WO2012073313A1 - 二次電池用負極材、二次電池用負極、二次電池用負極材の製造方法および二次電池用負極の製造方法 - Google Patents
二次電池用負極材、二次電池用負極、二次電池用負極材の製造方法および二次電池用負極の製造方法 Download PDFInfo
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- WO2012073313A1 WO2012073313A1 PCT/JP2010/071292 JP2010071292W WO2012073313A1 WO 2012073313 A1 WO2012073313 A1 WO 2012073313A1 JP 2010071292 W JP2010071292 W JP 2010071292W WO 2012073313 A1 WO2012073313 A1 WO 2012073313A1
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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
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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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
- H01M4/04—Processes of manufacture in general
- H01M4/0402—Methods of deposition of the material
- H01M4/0419—Methods of deposition of the material involving spraying
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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
- H01M4/134—Electrodes based on metals, Si or alloys
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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
- H01M4/1395—Processes of manufacture of electrodes based on metals, Si or alloys
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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
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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
- H01M4/362—Composites
- H01M4/366—Composites as layered products
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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
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/386—Silicon or alloys based on silicon
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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
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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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Definitions
- the present invention relates to a negative electrode material for a secondary battery, a negative electrode for a secondary battery, a method for producing a negative electrode material for a secondary battery, and a method for producing a negative electrode for a secondary battery, and in particular, a negative electrode for a secondary battery constituting an active material layer.
- the present invention relates to a material, a manufacturing method thereof, a negative electrode for a secondary battery including an active material layer, and a manufacturing method thereof.
- Si having a large charge / discharge capacity is promising as an active material (negative electrode material for secondary batteries) of a negative electrode for secondary batteries.
- the discharge capacity of the negative electrode for the secondary battery is greatly reduced from the initial value (the charge / discharge cycle life is short). ing.
- the reason why the charge / discharge cycle life is short in Si is that stress generated in the secondary battery negative electrode due to the difference in the volume of the secondary battery negative electrode during charging and the volume of the secondary battery negative electrode during discharge. It is thought that this is because a part of the negative electrode for secondary battery does not function.
- Japanese Patent Application Laid-Open No. 2005-63767 discloses an active material particle constituting an active material layer of a negative electrode for a secondary battery, and a metal thin film made of Si particles and Ni plating formed so as to cover the surface of the Si particles Active material particles (anode material for secondary battery) are disclosed. In this way, by performing Ni plating so as to cover the surface of the Si particles, it is possible to withstand the stress generated in the negative electrode for the secondary battery and suppress collapse, so the charge / discharge cycle life is shortened. Can be suppressed.
- the active material particles made of Ni-plated Si particles described in Japanese Patent Application Laid-Open No. 2005-63767 can increase the charge / discharge cycle life and charge / discharge in the negative electrode for secondary batteries. While it is possible to improve the capacity to some extent, in recent years, it has been desired to further improve the charge / discharge capacity while extending the charge / discharge cycle life.
- the present invention has been made in order to solve the above-described problems, and one object of the present invention is to provide a negative electrode for a secondary battery while increasing the charge / discharge cycle life in the secondary battery. It is providing the negative electrode material for secondary batteries which can further improve charge / discharge capacity of this, and its manufacturing method, the negative electrode for secondary batteries, and its manufacturing method.
- a coating material containing Ni and P is distributed in an island shape, a dot shape, or a net shape so as to partially cover the surface of the Si particles.
- the negative electrode material for a secondary battery according to the first aspect of the present invention is a negative electrode material for a secondary battery that constitutes an active material layer formed on a current collector layer of a negative electrode for a secondary battery, And a coating material containing Ni and P formed in an island shape, a dot shape, or a net shape so as to partially cover the surface of the Si particles.
- the coating material containing Ni and P is formed in an island shape, a dot shape, or a net shape so as to partially cover the surface of the Si particles.
- the coating material covers a surface of 1% to 25% of the surface of the Si particles. If comprised in this way, when the negative electrode material for secondary batteries is used for the active material layer of the negative electrode for secondary batteries by making the ratio which a coating
- the covering material containing Ni and P has a crystal structure of Ni 3 P. According to this structure, when the secondary battery negative electrode material is used for the active material layer of the secondary battery negative electrode, the stress caused by the volume change of the secondary battery negative electrode during charge / discharge is covered. Since Ni 3 P contained in the material can withstand the stress and suppress collapse, the charge / discharge cycle life can be extended.
- the coating material is composed of 0.5 mass% or more and 50 mass% or less of P and Ni. If comprised in this way, when the negative electrode material for secondary batteries containing the coating material which consists of 0.5 mass% or more and 50 mass% or less of P and Ni is used for the active material layer of the negative electrode for secondary batteries. Since the crystal structure of Ni containing P contains Ni 3 P, the charge / discharge cycle life can be extended.
- the covering material is composed of 5 mass% to 16 mass% of P and Ni. If comprised in this way, when the negative electrode material for secondary batteries containing the coating material which consists of 5 mass% or more and 16 mass% or less of P and Ni is used for the active material layer of the negative electrode for secondary batteries, The charge / discharge cycle life of the secondary battery negative electrode can be further improved.
- a negative electrode for a secondary battery includes a current collector layer and an active material layer formed on a surface of the current collector layer.
- the active material layer includes an Si portion and an Si portion.
- a covering portion having Ni and P formed so as to be distributed in an island shape, a dot shape, or a net shape between Si portions is included.
- the active material layer is formed so as to be distributed in an island shape, a dot shape, or a net shape between the Si portion and the Si portion or the Si portion. Further, by including the covering portion having Ni and P, the charge / discharge cycle life of the secondary battery negative electrode can be further extended as compared with the case where the covering portion is made only of Ni. These points are also apparent from the experimental results described later.
- the active material layer includes a Si portion and a covering portion having Ni and P formed so as to be distributed in an island shape, a dot shape, or a net shape between the Si portions or the Si portions.
- voids are formed between the Si portions or the Si portions of the active material layer. If comprised in this way, the stress which generate
- the voids are preferably formed at a ratio of 20% by volume or more and 70% or less by volume of the active material layer. If comprised in this way, since a space
- the thickness of the active material layer is not less than 1 ⁇ m and not more than 20 ⁇ m. If comprised in this way, it can suppress that the charging / discharging capacity
- the covering portion of the active material layer includes 0.5% by mass or more and 50% by mass or less of P and Ni.
- the active material layer is a coating having a Si layer and Ni and P formed on the Si layer so as to be distributed in an island shape, a dot shape, or a net shape. Part. If comprised in this way, since it becomes easy for a Si layer to contact an electrolyte at the time of charging / discharging, the improvement of the charging / discharging capacity
- the active material layer is formed by being distributed in a plurality of Si particles and islands, dots, or nets so as to partially cover the surface of the Si particles. And a covering material having Ni and P. If comprised in this way, since several Si particle
- a method for producing a negative electrode material for a secondary battery according to a third aspect of the present invention includes a step of preparing Si particles, and a covering material containing Ni and P so as to partially cover the surface of Si particles, And a step of distributing in a dot or net form.
- the coating containing Ni and P in an island shape, a dot shape, or a net shape so as to partially cover the surface of the Si particles By providing the step of distributing the material, the charge / discharge cycle life of the secondary battery negative electrode can be further extended as compared with the case where the coating material is made of only Ni.
- the step of distributing the coating material includes a step of distributing the coating material by performing a plating treatment. If comprised in this way, the coating material containing Ni and P can be easily distributed in an island shape, a dot shape, or a net shape so as to partially cover the surface of the Si particles by plating.
- the coating material is coated so as to cover a surface of 1% to 25% of the surface of the Si particles. Distributing the process. If comprised in this way, when the negative electrode material for secondary batteries is used for the active material layer of the negative electrode for secondary batteries by making the ratio which a coating
- capacitance (utilization rate of Si) of the negative electrode for secondary batteries can be improved more effectively.
- the covering material can withstand the stress caused by the volume change of the secondary battery negative electrode during charge and discharge, and collapse. Therefore, the charge / discharge cycle life can be extended.
- the step of distributing the coating material at least a part of the coating material containing Ni and P has a crystal structure of Ni 3 P. And a step of distributing the covering material.
- the coating material includes 0.5% by mass or more and 50% by mass or less P and Ni. If comprised in this way, when the negative electrode material for secondary batteries containing the coating material which consists of 0.5 mass% or more and 50 mass% or less of P and Ni is used for the active material layer of the negative electrode for secondary batteries. Since the crystal structure of Ni containing P contains Ni 3 P, the charge / discharge cycle life can be extended.
- a method for manufacturing a negative electrode for a secondary battery according to a fourth aspect of the present invention includes a step of preparing Si particles, and Ni and P in an island shape, a dot shape, or a net shape so as to partially cover the surface of the Si particles.
- a powdered negative electrode material for a secondary battery on the surface of the current collector, the Si portion and the Si Compared to the case where the covering portion is made of only Ni by providing a step of forming an active material layer including a covering portion having Ni and P while being distributed in the shape of islands, dots or nets between the portions or the Si portions. In addition, it is possible to extend the charge / discharge cycle life of the negative electrode for secondary battery.
- a powdered negative electrode for secondary battery on the surface of the current collector, it is distributed in the form of islands, dots or nets between the Si part and the Si part or Si part, and Ni and P
- the step of forming the active material layer is performed by using an aerosol deposition method to form a powdered negative electrode for a secondary battery on the surface of the current collector.
- a step of forming an active material layer by spraying a material is included.
- the active material layer easily includes the Si layer and the covering portion having Ni and P formed on the Si layer so as to be distributed in an island shape, a dot shape, or a net shape. Can be formed.
- the step of forming an active material layer applies a coating liquid containing a powdered negative electrode material for a secondary battery on the surface of the current collector.
- a step of forming an active material layer can be easily formed of a plurality of Si particles and Ni and P formed in an island shape, a dot shape, or a net shape so as to partially cover the surface of the Si particles.
- a covering material having the following structure.
- the step of forming the active material layer includes the Si material of the active material layer or the active material layer so as to form a void between the Si portions. Forming. If comprised in this way, the stress which generate
- the step of forming the negative electrode material for a secondary battery includes a coating material in which P is 0.5 mass% to 50 mass% and Ni Since the covering material is distributed so that the crystal structure of Ni containing P includes Ni 3 P due to the covering material composed of 0.5 mass% to 50 mass% of P and Ni, Longer charge / discharge cycle life can be achieved.
- the secondary battery negative electrode material 100 is a material constituting an active material layer 202 of a secondary battery negative electrode 200 described later, on the Si particles 1 and the surface 1 a of the Si particles 1. And a formed covering material 2.
- the Si particles 1 are made of Si and have a particle size of about 0.01 ⁇ m or more and about 20 ⁇ m or less.
- the covering material 2 is formed on each surface 1a of the plurality of Si particles 1 so as to partially cover the surface 1a and to be distributed in an island shape, a dot shape, or a net shape. Yes. Further, the covering material 2 is formed so as to cover an area of about 1% or more and about 25% or less of the surface 1a of the Si particle 1. That is, the covering material 2 is formed in an exposed state in an area of about 75% or more and about 99% or less of the surface 1a of the Si particle 1.
- part of the covering material 2 is made of a Ni—P alloy having a Ni 3 P crystal structure.
- the composition in the whole covering material 2 consists of about 0.5 mass% or more and about 50 mass% or less of P and Ni.
- the composition in the whole covering material 2 consists of about 5 mass% or more and about 16 mass% or less P and Ni, since it is possible to increase the ratio of Ni 3 P in the covering material 2. preferable.
- Si particles 1 (Si powder) as shown in FIG. 1 are prepared.
- the Si particles 1 are made of Si and have a particle size of about 0.01 ⁇ m or more and about 20 ⁇ m or less.
- the surface 1a is partially covered on each surface 1a of the plurality of Si particles 1, and the islands are formed.
- the covering material 2 is formed so as to be distributed in the form of dots or nets.
- a plurality of Si particles 1 about 0.14 g of Si powder
- about 0 in about 0.1 M H 2 SO 4 aqueous solution in which about 0.07 g of NiSO 4 .6H 2 O is dissolved.
- Add .05 g NaBH 4 about 0.05 g NaH 2 PO 2 .H 2 O, and about 0.01 g Na 3 C 6 H 5 O 7 .2H 2 O.
- the electroless-plating process is performed by stirring the produced solution on about 70 degreeC temperature conditions.
- the covering material 2 is formed on each surface 1a of the plurality of Si particles 1 so as to partially cover the surface 1a and to be distributed in an island shape, a dot shape, or a net shape. .
- a plurality of secondary battery negative electrode materials 100 are formed.
- the covering material 2 containing Ni and P is distributed in an island shape, a dot shape, or a net shape so as to partially cover the surface 1 a of the Si particles 1, thereby covering the covering material 2.
- the charge / discharge cycle life of the secondary battery negative electrode 200 can be further extended as compared with the case where 2 is made of only Ni.
- the covering material 2 containing Ni and P is distributed in an island shape, a dot shape, or a net shape so as to partially cover the surface 1a of the Si particle 1 instead of the entire surface, so that the electrolyte ( Insertion / extraction of Li cation) is facilitated, so that the charge / discharge capacity of the secondary battery negative electrode 200 can be improved.
- the secondary battery negative electrode material 100 is activated by the secondary battery negative electrode 200.
- the area where the Si layer 221 and the electrolyte (Li cation) of the lithium ion secondary battery come into contact can be increased.
- capacitance (utilization rate of Si) of the negative electrode 200 for secondary batteries can be improved more effectively.
- the ratio of the covering material 2 covering the surface 1a of the Si particles 1 is 1% or more, the stress generated due to the volume change of the secondary battery negative electrode 200 during charge / discharge is caused by the covering material 2. Since it can withstand stress and suppress collapse, the life of the charge / discharge cycle can be extended.
- the secondary battery negative electrode material 100 may be When used for the active material layer 202 of the secondary battery negative electrode 200, the stress caused by the volume change of the secondary battery negative electrode 200 during charging and discharging is caused by Ni 3 P contained in the coating material 2. It is possible to withstand the above and suppress the collapse so that the charge / discharge cycle life can be extended.
- the composition of the entire covering material 2 is composed of P and Ni of about 0.5 mass% or more and about 50 mass% or less, 0.
- Ni containing P is contained. Since the crystal structure contains Ni 3 P, the charge / discharge cycle life can be extended.
- the surface 1a is partially covered on each surface 1a of the plurality of Si particles 1 by using an electroless deposition (ELD) method which is a kind of plating treatment.
- ELD electroless deposition
- the covering material 2 is formed so as to be distributed in the form of islands, dots, or nets
- the surface 1a of the Si particles 1 can be partially applied to the covering material 2 containing Ni and P easily by electroless deposition. It can be distributed in an island shape, a dot shape, or a net shape so as to cover.
- composition measurement First, by using an electroless deposition (ELD) method, by forming a coating material on the surface of each of a plurality of Si particles made of Si and having a particle size of 0.01 ⁇ m or more and 20 ⁇ m or less, as follows: A plurality of negative electrode materials for secondary batteries corresponding to Examples and Comparative Examples 1 and 2 were produced. Further, as Comparative Example 3, a negative electrode material for a secondary battery made of Si particles not forming a coating material was prepared. And the composition of the some negative electrode material for secondary batteries corresponding to an Example and Comparative Examples 1 and 2 was measured.
- ELD electroless deposition
- a plurality of Si particles 1 (0... 0) are added to a 0.1 M H 2 SO 4 aqueous solution in which 0.070 g of NiSO 4 .6H 2 O is dissolved.
- the surface 1a is partially covered on each surface 1a of the plurality of Si particles 1, and the coating distributed in islands, dots, or nets Material 2 was formed.
- a plurality of secondary battery negative electrode materials 100 (see FIG. 1) corresponding to the examples were manufactured.
- Comparative Example 1 a 0.1M H 2 SO 4 aqueous solution in which 0.063 g of NiSO 4 .6H 2 O was dissolved, a plurality of Si particles (0.125 g of Si powder), and 0.500 g of NaBH 4 was added. And the coating material which consists of Ni was formed in the surface of each of several Si particle
- Comparative Example 2 a 0.1M H 2 SO 4 aqueous solution in which 0.070 g of NiSO 4 .6H 2 O was dissolved, a plurality of Si particles (0.140 g of Si powder), and 0.500 g of NaBH 4 and 0.002 g SnSO 4 were added.
- the prepared solution was stirred at room temperature to form a coating material made of a Ni—Sn alloy on the surface of each of the plurality of Si particles. Thereby, a negative electrode material for a secondary battery corresponding to Comparative Example 2 was produced.
- composition of the negative electrode material for secondary battery of the example and the composition of the negative electrode material for secondary battery of Comparative Examples 1 and 2 were analyzed by energy dispersive X-ray fluorescence analysis (EDX) and inductively coupled plasma emission analysis (ICP). It measured using.
- EDX energy dispersive X-ray fluorescence analysis
- ICP inductively coupled plasma emission analysis
- the total content of Ni and P (0.18 mass) compared to the Si content (99.8 mass%).
- % + 0.02 mass% 0.2 mass%) was found to be very small.
- lattice spacing measurement Next, the lattice spacing measurement will be described.
- an electron diffraction image related to the coating material 2 of the above-described example was obtained by electron diffraction using a transmission electron microscope.
- the lattice plane intervals on the five lattice planes ((211), (400), (222), (402), and (460)) of the covering material 2 made of the Ni—P alloy were measured.
- the lattice spacing was 0.297 nm on the lattice plane (211). Further, in the lattice plane (400), the lattice plane spacing was 0.225 nm. Further, in the lattice plane (222), the lattice plane spacing was 0.181 nm. Further, in the lattice plane (402), the interval between the lattice planes was 0.157 nm. Moreover, the lattice spacing was 0.124 nm on the lattice plane (460).
- the lattice plane spacing on the five lattice planes ((211), (400), (222), (402) and (460)) of the covering material 2 of the embodiment shown in FIG. 3 is 5 for Ni 3 P, respectively. It was found that the lattice plane spacing (theoretical value) on the two lattice planes ((211), (400), (222), (402) and (460)) was substantially the same. As a result, it was found that the coating material 2 contained Ni 3 P (P content: 15.2 mass%) as the Ni—P alloy.
- the P content in the coating material 2 made of the Ni—P alloy is 10% by mass, and Ni 3 P Is less than the P content (15.2 mass%). Therefore, the covering material 2 of the negative electrode material 100 for a secondary battery of Example, as Ni-P alloy, and Ni 3 P, when than Ni 3 P is present a Ni-P alloy content is small P considered It is done.
- the negative electrode 200 for secondary batteries by 2nd Embodiment of this invention is demonstrated.
- the negative electrode for secondary battery in which the active material layer 202 is formed on the current collector layer 201 by spraying the negative electrode material for secondary battery 100 of the first embodiment on the current collector layer 201. 200 will be described.
- the negative electrode 200 for a secondary battery according to the second embodiment of the present invention includes a current collector layer 201 and an active material layer 202 formed on one surface of the current collector layer 201. Yes.
- the current collector layer 201 has a thickness t1 of about 1 ⁇ m to about 20 ⁇ m, and the active material layer 202 has a thickness t2 of about 1 ⁇ m to about 20 ⁇ m.
- the current collector layer 201 is made of Cu foil.
- the active material layer 202 of the negative electrode for secondary battery 200 is distributed in a layered form of the Si layer 221 and islands, dots, or nets inside the Si layer 221. And a formed covering portion 222.
- the covering portion 222 is arranged so as to be distributed in an island shape, a dot shape, or a net shape over substantially the entire inside of the Si layer 221, and a part of the covering portion 222 is an arbitrary region of the Si layer 221. It arrange
- the Si layer 221 is an example of the “Si portion” in the present invention.
- Si in the Si layer 221 reacts with electrons transferred from the current collector layer 201 and Li cations contained in the electrolyte of the lithium ion secondary battery when charging the lithium ion secondary battery,
- An Li 4.4 Si alloy is formed with a composition having the highest Li ratio.
- the Li 4.4 Si alloy formed on the Si layer 221 at the time of charging (at the time of lithium insertion) is composed of electrons, Li cations, Si, and lithium when the lithium ion secondary battery is discharged (at the time of lithium desorption).
- the generated electrons are supplied to the current collector layer 201.
- an Li 4.4 Si alloy is formed when the lithium ion secondary battery is charged, while an Li 4.4 Si alloy is separated when the lithium ion secondary battery is discharged. It is configured such that the volume of the Si layer 221 changes during charge / discharge of the ion secondary battery. Due to the volume change, stress is generated in the secondary battery negative electrode 200.
- a part of the covering portion 222 is made of a Ni—P alloy having a crystal structure of Ni 3 P (P content is about 15.2% by mass). Further, the composition of the entire covering portion 222 is composed of P and Ni of about 0.5 mass% or more and about 50 mass% or less. Note that the entire covering portion 222 is preferably made of about 5 mass% or more and about 16 mass% or less of P and Ni because the ratio of Ni 3 P in the covering portion 222 can be increased.
- a plurality of voids 223 are formed in the Si layer 221 so as to be distributed and distributed.
- the voids 223 are formed in the active material layer 202 at a ratio of about 20 volume% or more and about 70 volume% or less.
- at least a part of the gap 223 is connected to another gap and connected to the outside (the surface of the Si layer 221 opposite to the current collector layer 201 (the surface of the Si layer 221 in contact with the electrolyte)). Is formed.
- the electrolyte (Li cation) of the lithium ion secondary battery can enter into the gap 223, the Si of the lithium ion secondary battery is placed in Si located inside the active material layer 202 (Si layer 221). It is possible for the electrolyte to reach.
- the some negative electrode material 100 for secondary batteries is sprayed on the one surface of the collector layer 201 which consists of Cu foil using the aerosol deposition method.
- a current collector layer 201 having a thickness t1 of about 1 ⁇ m or more and about 20 ⁇ m or less is disposed on the lower surface of the stage 301 in the decompressed chamber 300.
- a nozzle 302 having an inner diameter of about 0.8 mm is disposed on one surface side of the current collector layer 201 with a distance of about 10 mm.
- a plurality of secondary battery negative electrode materials 100 are sprayed onto one surface of the current collector layer 201 through a nozzle 302 together with an Ar gas having a gas pressure of about 6.0 ⁇ 10 5 Pa.
- the active material layer 202 having a thickness t2 of about 1 ⁇ m or more and about 20 ⁇ m or less is formed on one surface of the current collector layer 201.
- the secondary battery negative electrode 200 shown in FIG. 4 is formed.
- the negative electrode material 100 for the secondary battery is sprayed on the current collector layer 201 or the Si particles 1 (see FIG. 1) already arranged on the current collector layer 201, so that the Si particles 1 are bonded to each other. .
- the particulate Si particles 1 are substantially absent, and the Si layer 221 is formed by joining the Si particles 1 to each other.
- the voids 223 are formed in the Si layer 221 so as to be distributed at a ratio of about 20 volume% or more and about 70 volume% or less with respect to the active material layer 202.
- the secondary battery negative electrode material 100 is sprayed onto the current collector layer 201 or the Si particles 1 already disposed on the current collector layer 201, so that the covering material 2 (see FIG. 1) is inside the Si layer 221. Are distributed over almost the whole. At this time, a part of the covering material 2 formed on the surface 1 a (see FIG. 1) of the same Si particle 1 is formed on the surface of the Si particle 1 regardless of the bonding between the Si particles 1. There is a case to keep the position. In this case, a part of the covering portion 2 is formed so as to surround an arbitrary region 221a (region along the shape of the Si particles 1).
- the active material layer 202 is formed into a layered Si layer 221, and a covering portion formed so as to be distributed in an island shape, a dot shape, or a net shape inside the Si layer 221. 222, the charge / discharge cycle life of the secondary battery negative electrode 200 can be further extended as compared with the case where the covering portion 222 is made of only Ni.
- the active material layer 202 includes the Si layer 221 and the covering portion 222 having Ni and P formed on the Si layer 221 so as to be distributed in an island shape, a dot shape, or a net shape.
- the secondary battery negative electrode 200 can withstand the stress generated in the secondary battery negative electrode 200 and suppress collapse, and can easily insert and remove the electrolyte (Li cation) of the lithium ion secondary battery. 200 charge / discharge capacity can be improved.
- the voids 223 are formed at a ratio of 20% by volume or more of the active material layer 202, the voids 223 sufficient to relieve stress can be obtained.
- the stress generated in the secondary battery negative electrode 200 during discharge can be relaxed.
- the voids 223 are formed at a ratio of 70% by volume or less of the active material layer 202, the proportion occupied by the voids 223 becomes excessively large and reacts with the electrolyte (Li cation) of the lithium ion secondary battery. Therefore, it is possible to suppress the Si layer 221 to be excessively small. Thereby, it can suppress that the charging / discharging capacity
- the thickness t2 of the active material layer 202 when the thickness t2 of the active material layer 202 is 1 ⁇ m or more, it is possible to suppress the charge / discharge capacity of the secondary battery negative electrode 200 from decreasing. In addition, if the thickness t2 of the active material layer 202 is 20 ⁇ m or less, it is possible to suppress the Si in the vicinity of the current collector layer 201 from becoming difficult to react with the electrolyte (Li cation) of the lithium ion secondary battery. Moreover, it can suppress that the charging / discharging speed
- the composition of the entire covering portion 222 is composed of about 0.5 mass% to about 50 mass% of P and Ni, P is Since the Ni crystal structure contains Ni 3 P, the charge / discharge cycle life can be extended.
- the powdery negative electrode material 100 for secondary batteries may be sprayed on the one surface of the collector layer 201 which consists of Cu foils using the aerosol deposition method.
- the active material layer 202 can easily include the Si layer 221 and the covering portion 222 having Ni and P formed on the Si layer 221 so as to be distributed in the form of islands, dots, or nets. Can be formed.
- the negative electrode materials for secondary batteries of Examples and Comparative Examples 1 to 3 were combined with Ar gas having a gas pressure of 6.0 ⁇ 10 5 Pa at one surface of the current collector layer 201 at room temperature. Sprayed through. As a result, a negative electrode for a secondary battery comprising a current collector layer and an active material layer formed on one surface of the current collector layer, corresponding to Examples and Comparative Examples 1 to 3, was produced.
- the secondary battery negative electrode 410 corresponding to the example and the comparative examples 1 to 3 was attached to the tip of the negative electrode side terminal 400a of the charging / discharging device 400. Further, a positive electrode 420 made of Li foil having a thickness of 1 mm and a reference electrode electrode 430 made of Li foil having a thickness of 1 mm are attached to the positive electrode side terminal 400b and the reference electrode side terminal 400c of the charging / discharging device 400, respectively. It was.
- As the electrolyte a solution in which LiClO 4 was dissolved in a propylene carbonate (PC) solvent to a concentration of 1M was used. Then, the negative electrode side terminal 400a, the positive electrode side terminal 400b, and the reference electrode side terminal 400c were arrange
- a propylene carbonate (PC) solvent a concentration of 1M
- the negative electrode for the secondary battery of the example (Ni—P-coated Si) was the first time than the negative electrode for the secondary battery of the comparative example 3 (uncoated Si). It turned out that the capacity
- the negative electrode for the secondary battery of the example may have a larger capacity at the time of first charge and discharge than the negative electrode for the secondary battery of Comparative Example 1 (Ni-coated Si).
- the secondary battery negative electrode of the example had a larger capacity at the time of first charge and discharge than the secondary battery negative electrode of Comparative Example 2 (Ni—Sn-coated Si). This is presumably because a part of the negative electrode for secondary battery of Comparative Example 2 did not function due to phase separation of the Ni—Sn alloy.
- the negative electrode for secondary battery of Example is the negative electrode for secondary battery of Comparative Example 1 (Ni-coated Si) and Comparative Example 2. It was found that the discharge capacity at the 1000th time was larger than the (Ni—Sn-coated Si) secondary battery negative electrode and the comparative example 3 (uncoated Si) secondary battery negative electrode. Specifically, as shown in FIG. 9, the discharge capacity of the negative electrode for secondary battery of the example was 750 ⁇ 10 ⁇ 3 Ah / g. On the other hand, the discharge capacity of the secondary battery negative electrode of Comparative Example 1 was 600 ⁇ 10 ⁇ 3 Ah / g.
- the discharge capacity of the secondary battery negative electrode of Comparative Example 2 was 150 ⁇ 10 ⁇ 3 Ah / g.
- the discharge capacity of the secondary battery negative electrode of Comparative Example 3 was 30 ⁇ 10 ⁇ 3 Ah / g. From this, it was found that the negative electrode for secondary battery of the example had a very large discharge capacity of 750 ⁇ 10 ⁇ 3 Ah / g even when 1000 charge / discharge cycles were repeated. That is, while adopting a structure in which a coating portion made of a Ni—P alloy is formed on Si as an active material layer, as in the negative electrode for secondary batteries of the example, while extending the charge / discharge cycle life, It has been found that it is possible to further improve the discharge capacity.
- the secondary battery negative electrode of the example corresponding to the second embodiment can further improve the discharge capacity while extending the charge / discharge cycle life. It turned out to be possible.
- the negative electrode for the secondary battery of the example (Ni—P-coated Si) and the negative electrode for the secondary battery of Comparative Example 1 (Ni-coated Si) were the negative electrode for the secondary battery of Comparative Example 2 (Ni—Sn-coated Si). And it turned out that the decreasing rate of the discharge capacity in the charging / discharging cycle to the 100th time becomes smaller than the negative electrode for secondary batteries of Comparative Example 3 (Si without coating). This is because, in the negative electrode for a secondary battery of Comparative Example 2 (Ni—Sn-coated Si), the Sn released from the phase separation of the Ni—Sn alloy reacts with the Li cation of the electrolyte during charging and forms an alloy. The alloy is decomposed during discharge.
- the Ni—Sn alloy layer that had the role of bonding between the Si particles, the stress relaxation function, and the conductive function can no longer play its role, and as a result, some of the negative electrodes for secondary batteries do not function early. It is thought that it was because of.
- the stress generated in the negative electrode for secondary battery at the time of charging / discharging is reduced by the coating portion made of the Ni—P alloy containing Ni 3 P. It is considered that a part of the negative electrode for a secondary battery can be prevented from functioning because it can resist the collapse and suppress the collapse.
- the stress generated in the secondary battery negative electrode during charging and discharging is resisted by the Ni-coated portion and the collapse is suppressed. Therefore, it is thought that it can suppress that a part of negative electrode for secondary batteries stops functioning.
- the elastic modulus of the active material layer (portion 202 in FIG. 4) in the negative electrodes for secondary batteries of Examples and Comparative Examples 1 to 3 was measured using an indented hardness measurement method. .
- the indenter made of diamond having a tip angle of 115 degrees is subjected to a secondary pressure in Examples and Comparative Examples 1 to 3 at a pressure that increases by 0.29 mN per second. It pressed against the negative electrode for batteries from the active material layer side.
- the pressure When the pressure reaches 4.9 mN, the pressure is applied to the negative electrodes for secondary batteries of Examples and Comparative Examples 1 to 3 so that the pressure is maintained for 5 seconds and then decreased by 0.29 mN every second. Released.
- the amount of change in strain of the negative electrode for secondary battery in this series of operations was measured using a hardness meter (not shown). Then, the elastic modulus was measured from the strain change with respect to the pressure.
- the negative electrode for secondary battery of Example (Ni—P coated Si), the negative electrode for secondary battery of Comparative Example 1 (Ni coated Si), and Comparative Example 2 (Ni—
- the secondary battery negative electrode of Sn-coated Si has an elastic modulus that is 8 times or more larger than that of the secondary battery negative electrode of Comparative Example 3 (uncoated Si), that is, the durability against expansion and contraction of Si is large.
- the active material layer includes Ni—P alloy, Ni, or Ni—Sn alloy in addition to Si
- the active material layer includes Si in comparison with the negative electrode for a secondary battery. Since the bonding force between the crystal grains increases, it is considered that it resists the collapse by resisting the stress generated in the negative electrode.
- the Si content (see FIG. 4) is larger than the negative electrode for secondary batteries of Comparative Example 1 (Ni-coated Si) and the negative electrode for secondary batteries of Comparative Example 2 (Ni-Sn-coated Si) (Ni).
- the negative electrode for the secondary battery of the example has the same elasticity as the negative electrode for the secondary battery of Comparative Example 1 and the negative electrode for the secondary battery of Comparative Example 2 It was found to have a coefficient.
- the Ni—P alloy containing Ni 3 P can withstand the stress generated in the negative electrode because the bonding force between the Si crystal grains is increased even in a small amount compared to the Ni or Ni—Sn alloy. It is thought to suppress collapse.
- the active material layer 502 is formed by forming the active material layer 502 on the surface of the current collector layer 201 by a coating method. A case where a plurality of Si particles 1 and a covering material 2 are included will be described.
- the negative electrode 500 for a secondary battery according to the third embodiment of the present invention includes a current collector layer 201 and an active material layer 502 formed on both surfaces of the current collector layer 201.
- the thickness t1 of the current collector layer 201 is about 1 ⁇ m or more and about 20 ⁇ m or less
- the thickness t2 of the active material layer 502 is about 1 ⁇ m or more and about 20 ⁇ m or less.
- the active material layer 502 of the secondary battery negative electrode 500 is formed by forming the active material layer 502 on the surface of the current collector layer 201 using a coating method described later.
- the secondary battery negative electrode material 100 illustrated in FIG. 1 is formed by stacking a plurality of Si particles 1 while maintaining the particle shape of the Si particles 1. Accordingly, the active material layer 502 partially covers the plurality of Si particles 1 and the surfaces 1a of the plurality of Si particles 1, and is disposed so as to be distributed in an island shape, a dot shape, or a net shape. 2 is included.
- the Si particles 1 are an example of the “Si portion” in the present invention
- the coating material 2 is an example of the “cover portion” in the present invention.
- a plurality of voids 523 are formed between the Si particles 1 by stacking a plurality of the negative electrode materials 100 for secondary batteries while maintaining the particle shape of the Si particles 1.
- the voids 523 are formed in the active material layer 502 at a ratio of about 20 volume% or more and about 70 volume% or less. At least a part of the gap 523 is connected to another gap and connected to the outside (the surface of the active material layer 502 opposite to the current collector layer 201 (the surface of the active material layer 502 in contact with the electrolyte)). ing.
- the other structure of the negative electrode 500 for secondary batteries of 3rd Embodiment is the same as that of the said 2nd Embodiment.
- a plurality of secondary battery negative electrode materials 100 are mixed with a solvent / binder to form a coating solution. Then, a coating liquid is apply
- the secondary battery negative electrode 500 provided is formed.
- the Si particles 1 are stacked with their particle shapes maintained to some extent as shown in FIG.
- the voids 523 are formed between the Si particles 1 so as to be distributed at a ratio of about 20% by volume or more and about 70% by volume or less with respect to the active material layer 502.
- the volume ratio of the voids to the active material layer tends to be larger than that in the manufacturing process by the aerosol deposition method in the second embodiment.
- the coating material 2 partially covers the surface 1 a of the Si particles 1 and is distributed in islands, dots, or nets. Thus, the arrangement state is maintained.
- the active material layer 502 is formed to be distributed in an island shape, a dot shape, or a net shape so as to partially cover the plurality of Si particles 1 and the surface 1a of the Si particles 1.
- the covering material 2 containing Ni and P the charge / discharge capacity of the secondary battery negative electrode 500 can be further improved as compared with the case where the covering material 2 is made of only Ni. .
- it can withstand the stress generated in the secondary battery negative electrode 500 during charge and discharge and suppress collapse, and also facilitates insertion / extraction of the electrolyte (Li cation) of the lithium ion secondary battery.
- the charge / discharge capacity of the secondary battery negative electrode 500 can be improved.
- the current collector layer 201 and the current collector layer 201 are formed by applying a coating solution containing a plurality of secondary battery negative electrode materials 100 on both surfaces of the current collector layer 201 made of Cu foil. If the negative electrode 500 for a secondary battery including the active material layers 502 formed on both surfaces of the current collector layer 201 is formed, the active material layer 502 can be easily formed from a plurality of Si particles 1 and Si It can be formed so as to include a covering material 2 having Ni and P formed in an island shape, a dot shape, or a net shape so as to partially cover the surface 1 a of the particle 1. The remaining effects of the secondary battery negative electrode 500 of the third embodiment are similar to those of the aforementioned second embodiment.
- an electroless deposition (ELD) method which is a kind of plating treatment, is used to partially cover the surface 1a on each surface 1a of the plurality of Si particles 1 and to form islands.
- ELD electroless deposition
- network shape was shown, this invention is not limited to this.
- the surface 1a is partially covered on each surface 1a of the plurality of Si particles 1 by using an electrolytic plating method, a sputtering method, a vapor deposition method, or the like, and is coated so as to be distributed in islands, dots, or nets.
- the material 2 may be formed.
- a part of the covering material 2 is made of a Ni—P alloy having a crystal structure of Ni 3 P is shown.
- the covering material 2 contains a Ni—P alloy that contributes to an increase in bonding force between Si crystal grains
- the covering material 2 contains Ni 3 P. It may be configured to be made of a non-Ni—P alloy.
- the current collector layer 201 is made of Cu foil.
- the present invention is not limited to this.
- the present invention is not limited to this. I can't. In the present invention, all of the covering portion 222 may be disposed over substantially the entire inside of the Si layer 221.
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Abstract
Description
まず、図1を参照して、本発明の第1実施形態による二次電池用負極材100の構成について説明する。
次に、図1~図3を参照して、上記第1実施形態による二次電池用負極材100の組成を確認するために行った組成測定と格子面間隔測定とについて説明する。
まず、無電解析出(ELD)法を用いて、Siからなるとともに、0.01μm以上20μm以下の粒径を有する複数のSi粒子の各々の表面に被覆材を下記のように形成することによって、実施例および比較例1および2に対応する複数の二次電池用負極材を作製した。また、比較例3として、被覆材を形成しないSi粒子からなる二次電池用負極材を準備した。そして、実施例および比較例1および2に対応する複数の二次電池用負極材の組成を測定した。
次に、格子面間隔測定について説明する。格子面間隔測定では、透過型電子顕微鏡を用いた電子回折により、上記した実施例の被覆材2に関する電子回折画像を得た。そして、Ni-P合金からなる被覆材2の5つの格子面((211)、(400)、(222)、(402)および(460))における格子面間隔をそれぞれ測定した。
次に、図1および図4を参照して、本発明の第2実施形態による二次電池用負極200について説明する。この第2実施形態では、上記第1実施形態の二次電池用負極材100を集電体層201に吹き付けることによって、集電体層201上に活物質層202を形成した二次電池用負極200について説明する。
次に、図4~図10を参照して、上記第2実施形態による二次電池用負極200の効果を確認するために行った充放電容量測定と弾性係数測定とについて説明する。
まず、放電(リチウム脱離)容量の測定について説明する。この充放電容量の測定では、まず、エアロゾルデポジション法を用いて、上記した実施例および比較例1~3の二次電池用負極材を、20μmの厚みを有するCu箔からなる集電体層の一方表面に吹き付けて、集電体層の一方表面上に活物質層を形成した。具体的には、図5に示すように、減圧したチャンバー300内のステージ301の下面に、厚さ20μmの集電体層201を配置した。そして、室温下で、実施例および比較例1~3の二次電池用負極材を、6.0×105Paのガス圧を有するArガスと共に、集電体層201の一方表面にノズル302を介して吹き付けた。これにより、実施例および比較例1~3に対応する、集電体層と、集電体層の一方表面に形成された活物質層とを備える二次電池用負極を作製した。
次に、弾性係数の測定について説明する。この弾性係数の測定では、インデント式硬度測定法を用いて、上記した実施例および比較例1~3の二次電池用負極における活物質層(図4の202の部位)の弾性係数を測定した。具体的には、先端の角度が115度であるダイヤモンドからなるインデンター(図示せず)を1秒ごとに0.29mNずつ大きくなるような圧力で、実施例および比較例1~3の二次電池用負極に活物質層側から押し付けた。そして、4.9mNになった際に5秒維持し、その後、1秒ごとに0.29mNずつ小さくなるように実施例および比較例1~3の二次電池用負極に加えた圧力を徐々に解除した。この一連の操作における二次電池用負極のひずみ変化量を図示しない硬度計を用いて測定した。そして、圧力に対するひずみ変化量から弾性係数を測定した。
次に、図1、図11および図12を参照して、本発明の第3実施形態について説明する。この第3実施形態による二次電池用負極500では、上記第2実施形態と異なり、塗布法により、集電体層201の表面上に活物質層502を形成することによって、活物質層502が複数のSi粒子1と、被覆材2とを含んでいる場合について説明する。
Claims (22)
- 二次電池用負極(200、500)の集電体層(201)上に形成される活物質層(202、502)を構成する二次電池用負極材(100)であって、
Si粒子(1)と、
前記Si粒子の表面(1a)を部分的に覆うように島状、点状または網状に分布して形成されたNiとPとを含む被覆材(2)とを備える、二次電池用負極材。 - 前記被覆材は、前記Si粒子の表面のうち、1%以上25%以下の前記表面を覆っている、請求項1に記載の二次電池用負極材。
- 前記NiとPとを含む被覆材の少なくとも一部は、Ni3Pの結晶構造である、請求項1に記載の二次電池用負極材。
- 前記被覆材は、0.5質量%以上50質量%以下のPと、Niとからなる、請求項1に記載の二次電池用負極材。
- 前記被覆材は、5質量%以上16質量%以下のPと、Niとからなる、請求項4に記載の二次電池用負極材。
- 集電体層と、
前記集電体層の表面上に形成される活物質層とを備え、
前記活物質層は、
Si部分(1、221)と、
前記Si部分または前記Si部分間に島状、点状または網状に分布するように形成されたNiとPとを有する被覆部分(2、222)とを含む、二次電池用負極。 - 前記活物質層の前記Si部分または前記Si部分間には、空隙(223、523)が形成されている、請求項6に記載の二次電池用負極。
- 前記空隙は、前記活物質層の20体積%以上70%体積以下の割合で形成されている、請求項7に記載二次電池用負極。
- 前記活物質層の厚みは、1μm以上20μm以下である、請求項6に記載の二次電池用負極。
- 前記活物質層の被覆部分は、0.5質量%以上50質量%以下のPと、Niとからなる、請求項6に記載の二次電池用負極。
- 前記活物質層は、Si層(221)と、前記Si層に島状、点状または網状に分布するように形成されたNiとPとを有する前記被覆部分とを含む、請求項6に記載の二次電池用負極。
- 前記活物質層は、複数のSi粒子(1)と、前記Si粒子の表面を部分的に覆うように島状、点状または網状に分布して形成されたNiとPとを有する被覆材(2)とを含む、請求項6に記載の二次電池用負極。
- Si粒子を準備する工程と、
前記Si粒子の表面を部分的に覆うように島状、点状または網状にNiとPとを含む被覆材を分布させる工程とを備える、二次電池用負極材の製造方法。 - 前記被覆材を分布させる工程は、めっき処理を行うことによって、前記被覆材を分布させる工程を含む、請求項13に記載の二次電池用負極材の製造方法。
- 前記被覆材を分布させる工程は、前記Si粒子の表面のうち、1%以上25%以下の前記表面を覆うように、前記被覆材を分布させる工程を含む、請求項13に記載の二次電池用負極材の製造方法。
- 前記被覆材を分布させる工程は、前記NiとPとを含む被覆材の少なくとも一部がNi3Pの結晶構造となるように、前記被覆材を分布させる工程を含む、請求項13に記載の二次電池用負極材の製造方法。
- 前記被覆材は、0.5質量%以上50質量%以下のPと、Niとからなる、請求項13に記載の二次電池用負極材の製造方法。
- Si粒子を準備する工程と、
前記Si粒子の表面を部分的に覆うように島状、点状または網状にNiとPとを含む被覆材を分布させることによって、粉末状の二次電池用負極材を形成する工程と、
前記粉末状の二次電池用負極材を所定の方法により集電体の表面上に配置することによって、Si部分と、前記Si部分または前記Si部分間に島状、点状または網状に分布するとともにNiとPとを有する被覆部分とを含む活物質層を形成する工程とを備える、二次電池用負極の製造方法。 - 前記活物質層を形成する工程は、エアロゾルデポジション法を用いて前記集電体の表面上に前記粉末状の二次電池用負極材を吹き付けることによって、前記活物質層を形成する工程を含む、請求項18に記載の二次電池用負極の製造方法。
- 前記活物質層を形成する工程は、前記集電体の表面上に前記粉末状の二次電池用負極材を含む塗布液を塗布することによって、前記活物質層を形成する工程を含む、請求項18に記載の二次電池用負極の製造方法。
- 前記活物質層を形成する工程は、前記活物質層の前記Si部分または前記Si部分間に空隙を形成するように、前記活物質層を形成する工程を含む、請求項18に記載の二次電池用負極の製造方法。
- 前記二次電池用負極材を形成する工程は、前記被覆材が、0.5質量%以上50質量%以下のPと、Niとからなるように前記被覆材を分布させることによって、前記二次電池用負極材を形成する工程を含む、請求項18に記載の二次電池用負極の製造方法。
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JP2012546595A JP5755246B2 (ja) | 2010-11-29 | 2010-11-29 | 二次電池用負極材、二次電池用負極、二次電池用負極材の製造方法および二次電池用負極の製造方法 |
CN2010800704122A CN103229334A (zh) | 2010-11-29 | 2010-11-29 | 二次电池用负极材料、二次电池用负极、二次电池用负极材料的制造方法和二次电池用负极的制造方法 |
KR1020137012757A KR20130132813A (ko) | 2010-11-29 | 2010-11-29 | 2차 전지용 부극재, 2차 전지용 부극, 2차 전지용 부극재의 제조 방법 및 2차 전지용 부극의 제조 방법 |
US13/903,738 US9350011B2 (en) | 2010-11-29 | 2013-05-28 | Secondary battery negative electrode material, secondary battery negative electrode, method for manufacturing secondary battery negative electrode material, and method for manufacturing secondary battery negative electrode |
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Cited By (3)
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JP2015072849A (ja) * | 2013-10-04 | 2015-04-16 | 国立大学法人鳥取大学 | 二次電池用負極材、二次電池用負極材の製造方法および二次電池用負極 |
JP2019501499A (ja) * | 2015-12-22 | 2019-01-17 | ローベルト ボッシュ ゲゼルシャフト ミット ベシュレンクテル ハフツング | 電池セルを製造する方法 |
JP2022528543A (ja) * | 2019-04-12 | 2022-06-14 | 財團法人國家同▲歩▼輻射研究中心 | リチウム電池の純シリコン陽極に用いられるリチウム-シリコン化合物結晶多形及びその用途 |
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JP6410933B2 (ja) * | 2015-06-02 | 2018-10-24 | 富士フイルム株式会社 | 負極用材料、全固体二次電池用電極シートおよび全固体二次電池ならびに全固体二次電池用電極シートおよび全固体二次電池の製造方法 |
WO2017062788A1 (en) * | 2015-10-09 | 2017-04-13 | Rutgers, The State University Of New Jersey | Nickel phosphide catalysts for direct electrochemical co2 reduction to hydrocarbons |
CN111916686B (zh) * | 2019-05-08 | 2022-08-12 | 中国石油化工股份有限公司 | 含磷锂离子电池负极材料及其制备工艺 |
CN114023568B (zh) * | 2021-09-24 | 2022-10-14 | 多助科技(武汉)有限公司 | 一种镍锡合金@氢氧化镍核壳结构复合材料及其制备和应用 |
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- 2010-11-29 WO PCT/JP2010/071292 patent/WO2012073313A1/ja active Application Filing
- 2010-11-29 KR KR1020137012757A patent/KR20130132813A/ko not_active Application Discontinuation
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JP2015072849A (ja) * | 2013-10-04 | 2015-04-16 | 国立大学法人鳥取大学 | 二次電池用負極材、二次電池用負極材の製造方法および二次電池用負極 |
JP2019501499A (ja) * | 2015-12-22 | 2019-01-17 | ローベルト ボッシュ ゲゼルシャフト ミット ベシュレンクテル ハフツング | 電池セルを製造する方法 |
JP2022528543A (ja) * | 2019-04-12 | 2022-06-14 | 財團法人國家同▲歩▼輻射研究中心 | リチウム電池の純シリコン陽極に用いられるリチウム-シリコン化合物結晶多形及びその用途 |
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Also Published As
Publication number | Publication date |
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KR20130132813A (ko) | 2013-12-05 |
CN103229334A (zh) | 2013-07-31 |
US9350011B2 (en) | 2016-05-24 |
US20130252094A1 (en) | 2013-09-26 |
JP5755246B2 (ja) | 2015-07-29 |
JPWO2012073313A1 (ja) | 2014-05-19 |
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