CN1855586B - Cathode materials for secondery lithium ion batteries - Google Patents
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- CN1855586B CN1855586B CN2005100665190A CN200510066519A CN1855586B CN 1855586 B CN1855586 B CN 1855586B CN 2005100665190 A CN2005100665190 A CN 2005100665190A CN 200510066519 A CN200510066519 A CN 200510066519A CN 1855586 B CN1855586 B CN 1855586B
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention uses silicon material as main materials of cathode. Wherein, said cathode material at least comprises a silicon core fine grain having a silicon grain and a surface covering. Said surface covering at least comprises one kind of metal oxide. In an optimizing embodiment, the metal oxide can be selected from titanium oxide or zirconia or their combination. A process thereof for preparing said cathode material is a chemical vapor deposition and a sol gel method.
Description
Technical field
The present invention relates to a kind of secondary lithium battery, particularly a kind of lithium ion battery negative material, and its related production based on silicon materials.
Background technology
So-called secondary lithium battery is meant lithium ion battery chargeable and discharge.For business-like secondary lithium battery on the market, its negative material is based on graphite material mostly.Compared to graphite material, silicon materials have sizable theoretical specific capacitance (～4000mAh/g), to exceed about order of magnitude than graphite material (372mAh/g).Therefore, silicon materials are considered to the emerging secondary lithium battery negative material that a suitable potentialization also has developing target market.
Yet, silicon materials are applied to the reason of lithium ion battery with delaying enough commercializations, mainly comprise: problems such as the low electrical conductivity of charge and discharge process cubical expansivity big (300%), silicon pole plate powdered, silicon, the solid phase-electrolyte boundary (SEI, Solid ElectrolyteInterface) of silicon are unstable, the electrochemical reaction power of the contacting of silicon and assistant director of a film or play's agent, silicon is not good, pole plate interface impedance.
These problems make with silicon be the secondary lithium battery of negative material in charge-discharge test, less than ten cycle-indexes, capacitance is decline widely just.To this, there are many patents or research document to want to improve in recent years for the silicium cathode material, below enumerate two representative patents about the silicium cathode material.
1) Sanyo company is open in No. 6649033 patent of the U.S.: with the silicon thin film (thin film) of mode sputter one deck 2 μ m to 5 μ m on Copper Foil of sputter (sputtering), it breaks through traditional mixed slurry coating process (30 μ m to 80 μ m), declare in this part patent that its charge and discharge capacitance can reach 3000mAh/g, and cycle life can reach hundreds of times.But because this processing procedure must use low-voltage vacuum system coating technique, manufacturing cost is mixed the slurry coating process and is exceeded a lot.
2) Matsushita company is open in No. 6548208 patent of the U.S.: form alloy phase with different metals and silicon materials at the high temperature dewatered melted type, matrix (Matrix) framework of hope by alloy phase is to reach constitutionally stable effect in charging and discharging process.Because coating layer is played the part of the matrix role, can absorb and cushion silicon materials and embed the violent volumetric expansion of moving out and causing because of lithium ion.
3) No. 6548208 patent of the U.S. of Mitsui Mining company: " secondary lithium battery and its negative material and charging method thereof ", its mode of openly utilizing TVD plates a carbon-coating with the silicon materials surface of powder.The silicon materials of powder adopt commercial product, and its size is between 0.1～50 μ m, and carbon-coating content accounts for 5% of percentage by weight, and the step of plating carbon-coating is to utilize fluidized bed, and 900 degrees centigrade are carried out.The carbon-coating that obtains is required to be suitable graphitization material, suppresses the expansion of silicon materials when the lithiumation to have enough intensity.Among the embodiment, the charging voltage of suggestion is between 0.05～0.08V, and it has the stable circulation capacitance greater than 900mAh/g approximately.
The present invention also still can not be applied to commercialization the shortcoming of the negative pole of lithium ion battery at above-mentioned silicon materials, seek the breakthrough of technology.The present invention institute is based on silicon materials with disclosed secondary lithium battery negative material, yet, negative material finished product provided by the present invention is different from the category of above-mentioned three representative patents fully, and relative manufacturing process provided by the present invention does not also have for known technology, and the notion that the present invention is correlated with, technological means and the effect of being reached will be disclosed among following explanation and the relevant embodiment.
Summary of the invention
Main purpose of the present invention provides a kind of secondary lithium battery negative material based on silicon materials.
Another object of the present invention is the high theoretical specific capacitance that the applying silicon material is had, in order to the usefulness performance of secondary lithium battery.
Another object of the present invention is to improve the known various every known disadvantage that silicon materials are applied to the secondary lithium battery negative pole that influences.
The invention provides a kind of secondary lithium battery negative material, comprise several silicon core particles, the silicon core particle comprises a silicon grain and a coating layer is coated in the silicon grain surface, and this coating layer comprises a metal oxide at least.The thickness of coating layer can be between 1nm to 1000nm, and it can be a single layer structure or a sandwich construction.And the diameter of silicon grain is substantially less than 100 microns.The present invention utilize theoretical capacitance more the silicon materials of 1000mAh/g be used as the main body of secondary lithium battery negative material, and can be used as the passage of lithium ion.Thus, not only can increase in the secondary lithium battery, the uniformity that lithium ion distributes, and metal oxide layer can be used as the passivation layer of artificial solid phase-electrolyte boundary (SEI, Solid Electrolyte Interface).Wherein, the optional autoxidation titanium of this metal oxide (TiO
2), zirconia (ZrO
2) or its combination.
In a manufacture method embodiment, the open secondary lithium battery negative material of the present invention utilizes the situation of chemical vapour deposition technique (Chemical Vapor Deposition) preparation.
In another manufacture method embodiment, the open secondary lithium battery negative material of the present invention utilizes the situation of sol-gal process (sol-gel process) preparation.
The negative material of secondary lithium battery of the present invention wherein comprises several silicon core particles, and above-mentioned this silicon core particle comprises:
One silicon grain (silicon particle); And
One coating layer is coated in this silicon grain surface, and this coating layer comprises a metal oxide at least.
Negative material of the present invention, wherein this coating layer is a single layer structure.
Negative material of the present invention, wherein this coating layer is a sandwich construction.
Negative material of the present invention, wherein the thickness of this coating layer is between 1nm to 1000nm.
Negative material of the present invention, wherein this metal oxide is selected from titanium oxide (TiO
2), zirconia (ZrO
2) or its combination.
Negative material of the present invention, wherein this coating layer comprises carbon.
Negative material of the present invention, wherein this metal oxide accounts for 0.01% to 100% of this coating layer percentage by weight.
Negative material of the present invention, wherein this silicon grain diameter is less than 100 microns.
The negative material manufacture method of secondary lithium battery of the present invention is wherein utilized pulsed chemical vapour deposition technique (Chemical Vapor Deposition), and this method comprises:
Import silicon materials in a reactor;
Control this reactor in a predetermined temperature; And
One burning predecessor (precursor) of the gas phase mode with pulsed vapour deposition (pulse-flow CVD) is imported in this reactor,
Thus, include the negative material of the secondary lithium battery of several silicon core particles with formation, above-mentioned this silicon core particle comprises that the surperficial coating of a silicon grain (silicon particle) contains the coating layer of a metal oxide.
Manufacture method of the present invention, wherein this predetermined temperature is substantially 300 degree Celsius to 1000 degree.
Manufacture method of the present invention, wherein the pulse frequency of this pulsed vapour deposition is between 0.1Hz to 10Hz.
Manufacture method of the present invention, wherein this burning predecessor be titanium oxide predecessor, zirconic predecessor or its combination.
Manufacture method of the present invention, wherein the predecessor of this titanium oxide is to be selected from the pure oxide (titanium alkoxide) that contains titanium or the salt compounds of titanium.
Manufacture method of the present invention, wherein this zirconic predecessor is the pure oxide (zirconium alkoxide) of selected among zirconium or the salt compounds of zirconium.
The negative material manufacture method of secondary lithium battery of the present invention is wherein utilized sol-gal process (sol-gel process), and this method comprises:
One silicon materials of powder are mixed mutually with a burning precursor solution, to obtain a mixed liquor;
Make this mixed liquor form colloidal state; And
This mixed liquor of calcination colloidal state is with the negative material of the secondary lithium battery that obtains powder,
Wherein, the negative material of above-mentioned this secondary lithium battery includes several silicon core particles, and it is that the surperficial coating of silicon grain (silicon particle) contains the coating layer of a metal oxide.
Manufacture method of the present invention, wherein this burning predecessor be titanium oxide predecessor, zirconic predecessor or its combination in any.
Manufacture method of the present invention, wherein the predecessor of this titanium oxide is selected from the pure oxide (titanium alkoxide) that contains titanium or the salt compounds of titanium.
Manufacture method of the present invention, the wherein salt compounds of pure oxide of this zirconic predecessor selected among zirconium (zirconium alkoxide) or zirconium.
Manufacture method of the present invention, wherein the employed solvent of this burning precursor solution is selected from H
2O or CxHyOHz, wherein x is between 1 to 10, and y is between 1 to 20, and z is between 1 to 10.
Manufacture method of the present invention wherein before this makes this mixed liquor form the step of colloidal state, more comprises this mixed liquor is bled, with the air in this silicon materials hole of getting rid of powder.
The present invention has also openly used the relevant electrically experiment of the made secondary lithium battery of negative material of the present invention, the effect of being reached with practical illustration the present invention.The invention provides a kind of secondary lithium battery negative material based on silicon, it comprises several silicon core particles, the coating on silicon core particle surface comprises a metal oxide at least, the optional autoxidation titanium of this metal oxide, zirconia or its combination in the preferable example.Metal oxide layer can be titanium oxide or zirconia, and negative material of the present invention can pulsed chemical vapour deposition technique or directly row manufacturing of sol-gal process.The present invention utilizes the advantage of the high theoretical amount capacity of silicon materials, yet overcome the known disadvantage that numerous silicon materials fail to be applied to commercial secondary lithium battery, and, the invention provides different means and reach better charge and discharge circulation life performance compared to the more close known technology of notion.
Description of drawings
Fig. 1 is a secondary lithium battery negative material schematic diagram of the present invention;
Fig. 2 is negative material one a manufacture method flow chart of the present invention;
Fig. 3 is the X-ray diffraction collection of illustrative plates of Fig. 2 embodiment;
Fig. 4 is another manufacture method flow chart of negative material of the present invention;
Fig. 5 is the X-ray diffraction collection of illustrative plates of Fig. 4 embodiment;
Fig. 6 is a comparative example charge and discharge cycles number of times-capacitance graph of a relation;
Fig. 7 A is the Si-ZrO of Fig. 6
2Capacitance-electric potential relation figure when embodiment discharges and recharges for the first time;
Fig. 7 B is the Si-TiO of Fig. 6
2Capacitance-electric potential relation figure when embodiment discharges and recharges for the first time;
Fig. 8 is another comparative example charge and discharge cycles number of times-capacitance graph of a relation of the present invention.
Embodiment
Please refer to Fig. 1, Fig. 1 is a secondary lithium battery negative material schematic diagram of the present invention.Secondary lithium battery negative material provided by the present invention comprises a silicon core particle 10 shown in Figure 1 at least.Silicon core particle 10 comprises a silicon grain 12 and a coating layer 14 is coated in silicon grain 12 surfaces.The thickness of coating layer 14 can be between 1nm to 1000nm, should include a metal oxide at least in the coating layer 14, the optional autoxidation titanium of this metal oxide (TiO
2), zirconia (ZrO
2) or its combination.
During enforcement, the diameter of silicon grain 12 is substantially less than 100 microns.And coating layer 14 can be a single layer structure, also can utilize plated film step repeatedly on processing procedure, and form a sandwich construction.The coating layer 14 of sandwich construction, the material of its each layer also can comprise graphite or carbon-coating except above-mentioned titanium oxide or zirconia.Above-mentioned material is selected from titanium oxide or zirconic metal oxide layer, accounts for 0.01% to 100% of these coating layer 14 percentage by weights.
The silicon materials (silicon grain 12) that the present invention utilizes theoretical capacitance can reach 4000mAh/g are used as the main body of secondary lithium battery negative material, and utilize metal oxide titanium oxide or zirconia to increase (belonging to coating layer 14) cycle life of silicon grain 12.Thus, not only can increase the uniformity that lithium ion distributes in the secondary lithium battery, and coating layer 14 can be used as artificial solid phase-electrolyte boundary (SEI, SolidElectrolyte Interface).Below the manufacture method that the present invention is correlated with will be disclosed, and relevant electrical experiment, to strengthen illustrating means of the present invention and the effect of being reached.
Manufacture method embodiment 1
Please refer to Fig. 2, Fig. 2 is negative material one a manufacture method flow chart of the present invention.The silicon core particle 10 that this embodiment utilizes chemical vapour deposition technique to prepare to contain metal oxide in the coating layer 14.
Implementation method is as follows: the predecessor of titanium oxide (precursor) is tetraisopropyl titanate (Titanium isopropoxide, Ti[OCH (CH in the present embodiment
3)
2]
4) solution, wherein with 3% H
2/ 97% N
2As the flow velocity of current-carrying gas with 2l/min, the frequency of the frequency of 1Hz (per second pulsatile once) is carried out pulsed ground fluidisation to the silicon materials of 10g powder, and enters in the fluid fluidized bed reactor.
After about one hour, make this current-carrying gas squeeze into this tetraisopropyl titanate solution again, and carry it in this fluidized bed reactor.
Be to react in the present embodiment with 800 degrees centigrade reaction temperature.Thus, the negative material that can obtain being scheduled to then, it comprises several silicon core particles 10 shown in Figure 1.In each silicon core particle 10, the diameter of silicon grain 12 is substantially less than 100 microns.And coating layer 14 is one to contain the single layer structure of titanium oxide.
Please refer to Fig. 3, Fig. 3 is the X-ray diffraction collection of illustrative plates of Fig. 2 embodiment.Wherein target is copper target CuK α
Scanning speed is 5deg./min.By the analysis of Fig. 3 as can be known the prepared negative material that goes out of this experiment be a silicon core particle (Fig. 1 label 10) of crystalline phase titanium dioxide, its titanium dioxide is criticized equably and is overlying on silicon grain (Fig. 1 label 12) surface.
In another embodiment of the present invention, utilize Zr (OC
4H
9)
4As predecessor, the repeatedly step 203 of execution graph 2 and step 204 with plated film repeatedly, and form the coating layers 14 of sandwich constructions on silicon grain 12 surfaces.
In another relevant embodiment, form the zirconia (ZrO of individual layer on silicon grain 12 surfaces
2) with as coating layer 14, and replace above-mentioned embodiment about titanium oxide.
In another relevant embodiment, plated film repeatedly, yet during plated film be each time can adopt different oxidized metals predecessor (for example: TiO (C
3H
7)
4, Zr (OC
4H
9)
4) in step 203, perhaps also can plate graphite linings, have the silicon core particle 10 of sandwich construction coating layer 14 with formation, wherein sandwich construction drapes over one's shoulders layer 14 and can have titanium oxide, zirconia or graphite.
Manufacture method embodiment two
Please refer to Fig. 4, Fig. 4 is another manufacture method flow chart of negative material of the present invention.This embodiment utilizes the silicon core particle 10 that contains metal oxide layer in the Prepared by Sol Gel Method coating layer 14.
Implementation method is as follows: with solvent with zirconic burning predecessor Zr (OC
4H
9)
4Mixed with percentage by weight four to.
For example be in one embodiment with n-butanol (1-butanol) as solvent, and with 2.35 the gram Zr (OC
4H
9) dropwise join in the n-butanol of 9.4 grams.
In order to make both mixing more even, can put it into the ultrasonic waves oscillator in the enforcement, earthquake promptly has good mixed effect after 15 minutes approximately, and mixed liquor can present the sample attitude of suitable clarification, and it is a faint yellow transparent liquid.
At this moment, then the powder silicon materials at baking oven preliminary drying (about 15 minutes) can be mixed mutually with a burning precursor solution, to obtain a mixed liquor (step 400).
Stir this mixed liquor so that the burning precursor solution fully infiltrates in the hole of silicon materials,, also can bleed, to get rid of the air in this silicon materials hole this mixed liquor in order to make the adhesion effect of metal oxide better.
Then, this mixed liquor is heated, so that this mixed liquor forms colloidal state (step 401).It can heat the mixed liquor that the mixes mode with oil bath on heating plate, with 85 degrees centigrade heating-up temperatures and can cooperate the stirring of magnetite, then the viscosity of mixed liquor can slowly become big and become colloidal state.
Thereafter, this mixed liquor of then calcination colloidal state is with the negative material (step 402) of the secondary lithium battery that obtains powder.It can place pipe furnace with this mixed liquor of colloidal state, with for example per hour 50 degrees centigrade programming rate be warming up to 700 degrees centigrade, and this temperature maintenance six hours.Treat that stove is chilled to after the room temperature, through grinding, sieve (for example 270mesh) then obtains secondary lithium battery negative material of the present invention with the powder of gained, and it includes several silicon core particles 10, and it is one silicon-zirconia (Si-ZrO among this embodiment
2) composite material.Making negative material about present embodiment can be with reference to Fig. 5, and Fig. 5 is the X-ray diffraction collection of illustrative plates of Fig. 4 embodiment, and wherein target is copper target CuK α
Scanning speed is 5deg./min.
In the foregoing description, the reaction equation of sol-gal process is:
Zr(OR)
4+H
2O→Zr(OR)
3-OH+ROH
Surface-OH+Zr(OR)
3-OH→surface-O-Zr(OR)
3+H
2O
Present embodiment is to have zirconic coating layer 14 with as an illustration template, in another relevant embodiment, is to form the coating layers 14 with titanium oxide on silicon grain 12 surfaces, and is above-mentioned about zirconic embodiment to replace.
In the various execution modes about the present invention, the predecessor of relevant titanium oxide is selected from the pure oxide (titanium alkoxide) that contains titanium or the salt compounds of titanium.And the salt compounds of pure oxide of zirconic predecessor selected among zirconium (zirconium alkoxide) or zirconium.
And about in the manufacturing execution mode that uses sol-gal process, the related solvents of metal oxide can be selected from H
2O or CxHyOHz, wherein x is between 1 to 10, and y is between 1 to 20, and z is between 1 to 10.
Please refer to Fig. 6, Fig. 6 is a comparative example charge and discharge cycles number of times-capacitance graph of a relation.By Fig. 6 with illustrate negative material provided by the present invention the actual effect of reaching.Wherein select three kinds of different negative materials for use,, then carry out the charge and discharge circulation life test with assembled battery.The condition of discharging and recharging be 1000mAh/g decide electric capacity charging, electric current is that 0.3mA/mg, voltage range are at 0-1.2V (V vs.Li/Li+).Three kinds of materials are that pure silicon sample (label 600), silicon-zirconium oxide composite material of the present invention are (hereinafter to be referred as Si-ZrO
2, label 601), silicon of the present invention-titanium oxide composite material is (hereinafter to be referred as Si-TiO
2, label 602).
Can cooperate Fig. 7 A and Fig. 7 B, Fig. 7 A is the Si-ZrO of Fig. 6
2Capacitance-electric potential relation figure when embodiment discharges and recharges for the first time; Fig. 7 B is the Si-TiO of Fig. 6
2Capacitance-electric potential relation figure when embodiment discharges and recharges for the first time.
At first, pure silicon sample (can referring to label 600) being very poor in the cycle life that discharges and recharges, capacitance just begins to successively decrease apace after only discharging and recharging five times, described just as many research documents, because silicon materials cause violent volumetric expansion in the lithium ion entry/leave, make many breaking and chipped area of pole plate generation of lithium battery, such chipped area can make the variation that contacts of silicon materials and Copper Foil, and then after discharge and recharge, electronics can't be derived from Copper Foil (current collector); Another one silicium cathode material shows the low electrical conductivity that bad reason is silicon materials itself in cycle life, makes lithium ion after moving out, even fine also being difficult for that contact of silicon materials and Copper Foil derives.When the 8th charge and discharge cycles, its capacitance begins obvious decline compared to the pure silicon sample, and no matter negative material provided by the present invention is Si-ZrO
2Perhaps Si-TiO
2, all have the charge and discharge circulation life performance that far surmounts the pure silicon sample.
Please refer to Fig. 8, Fig. 8 is another comparative example charge and discharge cycles number of times-capacitance graph of a relation of the present invention.Fig. 8 shows negative material provided by the present invention, with the negative material that the technology of No. 6548208 patent of the U.S. of Mitsui Mining company is made, carries out the comparison of charge and discharge circulation life performance; U.S.'s notion that No. 6548208 patent is main is that the silicon materials surface with powder plates a carbon-coating.This experiment is (hereinafter to be referred as Si-TiO with silicon of the present invention-titanium oxide composite material
2Label 702), the silico-carbo composite material (label 701) of No. 6548208 patent of the U.S., with pure silicon sample (label 700) be assembled into battery respectively, then carry out charge and discharge circulation life test, the condition of discharging and recharging be 1000mAh/g decide the electric capacity charging, electric current is that 0.3mA/mg, voltage range are at 0-1.2V (V vs.Li/Li+).
Can find that by Fig. 8 silico-carbo composite material 701 helps to promote the structural stability of the negative material of silicon main body really, therefore better cycle life be arranged compared to pure silicon sample 700, however Si-TiO provided by the present invention
2The charge and discharge circulation life of (label 702) then further has more superior performance than silico-carbo composite material 701.What deserves to be mentioned is that the present invention can plate coating layer than low weight percentage on silicon grain (Fig. 1 label 12) surface, and (Fig. 1 label 14 is with this embodiment: the TiO of percentage by weight 8% only
2), in comparison, the known technology of No. 6548208 patent of the U.S. then needs to plate carbon-coating and reaches percentage by weight 27%.Even the present invention under the situation of the coating layer 14 that silicon grain 12 surface coatings approach comparatively speaking, still can have better charge and discharge circulation life performance.
Comprehensive the above, the invention provides a kind of secondary lithium battery negative material based on silicon, it comprises several silicon core particles, the coating on silicon core particle surface comprises a metal oxide at least, the optional autoxidation titanium of this metal oxide, zirconia or its combination in the preferable example.Metal oxide layer can be titanium oxide or zirconia, and negative material of the present invention can pulsed chemical vapour deposition technique or directly row manufacturing of sol-gal process.The present invention utilizes the advantage of the high theoretical amount capacity of silicon materials, yet overcome the known disadvantage that numerous silicon materials fail to be applied to commercial secondary lithium battery, and, the invention provides different means and reach better charge and discharge circulation life performance compared to the more close known technology of notion.
Though the present invention illustrates as above with preferred embodiments, so it is not only to terminate in the foregoing description in order to limit the present invention's spirit with the invention entity.To being familiar with this operator, when understanding and utilize other element or mode to produce identical effect easily.For example, be familiar with this operator and can in forming the coating layer that the present invention contains oxide, add the carbon material to be used for regulating the electron conduction degree of coating layer integral body.For example, in another related embodiment of the present invention, in current-carrying gas, have tetraisopropyl titanate and benzene simultaneously, mode with pulsed vapour deposition (pulse-flow CVD), temperature at 800 degrees centigrade is reacted, and at the silicon grain 12 surperficial coating layers 14 that form single layer structures, wherein coating layer 14 contains titanium dioxide and carbon simultaneously.
Though the present invention with preferred embodiment openly as above; right its is not in order to limiting the present invention, anyly is familiar with this skill person, without departing from the spirit and scope of the present invention; when can being used for a variety of modifications and variations, so protection scope of the present invention is as the criterion when looking the scope that claims define.
Symbol description
Claims (5)
1. the negative material manufacture method of a secondary lithium battery is characterized in that utilizing the pulsed chemical vapour deposition technique, and this method comprises:
Import silicon materials in reactor;
Control this reactor in predetermined temperature; And
The burning predecessor of titania precursor thing, zirconia predecessor or its combination of the gas phase mode with the pulsed vapour deposition is imported in this reactor,
Thus, the negative material that includes the secondary lithium battery of several silicon core particles with formation, above-mentioned this silicon core particle comprises that silicon grain and coating layer are coated in this silicon grain surface, and this coating layer contains the metal oxide of titanium oxide, zirconia or its combination.
2. manufacture method according to claim 1 is characterized in that this predetermined temperature is that 300 degree Celsius are to 1000 degree.
3. manufacture method according to claim 1, the pulse frequency that it is characterized in that this pulsed vapour deposition is between 0.1Hz to 10Hz.
4. manufacture method according to claim 1, the predecessor that it is characterized in that this titanium oxide are to be selected from the pure oxide that contains titanium or the salt compounds of titanium.
5. manufacture method according to claim 1 is characterized in that this zirconic predecessor is the pure oxide of selected among zirconium or the salt compounds of zirconium.
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| FR2928036B1 (en) * | 2008-02-26 | 2010-12-24 | Commissariat Energie Atomique | METHOD FOR MANUFACTURING SILICON ELECTRODE, SILICON ELECTRODE, AND LITHIUM BATTERY COMPRISING SUCH ELECTRODE |
| JP5217536B2 (en) * | 2008-03-17 | 2013-06-19 | ソニー株式会社 | Secondary battery and electronic equipment |
| JP5215978B2 (en) | 2009-10-28 | 2013-06-19 | 信越化学工業株式会社 | Anode material for non-aqueous electrolyte secondary battery, method for producing the same, and lithium ion secondary battery |
| JP5961922B2 (en) * | 2010-05-31 | 2016-08-03 | 日産自動車株式会社 | Negative electrode for secondary battery and method for producing the same |
| JP6216154B2 (en) | 2012-06-01 | 2017-10-18 | 株式会社半導体エネルギー研究所 | Negative electrode for power storage device and power storage device |
| KR101708363B1 (en) * | 2013-02-15 | 2017-02-20 | 삼성에스디아이 주식회사 | Negative active material, and negative electrode and lithium battery containing the material |
| EP3589438A4 (en) * | 2017-03-03 | 2020-09-30 | Hydro-Québec | Nanoparticles comprising a core covered with a passivation layer, process for manufacture and uses thereof |
| CN106972151A (en) * | 2017-03-24 | 2017-07-21 | 江苏乐能电池股份有限公司 | A kind of negative electrode of lithium ion battery composite pole piece and its lithium ion battery |
| CN110048114A (en) * | 2019-04-30 | 2019-07-23 | 中国科学院宁波材料技术与工程研究所 | A kind of bivalve silicon carbon material and preparation method thereof |
| CN111755679A (en) * | 2020-07-06 | 2020-10-09 | 马鞍山科达普锐能源科技有限公司 | Silicon-containing powder for lithium ion battery negative electrode material and preparation method thereof |
| CN113793934A (en) * | 2021-09-15 | 2021-12-14 | 常州硅源新能材料有限公司 | Double-layer coated silica anode material, preparation method thereof and lithium ion battery with double-layer coated silica anode material |
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| JP特开2000-12018A 2000.01.14 |
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