Sign In to Follow Application
View All Documents & Correspondence

Non Aqueous Electrolyte Secondary Battery

Abstract: The present invention pertains to a non aqueous electrolyte that contains a non aqueous electrolyte solvent a supporting electrolyte and a sulfonate represented by a predetermined formula and is characterized by the concentration of the sulfonate being at least 0.001 wt% and less than 0.2 wt% with respect to the total mass of the non aqueous electrolyte.

Get Free WhatsApp Updates!
Notices, Deadlines & Correspondence

Patent Information

Application #
Filing Date
16 January 2015
Publication Number
25/2015
Publication Type
INA
Invention Field
ELECTRICAL
Status
Email
remfry-sagar@remfry.com
Parent Application
Patent Number
Legal Status
Grant Date
2024-02-26
Renewal Date

Applicants

NEC CORPORATION
7 1 Shiba 5 chome Minato ku Tokyo 1088001

Inventors

1. ISHIKAWA Hitoshi
c/o NEC Corporation 7 1 Shiba 5 chome Minato ku Tokyo 1088001
2. NAKAMURA Akinobu
c/o NEC Corporation 7 1 Shiba 5 chome Minato ku Tokyo 1088001
3. UTSUGI Koji
c/o NEC Corporation 7 1 Shiba 5 chome Minato ku Tokyo 1088001

Specification

NON-AQUEOUS ELECTROLYTE SECONDARY BATTERY Technical Field [OOOll The present invention relates to a non-aqueous electrolyte secondary battery excellent in stability. Background Art [0002l The uses of a lithium ion secondary battery among secondary batteries have been spreading not only as a power source for consumer products such as notebook computers and mobile devices including a cellular phone but also, in recent years, as a power source for driving machines such as an electric vehicle, an electric motor cycle, and a power-assisted bicycle, a power source for small electrically driven machine, and a power source for a power storage system making use of its characteristics such as small and light weight and high energy density. [00031 As a substance capable of desorbing and inserting a lithium ion, a lithium based complex oxide of a transition metal, a carbon material, lithium metal, an alloy based compound, and an oxide carbon material are generally used for a material for positive and negative electrode active materials of a lithium ion secondary battery. Moreover, a carbonate based solvent and a lithium salt as a supporting salt are generally used as a non-aqueous electrolyte. [00041 In a charging and discharging process of the secondary battery, a desorption and insertion reaction of a lithium ion occurs a t an interface of an electrode and an electrolyte. However, besides the reaction, an electrolyte solvent or the supporting salt causes a decomposition reaction to form a coating film having a high resistance on the surface of the electrode, which inhibits the desorption and insertion reaction of the lithium ion that primarily should occur. As a result thereof, irreversible lowering of discharging capacity or the like is accelerated, which leads to deterioration of the battery. Therefore, various ideas have been devised to suppress the deterioration. [00051 As one of the ideas, a method for suppressing the decomposition reaction by forming a protective film on the surface of the electrode is included, and the means thereof proposes adding an additive having coating film-forming capability to the electrolyte. Patent Literatures 1 to 3, for example, discloses that when a cyclic monosulfonic acid ester is used as an additive, a coating film is formed on the surface of the electrode to improve battery properties. A proposal to use a cyclic disulfonic acid ester has also been made recently as shown by Patent Literature 4 because the cycle properties and the storage properties (suppression of an increase in resistance and the suppression of lowering in a capacity holding ratio) can be more improved than those for the secondary battery using the cyclic monosulfonic acid ester. As described herein, a sulfonic acid ester-based compound is useful as an electrolyte additive having a coating film-forming capability. Citation List Patent Literature [00061 Patent Literature 1: Japanese Patent Laid-Open No. 63-102173 Patent Literature 2: Japanese Patent Laid-Open No. 2000-3724 Patent Literature 3: Japanese Patent Laid-Open No. 11-339850 Patent Literature 4: Japanese Patent Laid-Open No. 2004-281368 Summary of Invention Technical Problem [00071 However, when the non-aqueous electrolyte containing the sulfonic acid ester-based additive is used for production of the secondary battery after the non-aqueous electrolyte is left standing under, for example, a high temperature, there has been a problem that the lowering of the battery capacity or the deterioration of storage and cycle properties for the secondary battery occurs. Solution to Problem [0008l The present invention relates to a non-aqueous electrolyte comprising a non-aqueous electrolyte solvent, a supporting salt, and a sulfonate represented by the following general formula (1): [00091 wherein R1 and R2 each independently represent a hydrogen atom, a halogen atom, or C1 to C5 alkyl group, alkenyl group or alkoxy group, and M represents an alkali metal or an alkaline earth metal, wherein the concentration of the sulfonate is 0.001 wt% or more and less than 0.2 wt% based on the total mass of the non-aqueous electrolyte. Advantageous Effects of Invention [00101 According to the present invention, the charging and discharging efficiency, the cycle properties, and so on of a non-aqueous electrolyte secondary battery can be improved. Brief Description of Drawing [00111 Figure 1 is a schematic drawing of a non-aqueous electrolyte secondary battery of the present invention. Description of Embodiments [0012l According to the present embodiment, the battery life in a cycle test or a storage evaluation test can be improved particularly in a non-aqueous electrolyte secondary battery using a non-aqueous electrolyte containing a sulfonic acid ester-based compound. [00131 Hereinafter, the constitution of the non-aqueous electrolyte and the non-aqueous electrolyte secondary battery using the non-aqueous electrolyte of the present invention will be described. [00141 (Non-Aqueous Electrolyte) In the present embodiment, the non-aqueous electrolyte comprises a non-aqueous electrolyte solvent, a supporting salt, and a sulfonate represented by the following formula (I), and the concentration of the sulfonate represented by the following formula (1) is 0.001 wt% or more and less than 0.2 wt% based on the total mass of the non-aqueous electrolyte. In addition, the sulfonate represented by the following formula (1) is hereinafter sometimes described simply as the "sulfonate". [00151 [00161 In the formula (I), RI and Rz each independently represent a hydrogen atom, a halogen atom, or C1 to C5 alkyl group, alkenyl group, or alkoxy group, and M represents an alkali metal or an alkaline earth metal, preferably lithium. [00171 In the formula (I), it is preferable that RI and R3 are each independently a hydrogen atom, C1 to C5 alkyl group, or alkoxy group, more preferably a hydrogen atom, methyl group, ethyl group, methoxy group, or ethoxy group, further more preferably a hydrogen atom, methyl group, or ethyl group. [OOl8l Examples of the compound represented by the general formula (I) include dilithium methanedisulfonate, dilithium 1,l-ethanedisulfonate, dilithium 1-methyl-1,l-ethanedisulfonatdei,l ithium 1,l-propanedisulfonate, dilithium 2-methyl-1,l-propanedisulfonate, dilithium 1,l-butanedisulfonate, dilithium methoxymethanedisulfonate, dilithium ethoxymethanedisulfonate, dilithium 1,l-prop-2-yldisulfonateb;u t the present invention is not limited to these. Moreover, the non-aqueous electrolyte of the present embodiment may contain the compound represented by the general formula (1) alone or in combinations of two or more. [00191 The non-aqueous electrolyte of the present embodiment contains the sulfonate represented by the formula (1) i n an amount of 0.001 wt% or more and less than 0.2 wt% based on the total mass of the non-aqueous electrolyte, preferably 0.001 wt% or more and 0.15 wt% or less. The inventors of the present invention have made diligent studies and, as a result thereof, have found that when the sulfonate concentration in the non-aqueous electrolyte is made within the above-described range, the lowering of the capacity of the non-aqueous electrolyte secondary battery manufactured using the nonaqueous electrolyte is small and the battery properties are favorable. When the concentration of the sulfonate represented by the formula (1) is 0.2 wt% or more based on the total mass of the non-aqueous electrolyte, the deterioration of the electrolyte becomes remarkable, and when a secondary battery is manufactured using the non-aqueous electrolyte having a sulfonate concentration of 0.2 wt% or more based on the total mass of the electrolyte, the battery properties become worse in such a way that the capacity retention ratio in the cycle property evaluation is lowered. [0020l It is preferable that the non-aqueous electrolyte of the present invention contains a disulfonic acid ester compound such as a chain disulfonic acid ester compound and a cyclic disulfonic acid ester compound. A coating film is formed on the surface of the electrode to improve battery properties by the electrolyte containing the disulfonic acid ester compound. [00211 Specific examples of the disulfonic acid ester compound include, but not limited to these in the present invention, dimethyl rnethanedisulfonate, diethyl rnethanedisulfonate, bis(trifluoromethyl) rnethanedisulfonate, bis(trimethylsilyl) rnethanedisulfonate, ethylene ethylenedisulfonate, ethylene rnethanedisulfonate, methylene rnethanedisulfonate, propylene rnethanedisulfonate, ethylene 1,l-ethanedisulfonate, and dimethyl 1,lethanedisulfonate. The electrolyte of the present embodiment may contain the disulfonic acid ester compound alone or in combinations of two or more. Loo221 The concentration of the disulfonic acid ester compound in the nonaqueous electrolyte is not particularly limited, however it is preferably 0.2 wt% or more and less than 10 wt%, more preferably 0.2 wt% or more and 5 wt% or less, further more preferably 0.2 wt% or more and 3 wt% or less. [00231 It is considered that the sulfonate represented by the formula (1) is generated due to the occurrence of the decomposition of the disulfonic acid ester compound caused by the reaction of the decomposition product or the like of the supporting salt with the disulfonic acid ester compound in the non-aqueous electrolyte containing the disulfonic acid ester compound. On this occasion, it is anticipated that a free acid is generated, and it is considered that the free acid becomes a cause of the lowering of the battery capacity and the deterioration of storage and cycle properties. Loo241 The sulfonate represented by the formula (1) becomes liable to be generated in the case where, for example, the non-aqueous electrolyte containing the disulfonic acid ester compound is stored at a high temperature for a long period of time (3 months or more at 35OC, for example) or water is mixed into the non-aqueous electrolyte. Accordingly, it is preferable that the non-aqueous electrolyte is stored at a low temperature (room temperature or less, for example, preferably 10°C or less) or the water content in the non-aqueous electrolyte is made 20 ppm or less for the purpose of making the concentration of the sulfonate in the non-aqueous electrolyte within the above-described range. [00251 Examples of the supporting salt include compounds such as LiPFs, LiBF4, LiAsFs, LiSbFs, LiC104, LiAlC14, LiN(CkFzk+lSO2)2, and L ~ N ( C ~ F ~ ~ + ~ S O ~ ) ( C(k~, Fn,Z a~nd+ m~ SeaOch~ i)n dependently represent a natural number), or a mixture thereof. It is preferable that the concentration of the supporting salt in the non-aqueous electrolyte is 0.5 to 2.0 mollL. It becomes easy to adjust the density, the viscosity, the conductivity, and so on i n an appropriate range by making the concentration of the supporting salt within the above-described range. [00261 In the present embodiment, examples of the non-aqueous electrolyte solvent of the non-aqueous electrolyte include, but not particularly limited to, cyclic carbonate compounds, chain carbonate compounds, chain carboxylic acid ester compounds, cyclic carboxylic acid ester compounds, cyclic ether compounds, chain ether compounds, phosphoric acid ester compounds, and fluorinated derivatives thereof. And, among these compounds, it is preferable that the non-aqueous electrolyte solvent of the non-aqueous electrolyte contains a cyclic carbonate compound and more preferably contains 10 to 60% of the cyclic carbonate compound based on 100% (volume ratio) of the non-aqueous electrolyte solvent. The non-aqueous electrolyte solvent may be used alone or in combinations of two or more. [00271 Examples of the cyclic carbonate compound include ethylene carbonate (EC), propylene carbonate (PC), butylene carbonate (BC), vinylene carbonate (vc), and, among these compounds, ethylene carbonate (EC) and propylene carbonate (PC) are more preferable. [00281 Examples of the chain carbonate compound include dimethyl carbonate (DMC), diethyl carbonate (DEC), and methyl ethyl carbonate (MEC). Examples of the chain carboxylic acid ester compound include ethyl acetate, methyl propionate, ethyl formate, ethyl propionate, methyl butyrate, ethyl butyrate, methyl acetate, and methyl formate. Examples of the cyclic carboxylic acid ester compound include y-butyrolactone. Examples of the cyclic ether compound include tetrahydrofuran and 2-methyltetrahydrofuran. Examples of the chain ether compound include 1,2-ethoxy ethane (DEE) and ethoxy methoxy ethane (EME). Examples of the phosphoric acid ester compound include trimethyl phosphate, triethyl phosphate, and tributyl phosphate. [00291 The non-aqueous electrolyte of the present embodiment may contain a monosulfonic acid ester compound such as 1,3-propane sultone, 1,4-butane sultone, methyl methanesulfonate, methyl ethanesulfonate, methyl trifluoromethanesulfonate. [00301 Hereinafter, the constitution of the non-aqueous electrolyte secondary battery of the present invention will be described with reference to the drawing. Figure 1 is an example of a schematic drawing of a non-aqueous electrolyte secondary battery of the present invention. [00311 The battery relating to the present invention has a structure shown in Figure 1, for example. The battery has a layered structure in which a porous separator 16 is present between a positive electrode and a negative electrode. The positive electrode is manufactured by forming a layer 12 containing a positive electrode active material as a film on a surface of a positive electrode collector 11. The negative electrode is manufactured by forming a layer 13 containing a negative electrode active material as a film on a surface of a negative electrode collector 14. [00321 Examples of the positive electrode active material used for the layer 12 containing a positive electrode active material include lithium-containing complex oxides such as LiCoOz, LiNiOs, and LiMneOa which are compounds capable of desorbing and inserting a lithium ion. Moreover, compounds in which the portion of the transition metal in these lithium-containing complex oxides is replaced with another element may be used. [00331 Moreover, a lithium-containing complex oxide having a plateau at 4.5 V or more in terms of electric potential vs. lithium metal can also be used as a positive electrode active material. Examples of the lithium-containing complex oxide include spinel type lithium manganese complex oxides, olivine type lithium complex oxides, and inverse spinel type lithium-containing complex oxides. The lithium-containing complex oxide may be, for example, a compound represented by Li,(MxMnz-J04 (where 0

Documents

Orders

Section Controller Decision Date

Application Documents

# Name Date
1 402-DELNP-2015.pdf 2015-01-20
2 402-delnp-2015-Form-1-(02-02-2015).pdf 2015-02-02
3 402-delnp-2015-Correspondence Others-(02-02-2015).pdf 2015-02-02
4 Power of authoirty.pdf 2015-03-12
5 PCT-IB-304.pdf 2015-03-12
6 Other relevant document.pdf 2015-03-12
7 Form 5.pdf 2015-03-12
8 Form 3.pdf 2015-03-12
9 Form 2+ Sepecification.pdf 2015-03-12
10 Drawings.pdf 2015-03-12
11 402-delnp-2015-Form-3-(13-04-2015).pdf 2015-04-13
12 402-delnp-2015-Correspondence Others-(13-04-2015).pdf 2015-04-13
13 402-DELNP-2015-FER.pdf 2018-09-28
14 402-DELNP-2015-OTHERS [28-12-2018(online)].pdf 2018-12-28
15 402-DELNP-2015-FORM 3 [28-12-2018(online)].pdf 2018-12-28
16 402-DELNP-2015-FER_SER_REPLY [28-12-2018(online)].pdf 2018-12-28
17 402-DELNP-2015-DRAWING [28-12-2018(online)].pdf 2018-12-28
18 402-DELNP-2015-CORRESPONDENCE [28-12-2018(online)].pdf 2018-12-28
19 402-DELNP-2015-COMPLETE SPECIFICATION [28-12-2018(online)].pdf 2018-12-28
20 402-DELNP-2015-CLAIMS [28-12-2018(online)].pdf 2018-12-28
21 402-DELNP-2015-ABSTRACT [28-12-2018(online)].pdf 2018-12-28
22 402-DELNP-2015-Correspondence-030119.pdf 2019-01-05
23 402-DELNP-2015-Power of Attorney-030119.pdf 2019-02-02
24 402-DELNP-2015-US(14)-HearingNotice-(HearingDate-01-02-2024).pdf 2024-01-01
25 402-DELNP-2015-Correspondence to notify the Controller [25-01-2024(online)].pdf 2024-01-25
26 402-DELNP-2015-Written submissions and relevant documents [15-02-2024(online)].pdf 2024-02-15
27 402-DELNP-2015-PatentCertificate26-02-2024.pdf 2024-02-26
28 402-DELNP-2015-IntimationOfGrant26-02-2024.pdf 2024-02-26

Search Strategy

1 case35search_09-07-2018.pdf

ERegister / Renewals

3rd: 14 May 2024

From 26/06/2015 - To 26/06/2016

4th: 14 May 2024

From 26/06/2016 - To 26/06/2017

5th: 14 May 2024

From 26/06/2017 - To 26/06/2018

6th: 14 May 2024

From 26/06/2018 - To 26/06/2019

7th: 14 May 2024

From 26/06/2019 - To 26/06/2020

8th: 14 May 2024

From 26/06/2020 - To 26/06/2021

9th: 14 May 2024

From 26/06/2021 - To 26/06/2022

10th: 14 May 2024

From 26/06/2022 - To 26/06/2023

11th: 14 May 2024

From 26/06/2023 - To 26/06/2024

12th: 14 May 2024

From 26/06/2024 - To 26/06/2025

13th: 25 Jun 2025

From 26/06/2025 - To 26/06/2026

14th: 18 Jun 2026

From 26/06/2026 - To 26/06/2027