Nonaqueous electrolyte secondary battery

Patent metadata

Field	Value
Publication number	US-10153493-B2
Application number	US-201715445495-A
Country	US
Kind code	B2
Filing date	Feb 28, 2017
Priority date	Jul 5, 2013
Publication date	Dec 11, 2018
Grant date	Dec 11, 2018

Abstract

A secondary battery comprising a positive electrode, a negative electrode, a separator, and a nonaqueous electrolyte is provided. The electrode material of which the positive and/or negative electrode is made contains hydrophobic spherical silica particles, which are obtained by introducing R1SiO3/2 units on surfaces of hydrophilic spherical silica particles of SiO2 units, and further introducing R23SiO1/2 units on the surfaces, and have an average particle size of 5-1,000 nm, a particle size distribution D90/D10 of 2-3, and an average circularity of 0.8-1. All components of the battery are made hydrophobic for suppressing absorption of water within the battery and entry of water into the battery.

First claim

The invention claimed is:

1. A method of manufacturing a nonaqueous electrolyte secondary battery having a positive electrode, a negative electrode, a separator interposed between the positive and negative electrodes, and a nonaqueous electrolyte,
wherein the positive and/or negative electrode is made of an electrode material containing hydrophobic spherical silica particles,
wherein said hydrophobic spherical silica particles comprise introduced R 1 SiO 3/2 units wherein R 1 is a substituted or unsubstituted monovalent hydrocarbon group of 1 to 20 carbon atoms on surfaces of hydrophilic spherical silica particles consisting essentially of SiO 2 units, and wherein said hydrophobic spherical silica particles further comprise introduced R 2 3 SiO 1/2 units wherein R 2 is independently a substituted or unsubstituted monovalent hydrocarbon group of 1 to 6 carbon atoms on the surfaces of the hydrophilic spherical silica particles consisting essentially of SiO 2 units having R 1 SiO 3/2 units introduced therein, and
wherein said hydrophobic spherical silica particles have an average particle size of 5 nm to 1.00 μm, a particle size distribution D 90 /D 10 of up to 3, and an average circularity of 0.8 to 1, which method comprises the following steps:
(A1) forming hydrophilic spherical silica particles, conducting a (A2) first hydrophobic surface treatment with trifunctional silane compound, and conducting a (A3) second hydrophobic surface treatment with monofunctional silane compound, wherein
the step (A1) of forming hydrophilic spherical silica particles includes subjecting a tetrafunctional silane compound having the general formula (I):
Si(OR 3 ) 4   (I)

wherein R 3 is each independently a monovalent hydrocarbon group of 1 to 6 carbon atoms, a partial hydrolyzate thereof or a mixture thereof to hydrolysis and condensation in a mixture of a hydrophilic organic solvent and water in the presence of a basic substance, thereby forming a dispersion of hydrophilic spherical silica particles consisting essentially of SiO 2 units in the solvent mixture,
the first hydrophobic surface treatment (A2) includes adding a trifunctional silane compound having the general formula (II):
R 1 Si(OR 4 ) 3   (II)

wherein R 1 is a substituted or unsubstituted monovalent hydrocarbon group of 1 to 20 carbon atoms, and R 4 is each independently a monovalent hydrocarbon group of 1 to 6 carbon atoms, a partial hydrolyzate thereof or a mixture thereof to the dispersion from step (A1), for conducting surface treatment of the hydrophilic spherical silica particles, thereby obtaining a dispersion of spherical silica particles having R 1 SiO 3/2 units introduced on their surface in the solvent mixture,
step (A2) is followed by a concentration step of removing a portion of the hydrophilic organic solvent and water from the dispersion resulting from step (A2), thereby providing a concentrated dispersion (A′) containing 15 to 40% by weight of spherical silica particles, and
the second hydrophobic surface treatment (A3) includes adding a silazane compound having the general formula (III):
R 2 3 SiNHSiR 2 3   (III)

wherein R 2 is each independently a substituted or unsubstituted monovalent hydrocarbon group of 1 to 6 carbon atoms, a monofunctional silane compound having the general formula (IV):
R 2 3 SiX  (IV)

wherein R 2 is as defined above and X is an OH group or hydrolyzable group, or a mixture thereof to the dispersion from step (A2), for conducting surface treatment of the spherical silica particles having R 1 SiO 3/2 units introduced thereon, thereby introducing R 2 3 SiO 1/2 units on their surface, whereby hydrophobic spherical silica particles are obtained; and
(B) incorporating obtained hydrophobic spherical silica particles in positive and/or negative electrode material.

2. The method of manufacturing a nonaqueous electrolyte secondary battery of claim 1 ,
wherein the positive electrode is made of a positive electrode material containing 0.1 to 5% by weight as solids of the hydrophobic spherical silica particles based on the weight of the positive electrode material, and
wherein the negative electrode is made of a negative electrode material containing 0.1 to 5% by weight as solids of the hydrophobic spherical silica particles based on the weight of the negative electrode material.

3. The method of manufacturing a nonaqueous electrolyte secondary battery of claim 1 , wherein the positive electrode comprises positive electrode active material selected from the group consisting of lithium, lithium-containing complex oxides, NbSe 2 , TiS 2 , MoS 2 , NbS 2 , ZrS 2 , VS 2 , V 2 O 5 , MoO 3 , and Mg(V 3 O 8 ) 2 .

4. The method of manufacturing a nonaqueous electrolyte secondary battery of claim 1 , wherein the negative electrode comprises negative electrode active material selected from the group consisting of non-graphitizable carbon, graphitizable carbon, graphite, pyrolytic carbons, coke, vitreous carbons, fired organic polymers, carbon fibers, active carbon, silicon, silicon oxides of the formula SiO x wherein 0.5≤x<1.6, silicon-free metal oxides of the formula MO a wherein M is Ge, Sn, Pb, Bi, Sb, Zn, In, or Mg and “a” is a positive number of 0.1 to 4, and lithium complex oxides of the formula LiM b O 0 wherein M is Ge, Sn, Pb, Bi, Sb, Zn, In, Mg, or Si, b is a positive number of 0.1 to 4, and c is a positive number of 0.1 to 8.

5. The method of manufacturing a nonaqueous electrolyte secondary battery of claim 1 , wherein the separator comprises a porous sheet or nonwoven fabric of polyethylene, polypropylene, or copolymers thereof or an aramid resin.

6. The method of manufacturing a nonaqueous electrolyte secondary battery of claim 1 , wherein the nonaqueous electrolyte comprises a salt of an alkali metal, a salt of an alkaline earth metal, or an aluminum salt.

Assignees

• Shinetsu Chemical Co

Inventors

• Matsumura Kazuyuki
• Nakanishi Tetsuo

Classifications

• H01M2004/021

  Physical characteristics, e.g. porosity, surface area · CPC title

• H01M4/628 Primary

  Inhibitors, e.g. gassing inhibitors, corrosion inhibitors · CPC title

• H01M10/0525 Primary

  Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries · CPC title

• H01M4/049

  Manufacturing of an active layer by chemical means · CPC title

• C01P2004/61

  Micrometer sized, i.e. from 1-100 micrometer · CPC title