JP2016201244A - Coating agent for electrode surface modification of electrode for nonaqueous electrolyte battery, manufacturing method for surface modification of electrode, and manufacturing method for nonaqueous electrolyte battery - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a coating agent for electrode surface modification capable of omitting the gas evacuation operation, by suppressing production of decomposition gas to be evacuated, because the battery container was conventionally brought into sealed state, after gas is evacuated at the time of initial charging.SOLUTION: A manufacturing method for nonaqueous electrolyte battery includes a first step for coating the surface of an electrode for a nonaqueous electrolyte battery with a coating agent for electrode surface modification where an ester compound is dissolved or dispersed into a solvent, and a second step of obtaining a surface modified electrode by heating the coating agent for electrode surface modification on the electrode after the first step, at 80-150°C, thereby forming a coating on the electrode surface. Heating in the second step is carried out until the following formula is satisfied. (A-B2)×100/(A-B1)≥50. (A is the solid component of the coating agent for electrode surface modification applied onto the electrode after the first step, B1 is the mass of a coat obtained when heated at 150°C for one hour in the normal pressure atmosphere, as sample test, B2 is the mass of a coat when actually heated at 80-150°C).SELECTED DRAWING: None

Description

  The present invention relates to a method for producing a surface modified electrode for a non-aqueous electrolyte battery, a method for producing a non-aqueous electrolyte battery using the surface-modified electrode, and an electrode surface modification for a non-aqueous electrolyte battery electrode. It relates to a coating agent.

  In recent years, information-related equipment, communication equipment, ie personal computers, video cameras, digital still cameras, mobile phones, etc., large storage systems for high energy density applications, electric vehicles, hybrid vehicles, fuel cell vehicle auxiliary power supplies, power storage, etc. Power storage systems for power applications are attracting attention. As one candidate, non-aqueous electrolyte batteries such as lithium ion batteries, lithium batteries, and lithium ion capacitors have been actively developed.

  Many of these nonaqueous electrolyte batteries have already been put into practical use, but they are not satisfactory in various applications in terms of durability, and particularly when the environmental temperature is 45 ° C. or higher, the deterioration is large. There is a problem in applications that are used in a high temperature environment for a long time such as for automobiles.

  So far, as a means for improving the durability of non-aqueous electrolyte batteries, optimization of various battery components including positive and negative electrode active materials has been studied. Non-aqueous electrolytes are no exception, and it has been proposed that degradation due to decomposition of the electrolyte on the surface of the active positive electrode or negative electrode is suppressed by decomposition coatings with various durability improvers.

  In Patent Documents 1 and 2 and Non-Patent Documents 1 to 3, high temperature cycle characteristics and output characteristics are improved by the effect of a film formed on the electrode interface when boron having an oxalic acid group and a complex salt of phosphorus are added to the electrolyte. It is described to do. However, these complex salts having an oxalic acid group generate a gas during a film formation reaction by electrolysis, which may cause swelling and deterioration of performance due to an increase in the internal pressure of the battery, which is a problem. .

  In Patent Documents 3 to 5, as a method of avoiding an increase in the internal pressure of the battery, a method of sealing the battery container after degassing during initial charging is proposed. However, degassing requires a long time, which hinders productivity improvement.

  Patent Document 6 proposes to improve battery characteristics by adding vinylene carbonate to an electrolytic solution. In this method, the electrode is coated with a polymer film by polymerization of vinylene carbonate to prevent decomposition of the electrolyte solution on the electrode surface, and it is difficult for gas to be generated during film formation, and the film is formed during electrode preparation. Therefore, there is no risk of performance deterioration due to an increase in the internal pressure of the battery. However, since lithium ions hardly pass through this coating, the internal resistance of the electrode is increased, which is disadvantageous in terms of input / output characteristics.

  Patent Documents 7 to 10 report a method of reducing the internal resistance of the electrode by forming a film derived from the durability improver on the electrode surface by including the durability improver inside the electrode mixture layer. . However, it does not suppress the generation of gas during the initial charge.

JP 2002-110235 A JP 2005-005116 A JP 2014-107020 A International Publication No. 2013/136445 JP 2008-262895 A JP 2000-123867 A International Publication No. 2014/155589 JP 2008-270199 A JP 2008-027778 A JP 2012-064456 A

Electrochim. Acta, 51, 3322-3326 (2006) Electrochemistry Communications, 9, 475-479 (2007) Electrochemical and Solid-State Letters, 13 (2), A11-A14 (2007)

  In the manufacture of conventional nonaqueous electrolyte batteries, as a method of avoiding an increase in the internal pressure of the battery, a method of degassing during initial charging and then sealing the battery container has been adopted. Required a long time, which hindered productivity improvement.

  The present invention relates to a method for producing an electrode for a non-aqueous electrolyte battery, which has been modified by a predetermined operation (including heating) (referred to as “surface modified electrode” in the present invention), the surface A method for producing a non-aqueous electrolyte battery using a modified electrode, and a composition used for obtaining the surface-modified electrode (referred to as “electrode surface modifying coating agent” in the present invention) are provided. is there.

As a result of intensive studies to solve the above problems, the present inventors have found that a surface-modified electrode obtained by thermally decomposing an electrode surface-modifying coating agent on an electrode can meet the purpose, The present invention has been made based on this finding. By assembling the battery using the surface-modified electrode, it is possible to suppress an increase in internal pressure due to electrolysis of the assembled battery (that is, generation of decomposition gas of the electrolyte due to electrolysis). As a result, the conventional degassing operation can be omitted, and the productivity of the non-aqueous electrolyte battery can be improved.
That is, the present invention provides a method for producing a surface-modified electrode for a non-aqueous electrolyte battery, a method for producing a non-aqueous electrolyte battery using the surface-modified electrode, and an electrode surface modification of the electrode for a non-aqueous electrolyte battery. A quality coating agent is provided.

The present invention includes at least
Applying a coating agent for electrode surface modification containing an ester compound dissolved or dispersed in a solvent to the surface of an electrode for a nonaqueous electrolyte battery;
A second step of obtaining a surface-modified electrode by forming a film on the surface of the electrode by heating the electrode surface-modifying coating agent on the electrode after the first step at 80 to 150 ° C .;
Assembling a non-aqueous electrolyte battery comprising at least the surface-modified electrode, the non-aqueous electrolyte, and the separator;
Including
It is a manufacturing method of the nonaqueous electrolyte battery characterized by performing heating of said 2nd process until the following formula [1] is satisfy | filled.
(A-B2) × 100 / (A-B1) ≧ 50 [1]
here,
Application amount A: Calculated value of solid content of electrode surface modification coating agent applied on electrode after first step (ie, mass of electrode surface modification coating agent applied on electrode × electrode surface modification) Solid content concentration of quality coating agent)
Coating mass B1: As a sample test, measured value of coating mass obtained when heated at 150 ° C. for 1 hour in atmospheric pressure as the second step Coating mass B2: Actually heated at 80 to 150 ° C. as the second step The measured value of the mass of the coating obtained at this time. The solid content concentration of the electrode surface modifying coating agent means the total mass ratio of components other than the solvent to the total mass of the electrode surface modifying coating agent.

The heating in the second step is preferably performed until the following formula [2] is satisfied.
50 ≦ (A−B2) × 100 / (A−B1) ≦ 100 [2]
here,
The coating amount A, the coating mass B1, and the coating mass B2 are the same as those in the formula [1].

  Moreover, it is preferable that the heating temperature of said 2nd process is 100-150 degreeC.

  The electrode surface modification coating agent provided for the first step is at least selected from the group consisting of a thioester compound, a carbonate ester compound, a phosphate ester compound, a sulfate ester compound, and a carbonate ester compound as a solvent. It is preferable that one is dissolved or dispersed.

［一般式［３］中、Ｍはホウ素原子、リン原子又はケイ素原子を表し、ｍは１〜３、ｎは１〜４、ｐは０又は１である。Ｒ^１は炭素数が３〜１０のアルキレン基、炭素数が３〜１０のハロゲン化アルキレン基、炭素数が６〜２０のアリーレン基、又は炭素数が６〜２０のハロゲン化アリーレン基（これらの基はその構造中に置換基を含有してもよいし、ヘテロ原子を含有してもよい。また、ｍが２以上の場合、ｍ個存在するＲ^１はそれぞれが互いに結合していてもよい）を表し、Ｒ^２はハロゲン原子を表し、Ｘ^１、Ｘ^２はそれぞれ互いに独立して酸素原子又は硫黄原子を表し、Ｘ^３は炭素原子又は硫黄原子を表す。ｑは、Ｘ^３が炭素原子の場合は１、硫黄原子の場合は１又は２である。Ａ^ａ＋はアルカリ金属カチオン、アルカリ土類金属カチオン、又はオニウムカチオンを表し、ａは該当するカチオンの価数を表す。ａ〜ｄは１又は２であり、かつ、ａ×ｂ＝ｃ×ｄを満たす。］

［一般式［４］中、Ａ^ａ＋はアルカリ金属カチオン、アルカリ土類金属カチオン、又はオニウムカチオンを表し、ａは該当するカチオンの価数を表す。ａ〜ｄは１又は２であり、かつ、ａ×ｂ＝ｃ×ｄを満たす。］

［一般式［５］中、Ｘは（−ＣＨ_２−）_ｒ、−ＣＨ（ＣＨ_３）−、−Ｃ（ＣＨ_３）_２−、−ＣＦ_２−、−Ｃ（ＣＦ_３）_２−、及び−Ｃ（Ｃ_６Ｈ_５）_２−からなる群から選ばれる基であり、ｒは１〜４のいずれかである。Ｚ^１及びＺ^２は、それぞれ独立で、水素原子、−ＣＦ_３基、及び−ＣＨ_２ＣＦ_３基からなる群から選ばれる基である。］

［一般式［６］中、
Ｄはハロゲンイオン、ヘキサフルオロリン酸アニオン、テトラフルオロホウ酸アニオン、ビス（トリフルオロメタンスルホニル）イミドアニオン、ビス（フルオロスルホニル）イミドアニオン、（フルオロスルホニル）（トリフルオロメタンスルホニル）イミドアニオン、ビス（ジフルオロホスホニル）イミドアニオンから選ばれる少なくとも一つであり、
Ｆはフッ素であり、
Ｍは１３族元素（Ａｌ、Ｂ）、１４族元素（Ｓｉ）及び１５族元素（Ｐ、Ａｓ、Ｓｂ）からなる群から選ばれるいずれか１つであり
Ｏは酸素であり、
Ｎは窒素である。
Ｙは炭素又は硫黄であり、Ｙが炭素である場合ｑは１であり、Ｙが硫黄である場合ｑは１又は２である。
Ｘは炭素又は硫黄であり、Ｘが炭素である場合ｒは１であり、Ｘが硫黄である場合ｒは１又は２である。
Ｒ^１は炭素数１〜１０の環やヘテロ原子やハロゲン原子を有していてもよい炭化水素基（炭素数が３以上の場合にあっては、分岐鎖あるいは環状構造のものも使用できる）、又は−Ｎ（Ｒ^２）−を表す。このとき、Ｒ^２は水素、アルカリ金属、炭素数１〜１０の環やヘテロ原子やハロゲン原子を有していてもよい炭化水素基を表す。炭素数が３以上の場合にあっては、Ｒ^２は分岐鎖あるいは環状構造をとることもできる。
Ｒ^４、Ｒ^５はそれぞれ独立で炭素数１〜１０の環やヘテロ原子やハロゲン原子を有していてもよい炭化水素基であり、炭素数が３以上の場合にあっては、分岐鎖あるいは環状構造のものも使用できる。また、下記一般式［７］の様にお互いを含む環状構造を有しても良い。

ｃは０又は１であり、ｎが１の場合、ｃは０（ｃが０のときＤは存在しない）であり、ｎが２の場合、ｃは１となる。
ｏは２又は４、ｎは１又は２、ｐは０又は１、ｑは１又は２、ｒは１又は２、ｓは０又は１である。ｐが０の場合、Ｙ−Ｘ間に直接結合を形成する。
ｓが０の場合、Ｎ（Ｒ^４）（Ｒ^５）とＲ^１は直接結合し、その際は下記の［８］〜［１１］のような構造をとることもできる。直接結合が二重結合となる［９］、［１１］の場合、Ｒ^５は存在しない。また［１０］の様に二重結合が環の外に出た構造を取ることも出来る。この場合のＲ^６、Ｒ^７はそれぞれ独立で水素、又は炭素数１〜１０の環やヘテロ原子やハロゲン原子を有していてもよい炭化水素基であり、炭素数が３以上の場合にあっては、分岐鎖あるいは環状構造のものも使用できる。］

In the electrode surface modification coating agent provided in the first step, at least one selected from compounds represented by the following general formulas [3] to [6] is dissolved or dispersed in at least a solvent. It is preferably included.

[In General Formula [3], M represents a boron atom, a phosphorus atom, or a silicon atom, m is 1-3, n is 1-4, and p is 0 or 1. R ¹ is an alkylene group having 3 to 10 carbon atoms, a halogenated alkylene group having 3 to 10 carbon atoms, an arylene group having 6 to 20 carbon atoms, or a halogenated arylene group having 6 to 20 carbon atoms (these The group may contain a substituent or a hetero atom in the structure, and when m is 2 or more, m R ^{1 s} may be bonded to each other. R ² represents a halogen atom, X ¹ and X ² each independently represent an oxygen atom or a sulfur atom, and X ³ represents a carbon atom or a sulfur atom. q is 1 when X ³ is a carbon atom, and 1 or 2 when X ³ is a sulfur atom. A ^{a +} represents an alkali metal cation, an alkaline earth metal cation, or an onium cation, and a represents the valence of the corresponding cation. a to d are 1 or 2, and a × b = c × d is satisfied. ]

[In General Formula [4], A ^{a +} represents an alkali metal cation, an alkaline earth metal cation, or an onium cation, and a represents the valence of the corresponding cation. a to d are 1 or 2, and a × b = c × d is satisfied. ]

[In the general formula [5], X represents (—CH ₂ —) _r , —CH (CH ₃ ) —, —C (CH ₃ ) ₂ —, —CF ₂ —, —C (CF ₃ ) ₂ —, and It is a group selected from the group consisting of —C (C ₆ H ₅ ) ₂ —, and r is any one of 1 to 4. Z ¹ and Z ² are each independently a group selected from the group consisting of a hydrogen atom, a —CF ₃ group, and a —CH ₂ CF ₃ group. ]

[In the general formula [6],
D is a halogen ion, hexafluorophosphate anion, tetrafluoroborate anion, bis (trifluoromethanesulfonyl) imide anion, bis (fluorosulfonyl) imide anion, (fluorosulfonyl) (trifluoromethanesulfonyl) imide anion, bis (difluorophospho Nyl) imide anion,
F is fluorine,
M is any one selected from the group consisting of Group 13 elements (Al, B), Group 14 elements (Si), and Group 15 elements (P, As, Sb), O is oxygen,
N is nitrogen.
Y is carbon or sulfur. When Y is carbon, q is 1. When Y is sulfur, q is 1 or 2.
X is carbon or sulfur, r is 1 when X is carbon, and r is 1 or 2 when X is sulfur.
R ¹ is a hydrocarbon group which may have a ring having 1 to 10 carbon atoms, a hetero atom or a halogen atom (in the case of 3 or more carbon atoms, a branched chain or cyclic structure can be used) , or -N ^{(R 2)} - represents a. At this time, R ² represents hydrogen, an alkali metal, a hydrocarbon group which may have a ring having 1 to 10 carbon atoms, a hetero atom, or a halogen atom. When the number of carbon atoms is 3 or more, R ² can also take a branched chain or a cyclic structure.
R ⁴ and R ⁵ are each independently a hydrocarbon group optionally having a ring having 1 to 10 carbon atoms, a heteroatom, or a halogen atom. If the number of carbon atoms is 3 or more, a branched chain or An annular structure can also be used. Moreover, you may have a cyclic structure containing each other like following General formula [7].

When c is 0 or 1, when n is 1, c is 0 (D is not present when c is 0), and when n is 2, c is 1.
o is 2 or 4, n is 1 or 2, p is 0 or 1, q is 1 or 2, r is 1 or 2, and s is 0 or 1. When p is 0, a direct bond is formed between Y and X.
When s is 0, N (R ⁴ ) (R ⁵ ) and R ¹ are directly bonded, and in this case, the following structures [8] to [11] can be taken. In the case of [9] and [11] in which the direct bond is a double bond, R ⁵ does not exist. Moreover, it can also take the structure where the double bond went out of the ring like [10]. In this case, R ⁶ and R ⁷ are each independently hydrogen, or a hydrocarbon group that may have a ring having 1 to 10 carbon atoms, a hetero atom, or a halogen atom. For example, a branched chain or cyclic structure can be used. ]

  Moreover, it is preferable that the total amount of the compounds represented by the above general formulas [3] to [6] is 20 to 100% by mass out of the total amount of 100% by mass of the solid content in the electrode surface modification coating agent. .

The present invention also includes at least
Applying a coating agent for electrode surface modification containing an ester compound dissolved or dispersed in a solvent to the surface of an electrode for a nonaqueous electrolyte battery;
A second step of obtaining a surface-modified electrode by forming a film on the surface of the electrode by heating the electrode surface-modifying coating agent on the electrode after the first step at 80 to 150 ° C .;
Including
It is a manufacturing method of the surface modification electrode for nonaqueous electrolyte batteries characterized by performing heating of said 2nd process until the following formula [1] is satisfied.
(A-B2) × 100 / (A-B1) ≧ 50 [1]
here,
Amount of coating A: Calculated value of the solid content of the coating agent for electrode surface modification coated on the electrode after the first step (ie, the mass of the coating agent for electrode surface modification coated on the electrode × electrode surface modification) Solid content concentration of coating agent for quality)
Coating mass B1: As a sample test, measured value of coating mass obtained when heated at 150 ° C. for 1 hour in atmospheric pressure as the second step Coating mass B2: Actually heated at 80 to 150 ° C. as the second step Measured value of the coating film mass

The heating in the second step is preferably performed until the following formula [2] is satisfied.
50 ≦ (A−B2) × 100 / (A−B1) ≦ 100 [2]
here,
The coating amount A, the coating mass B1, and the coating mass B2 are the same as those in the formula [1].

  Moreover, it is preferable that the heating temperature of said 2nd process is 100-150 degreeC.

  The electrode surface modification coating agent provided for the first step is at least selected from the group consisting of a thioester compound, a carbonate ester compound, a phosphate ester compound, a sulfate ester compound, and a carbonate ester compound as a solvent. It is preferable that one is dissolved or dispersed.

［一般式［３］中、Ｍはホウ素原子、リン原子又はケイ素原子を表し、ｍは１〜３、ｎは１〜４、ｐは０又は１である。Ｒ^１は炭素数が３〜１０のアルキレン基、炭素数が３〜１０のハロゲン化アルキレン基、炭素数が６〜２０のアリーレン基、又は炭素数が６〜２０のハロゲン化アリーレン基（これらの基はその構造中に置換基を含有してもよいし、ヘテロ原子を含有してもよい。また、ｍが２以上の場合、ｍ個存在するＲ^１はそれぞれが互いに結合していてもよい）を表し、Ｒ^２はハロゲン原子を表し、Ｘ^１、Ｘ^２はそれぞれ互いに独立して酸素原子又は硫黄原子を表し、Ｘ^３は炭素原子又は硫黄原子を表す。ｑは、Ｘ^３が炭素原子の場合は１、硫黄原子の場合は１又は２である。Ａ^ａ＋はアルカリ金属カチオン、アルカリ土類金属カチオン、又はオニウムカチオンを表し、ａは該当するカチオンの価数を表す。ａ〜ｄは１又は２であり、かつ、ａ×ｂ＝ｃ×ｄを満たす。］

［一般式［４］中、Ａ^ａ＋はアルカリ金属カチオン、アルカリ土類金属カチオン、又はオニウムカチオンを表し、ａは該当するカチオンの価数を表す。ａ〜ｄは１又は２であり、かつ、ａ×ｂ＝ｃ×ｄを満たす。］

［一般式［５］中、Ｘは（−ＣＨ_２−）_ｒ、−ＣＨ（ＣＨ_３）−、−Ｃ（ＣＨ_３）_２−、−ＣＦ_２−、−Ｃ（ＣＦ_３）_２−、及び−Ｃ（Ｃ_６Ｈ_５）_２−からなる群から選ばれる基であり、ｒは１〜４のいずれかである。Ｚ^１及びＺ^２は、それぞれ独立で、水素原子、−ＣＦ_３基、及び−ＣＨ_２ＣＦ_３基からなる群から選ばれる基である。］

［一般式［６］中、
Ｄはハロゲンイオン、ヘキサフルオロリン酸アニオン、テトラフルオロホウ酸アニオン、ビス（トリフルオロメタンスルホニル）イミドアニオン、ビス（フルオロスルホニル）イミドアニオン、（フルオロスルホニル）（トリフルオロメタンスルホニル）イミドアニオン、ビス（ジフルオロホスホニル）イミドアニオンから選ばれる少なくとも一つであり、
Ｆはフッ素であり、
Ｍは１３族元素（Ａｌ、Ｂ）、１４族元素（Ｓｉ）及び１５族元素（Ｐ、Ａｓ、Ｓｂ）からなる群から選ばれるいずれか１つであり
Ｏは酸素であり、
Ｎは窒素である。
Ｙは炭素又は硫黄であり、Ｙが炭素である場合ｑは１であり、Ｙが硫黄である場合ｑは１又は２である。
Ｘは炭素又は硫黄であり、Ｘが炭素である場合ｒは１であり、Ｘが硫黄である場合ｒは１又は２である。
Ｒ^１は炭素数１〜１０の環やヘテロ原子やハロゲン原子を有していてもよい炭化水素基（炭素数が３以上の場合にあっては、分岐鎖あるいは環状構造のものも使用できる）、又は−Ｎ（Ｒ^２）−を表す。このとき、Ｒ^２は水素、アルカリ金属、炭素数１〜１０の環やヘテロ原子やハロゲン原子を有していてもよい炭化水素基を表す。炭素数が３以上の場合にあっては、Ｒ^２は分岐鎖あるいは環状構造をとることもできる。
Ｒ^４、Ｒ^５はそれぞれ独立で炭素数１〜１０の環やヘテロ原子やハロゲン原子を有していてもよい炭化水素基であり、炭素数が３以上の場合にあっては、分岐鎖あるいは環状構造のものも使用できる。また、下記一般式［７］の様にお互いを含む環状構造を有しても良い。

ｃは０又は１であり、ｎが１の場合、ｃは０（ｃが０のときＤは存在しない）であり、ｎが２の場合、ｃは１となる。
ｏは２又は４、ｎは１又は２、ｐは０又は１、ｑは１又は２、ｒは１又は２、ｓは０又は１である。ｐが０の場合、Ｙ−Ｘ間に直接結合を形成する。
ｓが０の場合、Ｎ（Ｒ^４）（Ｒ^５）とＲ^１は直接結合し、その際は下記の［８］〜［１１］のような構造をとることもできる。直接結合が二重結合となる［９］、［１１］の場合、Ｒ^５は存在しない。また［１０］の様に二重結合が環の外に出た構造を取ることも出来る。この場合のＲ^６、Ｒ^７はそれぞれ独立で水素、又は炭素数１〜１０の環やヘテロ原子やハロゲン原子を有していてもよい炭化水素基であり、炭素数が３以上の場合にあっては、分岐鎖あるいは環状構造のものも使用できる。］

In the electrode surface modification coating agent provided in the first step, at least one selected from compounds represented by the following general formulas [3] to [6] is dissolved or dispersed in at least a solvent. It is preferably included.

[In General Formula [3], M represents a boron atom, a phosphorus atom, or a silicon atom, m is 1-3, n is 1-4, and p is 0 or 1. R ¹ is an alkylene group having 3 to 10 carbon atoms, a halogenated alkylene group having 3 to 10 carbon atoms, an arylene group having 6 to 20 carbon atoms, or a halogenated arylene group having 6 to 20 carbon atoms (these The group may contain a substituent or a hetero atom in the structure, and when m is 2 or more, m R ^{1 s} may be bonded to each other. R ² represents a halogen atom, X ¹ and X ² each independently represent an oxygen atom or a sulfur atom, and X ³ represents a carbon atom or a sulfur atom. q is 1 when X ³ is a carbon atom, and 1 or 2 when X ³ is a sulfur atom. A ^{a +} represents an alkali metal cation, an alkaline earth metal cation, or an onium cation, and a represents the valence of the corresponding cation. a to d are 1 or 2, and a × b = c × d is satisfied. ]

[In General Formula [4], A ^{a +} represents an alkali metal cation, an alkaline earth metal cation, or an onium cation, and a represents the valence of the corresponding cation. a to d are 1 or 2, and a × b = c × d is satisfied. ]

[In the general formula [5], X represents (—CH ₂ —) _r , —CH (CH ₃ ) —, —C (CH ₃ ) ₂ —, —CF ₂ —, —C (CF ₃ ) ₂ —, and It is a group selected from the group consisting of —C (C ₆ H ₅ ) ₂ —, and r is any one of 1 to 4. Z ¹ and Z ² are each independently a group selected from the group consisting of a hydrogen atom, a —CF ₃ group, and a —CH ₂ CF ₃ group. ]

[In the general formula [6],
D is a halogen ion, hexafluorophosphate anion, tetrafluoroborate anion, bis (trifluoromethanesulfonyl) imide anion, bis (fluorosulfonyl) imide anion, (fluorosulfonyl) (trifluoromethanesulfonyl) imide anion, bis (difluorophospho Nyl) imide anion,
F is fluorine,
M is any one selected from the group consisting of Group 13 elements (Al, B), Group 14 elements (Si), and Group 15 elements (P, As, Sb), O is oxygen,
N is nitrogen.
Y is carbon or sulfur. When Y is carbon, q is 1. When Y is sulfur, q is 1 or 2.
X is carbon or sulfur, r is 1 when X is carbon, and r is 1 or 2 when X is sulfur.
R ¹ is a hydrocarbon group which may have a ring having 1 to 10 carbon atoms, a hetero atom or a halogen atom (in the case of 3 or more carbon atoms, a branched chain or cyclic structure can be used) , or -N ^{(R 2)} - represents a. At this time, R ² represents hydrogen, an alkali metal, a hydrocarbon group which may have a ring having 1 to 10 carbon atoms, a hetero atom, or a halogen atom. When the number of carbon atoms is 3 or more, R ² can also take a branched chain or a cyclic structure.
R ⁴ and R ⁵ are each independently a hydrocarbon group optionally having a ring having 1 to 10 carbon atoms, a heteroatom, or a halogen atom. If the number of carbon atoms is 3 or more, a branched chain or An annular structure can also be used. Moreover, you may have a cyclic structure containing each other like following General formula [7].

When c is 0 or 1, when n is 1, c is 0 (D is not present when c is 0), and when n is 2, c is 1.
o is 2 or 4, n is 1 or 2, p is 0 or 1, q is 1 or 2, r is 1 or 2, and s is 0 or 1. When p is 0, a direct bond is formed between Y and X.
When s is 0, N (R ⁴ ) (R ⁵ ) and R ¹ are directly bonded, and in this case, the following structures [8] to [11] can be taken. In the case of [9] and [11] in which the direct bond is a double bond, R ⁵ does not exist. Moreover, it can also take the structure where the double bond went out of the ring like [10]. In this case, R ⁶ and R ⁷ are each independently hydrogen, or a hydrocarbon group that may have a ring having 1 to 10 carbon atoms, a hetero atom, or a halogen atom. For example, a branched chain or cyclic structure can be used. ]

  Moreover, it is preferable that the total amount of the compounds represented by the above general formulas [3] to [6] is 20 to 100% by mass out of the total amount of 100% by mass of the solid content in the electrode surface modification coating agent. .

  In the present invention, at least one selected from the group consisting of a thioester compound, a carbonate ester compound, a phosphate ester compound, a sulfate ester compound, and a carbonate ester compound is dissolved or dispersed in the solvent. An electrode surface modification coating agent for forming a film by coating and heating on the surface of an electrode that is a constituent member of a nonaqueous electrolyte battery.

［一般式［３］中、Ｍはホウ素原子、リン原子又はケイ素原子を表し、ｍは１〜３、ｎは１〜４、ｐは０又は１である。Ｒ^１は炭素数が３〜１０のアルキレン基、炭素数が３〜１０のハロゲン化アルキレン基、炭素数が６〜２０のアリーレン基、又は炭素数が６〜２０のハロゲン化アリーレン基（これらの基はその構造中に置換基を含有してもよいし、ヘテロ原子を含有してもよい。また、ｍが２以上の場合、ｍ個存在するＲ^１はそれぞれが互いに結合していてもよい）を表し、Ｒ^２はハロゲン原子を表し、Ｘ^１、Ｘ^２はそれぞれ互いに独立して酸素原子又は硫黄原子を表し、Ｘ^３は炭素原子又は硫黄原子を表す。ｑは、Ｘ^３が炭素原子の場合は１、硫黄原子の場合は１又は２である。Ａ^ａ＋はアルカリ金属カチオン、アルカリ土類金属カチオン、又はオニウムカチオンを表し、ａは該当するカチオンの価数を表す。ａ〜ｄは１又は２であり、かつ、ａ×ｂ＝ｃ×ｄを満たす。］

［一般式［４］中、Ａ^ａ＋はアルカリ金属カチオン、アルカリ土類金属カチオン、又はオニウムカチオンを表し、ａは該当するカチオンの価数を表す。ａ〜ｄは１又は２であり、かつ、ａ×ｂ＝ｃ×ｄを満たす。］

［一般式［５］中、Ｘは（−ＣＨ_２−）_ｒ、−ＣＨ（ＣＨ_３）−、−Ｃ（ＣＨ_３）_２−、−ＣＦ_２−、−Ｃ（ＣＦ_３）_２−、及び−Ｃ（Ｃ_６Ｈ_５）_２−からなる群から選ばれる基であり、ｒは１〜４のいずれかである。Ｚ^１及びＺ^２は、それぞれ独立で、水素原子、−ＣＦ_３基、及び−ＣＨ_２ＣＦ_３基からなる群から選ばれる基である。］

［一般式［６］中、
Ｄはハロゲンイオン、ヘキサフルオロリン酸アニオン、テトラフルオロホウ酸アニオン、ビス（トリフルオロメタンスルホニル）イミドアニオン、ビス（フルオロスルホニル）イミドアニオン、（フルオロスルホニル）（トリフルオロメタンスルホニル）イミドアニオン、ビス（ジフルオロホスホニル）イミドアニオンから選ばれる少なくとも一つであり、
Ｆはフッ素であり、
Ｍは１３族元素（Ａｌ、Ｂ）、１４族元素（Ｓｉ）及び１５族元素（Ｐ、Ａｓ、Ｓｂ）からなる群から選ばれるいずれか１つであり
Ｏは酸素であり、
Ｎは窒素である。
Ｙは炭素又は硫黄であり、Ｙが炭素である場合ｑは１であり、Ｙが硫黄である場合ｑは１又は２である。
Ｘは炭素又は硫黄であり、Ｘが炭素である場合ｒは１であり、Ｘが硫黄である場合ｒは１又は２である。
Ｒ^１は炭素数１〜１０の環やヘテロ原子やハロゲン原子を有していてもよい炭化水素基（炭素数が３以上の場合にあっては、分岐鎖あるいは環状構造のものも使用できる）、又は−Ｎ（Ｒ^２）−を表す。このとき、Ｒ^２は水素、アルカリ金属、炭素数１〜１０の環やヘテロ原子やハロゲン原子を有していてもよい炭化水素基を表す。炭素数が３以上の場合にあっては、Ｒ^２は分岐鎖あるいは環状構造をとることもできる。
Ｒ^４、Ｒ^５はそれぞれ独立で炭素数１〜１０の環やヘテロ原子やハロゲン原子を有していてもよい炭化水素基であり、炭素数が３以上の場合にあっては、分岐鎖あるいは環状構造のものも使用できる。また、下記一般式［７］の様にお互いを含む環状構造を有しても良い。

ｃは０又は１であり、ｎが１の場合、ｃは０（ｃが０のときＤは存在しない）であり、ｎが２の場合、ｃは１となる。
ｏは２又は４、ｎは１又は２、ｐは０又は１、ｑは１又は２、ｒは１又は２、ｓは０又は１である。ｐが０の場合、Ｙ−Ｘ間に直接結合を形成する。
ｓが０の場合、Ｎ（Ｒ^４）（Ｒ^５）とＲ^１は直接結合し、その際は下記の［８］〜［１１］のような構造をとることもできる。直接結合が二重結合となる［９］、［１１］の場合、Ｒ^５は存在しない。また［１０］の様に二重結合が環の外に出た構造を取ることも出来る。この場合のＲ^６、Ｒ^７はそれぞれ独立で水素、又は炭素数１〜１０の環やヘテロ原子やハロゲン原子を有していてもよい炭化水素基であり、炭素数が３以上の場合にあっては、分岐鎖あるいは環状構造のものも使用できる。］

The electrode surface modification coating agent may contain at least one selected from the compounds represented by the following general formulas [3] to [6] dissolved or dispersed in a solvent. preferable.

[In General Formula [3], M represents a boron atom, a phosphorus atom, or a silicon atom, m is 1-3, n is 1-4, and p is 0 or 1. R ¹ is an alkylene group having 3 to 10 carbon atoms, a halogenated alkylene group having 3 to 10 carbon atoms, an arylene group having 6 to 20 carbon atoms, or a halogenated arylene group having 6 to 20 carbon atoms (these The group may contain a substituent or a hetero atom in the structure, and when m is 2 or more, m R ^{1 s} may be bonded to each other. R ² represents a halogen atom, X ¹ and X ² each independently represent an oxygen atom or a sulfur atom, and X ³ represents a carbon atom or a sulfur atom. q is 1 when X ³ is a carbon atom, and 1 or 2 when X ³ is a sulfur atom. A ^{a +} represents an alkali metal cation, an alkaline earth metal cation, or an onium cation, and a represents the valence of the corresponding cation. a to d are 1 or 2, and a × b = c × d is satisfied. ]

[In General Formula [4], A ^{a +} represents an alkali metal cation, an alkaline earth metal cation, or an onium cation, and a represents the valence of the corresponding cation. a to d are 1 or 2, and a × b = c × d is satisfied. ]

[In the general formula [5], X represents (—CH ₂ —) _r , —CH (CH ₃ ) —, —C (CH ₃ ) ₂ —, —CF ₂ —, —C (CF ₃ ) ₂ —, and It is a group selected from the group consisting of —C (C ₆ H ₅ ) ₂ —, and r is any one of 1 to 4. Z ¹ and Z ² are each independently a group selected from the group consisting of a hydrogen atom, a —CF ₃ group, and a —CH ₂ CF ₃ group. ]

[In the general formula [6],
D is a halogen ion, hexafluorophosphate anion, tetrafluoroborate anion, bis (trifluoromethanesulfonyl) imide anion, bis (fluorosulfonyl) imide anion, (fluorosulfonyl) (trifluoromethanesulfonyl) imide anion, bis (difluorophospho Nyl) imide anion,
F is fluorine,
M is any one selected from the group consisting of Group 13 elements (Al, B), Group 14 elements (Si), and Group 15 elements (P, As, Sb), O is oxygen,
N is nitrogen.
Y is carbon or sulfur. When Y is carbon, q is 1. When Y is sulfur, q is 1 or 2.
X is carbon or sulfur, r is 1 when X is carbon, and r is 1 or 2 when X is sulfur.
R ¹ is a hydrocarbon group which may have a ring having 1 to 10 carbon atoms, a hetero atom or a halogen atom (in the case of 3 or more carbon atoms, a branched chain or cyclic structure can be used) , or -N ^{(R 2)} - represents a. At this time, R ² represents hydrogen, an alkali metal, a hydrocarbon group which may have a ring having 1 to 10 carbon atoms, a hetero atom, or a halogen atom. When the number of carbon atoms is 3 or more, R ² can also take a branched chain or a cyclic structure.
R ⁴ and R ⁵ are each independently a hydrocarbon group optionally having a ring having 1 to 10 carbon atoms, a heteroatom, or a halogen atom. If the number of carbon atoms is 3 or more, a branched chain or An annular structure can also be used. Moreover, you may have a cyclic structure containing each other like following General formula [7].

When c is 0 or 1, when n is 1, c is 0 (D is not present when c is 0), and when n is 2, c is 1.
o is 2 or 4, n is 1 or 2, p is 0 or 1, q is 1 or 2, r is 1 or 2, and s is 0 or 1. When p is 0, a direct bond is formed between Y and X.
When s is 0, N (R ⁴ ) (R ⁵ ) and R ¹ are directly bonded, and in this case, the following structures [8] to [11] can be taken. In the case of [9] and [11] in which the direct bond is a double bond, R ⁵ does not exist. Moreover, it can also take the structure where the double bond went out of the ring like [10]. In this case, R ⁶ and R ⁷ are each independently hydrogen, or a hydrocarbon group that may have a ring having 1 to 10 carbon atoms, a hetero atom, or a halogen atom. For example, a branched chain or cyclic structure can be used. ]

  Of the total amount of solids in the electrode surface modification coating agent of 100% by mass, the total amount of the compounds represented by the general formulas [3] to [6] is preferably 20 to 100% by mass.

In the manufacture of conventional non-aqueous electrolyte batteries, gas is generated in the electrolyte along with the electrolysis after the battery is assembled, so it was necessary to degas to avoid the increase in the internal pressure of the battery. ,
In the present invention, by assembling a battery using a surface-modified electrode that has been surface-modified by previously forming a film on the electrode surface, an increase in internal pressure due to electrolysis of the battery after assembly can be suppressed.
As a result, the degassing operation that has conventionally been required can be omitted, and the productivity of the non-aqueous electrolyte battery can be improved.

  Hereinafter, the present invention will be described in detail. However, the description of the constituent elements described below is an example of an embodiment of the present invention, and the specific contents thereof are not limited. Various modifications can be made within the scope of the gist.

[About the first step]
(1) Coating agent for electrode surface modification Non-water used in the method for producing a surface modified electrode for a nonaqueous electrolyte battery of the present invention and the method for producing a nonaqueous electrolyte battery using the surface modified electrode The coating agent for modifying the electrode surface of the electrode for an electrolyte battery preferably contains at least one selected from a solvent and a compound represented by the above general formulas [3] to [6].

中でも、熱分解に伴う被膜形成のし易さの観点から、上記の［３−１］、［３−３］、［３−４］、及び［３−５］が特に好ましい。 Examples of the compound represented by the general formula [3] include [3-1] to [3-5]. [3-3] and [3-4] are structural isomers, [3-3] represents a trans isomer, and [3-4] represents a cis isomer.

Among them, the above [3-1], [3-3], [3-4], and [3-5] are particularly preferable from the viewpoint of easy film formation accompanying thermal decomposition.

As the compound represented by the general formula [4], [4-1] is particularly preferable.

中でも、熱分解性の観点から、［５−１］が特に好ましい。 Examples of the compound represented by the general formula [5] include [5-1] to [5-4].

Among these, [5-1] is particularly preferable from the viewpoint of thermal decomposability.

中でも、非水電解液電池のサイクル特性が高まる点で、（６−Ｐ１）、（６−Ｐ２）、（６−Ｐ４）、（６−Ｐ７）、（６−Ｂ１）、（６−Ｂ２）、（６−Ｂ６）、（６−Ｂ７）及び（６−Ｂ９）からなる群から選ばれるいずれか１つであることが好ましい。なお、該サイクル特性向上の効果の強さは、６−Ｐ１＞＞６−Ｐ２＞６−Ｂ９、６−Ｂ６＞＞６−Ｐ４である。そのため、６−Ｐ１が特に好ましい。 Examples of the compound represented by the general formula [6] include [6-P1] to [6-P9], [6-B1] to [6-B9], and the like.

Among these, (6-P1), (6-P2), (6-P4), (6-P7), (6-B1), (6-B2) is the point that the cycle characteristics of the nonaqueous electrolyte battery are enhanced. , (6-B6), (6-B7) and (6-B9) are preferred. The strength of the effect of improving the cycle characteristics is 6-P1 >>6-P2> 6-B9, 6-B6 >> 6-P4. Therefore, 6-P1 is particularly preferable.

  As solid content contained in the coating agent for electrode surface modification, compounds other than the compounds represented by the general formulas [3] to [6] can be included. Of the total solid content of 100% by mass, the total amount of the compounds represented by the above general formulas [3] to [6] is preferably 20 to 100% by mass. When the content is less than 20% by mass, the film formation by the compound is not sufficiently performed, and an effect of suppressing an increase in internal pressure due to electrolysis of the battery after assembly (that is, generation of decomposition gas of the electrolyte due to electrolysis) is obtained. hard. More preferably, it is 50 mass% or more, and it is especially preferable that it is 80 mass% or more.

As compounds other than the compounds represented by the general formulas [3] to [6], for example, a polymerizable compound may be contained. Examples of the polymerizable compound include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, n-propyl methacrylate, isopropyl acrylate, isopropyl methacrylate, n-butyl acrylate, n-butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, Acrylamide, methacrylamide, N-methylolacrylamide, N-methylolmethacrylamide, diacetoneacrylamide, acrylonitrile, methacrylonitrile, styrene, vinyl fluoride, vinylidene fluoride, trifluoroethylene, chlorotrifluoroethylene, tetrafluoroethylene, hexa Fluoropropylene, norbornene, 1-methylnorbornene, 5-methylno Borene, 5-ethylnorbornene, 5,6-dimethylnorbornene, 7-methylnorbornene, 5,5,6-trimethylnorbornene, tricyclo [4.3.0.12.5] -3-decene, tricyclo [4.4 0.12.5] -3-undecene, tetracyclo [4.4.0.12.5. 17.10] -3-dodecene, 8-methyltetracyclo [4.4.0.12.5. 17.10] -3-dodecene, 2-hydroxyethyl acrylate, hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 3- (trimethoxysilyl) propyl acrylate, 3-chloro-2-hydroxypropyl methacrylate, 2- (hydroxymethyl) ethyl acrylate, 2-hydroxyethyl methacrylate, hydroxypropyl methacrylate, 3- (trimethoxysilyl) propyl methacrylate, 3- [tris (trimethylsilyloxy) silyl] propyl methacrylate, methacrylic acid 2 -(Trimethylsilyloxy) ethyl, 3- (triethoxysilyl) propyl methacrylate, allyltriethoxysilane, allyltrimethoxysilane, 3- (acryloxy) propyltrimethoxysilane, [bicyclo [2.2.1] To-5-en-2-yl] triethoxysilane, vinyltrimethoxysilane, triethoxyvinylsilane, vinyltris (2-methoxyethoxy) silane, N- [2- (N-vinylbenzylamino) ethyl] -3-amino Propyltrimethoxysilane hydrochloride, allyltrichlorosilane, trichlorovinylsilane, 3-methyl-1-penten-4-in-3-ol, 2- (furfurylthio) ethylamine, trans-aconitic acid, acrylic acid, 4-aminocinnamic Acid, angelic acid, 2-acetamidoacrylic acid, 3-butene-1,2,3-tricarboxylic acid, 2-bromocinnamic acid, 4-bromocrotonic acid, 2-benzylacrylic acid, caffeic acid, 4-chloro Cinnamic acid, trans-cinnamic acid, citraconic acid, trans-p-coumaric acid, trans-o-coumaric acid, trans-m-coumaric acid, crotonic acid, α-cyanocinnamic acid, 1-cyclohexene-1-carboxylic acid, 1-cyclopentenecarboxylic acid, α-cyano-4-hydroxycinnamic acid, Traumatic acid, trans-2-decenoic acid, 3,4-dimethoxycinnamic acid, trans-2,3-dimethoxycinnamic acid, trans-2,5-dichlorocinnamic acid, fumaric acid, monoethyl fumarate, trans 2-hexenoic acid, 2-heptenoic acid, monomethyl itaconic acid, maleic acid monoamide, mesaconic acid, methacrylic acid, 4-methyl-2-pentenoic acid, trans, trans-muconic acid, mucobromic acid, mucochloroic acid, 3-methyl Crotonic acid, 4-methoxycinnamic acid, succinic acid mono (2-acryloyloxyethyl), 3- (5- Tro-2-furyl) acrylic acid, 3- (3-pyridyl) acrylic acid, α-phenylcinnamic acid, shikimic acid, tiglic acid, 2-thiophene acrylic acid, 2- (trifluoromethyl) acrylic acid, 3- (Trifluoromethyl) cinnamic acid, 4- (trifluoromethyl) cinnamic acid, 2- (trifluoromethyl) cinnamic acid, allyl mercaptan, allyl glycidyl ether, 1,3-butadiene monoepoxide, 1, 2-epoxy-5-hexene, 1,2-epoxy-9-decene, allobarbital, 1,9-decadiene, 1,11-dodecadiene, dicyclopentadiene, 2,5-dimethyl-1,5-hexadiene, di Isopropylideneacetone, 2,3-dimethyl-1,3-butadiene, diethyl diallylmalonate, 1,3-dibenzylidene-2-cycl Lohexanone, 2,6-dimethyl-2,4,6-octatriene, 1,5,9-decatriene, 9,10-epoxy-1,5-cyclododecadiene, farnesyl acetate, geranyl-linalool, geranyl nitrile, 1,5-hexadiene, 1,4-hexadiene, 1,5-hexadiene-3,4-diol, isoprene, (±) -limonene, myrcene, methylcyclopentadiene, 2,5-norbornadiene, 1,7-octadiene, Monoethyl fumarate, ethyl hydrogen maleate, monooctyl maleate, monomethyl maleate, monoisopropyl fumarate, mono (2-acryloyloxyethyl) succinate, 6-acrylamidohexanoic acid, allylamine, 1-allyl-2-thiourea 1-allyl-3- (2-hydroxyethyl) 2-thiourea, allylurea, methyl 3-aminocrotonate, 3-amino-5,5-dimethyl-2-cyclohexen-1-one, S-allyl-L-cysteine, 3-amino-4,4,4 -Ethyl trifluorocrotonate, 3-amino-2-cyclohexen-1-one, 3-benzalbutyramide, crotonamide, cinnamic acid amide, 2- (1-cyclohexenyl) ethylamine, glycidyl methacrylate, vinylene carbonate , Polyethylene glycol diacrylate (for example, Shin-Nakamura Chemical Co., Ltd., product name: A-200, A-400, A-600), urethane acrylate (for example, Shin-Nakamura Chemical Co., Ltd., product name: UA- 122P, UA-4HA, UA-6HA, UA-6LPA, UA-1100H, UA-53H, UA-42 00, UA-200PA, UA-33H, UA-7100, UA-7200). In the present invention, these compounds may be used alone or in combination of two or more.
When a polymerizable compound is contained, azobisisobutyronitrile, tert-butyl peroxypivalate, di-tert-butyl peroxide, i-butyryl peroxide, lauroyl peroxide, succinic acid peroxide, dicinnami A radical polymerization initiator such as luperoxide, di-n-propyl peroxydicarbonate, tert-butylperoxyallyl monocarbonate, benzoyl peroxide, hydrogen peroxide, or ammonium persulfate may be further contained.

  The solvent used for the electrode surface modification coating agent is not particularly limited as long as it is a nonaqueous solvent capable of dissolving the compounds represented by the above general formulas [3] to [6]. , Esters, ethers, lactones, nitriles, imides, sulfones and the like can be used. Moreover, not only a single solvent but 2 or more types of mixed solvents may be sufficient. Specific examples include ethyl methyl carbonate, dimethyl carbonate, diethyl carbonate, methyl propyl carbonate, ethyl propyl carbonate, methyl butyl carbonate, ethylene carbonate, propylene carbonate, butylene carbonate, methyl acetate, ethyl acetate, methyl propionate, ethyl propionate, Diethyl ether, acetonitrile, propionitrile, tetrahydrofuran, 2-methyltetrahydrofuran, furan, tetrahydropyran, 1,3-dioxane, 1,4-dioxane, dibutyl ether, diisopropyl ether, 1,2-dimethoxyethane, N, N- Examples thereof include dimethylformamide, dimethyl sulfoxide, sulfolane, γ-butyrolactone, and γ-valerolactone.

  Moreover, it is preferable that the said solvent contains at least 1 sort (s) chosen from the group which consists of a cyclic carbonate and a chain carbonate. Examples of the cyclic carbonate include ethylene carbonate and propylene carbonate, and examples of the chain carbonate include ethyl methyl carbonate, dimethyl carbonate, diethyl carbonate, and methyl propyl carbonate.

  The concentration of the solid content of the electrode surface modification coating agent is preferably 1 to 30% by mass, more preferably 2 to 20% by mass, from the viewpoint of ease of application and film formation.

(2) Electrode The electrode for applying the electrode surface modification coating agent is not particularly limited as long as it contains an electrode active material. For example, when the cation in the non-aqueous electrolyte is lithium, the positive electrode is not particularly limited, but alkali metal ions such as lithium ions and sodium ions, or alkaline earth metal ions such as magnesium ions are reversible. A material capable of insertion and desorption is used, and the negative electrode active material is not particularly limited, but alkali metal ions such as lithium ions and sodium ions, or alkaline earth metal ions such as magnesium ions are reversibly inserted. A removable material is used.

As the positive electrode active material, for example, when the cation in the non-aqueous electrolyte is lithium, it contains at least one metal of nickel, manganese, cobalt such as LiCoO ₂ , LiNiO ₂ , LiMnO ₂ , and has a layered structure Lithium-containing transition metal composite oxides, and those obtained by mixing a plurality of transition metals such as Co, Mn, Ni, etc. of these lithium-containing transition metal composite oxides (LiNi _0.8 Co _0.2 O ₂ , LiNi _0.33 Co _0.33 Mn _0.33 O ₂ etc.), in which a part of the transition metal of the lithium-containing transition metal composite oxide is replaced with a metal other than the transition metal (LiNi _0.85 Co _0.10 Al _0.05 O ₂ etc.), LiMn ₂ O ₄ and LiMn _1.95 Al _0.05 O ₄ etc. Lithium-containing olivine-type phosphates of transition metals such as FePO ₄ , LiCoPO ₄ , LiMnPO ₄ , oxides such as TiO ₂ , V ₂ O ₅ , MoO ₃ , sulfides such as TiS ₂ and FeS, or polyacetylene, polypara Conductive polymers such as phenylene, polyaniline, and polypyrrole, activated carbon, polymers that generate radicals, carbon materials, and the like are used.
In the case the cation of the non-aqueous electrolytic solution of the _{sodium, NaFeO 2, NaCrO 2, NaNiO} 2, NaMnO 2, NaCoO sodium-containing transition metal composite oxides such as _2, Fe of their sodium-containing transition metal composite oxide , A mixture of a plurality of transition metals such as Cr, Ni, Mn, Co, etc., a transition metal in which a transition metal of the sodium-containing transition metal composite oxide is partially substituted with a metal other than the transition metal, Na ₂ FeP Transition metal phosphate compounds such as ₂ O ₇ and NaCo ₃ (PO ₄ ) ₂ P ₂ O ₇ , sulfides such as TiS ₂ and FeS, or conductive polymers such as polyacetylene, polyparaphenylene, polyaniline, and polypyrrole Activated carbon, polymers that generate radicals, carbon materials, and the like.

As the negative electrode active material, for example, when the cation in the non-aqueous electrolyte is lithium, various carbon materials capable of inserting and extracting lithium metal, alloys of lithium and other metals, intermetallic compounds, and lithium Oxide of one or more metals selected from Si, Sn, Al, one or more metals selected from Si, Sn, Al, alloys containing these metals, alloys of these metals or alloys with lithium, lithium titanium Oxides, metal nitrides, activated carbon, conductive polymers and the like are used. Examples of the carbon material include amorphous carbon (for example, non-graphitizable carbon (also called hard carbon) and coke) whose (002) plane spacing exceeds 0.34 nm, and (002) plane spacing. Is 0.34 nm or less, and the latter is artificial graphite, natural graphite, or the like. Examples of one or more metals selected from Si, Sn, and Al, alloys containing these metals, or alloys of these metals or alloys and lithium include metals such as silicon, tin, and aluminum, silicon alloys, tin alloys, and aluminum alloys. A material in which these metals and alloys are alloyed with lithium along with charge and discharge can also be used. Examples of the lithium titanium oxide include lithium titanate having a spinel structure and lithium titanate having a ramsdellite structure.
When the cation in the non-aqueous electrolyte is sodium, hard carbon, oxides such as TiO ₂ , V ₂ O ₅ , and MoO ₃ are used.

  Next, a method for manufacturing the electrode will be described. In addition, a binder (binder) is contained in the electrode used as the object which apply | coats the coating agent for electrode surface modification by this invention.

For example, when producing an electrode using a positive electrode active material, a positive electrode active material is mixed with a conductive agent and a binder (binder) as necessary to prepare a positive electrode mixture, and N-methyl-2- A positive electrode mixture slurry is prepared by dispersing in a dispersion medium such as pyrrolidone. This positive electrode mixture slurry is applied to a positive electrode current collector such as aluminum or an aluminum alloy, dried, and compression molded to obtain a positive electrode.
The conductive agent is not limited to a specific conductive agent as long as it is conventionally used in this type of non-aqueous electrolyte battery. For example, carbon materials such as carbon powder and carbon fiber can be used. As the carbon powder, various carbon blacks (for example, acetylene black, furnace black, ketjen black, etc.), carbon powders such as graphite powder can be used. Among these, you may use together 1 type, or 2 or more types.
As said binder, the thing similar to the binder used for the positive electrode of a common nonaqueous electrolyte battery can be employ | adopted suitably. For example, when a positive electrode mixture slurry dispersed in N-methyl-2-pyrrolidone is used for producing a positive electrode, a polymer material that is dissolved or dispersed in an organic solvent (non-aqueous solvent) can be preferably used. Examples of the polymer material dissolved or dispersed in an organic solvent (non-aqueous solvent) include polyvinylidene fluoride (PVDF) and polyvinylidene chloride (PVDC). Alternatively, polymeric materials that dissolve or disperse in water can be used.

For example, when producing an electrode using a negative electrode active material, a negative electrode active material is mixed with a binder and a thickener as necessary to prepare a negative electrode mixture, and water or N-methyl-2- A negative electrode mixture slurry is prepared by dispersing in a dispersion medium such as pyrrolidone. This negative electrode mixture slurry is applied to a negative electrode current collector such as copper, dried, and compression molded to obtain a negative electrode.
As said binder, the thing similar to the binder used for the negative electrode of a common nonaqueous electrolyte battery can be employ | adopted suitably. For example, when a negative electrode mixture slurry dispersed in water is used to form a negative electrode, a polymer material that dissolves or disperses in water can be preferably used. Examples of the polymer material dispersed in water include styrene butadiene rubber (SBR), polyethylene oxide (PEO), and vinyl acetate copolymer. When a negative electrode mixture slurry dispersed in N-methyl-2-pyrrolidone is used to form a negative electrode, an organic solvent (non-aqueous solvent) such as polyvinylidene fluoride (PVDF) or polyvinylidene chloride (PVDC) is used. ) Can be used.
As the thickener, a polymer material that is dissolved or dispersed in water or an organic solvent (non-aqueous solvent) can be used. Examples of polymer materials that dissolve in water include cellulose polymers such as carboxymethyl cellulose (CMC), methyl cellulose (MC), cellulose acetate phthalate (CAP), and hydroxypropylmethyl cellulose (HPMC); polyvinyl alcohol (PVA); Can be mentioned.

(3) Coating method As a method of coating the electrode surface modifying coating agent on the surface of the electrode, a technique similar to a conventionally known method can be appropriately employed. For example, by using an appropriate coating apparatus such as a slit coater, a die coater, a gravure coater, a dip coater, or a spin coater, the electrode surface modification coating agent can be suitably coated on the surface of the electrode.

[About the second step]
In the second step, the electrode surface modification coating agent on the electrode after the first step is heated at 80 to 150 ° C. to form a film on the surface of the electrode to obtain a surface modified electrode. The heating in the second step is performed until the following formula [1] is satisfied.
(A-B2) × 100 / (A-B1) ≧ 50 [1]
here,
Amount of coating A: Calculated value of the solid content of the coating agent for electrode surface modification coated on the electrode after the first step (ie, the mass of the coating agent for electrode surface modification coated on the electrode × electrode surface modification) Solid content concentration of coating agent for quality)
Coating mass B1: As a sample test, measured value of coating mass obtained when heated at 150 ° C. for 1 hour in atmospheric pressure as the second step Coating mass B2: Actually heated at 80 to 150 ° C. as the second step Measured value of the coating film mass

When the electrode surface modification coating agent on the electrode after the first step is heated at 150 ° C. in atmospheric pressure for 1 hour, the solvent in the electrode surface modification coating agent is volatilized and the electrode surface modification coating is performed. The solid content in the agent is sufficiently pyrolyzed and a good quality film is formed on the electrode. By the above thermal decomposition, the solid content (component derived from) of the electrode surface modification coating agent is reduced by a predetermined amount. Although details are unknown, it is considered that the mass reduction is caused by gas generation and volatilization of decomposition components.
The above formula [1] is
As a sample test, with respect to the mass (A-B1) of the solid content of the electrode surface modification coating agent reduced by thermal decomposition when heated at 150 ° C. in atmospheric pressure for 1 hour,
Mass of solid content of electrode surface modification coating agent decreased by thermal decomposition when actually heated at 80 to 150 ° C. as second step (A-B2)
Means that the ratio (% by mass) is 50 (%) or more,
When the surface-modified electrode having a ratio of 50 (%) or more is used, an increase in internal pressure due to electrolysis of the battery after assembly (that is, generation of decomposition gas of the electrolyte due to electrolysis) can be suppressed. Since the conventional degassing operation can be omitted, the productivity of the nonaqueous electrolyte battery can be improved.

  When heated at 80 to 150 ° C. as the second step, the solvent in the electrode surface modifying coating applied on the electrode volatilizes and the solid content in the electrode surface modifying coating is decomposed. Pyrolysis accompanied with gas generation forms a film on the surface of the electrode. In addition, when actually heating at 80-150 degreeC as a 2nd process, you may be under atmospheric pressure, may be under pressure, and may be under pressure reduction. Furthermore, it may be performed in the air, may be performed in an inert atmosphere, or may be performed while flowing a predetermined gas.

It is more preferable to perform the heating in the second step until the following formula [2] is satisfied.
50 ≦ (A−B2) × 100 / (A−B1) ≦ 100 [2]
here,
The coating amount A, the coating mass B1, and the coating mass B2 are the same as those in the formula [1].
The above equation [2] is
As a sample test, with respect to the mass (A-B1) of the solid content of the electrode surface modification coating agent reduced by thermal decomposition when heated at 150 ° C. in atmospheric pressure for 1 hour,
Mass of solid content of electrode surface modification coating agent decreased by thermal decomposition when actually heated at 80 to 150 ° C. as second step (A-B2)
It means that the ratio (mass%) is 50 to 100 (%).
When the surface-modified electrode having a ratio of 50 (%) or more is used, an increase in internal pressure due to electrolysis of the battery after assembly (that is, generation of decomposition gas of the electrolyte due to electrolysis) can be suppressed. Since the conventional degassing operation can be omitted, the productivity of the nonaqueous electrolyte battery can be improved. Moreover, when this ratio exceeds 100 (%), there exists a possibility that the solid content (component derived from) of the coating agent for electrode surface modification may decompose | disassemble too much and battery performance may be reduced. It is more preferable to actually heat at 80 to 150 ° C. as the second step until the above ratio becomes 53 to 100 (%).

  If the heating temperature is less than 80 ° C., the thermal decomposition of the electrode surface modification coating agent on the electrode after the first step does not proceed sufficiently. Further, if the heating temperature is higher than 150 ° C., the phenomenon of melting of the electrode binder such as PVDF is remarkably caused, resulting in a decrease in electrode performance and an increase in the amount of gas generated at the initial charge. The heating temperature of 100 to 150 ° C. is more preferable because the electrode surface modification coating agent can be effectively decomposed without breaking the electrode structure.

  As the heating method, a technique similar to a conventionally known heating method can be appropriately employed. For example, a film is formed on the surface of the electrode by thermally decomposing the electrode surface modification coating agent with hot air, low-humidity air, etc. in the atmosphere such as air or in an inert gas atmosphere such as nitrogen or argon gas. Can do. In addition, although the solvent in the electrode surface modification coating agent is evaporated and removed by the heating (second step), the solvent may be decomposed by heating or may partially remain on the electrode. Moreover, although the solid content in the electrode surface modification coating agent is thermally decomposed with the generation of a decomposition gas by the heating (second step), a part may remain on the electrode as it is.

Here, the film described above may be formed on the entire surface of the electrode, or may be formed on a part thereof. For example, in a positive electrode having a structure in which a positive electrode current collector is coated with a positive electrode active material layer containing a positive electrode active material, if the above-described coating is formed on all or part of the surface of the positive electrode active material layer Good. Further, when the positive electrode contains a particulate positive electrode active material, it is sufficient that the above-described coating is formed on the whole or a part of the surface, and the coating is formed on the whole or a part of the particulate positive electrode active material. It only has to be formed.
Similarly, in a negative electrode having a structure in which a negative electrode current collector is coated with a negative electrode active material layer containing a negative electrode active material, the above-described coating is formed on all or part of the surface of the negative electrode active material layer. That's fine. Further, when the negative electrode contains a particulate negative electrode active material, it is sufficient that the above-described coating is formed on all or part of the surface, and the coating is formed on the whole or part of the particulate negative electrode active material. It only has to be formed.
Moreover, it is preferable that the thickness of a film is 200 nm or less, for example. If the film thickness is greater than 200 nm, the electrode resistance may increase.

[About the third step]
In the third step, a non-aqueous electrolyte battery including at least the surface modified electrode obtained in the second step, the non-aqueous electrolyte, and the separator is assembled. In that case, the said surface modification electrode is used for any one of a positive electrode and a negative electrode at least. Examples of other components include a positive electrode, a negative electrode, an electrolytic solution, a separator, and a container that are used in general non-aqueous electrolyte batteries.

  The non-aqueous electrolyte battery electrolyte is generally called a non-aqueous electrolyte if a non-aqueous solvent is used, and is called a polymer solid electrolyte if a polymer is used. The polymer solid electrolyte includes those containing a non-aqueous solvent as a plasticizer.

  This non-aqueous electrolyte battery electrolyte, a negative electrode material capable of reversibly inserting and removing alkali metal ions such as lithium ions and sodium ions, or alkaline earth metal ions, lithium ions and sodium An electrochemical device using a positive electrode material into which alkali metal ions such as ions or alkaline earth metal ions can be reversibly inserted and removed is called a non-aqueous electrolyte battery.

  The solute used in the non-aqueous electrolyte is not particularly limited, and a salt composed of an arbitrary cation and anion pair can be used. Specific examples include alkali metal ions such as lithium ions and sodium ions, alkaline earth metal ions, quaternary alkylammonium ions, etc. as cations. Examples of anions include hexafluorophosphoric acid, tetrafluoroboric acid, peroxides. Chloric acid, hexafluoroarsenic acid, hexafluoroantimonic acid, trifluoromethanesulfonic acid, bis (trifluoromethanesulfonyl) imide, bis (pentafluoroethanesulfonyl) imide, (trifluoromethanesulfonyl) (pentafluoroethanesulfonyl) imide, bis ( Fluorosulfonyl) imide, (trifluoromethanesulfonyl) (fluorosulfonyl) imide, (pentafluoroethanesulfonyl) (fluorosulfonyl) imide, tris (trifluoromethanesulfo Le) methide include anions such as bis (difluoromethyl phosphonate) imide. One kind of these solutes may be used alone, or two or more kinds of solutes may be mixed and used in any combination and ratio according to the application. Among them, considering the energy density, output characteristics, life, etc. of the battery, the cation is lithium, sodium, magnesium, quaternary alkyl ammonium, and the anion is hexafluorophosphoric acid, tetrafluoroboric acid, bis (trifluoromethanesulfonyl) imide. Bis (fluorosulfonyl) imide and bis (difluorophosphonyl) imide are preferable.

  The non-aqueous solvent is not particularly limited as long as it is an aprotic solvent capable of dissolving the electrolyte and the additive, and examples thereof include carbonates, esters, ethers, lactones, nitriles, imides, sulfones. Can be used. Moreover, not only a single solvent but 2 or more types of mixed solvents may be sufficient. Specific examples include ethyl methyl carbonate, dimethyl carbonate, diethyl carbonate, methyl propyl carbonate, ethyl propyl carbonate, methyl butyl carbonate, ethylene carbonate, propylene carbonate, butylene carbonate, methyl acetate, ethyl acetate, methyl propionate, ethyl propionate, Diethyl ether, acetonitrile, propionitrile, tetrahydrofuran, 2-methyltetrahydrofuran, furan, tetrahydropyran, 1,3-dioxane, 1,4-dioxane, dibutyl ether, diisopropyl ether, 1,2-dimethoxyethane, N, N- Examples thereof include dimethylformamide, dimethyl sulfoxide, sulfolane, γ-butyrolactone, and γ-valerolactone.

  Moreover, it is preferable that a nonaqueous solvent contains at least 1 sort (s) chosen from the group which consists of a cyclic carbonate and a chain carbonate. Examples of the cyclic carbonate include ethylene carbonate and propylene carbonate, and examples of the chain carbonate include ethyl methyl carbonate, dimethyl carbonate, diethyl carbonate, and methyl propyl carbonate.

  The surface-modified electrode may be used after being washed with the non-aqueous solvent before assembling the non-aqueous electrolyte battery.

  Furthermore, as long as the gist of the present invention is not impaired, an additive generally used in the non-aqueous electrolyte may be added and contained in an arbitrary ratio. Specific examples include cyclohexylbenzene, biphenyl, tert-butylbenzene, vinylene carbonate, vinylethylene carbonate, ethynylethylene carbonate, tert-amylbenzene, biphenyl, o-terphenyl, 4-fluorobiphenyl, fluorobenzene, 2,4- Difluorobenzene, difluoroanisole, fluoroethylene carbonate, propane sultone, 1,3-propene sultone, dimethyl vinylene carbonate, methylene methane disulfonate, dimethylene methane disulfonate, trimethylene methane disulfonate, the above general formulas [3] to [3] 6] and the like, compounds having an effect of preventing overcharge, an effect of forming a negative electrode film, and an effect of protecting the positive electrode are included. Moreover, it is also possible to use the non-aqueous electrolyte battery electrolyte in a quasi-solid state with a gelling agent or a crosslinked polymer, as in the case of use in a non-aqueous electrolyte battery called a polymer battery.

  As the separator for preventing the contact between the positive electrode and the negative electrode, a polyolefin such as polypropylene or polyethylene, a nonwoven fabric made of paper, glass fiber, or the like, or a porous sheet is used. These films are preferably microporous so that the electrolyte can penetrate and ions can easily pass therethrough.

  Examples of the polyolefin separator include a membrane that electrically insulates the positive electrode and the negative electrode and allows lithium ions to pass therethrough, such as a microporous polymer film such as a porous polyolefin film. As a specific example of the porous polyolefin film, for example, a porous polyethylene film alone or a porous polyethylene film and a porous polypropylene film may be overlapped and used as a multilayer film. Moreover, the film etc. which compounded the porous polyethylene film and the polypropylene film are mentioned.

  From the above elements, an electrochemical device having a shape such as a coin shape, a cylindrical shape, a square shape, or an aluminum laminate sheet shape is assembled.

Hereinafter, specific experimental results will be described.
In the following examples, specific compound names and numerical values are described for explanation, but the present invention is not limited to these.

  Although the synthesis example of the coating agent for electrode surface modification is shown below, it is also possible to synthesize by other methods. Any raw material or product was handled in a nitrogen atmosphere with a dew point of −50 ° C. or lower. The glass reactor used was one that had been dried at 150 ° C. for 12 hours or more and then cooled to room temperature under a nitrogen stream having a dew point of −50 ° C. or less.

[Synthesis Example 1 of Electrode Surface Modification Coating Agent] Synthesis of Electrode Surface Modification Coating Agent 1 According to the method disclosed in Japanese Patent Application Laid-Open No. 2003-137890, lithium tetrafluoroborate and oxalic acid were mixed with silicon tetrachloride. Dissolving lithium difluorooxalatoborate (the above-mentioned compound [3-1]) synthesized by reacting in the presence in an ethylmethyl carbonate (hereinafter referred to as EMC) solvent to a concentration of 2% by mass. Thus, a coating agent 1 for electrode surface modification was obtained.

[Synthesis Example 2 of Electrode Surface Modification Coating Agent] Synthesis of Electrode Surface Modification Coating Agent 2 According to the method disclosed in International Publication No. 2010/071097, lithium hexafluorophosphate and oxalic acid were mixed with silicon tetrachloride. The trans isomer of lithium difluorobis (oxalato) phosphate (the above-mentioned compound [3-3]) synthesized by reacting in the presence of crystallization and further purification by crystallization was added to an EMC solvent at a concentration of 2% by mass. The electrode surface modification coating agent 2 was obtained by dissolving in such a manner.

[Synthesis Example 3 of Electrode Surface Modification Coating Agent] Synthesis of Electrode Surface Modification Coating Agent 3 According to the method disclosed in International Publication No. 2010/071097, lithium hexafluorophosphate and oxalic acid were mixed with silicon tetrachloride. The cis-form of the difluorobis (oxalato) lithium phosphate (the above-mentioned compound [3-4]), which was synthesized by reacting in the presence of water and further purified by crystallization, was dissolved in an EMC solvent at a concentration of 2% by mass. The electrode surface modification coating agent 3 was obtained by dissolving in such a manner.

[Synthesis Example 4 of Electrode Surface Modification Coating Agent] Synthesis of Electrode Surface Modification Coating Agent 4 According to the method disclosed in Japanese Patent No. 4695802, after reacting phosphorus pentachloride with oxalic acid, lithium hydride was added. Electrode surface modification by dissolving lithium tris (oxalato) phosphate (the above-mentioned compound [3-5]) synthesized by adding and reacting in an EMC solvent to a concentration of 2% by mass Coating agent 4 was obtained.

[Synthesis Example 5 of Electrode Surface Modification Coating Agent] Synthesis of Electrode Surface Modification Coating Agent 5 According to the method disclosed in Japanese Patent Application Laid-Open No. 2008-222484, halides other than lithium hexafluorophosphate, water, and fluoride. The electrode surface modification coating agent 5 is obtained by dissolving lithium difluorophosphate synthesized as described above (the above-mentioned compound [4-1]) in an ethyl acetate solvent to a concentration of 2% by mass. Got.

[Synthesis Example 6 of Electrode Surface Modification Coating Agent] Synthesis of Electrode Surface Modification Coating Agent 6 According to the method disclosed in Japanese Patent No. 5247436, methanedisulfonic acid, water, and paraformaldehyde were present in the presence of diphosphorus pentoxide. The methylenemethane disulfonate (the above-mentioned compound [5-1]) synthesized by reacting under the above condition is dissolved in an EMC solvent so as to have a concentration of 2% by mass, whereby an electrode surface modification coating agent 6 is obtained. Got.

[Synthesis Example 7 of Electrode Surface Modification Coating Agent] Synthesis of Electrode Surface Modification Coating Agent Tetrafluoride synthesized by reacting lithium picolinate with phosphorus pentafluoride and further crystallization and purification. (Pyridinium-2-carboxylato-κN, κO) phosphoric acid (the above-mentioned compound [6-P1]) is dissolved in an EMC solvent so as to have a concentration of 2% by mass, thereby applying a coating agent for electrode surface modification. 7 was obtained.

  A method for producing a positive electrode and a negative electrode for testing is shown below.

[Preparation of NMC positive electrode]
Mixing 90% by mass of LiNi _1/3 Mn _1/3 Co _1/3 O ₂ powder with 5% by mass of polyvinylidene fluoride (hereinafter PVDF) (binder) and 5% by mass of acetylene black (conductive material), N-methylpyrrolidone (hereinafter referred to as NMP) was added to produce a positive electrode mixture paste. This paste was applied onto an aluminum foil (current collector), dried and pressurized, and then punched into a predetermined size to obtain a test NMC positive electrode.

[Preparation of NaFe _0.5 Co _0.5 O ₂ Positive Electrode]
85% by mass of NaFe _0.5 Co _0.5 O ₂ powder, 5% by mass of PVDF (binder) and 10% by mass of acetylene black (conductive material) are mixed, and NMP is further added to produce a positive electrode mixture paste. did. This paste was applied onto an aluminum foil (current collector), dried and pressurized, and then punched out to a predetermined size to obtain a test NaFe _0.5 Co _0.5 O ₂ positive electrode.

[Preparation of NCA positive electrode]
LiNi _0.85 Co _0.10 Al _0.05 O ₂ (NCA) powder (manufactured by Toda Kogyo Co., Ltd.) and acetylene black (conductive agent) as a lithium / nickel / cobalt / aluminum composite oxide are dry-mixed and used as a binder. A certain PVDF was uniformly dispersed in previously dissolved NMP, mixed, and NMP for viscosity adjustment was further added to prepare an NCA mixture paste. This paste was applied on an aluminum foil (current collector), dried and pressurized, and then a test NCA positive electrode processed into a predetermined size was obtained. The solid content ratio in the positive electrode was NCA: conductive agent: PVDF = 85: 5: 10 (mass ratio).

[Production of LMO positive electrode]
LiMn _1.95 Al _0.05 O ₄ (LMO) powder and acetylene black (conductive agent) are dry-mixed as a lithium manganese composite oxide, and uniformly dispersed in NMP in which PVDF as a binder is dissolved beforehand. Then, NMP for viscosity adjustment was further added to prepare an LMO mixture paste. This paste was applied on an aluminum foil (current collector), dried and pressurized, and then a test LMO positive electrode processed into a predetermined size was obtained. The solid content ratio in the positive electrode was LMO: conductive agent: PVDF = 85: 5: 10 (mass ratio).

[Production of LFP positive electrode]
LiFePO ₄ (LFP) powder, acetylene black (conductive agent 1), and vapor grown carbon fiber (VGCF (registered trademark) -H manufactured by Showa Denko) (conductive agent 2) as a lithium-containing olivine-type phosphate The mixture was mixed, uniformly dispersed in NMP in which PVDF as a binder was previously dissolved, mixed, and NMP for viscosity adjustment was further added to prepare an LFP mixture paste. This paste was applied on an aluminum foil (current collector), dried and pressurized, and then a test LFP positive electrode processed into a predetermined size was obtained. The solid content ratio in the positive electrode was LFP: conductive agent 1: conductive agent 2: PVDF = 85: 4: 1: 10 (mass ratio).

[Production of graphite negative electrode]
90% by mass of graphite powder was mixed with 10% by mass of PVDF as a binder, and NMP was further added to prepare a negative electrode mixture paste. This paste was applied on a copper foil (current collector), dried and pressurized to obtain a sheet-like graphite negative electrode.

[Production of hard carbon negative electrode]
90% by mass of hard carbon powder was mixed with 10% by mass of PVDF as a binder, and NMP was further added to prepare a negative electrode mixture paste. This paste was applied on a copper foil (current collector), dried and pressurized, and then punched into a predetermined size to obtain a test hard carbon negative electrode.

[Production of amorphous carbon anode]
As amorphous carbon powder, Kaboha Co., Ltd. Carbotron (registered trademark) P is used, and PVDF as a binder is uniformly dispersed and mixed in NMP previously dissolved, and further NMP for viscosity adjustment is added. In addition, an amorphous carbon mixture paste was prepared. This paste was applied onto a copper foil (current collector), dried and pressurized, and then an amorphous carbon negative electrode for testing processed into a predetermined size was obtained. The solid content ratio in the negative electrode was amorphous carbon powder: PVDF = 90: 10 (mass ratio).

[Production of (artificial graphite + natural graphite mixed) negative electrode]
SCMG (registered trademark) -AR powder manufactured by Showa Denko KK as artificial graphite and natural graphite particles (average particle diameter of 25 μm) manufactured by Kansai Thermochemical Co., Ltd. as natural graphite, and PVDF as a binder are dissolved in advance. The mixture was uniformly dispersed and mixed in NMP, and NMP for viscosity adjustment was further added to prepare a mixture paste of (artificial graphite + natural graphite). This paste was applied on a copper foil (current collector), dried and pressurized, and then a test (artificial graphite + natural graphite mixed) negative electrode processed into a predetermined size was obtained. The solid content ratio in the negative electrode was artificial graphite powder: natural graphite powder: PVDF = 72: 18: 10 (mass ratio).

[Preparation of SiO _x negative electrode]
As silicon oxide powder, silicon oxide powder disproportionated by heat treatment (SiO _x (x is 0.3 to 1.6) manufactured by Sigma-Aldrich Japan, average particle diameter 5 μm), Hitachi Using a mixed powder of MAG-D (particle size of 20 μm or less) manufactured by Kasei Kogyo Co., Ltd., uniformly dispersing it in NMP in which PVDF, which is a binder, was previously dissolved, and adding ketjen black (conductive agent) and mixing. Further, NMP for viscosity adjustment was added to prepare a SiO _x mixture paste. This paste was applied on a copper foil (current collector), dried and pressurized, and then a test SiO _x negative electrode processed into a predetermined size was obtained. The solid content ratio in the negative electrode was SiO _x : MAG-D: conductive agent: PVDF = 35: 47: 8: 10 (mass ratio).
The amount of the positive electrode active material and the SiO _x powder is adjusted so that the charge capacity of the SiO _x negative electrode is larger than the charge capacity of the positive electrode, and applied so that lithium metal does not deposit on the SiO _x negative electrode during charging. The amount was also adjusted.

[Preparation of Si negative electrode]
As Si powder, Si powder (average particle size: 10 μm / 6 μm = mixed powder with a mass ratio of 9/1) is used, and uniformly dispersed in NMP in which PVDF as a binder is previously dissolved. (Conductive agent 1) and vapor grown carbon fiber (Showa Denko VGCF (registered trademark) -H) (conductive agent 2) were added and mixed, and NMP for viscosity adjustment was further added to prepare a Si mixture paste. . This paste was applied onto a copper foil (current collector), dried and pressurized, and then a test Si negative electrode processed into a predetermined size was obtained. The solid content ratio in the negative electrode was Si powder: conductive agent 1: conductive agent 2: PVDF = 78: 7: 3: 12 (mass ratio).
The amount of positive electrode active material and Si powder is adjusted so that the charge capacity of the Si negative electrode is larger than the charge capacity of the positive electrode, and the coating amount is also adjusted so that lithium metal does not deposit on the Si negative electrode during charging. did.

[Preparation of Sn negative electrode]
Sn powder having an average particle diameter of 10 μm was used as Sn powder, and was uniformly dispersed in NMP in which PVDF as a binder was previously dissolved. Further, graphite (KS-15 made by Lonza) (conductive agent 1) and air Phase method carbon fiber (Showa Denko VGCF (registered trademark) -H) (conductive agent 2) was added and mixed, and NMP for viscosity adjustment was further added to prepare Sn mixture paste. This paste was applied on a copper foil (current collector), dried and pressurized, and then a test Sn negative electrode processed into a predetermined size was obtained. The solid content ratio in the negative electrode was Sn powder: conductive agent 1: conductive agent 2: PVDF = 78: 8: 3: 11 (mass ratio).
The amount of the positive electrode active material and the Sn powder is adjusted so that the charge capacity of the Sn negative electrode is larger than the charge capacity of the positive electrode, and the coating amount is also adjusted so that lithium metal does not deposit on the Sn negative electrode during the charge. did.

[Preparation of Sn alloy negative electrode]
For the production of the Sn alloy negative electrode for this test, the procedure described in JP-A-2008-016424 was followed. That is, the raw material Co · Sn alloy powder and the carbon powder were mixed at a predetermined ratio, and the total amount of the charged powder was 10 g and dry-mixed. This mixture was set together with about 400 g of steel balls having a diameter of 9 mm in a reaction vessel of a planetary ball mill. The inside of the reaction vessel was replaced with an argon atmosphere, and the operation of 10 minutes of operation and the pause of 10 minutes at a rotation speed of 250 revolutions per minute was repeated until the total operation time reached 20 hours. Thereafter, the composition of the negative electrode active material powder synthesized by cooling the reaction vessel to room temperature was analyzed. As a result, the Sn content was 49.5% by mass, the Co content was 29.7% by mass, and the carbon content was The amount was 20.8% by mass, the ratio of Co to the total of Sn and Co, and Co / (Sn + Co) was 37.5% by mass.
The carbon content was measured by a carbon / sulfur analyzer, and the Sn and Co contents were measured by ICP-MS (inductively coupled plasma mass spectrometry).
Using this negative electrode active material, PVDF as a binder was uniformly dispersed in NMP previously dissolved, and further Ketjen black (conductive agent 1) and vapor grown carbon fiber (VGCF (registered trademark) manufactured by Showa Denko) -H) (conductive agent 2) was added and mixed, and NMP for viscosity adjustment was further added to prepare a Sn alloy mixture paste.
This paste was applied on a copper foil (current collector), dried and pressurized, and then a test Sn alloy negative electrode processed into a predetermined size was obtained.
The solid content ratio in the negative electrode was Co / Sn alloy powder: conductive agent 1: conductive agent 2: PVDF = 80: 7: 3: 10 (mass ratio).
The amount of the positive electrode active material and the Sn alloy powder is adjusted so that the charge capacity of the Sn alloy negative electrode is larger than the charge capacity of the positive electrode, and applied so that lithium metal does not deposit on the Sn alloy negative electrode during charging. The amount was also adjusted.

[Production of LTO negative electrode]
As Li ₄ Ti ₅ O ₁₂ (LTO) powder, LTO powder (average particle size: 0.90 μm / 3.40 μm = mixed powder with a mass ratio of 9/1) was used, and PVDF as a binder was dissolved in advance. Disperse uniformly in NMP, add ketjen black (conductive agent 1) and vapor-grown carbon fiber (Showa Denko VGCF (registered trademark) -H) (conductive agent 2), mix, and further adjust viscosity NMP was added to prepare an LTO mixture paste.
This paste was applied on a copper foil (current collector), dried and pressurized, and then a test LTO negative electrode processed into a predetermined size was obtained. The solid content ratio in the negative electrode was LTO powder: conductive agent 1: conductive agent 2: PVDF = 83: 5: 2: 10 (mass ratio).
The amount of positive electrode active material and LTO powder is adjusted so that the charge capacity of the LTO negative electrode is larger than the charge capacity of the positive electrode, and the coating amount is also adjusted so that lithium metal does not deposit on the LTO negative electrode during charging. did.

[Example of preparation of surface modified NMC positive electrode]
On the test NMC positive electrode, the electrode surface modification coating agents 1 to 7 are applied using a slit coater, and the second step described in Table 1 below is performed in a thermostatic chamber under an air atmosphere. A surface-modified NMC positive electrode was obtained by heating under heating conditions.
The progress of thermal decomposition by heating in the second step is shown in Table 1 as the value of equation [1], that is, the value of (A−B2) × 100 / (A−B1).
here,
Amount of coating A: Calculated as 2% of the mass of the electrode surface modifying coating applied on the electrode.
Coating mass B1: As a sample test, the mass of the coating obtained when heated at 150 ° C. in atmospheric pressure for 1 hour as the second step was determined by measurement.
Film mass B2: The mass of the film obtained when heated at 50 ° C., 90 ° C., 110 ° C., 150 ° C., and 200 ° C. was actually measured as the second step. (The film thickness of the film obtained at this time was also measured)

[Production Example of Surface Modified NaFe _0.5 Co _0.5 O ₂ Positive Electrode]
Surface modified NaFe as shown in Table 2 by the same method as in the preparation of the surface modified NMC positive electrode except that the above test NaFe _0.5 Co _0.5 O ₂ positive electrode was used instead of the NMC positive electrode. _{A 0.5} Co _0.5 O ₂ positive electrode was obtained.

[Example of preparation of surface modified NCA cathode]
A surface modified NCA positive electrode was obtained as shown in Table 3 in the same manner as in the preparation example of the surface modified NMC positive electrode except that the above test NCA positive electrode was used instead of the NMC positive electrode.

[Example of preparation of surface modified LMO positive electrode]
A surface-modified LMO positive electrode was obtained as shown in Table 4 in the same manner as in the preparation of the surface-modified NMC positive electrode except that the test LMO positive electrode was used instead of the NMC positive electrode.

[Example of production of surface modified LFP positive electrode]
A surface-modified LFP positive electrode was obtained as shown in Table 5 by the same method as in the preparation example of the surface-modified NMC positive electrode except that the above test LFP positive electrode was used instead of the NMC positive electrode.

[Production example of surface modified graphite anode]
A surface-modified graphite negative electrode was obtained as shown in Table 6 by the same method as in the preparation example of the surface-modified NMC positive electrode, except that the test graphite negative electrode was used instead of the NMC positive electrode.

[Production example of surface modified hard carbon anode]
A surface-modified hard carbon negative electrode was obtained as shown in Table 7 in the same manner as in the preparation example of the surface-modified NMC positive electrode except that the test hard carbon negative electrode was used instead of the NMC positive electrode.

[Production example of surface-modified amorphous carbon anode]
A surface-modified amorphous carbon negative electrode was obtained as shown in Table 8 in the same manner as in the preparation of the surface-modified NMC positive electrode except that the test amorphous carbon negative electrode was used instead of the NMC positive electrode. It was.

[Example of surface modification (artificial graphite + natural graphite mixed) negative electrode]
Surface modified (artificial graphite) as shown in Table 9 in the same manner as in the preparation of the surface modified NMC positive electrode except that the above test (artificial graphite + natural graphite mixed) negative electrode was used instead of the NMC positive electrode. + Natural graphite mixed) Negative electrode (denoted as “mixed graphite” in the table) was obtained.

[Example of preparation of surface-modified SiO _x negative electrode]
A surface-modified SiO _x negative electrode was obtained as shown in Table 10 by the same method as in the preparation example of the surface-modified NMC positive electrode except that the test SiO _x negative electrode was used instead of the NMC positive electrode.

[Production example of surface-modified Si negative electrode]
A surface-modified Si negative electrode was obtained as shown in Table 11 by the same method as in the preparation example of the surface-modified NMC positive electrode except that the test Si negative electrode was used instead of the NMC positive electrode.

[Example of preparation of surface-modified Sn negative electrode]
A surface-modified Sn negative electrode was obtained as shown in Table 12 by the same method as in the preparation example of the surface-modified NMC positive electrode except that the test Sn negative electrode was used instead of the NMC positive electrode.

[Example of preparation of surface-modified Sn alloy negative electrode]
A surface-modified Sn alloy negative electrode was obtained as shown in Table 13 by the same method as in the preparation of the surface-modified NMC positive electrode except that the test Sn alloy negative electrode was used instead of the NMC positive electrode.

[Example of preparation of surface modified LTO negative electrode]
A surface-modified LTO negative electrode was obtained as shown in Table 14 in the same manner as in the preparation example of the surface-modified NMC positive electrode except that the test LTO negative electrode was used instead of the NMC positive electrode.

[Preparation of test electrolyte]
As shown in Table 15, the solute was mixed with a non-aqueous solvent so as to have a concentration of 1.0 mol / liter. 1 was obtained. In addition, the electrolytic solution No. 1 with respect to compound [3-1], [3-3], [3-4], [3-5], [4-1], [5-1], and [6-P1], respectively. By adding to a concentration of 0.2% by mass and stirring for 1 hour, the electrolyte No. for non-aqueous electrolyte battery was obtained. 2-8 were obtained. In the table, EMC is ethyl methyl carbonate, EC is ethylene carbonate, and LiPF ₆ is lithium hexafluorophosphate. The above electrolytic solution was prepared while maintaining the liquid temperature at 40 ° C. or lower.

[Examples 1-1 to 1-28, Comparative examples 1-1 to 1-22]
As shown in Table 16, the surface-modified NMC positive electrodes 1-1 to 1-6, 2-1 to 2-6, 3-1 to 3-6, 4-1 to 4-6, and 5-1 to 5 -6, 6-1 to 6-6, and 7-1 to 7-6, an electrode combining a test NMC positive electrode, a test graphite negative electrode, and microporous soaked with the electrolytes 1 to 8 Non-aqueous electrolyte batteries according to Examples 1-1 to 1-28 and Comparative Examples 1-1 to 1-22 by assembling an aluminum laminate exterior cell (capacity 30 mAh) including a separator made of a polypropylene-polyethylene two-layer film Got. In addition, the electrode was cut out and used in a size having a predetermined capacity.

First, using the produced cell, at an ambient temperature of 25 ° C., at a rate (3 mA) of 0.1 C (the rated capacity due to the discharge capacity of 1 hour rate is 1 C, the current value for discharging in 1 hour is the same hereinafter). The battery was charged at a constant current and a constant voltage up to a charge upper limit voltage of 4.3 V, and the gas generation amount (gas generation amount after initial charge) was evaluated by a buoyancy method using silicon oil. “Gas generation after initial charge” is shown in Table 16. Naturally, the smaller the amount of gas generated after the initial charge, the easier it is to avoid an increase in the internal pressure and swelling of the battery, and the degassing operation conventionally required in the manufacture of the battery can be omitted.
Thereafter, discharging is performed at a constant current of 0.2 C rate (6 mA) to a final discharge voltage of 3.0 V, and then charging is performed at a constant current and constant voltage at a charging upper limit voltage of 4.3 V and a 0.2 C rate (6 mA). A charge / discharge cycle of discharging to 3.0 V at a constant current of 0.2 C rate (6 mA) was repeated three times (conditioning operation).

After this conditioning, a charge / discharge test at an environmental temperature of 60 ° C. was performed. Charging is performed at a constant current / constant voltage charging at a 3C rate (90 mA) up to a charging upper limit voltage of 4.3V, and discharging is performed at a charging / discharging cycle in which discharging is performed at a 3C rate (90 mA) constant current up to a discharge end voltage of 3.0V. Repeated 500 times. In this evaluation, in consideration of safety and the like, the nonaqueous electrolyte battery was fixed during all evaluations.
Table 16 shows “capacity maintenance ratio after cycle” which is a value obtained by expressing the discharge capacity after 500 cycles as a percentage of the initial discharge capacity. The capacity retention rate after cycling in Table 16 is a relative value when the capacity retention rate after cycling of the battery according to Comparative Example 1-22 is set to 100. Naturally, the higher the post-cycle capacity retention rate, the longer the battery life, which is preferable.

  The amount of gas generated after the initial charge in Examples 1-1 to 1-28 using the surface-modified NMC positive electrode defined by the present invention is significantly reduced as compared with Comparative Example 1-22 using the NMC positive electrode. It has been confirmed. It is inferred that the coating formed on the NMC positive electrode by the surface modification suppressed the decomposition of the electrolytic solution.

  Moreover, the comparative example which remove | deviates from the heating conditions of the 2nd process of this invention is all the gas after initial charge compared with Examples 1-1 to 1-28 using the surface modification NMC positive electrode prescribed | regulated by this invention. It was confirmed that the generation amount was large and the effect of reducing the gas generation amount was insufficient (Comparison between Examples 1-1 to 1-4 and Comparative Examples 1-1 and 1-2, Example 1-5) To 1-8 and Comparative Examples 1-4 and 1-5, Examples 1-9 to 1-12 and Comparative Examples 1-7 and 1-8, and Examples 1-13 to 1-16 And Comparative Examples 1-10 and 1-11, Examples 1-17 to 1-20 and Comparative Examples 1-13 and 1-14, Examples 1-21 to 1-24 and Comparative Example 1 -16, comparison with 1-17, comparison between Examples 1-25 to 1-28 and Comparative Examples 1-19 and 1-20). When heating in the second step was performed at 50 ° C. for 1 hour, a coating with insufficient decomposition of the electrode surface modification coating agent was formed, and decomposition of the electrode surface modification coating agent that was unreacted at the first charge It is assumed that the amount of gas generated increased with this. Further, when the heating in the second step is performed at 200 ° C. for 1 hour, it is presumed that the gas generation amount increased because the electrode binder probably melted and the structure of the electrode was damaged.

  Compounds [3-1], [3-3], [3-4], [3-5], [4-1], [5-1] having a film forming effect on the electrode at the initial charge, and The comparative examples using [6-P1] containing electrolytes 2 to 8 each containing an additive and using the test NMC positive electrode as the positive electrode each use a coating agent for electrode surface modification containing the corresponding compound. Compared with the Example using the produced surface-modified NMC positive electrode, it was confirmed that all had a large amount of gas generation after the initial charge, and the effect of reducing the amount of gas generation was insufficient (Example 1). 1 to 1-4 and Comparative Example 1-3, Examples 1-5 to 1-8 and Comparative Example 1-6, Examples 1-9 to 1-12 and Comparative Example 1-9 Comparison, Examples 1-13 to 1-16 and Comparative Example 1-12, Examples 1-17 to 1-20 and Comparative Example 1-15, and Examples -21～1-24 a comparison with Comparative Example 1-18, the comparison of Comparative Example 1-21 to Example 1-25～1-28). In the above comparative example, it is surmised that the amount of gas generation increased due to the above-described compound present in the electrolytic solution as an additive and the electrolysis of the electrolytic solution.

  In addition, the capacity retention ratio after cycles in Examples 1-1 to 1-28 using the surface-modified NMC positive electrode defined in the present invention is an electrolytic solution to which a compound having a film forming effect on the electrode at the first charge is added. (Comparison between Examples 1-1 to 1-4 and Comparative Example 1-3, Examples 1-5 to 1-8 and Comparative Example 1-6) Comparison between Examples 1-9 to 1-12 and Comparative Example 1-9, Comparison between Examples 1-13 to 1-16 and Comparative Example 1-12, Examples 1-17 to 1- 20 and Comparative Example 1-15, Examples 1-21 to 1-24 and Comparative Example 1-18, and Examples 1-25 to 1-28 and Comparative Example 1-21). This is presumably because a good-quality film was formed on the electrode by thermally decomposing the electrode surface modification coating agent.

  Therefore, when the surface-modified NMC positive electrode defined in the present invention is used, gas generation due to electrolysis of the assembled battery is suppressed, and an increase in internal pressure can be suppressed. As a result, it is possible to improve the productivity of the non-aqueous electrolyte battery because it is possible to omit the degassing operation that has been conventionally required.

[Examples 2-1 to 2-28, Comparative examples 2-1 to 2-22]
[Examples 3-1 to 3-28, Comparative examples 3-1 to 3-22]
[Examples 4-1 to 4-28, Comparative examples 4-1 to 4-22]
[Examples 5-1 to 5-28, Comparative examples 5-1 to 5-22]
[Examples 6-1 to 6-28, Comparative Examples 6-1 to 6-22]
[Examples 7-1 to 7-28, Comparative examples 7-1 to 7-22]
[Examples 8-1 to 8-28, Comparative Examples 8-1 to 8-22]
[Examples 9-1 to 9-28, Comparative Examples 9-1 to 9-22]
[Examples 10-1 to 10-28, Comparative Examples 10-1 to 10-22]
[Examples 11-1 to 11-28, Comparative Examples 11-1 to 11-22]
[Examples 12-1 to 12-28, Comparative Examples 12-1 to 12-22]
[Examples 13-1 to 13-28, Comparative Examples 13-1 to 13-22]
[Examples 14-1 to 14-28, Comparative Examples 14-1 to 14-22]
As shown in Tables 17 to 29, Examples 1-1 to 1-28, Comparative Example 1 except that the types of electrodes (surface-modified positive electrode, surface-modified negative electrode, test positive electrode, test negative electrode) were changed. The non-aqueous electrolyte batteries according to the respective examples and comparative examples were prepared by the same method as -1 to 1-22, and the gas generation amount after the initial charge and the capacity retention rate after the cycle were determined by the same method. evaluated.
In Examples 2-1 to 2-28 and Comparative Examples 2-1 to 2-22, the charge upper limit voltage was 4.2 V, and the discharge end voltage was 2.7 V. Further, the post-cycle capacity retention rate in Table 17 is a relative value when the post-cycle capacity retention rate of the battery according to Comparative Example 2-22 is taken as 100.
In Examples 3-1 to 3-28 and Comparative Examples 3-1 to 3-22, the charging upper limit voltage was set to 4.2V. Further, the post-cycle capacity retention rate in Table 18 is a relative value when the post-cycle capacity retention rate of the battery according to Comparative Example 3-22 is 100.
In Examples 4-1 to 4-28 and Comparative Examples 4-1 to 4-22, the charging upper limit voltage was set to 4.2V. In addition, the capacity retention rate after cycling in Table 19 is a relative value when the capacity retention rate after cycling of the battery according to Comparative Example 4-22 is 100.
In Examples 5-1 to 5-28 and Comparative Examples 5-1 to 5-22, the charge upper limit voltage was 4.0 V and the discharge end voltage was 2.0 V. Further, the after-cycle capacity retention rate in Table 20 is a relative value when the after-cycle capacity retention rate of the battery according to Comparative Example 5-22 is taken as 100.
In Examples 6-1 to 6-28 and Comparative Examples 6-1 to 6-22, the post-cycle capacity retention rate in Table 21 was set to 100 after the cycle capacity retention rate of the battery according to Comparative Example 6-22. Relative value.
In Examples 7-1 to 7-28 and Comparative Examples 7-1 to 7-22, the charge upper limit voltage was 4.2 V, and the discharge end voltage was 2.7 V. Further, the post-cycle capacity retention rate in Table 22 is a relative value when the post-cycle capacity retention rate of the battery according to Comparative Example 7-22 is taken as 100.
In Examples 8-1 to 8-28 and Comparative Examples 8-1 to 8-22, the charge upper limit voltage was 4.2 V, and the discharge end voltage was 2.7 V. Further, the post-cycle capacity retention rate in Table 23 is a relative value when the post-cycle capacity retention rate of the battery according to Comparative Example 8-22 is taken as 100.
In Examples 9-1 to 9-28 and Comparative Examples 9-1 to 9-22, the charge upper limit voltage was 4.2 V, and the discharge end voltage was 2.7 V. Further, the post-cycle capacity retention rate in Table 24 is a relative value when the post-cycle capacity retention rate of the battery according to Comparative Example 9-22 is 100.
In Examples 10-1 to 10-28 and Comparative Examples 10-1 to 10-22, charging was performed at a 0.05 C rate (1.5 mA) to a charging upper limit voltage of 4.2 V, and the discharge end voltage was 2 .5V. Further, the post-cycle capacity retention rate in Table 25 is a relative value when the post-cycle capacity retention rate of the battery according to Comparative Example 10-22 is 100.
In Examples 11-1 to 11-28 and Comparative Examples 11-1 to 11-22, the battery was charged to a charge upper limit voltage of 4.2 V at a 0.05 C rate (1.5 mA). .5V. Further, the post-cycle capacity retention rate in Table 26 is a relative value when the post-cycle capacity retention rate of the battery according to Comparative Example 11-22 is 100.
In Examples 12-1 to 12-28 and Comparative Examples 12-1 to 12-22, the battery is charged to a charge upper limit voltage of 4.2 V at a 0.05 C rate (1.5 mA). .5V. The post-cycle capacity retention rate in Table 27 is a relative value when the post-cycle capacity retention rate of the battery according to Comparative Example 12-22 is 100.
In Examples 13-1 to 13-28 and Comparative Examples 13-1 to 13-22, the battery was charged to a charge upper limit voltage of 4.2 V at a 0.05 C rate (1.5 mA). .5V. Further, the post-cycle capacity retention rate in Table 28 is a relative value when the post-cycle capacity retention rate of the battery according to Comparative Example 13-22 is 100.
In Examples 14-1 to 14-28 and Comparative Examples 14-1 to 14-22, the charge upper limit voltage was 4.2 V, and the discharge end voltage was 2.7 V. Further, the post-cycle capacity retention rate in Table 29 is a relative value when the post-cycle capacity retention rate of the battery according to Comparative Example 14-22 is 100.
The above Examples and Comparative Examples showed the same tendency as Examples 1-1 to 1-28 and Comparative Examples 1-1 to 1-22. Therefore, even if the type of electrode to be surface-modified is changed, if the surface-modified electrode (surface-modified positive electrode, surface-modified negative electrode) defined in the present invention is used, the gas generated by the electrolysis of the assembled battery Generation | occurrence | production is suppressed and the raise of an internal pressure can be suppressed. As a result, it is possible to improve the productivity of the non-aqueous electrolyte battery because it is possible to omit the degassing operation that has been conventionally required.

As shown in Table 30, Examples 1-1 to 1-28 and Comparative Example 1-1 except that the types of electrodes (surface modified positive electrode, surface modified negative electrode, test positive electrode, test negative electrode) were changed. The non-aqueous electrolyte batteries according to the respective examples and comparative examples were produced by the same method as in ˜1-22, and the gas generation amount after the initial charge and the capacity retention rate after the cycle were evaluated by the same method. .
In Example 15-1 and Comparative Example 15-1, the charge upper limit voltage was 4.3 V and the discharge end voltage was 3.0 V. In addition, the capacity retention rate after cycle in Table 30 is a relative value when the capacity retention rate after cycle of the battery according to Comparative Example 15-1 is 100.
In Example 15-2 and Comparative Example 15-2, the charge upper limit voltage was 4.2 V, and the discharge end voltage was 2.7 V. In addition, the capacity retention rate after cycling in Table 30 is a relative value when the capacity retention rate after cycling of the battery according to Comparative Example 15-2 is 100.
In Example 15-3 and Comparative Example 15-3, the charge upper limit voltage was 4.2 V and the discharge end voltage was 2.7 V. Further, the capacity retention rate after cycle in Table 30 is a relative value when the capacity retention rate after cycle of the battery according to Comparative Example 15-3 is 100.
In Example 15-4 and Comparative Example 15-4, the charge upper limit voltage was 4.2 V, and the discharge end voltage was 2.7 V. Further, the post-cycle capacity retention rate in Table 30 is a relative value when the post-cycle capacity retention rate of the battery according to Comparative Example 15-4 is 100.
In Example 15-5 and Comparative Example 15-5, the battery was charged to a charge upper limit voltage of 4.2 V at a 0.05 C rate (1.5 mA), and the discharge end voltage was set to 2.5 V. Further, the post-cycle capacity retention rate in Table 30 is a relative value when the post-cycle capacity retention rate of the battery according to Comparative Example 15-5 is 100.
In Example 15-6 and Comparative Example 15-6, charging was performed at a 0.05 C rate (1.5 mA) to a charging upper limit voltage of 4.2 V, and a discharge final voltage was set to 2.5 V. Further, the post-cycle capacity retention rate in Table 30 is a relative value when the post-cycle capacity retention rate of the battery according to Comparative Example 15-6 is 100.
In Example 15-7 and Comparative Example 15-7, charging was performed at a 0.05 C rate (1.5 mA) to a charging upper limit voltage of 4.2 V, and a discharge final voltage was set to 2.5 V. Further, the post-cycle capacity retention rate in Table 30 is a relative value when the post-cycle capacity retention rate of the battery according to Comparative Example 15-7 is 100.
In Example 15-8 and Comparative Example 15-8, the battery was charged to a charge upper limit voltage of 4.2 V at a 0.05 C rate (1.5 mA), and the discharge end voltage was set to 2.5 V. Further, the post-cycle capacity retention rate in Table 30 is a relative value when the post-cycle capacity retention rate of the battery according to Comparative Example 15-8 is 100.
In Example 15-9 and Comparative Example 15-9, the charge upper limit voltage was 4.2 V, and the discharge end voltage was 2.7 V. Further, the post-cycle capacity retention rate in Table 30 is a relative value when the post-cycle capacity retention rate of the battery according to Comparative Example 15-9 is 100.
In Example 15-10 and Comparative Example 15-10, the charge upper limit voltage was 4.3 V, and the discharge end voltage was 3.0 V. Further, the post-cycle capacity retention rate in Table 30 is a relative value when the post-cycle capacity retention rate of the battery according to Comparative Example 15-10 is taken as 100.

In Examples 15-1 to 15-10 using the surface-modified positive electrode and the surface-modified negative electrode specified in the present invention, the amounts of gas generated after the initial charge were compared using the corresponding test positive electrode and test negative electrode, respectively. Compared with the example, a significant reduction effect of gas generation was confirmed. It is inferred that the coating formed on the positive electrode and the negative electrode by surface modification suppressed the decomposition of the electrolytic solution.
In addition, by using “a surface modified positive electrode and a surface modified negative electrode in combination”, “when using a surface modified positive electrode and a test negative electrode” or “when using a test positive electrode and a surface modified negative electrode” In comparison, an effect of reducing the amount of gas generated and improving the capacity retention rate after cycling was obtained (for example, comparison between Example 15-1, Example 1-3, and Example 6-3).

From the above results,
A battery using the surface-modified positive electrode and the surface-modified negative electrode defined in the present invention as at least one of the positive electrode and the negative electrode (hereinafter, sometimes referred to as “battery of the present invention”)
Compared to “conventional batteries” using positive and negative electrodes that are not surface modified,
The amount of gas generated after the initial charge is greatly reduced, and an increase in internal pressure can be suppressed.
As a result, it is possible to omit the degassing operation that is necessary in the production of the conventional battery, and thus it is possible to improve the productivity of the nonaqueous electrolyte battery.
Further, the battery of the present invention, in addition to the gas generation suppression effect described above,
As a result of a good quality film being formed on the electrode as the electrode surface modification coating agent is appropriately pyrolyzed,
Uses an electrolyte containing a compound that has a film-forming effect on the electrode during the initial charge as an additive, and uses the positive and negative electrodes that are not surface-modified. To do.
In addition, the battery which combined the above-mentioned positive electrode, negative electrode, and electrolyte solution shows an example of this invention, and it is confirmed that the battery of other combinations also shows the tendency of the same evaluation result. .

Claims (15)

at least,
Applying a coating agent for electrode surface modification containing an ester compound dissolved or dispersed in a solvent to the surface of an electrode for a nonaqueous electrolyte battery;
A second step of obtaining a surface-modified electrode by forming a film on the surface of the electrode by heating the electrode surface-modifying coating agent on the electrode after the first step at 80 to 150 ° C .;
Assembling a non-aqueous electrolyte battery comprising at least the surface-modified electrode, the non-aqueous electrolyte, and a separator;
Including
The method of manufacturing a non-aqueous electrolyte battery, wherein the heating in the second step is performed until the following formula [1] is satisfied.
(A-B2) × 100 / (A-B1) ≧ 50 [1]
here,
Application amount A: Calculated value of solid content of electrode surface modification coating agent applied on electrode after first step (ie, mass of electrode surface modification coating agent applied on electrode × electrode surface modification) Solid content concentration of quality coating agent)
Coating mass B1: As a sample test, measured value of coating mass obtained when heated at 150 ° C. for 1 hour in atmospheric pressure as the second step Coating mass B2: Actually heated at 80 to 150 ° C. as the second step Measured value of the coating film mass The method for producing a non-aqueous electrolyte battery according to claim 1, wherein the heating in the second step is performed until the following formula [2] is satisfied.
50 ≦ (A−B2) × 100 / (A−B1) ≦ 100 [2]
here,
The coating amount A, the coating mass B1, and the coating mass B2 are the same as those in the formula [1]. The method for producing a nonaqueous electrolyte battery according to claim 1 or 2, wherein the heating temperature in the second step is 100 to 150 ° C. The coating agent for electrode surface modification provided for the first step is at least one selected from the group consisting of a thioester compound, a carbonate ester compound, a phosphate ester compound, a sulfate ester compound, and a carbonate ester compound as a solvent. The method for producing a non-aqueous electrolyte battery according to any one of claims 1 to 3, wherein the non-aqueous electrolyte battery is contained by being dissolved or dispersed. The electrode surface modification coating agent provided for the first step includes at least one selected from the compounds represented by the following general formulas [3] to [6] dissolved or dispersed in a solvent. The method for producing a non-aqueous electrolyte battery according to claim 1, wherein the battery is a non-aqueous electrolyte battery.

[In General Formula [3], M represents a boron atom, a phosphorus atom, or a silicon atom, m is 1-3, n is 1-4, and p is 0 or 1. R ¹ is an alkylene group having 3 to 10 carbon atoms, a halogenated alkylene group having 3 to 10 carbon atoms, an arylene group having 6 to 20 carbon atoms, or a halogenated arylene group having 6 to 20 carbon atoms (these The group may contain a substituent or a hetero atom in the structure, and when m is 2 or more, m R ^{1 s} may be bonded to each other. R ² represents a halogen atom, X ¹ and X ² each independently represent an oxygen atom or a sulfur atom, and X ³ represents a carbon atom or a sulfur atom. q is 1 when X ³ is a carbon atom, and 1 or 2 when X ³ is a sulfur atom. A ^{a +} represents an alkali metal cation, an alkaline earth metal cation, or an onium cation, and a represents the valence of the corresponding cation. a to d are 1 or 2, and a × b = c × d is satisfied. ]

[In General Formula [4], A ^{a +} represents an alkali metal cation, an alkaline earth metal cation, or an onium cation, and a represents the valence of the corresponding cation. a to d are 1 or 2, and a × b = c × d is satisfied. ]

[In the general formula [5], X represents (—CH ₂ —) _r , —CH (CH ₃ ) —, —C (CH ₃ ) ₂ —, —CF ₂ —, —C (CF ₃ ) ₂ —, and It is a group selected from the group consisting of —C (C ₆ H ₅ ) ₂ —, and r is any one of 1 to 4. Z ¹ and Z ² are each independently a group selected from the group consisting of a hydrogen atom, a —CF ₃ group, and a —CH ₂ CF ₃ group. ]

[In the general formula [6],
D is a halogen ion, hexafluorophosphate anion, tetrafluoroborate anion, bis (trifluoromethanesulfonyl) imide anion, bis (fluorosulfonyl) imide anion, (fluorosulfonyl) (trifluoromethanesulfonyl) imide anion, bis (difluorophospho Nyl) imide anion,
F is fluorine,
M is any one selected from the group consisting of Group 13 elements (Al, B), Group 14 elements (Si), and Group 15 elements (P, As, Sb), O is oxygen,
N is nitrogen.
Y is carbon or sulfur. When Y is carbon, q is 1. When Y is sulfur, q is 1 or 2.
X is carbon or sulfur, r is 1 when X is carbon, and r is 1 or 2 when X is sulfur.
R ¹ is a hydrocarbon group which may have a ring having 1 to 10 carbon atoms, a hetero atom or a halogen atom (in the case of 3 or more carbon atoms, a branched chain or cyclic structure can be used) , or -N ^{(R 2)} - represents a. At this time, R ² represents hydrogen, an alkali metal, a hydrocarbon group which may have a ring having 1 to 10 carbon atoms, a hetero atom, or a halogen atom. When the number of carbon atoms is 3 or more, R ² can also take a branched chain or a cyclic structure.
R ⁴ and R ⁵ are each independently a hydrocarbon group optionally having a ring having 1 to 10 carbon atoms, a heteroatom, or a halogen atom. If the number of carbon atoms is 3 or more, a branched chain or An annular structure can also be used. Moreover, you may have a cyclic structure containing each other like following General formula [7].

When c is 0 or 1, when n is 1, c is 0 (D is not present when c is 0), and when n is 2, c is 1.
o is 2 or 4, n is 1 or 2, p is 0 or 1, q is 1 or 2, r is 1 or 2, and s is 0 or 1. When p is 0, a direct bond is formed between Y and X.
When s is 0, N (R ⁴ ) (R ⁵ ) and R ¹ are directly bonded, and in this case, the following structures [8] to [11] can be taken. In the case of [9] and [11] in which the direct bond is a double bond, R ⁵ does not exist. Moreover, it can also take the structure where the double bond went out of the ring like [10]. In this case, R ⁶ and R ⁷ are each independently hydrogen, or a hydrocarbon group that may have a ring having 1 to 10 carbon atoms, a hetero atom, or a halogen atom. For example, a branched chain or cyclic structure can be used. ]

The total amount of the compounds represented by the general formulas [3] to [6] is 20 to 100% by mass out of 100% by mass of the total solid content in the electrode surface modification coating agent. The manufacturing method of the nonaqueous electrolyte battery of Claim 5. at least,
Applying a coating agent for electrode surface modification containing an ester compound dissolved or dispersed in a solvent to the surface of an electrode for a nonaqueous electrolyte battery;
A second step of obtaining a surface-modified electrode by forming a film on the surface of the electrode by heating the electrode surface-modifying coating agent on the electrode after the first step at 80 to 150 ° C .;
Including
The method for producing a surface-modified electrode for a non-aqueous electrolyte battery, wherein the heating in the second step is performed until the following formula [1] is satisfied.
(A-B2) × 100 / (A-B1) ≧ 50 [1]
here,
Application amount A: Calculated value of solid content of electrode surface modification coating agent applied on electrode after first step (ie, mass of electrode surface modification coating agent applied on electrode × electrode surface modification) Solid content concentration of quality coating agent)
Coating mass B1: As a sample test, measured value of coating mass obtained when heated at 150 ° C. for 1 hour in atmospheric pressure as the second step Coating mass B2: Actually heated at 80 to 150 ° C. as the second step Measured value of the coating film mass The method for producing a surface-modified electrode for a non-aqueous electrolyte battery according to claim 7, wherein the heating in the second step is performed until the following formula [2] is satisfied.
50 ≦ (A−B2) × 100 / (A−B1) ≦ 100 [2]
here,
The coating amount A, the coating mass B1, and the coating mass B2 are the same as those in the formula [1]. The method for producing a surface-modified electrode according to claim 7 or 8, wherein the heating temperature in the second step is 100 to 150 ° C. The coating agent for electrode surface modification provided for the first step is at least one selected from the group consisting of a thioester compound, a carbonate ester compound, a phosphate ester compound, a sulfate ester compound, and a carbonate ester compound as a solvent. The method for producing a surface-modified electrode according to any one of claims 7 to 9, wherein the surface-modified electrode is contained by being dissolved or dispersed. The coating agent for electrode surface modification provided for the first step includes at least one selected from compounds represented by the following general formulas [3] to [6] dissolved or dispersed in a solvent. The method for producing a surface-modified electrode according to any one of claims 7 to 10, wherein the method is a product.

[In General Formula [3], M represents a boron atom, a phosphorus atom, or a silicon atom, m is 1-3, n is 1-4, and p is 0 or 1. R ¹ is an alkylene group having 3 to 10 carbon atoms, a halogenated alkylene group having 3 to 10 carbon atoms, an arylene group having 6 to 20 carbon atoms, or a halogenated arylene group having 6 to 20 carbon atoms (these The group may contain a substituent or a hetero atom in the structure, and when m is 2 or more, m R ^{1 s} may be bonded to each other. R ² represents a halogen atom, X ¹ and X ² each independently represent an oxygen atom or a sulfur atom, and X ³ represents a carbon atom or a sulfur atom. q is 1 when X ³ is a carbon atom, and 1 or 2 when X ³ is a sulfur atom. A ^{a +} represents an alkali metal cation, an alkaline earth metal cation, or an onium cation, and a represents the valence of the corresponding cation. a to d are 1 or 2, and a × b = c × d is satisfied. ]

[In General Formula [4], A ^{a +} represents an alkali metal cation, an alkaline earth metal cation, or an onium cation, and a represents the valence of the corresponding cation. a to d are 1 or 2, and a × b = c × d is satisfied. ]

[In the general formula [5], X represents (—CH ₂ —) _r , —CH (CH ₃ ) —, —C (CH ₃ ) ₂ —, —CF ₂ —, —C (CF ₃ ) ₂ —, and It is a group selected from the group consisting of —C (C ₆ H ₅ ) ₂ —, and r is any one of 1 to 4. Z ¹ and Z ² are each independently a group selected from the group consisting of a hydrogen atom, a —CF ₃ group, and a —CH ₂ CF ₃ group. ]

[In the general formula [6],
D is a halogen ion, hexafluorophosphate anion, tetrafluoroborate anion, bis (trifluoromethanesulfonyl) imide anion, bis (fluorosulfonyl) imide anion, (fluorosulfonyl) (trifluoromethanesulfonyl) imide anion, bis (difluorophospho Nyl) imide anion,
F is fluorine,
M is any one selected from the group consisting of Group 13 elements (Al, B), Group 14 elements (Si), and Group 15 elements (P, As, Sb), O is oxygen,
N is nitrogen.
Y is carbon or sulfur. When Y is carbon, q is 1. When Y is sulfur, q is 1 or 2.
X is carbon or sulfur, r is 1 when X is carbon, and r is 1 or 2 when X is sulfur.
R ¹ is a hydrocarbon group which may have a ring having 1 to 10 carbon atoms, a hetero atom or a halogen atom (in the case of 3 or more carbon atoms, a branched chain or cyclic structure can be used) , or -N ^{(R 2)} - represents a. At this time, R ² represents hydrogen, an alkali metal, a hydrocarbon group which may have a ring having 1 to 10 carbon atoms, a hetero atom, or a halogen atom. When the number of carbon atoms is 3 or more, R ² can also take a branched chain or a cyclic structure.
R ⁴ and R ⁵ are each independently a hydrocarbon group optionally having a ring having 1 to 10 carbon atoms, a heteroatom, or a halogen atom. If the number of carbon atoms is 3 or more, a branched chain or An annular structure can also be used. Moreover, you may have a cyclic structure containing each other like following General formula [7].

When c is 0 or 1, when n is 1, c is 0 (D is not present when c is 0), and when n is 2, c is 1.
o is 2 or 4, n is 1 or 2, p is 0 or 1, q is 1 or 2, r is 1 or 2, and s is 0 or 1. When p is 0, a direct bond is formed between Y and X.
When s is 0, N (R ⁴ ) (R ⁵ ) and R ¹ are directly bonded, and in this case, the following structures [8] to [11] can be taken. In the case of [9] and [11] in which the direct bond is a double bond, R ⁵ does not exist. Moreover, it can also take the structure where the double bond went out of the ring like [10]. In this case, R ⁶ and R ⁷ are each independently hydrogen, or a hydrocarbon group that may have a ring having 1 to 10 carbon atoms, a hetero atom, or a halogen atom. For example, a branched chain or cyclic structure can be used. ]

The total amount of the compounds represented by the general formulas [3] to [6] is 20 to 100% by mass out of 100% by mass of the total solid content in the electrode surface modification coating agent. The method for producing a surface-modified electrode according to claim 11. The solvent contains at least one selected from the group consisting of a thioester compound, a carbonate ester compound, a phosphate ester compound, a sulfate ester compound, and a carbonate ester compound, dissolved or dispersed therein, An electrode surface modification coating agent for forming a film by coating and heating the surface of an electrode which is a constituent member of a water electrolyte battery. The electrode surface according to claim 13, wherein at least one selected from the compounds represented by the following general formulas [3] to [6] is dissolved or dispersed in the solvent. Coating agent for modification.

[In General Formula [3], M represents a boron atom, a phosphorus atom, or a silicon atom, m is 1-3, n is 1-4, and p is 0 or 1. R ¹ is an alkylene group having 3 to 10 carbon atoms, a halogenated alkylene group having 3 to 10 carbon atoms, an arylene group having 6 to 20 carbon atoms, or a halogenated arylene group having 6 to 20 carbon atoms (these The group may contain a substituent or a hetero atom in the structure, and when m is 2 or more, m R ^{1 s} may be bonded to each other. R ² represents a halogen atom, X ¹ and X ² each independently represent an oxygen atom or a sulfur atom, and X ³ represents a carbon atom or a sulfur atom. q is 1 when X ³ is a carbon atom, and 1 or 2 when X ³ is a sulfur atom. A ^{a +} represents an alkali metal cation, an alkaline earth metal cation, or an onium cation, and a represents the valence of the corresponding cation. a to d are 1 or 2, and a × b = c × d is satisfied. ]

[In General Formula [4], A ^{a +} represents an alkali metal cation, an alkaline earth metal cation, or an onium cation, and a represents the valence of the corresponding cation. a to d are 1 or 2, and a × b = c × d is satisfied. ]

[In the general formula [5], X represents (—CH ₂ —) _r , —CH (CH ₃ ) —, —C (CH ₃ ) ₂ —, —CF ₂ —, —C (CF ₃ ) ₂ —, and It is a group selected from the group consisting of —C (C ₆ H ₅ ) ₂ —, and r is any one of 1 to 4. Z ¹ and Z ² are each independently a group selected from the group consisting of a hydrogen atom, a —CF ₃ group, and a —CH ₂ CF ₃ group. ]

[In the general formula [6],
D is a halogen ion, hexafluorophosphate anion, tetrafluoroborate anion, bis (trifluoromethanesulfonyl) imide anion, bis (fluorosulfonyl) imide anion, (fluorosulfonyl) (trifluoromethanesulfonyl) imide anion, bis (difluorophospho Nyl) imide anion,
F is fluorine,
M is any one selected from the group consisting of Group 13 elements (Al, B), Group 14 elements (Si), and Group 15 elements (P, As, Sb), O is oxygen,
N is nitrogen.
Y is carbon or sulfur. When Y is carbon, q is 1. When Y is sulfur, q is 1 or 2.
X is carbon or sulfur, r is 1 when X is carbon, and r is 1 or 2 when X is sulfur.
R ¹ is a hydrocarbon group which may have a ring having 1 to 10 carbon atoms, a hetero atom or a halogen atom (in the case of 3 or more carbon atoms, a branched chain or cyclic structure can be used) , or -N ^{(R 2)} - represents a. At this time, R ² represents hydrogen, an alkali metal, a hydrocarbon group which may have a ring having 1 to 10 carbon atoms, a hetero atom, or a halogen atom. When the number of carbon atoms is 3 or more, R ² can also take a branched chain or a cyclic structure.
R ⁴ and R ⁵ are each independently a hydrocarbon group optionally having a ring having 1 to 10 carbon atoms, a heteroatom, or a halogen atom. If the number of carbon atoms is 3 or more, a branched chain or An annular structure can also be used. Moreover, you may have a cyclic structure containing each other like following General formula [7].

When c is 0 or 1, when n is 1, c is 0 (D is not present when c is 0), and when n is 2, c is 1.
o is 2 or 4, n is 1 or 2, p is 0 or 1, q is 1 or 2, r is 1 or 2, and s is 0 or 1. When p is 0, a direct bond is formed between Y and X.
When s is 0, N (R ⁴ ) (R ⁵ ) and R ¹ are directly bonded, and in this case, the following structures [8] to [11] can be taken. In the case of [9] and [11] in which the direct bond is a double bond, R ⁵ does not exist. Moreover, it can also take the structure where the double bond went out of the ring like [10]. In this case, R ⁶ and R ⁷ are each independently hydrogen, or a hydrocarbon group that may have a ring having 1 to 10 carbon atoms, a hetero atom, or a halogen atom. For example, a branched chain or cyclic structure can be used. ]

The total amount of the compounds represented by the general formulas [3] to [6] is 20 to 100% by mass out of 100% by mass of the total solid content in the electrode surface modification coating agent. The coating agent for electrode surface modification according to claim 13 or 14.