Method of producing lithium ion-storing/releasing material, lithium ion-storing/releasing material, and electrode structure and energy storage device using the material

Abstract

A method of producing a material capable of electrochemically storing and releasing a large amount of lithium ions is provided. The material is used as an electrode material for a negative electrode, and includes silicon or tin primary particles composed of crystal particles each having a specific diameter and an amorphous surface layer formed of at least a metal oxide, having a specific thickness. Gibbs free energy when the metal oxide is produced by oxidation of a metal is smaller than Gibbs free energy when silicon or tin is oxidized, and the metal oxide has higher thermodynamic stability than silicon oxide or tin oxide. The method of producing the electrode material includes reacting silicon or tin with a metal oxide, reacting a silicon oxide or a tin oxide with a metal, or reacting a silicon compound or a tin compound with a metal compound to react with each other.

Description

CROSS-REFERENCE TO RELATED APPLICATIONS[0001]This application is a continuation of International Application No. PCT / JP2008 / 066506, filed Sep. 8, 2008, which claims the benefit of Japanese Patent Applications No. 2007-232090, filed Sep. 6, 2007, and No. 2007-321373, filed Dec. 12, 2007.BACKGROUND OF THE INVENTION[0002]1. Field of the Invention[0003]The present invention relates to a method of producing a lithium ion-storing / releasing material mainly composed of a metal which alloys with lithium by an electrochemical reaction such as silicon or tin and a metal oxide, an electrode structure formed of the material, and an energy storage device having the electrode structure.[0004]2. Description of the Related Arts[0005]It has been pointed out that global warming may occur owing to a greenhouse effect because the amount of CO2 gas in the air has been recently increasing. In addition, air pollution due to, for example, CO2, NOx, and a hydrocarbon exhausted from automobiles is of serious ...

AI Technical Summary

Benefits of technology

[0079]Another object of the present invention is to provide a material prepared by the above production method and capable of electrochemically storing or releasing a large amount of lithium ions, an electrode structure formed of the material, and an energy storage device provided with the electrode structure and having such a characteristic that a reduction in capacity is small even when charging and discharging are repeatedly performed, in conjunction with high power density and a high energy density.

[0082]As a result of various experiments, the inventors of the present invention have found the following: the oxide of Si or Sn in particles formed of Si, Sn, or an alloy of any one of such elements is allowed to react with a metal so that a metal oxide stabler than the oxide of Si or Sn is produced, and the particles formed of Si, Sn, or an alloy of any one of such elements are coated with the metal oxide stabler than the oxide of Si or Sn, whereby the content of the oxide of Si or Sn can be reduced, and hence the oxidation of the particles formed of Si, Sn, or an alloy of any one of such elements can be suppressed, and the coulombic efficiency of a cell for the first charging and discharging can be improved. In addition, the inventors have found that an electrode produced by using an active material having a network structure made up from Si particles with fibrous (filamentous) substances each having a diameter of a nanometer to submicron size shows an additional improvement in durability.

[0084]It should be noted that Gibbs free energy at the time of producing a metal oxide by oxidation of a metal element included in the metal oxide or the metal is smaller than Gibbs free energy at the time of oxidizing silicon or tin, and the metal oxide has higher thermodynamic stability than silicon oxide or tin oxide.

[0093]According to the method of producing a lithium ion-storing / releasing material of the present invention, a material capable of electrochemically storing and releasing a large amount of lithium ions can be produced without using any complicated production step.

[0094]In addition, the energy storage device of the present invention utilizing the electrochemical oxidation-reduction reaction of lithium ions using the electrode structure of the present invention can provide high initial charge and discharge efficiency, high power density and high energy density, and the long cycle life of the device for charging and discharging can be ensured. In addition, the energy storage device thus obtained can be charged quickly.

Problems solved by technology

Si and Sn capable of electrochemically absorbing and releasing a large amount of Li has conventionally involved such problems that they show a large volume expansion at the time of the absorption of Li, and are turned into a fine powder by volume expansion or shrinkage due to the absorption or release of Li to increase the resistance of an electrode, and a reduction in performance of a cell occurs owing to the repetition of charging and discharging.

The problem referred to as the reduction in performance of the cell due to the repetition of charging and discharging has been alleviated by those approaches, but the extent to which the problem is alleviated is still insufficient.

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