCl, CaCl
2, MgCl
2powder ball milling mixes, and ball milling condition is: rotating speed is 300rpm, and Ball-milling Time is 4h, and ratio of grinding media to material is 15: 1; Carry out magnesiothermic reduction reaction under argon gas atmosphere protection, be incubated 4h under 450 DEG C of conditions, heating rate is 6 DEG C/min, and adopt the HCl of excessive 0.5mol/L to leave standstill corrosion after being down to normal temperature, filtering and washing, vacuumize, can obtain Si oxide.
2) by the Si oxide of above-mentioned preparation and Delanium be in mass ratio 10: 3 argon gas atmosphere protection under mix in planetary ball mill, ball milling condition is: rotating speed is 400rpm, and Ball-milling Time is 12h, and ratio of grinding media to material is 15: 1, obtains once mixture.Then, under argon gas atmosphere protection, then be that 13: 3 ball millings are mixed to get secondary mixture in mass ratio by the once mixture of above-mentioned preparation and pitch.
3) under inert atmosphere protection, carry out high-temperature heat treatment to secondary mixture, be incubated 2h under 700 DEG C of conditions, heating rate is 8 DEG C/min, naturally cools to room temperature and namely obtains final composite negative pole material.
The XPS spectrum figure that the Si2p spectrum peak after 5min peeled off by composite material obtained under above-mentioned condition is similar to Fig. 1 with Fig. 2 in embodiment 1 with XRD spectra, indicate prepared composite material to be made up of Si oxide and carbon, in this composite material, the mass ratio of silicon monoxide and silicon dioxide is 8.4: 1.
With the composite material of above-mentioned preparation for electrode active material, test loop performance in 2032 type button cells equally, test condition is identical with embodiment 1.This electrode first discharge capacity is 1176.1mAh/g, and coulombic efficiency is 79.2% first, and after circulating 50 weeks, electrode reversible capacity is 684.3mAh/g.
The above is only the preferred embodiment of the present invention.It should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention, can also make some improvements and modifications, these improvements and modifications also should be considered as protection scope of the present invention.
Claims (10)
1. a lithium rechargeable battery Si oxide composite negative pole material, it is characterized in that it is with Si oxide, graphite-like material with carbon element and amorphous carbon material precursor for raw material, is 10: 1-10: 1-5 to be prepared from according to the mass ratio of Si oxide, graphite-like material with carbon element and amorphous carbon material precursor; Concrete technology is: after SiO 2 powder, magnesium powder, alkali metal or alkaline earth metal chloride Homogeneous phase mixing, ball milling; 300-600 DEG C of high temperature magnesiothermic reduction reaction is carried out under the Buchholz protection of falling property; product hcl corrosion, dissolving, washing; obtain Si oxide; Si oxide again with the even once mixture of graphite-like material with carbon element ball milling; add organic carbon source ball milling again and be mixed to get secondary mixture, 500-1000 DEG C of high-temperature heat treatment, naturally cool.
2. Si oxide composite negative pole material according to claim 1, is characterized in that described Si oxide is made up of the mixture of silicon monoxide and silicon dioxide, and wherein the mass ratio of silicon monoxide and silicon dioxide is 10-2: 1.
3. Si oxide composite negative pole material according to claim 1, is characterized in that described graphite-like material with carbon element is the one in native graphite, Delanium and meso-phase graphite.
4. Si oxide composite negative pole material according to claim 1, it is characterized in that described amorphous carbon material precursor is organic carbon source, wherein organic carbon source is at least one in glucose, sucrose, polyvinyl alcohol, citric acid, phenolic resins, pitch.
5. a preparation method for lithium rechargeable battery Si oxide composite negative pole material according to claim 1, is characterized in that specifically through following steps:
1) by metering SiO 2 powder, magnesium powder, alkali metal chloride or and alkaline earth metal chloride powder ball milling mixing, magnesiothermic reduction reaction is carried out under argon gas atmosphere protection, the HCl of excessive 0.5mol/L is adopted to leave standstill corrosion after being down to normal temperature, filtering and washing, vacuumize, can obtain Si oxide;
2) above-mentioned Si oxide and graphite-like material with carbon element are mixed under argon gas atmosphere protection in planetary ball mill, obtain once mixture; Under argon gas atmosphere protection, then precursor organic carbon source is mended join ball milling in once mixture and be mixed to get secondary mixture;
3) under inert atmosphere protection, high-temperature heat treatment is carried out to secondary mixture, naturally cool to room temperature and namely obtain final composite negative pole material.
6. method according to claim 5, is characterized in that step 1) described in metal chloride be NaCl, MgCl
2, CaCl
2, at least one in LiCl.
7. method according to claim 5, is characterized in that step 1) and step 2) described in ball milling condition be respectively: rotating speed is 300-500rpm, and Ball-milling Time is 1h-30h, and ratio of grinding media to material is 5-20: 1.
8. method according to claim 5, is characterized in that step 1) described in magnesiothermic reduction, reaction temperature is 300-600 DEG C, and temperature retention time is 2-6h, and heating rate is 3-20 DEG C/min.
9. method according to claim 5, is characterized in that step 3) described high-temperature heat treatment temperature is 500-1000 DEG C, the processing time is 0.5-10h, and heating rate is 2-20 DEG C/min.
10. a preparation method for lithium rechargeable battery Si oxide composite negative pole material, is characterized in that through following steps:
1) by the SiO 2 powder of proportioning 1:0.2-0.5:1-20, magnesium powder, alkali metal chloride or and alkaline earth metal chloride powder ball milling mixing, rotating speed is 300-500rpm, and Ball-milling Time is 1h-30h, and ratio of grinding media to material is 5-20: 1; Then, carry out magnesiothermic reduction reaction under argon gas atmosphere protection, reaction temperature is 300-600 DEG C, and temperature retention time is 2-6h, and heating rate is 3-20 DEG C/min; Adopt the standing corrosion of excessive 0.5mol/L after being down to normal temperature, filtering and washing, vacuumize, can obtain Si oxide, wherein the mass ratio of silicon monoxide and silicon dioxide is 10-2: 1.
2) above-mentioned Si oxide and graphite-like material with carbon element are mixed under argon gas atmosphere protection in planetary ball mill, obtain once mixture; Under argon gas atmosphere protection, then precursor organic carbon source is mended join ball milling in once mixture and be mixed to get secondary mixture; Described ball milling condition is respectively: rotating speed is 300-500rpm, and Ball-milling Time is 1h-30h, and ratio of grinding media to material is 5-20: 1; Described graphite-like material with carbon element is the one in native graphite, Delanium and meso-phase graphite; Described organic carbon source is at least one in glucose, sucrose, polyvinyl alcohol, citric acid, phenolic resins, pitch.
3) under inert atmosphere protection, high-temperature heat treatment is carried out to secondary mixture, naturally cool to room temperature and namely obtain final composite negative pole material; Described high-temperature heat treatment temperature is 500-1000 DEG C, and the processing time is 0.5-10h, and heating rate is 2-20 DEG C/min.
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