JP6315267B2 - Method for producing electrode for non-aqueous secondary battery - Google Patents

Description

  The present invention relates to a method for producing an electrode for a non-aqueous secondary battery.

  The number of products using non-aqueous secondary batteries continues to increase, and in general, non-aqueous secondary batteries are recognized as essential for portable devices such as mobile phones and notebook computers. Among non-aqueous secondary batteries, lithium ion secondary batteries are widely used because of their small size and large capacity. A lithium ion secondary battery includes a pair of electrodes, a positive electrode and a negative electrode, as essential components. Each electrode has an active material layer and a current collector to which the active material layer is bound. The active material layer generally contains a binder for playing a role of securing the active material to the surface of the current collector.

  Now, it is already known that polyacrylic acid and polymethacrylic acid can be used as a binder, but since it was also known that the strength is inferior, polyacrylic acid itself or polymethacrylic acid itself was used as a binder. It was not common to be done.

  For example, Patent Document 1 describes an electrode for a lithium ion secondary battery in which a polyacrylic acid lithium salt or a polyacrylic acid sodium salt is employed as a binder instead of polyacrylic acid itself.

  Patent Document 2 discloses not only polyacrylic acid as a binder, but also an electrode for a lithium ion secondary battery using polyacrylic acid and carboxymethylcellulose in combination as a binder, and polyacrylic acid as a binder. An electrode for a lithium ion secondary battery using polyethyleneimine and polyvinylidene fluoride in combination is described, and it is described that the polymer forms a crosslinked network by the above combination.

JP 2009-80971 A JP 2009-135103 A

  The description in Patent Document 1 and Patent Document 2 disclosed a limited method of using polyacrylic acid.

  However, polyacrylic acid and polymethacrylic acid are binders that can be obtained at low cost, and it is very beneficial to industrial development to expand the possibility of use as these binders.

  The present invention has been made in view of such circumstances, and polyacrylic acid, polymethacrylic acid, or a copolymer of acrylic acid and methacrylic acid (hereinafter referred to as “poly (meth)” as a binder. It is an object of the present invention to provide a new method for producing an electrode comprising “acrylic acid”.

  The present inventor conducted intensive studies on an electrode having poly (meth) acrylic acid as a binder while performing trial and error. Here, the carboxylic acid groups of poly (meth) acrylic acid existing on the electrode surface layer are cross-linked through another substance to form a binder network, and the network increases the hardness of the electrode. The inventor recalled this. And this inventor came to complete this invention.

The method for producing an electrode for a non-aqueous secondary battery according to the present invention is a step of preparing an electrode body comprising polyacrylic acid, polymethacrylic acid, or a copolymer of acrylic acid and methacrylic acid,
Preparing a solution containing a compound represented by the following general formula (1):
MH _m (OR) _n General formula (1)
(M is Ti, Si, P or B, R is each independently H or alkyl, m and n are integers of 0 or more, and satisfy m + n = (absolute value of M valence)). .)
A step of bringing the electrode body into contact with the solution.

  A new method for producing an electrode comprising poly (meth) acrylic acid as a binder can be provided.

It is a cross-sectional schematic diagram which shows the one aspect | mode of the electrode for non-aqueous secondary batteries of this invention.

  Below, the form for implementing this invention is demonstrated. Unless otherwise specified, the numerical range “ab” described herein includes the lower limit “a” and the upper limit “b”. The numerical range can be configured by arbitrarily combining these upper limit value and lower limit value and the numerical values listed in the examples. Furthermore, numerical values arbitrarily selected from the numerical value range can be used as upper and lower numerical values.

The method for producing an electrode for a non-aqueous secondary battery of the present invention (hereinafter sometimes referred to as “the electrode of the present invention”) comprises polyacrylic acid, polymethacrylic acid, or a copolymer of acrylic acid and methacrylic acid. A step of preparing an electrode body, a step of preparing a solution containing a compound represented by the following general formula (1),
MH _m (OR) _n General formula (1)
(M is Ti, Si, P or B, R is each independently H or alkyl, m and n are integers of 0 or more, and satisfy m + n = (absolute value of M valence)). .)
A step of bringing the electrode body into contact with the solution. And the non-aqueous secondary battery of this invention comprises the electrode of this invention, It is characterized by the above-mentioned.

  A non-aqueous secondary battery refers to a secondary battery using a non-aqueous solvent as a solvent for an electrolytic solution. As a typical non-aqueous secondary battery, a lithium ion secondary battery can be given. The electrode of the present invention may be a negative electrode or a positive electrode.

Hereinafter, the present invention will be described along the method for producing an electrode for a non-aqueous secondary battery of the present invention.
First, a process for preparing an electrode body including poly (meth) acrylic acid will be described.
Poly (meth) acrylic acid functions as a binder in the electrode.
The molecular weight of poly (meth) acrylic acid is preferably 1,000 to 3,000,000, more preferably 10,000 to 2,000,000, and even more preferably 100,000 to 1,000,000 in terms of number average molecular weight or weight average molecular weight.

  The electrode body includes a current collector and an active material layer containing poly (meth) acrylic acid as a binder and an active material.

  A current collector refers to a chemically inert electronic high conductor that keeps a current flowing through an electrode during discharge or charging of a secondary battery. As the current collector, at least one selected from silver, copper, gold, aluminum, magnesium, tungsten, cobalt, zinc, nickel, iron, platinum, tin, indium, titanium, ruthenium, tantalum, chromium, molybdenum, and stainless steel Examples of such a metal material can be given. The current collector may be covered with a known protective layer.

  The current collector can take the form of a foil, a sheet, a film, a line, a bar, and the like. Therefore, metal foils, such as copper foil, nickel foil, aluminum foil, stainless steel foil, can be used suitably as a collector. When the current collector is in the form of foil, sheet or film, the thickness is preferably in the range of 10 μm to 100 μm.

  Examples of the active material include a negative electrode active material used for a negative electrode and a positive electrode active material used for a positive electrode.

  Examples of the negative electrode active material include a lithium alloy, a carbon-based material capable of inserting and extracting lithium, an element that can be alloyed with lithium, a compound having an element that can be alloyed with lithium, or a polymer material. .

  Examples of the carbon-based material include non-graphitizable carbon, natural graphite, artificial graphite, cokes, graphites, glassy carbons, organic polymer compound fired bodies, carbon fibers, activated carbon, and carbon blacks. Here, the organic polymer compound fired body refers to a material obtained by firing and carbonizing a polymer material such as phenols and furans at an appropriate temperature.

  Specifically, elements that can be alloyed with lithium include Na, K, Rb, Cs, Fr, Be, Mg, Ca, Sr, Ba, Ra, Ti, Ag, Zn, Cd, Al, Ga, In, Si. , Ge, Sn, Pb, Sb, Bi can be exemplified, and Si or Sn is particularly preferable.

Specific examples of compounds having elements that can be alloyed with lithium include ZnLiAl, AlSb, SiB ₄ , SiB ₆ , Mg ₂ Si, Mg ₂ Sn, Ni ₂ Si, TiSi ₂ , MoSi ₂ , CoSi ₂ , NiSi ₂ , _{CaSi 2, CrSi 2, Cu 5} Si, FeSi 2, MnSi 2, NbSi 2, TaSi 2, VSi 2, WSi 2, ZnSi 2, SiC, Si 3 N 4, Si 2 N 2 O, SiO v (0 <v ≦ 2), SnO _w (0 <w ≦ 2), SnSiO ₃ , LiSiO or LiSnO, TiO _y , ZrO _y , VO _y , CrO _y , MnO _y , FeO _y , CoO _y , NiO _y , CuO _y , ZnO _{y , LiTi z O y, LiV z} O y (0 <y ≦ 3,0 <Z ≦ 1) transition metal oxides, such as, _Li 3 N LiCo _0.4 N can be exemplified such as lithium nitride compounds such as _0.6, in _{particular, SiO x (0.3 ≦ x ≦} 1.6) is preferable. Moreover, tin compounds, such as a tin alloy (Cu-Sn alloy, Co-Sn alloy, etc.), can be illustrated as a compound which has an element which can be alloyed with lithium. The above-mentioned material may be heated with a carbon source and used as a carbon coat or composite.

  Specific examples of the polymer material include polyacetylene, polypyrrole, and terephthalic acid.

Further, the layered polysilane obtained by treating CaSi ₂ with an acid such as hydrochloric acid or hydrofluoric acid, may be employed Si material obtained by heating at 300 to 1000 ° C. as the negative electrode active material. Further, a material obtained by heating the Si material together with a carbon source to form a carbon coat or composite may be employed as the negative electrode active material.

  As the negative electrode active material, one or more of the above can be used. As will be described later, the electrode of the present invention has the advantage that it can withstand the expansion and contraction of the active material. In order to take advantage of this advantage, it is preferable to employ a high-capacity Si-containing material as a negative electrode active material that has a large degree of expansion and contraction during charge and discharge.

As the positive electrode active material, the layered compound Li _a Ni _b Co _c Mn _{d De} O _f (0.2 ≦ a ≦ 1.2, b + c + d + e = 1, 0 ≦ e <1, D is Li, Fe, Cr, At least one element selected from Cu, Zn, Ca, Mg, S, Si, Na, K, Al, Zr, Ti, P, Ga, Ge, V, Mo, Nb, W, La, 1.7 ≦ f ≦ 2.1) and Li ₂ MnO ₃ . Further, as a positive electrode active material, a solid solution composed of a spinel such as LiMn ₂ O ₄ and Li ₂ Mn ₂ O ₄ and a mixture of a spinel and a layered compound, LiMPO ₄ , LiMVO _4, or Li ₂ MSiO ₄ (M in the formula) Are selected from at least one of Co, Ni, Mn, and Fe). Furthermore, as the positive electrode active material, tavorite compound (the M a transition metal) LiMPO ₄ F, such as LiFePO ₄ F represented by, Limbo ₃ such LiFeBO ₃ (M is a transition metal) include borate-based compound represented by be able to. Any metal oxide used as the positive electrode active material may have the above composition formula as a basic composition, and a metal element contained in the basic composition may be substituted with another metal element. Further, as the positive electrode active material, a positive electrode active material that does not contain lithium ions contributing to charge / discharge, for example, sulfur alone (S), a compound in which sulfur and carbon are combined, a metal sulfide such as TiS ₂ , V ₂ O, etc. ₅ , oxides such as MnO ₂ , polyaniline and anthraquinone, compounds containing these aromatics in the chemical structure, conjugated materials such as conjugated diacetic acid organic materials, and other known materials can also be used. Further, a compound having a stable radical such as nitroxide, nitronyl nitroxide, galvinoxyl, phenoxyl, etc. may be adopted as the positive electrode active material. When using a positive electrode active material that does not contain lithium, it is necessary to add ions to the positive electrode and / or the negative electrode in advance by a known method. Here, in order to add the ion, a metal or a compound containing the ion may be used.

  The active material layer includes an active material, poly (meth) acrylic acid as a binder, and, if necessary, a conductive aid. As the binder, poly (meth) acrylic acid is essential, but other binders may be used in combination.

  The blending ratio of the binder in the active material layer is preferably a mass ratio of active material: binder = 1: 0.001 to 1: 0.3, and 1: 0.005 to 1: 0. .2 is more preferable, and 1: 0.01 to 1: 0.15 is still more preferable. This is because when the amount of the binder is too small, the moldability of the electrode is lowered, and when the amount of the binder is too large, the energy density of the electrode is lowered.

  The conductive assistant is added to increase the conductivity of the electrode. Therefore, the conductive auxiliary agent may be added arbitrarily when the electrode conductivity is insufficient, and may not be added when the electrode conductivity is sufficiently excellent. The conductive auxiliary agent may be any chemically inert electronic high conductor, such as carbon black, graphite, acetylene black, ketjen black (registered trademark), vapor grown carbon fiber (Vapor Grown Carbon). Fiber: VGCF) and various metal particles are exemplified. These conductive assistants can be added to the active material layer alone or in combination of two or more. The blending ratio of the conductive additive in the active material layer is preferably a mass ratio of active material: conductive additive = 1: 0.005 to 1: 0.5, and 1: 0.01 to 1: 0. .2 is more preferable, and 1: 0.03 to 1: 0.1 is even more preferable. This is because if the amount of the conductive auxiliary is too small, an efficient conductive path cannot be formed, and if the amount of the conductive auxiliary is too large, the moldability of the active material layer is deteriorated and the energy density of the electrode is lowered.

The active material layer is formed on the surface of the current collector, and as a result, an electrode body can be obtained. In order to obtain an electrode body by forming an active material layer on the surface of the current collector, conventionally known methods such as a roll coating method, a die coating method, a dip coating method, a doctor blade method, a spray coating method, and a curtain coating method are used. The active material may be applied to the surface of the current collector. Specifically, an active material layer-forming composition containing an active material, a binder, and, if necessary, a conductive aid is prepared, and an appropriate solvent is added to the composition to form a slurry, and then current collection is performed. After applying to the surface of the body, it is dried to obtain an electrode body. Examples of the solvent include N-methyl-2-pyrrolidone, methanol, methyl isobutyl ketone, and water. In order to increase the electrode density, the dried body may be compressed to form an electrode body.
As described above, an electrode body including poly (meth) acrylic acid can be prepared.

Next, a step of preparing a solution containing a compound represented by the following general formula (1) (hereinafter sometimes referred to as “M-containing solution”) will be described.
MH _m (OR) _n General formula (1)
(M is Ti, Si, P or B, R is each independently H or alkyl, m and n are integers of 0 or more, and satisfy m + n = (absolute value of M valence)). .)

  As alkyl of General formula (1), C1-C6 alkyl, such as methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, pentyl, is preferable.

  The absolute value of the valence of M is the absolute value of the number of valences that can theoretically be taken for Ti, Si, P, or B. As the absolute value of the valence of M, Ti is 2, 3, 4, Si is 2, 3, 4, P is 3, 4, 5, B is preferably 3, 4, Ti is 4, Si is 4, P is more preferably 3, and B is more preferably 3.

Specific examples of the compound represented by the general formula (1) include Ti (Oi-Pr) ₄ , Ti (OEt) ₄ , Ti (OMe) ₄ , Ti (On-Bu) ₄ , Ti ( O-i-Bu) ₄ , Ti (Oi-Pr) ₃ , Ti (On-Bu) ₃ , Ti (Oi-Pr) ₂ , Ti (On-Bu) ₂ , Ti ( OH) ₄ , TiH ₄ , TiH ₂ , Si (Oi-Pr) ₄ , Si (OEt) ₄ , Si (OMe) ₄ , Si (On-Bu) ₄ , Si (Oi-Bu) ₄ , Si (OH) ₄ , SiH (OMe) ₃ , SiH ₂ (OMe) ₂ , SiH (OEt) ₃ , SiH ₂ (OEt) ₂ , SiH ₄ , P (Oi-Pr) ₃ , P (OEt) ) ₃ , P (OMe) ₃ , P (On-Bu) ₃ , P (Oi-Bu) ₃ , P (OH) ₃ , PH ₃ , _{B (O-i-Pr)} 3, B (OEt) 3, B (OMe) 3, B (O-n-Bu) 3, B (O-i-Bu) 3, B (OH) 3, BH 2 (Oi-Pr), BH ₂ (OEt), BH ₂ (OMe), BH (OMe) ₂ , and BH ₃ can be exemplified.

  What is necessary is just to select suitably as a solvent of M containing solution according to the solubility and stability of the compound represented by General formula (1). Examples of the solvent include methanol, ethanol, propanol, tetrahydrofuran, N-methyl-2-pyrrolidone and the like, and these solvents may be used alone or in combination.

In order to prepare the M-containing solution, the compound represented by the general formula (1) and the solvent may be mixed. In this case, a complex containing a compound represented by the general formula (1) such as BH ₃ · THF complex may be used. Although there is no limitation in particular in the compound density | concentration represented by General formula (1) in M containing solution, the inside of the range of 0.01 mass%-10 mass% is preferable, and the inside of the range of 0.05 mass%-5 mass% is preferable. More preferably, it is more preferably in the range of 0.1% by mass to 3% by mass, and particularly preferably in the range of 0.2% by mass to 2% by mass.

Next, the process of bringing the electrode body into contact with the M-containing solution will be described.
In order to bring the electrode body into contact with the M-containing solution, for example, a method in which the electrode body is immersed in the M-containing solution, a method in which the M-containing solution is applied to the electrode body, and a method in which the M-containing solution is applied to the electrode body in a spray state are given. be able to. From the viewpoint of ease of work, a method of immersing the electrode body in the M-containing solution is preferable. In the method, the M-containing solution may be stirred, or may be carried out under normal pressure, under pressure or under reduced pressure, or under normal temperature and under heating conditions. The time for immersing the electrode body in the M-containing solution may be appropriately selected depending on the type and concentration of the M-containing solution. Examples of the time include 5 seconds to 5 minutes, preferably 10 seconds to 2 minutes.

  When the electrode body is brought into contact with the M-containing solution, M is presumed to form an ionic bond or a coordinate bond with a plurality of poly (meth) acrylic acid carboxylic acids present on the electrode body surface layer. By the ionic bond or coordinate bond, the poly (meth) acrylic acid molecule on the surface of the electrode of the present invention can build a strong network with other poly (meth) acrylic acid molecules. As a result, it is estimated that the hardness of the surface of the electrode of the present invention is increased.

  When the step of bringing the electrode body into contact with the M-containing solution is completed, an M-containing portion is present on the surface of the electrode body comprising poly (meth) acrylic acid. Then, as one aspect of the electrode of the present invention, an electrode main body comprising polyacrylic acid, polymethacrylic acid, or a copolymer of acrylic acid and methacrylic acid, an M-containing portion formed on the surface of the electrode main body, The electrode for non-aqueous secondary batteries which has can be grasped | ascertained. FIG. 1 is a schematic cross-sectional view showing one embodiment of a nonaqueous secondary battery electrode of the present invention. The current collector 1 is made of an electronic high conductor. An active material layer 2 having an active material and poly (meth) acrylic acid as a binder is formed on the surface of the current collector 1. The electrode body 3 includes a current collector 1 and an active material layer 2. An M-containing portion 4 is formed on the surface of the electrode body 3. The electrode 5 includes an electrode body 3 and an M-containing portion 4.

  After the step of bringing the electrode main body into contact with the M-containing solution, a drying step for removing the solvent of the M-containing solution is preferably performed. The drying temperature is less than 200 ° C, preferably 150 ° C or less, and more preferably in the range of 70 to 140 ° C. The drying step is preferably performed under reduced pressure. The drying time may be set appropriately as long as the solvent of the M-containing solution is removed. Examples of the drying time include 1 to 5 hours.

  In the electrode of the present invention, the electrode surface is cured by bringing the electrode body comprising poly (meth) acrylic acid into contact with the M-containing solution. The curing can compensate for the insufficient hardness of poly (meth) acrylic acid as a binder. In addition, the poly (meth) acrylic acid inside the electrode is relatively low in hardness but can be said to have flexibility, and in order to have such flexibility, the stress due to expansion and contraction of the active material accompanying charge / discharge is buffered. Presumed to be possible.

  The lithium ion secondary battery as a typical example of the non-aqueous secondary battery of the present invention includes a positive electrode, a negative electrode, a separator, and an electrolytic solution as battery components.

  Although both the positive electrode and the negative electrode may be the electrode of the present invention, either the positive electrode or the negative electrode may be the electrode of the present invention. Any known positive electrode or negative electrode that is not an electrode of the present invention may be employed.

  The separator separates the positive electrode and the negative electrode and allows lithium ions to pass while preventing a short circuit of current due to contact between the two electrodes. As separators, natural resins such as polytetrafluoroethylene, polypropylene, polyethylene, polyimide, polyamide, polyaramid (Aromatic polymer), polyester, polyacrylonitrile and other polysaccharides, cellulose, amylose and other polysaccharides, fibroin, keratin, lignin and suberin Examples thereof include porous bodies, nonwoven fabrics, and woven fabrics using one or more electrically insulating materials such as polymers and ceramics. The separator may have a multilayer structure.

  The electrolytic solution includes a nonaqueous solvent and an electrolyte dissolved in the nonaqueous solvent.

  As the non-aqueous solvent, cyclic esters, chain esters, ethers and the like can be used. Examples of cyclic esters include ethylene carbonate, propylene carbonate, butylene carbonate, gamma butyrolactone, vinylene carbonate, 2-methyl-gamma butyrolactone, acetyl-gamma butyrolactone, and gamma valerolactone. Examples of chain esters include dimethyl carbonate, diethyl carbonate, dibutyl carbonate, dipropyl carbonate, methyl ethyl carbonate, propionic acid alkyl ester, malonic acid dialkyl ester, and acetic acid alkyl ester. Examples of ethers include tetrahydrofuran, 2-methyltetrahydrofuran, 1,4-dioxane, 1,2-dimethoxyethane, 1,2-diethoxyethane, and 1,2-dibutoxyethane. As the non-aqueous solvent, a compound in which part or all of hydrogen in the chemical structure of the specific solvent is substituted with fluorine may be employed.

Examples of the electrolyte include lithium salts such as LiClO ₄ , LiAsF ₆ , LiPF ₆ , LiBF ₄ , LiCF ₃ SO ₃ , and LiN (CF ₃ SO ₂ ) ₂ .

As an electrolytic solution, 0.5 mol / l to 1.7 mol of a lithium salt such as LiClO ₄ , LiPF ₆ , LiBF ₄ , LiCF ₃ SO _{3 in} a nonaqueous solvent such as ethylene carbonate, dimethyl carbonate, propylene carbonate, and diethyl carbonate. A solution dissolved at a concentration of about 1 / l can be exemplified.

  A method for producing a lithium ion secondary battery as a representative example of the non-aqueous secondary battery of the present invention will be described below.

  A separator is sandwiched between the positive electrode and the negative electrode to form an electrode body. The electrode body may be either a stacked type in which the positive electrode, the separator and the negative electrode are stacked, or a wound type in which the positive electrode, the separator and the negative electrode are sandwiched. After connecting between the positive electrode current collector and the negative electrode current collector to the positive electrode terminal and the negative electrode terminal connected to the outside using a current collecting lead or the like, an electrolytic solution is added to the electrode body to form a lithium ion secondary battery. It is good to do.

  The shape of the nonaqueous secondary battery of the present invention is not particularly limited, and various shapes such as a cylindrical shape, a square shape, a coin shape, and a laminate shape can be employed.

  The non-aqueous secondary battery of the present invention may be mounted on a vehicle. The vehicle may be a vehicle that uses electric energy from a non-aqueous secondary battery for all or a part of its power source. For example, the vehicle may be an electric vehicle, a hybrid vehicle, or the like. When a non-aqueous secondary battery is mounted on a vehicle, a plurality of non-aqueous secondary batteries may be connected in series to form an assembled battery. Examples of devices equipped with non-aqueous secondary batteries include various home appliances driven by batteries such as personal computers and portable communication devices, office devices, and industrial devices in addition to vehicles. Furthermore, the non-aqueous secondary battery of the present invention includes a wind power generation, solar power generation, hydroelectric power generation and other power system power storage device and power smoothing device, power for ships and / or power supply sources for auxiliary equipment, aircraft, Power supply for spacecraft and / or auxiliary equipment, auxiliary power supply for vehicles that do not use electricity as a power source, power supply for mobile home robots, power supply for system backup, power supply for uninterruptible power supply, You may use for the electrical storage apparatus which stores temporarily the electric power required for charge in the charging station for electric vehicles.

  As mentioned above, although embodiment of this invention was described, this invention is not limited to the said embodiment. The present invention can be implemented in various forms without departing from the gist of the present invention, with modifications and improvements that can be made by those skilled in the art.

  Hereinafter, the present invention will be described in more detail with reference to examples. In addition, this invention is not limited to a following example.

(Production Example 1)
Si material used as a negative electrode active material was manufactured as follows.
5 g of CaSi ₂ was added to 20 mL of concentrated hydrochloric acid containing 1% by mass of hydrogen fluoride bathed in an ice bath at 0 ° C. and stirred for 1 hour. Thereafter, water was added and the mixture was further stirred for 5 minutes, and the reaction solution was filtered to obtain a yellow powder. The yellow powder was washed with water and ethanol, and dried under reduced pressure to obtain 5.5 g of layered polysilane. The layered polysilane was heated to 500 ° C. under an argon atmosphere to obtain a Si material from which hydrogen was released from the polysilane.

Example 1
The electrode of the present invention was manufactured as follows.

50 parts by mass of the Si material obtained in Production Example 1 as the negative electrode active material, 35 parts by mass of natural graphite as the negative electrode active material, 5 parts by mass of acetylene black as the conductive additive, and 10 parts of polyacrylic acid as the binder Partial mixing was performed to obtain an active material layer forming composition. N-methyl-2-pyrrolidone was added to the composition to form a slurry.
An electrolytic copper foil having a thickness of 20 μm was prepared as a current collector. The slurry was applied to the surface of the copper foil using a doctor blade so as to form a film. The copper foil coated with the slurry was dried at 80 ° C. for 20 minutes to remove N-methyl-2-pyrrolidone by volatilization. As a result, a copper foil having a negative electrode active material layer formed on the surface was obtained. The copper foil was compressed with a roll press so that the negative electrode active material layer had a thickness of 20 μm to obtain a bonded product. This joined product was used as the electrode body of Example 1.
The polyacrylic acid used was Aqualic AS58 (Nippon Shokubai Co., Ltd.), and its weight average molecular weight was 800,000.

Ti (Oi-Pr) ₄ (Aldrich) was employed as the compound represented by the general formula (1). Ti (Oi-Pr) ₄ was dissolved in tetrahydrofuran to prepare a 0.5 mass% M-containing solution.

  The electrode body was immersed in the M-containing solution for 1 minute at room temperature. The immersed electrode was air-dried for 1 hour, and then dried under reduced pressure at 130 ° C. for 3 hours. The electrode thus obtained was used as the electrode of Example 1.

A half cell was manufactured using the electrode of Example 1 as follows.
The electrode of Example 1 was cut at a diameter of 11 mm to obtain an evaluation electrode. A metal lithium foil was cut to a diameter of 13 mm to make a counter electrode. As a separator, a glass filter (Hoechst Celanese) and celgard 2400 (Polypore Corporation), which is a single-layer polypropylene, were prepared. It was also prepared an electrolyte solution obtained by dissolving LiPF ₆ at 1 mol / L in a solvent obtained by mixing 50 parts by volume of ethylene carbonate and diethyl carbonate 50 parts by volume. Two kinds of separators were sandwiched between the counter electrode and the evaluation electrode in the order of the counter electrode, the glass filter, celgard 2400, and the evaluation electrode, thereby forming an electrode body. This electrode body was accommodated in a coin-type battery case CR2032 (Hosen Co., Ltd.), and an electrolyte was further injected to obtain a coin-type battery. This was designated as the lithium ion secondary battery of Example 1.

(Example 2)
Except for employing 45 parts by mass of SiO (Aldrich) as the negative electrode active material and 40 parts by mass of natural graphite as the negative electrode active material, the electrode body of Example 2, the electrode of Example 2, A lithium ion secondary battery of Example 2 was manufactured.

(Example 3)
The electrode body of Example 3, the electrode of Example 3, the lithium ion of Example 3 were the same as in Example 1, except that Si (OEt) ₄ was used as the compound represented by the general formula (1). A secondary battery was manufactured.

Example 4
P (OEt) ₃ was employed as the compound represented by the general formula (1). P (OEt) ₃ was dissolved in tetrahydrofuran to prepare a 1% by mass M-containing solution. And the electrode main body of Example 4, the electrode of Example 4, the lithium ion secondary battery of Example 4 is the same method as Example 1 except having employ | adopted the said 1 mass% M containing solution as M containing solution. Manufactured.

(Example 5)
P (OH) ₃ was employed as the compound represented by the general formula (1). P (OH) ₃ was dissolved in ethanol to prepare a 1 mass% M-containing solution. And the electrode main body of Example 5, the electrode of Example 5, the lithium ion secondary battery of Example 5 are the same methods as Example 1 except having employ | adopted the said 1 mass% M containing solution as M containing solution. Manufactured.

(Example 6)
B (Oi-Pr) ₃ was employed as the compound represented by the general formula (1). B (Oi-Pr) ₃ was dissolved in tetrahydrofuran to prepare a 1% by mass M-containing solution. And the electrode main body of Example 6, the electrode of Example 6, the lithium ion secondary battery of Example 6 are the same as Example 1 except having employ | adopted the said 1 mass% M containing solution as M containing solution. Manufactured.

(Example 7)
BH ₃ was employed as the compound represented by the general formula (1). BH ₃ · THF complex was dissolved in tetrahydrofuran so as to be 1% by mass to prepare an M-containing solution. An electrode body of Example 7, an electrode of Example 7, and a lithium ion secondary battery of Example 7 were produced in the same manner as in Example 1, except that the M-containing solution was employed.

(Comparative Example 1)
A lithium ion secondary battery of Comparative Example 1 was produced in the same manner as in Example 1, except that the electrode body of Example 1 was changed to the electrode of Comparative Example 1.

(Comparative Example 2)
A lithium ion secondary battery of Comparative Example 2 was produced in the same manner as in Example 1 except that the electrode body of Example 2 was changed to the electrode of Comparative Example 2.

(Evaluation example 1)
For each lithium ion secondary battery, discharging was performed at a DC current of 0.2 mA until the voltage with respect to the counter electrode of the evaluation electrode reached 0.01 V, and 10 minutes after the discharge was completed, the evaluation electrode was tested at a DC current of 0.2 mA. It charged until the voltage with respect to a counter electrode became 1.0V. The discharge capacity at this time was defined as the initial discharge capacity, and the charge capacity was defined as the initial charge capacity. The initial efficiency (%) was defined as (initial charge capacity / initial discharge capacity) × 100.

  Moreover, 20 cycles of discharge charging were performed on each lithium ion secondary battery, with the above discharging and charging as one cycle. (Charge capacity after 20 cycles / initial charge capacity) × 100 was defined as a capacity retention rate (%).

  In Evaluation Example 1, storing Li in the evaluation electrode is referred to as discharging, and discharging Li from the evaluation electrode is referred to as charging.

  The results of the lithium ion secondary batteries of Examples 1 and 3 to 7 and Comparative Example 1 are shown in Table 1, and the results of the lithium ion secondary batteries of Example 2 and Comparative Example 2 are shown in Table 2, respectively.

  The capacity retention rates of the lithium ion secondary batteries of Examples 1 and 3 to 7 were significantly higher than the lithium ion secondary battery of Comparative Example 1. Similarly, the capacity retention rate of the lithium ion secondary battery of Example 2 was significantly higher than that of the lithium ion secondary battery of Comparative Example 2. The suitable effect of the electrode of this invention by having changed the electrode surface by M containing solution process has been confirmed. In particular, it is worthy to note that advantageous effects were confirmed in the electrode of the present invention using an Si-containing material known to have a large degree of expansion and contraction associated with insertion and extraction of lithium as an active material.

Claims (4)

Preparing an electrode body comprising polyacrylic acid, polymethacrylic acid, or a copolymer of acrylic acid and methacrylic acid,
Preparing a solution containing a compound represented by the following general formula (1):
MH _m (OR) _n General formula (1)
(M is Ti, Si, P or B, R is each independently H or alkyl, m and n are integers of 0 or more, and satisfy m + n = (absolute value of M valence)). .)
Contacting the electrode body with the solution;
The manufacturing method of the electrode for non-aqueous secondary batteries characterized by including. An electrode body comprising polyacrylic acid, polymethacrylic acid, or a copolymer of acrylic acid and methacrylic acid;
The M-containing portion formed on the surface of the electrode body and (M is Ti, Si, a P or B.), Have a,
M of said M containing part has couple | bonded with polycarboxylic acid, polymethacrylic acid, or several carboxylic acid of the copolymer of acrylic acid and methacrylic acid, The electrode for nonaqueous secondary batteries characterized by the above-mentioned. A nonaqueous secondary battery comprising the electrode for a nonaqueous secondary battery according to claim 2 . A non-aqueous secondary battery manufacturing method using the non-aqueous secondary battery electrode obtained by the manufacturing method according to claim 1.

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