JP2010262752A - Negative electrode for lithium ion secondary battery, lithium ion secondary battery using the same, and method of manufacturing negative electrode for lithium ion secondary battery - Google Patents

Negative electrode for lithium ion secondary battery, lithium ion secondary battery using the same, and method of manufacturing negative electrode for lithium ion secondary battery Download PDF

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JP2010262752A
JP2010262752A JP2009110595A JP2009110595A JP2010262752A JP 2010262752 A JP2010262752 A JP 2010262752A JP 2009110595 A JP2009110595 A JP 2009110595A JP 2009110595 A JP2009110595 A JP 2009110595A JP 2010262752 A JP2010262752 A JP 2010262752A
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negative electrode
silicon
linear body
lithium ion
ion secondary
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Takeshi Nishimura
Michihiro Shimada
道宏 島田
健 西村
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Furukawa Electric Co Ltd:The
古河電気工業株式会社
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    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50Manufacturing or production processes characterised by the final manufactured product
    • Y02P70/54Manufacturing of lithium-ion, lead-acid or alkaline secondary batteries

Abstract

A negative electrode for a lithium ion secondary battery that achieves a high capacity and a long life is obtained. A metal current collector and a silicon linear body grown on the current collector are provided. A lithium ion secondary battery wherein at least one end of the silicon linear body is bonded to the current collector by a metal bond, or is bonded to a metal on the current collector by a metal bond For negative electrode. Moreover, it is a lithium ion secondary battery using this negative electrode. This silicon linear body is formed by the VLS method.
[Selection] Figure 1

Description

  The present invention relates to a negative electrode for a lithium ion secondary battery, and more particularly to a negative electrode for a lithium ion secondary battery having a high capacity and a long life.

  Conventionally, lithium ion secondary batteries using graphite as a negative electrode active material have been put into practical use. Also, a negative electrode is formed by kneading a negative electrode active material, a conductive aid such as carbon nanofiber, and a resin binder to form a slurry, and applying and drying on a copper foil. ing.

  On the other hand, with the aim of increasing the capacity, negative electrodes for lithium ion secondary batteries using metals, particularly silicon alloys, as negative electrode active materials have been developed. Silicon alloyed by occlusion of lithium ions expands in volume up to about 4 times that of silicon before occlusion, so a negative electrode using a silicon-based alloy as a negative electrode active material expands and contracts during a charge / discharge cycle. repeat.

  Therefore, a negative electrode for a non-aqueous electrolyte secondary battery that grows carbon nanofibers on the surface of a silicon-based active material, relaxes strain due to expansion and contraction of negative electrode active material particles by its elastic action, and improves cycle characteristics. It is disclosed (see, for example, Patent Document 1).

  In addition, in order to eliminate the need for a binder and a conductive additive, a method of manufacturing a lithium battery electrode by directly depositing silicon on a current collector by a CVD method or the like is known (for example, Patent Document 2) See).

JP 2006-244984 A Japanese Patent No. 3733069

  However, a conventional negative electrode that forms a negative electrode by applying and drying a slurry of a negative electrode active material, a conductive additive, and a binder, binds the negative electrode active material and the current collector with a resin binder. The bonding strength of the resin is weak. For this reason, there is a problem in that the capacity is reduced due to peeling during charging / discharging of the negative electrode active material, cracking of the negative electrode, conductivity decrease between the negative electrode active materials, the cycle characteristics are poor, and the life of the secondary battery is short. was there.

  However, the invention described in Patent Document 1 binds the negative electrode active material and the current collector with a resin, and the cycle characteristics cannot be sufficiently prevented from being deteriorated. In addition, the productivity was poor due to the formation process of carbon nanofibers.

  Further, when the silicon film is directly formed on the current collector, the thickness of the silicon film must be within 2 μm in order to obtain a sufficient cycle life. In a silicon film with a thickness of 8 μm that achieves the target capacity per unit area, the silicon film becomes a current collector because wrinkles or cracks occur in the silicon film during repeated charging and discharging. There was a problem that the capacity was reduced and the cycle characteristics were poor.

  The present invention has been made in view of the above-described problems, and an object of the present invention is to obtain a negative electrode for a lithium ion secondary battery that realizes a high capacity and a long life.

  In order to achieve the above-described object, the first invention includes a metal current collector and a silicon linear body grown on the current collector, and at least one end of the silicon linear body is at least one end. A negative electrode for a lithium ion secondary battery, wherein the negative electrode is bonded to the current collector by a metal bond, or is bonded to a metal on the current collector by a metal bond.

  Furthermore, the negative electrode preferably contains a conductive additive, and the outer diameter of the silicon linear body is preferably 4 nm to 1000 nm.

  Moreover, it is preferable that at least a part of the silicon linear body has a crimped shape, or at least a part of the silicon linear body has a linear shape.

  A second invention includes a metal current collector, a silicon layer or a metal layer formed on the current collector, and a silicon linear body grown on the silicon layer or the metal layer. A negative electrode for a lithium ion secondary battery, wherein at least one end of the silicon linear body is bonded to the silicon layer or the metal layer by a metal bond. Moreover, it is preferable that the said silicon layer is a porous shape or a substantially sarcophagus shape.

  In the first invention and the second invention, it is preferable that the silicon linear body is coated with a conductive additive. As the conductive assistant, for example, carbon having a thickness of about 2 nm, electrolytic copper plating, electroless copper plating and the like are suitable. This configuration has the effect of promoting lithium desolvation during the initial charge and forming a good non-conductive coating (SEI).

  In the first invention and the second invention, it is preferable that the silicon linear body is embedded with a conductive additive. With this configuration, the effective surface area can be reduced to reduce the irreversible capacity during the first charge / discharge, and the coulomb efficiency can be improved. Further, since the irreversible reaction of the electrolytic solution is reduced, the consumption of the electrolytic solution can be suppressed and the capacity can be increased.

  Moreover, it is preferable that the said conductive support agent which coat | covers or embeds the said silicon | silicone linear body is porous. When the conductive assistant forms a dense film, it takes time for the lithium to permeate, the internal resistance increases, and there is a problem that it cannot be used as an electrode. This is because solvated lithium ions are difficult to permeate when the conductive assistant is a dense film.

  3rd invention is a lithium ion secondary battery using the negative electrode for lithium ion secondary batteries which concerns on 1st invention or 2nd invention.

  According to a fourth aspect of the present invention, there is provided a step (a) of supporting a metal catalyst on a current collector, maintaining the current collector in the chamber at a temperature between 350 to 800 ° C., and reducing the pressure in the chamber to 0. (B) supplying a raw material gas into the chamber for 20 minutes to 2 hours while maintaining a certain pressure between 5 and 50 Torr, and growing a silicon linear body on the current collector by a VLS method; It is a manufacturing method of the negative electrode for lithium ion secondary batteries characterized by having.

  Note that “at least one end of the silicon linear body is bonded to the current collector by a metal bond” means that silicon grows on the surface of the current collector by a VLS (Vapor-Liquid-Solid) mechanism. It does not indicate that the silicon linear body is bonded to the current collector with a resin binder or is in contact with physical adsorption. That is, silicon supplied as a source gas such as silane or disilane is adsorbed on the surface of the catalyst in a liquid state, desorbs hydrogen, and atomic silicon dissolves in the catalyst and forms an alloy. By supplying silicon, atomic silicon is regularly rearranged according to the atomic arrangement of the current collector, and precipitation proceeds. By repeating the deposition of silicon repeatedly, the catalyst is lifted from the surface of the current collector, and silicon crystal grows linearly. At this time, silicon changes from a liquid to a solid, but the current collector is bonded to each other by atoms, and free electrons can freely move at the interface between the current collector and the silicon linear body. That is, the current collector and the silicon linear body are bonded by a metal bond. In addition to the case where the linear silicon linear body grows from the current collector surface and one end of the silicon linear body is metal-bonded to the current collector surface, the arch-shaped silicon linear body is the current collector surface. When one end of the silicon linear body is metal-bonded to the current collector surface, and the other end of the silicon linear body is in contact with the current collector surface, or a crimped silicon linear body is It grows from the surface of the body, one end of the silicon linear body is metal-bonded to the current collector surface, and more than one part of the silicon linear body is in contact with the current collector surface. This includes the case where two silicon linear bodies are intertwined. Note that the silicon linear body becomes amorphous after insertion and extraction of lithium.

  In addition, “the silicon linear body has a crimped shape” means that the silicon linear body is curved, wound, twisted, twisted, twisted, or spiral. , Refers to non-periodic shapes and the like. In addition, “at least a part of the silicon linear body is a crimped shape” means that the negative electrode includes a silicon linear body that is a crimped shape, or a part of one silicon linear body is It means that it is a crimped shape, and “at least a part of the silicon linear body is linear” means that the negative electrode includes a linear silicon linear body or a single silicon wire. It means that a part of the shape is linear.

  Further, “at least a part of the silicon layer has a porous shape” means that a part of the silicon layer has a porous shape, and “at least a part of the silicon layer has a substantially sarcophagus shape”. The term “a part of the silicon layer” means a substantially sarcophagus shape.

  According to the present invention, a negative electrode for a lithium ion secondary battery that achieves a high capacity and a long life can be obtained.

The figure which shows the negative electrode 1 for lithium ion secondary batteries which concerns on embodiment of this invention. (A)-(d) The figure which shows the manufacturing method of the negative electrode 1 for lithium ion secondary batteries which concerns on embodiment of this invention. (A), (b) The figure which shows the use condition of the negative electrode 1 for lithium ion secondary batteries which concerns on embodiment of this invention. (A), (b) The figure which shows the other example of the negative electrode for lithium ion secondary batteries which concerns on embodiment of this invention. The figure which shows an example of the manufacturing method of the negative electrode 1 for lithium ion secondary batteries which concerns on embodiment of this invention. (A), (b) The figure which shows the other example of the negative electrode for lithium ion secondary batteries which concerns on embodiment of this invention. (A), (b) SEM photograph of catalyst layer on current collector according to Example 1 (A), (b) The SEM photograph of the negative electrode for lithium ion secondary batteries which concerns on Example 1. FIG. (A)-(d) The TEM photograph of the silicon | silicone linear body which concerns on Example 1. FIG. (A), (b) The STEM photograph of the silicon | silicone linear body which concerns on Example 1. FIG. The STEM-EDS analysis result of the silicon | silicone linear body which concerns on Example 1. FIG. (A), (b) The SEM photograph after 50 cycles charging / discharging of the negative electrode for lithium ion secondary batteries which concerns on Example 1. FIG. (A), (b) The other SEM photograph after 50 cycles charging / discharging of the negative electrode for lithium ion secondary batteries which concerns on Example 1. FIG. (A), (b) The SEM photograph of the negative electrode for lithium ion secondary batteries which concerns on Example 2. FIG. (A), (b) The SEM photograph of the negative electrode for lithium ion secondary batteries which concerns on Example 3. FIG. (A), (b) The SEM photograph of the negative electrode for lithium ion secondary batteries which concerns on Example 4. FIG. 4 is another SEM photograph of a negative electrode for a lithium ion secondary battery according to Example 4. FIG. (A), (b) The other SEM photograph of the negative electrode for lithium ion secondary batteries which concerns on Example 4. FIG. (A), (b) Electron-beam diffraction pattern (b) in the visual field (a) of the silicon | silicone linear body which concerns on Example 5. FIG. (A), (b) The STEM photograph of the silicon | silicone linear body which concerns on Example 5. FIG. The STEM-EDS analysis result of the silicon | silicone linear body which concerns on Example 5. FIG. (A), (b) The SEM photograph of the negative electrode for lithium ion secondary batteries which concerns on the comparative example 1. FIG. (A), (b) The SEM photograph after 50 cycles charging / discharging of the negative electrode for lithium ion secondary batteries which concerns on the comparative example 1. FIG. (A) The SEM photograph of the negative electrode for lithium ion secondary batteries which concerns on the comparative example 2, (b) The SEM photograph after 50 cycles charge / discharge of the negative electrode which concerns on the comparative example 2. (A), (b) The SEM photograph after 50 cycles charging / discharging of the negative electrode for lithium ion secondary batteries which concerns on the comparative example 2. FIG. The another SEM photograph after 50 cycles charging / discharging of the negative electrode for lithium ion secondary batteries which concerns on the comparative example 2. FIG.

Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings. Each drawing schematically shows each component, and does not represent an actual scale.
The negative electrode 1 according to the first embodiment will be described.
FIG. 1 is a diagram showing a negative electrode 1. In the negative electrode 1, a silicon linear body 13 is grown directly on the current collector 3, and a catalyst 7 is provided at the tip of the silicon linear body 13.

  The current collector 3 is a metal foil such as copper, nickel, molybdenum, tungsten, tantalum, and stainless steel. These may be used alone or an alloy thereof. The thickness is preferably 4 μm to 35 μm, and more preferably 8 μm to 18 μm.

  The silicon linear body 13 is one-dimensional wire-like silicon, and if the outer diameter is nano-size, it is also called nanorod, nanowhisker, nanotube (hollow), nanofiber, nanobelt, etc. in addition to nanowire. The silicon linear body 13 is crystal-grown from the current collector 3 by the VLS mechanism, and is directly metal-bonded to the current collector 3. The outer diameter of the silicon linear body 13 is 4 nm to 1000 nm, and more preferably 25 nm to 200 nm. When the outer diameter of the silicon linear body 13 is thicker than 4 nm, synthesis is easy, and when the outer diameter is thinner than 1000 nm, the negative electrode active material can be prevented from being pulverized. The measuring method of the outer diameter and length of the negative electrode active material was performed by image analysis using SEM.

  The silicon linear body 13 may be single crystal, polycrystalline, or amorphous. When a crystalline silicon linear body occludes or desorbs lithium, the regular atomic arrangement is disturbed and becomes amorphous. Moreover, even if a part or all of the silicon linear body 13 grows linearly, it may grow while shrinking while curving.

  The catalyst 7 is formed by sputtering or vapor-depositing a catalyst layer 5 described later, and is a catalyst for growing the silicon linear body 13 by the VLS method. The catalyst 7 is a particle having a diameter of 4 nm to 1000 nm made of copper, nickel, titanium, iron, gold, silver, palladium, magnesium, osmium, or an alloy thereof such as copper sulfide, silver sulfide, or gold sulfide. Although the catalyst 7 is located at the tip of the silicon linear body 13 grown by the VLS method, it may be observed attached to the middle. Further, a part of the catalyst 7 may remain on the surface of the current collector 3, and the silicon linear body 13 may grow from the catalyst 7. In this case, the current collector 3 and the catalyst 7 form a metal bond, and the catalyst 7 and the silicon linear body 13 form a metal bond.

Next, the manufacturing method of the negative electrode 1 is demonstrated.
First, as shown in FIG. 2A, the catalyst layer 5 is formed on the current collector 3. The catalyst layer 5 is obtained by spraying fine particles of copper, nickel, titanium, iron, gold, silver, palladium, magnesium, osmium, and alloys thereof, for example, copper sulfide, silver sulfide, gold sulfide, and the like. Or by vapor deposition or CVD.

  Next, as shown in FIG. 2B, the current collector 3 is placed in a chamber 10 and heated to a predetermined temperature with a heater 11 using Ar gas as a carrier under reduced pressure by a vacuum pump.

  Next, as shown in FIG. 2 (c), after the temperature inside the chamber 10 is set to a predetermined temperature by the heater 11, the source gas 9 is introduced while the pressure is reduced by the vacuum pump, and the silicon linear body 13 is changed to VLS (Vapor− The growth is performed by a liquid-solid method.

  The chamber 10 is surrounded by a heater 11 and a source gas 9 is supplied to the chamber 10. The reaction temperature in the chamber 10 is preferably 350 ° C to 800 ° C, more preferably 400 ° C to 500 ° C. In addition to the method of heating the entire chamber formed from a quartz glass tube or the like with a heater, the reaction temperature may be set by contact by heating the substrate on which the current collector is installed or the drum itself. The pressure is preferably 0.5 to 50 Torr, the reaction time is about 20 minutes to 2 hours, and preferably about 1 hour.

  As the source gas 9, silane, disilane, dichlorosilane, trichlorosilane, or the like can be used. The source gas 9 is preferably diluted with a gas such as hydrogen gas or argon gas. The chamber 10 is adjusted so that the source gas 9 is maintained at a set pressure.

  In order to increase the reaction rate and improve the productivity, plasma may be generated in the chamber 10 and the source gas 9 may be radicalized by the plasma and then reacted with the catalyst 7. For example, silane is used as a source gas, silane plasma is generated in the chamber 10 by a VHF high frequency oscillator, and a silicon linear body is grown by the VLS method using silane plasma as a source.

  Next, as shown in FIG. 2D, after the reaction, the silicon linear body 13 grows.

Next, a method for using the negative electrode 1 will be described.
FIG. 3 is a diagram for explaining a use state of the negative electrode 1. 3A shows the negative electrode 1 before occlusion of lithium ions, and FIG. 3B shows the negative electrode 1 in which the volume of the silicon linear body 13 is expanded by occlusion of lithium ions.

  As shown in FIG. 1, the negative electrode 1 does not need to add the conductive auxiliary 15, but as shown in FIG. 3A, the conductive auxiliary 15 is added between the silicon linear bodies 13. Also good. Further, as shown in FIG. 4 (a), the entire surface of the silicon linear body 13 is covered with the conductive auxiliary agent 15, or the silicon linear body 13 is embedded with the conductive auxiliary agent 15 as shown in FIG. 4 (b). You may do it. Use of the conductive additive 15 has an effect of reducing the internal resistance of the negative electrode 1 and is effective in charge / discharge characteristics at a high rate. In addition, when the conductive additive 15 is used, there are effects such as an increase in capacity, an improvement in the utilization rate of the negative electrode active material, and a reduction in decomposition of the electrolyte.

  The conductive assistant 15 is also called a conductive agent, and is a substance that is added to the electrode to enhance conductivity. The conductive assistant 15 is at least one conductive material selected from the group consisting of carbon, copper, tin, zinc, nickel, and silver. The conductive additive 15 may be a single powder of carbon, copper, tin, zinc, nickel, or silver, or may be a powder of these alloys. For example, general carbon black such as furnace black and acetylene black can be used. Moreover, the conductive support agent 15 may be nanowires of these conductive substances, and carbon fibers, carbon nanotubes, copper nanowires, nickel nanowires, and the like can be used.

  For example, when the conductive assistant 15 is added to the silicon linear body 13, the conductive assistant 15 may be dispersed in a solvent such as water, applied as a slurry, and dried. If necessary, a binder or thickener may be added to adjust the viscosity of the slurry, or the dried electrode may be pressed with a two-stage roll or the like as a strong film to adjust the film thickness. .

  Further, as shown in FIG. 4A, the silicon linear body 13 may be covered with a conductive material such as a conductive additive 15. Examples of the conductive material include carbon, copper, tin, zinc, nickel, silver, and alloys thereof.

  For example, when the silicon linear body 13 is coated with a carbon-based conductive material, a method of impregnating the silicon linear body 13 of the current collector 3 with a polymer material and baking it can be considered. For example, after applying a 3 to 15 wt% polyvinyl alcohol aqueous solution, baking may be performed at 700 ° C. for about 3 hours in an inert atmosphere. In addition to the alcohol-based resin, as the polymer material, a polymer material that is fired into a carbon-based material by heat treatment, such as a vinyl-based resin, a phenol-based resin, a cellulose-based resin, a pitch-based resin, and a tar-based resin is used. be able to. In particular, when a saccharide such as sucrose or syrup is used as a carbon source, a silicon linear body can be embedded as shown in FIG. As a method for embedding the silicon linear body with a conductive material, for example, there is a method in which a 5 to 10 wt% sucrose aqueous solution is applied and then baked at 700 ° C. for about 3 hours in an inert atmosphere.

  Moreover, it is preferable that the conductive additive 15 for covering or embedding the silicon linear body 13 forms a porous structure film having voids. This is because if the conductive assistant film is dense, it takes time for the solvated lithium ions to permeate and the internal resistance increases, which is disadvantageous as an electrode.

  Further, when the silicon linear body 13 is covered with a metal-based conductive material, a method of performing the current collector 3 by using sputtering or vapor deposition in a vacuum chamber is conceivable. For example, in the case of covering with copper, a copper target is installed, a DC high voltage is applied between the substrates on which the current collector 3 is placed, and Ar gas is introduced to form a silicon linear body 13. The body 3 can be coated with copper.

  As shown in FIG. 3B, when lithium ions are occluded in the negative electrode 1, silicon as the negative electrode active material expands, and the silicon linear body 13 becomes thick and long. When the silicon linear body 13 occludes lithium during charging and is alloyed, the silicon linear body 13 becomes thick and long due to volume expansion, but remains bonded to the current collector 3 by a metal bond. Then, the mechanical and electrical connection with the current collector 3 is maintained only by returning to the original size. Thus, since the silicon | silicone linear body 13 is a linear shape, the distortion accompanying the volume change of a negative electrode active material is absorbed. Therefore, since the pulverization of the negative electrode active material during charge / discharge and the peeling between the negative electrode active material and the current collector are suppressed, the capacity is high and the cycle life is long.

  Moreover, the negative electrode 1 can be mass-produced by Role to Role with an apparatus as shown in FIG. The current collector 3 is supplied by a roll-shaped current collector 3 wound around a drum 17. After the current collector 3 is unwound from the drum 17, the catalyst support device 19 forms the catalyst layer 5. Thereafter, the current collector 3 enters the chamber 10 and is held at a predetermined temperature on a drum having a built-in heater 11, so that the silicon linear body 13 grows. After the current collector 3 exits the chamber 10, it is wound around the drum 23.

  The chamber 10 is placed in a reduced pressure environment by a vacuum exhaust device, and the source gas 9 is supplied. The pressure in the chamber 10 is monitored by a pressure gauge 21, and the supply of the source gas 9 and the valve on the evacuation side are adjusted so as to keep the pressure in the chamber 10 constant. Further, the current collector 3 on the drum is maintained at a predetermined reaction temperature by the heater 11 installed in the drum. Needless to say, the negative electrode 1 can be cut into a predetermined size to form the silicon linear body 13 in a single sheet.

  Next, a method for producing a lithium ion secondary battery using the negative electrode 1 of the present invention will be described.

  First, a positive electrode active material, a conductive additive, a binder, a thickener, and a solvent are mixed to prepare a positive electrode active material composition. The composition of the positive electrode active material is directly applied on a metal current collector such as an aluminum foil and dried to prepare a positive electrode. It is also possible to manufacture a positive electrode by casting the composition of the positive electrode active material on a separate support, and then laminating the film obtained by peeling from the support on a metal current collector.

As the positive electrode active material, any lithium-containing metal oxide that is generally used can be used. For example, LiCoO 2 , LiMn x O 2x , LiNi 1-x Mn x O 2x (X = 1, 2), Ni 1-xy Co x Mn y O 2 (0 ≦ x ≦ 0.5, 0 ≦ y ≦ 0.5), etc., more specifically, LiMn 2 O 4, it is a LiMnO 2, LiNiO 2, LiFeO 2 , LiFePO 4, Li 2 FePO 4 F, V 2 O 5, TiS and MoS 2 and compounds capable redox lithium.

  Carbon black is used as a conductive additive, and vinylidene fluoride / hexafluoropropylene copolymer, polyvinylidene fluoride (PVdF), polyacrylonitrile, polymethyl methacrylate, polytetrafluoroethylene (PTFE) and the like are used as a binder. A mixture and a styrene butadiene rubber-based polymer are used, and N-methylpyrrolidone (NMP), acetone, water and the like are used as a solvent. At this time, the contents of the positive electrode active material, the conductive additive, the binder, the thickener, and the solvent are at levels normally used in lithium ion secondary batteries.

  Any separator can be used as long as it has a function of insulating electronic conduction between the positive electrode and the negative electrode and is usually used in a lithium ion secondary battery. In particular, it is preferable that the thickness is as low as about 20 microns from the viewpoint of the high capacity of the battery because of its low resistance to ion migration of the electrolyte. A typical separator is a three-layer laminate film of polypropylene (PP) / polyethylene (PE) / polypropylene (PP) microporous film, and PP and PE are thermoplastic resins of about 170 ° C. and about 130 ° C., respectively. The degree of polymerization and the like are designed so that the melting point becomes. When the temperature inside the battery exceeds 130 ° C., the PE film melts, the micropores are clogged and lithium ions cannot permeate, and the battery reaction can be stopped.

Examples of the electrolyte include propylene carbonate, ethylene carbonate, diethyl carbonate, ethyl methyl carbonate, methyl propyl carbonate, butylene carbonate, benzonitrile, acetonitrile, tetrahydrofuran, 2-methyltetrahydrofuran, γ-butyrolactone, dioxolane, 4-methyloxolane, N , N-dimethylformamide, dimethylacetamide, dimethyl sulfoxide, dioxane, 1,2-dimethoxyethane, sulfolane, dichloroethane, chlorobenzene, nitrobenzene, dimethyl carbonate, methyl ethyl carbonate, diethyl carbonate, methyl propyl carbonate, methyl isopropyl carbonate, ethyl propyl carbonate , dipropyl carbonate, LiPF 6 dibutyl carbonate, in a solvent or a mixed solvent thereof and the like diethylene glycol or dimethyl ether, LiBF 4, L SbF 6, LiAsF 6, LiClO 4 , LiCF 3 SO 3, Li (CF 3 SO 2) 2 N, LiC 4 F 9 SO 3, LiAlO 4, LiAlCl 4, LiN (C x F 2x + 1 SO 2) (C y F 2y + 1 SO 2 ) (where x and y are natural numbers), one of electrolytes composed of lithium salts such as LiCl and LiI, or a mixture of two or more thereof can be dissolved and used.

  A separator is disposed between the positive electrode and the negative electrode as described above to form a battery structure. When such a battery structure is wound or folded and placed in a cylindrical battery case or a rectangular battery case, an electrolyte is injected to complete a lithium ion secondary battery.

  Further, after the battery structure is laminated in a bicell structure, it is impregnated with an organic electrolyte, and the resultant product is put in a pouch and sealed to complete a lithium ion polymer battery.

  FIG. 6 shows a modification of the negative electrode 1 according to the first embodiment. As shown in FIG. 6A, the negative electrode 25 has a silicon layer 27 on the current collector 3, and the silicon linear body 13 is grown from the silicon layer 27. The silicon layer 27 is formed by depositing silicon on the surface of the current collector 3 according to conditions such as temperature and pressure when the silicon linear body 13 is grown by the VLS method.

  Note that the silicon layer 27 may contain not only silicon but also the metal of the catalyst layer 5 and the metal layer 31 described later. The silicon layer 27 may have a sarcophagus shape or a porous shape having pores. The sarcophagus is a protruding shape protruding from the surface.

Further, as shown in FIG. 6B, the negative electrode 29 has a metal layer 31 on the current collector 3, and the silicon linear body 13 is grown from the metal layer 31. The metal layer 31 is formed so that the current collector 3 and the silicon linear body 13 are not peeled off, and is formed on the current collector 3 prior to the formation of the catalyst layer 5. The metal layer 31 is formed by sputtering, vapor deposition, or CVD. The metal layer 31 is at least one metal selected from the group consisting of titanium, vanadium, zirconium, yttrium, tungsten, iron, nickel, chromium, and molybdenum, or an alloy thereof. The metal used for the metal layer 31 is preferably a metal that can easily form a silicide of Si 2 M or MSi 2 in which silicon (Si) and metal (M) are 2: 1. Specific examples of the silicide formed by the metal layer 31 include TiSi 2 , VSi 2 , Si 2 Zr, Si 2 Y, WSi 2 , FeSi 2 , NiSi 2 , CrSi 2 , and MoSi 2 . The metal layer 31 increases the adhesion between the current collector 3 and the silicon linear body 13. Furthermore, these silicides have electronic conductivity on the order of 10,000 to 100,000 times that of silicon, and promote the electron conduction between the metal of the current collector 3 and silicon, and charge and discharge of silicon in the vicinity of the interface. There is an effect to relieve the accompanying volume change. In particular, when the glossy surface of the electrolytic copper foil is used as the current collector 3, the adhesion with the silicon linear body 13 is improved, which is preferable.

  Note that a silicon layer 27 may be further provided on the metal layer 31, and the silicon linear body 13 may be grown on the silicon layer 27.

  For the negative electrode 25 as shown in FIG. 6 (a) and the negative electrode 29 as shown in FIG. 6 (b), as shown in FIG. 3 (a), a conductive additive is added between the silicon linear bodies. Alternatively, as shown in FIG. 4 (a), the silicon linear body may be coated with a conductive auxiliary agent, or as shown in FIG. 4 (b), the silicon linear body may be covered with a conductive auxiliary agent. It may be buried with.

  According to this embodiment, since silicon is used as the negative electrode active material, the capacity can be increased as compared with the conventional negative electrode using graphite as the negative electrode active material.

  Further, according to the present embodiment, since the negative electrode active material is a one-dimensional silicon linear body, even if the volume change of the negative electrode active material is large, the strain accompanying the volume change depends on the thickness and length of the silicon linear body. Since the silicon linear body and the current collector are absorbed and held in a metal bond, peeling between the negative electrode active material and the current collector is suppressed. Therefore, the capacity of the negative electrode is large and the life is long.

  In addition, according to the present embodiment, since one end of the silicon linear body and the current collector are metal-bonded, the electrical connection between the silicon linear body and the current collector is good, and the electrode film The electrical resistance is small. Further, the silicon linear body and the current collector are firmly bonded, and the silicon linear body is less likely to fall off from the negative electrode.

  Moreover, according to this embodiment, since a negative electrode can be manufactured not by batch processing but by continuous processing, it is excellent in productivity and mass production is possible.

  Further, according to the present embodiment, the current collector and the silicon linear body are directly bonded by a metal bond, the conductive auxiliary agent 15 is added or covered, and the silicon linear body is embedded with the conductive auxiliary agent. Therefore, the negative electrode can keep internal resistance low, and the lithium ion secondary battery using the negative electrode can reduce irreversible capacity. In particular, when a silicon linear body is embedded with a conductive additive, the effective surface area of the negative electrode can be reduced, and the effect of reducing irreversible capacity is great. The irreversible capacity is a capacity difference between the charge capacity and the discharge capacity at the first charge / discharge. One of the causes of irreversible capacity occurs when silicon, which is the active material, is in direct contact with the electrolyte, causing electrochemical reductive decomposition of the electrolyte and forming a non-conductive film (SEI) on the silicon surface. It can be alleviated by adding a conductive additive to the silicon linear body and covering or burying it with the conductive additive. Thus, reducing the irreversible capacity suppresses the consumption of the electrolytic solution, and the capacity of the entire lithium ion battery can be increased. Further, by covering or embedding the silicon linear body 13 with the conductive auxiliary agent 15, the internal resistance of the negative electrode can be further reduced, and the capacity at a high rate (high rate characteristic) is excellent.

  Further, according to the present embodiment, the current collector and the silicon linear body are metal-bonded, and the amount of the binder can be reduced, so that the ratio of the negative electrode active material in the negative electrode is increased, and the high capacity Is possible.

  As mentioned above, although preferred embodiment of the negative electrode for lithium ion secondary batteries concerning this invention was described referring an accompanying drawing, this invention is not limited to the example which concerns. It will be apparent to those skilled in the art that various changes and modifications can be made within the scope of the technical idea disclosed in the present application, and these are naturally within the technical scope of the present invention. Understood.

Hereinafter, the present invention will be specifically described using examples and comparative examples.
[Example 1]
After degreasing and cleaning the mat surface (electrodeposited side) of electrolytic copper foil (Furukawa Electric Co., Ltd., NC-WS, 10 μm thick), gold sputtering is performed for 20 seconds to form a gold thin film with a thickness of about 2 nm. did. Thereafter, the copper foil was placed in the chamber, the pressure inside the chamber was reduced, and after confirming that the chamber temperature was 450 ° C. and the pressure in the chamber reached 5 Torr in an Ar atmosphere, the supply of the source gas was started. Disilane (10% hydrogen dilution) was supplied as a source gas so that the inside of the chamber was 5 Torr. One hour after starting the supply of the raw material gas, the supply of the raw material gas was stopped. Thereafter, the chamber was returned to normal temperature and pressure. A silicon linear body grew on the mat surface of the electrolytic copper foil by the VLS mechanism.

  The characteristic test of the electrode was performed by the following method. A lithium ion secondary battery was constructed using metal Li foil as a reference electrode. The discharge capacity was set to 1200 mAh / g based on the effective active material Si. First, in a 25 ° C. environment, charging was performed under constant current and constant voltage conditions until the current value was 0.1 C and the voltage value was 0.02 V, and the charging was stopped when the current value decreased to 0.05 C. Next, discharge was performed under the condition of a current value of 0.1 C until the voltage with respect to the metal Li became 1.5V. 1C is a current value that can be fully charged in one hour. Both charging and discharging were performed in a 25 ° C. environment. Next, the above charge / discharge cycle was repeated 50 cycles at a charge / discharge rate of 0.2C.

[Example 2]
A negative electrode was produced in the same manner as in Example 1 except that the reaction temperature was 400 ° C.

[Example 3]
A negative electrode was produced in the same manner as in Example 1 except that the shiny surface of the electrolytic copper foil (the glossy surface peeled off from the drum) was used.

[Example 4]
A negative electrode was produced in the same manner as in Example 1 except that the shiny surface of the electrolytic copper foil was used and the reaction temperature was 400 ° C.

[Example 5]
Using the matte surface of the electrolytic copper foil described in Example 1, gold was sputtered for 20 seconds to form a gold thin film having a thickness of about 2 nm. Thereafter, the copper foil was placed in the chamber, the pressure inside the chamber was reduced, and after confirming that the chamber temperature reached 600 ° C. and the chamber pressure reached 1 Torr in an Ar atmosphere, the raw material gas described in Example 1 was used. Supply started. The inside of the chamber was set to 1 Torr. One hour after starting the supply of the raw material gas, the supply of the raw material gas was stopped. Thereafter, the chamber was returned to normal temperature and pressure. A silicon linear body grew on the mat surface of the electrolytic copper foil by the VLS mechanism.

  The conditions of Examples 1-5 are summarized in Table 1.

[Comparative Example 1]
(Preparation of negative electrode)
As conductive aid 1, carbon 1 composed of carbon nanohorns having an average particle size of 80 nm (manufactured by NEC Corporation, single-layer CNH), and acetylene black having an average particle size of 35 nm (made by Denki Kagaku Kogyo Co., Ltd., as conductive aid 2) Carbon 2 made of a powdery product), a negative electrode active material made of silicon powder having an average particle size of 5 μm (manufactured by High Purity Chemical Laboratory Co., Ltd., SIE23PB), and an emulsion of styrene butadiene rubber (SBR) 40 wt% (Nippon Zeon Corporation) An aqueous slurry with a resin binder made of BM400B) was prepared at a blending ratio (wt%) in terms of solid content in Table 2. In order to adjust the viscosity of the aqueous slurry, a 1 wt% solution of sodium carboxymethyl cellulose (CMC, manufactured by Daicel Chemical Industries, Ltd., # 2200) was used as a thickener.

  Using the prepared slurry, a doctor blade of an automatic coating apparatus (PI-1210 type, manufactured by Tester Sangyo Co., Ltd.), an electrolytic copper foil for lithium ion secondary batteries having a thickness of 10 μm (NC-WS, manufactured by Furukawa Electric Co., Ltd.) On the current collector, the film was applied with a thickness of 30 μm after drying, dried at 70 ° C., and adjusted to a thickness of 15 μm with a roll press to produce a negative electrode for a lithium ion secondary battery.

[Comparative Example 2]
In Comparative Example 2, spherical silicon powder having an average particle diameter of 60 nm (manufactured by Hefei Kai'er) was used in place of the silicon powder having an average particle diameter of 5 μm used in Comparative Example 1, and the aqueous slurry was used as a solid content in Table 2. Various preparations were made at a conversion ratio (wt%) in terms of conversion. The other raw materials of the aqueous slurry, the application / drying method of the aqueous slurry, and the property evaluation method were performed in the same manner as in the examples. In Comparative Example 2, the representative composition described in Table 2 and the composition in which the amounts of the conductive auxiliary agent 1, the conductive auxiliary agent 2, and the negative electrode active material were changed within the predetermined range shown in Table 2 were used. A negative electrode was produced.

  FIG. 7 is a scanning electron microscope (SEM) photograph (a) and an enlarged view (b) of the electrolytic copper foil mat surface after application of the gold catalyst in Example 1. It can be seen from the enlarged view that gold catalysts having a particle size of about 20 nm are distributed over the entire surface.

  FIG. 8 is an SEM photograph of the negative electrode according to Example 1. In FIG. 8A, what is formed in a protruding shape is a silicon nanowire (silicon linear body). As shown in an enlarged view in FIG. 8 (b), silicon linear bodies having a reduced outer diameter of about 100 nm are densely grown.

  FIG. 9 is a transmission electron microscope (TEM) photograph of the silicon linear body according to Example 1. The outer diameter of the crimped silicon linear body is about 60 to 70 nm, and the grain boundary and the striped pattern can be observed. Therefore, it is understood that the crimped silicon linear body is polycrystalline.

  FIG. 10 is a result of observation by a scanning transmission electron microscope (STEM) of the silicon linear body according to the first embodiment. In the bright field STEM image, black spots are observed in some places in the silicon linear body.

  FIG. 11 shows the results of STEM-EDS analysis of the silicon linear body according to Example 1. It can be seen that the black spots observed in the silicon linear bodies are copper. In this copper, copper fine particles deposited on the mat surface of the electrolytic copper foil are attached to the surface of the silicon linear body.

12 and 13 are SEM photographs of the negative electrode after charging and discharging the negative electrode according to Example 1 at 0.2 C for 50 cycles. A surface film (SEI) formed by electrochemical reductive decomposition of an electrolyte solution of solvated lithium ions is observed on the surface of the silicon linear body.
As shown in FIG. 4A, when a silicon linear body is coated with a conductive additive, particularly with a carbon having a thickness of about 2 nm, good SEI is formed in a small amount. Further, as shown in FIG. 4B, by embedding with a conductive aid such as carbon, it is possible to form a good SEI with a smaller amount. The conductive assistant at this time is porous, and it is essential that the electrolytic solution penetrates.

  Moreover, as shown in FIG. 13, even after charging and discharging 50 cycles of the negative electrode on which the silicon linear body was crystal-grown according to Example 1, the active material silicon was pulverized and dropped, and cracks were generated in the electrode. Was not observed. On the other hand, when combined with the results of Comparative Example 1 and Comparative Example 2 shown in FIGS. 22 to 26, the shape of silicon, which is the active material, is more excellent in cycle characteristics in the one-dimensional linear body than in the three-dimensional particle form. I understand that.

  FIG. 14 is an SEM photograph of the negative electrode according to Example 2. In FIG. 14A, a crimped silicon linear body is observed. As shown in an enlarged view in FIG. 14B, the outer diameter of the silicon linear body is about 40 nm to 90 nm.

  FIG. 15 is a SEM photograph of the negative electrode according to Example 3. In FIG. 15A, a thick and crimped silicon linear body and a thin and linear silicon linear body are observed. As shown in an enlarged view in FIG. 15B, the outer diameter of the crimped silicon linear body is about 10 to 200 nm, and the outer diameter of the linear silicon linear body is about 30 nm.

  16 to 18 are SEM photographs of the negative electrode according to Example 4. FIG. In FIG. 16 (a), the growth of stalagmite-like silicon having a flat tip and a thickness of 5 to 20 μm is observed. In FIG. 16B, the growth of the crimped silicon linear body is observed from the side surface of the stalagmite-like silicon. FIG. 17 is an enlarged view of the crimped silicon linear body, and it can be seen that the outer diameter of the crimped silicon linear body is about 70 nm. In FIG. 18, it was confirmed that the surface of the sarcophagus-like silicon had pores, and the sarcophagus-like silicon was porous.

  FIG. 19 is an electron diffraction pattern (b) in the visual field (a) of the silicon linear body according to the fifth embodiment. In FIG. 19, it can be seen that the silicon linear body is polycrystalline, as shown by the electron diffraction pattern in the field of view.

  FIG. 20 is a STEM photograph of a silicon linear body according to Example 5. In FIG. 20A, it can be seen that the outer diameter of the silicon linear body is thick and close to 1 μm.

  FIG. 21 is a diagram illustrating an STEM image of a silicon linear body according to Example 5 and an energy dispersive X-ray spectroscopic analysis (EDS) result. In FIG. 21, it can be seen that copper exists in addition to gold (not shown) as a catalyst at the tip of the silicon linear body. This copper is considered to be fine-particle copper deposited during the production of the electrolytic copper foil.

  In Examples 1-5, the crystal growth of the silicon linear body was confirmed. Further, as a result of the electrode test, it was confirmed that these silicon linear bodies had a high capacity and a long life.

  FIG. 22 is an SEM photograph of the negative electrode according to Comparative Example 1. 22A and 22B, the surface of the smooth silicon powder exposed on the surface of the electrode is observed as indicated by the arrows.

  FIG. 23 is a SEM photograph of the negative electrode after charging and discharging the negative electrode according to Comparative Example 1 at 0.2 C for 50 cycles. In FIG. 23A, it was observed that the silicon powder exposed on the surface of the electrode was pulverized at the position indicated by the arrow. Further, in FIG. 23B, the negative electrode active material film was observed to drop off at a part of the electrode along with the occurrence of cracks at the position indicated by the arrow. Such pulverization or dropping off of the negative electrode active material means that a part of the negative electrode active material is disconnected from the electrical connection, which is a main cause of capacity reduction.

  24A is an SEM photograph of the negative electrode active material of the negative electrode according to Comparative Example 2, and FIG. 24B is a negative electrode active material after charging and discharging the same negative electrode at 0.2C for 50 cycles. It is a SEM photograph of. As shown in FIG. 23 (a), in Comparative Example 1, the pulverization of silicon powder having a particle size of 5 μm, which is an active material, was observed. However, in Comparative Example 2, as shown in FIG. No micronization of silicon with a particle size of 60 nm was observed. Micron-sized active material causes pulverization and nano-sized active material does not pulverize because of the Hall Petch rule, the yield point is increased in inverse proportion to the 1/2 power of the crystal grain size. Conceivable.

  FIG. 25 is an SEM photograph of the negative electrode after charging and discharging the negative electrode according to Comparative Example 2 at 0.2 C for 50 cycles. In FIG. 25 (a), partial lifting was observed along with the occurrence of cracks at the locations indicated by arrows. In addition, in FIG. 25 (b), partial swells were observed at the locations indicated by arrows.

  FIG. 26 is another SEM photograph of the negative electrode after charging and discharging the negative electrode according to Comparative Example 2 at 0.2 C for 50 cycles. In FIG. 26, countless large cracks and small cracks that look like faults were observed at locations indicated by arrows. These cracks and falling off of the negative electrode active material tend to further expand when charging and discharging are repeated, and the electrical connection of the active material is broken, thereby reducing the capacity and shortening the life.

DESCRIPTION OF SYMBOLS 1 ......... Negative electrode 3 ......... Current collector 5 ......... Catalyst layer 7 ......... Catalyst 9 ......... Source gas 10 ......... Chamber 11 ......... Heater 13 ......... Silicon linear body 15 ... ... Conductive aid 17 ......... Drum 19 ......... Catalyst carrier 21 ......... Pressure gauge 23 ......... Drum 25 ......... Negative electrode 27 ......... Silicone layer 29 ......... Negative electrode 31 ......... Metal layer

Claims (16)

  1. A metal current collector,
    A silicon linear body grown on the current collector,
    At least one end of the silicon linear body is bonded to the current collector by a metal bond, or is bonded to a metal on the current collector by a metal bond. Negative electrode.
  2.   The negative electrode for a lithium ion secondary battery according to claim 1, further comprising a conductive additive in the negative electrode.
  3.   2. The negative electrode for a lithium ion secondary battery according to claim 1, wherein an outer diameter of the silicon linear body is 4 nm to 1000 nm.
  4.   The negative electrode for a lithium ion secondary battery according to claim 1, wherein at least a part of the silicon linear body has a crimped shape.
  5.   The negative electrode for a lithium ion secondary battery according to claim 1, wherein at least a part of the silicon linear body is linear.
  6.   2. The lithium ion secondary battery according to claim 1, wherein the current collector is a foil made of at least one metal selected from the group consisting of copper, nickel, molybdenum, tungsten, tantalum, and stainless steel. Negative electrode.
  7. A metal current collector,
    A silicon layer formed on the current collector;
    A silicon linear body grown on the silicon layer,
    A negative electrode for a lithium ion secondary battery, wherein at least one end of the silicon linear body is bonded to the silicon layer by a metal bond.
  8.   The negative electrode for a lithium ion secondary battery according to claim 7, wherein at least a part of the silicon layer is porous.
  9.   The negative electrode for a lithium ion secondary battery according to claim 7, wherein at least a part of the silicon layer has a substantially sarcophagus shape.
  10. A metal current collector,
    A metal layer formed on the current collector;
    A silicon linear body grown on the metal layer,
    The metal layer is at least one metal selected from the group consisting of titanium, vanadium, zirconium, yttrium, tungsten, iron, nickel, chromium and molybdenum, or an alloy thereof;
    A negative electrode for a lithium ion secondary battery, wherein at least one end of the silicon linear body is bonded to the metal layer by a metal bond.
  11.   The negative electrode for a lithium ion secondary battery according to any one of claims 1, 7, and 10, wherein the silicon linear body is coated with a conductive additive.
  12.   The negative electrode for a lithium ion secondary battery according to any one of claims 1, 7, and 10, wherein the silicon linear body is embedded with a conductive additive.
  13.   The negative electrode for a lithium ion secondary battery according to claim 11 or 12, wherein the conductive auxiliary agent that covers or embeds the silicon linear body is porous.
  14.   The lithium ion secondary battery using the negative electrode for lithium ion secondary batteries of any one of Claim 1, Claim 7, and Claim 10.
  15. A step (a) of supporting a metal catalyst on a current collector;
    The current collector in the chamber is kept at a certain temperature between 350-800 ° C., and the pressure in the chamber is kept at a certain pressure between 0.5-50 Torr, and 20 minutes-2 hours in the chamber. Supplying a source gas and growing a silicon linear body by the VLS method (b);
    The manufacturing method of the negative electrode for lithium ion secondary batteries characterized by having.
  16.   The method for producing a negative electrode for a lithium ion secondary battery according to claim 15, wherein in the step (b), the silicon linear body is grown by a VLS method in which the source gas is radicalized by plasma and supplied.
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Cited By (35)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011136028A1 (en) * 2010-04-28 2011-11-03 Semiconductor Energy Laboratory Co., Ltd. Power storage device and method for manufacturing the same
JP2012009431A (en) * 2010-05-28 2012-01-12 Semiconductor Energy Lab Co Ltd Power storage device, electrode, and electric device
JP2012009425A (en) * 2010-05-28 2012-01-12 Semiconductor Energy Lab Co Ltd Electric storage device and manufacturing method for the same
JP2012009432A (en) * 2010-05-28 2012-01-12 Semiconductor Energy Lab Co Ltd Electric storage device and manufacturing method for the same
JP2012015100A (en) * 2010-06-02 2012-01-19 Semiconductor Energy Lab Co Ltd Power storage device and its manufacturing method
JP2012033472A (en) * 2010-06-30 2012-02-16 Semiconductor Energy Lab Co Ltd Method of producing power storage device
JP2012031513A (en) * 2010-06-30 2012-02-16 Semiconductor Energy Lab Co Ltd Method for forming semi-conductor region, and method for manufacturing storage battery
WO2012070605A1 (en) 2010-11-25 2012-05-31 旭化成ケミカルズ株式会社 Shaped silica body, process for producing same, and method for manufacturing propylene using shaped silica body
JP2012129200A (en) * 2010-11-26 2012-07-05 Semiconductor Energy Lab Co Ltd Semiconductor film, method for preparing semiconductor film, and electricity storage device
JP2012138347A (en) * 2010-12-07 2012-07-19 Semiconductor Energy Lab Co Ltd Power storage device
KR20130007443A (en) * 2011-06-24 2013-01-18 가부시키가이샤 한도오따이 에네루기 켄큐쇼 Power storage device, electrode thereof, and method for manufacturing power storage device
JP2013035744A (en) * 2011-07-08 2013-02-21 Semiconductor Energy Lab Co Ltd Fabrication method of silicon film, and fabrication method of power storage device
WO2013027561A1 (en) * 2011-08-19 2013-02-28 Semiconductor Energy Laboratory Co., Ltd. Method for manufacturing graphene-coated object, negative electrode of secondary battery including graphene-coated object, and secondary battery including the negative electrode
JP2013062237A (en) * 2011-08-19 2013-04-04 Semiconductor Energy Lab Co Ltd Electrode for power storage device and power storage device
JP2013065548A (en) * 2011-08-30 2013-04-11 Semiconductor Energy Lab Co Ltd Power storage device
JP2013065550A (en) * 2011-09-02 2013-04-11 Semiconductor Energy Lab Co Ltd Electrode for power storage device, and power storage device
JP2013084588A (en) * 2011-09-30 2013-05-09 Semiconductor Energy Lab Co Ltd Power storage device
JP2013522859A (en) * 2010-03-22 2013-06-13 アンプリウス、インコーポレイテッド Interconnection of nanostructures of electrochemically active materials
JP2013545228A (en) * 2010-10-22 2013-12-19 アンプリウス、インコーポレイテッド Composite structure containing high volume porous active material confined in shell
US8835048B2 (en) 2010-06-11 2014-09-16 Semiconductor Energy Laboratory Co., Ltd. Power storage device
WO2015045341A1 (en) * 2013-09-27 2015-04-02 三洋電機株式会社 Negative electrode for nonaqueous electrolyte secondary batteries
KR101507537B1 (en) * 2013-12-20 2015-04-24 국립대학법인 울산과학기술대학교 산학협력단 Electrode complex, manufacturing method of the same, and lithium secondary battery containing the same
JP2015133326A (en) * 2010-02-26 2015-07-23 株式会社半導体エネルギー研究所 power storage device
JP2015524994A (en) * 2012-08-16 2015-08-27 エノビクス・コーポレイションEnovix Corporation Electrode structure for three-dimensional battery
US9172088B2 (en) 2010-05-24 2015-10-27 Amprius, Inc. Multidimensional electrochemically active structures for battery electrodes
US9231243B2 (en) 2009-05-27 2016-01-05 Amprius, Inc. Interconnected hollow nanostructures containing high capacity active materials for use in rechargeable batteries
JP2016207664A (en) * 2011-08-31 2016-12-08 株式会社半導体エネルギー研究所 Power storage device
JP2017033941A (en) * 2010-06-01 2017-02-09 株式会社半導体エネルギー研究所 Power storage device and manufacturing method of the same
US9780365B2 (en) 2010-03-03 2017-10-03 Amprius, Inc. High-capacity electrodes with active material coatings on multilayered nanostructured templates
US9923201B2 (en) 2014-05-12 2018-03-20 Amprius, Inc. Structurally controlled deposition of silicon onto nanowires
US9929407B2 (en) 2011-12-21 2018-03-27 Semiconductor Energy Laboratory Co., Ltd. Negative electrode for non-aqueous secondary battery, non-aqueous secondary battery, and manufacturing methods thereof
US9960225B2 (en) 2010-06-30 2018-05-01 Semiconductor Energy Laboratory Co., Ltd. Manufacturing method of power storage device
US10177400B2 (en) 2016-05-13 2019-01-08 Enovix Corporation Dimensional constraints for three-dimensional batteries
US10256507B1 (en) 2017-11-15 2019-04-09 Enovix Corporation Constrained electrode assembly
US10283807B2 (en) 2015-05-14 2019-05-07 Enovix Corporation Longitudinal constraints for energy storage devices

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002220300A (en) * 2001-01-18 2002-08-09 Vision Arts Kk Nanofiber and method of producing the same
JP2003168426A (en) * 2001-12-03 2003-06-13 Japan Storage Battery Co Ltd Non-aqueous electrolyte secondary battery
JP2008525954A (en) * 2004-12-23 2008-07-17 コミッサリア タ レネルジー アトミーク Electrodes for nanostructured microbatteries
JP2008269827A (en) * 2007-04-17 2008-11-06 Matsushita Electric Ind Co Ltd Electrode material of electrochemical element, its manufacturing method, electrode plate of electrode using it, and electrochemical element
WO2009038897A2 (en) * 2007-08-10 2009-03-26 The Board Of Trustees Of The Leland Stanford Junior University Nanowire battery methods and arrangements

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002220300A (en) * 2001-01-18 2002-08-09 Vision Arts Kk Nanofiber and method of producing the same
JP2003168426A (en) * 2001-12-03 2003-06-13 Japan Storage Battery Co Ltd Non-aqueous electrolyte secondary battery
JP2008525954A (en) * 2004-12-23 2008-07-17 コミッサリア タ レネルジー アトミーク Electrodes for nanostructured microbatteries
JP2008269827A (en) * 2007-04-17 2008-11-06 Matsushita Electric Ind Co Ltd Electrode material of electrochemical element, its manufacturing method, electrode plate of electrode using it, and electrochemical element
WO2009038897A2 (en) * 2007-08-10 2009-03-26 The Board Of Trustees Of The Leland Stanford Junior University Nanowire battery methods and arrangements

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
JPN6013044115; Candace K.Chan et al.: '"High-performance lithium battery anodes using silicon nanowires"' Nature Nanotechnology , 2008, p.31-35 *

Cited By (67)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9231243B2 (en) 2009-05-27 2016-01-05 Amprius, Inc. Interconnected hollow nanostructures containing high capacity active materials for use in rechargeable batteries
US10461359B2 (en) 2009-05-27 2019-10-29 Amprius, Inc. Interconnected hollow nanostructures containing high capacity active materials for use in rechargeable batteries
JP2015133326A (en) * 2010-02-26 2015-07-23 株式会社半導体エネルギー研究所 power storage device
US10141120B2 (en) 2010-02-26 2018-11-27 Semiconductor Energy Laboratory Co., Ltd. Power storage system and manufacturing method thereof and secondary battery and capacitor
US9780365B2 (en) 2010-03-03 2017-10-03 Amprius, Inc. High-capacity electrodes with active material coatings on multilayered nanostructured templates
JP2013522859A (en) * 2010-03-22 2013-06-13 アンプリウス、インコーポレイテッド Interconnection of nanostructures of electrochemically active materials
JP2012009414A (en) * 2010-04-28 2012-01-12 Semiconductor Energy Lab Co Ltd Power storage device and its manufacturing method
US10236502B2 (en) 2010-04-28 2019-03-19 Semiconductor Energy Laboratory Co., Ltd. Power storage device and method for manufacturing the same
WO2011136028A1 (en) * 2010-04-28 2011-11-03 Semiconductor Energy Laboratory Co., Ltd. Power storage device and method for manufacturing the same
US9685275B2 (en) 2010-04-28 2017-06-20 Semiconductor Energy Laboratory Co., Ltd. Power storage device and method for manufacturing the same
US9172088B2 (en) 2010-05-24 2015-10-27 Amprius, Inc. Multidimensional electrochemically active structures for battery electrodes
JP2015159121A (en) * 2010-05-28 2015-09-03 株式会社半導体エネルギー研究所 Manufacturing method for electric storage device
JP2012009432A (en) * 2010-05-28 2012-01-12 Semiconductor Energy Lab Co Ltd Electric storage device and manufacturing method for the same
US8852294B2 (en) 2010-05-28 2014-10-07 Semiconductor Energy Laboratory Co., Ltd. Power storage device and method for manufacturing the same
JP2012009425A (en) * 2010-05-28 2012-01-12 Semiconductor Energy Lab Co Ltd Electric storage device and manufacturing method for the same
JP2012009431A (en) * 2010-05-28 2012-01-12 Semiconductor Energy Lab Co Ltd Power storage device, electrode, and electric device
US9136530B2 (en) 2010-05-28 2015-09-15 Semiconductor Energy Laboratory Co., Ltd. Energy storage device and manufacturing method thereof
JP2015222727A (en) * 2010-05-28 2015-12-10 株式会社半導体エネルギー研究所 Power storage device, and method for producing power storage device
JP2017033941A (en) * 2010-06-01 2017-02-09 株式会社半導体エネルギー研究所 Power storage device and manufacturing method of the same
JP2016122658A (en) * 2010-06-02 2016-07-07 株式会社半導体エネルギー研究所 Method for manufacturing power storage device
JP2012015100A (en) * 2010-06-02 2012-01-19 Semiconductor Energy Lab Co Ltd Power storage device and its manufacturing method
US9281134B2 (en) 2010-06-02 2016-03-08 Semiconductor Energy Laboratory Co., Ltd. Power storage device and method for manufacturing the same
US9685277B2 (en) 2010-06-02 2017-06-20 Semiconductor Energy Laboratory Co., Ltd. Electrode
US8835048B2 (en) 2010-06-11 2014-09-16 Semiconductor Energy Laboratory Co., Ltd. Power storage device
US8846530B2 (en) 2010-06-30 2014-09-30 Semiconductor Energy Laboratory Co., Ltd. Method for forming semiconductor region and method for manufacturing power storage device
US9960225B2 (en) 2010-06-30 2018-05-01 Semiconductor Energy Laboratory Co., Ltd. Manufacturing method of power storage device
JP2015165506A (en) * 2010-06-30 2015-09-17 株式会社半導体エネルギー研究所 Method for forming semi-conductor region, and method for manufacturing storage battery
JP2012031513A (en) * 2010-06-30 2012-02-16 Semiconductor Energy Lab Co Ltd Method for forming semi-conductor region, and method for manufacturing storage battery
JP2012033472A (en) * 2010-06-30 2012-02-16 Semiconductor Energy Lab Co Ltd Method of producing power storage device
JP2013545228A (en) * 2010-10-22 2013-12-19 アンプリウス、インコーポレイテッド Composite structure containing high volume porous active material confined in shell
US9209456B2 (en) 2010-10-22 2015-12-08 Amprius, Inc. Composite structures containing high capacity porous active materials constrained in shells
JP2018026342A (en) * 2010-10-22 2018-02-15 アンプリウス、インコーポレイテッド Electrode material composite structure, electrode, lithium ion battery, and electrode manufacturing method
US9698410B2 (en) 2010-10-22 2017-07-04 Amprius, Inc. Composite structures containing high capacity porous active materials constrained in shells
WO2012070605A1 (en) 2010-11-25 2012-05-31 旭化成ケミカルズ株式会社 Shaped silica body, process for producing same, and method for manufacturing propylene using shaped silica body
JP2012129200A (en) * 2010-11-26 2012-07-05 Semiconductor Energy Lab Co Ltd Semiconductor film, method for preparing semiconductor film, and electricity storage device
KR101899374B1 (en) 2010-11-26 2018-09-17 가부시키가이샤 한도오따이 에네루기 켄큐쇼 Semiconductor film, method for manufacturing the same, and power storage device
JP2012138347A (en) * 2010-12-07 2012-07-19 Semiconductor Energy Lab Co Ltd Power storage device
US9362556B2 (en) 2010-12-07 2016-06-07 Semiconductor Energy Laboratory Co., Ltd. Power storage device
US10128498B2 (en) 2010-12-07 2018-11-13 Semiconductor Energy Laboratory Co., Ltd. Power storage device
US9620769B2 (en) 2011-06-24 2017-04-11 Semiconductor Energy Laboratory Co., Ltd. Power storage device, electrode thereof, and method for manufacturing power storage device
KR20130007443A (en) * 2011-06-24 2013-01-18 가부시키가이샤 한도오따이 에네루기 켄큐쇼 Power storage device, electrode thereof, and method for manufacturing power storage device
JP2013030464A (en) * 2011-06-24 2013-02-07 Semiconductor Energy Lab Co Ltd Power storage device, electrode thereof, and method of manufacturing power storage device
JP2017004964A (en) * 2011-06-24 2017-01-05 株式会社半導体エネルギー研究所 Electrode of power storage device
US10072331B2 (en) 2011-07-08 2018-09-11 Semiconductor Energy Laboratory Co., Ltd. Method for forming silicon film and method for manufacturing power storage device
JP2013035744A (en) * 2011-07-08 2013-02-21 Semiconductor Energy Lab Co Ltd Fabrication method of silicon film, and fabrication method of power storage device
US9815691B2 (en) 2011-08-19 2017-11-14 Semiconductor Energy Laboratory Co., Ltd. Method for manufacturing graphene-coated object, negative electrode of secondary battery including graphene-coated object, and secondary battery including the negative electrode
US10050273B2 (en) 2011-08-19 2018-08-14 Semiconductor Energy Laboratory Co., Ltd. Electrode for power storage device and power storage device
JP2017004982A (en) * 2011-08-19 2017-01-05 株式会社半導体エネルギー研究所 Secondary battery
JP2013060355A (en) * 2011-08-19 2013-04-04 Semiconductor Energy Lab Co Ltd Method for manufacturing graphene-coated object, negative electrode of secondary battery including carbon-based coating, and secondary battery including the negative electrode
JP2013062237A (en) * 2011-08-19 2013-04-04 Semiconductor Energy Lab Co Ltd Electrode for power storage device and power storage device
WO2013027561A1 (en) * 2011-08-19 2013-02-28 Semiconductor Energy Laboratory Co., Ltd. Method for manufacturing graphene-coated object, negative electrode of secondary battery including graphene-coated object, and secondary battery including the negative electrode
JP2013065548A (en) * 2011-08-30 2013-04-11 Semiconductor Energy Lab Co Ltd Power storage device
US9337475B2 (en) 2011-08-30 2016-05-10 Semiconductor Energy Laboratory Co., Ltd. Power storage device
JP2016207664A (en) * 2011-08-31 2016-12-08 株式会社半導体エネルギー研究所 Power storage device
JP2013065550A (en) * 2011-09-02 2013-04-11 Semiconductor Energy Lab Co Ltd Electrode for power storage device, and power storage device
JP2013084588A (en) * 2011-09-30 2013-05-09 Semiconductor Energy Lab Co Ltd Power storage device
US9929407B2 (en) 2011-12-21 2018-03-27 Semiconductor Energy Laboratory Co., Ltd. Negative electrode for non-aqueous secondary battery, non-aqueous secondary battery, and manufacturing methods thereof
US10038214B2 (en) 2012-08-16 2018-07-31 Enovix Corporation Electrode structures for three-dimensional batteries
JP2015524994A (en) * 2012-08-16 2015-08-27 エノビクス・コーポレイションEnovix Corporation Electrode structure for three-dimensional battery
WO2015045341A1 (en) * 2013-09-27 2015-04-02 三洋電機株式会社 Negative electrode for nonaqueous electrolyte secondary batteries
JPWO2015045341A1 (en) * 2013-09-27 2017-03-09 三洋電機株式会社 Anode for non-aqueous electrolyte secondary battery
US10109856B2 (en) 2013-09-27 2018-10-23 Sanyo Electric Co., Ltd. Negative electrode for nonaqueous electrolyte secondary batteries
KR101507537B1 (en) * 2013-12-20 2015-04-24 국립대학법인 울산과학기술대학교 산학협력단 Electrode complex, manufacturing method of the same, and lithium secondary battery containing the same
US9923201B2 (en) 2014-05-12 2018-03-20 Amprius, Inc. Structurally controlled deposition of silicon onto nanowires
US10283807B2 (en) 2015-05-14 2019-05-07 Enovix Corporation Longitudinal constraints for energy storage devices
US10177400B2 (en) 2016-05-13 2019-01-08 Enovix Corporation Dimensional constraints for three-dimensional batteries
US10256507B1 (en) 2017-11-15 2019-04-09 Enovix Corporation Constrained electrode assembly

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