CN1855586A - Cathode materials for secondery lithium ion batteries - Google Patents
Cathode materials for secondery lithium ion batteries Download PDFInfo
- Publication number
- CN1855586A CN1855586A CNA2005100665190A CN200510066519A CN1855586A CN 1855586 A CN1855586 A CN 1855586A CN A2005100665190 A CNA2005100665190 A CN A2005100665190A CN 200510066519 A CN200510066519 A CN 200510066519A CN 1855586 A CN1855586 A CN 1855586A
- Authority
- CN
- China
- Prior art keywords
- silicon
- precursor
- electrode material
- metal oxide
- negative electrode
- 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
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 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 invention relates to a secondary lithium ion battery, in particular to a lithium ion battery cathode material based on a silicon material and a related manufacturing method.
Background
The secondary lithium ion battery refers to a chargeable and dischargeable lithium ion battery. In most of the secondary lithium ion batteries that are commercially available, the negative electrode material is mainly made of graphite. Compared with the graphite material, the silicon material has a larger theoretical specific capacitance (4000 mAh/g) which is about an order of magnitude higher than that of the graphite material (372 mAh/g). Therefore, the silicon material is considered as an emerging secondary lithium ion battery cathode material with considerable potential and extremely high development market.
However, the reasons why silicon materials are not commercially available for lithium ion batteries in the late past mainly include: the volume expansion rate is large (300%) in the charging and discharging process, the silicon pole plate is powdered, the conductivity of silicon is low, the Solid Electrolyte Interface (SEI) of silicon is unstable, the silicon is contacted with a conductive aid, the electrochemical reaction power of silicon is poor, the pole plate interface impedance is low, and the like.
These problems have caused a significant decline in the capacity of secondary lithium ion batteries using silicon as the negative electrode material for less than ten cycles in the charge/discharge test. In contrast, there are many patents or research documents in recent years that aim to improve silicon negative electrode materials, and two representative patents relating to silicon negative electrode materials are listed below.
1) Sanyo corporation in U.S. Pat. No. 6649033 discloses: a silicon film (thin film) with the thickness of 2 mu m to 5 mu m is sputtered on the copper foil in a sputtering way, the traditional slurry coating process (30 mu m to 80 mu m) is broken through, the charge-discharge capacitance of the copper foil can reach 3000mAh/g, and the cycle life can reach hundreds of times. However, the manufacturing cost is much higher than that of the slurry coating process because the process must use the low-pressure vacuum system coating technique.
2) Matsushita corporation discloses in U.S. Pat. No. 6548208: an alloy phase is formed by different metals and silicon materials in a high-temperature molten state, and the effect of stable structure is expected to be achieved in the process of charging and discharging through a Matrix (Matrix) framework of the alloy phase. Since the coating layer plays a role of a matrix, it absorbs and buffers the severe volume expansion of the silicon material due to the intercalation and deintercalation of lithium ions.
3) U.S. patent No. 6548208 to Mitsui Mining: the secondary lithium ion battery, the negative electrode material thereof and the charging method thereof disclose that a carbon layer is plated on the surface of the silicon material of the powder in a TVD mode. The silicon material of the powder adopts commercial products, the size of the silicon material is between 0.1 and 50 mu m, the content of the carbon layer accounts for about 5 percent of the weight percentage, and the step of plating the carbon layer is carried out by utilizing a fluidized bed at 900 ℃. The resulting carbon layer needs to be a rather graphitizing substance to have sufficient strength to inhibit expansion of the silicon material upon lithiation. In the examples, the proposed charging voltage is between 0.05 and 0.08V, which has a stable cyclic capacity of more than about 900 mAh/g.
The present invention also addresses the shortcomings of the silicon materials described above that have not yet been commercially applicable to the negative electrode of lithium ion batteries, and seeks a breakthrough in technology. The negative electrode material of the secondary lithium ion battery disclosed by the invention takes a silicon material as a main body, however, the negative electrode material finished product provided by the invention is completely different from the scope of the three representative patents, the related manufacturing method provided by the invention is not known in the prior art, and the related concept, technical means and achieved efficacy of the invention are disclosed in the following description and related embodiments.
Disclosure of Invention
The invention mainly aims to provide a secondary lithium ion battery cathode material taking a silicon material as a main body.
Another objective of the present invention is to apply the high theoretical specific capacitance of the silicon material to facilitate the performance of the secondary lithium ion battery.
It is another object of the present invention to ameliorate various known disadvantages affecting the practical application of silicon materials to the negative electrode of secondary lithium ion batteries.
The invention provides a secondary lithium ion battery cathode material, which comprises a plurality of silicon core particles, wherein the silicon core particles comprise silicon particles and a coating layer coated on the surfaces of the silicon particles,the coating layer at least comprises a metal oxide. The thickness of the coating layer may be in the range of 1nm to 1000nm, and it may be a single layer structure or a multi-layer structure. While the silicon particles are substantially less than 100 microns in diameter. The invention uses the silicon material with the theoretical capacitance of more than 1000mAh/g as the main body of the cathode material of the secondary lithium ion battery and as the channel of lithium ions. Therefore, the uniformity of lithium ion distribution in the secondary lithium ion battery can be increased, and the metal oxide layer can be used as a passivation layer of an artificial Solid Electrolyte Interface (SEI). Wherein the metal oxide is selected from titanium oxide (TiO)2) Zirconium oxide (ZrO)2) Or a combination thereof.
In one embodiment of a method, the present invention discloses a method for preparing a negative electrode material of a secondary lithium ion battery by Chemical Vapor Deposition (Chemical Vapor Deposition).
In another embodiment of the method, the invention discloses a case that the secondary lithium ion battery negative electrode material is prepared by a sol-gel process.
The negative electrode material of the secondary lithium ion battery comprises a plurality of silicon core particles, wherein the silicon core particles comprise:
a silicon particle (silicon particle); and
a coating layer coated on the surface of the silicon particles, the coating layer at least comprises a metal oxide.
In the negative electrode material of the present invention, the coating layer has a single-layer structure.
In the negative electrode material of the present invention, the coating layer has a multi-layer structure.
The cathode material of the present invention, wherein the thickness of the coating layer is between 1nm and 1000 nm.
The negative electrode material of the present invention, wherein the metal oxide is selected from titanium oxide (TiO)2) Zirconium oxide (ZrO)2) Or a combination thereof.
In the negative electrode material of the present invention, the coating layer contains carbon.
The negative electrode material of the present invention comprises 0.01 to 100 wt% of the coating layer of the metal oxide.
The negative electrode material of the present invention, wherein the silicon particle diameter is less than 100 μm.
The invention relates to a method for manufacturing a negative electrode material of a secondary lithium ion battery, wherein a pulse Chemical Vapor Deposition method (Chemical Vapor Deposition) is utilized, and the method comprises the following steps:
introducing a silicon material into a reactor;
controlling the reactor at a predetermined temperature; and
introducing a metal oxide precursor (precursor) in a gas phase into the reactor by pulse-flow CVD,
therefore, the negative electrode material of the secondary lithium ion battery containing a plurality of silicon core particles is formed, wherein the silicon core particles comprise a silicon particle (silicon particle) surface coating layer containing a metal oxide.
The manufacturing method of the present invention is provided, wherein the predetermined temperature is substantially 300 to 1000 ℃.
The manufacturing method of the invention is characterized in that the pulse frequency of the pulse type vapor deposition is between 0.1Hz and 10 Hz.
The preparation method of the invention is characterized in that the metal oxide precursor is a precursor of titanium oxide, a precursor of zirconium oxide or a combination thereof.
The production method of the present invention is characterized in that the precursor of titanium oxide is selected from titanium alkoxide (titanium alkoxide) or a titanium salt compound.
The precursor of the zirconium oxide is selected from zirconium alkoxide (zirconium alkoxide) or a zirconium salt compound.
The invention relates to a method for manufacturing a negative electrode material of a secondary lithium ion battery, wherein a sol-gel process is utilized, and the method comprises the following steps:
mixing a silicon material of the powder with a metal oxide precursor solution to obtain a mixed solution;
forming the mixed solution into a colloidal state; and is
Calcining the mixed solution in a colloidal state to obtain a negative electrode material of a powdery secondary lithium ion battery,
the negative electrode material of the secondary lithium ion battery comprises a plurality of silicon core particles, wherein the silicon core particles are silicon particles (silicon particles), and the surfaces of the silicon particles are coated with a coating layer containing a metal oxide.
The preparation method of the invention is characterized in that the metal oxide precursor is a precursor of titanium oxide, a precursor of zirconium oxide or any combination thereof.
The production method of the present invention is characterized in that the precursor of titanium oxide is selected from titanium alkoxide (titanium alkoxide) or a titanium salt compound.
The precursor of the zirconium oxide is selected from zirconium alkoxide (zirconium alkoxide) or a zirconium salt compound.
The preparation method of the invention, wherein the solvent used by the metal oxide precursor solution is selected from H2O or CxHyOHz, wherein x is between 1 and 10, y is between 1 and 20, and z is between 1 and 10.
Before the step of forming the mixture into a colloidal state, the method further comprises the step of exhausting the mixture to remove air in the pores of the silicon material of the powder.
The invention also discloses a relevant electrical experiment of the secondary lithium ion battery prepared by applying the cathode material of the invention, so as to actually illustrate the efficacy achieved by the invention. The invention provides a secondary lithium ion battery cathode material taking silicon as a main body, which comprises a plurality of silicon core particles, wherein the coating on the surface of the silicon core particles at least comprises a metal oxide, and the metal oxide can be selected from titanium oxide, zirconium oxide or a combination of titanium oxide and zirconium oxide in a preferred example. The metal oxide layer can be titanium oxide or zirconium oxide, and the cathode material of the invention can be manufactured by a pulse chemical vapor deposition method or a sol-gel method. The invention utilizes the advantage of high theoretical capacity of silicon material, overcomes the known defects that a plurality of silicon materials cannot be practically applied to commercial secondary lithium ion batteries, and provides different means and achieves better charge-discharge cycle life performance compared with the known technology with similar concepts.
Drawings
FIG. 1 is a schematic diagram of a secondary lithium ion battery cathode material according to the present invention;
FIG. 2 is a flow chart of a method for manufacturing the negative electrode material of the present invention;
FIG. 3 is an X-ray diffraction pattern of the embodiment of FIG. 2;
FIG. 4 is a flow chart of another method for manufacturing the negative electrode material of the present invention;
FIG. 5 is an X-ray diffraction pattern of the embodiment of FIG. 4;
FIG. 6 is a graph of charge-discharge cycle number versus capacitance for a comparative example;
FIG. 7A is the Si-ZrO of FIG. 62Graph of capacitance-potential relationship at the first charge and discharge of example;
FIG. 7B is the Si-TiO of FIG. 62Graph of capacitance-potential relationship at the first charge and discharge of example;
FIG. 8 is a graph of the number of charge and discharge cycles versus capacitance for another comparative example of the present invention.
Detailed Description
Referring to fig. 1, fig. 1 is a schematic view of a negative electrode material of a secondary lithium ion battery according to the present invention. The negative electrode material of the secondary lithium ion battery at least comprises a silicon core particle 10 shown in figure 1. The silicon core particle 10 includes a silicon particle 12 and a coating layer 14 coated on the surface of the silicon particle 12. The thickness of the coating layer 14 may be in the range of 1nm to 1000nm, and the coating layer 14 at least includes a metal oxide selected from titanium oxide (TiO)2) Zirconium oxide (ZrO)2) Or a combination thereof.
In practice, the silicon particles 12 are substantially less than 100 microns in diameter. The coating layer 14 may be a single layer structure, or a multi-layer structure may be formed by multiple coating steps. The material of each layer of the multi-layer coating 14 may include graphite or carbon layer in addition to the titanium oxide or zirconium oxide. The material is selected from a metal oxide layer of titanium oxide or zirconium oxide, and accounts for 0.01-100% of the weight of the coating layer 14.
The invention uses silicon material (silicon particles 12) with theoretical capacitance up to 4000mAh/g as the main body of the secondary lithium ion battery cathode material, and uses metal oxide titanium oxide or zirconium oxide (belonging to the coating layer 14) to increase the cycle life of the silicon particles 12. Thus, not only the uniformity of lithium ion distribution in the secondary lithium ion battery can be increased, but also the coating layer 14 can be used as an artificial Solid Electrolyte Interface (SEI). The following will disclose the manufacturing method and the electrical experiment related thereto, so as to further illustrate the means and effect of the present invention.
Production method example 1
Referring to fig. 2, fig. 2 is a flow chart of a method for manufacturing the negative electrode material of the present invention. This embodiment utilizes chemical vapor deposition to prepare the silicon core particles 10 containing metal oxide in the cladding layer 14.
The implementation method comprises the following steps: in this embodiment, the precursor of Titanium oxide (precursor) is Titanium isopropoxide (Ti) OCH (CH)3)2]4) Solution of 3% H2/97％N210g of a silicon material powder was fluidized in a pulse manner as a carrier gas at a flow rate of 2l/min and a frequency of 1Hz (pulse per second), and the fluidized gas was introduced into a fluidized bed reactor.
After about one hour, the carrier gas is then pumped into the tetraisopropyl titanate solution and carried into the fluidized bed reactor.
In this example, the reaction was carried out at a reaction temperature of 800 ℃. Thus, a predetermined negative electrode material including a plurality of silicon core particles 10 shown in fig. 1 can be obtained. In each silicon core particle 10, the silicon particle 12 has a diameter substantially less than 100 microns. And the coating layer 14 is a single-layer structure containing titanium oxide.
Referring to fig. 3, fig. 3 is an X-ray diffraction pattern of the embodiment of fig. 2, wherein the target material is cu target CuK α (1.5418 Å) and the scan rate is 5deg./min, it can be seen from the analysis of fig. 3 that the negative electrode material prepared by the present experiment is a silicon core particle (fig. 1, 10) of crystalline phase titanium dioxide, which is uniformly coated on the surface of the silicon particle (fig. 1, 12).
In another embodiment of the present invention, Zr (OC) is utilized4H9)4As precursors, step 203 and step 205 of FIG. 2 are performed multiple times to deposit a plurality of coatings on the silicon particles 12The surface is formed with a multi-layer structure of a cladding layer 14.
In another related embodiment, a single layer of zirconium oxide (ZrO) is formed on the surface of the silicon particles 122) Instead of the titanium oxide embodiment described above, the coating layer 14 is formed.
In another related embodiment, multiple coatings are applied, but different metal oxide precursors (e.g., TiO (C)) may be used for each coating3H7)4，Zr(OC4H9)4In step 203, a graphite layer may be alternatively coated to form the silicon core particles 10 with a multi-layered coating layer 14, wherein the multi-layered coating layer 14 may comprise titanium oxide, zirconium oxide or graphite.
Example II of the manufacturing method
Referring to fig. 4, fig. 4 is a flowchart of another manufacturing method of the negative electrode material of the present invention. In this embodiment, the sol-gel method is used to prepare the silicon core particles 10 with the metal oxide layer in the coating layer 14.
The implementation method comprises the following steps: metal oxide precursor Zr (OC) of zirconium oxide with solvent4H9)4Mixing the components in a ratio of four to one by weight percent.
For example, in one embodiment, n-butanol (1-butanol) is used as the solvent, and 2.35 g of Zr (OC)4H9) Added dropwise to 9.4 g of n-butanol.
In order to mix the two solutions more uniformly, the two solutions can be put into an ultrasonic oscillator, and after oscillation for about 15 minutes, the mixture has a good mixing effect, and the mixture is quite clear and is a light yellow transparent solution.
At this time, the powder silicon material pre-baked in the oven (about 15 minutes) may be mixed with a metal oxide precursor solution to obtain a mixture (step 400).
The mixed liquid is stirred to enable the metal oxide precursor solution to fully permeate into the holes of the silicon material, and in order to enable the adhesion effect of the metal oxide to be better, the mixed liquid can also be pumped to remove air in the holes of the silicon material.
Next, the mixed solution is heated to form a colloidal state (step 401). The uniformly mixed liquid can be heated on a heating plate in an oil bath mode, and the viscosity of the liquid can gradually increase to form a colloidal state at a heating temperature of 85 ℃ in combination with the stirring of a magnet.
Thereafter, the mixed solution in a colloidal state is calcined to obtain a negative electrode material for a powder secondary lithium ion battery (step 402). The mixed solution in a colloidal state may be placed in a tube furnace, heated to 700 degrees celsius at a heating rate of, for example, 50 degrees celsius per hour, and maintained at that temperature for six hours. After the furnace is cooled to room temperature, the obtained powder is ground and sieved (e.g. 270mesh) to obtain the secondary lithium ion battery cathode material of the present invention, which comprises a plurality of silicon core particles 10, which in this embodiment is a silicon-zirconium oxide (Si-ZrO)2) Referring to fig. 5, fig. 5 is an X-ray diffraction pattern of the embodiment of fig. 4, wherein the target material is a copper target CuK α (1.5418 Å) and the scan rate is 5 deg./min.
In the above examples, the reaction equation of the sol-gel method is:
in the present embodiment, the coating layer 14 having zirconium oxide is used as a template for the description, and in another related embodiment, the coating layer 14 having titanium oxide is formed on the surface of the silicon particles 12 instead of the zirconium oxide embodiment described above.
In various embodiments of the present invention, the precursor for titanium oxide is selected from titanium alkoxide (titanium alkoxide) or a titanium salt. The precursor of the zirconium oxide is selected from zirconium alcohol oxide (zirconium alkoxide) or zirconium salt compound.
In the embodiment of the production using the sol-gel method, the solvent for the metal oxide may be selected from H2O or CxHyOHz, wherein x is between 1 and 10, y is between 1 and 20, and z is between 1 and 10.
Referring to FIG. 6, FIG. 6 is a graph showing the relationship between the number of charge/discharge cycles and the capacitance of the comparative example. The effect actually achieved by the negative electrode material provided by the present invention is illustrated by fig. 6. Three different cathode materials are selected to assemble the battery, and then the charge-discharge cycle life test is carried out. The charging and discharging conditions are 1000mAh/g, the constant capacitance charging is carried out, and the current is 0.3mA/mg, voltage range of 0-1.2V (V vs. Li +). The three materials are pure silicon sample (reference number 600) and silicon-zirconium oxide composite material (hereinafter referred to as Si-ZrO) of the invention2Reference numeral 601), the silicon-titanium oxide composite material of the present invention (hereinafter referred to as Si-TiO for short)2Reference numeral 602).
FIG. 7A and FIG. 7B can be combined, and FIG. 7A is the Si-ZrO of FIG. 62Graph of capacitance-potential relationship at the first charge and discharge of example; FIG. 7B is the Si-TiO of FIG. 62Example graph of capacitance-potential relationship at first charge and discharge.
Firstly, the pure silicon sample (see reference numeral 600) has very poor performance in the cycle life of charge and discharge, and the capacitance begins to decrease rapidly after only five times of charge and discharge, as described in many research documents, because the silicon material has severe volume expansion caused by the migration of lithium ions into and out of the silicon material, the polar plate of the lithium battery has many cracks and fracture surfaces, and such fracture surfaces can make the contact between the silicon material and the copper foil worse, and then, in the subsequent charge and discharge, electrons cannot be led out from the copper foil (current collector); the reason why the cycle life performance of the other silicon negative electrode material is poor is the low conductivity of the silicon material, so that lithium ions are not easy to be led out even if the silicon material and the copper foil are in good contact after the lithium ions are emigrated. Eighth charge-discharge cycle compared to pure silicon sampleWhen the capacitance begins to decline obviously, the invention provides the cathode material no matter Si-ZrO2Or Si-TiO2Both have charge-discharge cycle life performance far superior to that of pure silicon samples.
Referring to FIG. 8, FIG. 8 is a graph showing the relationship between the number of charge/discharge cycles and the capacitance according to another comparative example of the present invention. Fig. 8 shows the comparison of the charge and discharge cycle life performance of the negative electrode material of the present invention with that of the negative electrode material manufactured by the technology of U.S. Pat. No. 6548208 of Mitsui Mining company; the main concept of the us 6548208 patent is to coat a carbon layer on the surface of the silicon material of the powder. This experiment is conducted by using the silicon-titanium oxide composite material (hereinafter referred to as Si-TiO) of the present invention2702), the silicon-carbon composite material (701) of U.S. Pat. No. 6548208, and a pure silicon sample (700) were assembled into a battery, and then a charge-discharge cycle life test was performed under the charge-discharge conditions of a constant capacitance of 1000mAh/g, a current of 0.3mA/mg, and a voltage range of 0-1.2V(V vs.Li/Li+)。
It can be seen from fig. 8 that the silicon-carbon composite 701 does contribute to the structural stability of the silicon-based negative electrode material, and thus has better cycle life than the pure silicon sample 700, however, the present invention provides Si-TiO2The charge-discharge cycle life (reference numeral 702) is further superior to that of the silicon-carbon composite 701. It is worth mentioning that the present invention can coat the surface of the silicon particles (12 in FIG. 1) with a lower weight percentage of the coating (14 in FIG. 1, for the purposes of this example, only 8 wt% TiO)2) In contrast, the prior art of U.S. Pat. No. 6548208 requires a carbon coating of 27% by weight. The invention can still have better charge-discharge cycle life performance even under the condition of relatively thin coating layers 14 on the surfaces of the silicon particles 12.
In summary, the present invention provides a silicon-based negative electrode material for a secondary lithium ion battery, which comprises a plurality of silicon core particles, wherein the coating on the surface of the silicon core particles comprises at least one metal oxide, and in a preferred embodiment, the metal oxide is selected from titanium oxide, zirconium oxide or a combination thereof. The metal oxide layer can be titanium oxide or zirconium oxide, and the cathode material of the invention can be manufactured by a pulse chemical vapor deposition method or a sol-gel method. The invention utilizes the advantage of high theoretical capacity of silicon material, overcomes the known defects that a plurality of silicon materials cannot be practically applied to commercial secondary lithium ion batteries, and provides different means and achieves better charge-discharge cycle life performance compared with the known technology with similar concepts.
While the invention has been described in connection with what is presently considered to be the most practical and preferred embodiment, it is to be understood that the invention is not to be limited to the disclosed embodiment. It will be readily apparent to those skilled in the art that other elements or means may be used to achieve the same effect. For example, one skilled in the art can add carbon material to the oxide-containing coating layer to adjust the electron conductivity of the coating layer. For example, in another related embodiment of the present invention, a carrier gas containing tetraisopropyl titanate and benzene is reacted by pulse-flow CVD at 800 degrees celsius to form a single-layer coating layer 14 on the surface of the silicon particles 12, wherein the coating layer 14 contains both titanium dioxide and carbon.
Although the present invention has been described with reference to the preferred embodiments, it should be understood that various changes and modifications can be made therein by those skilled in the art without departing from the spirit and scope of the invention as defined by the appended claims.
Description of the symbols
Claims (20)
1. A negative electrode material for a secondary lithium ion battery, characterized by comprising a plurality of silicon core particles, said silicon core particles comprising:
silicon particles; and
and the coating layer is coated on the surface of the silicon particles and at least comprises a metal oxide.
2. The negative-electrode material of claim 1, wherein the coating layer has a single-layer structure.
3. The negative-electrode material of claim 1, wherein the coating layer has a multi-layer structure.
4. The negative-electrode material of claim 1, wherein the thickness of the coating layer is between 1nm and 1000 nm.
5. The negative electrode material of claim 1, wherein the metal oxide is selected from the group consisting of titanium oxide, zirconium oxide, and combinations thereof.
6. The anode material of claim 1, wherein the coating comprises carbon.
7. The negative electrode material of claim 1, wherein the metal oxide is 0.01 to 100 wt% of the coating layer.
8. The negative electrode material of claim 1, wherein the silicon particles have a diameter of less than 100 μm.
9. A method for manufacturing a negative electrode material of a secondary lithium ion battery is characterized by utilizing a pulse chemical vapor deposition method, and the method comprises the following steps:
introducing a silicon material into a reactor;
controlling the reactor at a predetermined temperature; and
introducing a metal oxide precursor in a vapor phase into the reactor by pulsed vapor deposition,
therefore, the negative electrode material of the secondary lithium ion battery containing a plurality of silicon core particles is formed, and the silicon core particles comprise a coating layer which is coated on the surface of a silicon particle and contains a metal oxide.
10. The method of claim 9, wherein the predetermined temperature is 300 ℃ to 1000 ℃.
11. The method of claim 9, wherein the pulsed vapor deposition is performed at a pulse frequency of 0.1Hz to 10 Hz.
12. The method of claim 9, wherein the metal oxide precursor is a precursor of titanium oxide, a precursor of zirconium oxide, or a combination thereof.
13. The method according to claim 12, wherein the precursor of titanium oxide is selected from titanium-containing alkoxide compounds and titanium-containing salt compounds.
14. The method according to claim 12, wherein the precursor of zirconium oxide is selected from the group consisting of zirconium alkoxide and zirconium salt.
15. A method for manufacturing a negative electrode material of a secondary lithium ion battery, characterized by using a sol-gel method, the method comprising:
mixing the silicon material of the powder with a metal oxide precursor solution to obtain a mixed solution;
forming the mixed solution into a colloidal state; and is
Calcining the mixed solution in a colloidal state to obtain a negative electrode material of a powdery secondary lithium ion battery,
the cathode material of the secondary lithium ion battery comprises a plurality of silicon core particles, wherein the silicon core particles are coated with a coating layer containing a metal oxide on the surface of silicon particles.
16. The method of claim 15, wherein the metal oxide precursor is a precursor of titanium oxide, a precursor of zirconium oxide, or any combination thereof.
17. The method according to claim 16, wherein the precursor of titanium oxide is selected from titanium alkoxide or titanium salt.
18. The method according to claim 16, wherein the precursor of zirconium oxide is selected from the group consisting of zirconium alkoxide and zirconium salt.
19. The method of claim 15, wherein the metal oxide isThe solvent used for dissolving the precursor solution is selected from H2O or CxHyOHz, wherein x is between 1 and 10, y is between 1 and 20, and z is between 1 and 10.
20. The method of claim 15, further comprising evacuating the mixture to remove air from the pores of the silicon material before the step of forming the mixture into a gel.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2005100665190A CN1855586B (en) | 2005-04-27 | 2005-04-27 | Cathode materials for secondery lithium ion batteries |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2005100665190A CN1855586B (en) | 2005-04-27 | 2005-04-27 | Cathode materials for secondery lithium ion batteries |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1855586A true CN1855586A (en) | 2006-11-01 |
| CN1855586B CN1855586B (en) | 2010-04-28 |
Family
ID=37195545
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2005100665190A Active CN1855586B (en) | 2005-04-27 | 2005-04-27 | Cathode materials for secondery lithium ion batteries |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1855586B (en) |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101981731A (en) * | 2008-02-26 | 2011-02-23 | 原子能与替代能源委员会 | Process for fabricating a silicon-based electrode, silicon-based electrode and lithium battery comprising such an electrode |
| CN102054983A (en) * | 2009-10-28 | 2011-05-11 | 信越化学工业株式会社 | Negative electrode material for non-aqueous electrolyte secondary batteries, manufacturing method therefor, and lithium-ion secondary batteries |
| CN102934262A (en) * | 2010-05-31 | 2013-02-13 | 日产自动车株式会社 | Negative electrode for secondary battery, and process for production thereof |
| CN103138006A (en) * | 2008-03-17 | 2013-06-05 | 索尼株式会社 | Secondary battery |
| CN103996826A (en) * | 2013-02-15 | 2014-08-20 | 三星Sdi株式会社 | Negative active material, and negative electrode and lithium battery each including the negative active material |
| 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 |
| US10541409B2 (en) | 2012-06-01 | 2020-01-21 | Semiconductor Energy Laboratory Co., Ltd. | Negative electrode for power storage device and power storage device |
| CN110753591A (en) * | 2017-03-03 | 2020-02-04 | 魁北克电力公司 | Nanoparticles comprising a core covered by a passivation layer, method for the production thereof and use 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 |
-
2005
- 2005-04-27 CN CN2005100665190A patent/CN1855586B/en active Active
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101981731A (en) * | 2008-02-26 | 2011-02-23 | 原子能与替代能源委员会 | Process for fabricating a silicon-based electrode, silicon-based electrode and lithium battery comprising such an electrode |
| CN103138006A (en) * | 2008-03-17 | 2013-06-05 | 索尼株式会社 | Secondary battery |
| US9287561B2 (en) | 2009-10-28 | 2016-03-15 | Shin-Etsu Chemical Co., Ltd. | Negative electrode material for non-aqueous electrolyte secondary batteries, manufacturing method therefor, and lithium-ion secondary batteries |
| CN102054983B (en) * | 2009-10-28 | 2015-05-13 | 信越化学工业株式会社 | Negative electrode material for non-aqueous electrolyte secondary batteries, manufacturing method therefor, and lithium-ion secondary batteries |
| CN102054983A (en) * | 2009-10-28 | 2011-05-11 | 信越化学工业株式会社 | Negative electrode material for non-aqueous electrolyte secondary batteries, manufacturing method therefor, and lithium-ion secondary batteries |
| CN102934262A (en) * | 2010-05-31 | 2013-02-13 | 日产自动车株式会社 | Negative electrode for secondary battery, and process for production thereof |
| US10541409B2 (en) | 2012-06-01 | 2020-01-21 | Semiconductor Energy Laboratory Co., Ltd. | Negative electrode for power storage device and power storage device |
| CN103996826A (en) * | 2013-02-15 | 2014-08-20 | 三星Sdi株式会社 | Negative active material, and negative electrode and lithium battery each including the negative active material |
| CN110753591A (en) * | 2017-03-03 | 2020-02-04 | 魁北克电力公司 | Nanoparticles comprising a core covered by a passivation layer, method for the production thereof and use 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1855586B (en) | 2010-04-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1855586A (en) | Cathode materials for secondery lithium ion batteries | |
| CN107579239B (en) | A kind of graphene/solid electrolyte compound coating silicon composite cathode and preparation method thereof | |
| CN1146062C (en) | Active material for positive electrode used in lithium secondary battery and method of manufacturing same | |
| CN1218418C (en) | Negative electrode active material for charging lithium accumulator and its producing method | |
| CN107681142B (en) | Molybdenum disulfide coated carbon nanofiber used as lithium ion battery negative electrode material and preparation method thereof | |
| CN1269244C (en) | Plus plate active material for chargable lithium cell and its preparation method | |
| CN1213495C (en) | Positive active material for lithium secondary battery with higher performance and preparation method of the same | |
| CN1189958C (en) | Method for producing electrode for lithium secondary cell | |
| CN1278440C (en) | Negative electrode for lithium secondary cell | |
| CN1306633C (en) | Lithium secondary battery-use electrode and lithium secondary battery | |
| CN100342566C (en) | Method for producing active material for lightium secondary battery | |
| CN1222062C (en) | Positive active material for lithium secondary battery and method of preparing the same | |
| CN101064367A (en) | Compound material of anode fit for producing secondary battery and its produced battery | |
| CN109888237B (en) | Sodium-ion battery negative electrode material and preparation method thereof | |
| CN1947283A (en) | Anode active material with improved electrochemical properties and electrochemical device comprising the same | |
| CN1412871A (en) | Negative electrode active material of charging lithium cell and its preparing method | |
| CN104103821A (en) | Preparation method for silicon-carbon anode material | |
| EP4318654A1 (en) | Negative electrode composite material, and preparation method therefor and application thereof | |
| CN108550789A (en) | A kind of sodium-ion battery cathode and preparation method thereof and sodium-ion battery | |
| CN111088513B (en) | Silver nanoparticle modified TiO2Preparation method and application of nanotube array | |
| CN1647298A (en) | Positive-electrode active material for non-aqueous electrolyte secondary cell and process for preparing the same | |
| CN114335681A (en) | Inorganic halide solid electrolyte, preparation method thereof, lithium ion battery and application | |
| CN108899499A (en) | Based on phosphatic negative electrode material of Sb/Sn and preparation method thereof and the application in sodium-ion battery | |
| CN1231984C (en) | Electrode material and preparation method thereof | |
| CN114335458A (en) | Ti3C2Tx @ g-C3N4 composite material and preparation method and application thereof |
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 |