JP2015187985A - Active material for nonaqueous secondary battery negative electrodes, negative electrode arranged by use thereof, and nonaqueous secondary battery - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an active material for nonaqueous secondary battery negative electrodes, which enables the suppression of gas generation owing to decomposition of a nonaqueous electrolyte and enables the achievement of superior charge and discharge efficiencies at the time of initial conditioning.SOLUTION: An active material for nonaqueous secondary battery negative electrodes comprises: an active material (A) which allows lithium ions to go thereinto and desorb therefrom; and an organic compound (D). The organic compound (D) includes: compound (B) having a radical-polymerizable unsaturated bond; and a polymer (C) hard to dissolve in a nonaqueous electrolyte.

Description

  The present invention relates to a non-aqueous secondary battery negative electrode active material useful for the production of a non-aqueous secondary battery that generates less gas due to decomposition of a non-aqueous electrolyte and has excellent battery storage characteristics. The present invention further relates to a negative electrode for a non-aqueous secondary battery obtained using the active material and a non-aqueous secondary battery including the negative electrode.

In recent years, with the development of electric vehicles and the like, lithium ion secondary batteries, which are non-aqueous secondary batteries, have been actively studied as high energy density type batteries. For lithium ion secondary batteries, it is known to use a carbon material such as graphite as the negative electrode active material.
Among them, graphite having a high degree of graphitization, when used as an active material for a negative electrode for a lithium ion secondary battery, has a capacity close to 372 mAh / g, which is the theoretical capacity for lithium occlusion of graphite. Since it is excellent also in the property, it is known that it is preferable as an active material for negative electrodes.

  When such a carbon material is used as an active material for a negative electrode of a lithium ion secondary battery, the surface of the carbon material is usually reacted with a polymer compound used as a binder or a non-aqueous electrolyte. A protective coating called SEI (Solid Electrolyte Interface) is formed. SEI prevents contact between the carbon material and the non-aqueous electrolyte, and suppresses decomposition of the non-aqueous electrolyte by the active carbon material. As a result, it is also known that the chemical stability of the negative electrode surface is maintained.

  However, in a lithium ion secondary battery using a carbon material as an active material for a negative electrode, the charge / discharge irreversible capacity during the initial cycle increases due to the generation of SEI film and the generation of gas as a side reaction product. There was a problem that the capacity could not be increased. Furthermore, the formation of the SEI film increases the interfacial resistance (negative electrode resistance) of the negative electrode, which degrades the input / output characteristics of the battery, and the peeling of the SEI film due to repeated charge and discharge of the battery and the SEI film. There was a problem that the storage characteristics deteriorated due to the re-formation.

In order to solve the above problems, there are known techniques for adhering a material that captures radicals generated in a battery to a carbon material that is an active material for a negative electrode or a technique for adding it in the form of being dissolved in an electrolyte. Yes.
For example, Patent Document 1 proposes a technique for improving high temperature characteristics, storage characteristics, cycle characteristics, and the like by including an unsaturated chain sulfone compound having a sulfonyl group and an unsaturated bond in the electrolyte. ing.

  Further, Patent Document 2 discloses that, based on the idea that free radicals are generated on the graphite surface during the pulverization of the graphite and become an active site for decomposing the non-aqueous electrolyte solution, the unsaturated bonded single substance is formed on the finely divided graphite. After acting as a masking material, a radical reaction reagent such as a monomer, radical polymerization initiator, radical polymerization terminator, the remaining masking agent is washed and removed with a solvent, and then the resulting graphite particles are sufficiently dried, There has been proposed a technique for suppressing the irreversible charge / discharge capacity seen during the initial cycle by suppressing the decomposition of the nonaqueous electrolyte solution.

Patent Document 3 discloses that a negative electrode, a positive electrode, or an electrolyte has a group in which at least one hydrogen group is eliminated from edaravone or hindered phenol, or a derivative thereof, and one or more carboxylate metal bases. Or the technique which suppresses decomposition | disassembly of non-aqueous electrolyte solution and improves cycling characteristics by containing the compound in which the sulfonic-acid metal base was introduce | transduced is proposed.

  Patent Document 4 discloses that the surface of a carbon material is added to a carbon material by adding an alkali metal salt of an organic acid having a pKa of 5.6 or more at 25 ° C. and / or an alkali metal salt of a polymer of the organic acid. There has been proposed a technique for suppressing the irreversible capacity of charge and discharge, which is observed during an initial cycle when a propylene carbonate solvent is used as an electrolytic solution, in particular, by suppressing the reaction between the electrolyte and the nonaqueous electrolytic solution.

JP 2007-273395 A JP-A-11-111292 JP 2010-44957 A JP 2011-210683 A

  However, according to studies by the present inventors, it is described that the additive dissolved in the electrolyte disclosed in Patent Document 1 improves storage characteristics or cycle characteristics by capturing radicals generated in the battery and forming a film. In practice, however, it acts not only on the surface of the negative electrode but also in the entire battery system. Therefore, the reduced polymer of the additive formed in the non-aqueous electrolyte solution seals the pores of the separator porous film and oxidizes at the positive electrode. This was a technology that had room for improvement, such as gas generation by decomposition.

  In the technique disclosed in Patent Document 2, a graphite surface is obtained by contacting and reacting a masking material such as an unsaturated bond monomer reactive with a radical, a radical polymerization initiator, and a radical polymerization terminator with graphite. Although it is described that the free radical-derived active sites are reduced and the reductive decomposition of the non-aqueous electrolyte solution is suppressed, the radicals generated in the battery during the initial charge / discharge cannot be suppressed after the battery is manufactured. In addition, suppression of reductive decomposition of the non-aqueous electrolyte solution on the surface of the graphite in contact with the non-aqueous electrolyte solution was not sufficient.

  Although the technique disclosed in Patent Document 3 describes that a low-molecular compound having radical scavenging ability is used to trap radicals generated in the battery and improve cycle characteristics, the compounds shown Since radicals always exist as low molecules even after radical scavenging, the contact between the negative electrode surface and the non-aqueous electrolyte in a state showing a very strong reducing atmosphere, such as when the negative electrode is fully charged, cannot be suppressed, and gas generation is suppressed. The improvement effect on was not sufficient.

  In the technique disclosed in Patent Document 4, by adding lithium maleate as an alkali metal salt of an organic acid having a pKa of 5.6 or more at 25 ° C., the charge / discharge irreversible capacity seen during the initial cycle is reduced. On the other hand, the inorganic lithium salt produced by the acid contact treatment has insufficient surface adhesion with the carbon material, so the inorganic lithium salt peels off and the non-aqueous electrolyte and the carbon material come into contact. Thus, the reductive decomposition of the non-aqueous electrolyte solution and the re-formation of the SEI film were repeated, and thus the improvement effect on the suppression of gas generation was not sufficient.

  The present invention has been made in view of such background art. In a non-aqueous secondary battery, the non-aqueous secondary battery is excellent in charge and discharge efficiency during initial conditioning while suppressing gas generation due to decomposition of the non-aqueous electrolyte. An object is to provide an active material for a secondary battery negative electrode.

As a result of intensive studies to solve the above problems, the present inventors have found that “insertion of lithium ions /
By using a non-aqueous secondary battery negative electrode active material containing an detachable active material (A) (hereinafter also referred to as “active material (A)”) and an organic compound (D), It has been found that an excellent non-aqueous secondary battery with improved generation suppression effect can be obtained, and the present invention has been completed.
In the present invention, the organic compound (D) is “a compound (B) having an unsaturated bond capable of radical polymerization and a hetero atom in a part of its chemical structure and / or a polymer of the compound (B)” (hereinafter referred to as “compound ( B) ”) and contains a polymer (C) that is hardly soluble in a non-aqueous electrolyte.

Here, although the details that the non-aqueous secondary battery negative electrode active material according to the present invention exhibits the above-mentioned effects are unclear, as a result of the study by the inventors, the excellent battery characteristics are considered to be due to the following effects.
That is, when the active material (A) and the organic compound (D) are included in the active material layer for the nonaqueous secondary battery negative electrode, the synergistic effect of the compound (B) and the polymer (C) in the organic compound (D) is obtained. The following effects are considered to be obtained for the active material (A). First, the compound (B) suppresses the activity on the surface of the active material (A) and reacts with radicals generated in the battery, thereby suppressing the reductive decomposition of the nonaqueous electrolytic solution. Furthermore, the polymer (C) also covers the surface of the active material (A), thereby suppressing the activity of the surface of the active material (A), and being hardly soluble in the non-aqueous electrolyte of the polymer (C). This prevents the contact between the compound (B) and the electrolytic solution and suppresses the elution of the compound (B) into the electrolytic solution.

  In addition, the compound (B) itself undergoes radical polymerization by radicals generated in the battery, thereby forming an electronic insulating film having high chemical stability that does not swell in the non-aqueous electrolyte solution on the surface of the active material (A). Since the formed coating derived from the compound (B) can greatly reduce the contact between the active material (A) and the non-aqueous electrolyte, the reduction reaction due to the contact between the active material (A) and the non-aqueous electrolyte is suppressed. Therefore, it is considered that gas generation in the battery during charging and discharging is reduced. At this time, the compound (B) can be physically and / or chemically more highly selective by interaction with the polymer (C) and can be present on the graphite surface in a form in which swelling and dissolution in the electrolyte are suppressed. It is considered that the radical polymerization of (B) is selectively performed on the negative electrode surface and grows as a non-swelled coating film. By this, it can suppress that a compound (B) becomes a generation gas source by oxidizing and decomposing on the positive electrode surface.

Furthermore, when the formed film derived from the compound (B) and the polymer (C) formed on the surface of the active material (A) by the above mechanism coexist, the battery is stored in a charged state at a high temperature. It is thought that the gas generation resulting from the reductive decomposition of the nonaqueous electrolyte solution which occurs can be suppressed.
Further, since the compound (B) of the present invention, the formed coating derived from the compound (B) after polymerization, and the polymer (C) are each hardly soluble in the non-aqueous electrolyte solution, the non-aqueous secondary battery negative electrode of the present invention is used. The resistance of the active material to the non-aqueous electrolyte is improved, and the elution of the compound (B) adsorbed on the active material (A), its polymer-forming film, and the polymer (C) into the non-aqueous electrolyte is suppressed. In addition to the effect, the surface of the active material (A) and the compound (B) and its polymer-forming film, and further, the surface between the active material (A) and the polymer (C), and between the compound (B) and the polymer (C) are high. It is thought that adsorptivity can be imparted.

  That is, the gist of the present invention is an active material for a negative electrode of a non-aqueous secondary battery containing an active material (A) capable of inserting and removing lithium ions and an organic compound (D), the organic compound (D) A non-aqueous secondary battery negative electrode active material characterized in that is an organic compound containing a compound (B) having an unsaturated bond capable of radical polymerization and a polymer (C) that is hardly soluble in a non-aqueous electrolyte solution Exist.

Another gist of the present invention resides in a negative electrode for a non-aqueous secondary battery, characterized by being formed using the carbon material for a non-aqueous secondary battery negative electrode.
Another aspect of the present invention is a non-aqueous secondary battery comprising a positive electrode and a negative electrode capable of inserting and extracting lithium ions, and an electrolyte, wherein the negative electrode is the negative electrode for a non-aqueous secondary battery. Next battery.

  According to the present invention, reductive decomposition of a non-aqueous electrolyte is suppressed by the organic compound (D), and it is useful for manufacturing a non-aqueous secondary battery that is further improved in initial charge / discharge efficiency and excellent in suppressing gas generation. Moreover, the outstanding active material for nonaqueous secondary battery negative electrodes can be provided. Moreover, the non-aqueous secondary battery provided with the said negative electrode for non-aqueous secondary batteries using the said active material for non-aqueous secondary battery negative electrodes, and the said negative electrode can be provided.

Hereinafter, the contents of the present invention will be described in detail. In addition, the following description is an example (representative example) of the embodiment of this invention, and this invention is not specified to these forms, unless the summary is exceeded.
[Non-aqueous secondary battery negative electrode active material]
The active material for a nonaqueous secondary battery negative electrode of the present invention contains at least an active material (A) and an organic compound (D).

<Active material (A)>
The active material (A) is not particularly limited as long as it is a material that can occlude and release lithium ions in its skeleton.
Examples thereof include graphite, amorphous carbon, various carbon materials typified by carbonaceous materials having a low degree of graphitization, silicon-based materials, and tin-based materials. Although these will be described in detail, lithium storage capacity, cycle characteristics, and cost balance are at least one selected from the group consisting of artificial graphite, natural graphite, amorphous carbon, silicon, and silicon oxide. To preferred. Further, those coated with amorphous carbon or graphitized material may be used.

In this invention, these can be used individually or in combination of 2 or more types. The material may contain an oxide or other metal.
The shape of the active material (A) is not particularly limited, and can be appropriately selected from spherical, flaky, fibrous, and amorphous particles, but is preferably spherical.
Examples of the carbon material include artificial graphite, natural graphite, amorphous carbon, and a carbonaceous material having a low degree of graphitization. From the viewpoint of low cost and ease of electrode production, artificial graphite or natural graphite is used. Is preferable, and natural graphite is more preferable.

These carbon materials preferably have few impurities, and are used after being subjected to various purification treatments as necessary.
Examples of the natural graphite include scaly graphite, scaly graphite, and soil graphite. The production area of the scaly graphite is mainly Sri Lanka, the production area of the scaly graphite is mainly Madagascar, China, Brazil, Ukraine, Canada, etc., and the main production area of the soil graphite is the Korean Peninsula, China, Such as Mexico.

Among these natural graphites, soil graphite generally has a small particle size and low purity. On the other hand, scaly graphite and scaly graphite have advantages such as a high degree of graphitization and a low amount of impurities, and therefore can be preferably used in the present invention.
The shape of the natural graphite is preferably spherical from the viewpoint of exhibiting the effects of the present invention, and particularly preferably spherical natural graphite as the active material (A).

More specifically, it is spheroidized natural graphite obtained by subjecting highly purified scale-like natural graphite to spheronization treatment. The method for the spheroidizing process will be described later.
Examples of the artificial graphite include coal tar pitch, coal heavy oil, atmospheric residue, petroleum heavy oil, aromatic hydrocarbon, nitrogen-containing cyclic compound, sulfur-containing cyclic compound, polyphenylene, polyvinyl chloride, Examples thereof include those obtained by baking and graphitizing organic substances such as polyvinyl alcohol, polyacrylonitrile, polyvinyl butyral, natural polymer, polyphenylene sulfide, polyphenylene oxide, furfuryl alcohol resin, phenol-formaldehyde resin, and imide resin.

The firing temperature can be in the range of 2500 ° C. or more and 3200 ° C. or less, and a silicon-containing compound, a boron-containing compound, or the like can be used as a graphitization catalyst during firing.
Examples of the amorphous carbon include particles obtained by firing a bulk mesophase and particles obtained by infusibilizing and firing a carbon precursor.
Examples of the carbonaceous material having a small degree of graphitization include those obtained by firing an organic material at a temperature of usually less than 2500 ° C. Organic substances include coal-based heavy oil such as coal tar pitch and dry distillation liquefied oil; straight-run heavy oil such as atmospheric residual oil and vacuum residual oil; ethylene tar produced as a by-product during thermal decomposition of crude oil, naphtha, etc. Heavy oils such as cracked heavy oils; aromatic hydrocarbons such as acenaphthylene, decacyclene and anthracene; nitrogen-containing cyclic compounds such as phenazine and acridine; sulfur-containing cyclic compounds such as thiophene; and aliphatic cyclics such as adamantane Compounds: Polyphenylene such as biphenyl and terphenyl; Polyvinyl esters such as polyvinyl chloride, polyvinyl acetate, and polyvinyl butyral; Thermoplastic polymers such as polyvinyl alcohol, and the like.

Depending on the degree of graphitization of the carbonaceous material, the firing temperature can usually be 600 ° C. or higher, preferably 900 ° C. or higher, more preferably 950 ° C. or higher, and usually lower than 2500 ° C. , Preferably it is 2000 degrees C or less, More preferably, it is the range of 1400 degrees C or less.
At the time of firing, acids such as phosphoric acid, boric acid and hydrochloric acid, alkalis such as sodium hydroxide and the like can be mixed with the organic matter.

Examples of the silicon-based material include silicon and silicon oxide. Specifically, any of SiO _y , SiC _x O _y , (wherein x and y may be in any ratio), a silicon-silicon oxide composite, or an alloy of silicon and other metals may be used. Of these, silicon (Si) and silicon oxide are preferable from the viewpoint of lithium storage capacity and cycle characteristics.
As the silicon-based material, a form capable of relieving volume expansion and contraction during lithium insertion / extraction, such as a small particle size, thin film, and porous structure, is preferable, and is used in combination with a carbon material or other active material as necessary. be able to.

As the tin-based material, any of tin, stannous oxide, stannic oxide, and tin amorphous alloy may be used. The tin-based material is preferably in a form that can relieve volume expansion and contraction during lithium insertion and desorption, such as small particle size, thin film, and porous structure, and can be combined with various carbon materials and other active material materials as necessary. And use.
Next, various physical properties of the active material (A) will be described. The active material (A) preferably satisfies at least one of the following physical properties.

(Average particle diameter (d50))
The average particle diameter (d50) of the active material (A) is usually 1 μm or more and 50 μm or less. Within this range, it is possible to prevent inconveniences in the process, such as striation of the negative electrode forming material, when forming a plate at the time of manufacturing the negative electrode.
The average particle diameter (d50) is preferably 4 μm or more, more preferably 10 μm or more, and preferably 30 μm or less, more preferably 25 μm or less.

  In the present specification, the average particle diameter (d50) means a volume-based median diameter. Specifically, 0.01 g of a sample is suspended in 10 mL of a 0.2% by mass aqueous solution of polyoxyethylene sorbitan monolaurate, which is a surfactant, and introduced into a commercially available laser diffraction / scattering particle size distribution analyzer. After irradiating a 28 kHz ultrasonic wave with an output of 60 W for 1 minute, it can be obtained as a value measured as a volume-based median diameter in a measuring apparatus.

(Tap density)
The tap density of the active material (A) is usually 0.7 g / cm ³ or more, 1.0 g / cm ³ or more. Moreover, it is 1.3 g / cm < ³ > or less normally, and 1.1 g / cm < ³ > or less is preferable.
If the tap density is too low, the high-speed charge / discharge characteristics are inferior when used for a negative electrode for a non-aqueous secondary battery. On the other hand, if the tap density is too high, the active material (A) in the particles that are the material constituting the negative electrode In some cases, the negative electrode forming material lacks rollability and it is difficult to form a high-density negative electrode sheet.

In the present invention, the tap density is measured by dropping a sample through a sieve having a mesh size of 300 μm into a cylindrical tap cell having a diameter of 1.6 cm and a volume capacity of 20 cm ³ using a powder density measuring instrument, A tap having a stroke length of 10 mm is performed 1000 times, and the density obtained from the volume after the tap and the weight of the sample is defined as the tap density.

(BET specific surface area (SA))
The specific surface area (BET method specific surface area) measured by the BET method of the active material (A) is usually 1 m ² / g or more and 11 m ² / g or less. If it is within this range, the portion where Li ions enter and exit is sufficient, so even when used as a negative electrode for a non-aqueous secondary battery, good high-speed charge / discharge characteristics and output characteristics can be obtained, and non-aqueous electrolysis of the active material. It is possible to control the activity with respect to the liquid, to reduce the initial irreversible capacity, and to easily increase the capacity.

The BET specific surface area is preferably 1.2 m ² / g or more, more preferably 1.5 m ² / g or more, preferably 10 m ² / g or less, more preferably 9 m ² / g or less, and still more preferably. Is 8 m ² / g or less.
In the present specification, the BET method specific surface area is a value measured by a BET 5-point method by a nitrogen gas adsorption flow method using a specific surface area measuring device.

(X-ray parameters)
When the active material (A) is a carbon material, a surface spacing _{d 002} of the carbon material by X-ray wide angle diffraction method (002) plane is generally 0.335nm or more and less than 0.340 nm, preferably 0.339nm or less More preferably, it is 0.337 nm or less. When the d ₀₀₂ value is less than 0.340 nm, appropriate crystallinity is obtained, and an increase in initial irreversible capacity can be suppressed when used for a negative electrode for a non-aqueous secondary battery. Note that 0.335 nm is a theoretical value of graphite.

(Raman R value)
When the active material (A) is a carbon material, the Raman R value of the carbon material is measured and the intensity _{I A} of the peak _{P A} in the vicinity of 1580 cm ^-1, and an intensity _{I B} of a peak _{P B} in the vicinity of 1360 cm ^-1 Then, the intensity ratio R (R = I _B / I _A ) is calculated and defined. The R value is usually 0.01 or more and 1 or less, preferably 0.6 or less. When the Raman R value is less than this range, the crystallinity of the particle surface becomes too high, and when the density is increased, the crystals tend to be oriented in the direction parallel to the electrode plate, and the load characteristics tend to be lowered. On the other hand, if it exceeds this range, the crystallinity of the particle surface is disturbed, the reactivity with the non-aqueous electrolyte increases, and when used in a negative electrode for a non-aqueous secondary battery, the efficiency decreases and the gas generation increases. Tend.

The Raman spectrum can be measured with a Raman spectrometer. Specifically, the sample particles are naturally dropped into the measurement cell to fill the sample, and the measurement cell is irradiated with an argon ion laser beam while rotating in a plane perpendicular to the laser beam irradiated to the measurement cell. Make measurements.
Argon ion laser light wavelength: 532 nm
Laser power on sample: 25 mW
Resolution: 4cm ^-1
Measurement range: 1100 cm ^{−1 to} 1730 cm ⁻¹
Peak intensity measurement, peak half-width measurement: background processing, smoothing processing (convolution 5 points by simple averaging)

(Method for producing active material (A))
The active material (A) described above can be produced by various known methods, and the production method is not particularly limited. Here, the manufacturing method from natural graphite is demonstrated about the spheroidized natural graphite preferably used as an active material (A) in this invention.

Spherical natural graphite is obtained by spheronizing natural graphite. As an apparatus used for the spheronization treatment, for example, an apparatus that repeatedly gives mechanical action such as compression, friction, shearing force, etc. including the interaction of particles mainly with impact force to the particles can be used.
Specifically, it has a rotor with a large number of blades installed inside the casing, and the rotor rotates at high speed, so that the natural graphite raw material introduced into the casing is mechanically compressed such as impact compression, friction, shear force, etc. An apparatus that provides an action and performs surface treatment is preferable.

By applying the spheroidizing treatment, the scaly natural graphite is folded or the peripheral edge portion is spherically pulverized, so that the base particles become spherical. The fine particles of 5 μm or less generated by pulverization adhere to the base particles. In addition, it is preferable to perform the spheronization treatment under the condition that the surface functional group amount O / C value of the natural graphite after the spheronization treatment is usually 1% or more and 4% or less.
In this case, it is preferable to perform the spheronization treatment in an active atmosphere so that the oxidation reaction of the natural graphite surface can be advanced by the energy of the mechanical treatment and acidic functional groups can be introduced into the natural graphite surface. For example, when processing using the above-mentioned apparatus, the peripheral speed of the rotating rotor is preferably 30 m / second or more and 100 m / second or less, preferably 40 m / second or more and 100 m / second or less, and 50 m / second or more and 100 m / second or less. It is more preferable to set it to 2 seconds or less.

(Coating treatment)
As for the active material (A) used for this invention, at least one part of the surface may be coat | covered with the carbonaceous material. The aspect of this coating can be confirmed with a scanning electron microscope (SEM) photograph or the like.
The carbonaceous material used for the coating treatment includes amorphous carbon and graphitized material, and those obtained are different depending on the difference in the firing temperature in the coating treatment described later.

Specifically, the material described in the following (1) or (2) is preferable as the carbon precursor of the carbonaceous material.
(1) Coal heavy oil, DC heavy oil, cracked heavy oil, aromatic hydrocarbon, N ring compound, S ring compound, polyphenylene, organic synthetic polymer, natural polymer, thermoplastic resin and At least one or more carbonizable organic substances selected from the group consisting of thermosetting resins;

(2) A material obtained by dissolving the carbonizable organic substance shown in (1) above in a low molecular organic solvent.
Among the above (1) and (2), coal-based heavy oil, direct-current heavy oil, cracked petroleum heavy oil, or those obtained by dissolving these in a low-molecular organic solvent is a carbonaceous material after firing. It is more preferable because it is uniformly coated.
In the coating treatment, for example, when spheroidized natural graphite is used as the active material (A) to form nuclear graphite, carbon precursors for obtaining carbonaceous materials are used as coating raw materials, and these are mixed and fired to obtain carbon. An active material (A) coated with a material is obtained.

<Organic compound (D)>
By containing the organic compound (D), the non-aqueous secondary battery negative electrode active material of the present invention suppresses the reaction between the active material (A) surface and the non-aqueous electrolyte and effectively suppresses the generation of gas. However, it is possible to improve the charge / discharge efficiency during initial conditioning.
The organic compound (D) contains the compound (B) and the polymer (C), but this form contains a compound (B) and a polymer (C), and the compound (B) reacts to form a polymer. A film and a polymer (C) -containing material, a compound (B) and a polymer (C) react, a compound (B) reacts to form a polymerization film and a polymer (C) reacts Any of these may be used, and two or more of the above forms may be present.
Hereinafter, the compound (B) and the polymer (C) constituting the organic compound (D) will be described in detail.

(Compound (B))
The organic compound (D) of the present invention contains the compound (B), thereby suppressing the reaction between the surface of the active material (A) and the non-aqueous electrolyte, effectively suppressing the generation of gas, and during initial conditioning. The charging / discharging efficiency of the battery can be improved.

The compound (B) used in the present invention has an unsaturated bond capable of radical polymerization. The unsaturated bond capable of radical polymerization is a carbon-carbon bond, and is not particularly limited as long as the bond is at least one unsaturated bond selected from a double bond and a triple bond. -A carbon double bond is preferred.
Carbon - carbon double bond vinyl group as having a _{(alkene) (H 2 C = CH-)} , allyl group _{(H 2 C = CH-CH} 2 -), acryloyl group _{(H 2 C = CH-C} ( = O)-), methacryloyl group (H ₂ C═C (CH ₃ ) —C (═O) —), carbon-carbon triple bond (alkyne) having acetylene group, propyne group, butyne group, pentyne Groups.

  If it has the said structure, the compound (B) of this invention will not be specifically limited, The formation film derived from the polymer of the compound (B) of this invention and a compound (B) is hardly soluble to non-aqueous electrolyte solution. Preferably, the resistance of the active material for a nonaqueous secondary battery negative electrode of the present invention to a nonaqueous electrolyte is improved, and the compound (B) adsorbed on the active material (A) and the polymer of the compound (B) are derived. The formed film becomes difficult to elute into the non-aqueous electrolyte.

As used herein, the term “slightly soluble in a non-aqueous electrolyte solution” means a compound whose solubility in water at 25 ° C. is usually 5% by mass or more, and more than 10% by mass can be dissolved. preferable.
That it is hardly soluble in the non-aqueous electrolyte solution preferably has an ionic group in so-called water. In the present specification, the ionic group is a group capable of generating an anion or cation in water, and an acid anhydride is also included herein. Examples thereof include an anionic group such as a carbamic acid group, a carboxylic acid group, a sulfonic acid group, a sulfinic acid group, a phosphoric acid group, a phosphonic acid group, a boronic acid group, a borinic acid group, and a hydroxyl group. Examples of the group include a primary amino group, a secondary amino group, a tertiary amino group, and a quaternary ammonium group.

These ionic groups may be salts. Examples of the salt of the anionic group include alkali metal salts such as lithium salt, sodium salt, and potassium salt, and alkali metal salts such as calcium salt and magnesium salt. Examples of the salt of the cationic group include hydrochloride and acetate. , Sulfates, amide sulfates, ammonium salts and the like. These ionic groups are preferable from the viewpoint of stability in the battery and suppression of resistance increase. Among these, from the viewpoint of gas generation when used for a negative electrode for a non-aqueous secondary battery, an anionic group or a salt thereof is preferable, a carboxylic acid group, a sulfonic acid group or a salt thereof is more preferable, and a sulfonic acid or a salt thereof. Is most preferred.

The compound (B) may be a low molecular compound or a high molecular compound (macromonomer) as long as it has an unsaturated bond capable of radical polymerization. A low molecular weight compound is particularly preferable from the viewpoint of forming a dense polymer film on the surface of the negative electrode active material in the battery.
Specific embodiments of the compound (B) of the present invention are described in detail below.

  Examples of the low molecular weight compound (B) include vinyl sulfonic acid, allyl sulfonic acid, allyl benzene sulfonic acid, allyl benzene disulfonic acid, allyl naphthalene sulfonic acid, allyl naphthalene disulfonic acid, allyl naphthalene trisulfonic acid, allyl anthracene sulfone. Acid, allyl anthracene disulfonic acid, allyl anthracene sulfonic acid, acryloyl sulfonic acid, acryloyl benzene sulfonic acid, acryloyl benzene disulfonic acid, acryloyl naphthalene sulfonic acid, acryloyl naphthalene disulfonic acid, acryloyl naphthalene trisulfonic acid, methacryloyl sulfonic acid, methacryloyl benzene sulfone Acid, methacryloylbenzenedisulfonic acid, methacryloylnaphthalenesulfonic acid, methacryloylnaphtha Disulfonic acid, methacryloylanthracenesulfonic acid, methacryloylanthracenedisulfonic acid, methacryloylanthracenesulfonic acid, styrenesulfonic acid, styrenedisulfonic acid, vinylnaphthalenesulfonic acid, vinylnaphthalenedisulfonic acid, vinylanthracenesulfonic acid, vinylanthracenedisulfonic acid, vinylanthracentriic acid Sulfonic acid,

  2-acrylamidosulfonic acid, 2-acrylamidobenzenesulfonic acid, 2-acrylamidobenzenedisulfonic acid, 2-acrylamidoethanesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, 2-acrylamido-t-butylsulfonic acid, 2- Methacrylamide amidosulfonic acid, 2-methacrylamido-2-methylpropanesulfonic acid, methacrylamidobenzenesulfonic acid, dimethacrylamideamidodisulfonic acid, 2-acryloyloxyethanesulfonic acid, 3-acryloyloxypropanesulfonic acid, 4-acryloyl Oxybutanesulfonic acid, 2-methacryloyloxyethanesulfonic acid, 3-methacryloyloxypropanesulfonic acid, 4-methacryloyloxybutanesulfonic acid, vinylimidazo Methane sulfonic acid, vinyl imidazoline ethane sulfonic acid, vinyl ether sulfonic acid, vinyl ether methyl sulfonic acid, vinyl ether ethyl sulfonic acid, vinyl ether phenyl sulfonic acid, vinyl ether phenyl disulfonic acid, vinyl ether naphthyl sulfonic acid, vinyl ether naphthyl disulfonic acid, vinyl ether anthracenyl sulfone Acid, vinyl ether anthracenyl disulfonic acid, vinyl aminobenzene sulfonic acid, vinyl aminobenzene disulfonic acid, acenaphthyl sulfonic acid, ethynyl sulfonic acid, ethynyl benzene sulfonic acid, cyclohexyl ethynyl sulfonic acid, cyclohexyl ethynyl benzene sulfonic acid,

Diallylbenzenesulfonic acid, diallylbenzenedisulfonic acid, diallylnaphthalenesulfonic acid, diallylnaphthalenedisulfonic acid, diallylnaphthalenetrisulfonic acid, diallylanthracenesulfonic acid, diallylanthracenedisulfonic acid, diallylanthracentrysulfonic acid, diacryloylbenzenesulfonic acid, diacryloyl Benzene disulfonic acid, diacryloylnaphthalene sulfonic acid, diacryloyl naphthalene disulfonic acid, diacryloyl naphthalene trisulfonic acid, dimethacryloyl benzene sulfonic acid, dimethacryloyl benzene disulfonic acid, dimethacryloyl naphthalene sulfonic acid, dimethacryloyl naphthalene disulfonic acid, dimethacryloyl anthracene Sulfonic acid, dimethacryloylanthracene disul Phosphate, dimethacryloyl anthracene trisulfonate, divinylbenzene sulfonic acid, divinyl benzene disulfonic acid, divinyl naphthalene sulfonic acid, divinyl naphthalene disulfonic acid, divinyl anthracene sulfonic acid, divinyl anthracene disulfonic acid, divinyl anthracene trisulfonate,

  Diacrylamide benzene sulfonic acid, diacrylamide benzene disulfonic acid, dimethacrylamide benzene sulfonic acid, dimethacrylamide benzene disulfonic acid, divinyl ether phenyl sulfonic acid, divinyl ether phenyl disulfonic acid, divinyl ether naphthyl sulfonic acid, divinyl ether naphthyl disulfonic acid, Divinyl ether anthracenyl sulfonic acid, divinyl ether anthracenyl disulfonic acid, diallyl phenyl sulfonic acid, diallyl phenyl disulfonic acid, divinyl aminobenzene sulfonic acid, diethynyl benzene sulfonic acid, cyclohexyldiethynyl benzene sulfonic acid,

  Vinylsulfinic acid, allylsulfinic acid, allylbenzenesulfinic acid, allylbenzenedisulfinic acid, allylnaphthalenesulfinic acid, allylnaphthalenedisulfinic acid, allylnaphthalenesulfuric acid, allylanthracenesulfinic acid, allylanthracenedisulfinic acid, allylanthracentri Sulfinic acid, acryloylsulfinic acid, acryloylbenzenesulfinic acid, acryloylbenzenedisulfinic acid, acryloylnaphthalenesulfinic acid, acryloylnaphthalenedisulfinic acid, acryloylnaphthalenesulfuric acid, methacryloylsulfinic acid, methacryloylbenzenesulfinic acid, methacryloylbenzenedisulfinic acid, Methacryloylnaphthalenesulfinic acid, methacryloylnaphtha Disulfinic acid, methacryloylanthracenesulfinic acid, methacryloylanthracenedisulfinic acid, methacryloylanthracensulfuric acid, styrenesulfinic acid, styrenedisulfinic acid, vinylnaphthalenesulfinic acid, vinylnaphthalenedisulfinic acid, vinylanthracenesulfinic acid, vinylanthracenedisulfin Acid, vinyl anthracentrisulfinic acid,

  2-acrylamidosulfinic acid, 2-acrylamidobenzenesulfinic acid, 2-acrylamidobenzenedisulfinic acid, 2-acrylamidoethanesulfinic acid, 2-acrylamido-2-methylpropanesulfinic acid, 2-acrylamido-t-butylsulfinic acid, 2 -Methacrylamidoethanesulfinic acid, 2-methacrylamideamido-2-methylpropanesulfinic acid, methacrylamideamidobenzenesulfinic acid, dimethacrylamideamidodisulfinic acid, 2-acryloyloxyethanesulfinic acid, 3-acryloyloxypropanesulfinic acid, 4 -Acryloyloxybutanesulfinic acid, 2-methacryloyloxyethanesulfinic acid, 3-methacryloyloxypropanesulfinic acid, 4-methacryloyloxybu Sulfinic acid, vinyl imidazoline methane sulfinic acid, vinyl imidazoline ethane sulfinic acid, vinyl ether sulfinic acid, vinyl ether methyl sulfinic acid, vinyl ether ethyl sulfinic acid, vinyl ether phenyl sulfinic acid, vinyl ether phenyl disulfinic acid, vinyl ether naphthyl sulfinic acid, vinyl ether naphthyl disulfinic acid , Vinyl ether anthracenyl sulfinic acid, vinyl ether anthracenyl disulfinic acid, vinyl aminobenzene sulfinic acid, vinyl aminobenzene disulfinic acid, acenaphthyl sulfinic acid, ethynyl sulfinic acid, ethynyl benzene sulfinic acid, cyclohexyl ethynyl sulfinic acid, cyclohexyl ethynyl benzene Sulfinic acid,

Diallylbenzenesulfinic acid, diallylbenzenedisulfinic acid, diallylnaphthalenesulfinic acid, diallylnaphthalenedisulfinic acid, diallylnaphthalenethrisulfinic acid, diallylanthracenesulfinic acid, diallylanthracenedisulfinic acid, diallylanthracensulfuric acid, diacryloylbenzenesulfinic acid , Diacryloylbenzenedisulfinic acid, diacryloylnaphthalenesulfinic acid, diacryloylnaphthalenedisulfinic acid, diacryloylnaphthalenesulfuric acid, dimethacryloylbenzenesulfinic acid, dimethacryloylbenzenedisulfinic acid, dimethacryloylnaphthalenesulfinic acid, dimethacryloylnaphthalene Disulfinic acid, dimethacryloylanthracenesulfinic acid Dimethacryloylanthracene disulfinic acid, dimethacryloylanthracentrisulfinic acid, divinylbenzenesulfinic acid, divinylbenzenedisulfinic acid, divinylnaphthalenesulfinic acid, divinylnaphthalenedisulfinic acid, divinylanthracenesulfinic acid, divinylanthracene disulfinic acid, divinylanthracentri Sulfinic acid,

  Diacrylamidebenzenesulfinic acid, diacrylamidebenzenedisulfinic acid, dimethacrylamideamidobenzenesulfinic acid, dimethacrylamideamidobenzenesulfinic acid, divinyletherphenylsulfinic acid, divinyletherphenyldisulfinic acid, divinylethernaphthylsulfinic acid, divinylethernaphthyl Disulfinic acid, divinyl ether anthracenyl sulfinic acid, divinyl ether anthracenyl disulfinic acid, diallylphenylsulfinic acid, diallylphenyldisulfinic acid, divinylaminobenzenesulfinic acid, diethynylbenzenesulfinic acid, cyclohexyldiethynylbenzenesulfinic acid, Or a salt thereof, or a sulfonyl group-containing monomer in which a part of the structure is fluorinated;

  Vinylphosphonic acid, allylphosphonic acid, allylbenzenephosphonic acid, allylbenzenediphosphonic acid, allylnaphthalenephosphonic acid, allylnaphthalenediphosphonic acid, allylnaphthalenetriphosphonic acid, allylanthracenephosphonic acid, allylanthracenediphosphonic acid, allylanthracentri Phosphonic acid, acryloylphosphonic acid, acryloylbenzenephosphonic acid, acryloylbenzenediphosphonic acid, acryloylnaphthalenephosphonic acid, acryloylnaphthalenediphosphonic acid, acryloylnaphthalenetriphosphonic acid, methacryloylphosphonic acid, methacryloylbenzenephosphonic acid, methacryloylbenzenediphosphonic acid, Methacryloylnaphthalenephosphonic acid, methacryloylnaphthalenediphosphonic acid, methacryloylanthra Phosphonic acid, methacryloylanthracenediphosphonic acid, methacryloylanthracenphosphonic acid, styrenephosphonic acid, styrenediphosphonic acid, vinylnaphthalenephosphonic acid, vinylnaphthalenediphosphonic acid, vinylanthracenephosphonic acid, vinylanthracenediphosphonic acid, vinylanthracenphosphoric acid Acid, 1-heptenylphosphonic acid, 6-heptenylphosphonic acid,

  2-acrylamidophosphonic acid, 2-acrylamidobenzenephosphonic acid, 2-acrylamidobenzenediphosphonic acid, 2-acrylamidoethanephosphonic acid, 2-acrylamido-2-methylpropanephosphonic acid, 2-acrylamido-t-butylphosphonic acid, 2 -Methacrylamidoethanephosphonic acid, 2-methacrylamideamido-2-methylpropanephosphonic acid, methacrylamideamidobenzenephosphonic acid, dimethacrylamideamidobenzenephosphonic acid, 2-acryloyloxyethanephosphonic acid, 3-acryloyloxypropanephosphonic acid, 4 -Acryloyloxybutanephosphonic acid, 2-methacryloyloxyethanephosphonic acid, 3-methacryloyloxypropanephosphonic acid, 4-methacryloyloxybutanephosphonic acid, vinylimidazo Methane phosphonic acid, vinyl imidazoline ethane phosphonic acid, vinyl ether phosphonic acid, vinyl ether methyl phosphonic acid, vinyl ether ethyl phosphonic acid, vinyl ether phenyl phosphonic acid, vinyl ether phenyl diphosphonic acid, vinyl ether naphthyl phosphonic acid, vinyl ether naphthyl diphosphonic acid, vinyl ether anthracenyl Phosphonic acid, vinyl ether anthracenyl diphosphonic acid, vinylaminobenzenephosphonic acid, vinylaminobenzenediphosphonic acid, acenaphthylphosphonic acid, ethynylphosphonic acid, ethynylbenzenephosphonic acid, cyclohexylethynylphosphonic acid, cyclohexylethynylbenzenephosphonic acid,

3-phenylacryloylphosphonic acid, 3-ethoxyacryloylphosphonic acid, 3-methoxyacryloylphosphonic acid, methacryloxyethyl phosphate, diphenyl-2
-Acryloyloxyethyl phosphate, diphenyl-2-methacryloyloxyethyl phosphate, dibutyl-2-acryloyloxyethyl phosphate, dibutyl-2-methacryloyloxyethyl phosphate, dioctyl-2- (meth) acryloyloxyethyl phosphate,

  Diallylbenzenephosphonic acid, diallylbenzenediphosphonic acid, diallylnaphthalenephosphonic acid, diallylnaphthalenediphosphonic acid, diallylnaphthalenetriphosphonic acid, diallylanthracenephosphonic acid, diallylanthracenediphosphonic acid, diallylanthracenphosphonic acid, diacryloylbenzenephosphonic acid Diacryloylbenzenediphosphonic acid, diacryloylnaphthalenephosphonic acid, diacryloylnaphthalenediphosphonic acid, diacryloylnaphthalenetriphosphonic acid, dimethacryloylbenzenephosphonic acid, dimethacryloylbenzenediphosphonic acid, dimethacryloylnaphthalenephosphonic acid, dimethacryloylnaphthalene Diphosphonic acid, dimethacryloylanthracenephosphonic acid, dimethacryloylanthracene diphos Phosphate, dimethacryloyl anthracene tri phosphonic acid, divinyl benzene phosphonic acid, divinyl benzene diphosphonic acid, divinyl naphthalene acid, divinyl naphthalene dicarboxylic acid, divinyl anthracene phosphonic acid, divinyl anthracene dicarboxylic acid, divinyl anthracene tri phosphonic acid,

  Diacrylamidebenzenephosphonic acid, diacrylamidebenzenediphosphonic acid, dimethacrylamideamidobenzenephosphonic acid, dimethacrylamideamidobenzenediphosphonic acid, divinyletherphenylphosphonic acid, divinyletherphenyldiphosphonic acid, divinylethernaphthylphosphonic acid, divinylethernaphthyl Diphosphonic acid, divinyl ether anthracenyl phosphonic acid, divinyl ether anthracenyl diphosphonic acid, diallyl phenyl phosphonic acid, diallyl phenyl diphosphonic acid, divinyl aminobenzene phosphonic acid, diethynyl benzene phosphonic acid, cyclohexyl diethynyl benzene phosphonic acid, Or a salt or the like, or a phosphoric acid / phosphonic acid group-containing monomer in which a part of the structure is fluorinated;

  Vinylboronic acid, allylboronic acid, allylphenylboronic acid, allylphenyldiboronic acid, allylnaphthaleneboronic acid, allylnaphthalenediboronic acid, allylnaphthalenetriboronic acid, allylanthraceneboronic acid, allylanthracenediboronic acid, allylanthracentriboronic acid , Acryloylboronic acid, acryloylbenzeneboronic acid, acryloylbenzenediboronic acid, acryloylnaphthaleneboronic acid, acryloylnaphthalenediboronic acid, acryloylnaphthalenetriboronic acid, acryloylaminophenylboronic acid, methacryloylboronic acid, methacryloylbenzeneboronic acid, methacryloylbenzene Diboronic acid, methacryloylnaphthaleneboronic acid, methacryloylnaphthalenediboronic acid, methacryloylanthracenebo Acid, methacryloylanthracene diboronic acid, methacryloylanthracentiboronic acid, vinylphenylboronic acid, vinylphenyldiboronic acid, vinylnaphthaleneboronic acid, vinylnaphthalenediboronic acid, vinylanthraceneboronic acid, vinylanthracenediboronic acid, vinylanthracene Triboronic acid,

2-acrylamidoboronic acid, 2-acrylamidobenzeneboronic acid, 2-acrylamidobenzenediboronic acid, 2-acrylamidoethaneboronic acid, 2-acrylamido-2-methylpropaneboronic acid, 2-acrylamido-t-butylboronic acid, 2- Methacrylamide ethaneboronic acid, 2-methacrylamide-2-methylpropaneboronic acid, methacrylamidephenylboronic acid, dimethacrylamideamidophenylboronic acid, 2-acryloyloxyethaneboronic acid, 3-acryloyloxypropaneboronic acid, 4- Acryloyloxybutaneboronic acid, 2-methacryloyloxyethaneboronic acid, 3-methacryloyloxypropane boronic acid, 4-methacryloyloxybutaneboronic acid, vinylimidazoline methaneboronic acid, vinylimida Phosphorus ethane boronic acid, vinyl ether boronic acid, vinyl ether methyl boronic acid, vinyl ether ethyl boronic acid, vinyl ether phenyl boronic acid, vinyl ether phenyl diboronic acid, vinyl ether naphthyl boronic acid, vinyl ether naphthyl diboronic acid, vinyl ether anthracenyl boronic acid, vinyl ether anthrac Senyldiboronic acid, vinylaminophenylboronic acid, vinylaminophenyldiboronic acid, acenaphthylboronic acid, ethynylboronic acid, ethynylphenylboronic acid, cyclohexylethynylboronic acid, cyclohexylethynylphenylboronic acid,

  Diallylbenzeneboronic acid, diallylbenzenediboronic acid, diallylnaphthaleneboronic acid, diallylnaphthalenediboronic acid, diallylnaphthalenetriboronic acid, diallylanthraceneboronic acid, diallylanthracenediboronic acid, diallylanthracenboronic acid, diacryloylbenzeneboronic acid , Diacryloylbenzenediboronic acid, diacryloylnaphthaleneboronic acid, diacryloylnaphthalene diboronic acid, diacryloylnaphthalenetriboronic acid, dimethacryloylbenzeneboronic acid, dimethacryloylbenzenediboronic acid, dimethacryloylnaphthaleneboronic acid, dimethacryloylnaphthalene Diboronic acid, dimethacryloylanthraceneboronic acid, dimethacryloylanthracene diboronic acid, dimethacryloylanthracene Boronic acid, divinyl benzene boronic acid, divinylbenzene acid, divinyl naphthalene acid, divinyl naphthalene dicarboxylic acid, divinyl anthracene boronic acid, divinyl anthracene dicarboxylic acid, divinyl anthracene tri boronic acid,

  Diacrylamide phenyl boronic acid, diacrylamide phenyl diboronic acid, dimethacrylamide amide phenyl boronic acid, dimethacrylamide amide phenyl diboronic acid, divinyl ether phenyl boronic acid, divinyl ether phenyl diboronic acid, divinyl ether naphthyl boronic acid, divinyl ether naphthyl Diboronic acid, divinyl ether anthracenyl boronic acid, divinyl ether anthracenyl diboronic acid, diallyl phenyl boronic acid, diallyl phenyl diboronic acid, divinyl aminophenyl boronic acid, diethynyl phenyl boronic acid, cyclohexyl diethynyl phenyl boronic acid, Or a salt of these, or a boronic acid group / borinic acid group-containing monomer in which a part of the structure is fluorinated;

  Acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, allyl carboxylic acid, allyl benzene carboxylic acid, allyl benzene dicarboxylic acid, allyl naphthalene carboxylic acid, allyl naphthalene dicarboxylic acid, allyl naphthalene tricarboxylic acid, allyl anthracene carboxylic acid, allyl Anthracene dicarboxylic acid, allyl anthracentricarboxylic acid, acryloyl carboxylic acid, acryloyl benzene carboxylic acid, acryloyl benzene dicarboxylic acid, acryloyl naphthalene carboxylic acid, acryloyl naphthalene dicarboxylic acid, acryloyl naphthalene tricarboxylic acid, methacryloyl carboxylic acid, methacryloyl benzene carboxylic acid, methacryloyl benzene dicarboxylic acid Acid, methacryloylnaphthalenecarboxylic acid, methacryloylnaphth Range carboxylic acid, methacryloyl anthracene carboxylic acid, methacryloyl anthracene dicarboxylic acid, methacryloyl anthracene tricarboxylic acid, vinyl benzoic acid, styrene dicarboxylic acid, vinyl naphthalene carboxylic acid, vinyl naphthalene dicarboxylic acid, vinyl anthracene carboxylic acid, vinyl anthracene dicarboxylic acid, vinyl anthracene carboxylic acid acid,

2-acrylamidocarboxylic acid, 2-acrylamidobenzenecarboxylic acid, 2-acrylamidobenzenedicarboxylic acid, 2-acrylamidoethanecarboxylic acid, 2-acrylamido-2-methylpropanecarboxylic acid, 2-acrylamido-t-butylcarboxylic acid, 2- Methacrylamidoethanecarboxylic acid, 2-methacrylamideamido-2-methylpropanecarboxylic acid, methacrylamideamidobenzenecarboxylic acid, dimethacrylamideamidobenzenedicarboxylic acid, 2-acryloyloxyethanecarboxylic acid, 3-acryloyloxypropanecarboxylic acid, 4-acryloyl Oxybutanecarboxylic acid, 2-methacryloyloxyethanecarboxylic acid, 3-methacryloyloxypropanecarboxylic acid, 4-methacryloyloxybutanecarboxylic acid, vinylimidazo Methane carboxylic acid, vinyl imidazoline ethane carboxylic acid, vinyl ether carboxylic acid, vinyl ether methyl carboxylic acid, vinyl ether ethyl carboxylic acid, vinyl ether phenyl carboxylic acid, vinyl ether phenyl dicarboxylic acid, vinyl ether naphthyl carboxylic acid, vinyl ether naphthyl dicarboxylic acid, vinyl ether anthracenyl carboxylic acid Acid, vinyl ether anthracenyl dicarboxylic acid, vinyl aminobenzene carboxylic acid, vinyl aminobenzene dicarboxylic acid, acenaphthyl carboxylic acid, ethynyl carboxylic acid, ethynyl benzene carboxylic acid, cyclohexyl ethynyl carboxylic acid, cyclohexyl ethynyl benzene carboxylic acid,

  Diallylbenzenecarboxylic acid, diallylbenzenedicarboxylic acid, diallylnaphthalenecarboxylic acid, diallylnaphthalenedicarboxylic acid, diallylnaphthalenetricarboxylic acid, diallylanthracenecarboxylic acid, diallylanthracenedicarboxylic acid, diallylanthracentricarboxylic acid, diacryloylbenzenecarboxylic acid, diacryloylbenzenedicarboxylic acid Acid, diacryloylnaphthalene carboxylic acid, diacryloyl naphthalene dicarboxylic acid, diacryloyl naphthalene tricarboxylic acid, dimethacryloyl benzene carboxylic acid, dimethacryloyl benzene dicarboxylic acid, dimethacryloyl naphthalene carboxylic acid, dimethacryloyl naphthalene dicarboxylic acid, dimethacryloyl anthracene carboxylic acid, Dimethacryloylanthracenical Phosphate, dimethacryloyl anthracene tricarboxylic acid, divinylbenzene acid, divinyl benzene dicarboxylic acids, divinyl naphthalene acid, divinyl naphthalene dicarboxylic acid, divinyl anthracene carboxylic acid, divinyl anthracene dicarboxylic acids, divinyl anthracene tricarboxylic acid,

  Diacrylamide benzene carboxylic acid, diacrylamide benzene dicarboxylic acid, dimethacrylamide benzene carboxylic acid, dimethacrylamide benzene dicarboxylic acid, divinyl ether phenyl carboxylic acid, divinyl ether phenyl dicarboxylic acid, divinyl ether naphthyl carboxylic acid, divinyl ether naphthyl dicarboxylic acid, Divinyl ether anthracenyl carboxylic acid, divinyl ether anthracenyl dicarboxylic acid, diallyl phenyl carboxylic acid, diallyl phenyl dicarboxylic acid, divinyl aminobenzene carboxylic acid, diethynyl benzene carboxylic acid, cyclohexyldiethynyl benzene carboxylic acid, or salts thereof Or a carboxylic acid group-containing monomer partially fluorinated in these structures; maleic anhydride, methacrylic acid Carboxylic acid anhydride monomers such as anhydrides;

  Vinylcarbamic acid, allylcarbamic acid, allylbenzenecarbamic acid, allylbenzenedicarbamic acid, allylnaphthalenecarbamic acid, allylnaphthalenedicarbamic acid, allylnaphthalenetricarbamic acid, allylanthracenecarbamic acid, allylanthracenedicarbamic acid, allylanthraccentric Carbamic acid, acryloylcarbamic acid, acryloylbenzenecarbamic acid, acryloylbenzenedicarbamic acid, acryloylnaphthalenecarbamic acid, acryloylnaphthalenedicarbamic acid, acryloylnaphthalenetricarbamic acid, methacryloylcarbamic acid, methacryloylbenzenecarbamic acid, methacryloylbenzenedicarbamic acid, Methacryloylnaphthalenecarbamic acid, methacryloylnaphtha Dicarbamic acid, methacryloylanthracenecarbamic acid, methacryloylanthracene dicarbamic acid, methacryloylanthracentricarbamic acid, styrenecarbamic acid, styrenedicarbamic acid, vinylnaphthalenecarbamic acid, vinylnaphthalenedicarbamic acid, vinylanthracenecarbamic acid, vinylanthracenedicarbamine Acid, vinyl anthracentricarbamic acid,

2-acrylamidocarbamic acid, 2-acrylamidobenzenecarbamic acid, 2-acrylamidobenzenedicarbamic acid, 2-acrylamidoethanecarbamic acid, 2-acrylamido-2-methylpropanecarbamic acid, 2-acrylamido-t-butylcarbamic acid, 2 -Methacrylamidoethanecarbamic acid, 2-methacrylamideamido-2-methylpropanecarbamic acid, methacrylamideamidobenzenecarbamic acid, dimethacrylamideamidodicarbamic acid, 2-acryloyloxyethanecarbamic acid, 3-acryloyloxypropanecarbamic acid, 4 -Acryloyloxybutanecarbamic acid, 2-methacryloyloxyethanecarbamic acid, 3-methacryloyloxypropanecarbamic acid, 4-methacryloyloxybu Carbamic acid, vinyl imidazoline methane carbamic acid, vinyl imidazoline ethane carbamic acid, vinyl ether carbamic acid, vinyl ether methyl carbamic acid, vinyl ether ethyl carbamic acid, vinyl ether phenyl carbamic acid, vinyl ether phenyl dicarbamic acid, vinyl ether naphthyl carbamic acid, vinyl ether naphthyl dicarbamic acid , Vinyl ether anthracenylcarbamic acid, vinyl ether anthracenyl dicarbamic acid, vinylaminobenzenecarbamic acid, vinylaminobenzenedicarbamic acid, acenaphthylcarbamic acid, ethynylcarbamic acid, ethynylbenzenecarbamic acid, cyclohexylethynylcarbamic acid, cyclohexylethynylbenzene Carbamic acid,

  Diallylbenzenecarbamic acid, diallylbenzenedicarbamic acid, diallylnaphthalenecarbamic acid, diallylnaphthalenedicarbamic acid, diallylnaphthalenetricarbamic acid, diallylanthracenecarbamic acid, diallylanthracenedicarbamic acid, diallylanthracentricarbamic acid, diacryloylbenzenecarbamic acid , Diacryloylbenzenedicarbamic acid, diacryloylnaphthalenecarbamic acid, diacryloylnaphthalenedicarbamic acid, diacryloylnaphthalenetricarbamic acid, dimethacryloylbenzenecarbamic acid, dimethacryloylbenzenedicarbamic acid, dimethacryloylnaphthalenecarbamic acid, dimethacryloylnaphthalene Dicarbamic acid, dimethacryloylanthracenecarbamic acid Dimethacryloylanthracene dicarbamic acid, dimethacryloylanthracentricarbamic acid, divinylbenzenecarbamic acid, divinylbenzenedicarbamic acid, divinylnaphthalenecarbamic acid, divinylnaphthalenedicarbamic acid, divinylanthracenecarbamic acid, divinylanthracene dicarbamic acid, divinylanthracentri Carbamic acid,

  Diacrylamidebenzenecarbamic acid, diacrylamidebenzenedicarbamic acid, dimethacrylamideamidobenzenecarbamic acid, dimethacrylamideamidobenzenedicarbamic acid, divinyletherphenylcarbamic acid, divinyletherphenyldicarbamic acid, divinylethernaphthylcarbamic acid, divinylethernaphthyl Dicarbamic acid, divinyl ether anthracenyl carbamic acid, divinyl ether anthracenyl dicarbamic acid, diallyl phenylcarbamic acid, diallylphenyl dicarbamic acid, divinylaminobenzenecarbamic acid, diethynylbenzenecarbamic acid, cyclohexyldiethynylbenzenecarbamic acid, Alternatively, these salts, etc., or carbamic acid group-containing monomers in which a part of these structures are fluorinated ;

1,4-cyclohexanedimethanol monoacrylate, 2-hydroxymethyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxybutyl acrylate, 2-hydroxymethyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl Methacrylate, 2-hydroxybutyl methacrylate, 4-hydroxymethyl acrylate, 4-hydroxyethyl acrylate, 4-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 4-hydroxymethyl methacrylate, 4-hydroxyethyl methacrylate, 4-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate, glycerin monomethacrylate, polyethylene glycol Over monoacrylate, polypropylene glycol monoacrylate, polyethylene glycol monomethacrylate, polypropylene glycol monomethacrylate, or their salts, or hydroxyl group-containing monomers some of these structures have been fluorinated;

  Vinylamine, allylamine, ethyleneimine, vinylaminonaphthalene, vinylaminoanthracene, vinylphenylamine, vinylphenyldiamine, vinylnaphthylamine, vinylnaphthyldiamine, vinylanthracenylamine, vinylanthracenyldiamine, divinylamine, diallylamine, diallyldimethylammonium, Examples include diallyldiethylammonium, or a salt or amine part thereof modified such as partially ureated or partially carbonated, and any other low molecular compound having a structure that satisfies the above conditions. Things can be used.

  Among these, from the viewpoint of high reactivity and poor solubility / non-swellability of the reaction product in non-aqueous electrolyte, maleic acid, methacrylic acid, maleic anhydride, methacrylic anhydride, vinyl sulfonic acid Sodium, lithium vinyl sulfonate, calcium vinyl sulfonate, sodium allyl sulfonate, lithium allyl sulfonate, calcium allyl sulfonate, sodium styrene sulfonate, lithium styrene sulfonate, calcium styrene sulfonate, diallylamine, allyl isocyanate, Due to its high radical polymerizability, maleic anhydride, sodium vinyl sulfonate, lithium vinyl sulfonate, sodium allyl sulfonate, lithium allyl sulfonate, sodium styrene sulfonate, lithium styrene sulfonate, More preferably Ann allyl, particularly preferably sodium vinyl sulfonate, sodium allyl sulfonate, an allyl isocyanate.

Examples of the polymer compound of the compound (B) are preferably those having a structure such as polycarbonate, polyamide, polyimide, polyester, polysaccharide, polyether, polyacrylate, polystyrene in addition to the radically polymerizable unsaturated bond. Those having water solubility are preferred from the viewpoint of suppressing swelling and dissolution in the electrolytic solution.
As the compound (B) described above, a commercially available product may be used, or it may be synthesized by a known method.
In addition, in this invention, a compound (B) can use 1 type of compound individually or in combination of 2 or more types.

(Polymer (C))
The organic compound (D) of the present invention contains the polymer (C) in addition to the compound (B), thereby further improving the effect of suppressing peeling of these coatings on the surface of the active material (A) due to its synergistic effect. The reaction between the active material (A) surface and the non-aqueous electrolyte can be further suppressed, the generation of gas can be effectively suppressed, and the charge / discharge efficiency during initial conditioning can be improved. This polymer (C) may be used independently and may be used in combination of 2 or more types.

Hereinafter, specific embodiments of the polymer (C) of the present invention will be described in detail.
The polymer (C) used in the present invention is preferably hardly soluble in the non-aqueous electrolyte solution, and the resistance of the non-aqueous secondary battery negative electrode active material of the present invention to the non-aqueous electrolyte solution is improved. The polymer (C) adsorbed on A) becomes difficult to elute into the non-aqueous electrolyte, and at the same time, the formed film itself derived from the polymer of compound (B) and compound (B) is further eluted into the non-aqueous electrolyte. There is an inhibitory effect.

In the present specification, “slightly soluble in non-aqueous electrolyte” means 24 hours in a solvent in which polymer (C) is mixed with ethyl carbonate (EC) and ethyl methyl carbonate (EMC) at a volume ratio of 3: 7. It is defined that the decrease in dry weight before and after immersion is 10% by mass or less.
The polymer (C) that is poorly soluble in the non-aqueous electrolyte preferably has an ionic group in its structure from the viewpoint of suppressing an increase in negative electrode resistance, and the polymer (C) itself is water-soluble. It is more preferable to have.

In the present specification, an ionic group is a group capable of generating an anion or cation in water. Examples thereof include an anionic group such as a carboxylic acid group, a sulfonic acid group, a sulfinic acid group, a phosphoric acid group, a phosphonic acid group, a boronic acid group, and a hydroxyl group. The cationic group includes a primary amino group, Secondary amino group, tertiary amino group, quaternary ammonium group and the like can be mentioned.
These ionic groups may be salts. Examples of the salt of the anionic group include alkali metal salts such as lithium salt, sodium salt, and potassium salt, and alkali metal salts such as calcium salt and magnesium salt. Examples of the salt of the cationic group include hydrochloride and acetate. , Sulfates, amide sulfates, ammonium salts and the like, and the amine part may be modified such as partially ureated or partially carbonated.

  These ionic groups can be expected to promote the desolvation from lithium ions solvated with the electrolytic solution, whereby reductive decomposition of the electrolytic solution is suppressed and the initial charge / discharge efficiency can be improved. Moreover, since an ion conductive group accelerates | stimulates the spreading | diffusion of the lithium ion in a film, it is possible to suppress a raise of negative electrode resistance. Among these, from the viewpoint of gas generation when used for a negative electrode for a non-aqueous secondary battery, a carboxylic acid group, a sulfonic acid group, a primary amino group, a secondary amino group, or a salt thereof is more preferable, a sulfonic acid group, Most preferred are primary amino groups, secondary amino groups, or salts thereof.

  The presence or absence of a chemical bond or chemical / physical interaction between the polymer (C) and the compound (B) is not limited, but there is a chemical bond or chemical / physical interaction. Is more preferable from the viewpoint of suppression of elution into the non-aqueous electrolyte and suppression of peeling during charging / discharging in the battery from the surface of the active material. Chemical bonds include covalent bonds and coordination bonds, and chemical interactions include ionic bonds and hydrogen bonds such as acid-base interactions, π-π interactions, π-cation interactions, Examples include charge transfer interaction, van der Waals interaction, halogen bond, electrostatic interaction, dipole interaction, etc., from the point of poor solubility in non-aqueous electrolyte, and the suppression of peeling from the active material (A). Chemical bonds, ionic bonds, π-π interactions, and π-cation interactions are more preferable.

In the case of an acid-base interaction, the polymer (C) is preferably cationic if the compound (B) is anionic, and if the compound (B) is cationic, the polymer (C C) is preferably anionic.
Here, the polymer is defined as having a weight average molecular weight of 500 or more or a viscosity average molecular weight of 1000 or more. In the present specification, the weight average molecular weight is the weight average molecular weight in terms of standard polystyrene measured by gel permeation chromatography (GPC) of the solvent tetrahydrofuran (THF), or the solvent is aqueous, dimethylformamide (DMF) or dimethyl sulfoxide. It is a weight average molecular weight in terms of standard polyethylene glycol measured by GPC of (DMSO).

The viscosity average molecular weight is not particularly limited, but is usually in the range of 1000 or more and 100,000 or less. In the present specification, the viscosity average molecular weight is the viscosity average molecular weight calculated by using the Mark-Kuhn-Houwink equation from the intrinsic viscosity (extreme viscosity) value measured using an Ubbelohde viscometer or other capillary viscometer. It is.
The weight average molecular weight of the polymer (C) is not particularly limited as long as it conforms to the above definition, but is usually in the range of 500 to 1,000,000, and handling points and electrolyte solution when coated on the active material (A) From the point of poor solubility, the range is preferably 500 or more and 100,000 or less, more preferably 50,000 or less, further preferably 20,000 or less, particularly preferably 10,000 or less, and further preferably 5,000 or less.

The viscosity average molecular weight is not particularly limited, but is usually in the range of 1000 or more and 100,000 or less.
Specific examples of such a polymer (C) will be described below. Examples of the anionic polymer include sulfonic acid and / or sulfinic acid group-containing monomers, phosphoric acid and / or phosphonic acid group-containing monomers, boronic acid and / or borinic acid group-containing monomers listed in the section of the compound (B). Groups consisting of homopolymers and copolymers of carboxylic acid group-containing monomers, carbamic acid group-containing monomers, hydroxyl group-containing monomers or their derivatives, pectin, glucomannan, dextrin, β-glucan, polydextrose, inulin, agarose, alginic acid, sodium alginate It is preferable to select from water-soluble polysaccharides such as carrageenan and fucoidan.

Further, naphthalenesulfonic acid formalin condensate synthesized by polycondensation, anthracenesulfonic acid formalin condensate, and salts thereof are also included.
Any one of the above homopolymers, the above two or more types of copolymers, or the above one or more types and one or more types of other components can be used.
As other components, maleic acid, acrylamide, styrene or the like may be used. Examples of such copolymers include styrene-vinyl sulfonate sodium copolymer, styrene-vinyl sulfonate lithium copolymer, polystyrene sulfonate, polystyrene sulfonate lithium, polystyrene sulfonate sodium, styrene-styrene sulfonate copolymer, Examples include styrene-lithium styrene sulfonate copolymer, styrene-sodium styrene sulfonate copolymer, styrene-vinyl benzoate copolymer, styrene-vinyl benzoate lithium copolymer, and styrene-vinyl benzoate sodium copolymer. It is done.

  Examples of the cationic polymer include vinylamine, allylamine, ethyleneimine, divinylamine, diallylamine, diallyldimethylammonium, diallyldiethylammonium, vinylaminonaphthalene, vinylaminoanthracene, aniline sulfonic acid or derivatives thereof, or salts and amines thereof. It is preferred that the moiety is selected from the group consisting of homopolymers and copolymers such as those modified such as partially ureated or partially carbonated.

  Examples of vinylamine, allylamine, ethyleneimine, and derivatives thereof include vinylamine, N-alkyl-substituted vinylamine (N-methylvinylamine, etc.), N, N-dialkyl-substituted vinylamine (N, N-dimethylvinylamine, etc.), and divinyl. Amine, N-alkyl-substituted divinylamine (N-methyldivinylamine, etc.), allylamine, N-alkyl-substituted allylamine (N-methylallylamine, etc.), N, N-dialkyl-substituted allylamine (N, N-dimethylallylamine, etc.), diallylamine , N-alkyl-substituted diallylamine (N-methyldiallylamine, etc.), ethyleneimine, and any one of the above homopolymers, two or more copolymers, or one or more of the above and one or more other components. Use copolymer, etc. It can be. As other components, maleic acid, acrylamide, sulfur dioxide or the like may be used. Examples of such a copolymer include diallylamine-maleic acid copolymer and diallylamine-sulfur dioxide copolymer. Other than this, any polymer that satisfies the above conditions may be used.

From the viewpoint of initial charge / discharge efficiency and suppression of generated gas, lithium vinyl sulfonate, sodium vinyl sulfonate, lithium styrene sulfonate, sodium styrene sulfonate, vinyl amine, allylamine, N-alkyl-substituted allylamine (N-methylallylamine) are more preferable. Etc.), N, N-dialkyl-substituted allylamines (N, N-dimethylallylamine etc.) or diallylamine homopolymers or copolymers, naphthalenesulfonic acid formalin condensates, alginic acid and lithium salts and sodium salts thereof, more preferably, Lithium polyvinyl sulfonate, sodium polyvinyl sulfonate, lithium polystyrene sulfonate, sodium polystyrene sulfonate, naphthalene sulfonate formalin condensate, alginic acid Umum salt, sodium salt, polyvinylamine, polyallylamine, poly-N-methylallylamine, poly-N, N-dimethylallylamine, polydiallylamine, polydiallylamine-sulfur dioxide copolymer, polyN-methyldiallylamine, polyethyleneimine Most preferred are lithium polystyrene sulfonate, sodium salt of formalin condensate of naphthalene sulfonate, sodium alginate, polyvinylamine, polyallylamine or polydiallylamine-sulfur dioxide copolymer.

As the polymer (C) described above, a commercially available polymer may be used, or it may be synthesized by a known method. In the present invention, the polymer (C) can be used alone or in combination of two or more compounds.
<Other ingredients>
In addition, the non-aqueous secondary battery negative electrode active material according to the present invention includes a conductive agent, an inorganic salt, a polyfunctional crosslinking agent that does not use a radical as an initiator, in order to improve the stability and conductivity of the negative electrode. You may make it contain.

The conductive agent is not particularly limited, and carbon black such as acetylene black, ketjen black and furnace black, fine powder made of Cu, Ni or an alloy thereof having an average particle diameter of 1 μm or less can be used.
It is preferable that the addition amount of the said electrically conductive agent is 10 mass% or less with respect to the active material for nonaqueous secondary battery negative electrodes of this invention.

  Specific examples of the inorganic salt include lithium hydroxide, calcium hydroxide, lithium carbonate, calcium carbonate, sodium sulfate, lithium sulfate, calcium sulfate, sodium dihydrogen phosphate, lithium dihydrogen phosphate, and calcium hydrogen phosphate. Lithium hydroxide, lithium carbonate, lithium sulfate, and lithium dihydrogen phosphate are preferable, and lithium sulfate and dihydrogen phosphate are more preferable from the viewpoint of the chemical stability in the battery and the affinity with the compound (B). Lithium may be mentioned, and a mixture or a reaction product obtained by combining two or more of these may be used.

  The polyfunctional crosslinking agent that does not use a radical as an initiator has a glycidyl group or an epoxy group, and its weight average molecular weight is not particularly limited, but is usually 50 or more, preferably 150 or more, more preferably 300 or more, and still more preferably. 350 or more. On the other hand, the weight average molecular weight is usually 1 million or less, preferably 500,000 or less, more preferably 10,000 or less, and still more preferably 5000 or less. Specific examples include polyoxyethylene glycol diglycidyl ether, polyoxypropylene glycol diglycidyl ether, butoxypolyethylene glycol glycidyl ether, and the like.

<Method for producing active material for negative electrode of non-aqueous secondary battery>
The active material for a non-aqueous secondary battery negative electrode of the present invention contains an active material (A), a compound (B), and a polymer (C), and the production method is not particularly limited, but for example, produced by the following method. can do.
The compound (B) and the polymer (C) are added to an organic solvent, water or a mixed solvent thereof, and the solution is mixed with the active material (A) and then dried by heating or / and reduced pressure. it can. For example, a solution of the compound (B) and a solution of the polymer (C) may be prepared separately, or a solution is prepared by adding the compound (B) and the polymer (C) to the same solvent. Also good. From the viewpoint of the initial charge / discharge efficiency of the lithium ion secondary battery, it is preferable to separately prepare a solution of the compound (B) and a solution of the polymer (C).

In addition, the solvent to be used is not particularly limited as long as the compound (B) and the polymer (C) are dissolved, but preferably water, ethyl methyl ketone, toluene, acetone, methyl isobutyl ketone, ethanol, methanol and the like can be mentioned. Among these, water, ethyl methyl ketone, acetone, methyl isobutyl ketone, ethanol, and methanol are more preferable because of cost and ease of drying.

  When a solution of the compound (B) and a solution of the polymer (C) are separately prepared, these solution and the active material (A) may be mixed at the same time, or after mixing these solutions, the active material ( A) may be mixed, or after mixing the active material (A) with either the solution of the compound (B) or the polymer (C), the other solution is added to the obtained mixed solution. Also good. It is also possible to improve the initial charge / discharge efficiency and suppress gas generation by adding a solution of the compound (B) or polymer (C) at the time of preparing the active material dispersion slurry before electrode coating and drying the electrode plate after coating. Since an effect is acquired and a manufacturing process can be simplified, it is preferable. Among them, in terms of the initial charge / discharge efficiency and gas generation suppression effect, after mixing either the solution of the compound (B) or the solution of the polymer (C) and the active material (A), the obtained mixture is mixed with the other solution. Is preferably added.

Further, the order of coating the active material surface is not particularly limited, but after mixing the polymer (C) solution and the active material (A) from the point that radicals can be captured on the outermost surface of the active material and film formation can be promoted, More preferably, the mixture (F) is mixed with a solution obtained by filtering or drying the mixture.
The concentration of the compound (B) and the polymer (C) in the solvent when mixed with the active material (A) is usually 0.01% by mass or more and 70% by mass or less. If it is this range, it can be expected that the compound (B) and the polymer (C) are uniformly present on the surface of the active material (A) in the non-aqueous secondary battery negative electrode active material, and the effect is obtained efficiently. It is done.

  The concentration of the solution is preferably 0.03% by mass or more, more preferably 0.05% by mass or more, and preferably 60% by mass or less, more preferably 40% by mass or less. The concentration of the solution is the concentration of the solution in contact with the active material (A), and the solution of the compound (B) and the solution of the polymer (C) are mixed simultaneously with the active material (A), and When these solutions are mixed and then mixed with the active material (A), the concentration is the sum of the compound (B) and the polymer (C), and either the solution of the compound (B) or the polymer (C) When the other solution is added after mixing the solution and the active material (A), the concentration is the concentration of the solution of the compound (B) and the solution of the polymer (C).

Moreover, the usage-amount of a compound (B) and a polymer (C) can be adjusted suitably, Preferably it mix | blends so that it may become preferable content in the active material for non-aqueous secondary battery negative electrodes of this invention demonstrated above. Adjust the amount.
When drying by heating, the temperature is usually 50 ° C or higher and 250 ° C or lower. Within this range, the drying efficiency is sufficient, battery performance deterioration due to residual solvent is avoided, the decomposition of compound (B) and polymer (C) is prevented, and active material (A) and compound (B). In addition, it is possible to easily prevent reduction of the effect due to weak interaction with the polymer (C). The temperature is preferably 200 ° C. or lower and preferably 100 ° C. or higher from the viewpoint of preventing the unsaturated bond of the compound (B) from causing thermal polymerization.

When drying is performed under reduced pressure, the pressure is usually 0 MPa or less and −0.2 MPa or more in gauge pressure notation. If it is this range, it can dry comparatively efficiently. The pressure is preferably −0.03 MPa or less, and preferably −0.15 MPa or more.
Prior to drying, the solution containing the active material (A), the compound (B) and the polymer (C) may be filtered. Thereby, the removal effect of the compound (B) and the polymer (C) which are not attached to the active material (A) can be expected.

In addition, when other components are included in the active material for a nonaqueous secondary battery negative electrode of the present invention, this is also added to an organic solvent, water, or a mixed solvent thereof as in the case of the compound (B) and the polymer (C). The solution is mixed with the active material (A) and then dried by heating and / or reduced pressure.
A solution of the compound (B) or polymer (C) and other components may be prepared separately, or a solution may be prepared by adding these compounds to the same solvent.

<Contents of Compound (B) and Polymer (C)>
The active material for a non-aqueous secondary battery negative electrode of the present invention is not particularly limited as long as it contains the active material (A), the compound (B), and the polymer (C), but the compound (B) and the polymer (C) The content of is usually 0.01% by mass or more and 10% by mass or less as the total amount of the compound (B) and the polymer (C) with respect to the active material (A). Within this range, the addition of the compound (B) and the polymer (C) can easily avoid a situation where the negative electrode resistance is increased and the charging rate is slow, or charging / discharging is impossible, Moreover, the effect of lowering the specific surface area of the carbon material by the addition of the compound (B) and the polymer (C) is sufficient, and good cycle characteristics and charging speed can be easily obtained. Content of a compound (B) and a polymer (C) becomes like this. Preferably it is 0.05 mass% or more, Preferably it is 8 mass% or less, More preferably, it is 5 mass% or less, More preferably, it is 3 mass% or less, Most preferably, it is 2 mass% or less.

  At this time, if the content of the compound (B) is too small, it may be difficult to sufficiently form a polymer film using radicals generated in the battery on the active material (A), and the effect is difficult to see. Therefore, the content of the compound (B) is usually 0.01% by mass or more and 10% by mass or less, preferably 0.05% by mass or more, and preferably 5% by mass or less, more preferably 3% by mass. % Or less, most preferably 2% by mass or less.

  The content of the compound (B) and the polymer (C) is determined by adding the compound (B) and the polymer (C) at the time of production in principle when the solution containing the compound (B) and the polymer (C) is dried at the time of production. For example, when filtration is performed, the amount is calculated from the weight loss in the TG-DTA analysis of the obtained carbon material or the amount of the compound (B) and the polymer (C) contained in the filtrate. be able to.

  The elution of the compound (B) and the polymer (C) in the non-aqueous secondary battery negative electrode active material of the present invention was obtained by immersing the carbon material in a non-aqueous solvent not containing salt at room temperature (25 ° C.) for 5 hours. In this case, it can be evaluated by measuring the elution amount of the compound (B) and the polymer (C) into the solution. The elution amount can be usually 20% by mass or less, preferably 15% by mass or less, more preferably 15% by mass or less of the total amount of the compound (B) and the polymer (C) contained in the non-aqueous secondary battery negative electrode active material. Is 10% by mass or less. From the viewpoint of the strength of the electrode plate, it is particularly preferably 5% by mass or less.

  The non-aqueous solvent used in the elution evaluation can be appropriately selected from known non-aqueous solvents as the solvent for the non-aqueous electrolyte, such as diethyl carbonate, dimethyl carbonate, ethyl methyl carbonate, etc. Chain carbonates such as ethylene carbonate, propylene carbonate, butylene carbonate, etc .; chain ethers such as 1,2-dimethoxyethane; tetrahydrofuran, 2-methyltetrahydrofuran, sulfolane, 1,3-dioxolane, etc. Ethers; chain esters such as methyl formate, methyl acetate and methyl propionate; and cyclic esters such as γ-butyrolactone and γ-valerolactone. A non-aqueous solvent may be individual or may use 2 or more types together. In the case of a mixed solvent, a combination of a mixed solvent containing a cyclic carbonate and a chain carbonate is preferable, and the cyclic carbonate is preferably ethylene carbonate.

As a method for quantifying the elution amounts of the compound (B) and the polymer (C), after immersing the carbon material in a non-aqueous solvent component, the supernatant was recovered and dried to drive off the solvent, and 100% elution was performed in NMR and GPC. The method of calculating by the ratio of the peak intensity of the eluted component to the peak intensity in the case is mentioned.
(Average particle diameter (d50))
Moreover, the average particle diameter (d50) of the active material for a nonaqueous secondary battery negative electrode of the present invention can be usually 50 μm or less, and can be 1 μm or more. Within this range, it is possible to prevent inconveniences in the process such as striping of the negative electrode forming material when the negative electrode is produced in the production of the negative electrode.

  The average particle diameter (d50) is preferably 30 μm or less, more preferably 25 μm or less, and preferably 4 μm or more, more preferably 10 μm or more. In addition, the measuring method of an average particle diameter (d50) is as having mentioned above. Moreover, the average particle diameter (d50) of the active material for a non-aqueous secondary battery negative electrode of the present invention can be adjusted by changing the average particle diameter (d50) of the active material (A) as the raw material. .

(Surface spacing (d ₀₀₂ ))
The inter-surface spacing (d ₀₀₂ ) of the 002 plane according to the X-ray wide angle diffraction method of the active material for a non-aqueous secondary battery negative electrode is usually 0.337 nm or less, preferably 0.336 nm or less. If the d value is too large, the crystallinity decreases and the discharge capacity tends to decrease. On the other hand, the lower limit of 0.3356 nm is a theoretical value of graphite.

  The crystallite size (Lc) of the non-aqueous secondary battery negative electrode active material is usually in the range of 30 nm or more, preferably 50 nm or more, more preferably 100 nm or more. Below this range, the crystallinity decreases and the discharge capacity of the battery tends to decrease.

(Surface functional group amount)
The active material for a non-aqueous secondary battery negative electrode has a surface functional group amount O / C value represented by the following formula (1) of usually 2% or more, preferably 3%, more preferably 4%, while usually 30. % Or less, preferably 20% or less, more preferably 15% or less.

Formula (1)
O / C value (%) = {O atom concentration obtained based on the peak area of the O1s spectrum in the X-ray photoelectron spectroscopy (XPS) analysis / C atom obtained based on the peak area of the C1s spectrum in the XPS analysis Density} × 100
The surface functional group amount O / C value in the present invention can be measured using X-ray photoelectron spectroscopy (XPS) as follows.

  An X-ray photoelectron spectrometer is used as an X-ray photoelectron spectroscopy measurement, the measurement object is placed on a sample stage so that the surface is flat, an aluminum Kα ray is used as an X-ray source, and C1s (280 to 300 eV) is obtained by multiplex measurement. ) And O1s (525-545 eV). The obtained C1s peak top is corrected to be 284.3 eV, the peak areas of the C1s and O1s spectra are obtained, and the device sensitivity coefficient is multiplied to calculate the surface atomic concentrations of C and O, respectively. The obtained O / C atomic concentration ratio O / C (O atomic concentration / C atomic concentration) is defined as the surface functional group amount O / C value of the sample (scale-like composite particles (A)).

(BET specific surface area (SA))
About the specific surface area measured by the BET method of the active material for nonaqueous secondary battery negative electrodes, it is 0.1 m < ² > / g or more normally, Preferably it is 0.7 m < ² > / g or more, More preferably, it is 1 m < ² > / g or more. Moreover, it is 20 m < ² > / g or less normally, Preferably it is 15 m < ² > / g or less, More preferably, it is 12 m < ² > / g or less, More preferably, it is 11 m < ² > / g or less, Most preferably, it is 8 m < ² > / g or less. Also,
The specific surface area of the nonaqueous secondary battery negative electrode active material usually tends to be larger than the specific surface area of the active material (A).

If the specific surface area is too small, the number of sites where lithium ions enter and exit is small and the high-speed charge / discharge characteristics and output characteristics are inferior. Since the irreversible capacity becomes large, there is a tendency that a high capacity battery cannot be manufactured.
In addition, the measuring method of a BET specific surface area is measured by a BET 1 point method by a nitrogen gas adsorption circulation method using a specific surface area measuring device.

(Tap density)
The tap density of the nonaqueous secondary battery negative electrode active material is usually preferably 0.5 g / cm ³ or more, preferably 0.6 g / cm ³ or more, and more preferably 0.7 g / cm ³ or more. Further, usually 1.5 g / cm ³ or less and 1.2 g / cm ³ or less are preferable, and 1.1 g / cm ³ or less is more preferable. If the tap density is too low, the high-speed charge / discharge characteristics are inferior. If the tap density is too high, the cycle characteristics may be deteriorated due to a reduction in the effect of suppressing the conduction path break.
Moreover, the tap density of the nonaqueous secondary battery negative electrode active material usually tends to be the same as or smaller than the tap density of the active material (A).

<Mixing with conductive aid>
The active material for a nonaqueous secondary battery negative electrode of the present invention may contain a conductive additive in order to improve the conductivity of the negative electrode. The conductive auxiliary agent is not particularly limited, and is a fine powder made of carbon black such as acetylene black, ketjen black, furnace black, conductive fibers such as carbon nanofiber, Cu, Ni having an average particle size of 1 μm or less, or an alloy thereof. Etc.
It is preferable that the addition amount of a conductive support agent is 10 mass% or less with respect to the active material for non-aqueous secondary battery negative electrodes of this invention.

[Negative electrode for non-aqueous secondary battery]
The negative electrode for a non-aqueous secondary battery of the present invention comprises a current collector and an active material layer formed on the current collector, and the active material layer is at least the active material for a non-aqueous secondary battery negative electrode of the present invention. It contains. The active material layer preferably further contains a binder.

The binder is not particularly limited, but preferably has an olefinically unsaturated bond in the molecule. Specific examples thereof include styrene-butadiene rubber, styrene / isoprene / styrene rubber, acrylonitrile-butadiene rubber, butadiene rubber, and ethylene / propylene / diene copolymer.
By using such a binder having an olefinically unsaturated bond, the swellability of the active material layer with respect to the non-aqueous electrolyte can be reduced. Of these, styrene-butadiene rubber is preferred because of its availability.

By using such a binder having an olefinically unsaturated bond in the molecule and the non-aqueous secondary battery negative electrode active material of the present invention in combination, the mechanical strength of the negative electrode plate can be increased. When the mechanical strength of the negative electrode plate is high, deterioration of the negative electrode due to charge / discharge is suppressed, and the cycle life can be extended.
The binder having an olefinically unsaturated bond in the molecule preferably has a large molecular weight and / or a large proportion of unsaturated bonds.

As the molecular weight of the binder, the weight average molecular weight is usually 10,000 or more and 1,000,000 or less. If it is this range, both mechanical strength and flexibility can be controlled to a favorable range. The weight average molecular weight is preferably 50,000 or more, and preferably 300,000 or less.
As the ratio of olefinically unsaturated bonds in the binder molecule, the number of moles of olefinically unsaturated bonds per 1 g of the total binder is usually 2.5 × 10 ⁻⁷ mol or more and 5 × 10 ⁻⁶ mol or less. If it is this range, the intensity | strength improvement effect will be acquired sufficiently and flexibility will also be favorable. The number of moles is preferably 8 × 10 ⁻⁷ or more, and preferably 1 × 10 ⁻⁶ or less.

Moreover, about the binder which has an olefinic unsaturated bond, the unsaturation degree is 15 to 90% normally. The degree of unsaturation is preferably 20% or more, more preferably 40% or more, and preferably 80% or less. In the present specification, the degree of unsaturation represents the ratio (%) of the double bond to the number of repeating units of the polymer.
As the binder, a binder having no olefinically unsaturated bond can also be used. By using a binder having no olefinically unsaturated bond in combination with a binder having an olefinically unsaturated bond in the molecule, an improvement in the coating properties of the active material of the present invention or the negative electrode forming material containing the binder can be expected. .

The mixing ratio of the binder having no olefinic unsaturated bond to the binder having an olefinically unsaturated bond is usually 150% by mass or less, preferably 120% by mass, in order to suppress a decrease in the strength of the active material layer. It is as follows.
Examples of the binder having no olefinically unsaturated bond include thickening polysaccharides such as methylcellulose, carboxymethylcellulose, starch, carrageenan, pullulan, guar gum, xanthan gum, and polyethers such as polyethylene oxide and polypropylene oxide. Vinyl alcohols such as polyvinyl alcohol and polyvinyl butyral; polyacids such as polyacrylic acid and polymethacrylic acid or metal salts of these polymers; fluorine-containing polymers such as polyvinylidene fluoride; alkane polymers such as polyethylene and polypropylene; A copolymer etc. are mentioned.

The negative electrode for a non-aqueous secondary battery according to the present invention is a slurry (negative electrode forming material) in which a non-aqueous secondary battery negative electrode active material of the present invention and a binder or a conductive agent are dispersed in a dispersion medium in some cases. It can be formed by applying to a current collector and drying. As the dispersion medium, an organic solvent such as alcohol or water can be used.
When preparing the slurry, the compound (B) is added to and mixed with the active material (A) together with the binder, etc., to produce the non-aqueous secondary battery negative electrode active material of the present invention and to prepare the negative electrode slurry. You may do it at the same time.

  The binder is usually used in an amount of 0.1% by mass or more, preferably 0.2% by mass or more, based on the active material for a negative electrode for a nonaqueous secondary battery of the present invention. By setting the ratio of the binder to 0.1% by mass or more with respect to the active material of the present invention, the binding force between the active materials and between the active material and the current collector is sufficient, and the active material of the present invention is formed from the negative electrode. It is possible to prevent a decrease in battery capacity and deterioration in cycle characteristics due to peeling.

  Moreover, it is preferable that a binder shall be normally 10 mass% or less and 7 mass% or less with respect to the active material for non-aqueous secondary battery negative electrodes of this invention. By reducing the binder ratio to 10% by mass or less with respect to the active material of the present invention, the capacity of the negative electrode is prevented from decreasing, and the lithium ion active material when the non-aqueous secondary battery is a lithium ion battery. Can prevent problems such as hindering the entry and exit.

After mixing these components, defoaming is performed as necessary to obtain a slurry that is a negative electrode forming material.
As said negative electrode collector, the well-known thing conventionally used for this use can be used. For example, copper, copper alloy, stainless steel, nickel, titanium, and carbon can be used.

The shape of the current collector is usually a sheet shape, and it is also preferable to use a surface with irregularities, a net or punching metal.
The density of the active material layer of the present invention when used as a negative electrode for a secondary battery varies depending on the application, but is usually 1.1 g / cm ³ in applications where input / output characteristics such as in-vehicle applications and power tool applications are important. As described above, it is 1.65 g / cm ³ or less. Within this range, it is possible to avoid an increase in contact resistance between particles due to the density being too low, and it is also possible to suppress a decrease in rate characteristics due to the density being too high.

The density is preferably 1.2 g / cm ³ or more, more preferably 1.25 g / cm ³ or more.
On the other hand, the density of the active material layer is usually 1.45 g / cm ³ or more and 1.9 g / cm ³ or less in applications where capacity is important, such as portable devices such as mobile phones and personal computers. If it is this range, the capacity | capacitance fall of the battery per unit volume by a density being too low can be avoided, On the other hand, the fall of the rate characteristic by a density being too high can also be suppressed.
The density is preferably 1.55 g / cm ³ or more, more preferably 1.65 g / cm ³ or more, particularly preferably 1.7 g / cm ³ or more.

<Non-aqueous secondary battery>
The basic configuration of the nonaqueous secondary battery according to the present invention can be the same as, for example, a known lithium ion secondary battery, and usually includes a positive electrode and a negative electrode capable of inserting and extracting lithium ions, and an electrolyte. The negative electrode is a negative electrode for a non-aqueous secondary battery according to the present invention described above.

<Positive electrode>
The positive electrode can include a current collector and an active material layer formed on the current collector. The active material layer preferably contains a binder in addition to the positive electrode active material.
Examples of the positive electrode active material include metal chalcogen compounds that can occlude and release alkali metal cations such as lithium ions during charge and discharge. Of these, metal chalcogen compounds capable of inserting and extracting lithium ions are preferred.

Examples of metal chalcogen compounds include transition metal oxides such as vanadium oxide, molybdenum oxide, manganese oxide, chromium oxide, titanium oxide, and tungsten oxide; vanadium sulfide, molybdenum sulfide, titanium sulfide, CuS, and the like transition metal _sulfides; NIPS 3, phosphorus transition metals such as FEPS ₃ - sulfur _compounds; VSe 2, selenium compounds of transition metals such as _{NbSe 3; Fe 0.25 V 0.75 S} 2, Na 0.1 CrS Composite oxides of transition metals such as ₂ ; composite sulfides of transition metals such as LiCoS ₂ and LiNiS ₂ .

Among them, from the viewpoint of occlusion / release of lithium ions, V ₂ O ₅ , V ₅ O ₁₃ , VO ₂ , Cr ₂ O ₅ , MnO ₂ , TiO ₂ , MoV ₂ O ₈ , LiCoO ₂ , LiNiO ₂ , LiMn ₂ O ₄ , TiS ₂ , V ₂ S ₅ , Cr _0.25 V _0.75 S ₂ , Cr _0.5 V _0.5 S _{2 and the} like are preferable, and LiCoO ₂ , LiNiO ₂ , LiMn ₂ O _4, and their transitions A lithium transition metal composite oxide in which a part of the metal is substituted with another metal is particularly preferable.

These positive electrode active materials may be used alone or in combination.
The binder for positive electrodes is not specifically limited, A well-known thing can be selected arbitrarily and can be used. Examples include inorganic compounds such as silicate and water glass, and resins having no unsaturated bond such as Teflon (registered trademark) and polyvinylidene fluoride. Among them, a resin having no unsaturated bond is preferable because it is difficult to decompose during the oxidation reaction.

The weight average molecular weight of the binder can usually be 10,000 or more, and can usually be 3 million or less. The weight average molecular weight is preferably 100,000 or more, and preferably 1,000,000 or less.
The positive electrode active material layer may contain a conductive additive in order to improve the conductivity of the positive electrode. The conductive aid is not particularly limited, and examples thereof include carbon powders such as acetylene black, carbon black, and graphite, various metal fibers, powders, and foils.

  The positive electrode of the present invention is a slurry obtained by dispersing an active material and, optionally, a binder and / or a conductive auxiliary agent in a dispersion medium in the same manner as the above-described negative electrode manufacturing method, and applying this to the surface of the current collector. Can be formed. The current collector for the positive electrode is not particularly limited, and examples thereof include aluminum, nickel, and stainless steel (SUS).

<Electrolyte>
The electrolyte (sometimes referred to as “non-aqueous electrolyte”) is not particularly limited, and a non-aqueous electrolyte obtained by dissolving a lithium salt as an electrolyte in a non-aqueous solvent, an organic polymer compound, etc. in the non-aqueous electrolyte And the like may be added to the gel, rubber, or solid sheet.

The non-aqueous solvent used for the non-aqueous electrolyte is not particularly limited, and a known non-aqueous solvent can be used.
For example, chain carbonates such as diethyl carbonate, dimethyl carbonate and ethyl methyl carbonate; cyclic carbonates such as ethylene carbonate, propylene carbonate and butylene carbonate; chain ethers such as 1,2-dimethoxyethane; tetrahydrofuran, 2-methyl Examples include cyclic ethers such as tetrahydrofuran, sulfolane, and 1,3-dioxolane; chain esters such as methyl formate, methyl acetate, and methyl propionate; and cyclic esters such as γ-butyrolactone and γ-valerolactone.

A non-aqueous solvent may be individual or may use 2 or more types together. In the case of a mixed solvent, a combination of a mixed solvent containing a cyclic carbonate and a chain carbonate is preferable from the balance of conductivity and viscosity, and the cyclic carbonate is preferably ethylene carbonate.
The lithium salt used in the non-aqueous electrolyte is not particularly limited, and a known lithium salt can be used. For example, halides such as LiCl and LiBr; perhalogenates such as LiClO ₄ , LiBrO ₄ and LiClO ₄ ; inorganic lithium salts such as inorganic fluoride salts such as LiPF ₆ , LiBF ₄ and LiAsF ₆ ; LiCF ₃ SO ₃ , Examples include perfluoroalkane sulfonates such as LiC ₄ F ₉ SO ₃ ; fluorine-containing organic lithium salts such as perfluoroalkane sulfonic acid imide salts such as Li trifluoromethanesulfonyl imide ((CF ₃ SO ₂ ) ₂ NLi), and the like. . Of these, LiClO ₄ , LiPF ₆ , and LiBF ₄ are preferable.

A lithium salt may be used independently or may use 2 or more types together. The concentration of the lithium salt in the non-aqueous electrolyte can be in the range of 0.5 mol / L or more and 2.0 mol / L or less.
When the organic polymer compound is included in the non-aqueous electrolyte solution described above and used in the form of a gel, rubber, or solid sheet, specific examples of the organic polymer compound include polyethylene oxide, polypropylene oxide, and the like. Polyether polymer compounds; Cross-linked polymers of polyether polymer compounds; Vinyl alcohol polymer compounds such as polyvinyl alcohol and polyvinyl butyral; Insolubilized vinyl alcohol polymer compounds; Polyepichlorohydrin; Polyphosphazene; Siloxane; vinyl polymer compounds such as polyvinylpyrrolidone, polyvinylidene carbonate, polyacrylonitrile; poly (ω-methoxyoligooxyethylene methacrylate), poly (ω-methoxyoligooxyethylene methacrylate-co-methyl methacrylate) And polymer copolymers such as poly (hexafluoropropylene-vinylidene fluoride).

The above non-aqueous electrolyte may further contain an electrolyte additive (E).
In the present invention, since the organic compound (D) is contained on the surface of the active material (A), the electrolytic solution additive (E) acting on the active sites on the surface of the active material tends to be effective in a smaller amount. .
Examples of the electrolytic solution additive (E) include a film forming agent and an overcharge preventing agent. Examples of the film forming agent include compounds such as carbonate compounds, alkene sulfides, sultone compounds, acid anhydrides, and isocyanate compounds. Specific examples include carbonate compounds such as vinylene carbonate, vinylethyl carbonate, and methylphenyl carbonate; ethylene sulfide. Alkene sulfide such as propylene sulfide; sultone compounds such as 1,3-propane sultone and 1,4-butane sultone; acid anhydrides such as maleic anhydride and succinic anhydride; 1,3-bis (isocyanatomethyl) Isocyanate compounds such as cyclohexane and allyl isocyanate.

Examples of the overcharge inhibitor include diphenyl ether and cyclohexyl benzene.
When using the electrolytic solution additive (E), the electrolytic solution additive (E) is used in order not to adversely affect other battery characteristics such as an increase in initial irreversible capacity, a low temperature characteristic, and a decrease in rate characteristic. The total content can usually be 10% by mass or less with respect to the entire electrolyte, and in particular, the range of 8% by mass or less, more preferably 5% by mass or less, and particularly preferably 2% by mass or less is preferable.

Further, as the electrolyte, a polymer solid electrolyte which is a conductor of an alkali metal cation such as lithium ion can be used.
Examples of the polymer solid electrolyte include those obtained by dissolving a Li salt in the aforementioned polyether polymer compound, and polymers in which the terminal hydroxyl group of the polyether is substituted with an alkoxide.

<Others>
In order to prevent a short circuit between the electrodes, a porous separator such as a porous membrane or a nonwoven fabric can usually be interposed between the positive electrode and the negative electrode, and the non-aqueous electrolyte is impregnated into the porous separator. It is convenient to use it. As a material for the separator, polyolefin such as polyethylene and polypropylene, polyethersulfone, and the like are used, and polyolefin is preferable.

  The form of the non-aqueous secondary battery is not particularly limited. For example, a cylinder type in which a sheet electrode and a separator are spiraled; a cylinder type having an inside-out structure in which a pellet electrode and a separator are combined; a coin type in which a pellet electrode and a separator are stacked Etc. Further, by storing batteries of these forms in an optional outer case, the battery can be used in an arbitrary shape and size such as a coin shape, a cylindrical shape, and a square shape.

  The procedure for assembling the non-aqueous secondary battery is not particularly limited, and can be assembled by an appropriate procedure according to the structure of the battery. For example, a negative electrode can be placed on an outer case, a non-aqueous electrolyte and a separator can be provided thereon, and a positive electrode can be placed so as to face the negative electrode, and can be caulked together with a gasket and a sealing plate to form a battery.

Next, specific embodiments of the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. The average particle size (d50) in the following is determined by suspending 0.01 g of a sample in 10 mL of a 0.2% by mass aqueous solution of polyoxyethylene sorbitan monolaurate, which is a surfactant, and measuring a laser diffraction / scattering particle size distribution analyzer. (Product name: LA-920 manufactured by HORIBA) After irradiating an ultrasonic wave of 28 kHz at an output of 60 W for 1 minute, it is a value measured as a volume-based median diameter in a measuring apparatus.

<Example 1>
(1) Preparation of non-aqueous secondary battery negative electrode active material Spherical natural graphite (average particle size (d50) 17 μm) particles (230 g) are used as the active material (A), and the graphite and polymer (C) as an aqueous solution ( Wako Pure Chemical Industries, Ltd. sodium alginate 2.3 g diluted with 227.7 g distilled water) was placed in a flask and stirred. Thereafter, the solvent was distilled off by heating. 20 g of the above-mentioned Na-alginate-coated graphite was weighed, and an aqueous solution (diluted by adding 19.9 g of distilled water to 0.1 g of sodium vinyl sulfonate manufactured by Tokyo Chemical Industry Co., Ltd.) as a compound (B) was stirred in the flask. did. Thereafter, the solvent was distilled off by heating to obtain a powdered active material a for a non-aqueous secondary battery negative electrode.

(2) Slurry preparation 20 g of the active material A prepared above and 20.2 g of an aqueous carboxymethyl cellulose solution (1% by mass) are mixed, 0.5 g of SBR-aqueous dispersion (40% by mass) is added, and after further mixing, a kneader An active material slurry A was prepared by kneading (2000 rpm, 5 min; defoaming: 2200 rpm, 130 sec) by (Awatori Netaro, manufactured by Shinky Co., Ltd.).

(3) Electrode plate preparation A copper foil (thickness: 18 μm) was placed on an Auto Film Applicator manufactured by Tester Sangyo Co., Ltd. and adsorbed by negative pressure. The active material slurry A was applied by placing an appropriate amount of the carbon material slurry prepared in Examples and Comparative Examples on a copper foil and sweeping a film applicator manufactured by Tester Sangyo at a speed of 10 mm / sec.
The copper foil coated with the active material slurry A was dried in an inert oven (EPEC-75, manufactured by Isuzu Seisakusho Co., Ltd.) (90 ° C., 50 min, nitrogen flow 10 L / min).
Thereafter, the electrode plate is passed through a press machine (3-ton mechanical precision roll press) to compress the active material layer, and the density of the active material layer is adjusted to 1.60 ± 0.03 g / cm ³ , Obtained.

(4) Laminate cell production Nickel manganese cobalt lithium (LiNi _1/3 Mn _1/3 Co _1/3 O ₂ ) is used as the positive electrode active material, and a conductive agent and polyvinylidene fluoride (PVdF) as a binder are mixed with this. To make a slurry. The obtained slurry was applied to an aluminum foil having a thickness of 15 μm, dried, and rolled with a press, and the positive electrode active material layer had a width of 30 mm, a length of 40 mm, and an uncoated portion for current collection. A positive electrode was cut out into a shape. The density of the positive electrode active material layer was 2.6 g / cm ³ .

The negative electrode was cut into a shape having the electrode sheet prepared in <Preparation of electrode plate> having a width of 32 mm as a size of the active material layer, a length of 42 mm, and an uncoated portion as a current collector tab welded portion. At this time, the density of the active material layer of the negative electrode was 1.6 g / cm ³ .
One positive electrode and one negative electrode were arranged so that the active material surfaces face each other, and a porous polyethylene sheet separator was sandwiched between the electrodes. At this time, the positive electrode active material surface was faced so as not to deviate from the negative electrode active material surface.

A laminate sheet in which a current collector tab is welded to an uncoated portion of each of the positive electrode and the negative electrode to form an electrode body, and a polypropylene film, an aluminum foil having a thickness of 0.04 mm, and a nylon film are laminated in this order (total Using a thickness of 0.1 mm), the polypropylene film was sandwiched between the laminated sheets so that the polypropylene film was on the inner surface side, and the region without electrodes was heat-sealed except for one side for injecting the non-aqueous electrolyte.

Thereafter, the non-aqueous electrolyte solution (ethylene carbonate (EC) / dimethyl carbonate (DMC) / ethyl methyl carbonate (EMC) = 3/3/4 (volume ratio)) was added to the active material layer at a concentration of 1.0 mol / L. 200 μL of lithium phosphate (LiPF ₆ ) dissolved therein was injected, sufficiently infiltrated into the electrode, and sealed to prepare a laminate cell. The rated capacity of this battery is 34 mAh. (5) Charge / discharge efficiency during initial conditioning of laminate cell

  Initially in a voltage range of 4.2 to 3.0 V and a current value of 0.2 C in a 25 ° C. environment (the rated capacity due to the discharge capacity at 1 hour rate is 1 C, and the same applies hereinafter). Conditioning was performed for 4 cycles of charge and discharge. The charge / discharge efficiency at the time of initial conditioning is obtained by calculating the respective charge capacities and discharge capacities from the energization amount in each cycle of the initial conditioning and calculating using the following equations. Initial charge / discharge efficiency (%) = discharge capacity in the fourth cycle / (discharge capacity in the fourth cycle + capacity loss in the first, second, third, and fourth cycles (= charge capacity−discharge capacity)) × 100 (%)

(6) Measurement of evolved gas Before and after conditioning the laminate cell and after the gas measurement in (5), put the cell in a constant temperature bath in a fully charged state, and measure the volume before and after the storage test of the laminate cell at 85 ° C. for 24 hours. The total amount of change was regarded as the amount of generated gas. For measuring the volume of the laminate cell, Archimedes method was used with EtOH as the immersion liquid.

<Example 2>
Spherical natural graphite (average particle size (d50) 17 μm) particles (230 g) were used as the active material (A), and the graphite and polymer (C) were used as an aqueous solution (PAA-03-E (polyallylamine manufactured by Nittobo Medical Co., Ltd.). , Weight average molecular weight 3000, 20% ethanol solution) (diluted by adding 224.25 g of distilled water to 5.75 g) was placed in a flask and stirred. Thereafter, the solvent was distilled off by heating. 20 g of the polyallylamine-coated graphite was weighed, and an aqueous solution (diluted by adding 19.9 g of distilled water to 0.1 g of sodium vinyl sulfonate manufactured by Tokyo Chemical Industry Co., Ltd.) as a compound (B) was stirred in the flask. did. Then, the solvent was distilled off by heating to obtain a powdery non-aqueous secondary battery negative electrode active material b. Evaluation was carried out in the same manner as in Example 1.

<Example 3>
Spherical natural graphite (average particle size (d50) 17 μm) particles (230 g) were used as the active material (A), and the graphite and polymer (C) were used as an aqueous solution (PAA-03-E (polyallylamine manufactured by Nittobo Medical Co., Ltd.). , Weight average molecular weight 3000, 20% ethanol solution) 2.3 g of distilled water diluted with 227.7 g was added to a flask and stirred. Thereafter, the solvent was distilled off by heating. 20 g of the polyallylamine-coated graphite was weighed, and an aqueous solution (diluted by adding 19.9 g of distilled water to 0.1 g of sodium vinyl sulfonate manufactured by Tokyo Chemical Industry Co., Ltd.) as a compound (B) was stirred in the flask. did. Then, the solvent was distilled off by heating to obtain a powdery non-aqueous secondary battery negative electrode active material c, which was evaluated in the same manner as in Example 1.

<Example 4>
Using spherical natural graphite (average particle diameter (d50) 17 μm) particles as the active material (A), 20 g of polyallylamine 0.5 wt% coated graphite prepared in the same manner as in Example 2 was weighed to obtain compound (B). An aqueous solution (diluted by adding 19.8 g of distilled water to 0.2 g of sodium vinyl sulfonate manufactured by Tokyo Chemical Industry Co., Ltd.) was placed in a flask and stirred. Thereafter, the solvent was distilled off by heating to obtain a powdery non-aqueous secondary battery negative electrode active material d, which was evaluated in the same manner as in Example 1.

<Example 5>
Example using a powdered non-aqueous secondary battery negative electrode active material b produced in the same manner as in Example 2 using spherical natural graphite (average particle diameter (d50) 17 μm) particles as the active material (A) The non-aqueous electrolyte was adjusted to a concentration of 0.25 wt% by adding 0.05 g of vinylene carbonate (manufactured by Tokyo Chemical Industry Co., Ltd.) as an electrolyte additive (E) to 19.95 g of the non-aqueous electrolyte described in 1. A battery was prepared by injecting 200 μL of a water electrolyte and evaluated in the same manner as in Example 1.

<Example 6>
Example using a powdered non-aqueous secondary battery negative electrode active material b produced in the same manner as in Example 2 using spherical natural graphite (average particle diameter (d50) 17 μm) particles as the active material (A) The non-aqueous electrolyte was adjusted to a concentration of 1.0 wt% by adding 0.1 g of vinylene carbonate (manufactured by Tokyo Chemical Industry Co., Ltd.) as an electrolyte additive (E) to 9.9 g of the non-aqueous electrolyte described in 1. A battery was prepared by injecting 200 μL of a water electrolyte and evaluated in the same manner as in Example 1.

<Example 7>
Example using a powdered non-aqueous secondary battery negative electrode active material b produced in the same manner as in Example 2 using spherical natural graphite (average particle diameter (d50) 17 μm) particles as the active material (A) 1 by adding 0.025 g of 1,3-bis (isocyanatomethyl) cyclohexane (manufactured by Tokyo Chemical Industry Co., Ltd.) as an electrolyte solution additive (E) to 9.975 g of the non-aqueous electrolyte solution described in 1. A battery was prepared by injecting 200 μL of a non-aqueous electrolyte adjusted to a concentration of 0.25 wt% and evaluated in the same manner as in Example 1.

<Example 8>
Example using a powdered non-aqueous secondary battery negative electrode active material b produced in the same manner as in Example 2 using spherical natural graphite (average particle diameter (d50) 17 μm) particles as the active material (A) 1 by adding 0.05 g of 1,3-bis (isocyanatomethyl) cyclohexane (manufactured by Tokyo Chemical Industry Co., Ltd.) as an electrolyte solution additive (E) to 9.95 g of the non-aqueous electrolyte solution described in 1. A battery was prepared by injecting 200 μL of a non-aqueous electrolyte adjusted to a concentration of 0.5 wt%, and evaluation was performed in the same manner as in Example 1.

<Example 9>
Using spherical natural graphite (average particle diameter (d50) 17 μm) particles as the active material (A), 20 g of polyallylamine 0.5 wt% coated graphite prepared in the same manner as in Example 2 was weighed to obtain compound (B). An aqueous solution (diluted by adding 19.89 g of distilled water to 0.11 g of sodium allyl sulfonate manufactured by Tokyo Chemical Industry Co., Ltd.) was placed in a flask and stirred. Thereafter, the solvent was distilled off by heating to obtain a powdery non-aqueous secondary battery negative electrode active material e, which was evaluated in the same manner as in Example 1.

<Example 10>
Using spherical natural graphite (average particle diameter (d50) 17 μm) particles as the active material (A), 20 g of polyallylamine 0.5 wt% coated graphite prepared in the same manner as in Example 2 was weighed to obtain compound (B). An aqueous solution (diluted by adding 19.9 g of distilled water to 0.1 g of lithium styrene sulfonate manufactured by Tosoh Organic Chemical Co., Ltd.) was placed in a flask and stirred. Then, the solvent was distilled off by heating to obtain a powdery non-aqueous secondary battery negative electrode active material f. Evaluation was performed in the same manner as in Example 1.

<Example 11>
Spherical natural graphite (average particle size (d50) 17 μm) particles (230 g) were used as the active material (A), and the graphite and polymer (C) were used as an aqueous solution (PAA-03-E (polyallylamine manufactured by Nittobo Medical Co., Ltd.). , Weight average molecular weight 3000, 20% ethanol solution) 11.5 g diluted with distilled water 218.5 g) was placed in a flask and stirred. Thereafter, the solvent was distilled off by heating. 20 g of the polyallylamine-coated graphite was weighed, and an aqueous solution (diluted by adding 19.9 g of distilled water to 0.04 g of maleic anhydride manufactured by Wako Pure Chemical Industries, Ltd.) as a compound (B) was placed in a flask. Stir. Thereafter, the solvent was distilled off by heating to obtain a powdery non-aqueous secondary battery negative electrode active material g, which was evaluated in the same manner as in Example 1.

<Example 12>
20 g of polyallylamine-coated graphite prepared in the same manner as in Example 2 was weighed using spherical natural graphite (average particle size (d50) 17 μm) particles as the active material (A), and an aqueous solution (Sigma Aldrich) was obtained as the compound (B). A solution obtained by adding 19.9 g of distilled water to 0.034 g of methacrylic anhydride manufactured by Japan Corporation and diluting it was placed in a flask and stirred. Then, the solvent was distilled off by heating to obtain a powdery non-aqueous secondary battery negative electrode active material h, which was evaluated in the same manner as in Example 1.

<Example 13>
Spherical natural graphite (average particle size (d50) 17 μm) particles (50 g) are used as the active material (A), and an aqueous solution of Naphthalenesulfonic acid Na formalin condensate as the graphite and polymer (C) (Demol N0 manufactured by Kao Corporation). A solution obtained by adding 49.7 g of distilled water to 25 g and diluting it) was placed in a flask and stirred. Thereafter, the solvent was distilled off by heating. 20 g of the above-mentioned naphthalenesulfonic acid Na formalin condensate 0.5% -coated graphite was weighed, and diluted as an aqueous solution (0.19.9 g of vinylsulfonic acid Na manufactured by Tokyo Chemical Industry Co., Ltd.) as compound (B). Was put in a flask and stirred. Thereafter, the solvent was distilled off by heating to obtain a powdery non-aqueous secondary battery negative electrode active material i, which was evaluated in the same manner as in Example 1.

<Example 14>
Using spherical natural graphite (average particle diameter (d50) 17 μm) particles as the active material (A), 20 g of naphthalenesulfonic acid Na formalin condensate 0.5% coated graphite prepared in the same manner as in Example 13 was weighed. As a compound (B), an aqueous solution (diluted by adding 19.9 g of distilled water to 0.04 g of diallylamine manufactured by Tokyo Chemical Industry Co., Ltd.) was placed in a flask and stirred. Thereafter, the solvent was distilled off by heating to obtain a powdery non-aqueous secondary battery negative electrode active material j, which was evaluated in the same manner as in Example 1.

<Example 15>
Spherical natural graphite (average particle size (d50) 17 μm) particles (50 g) are used as the active material (A), and an aqueous solution of diallylamine-sulfur dioxide copolymer (manufactured by Nittobo Medical Co., Ltd.) as the graphite and polymer (C). Diluted by adding 49.7 g of distilled water to 0.25 g of PAS-92A) was placed in a flask and stirred. Thereafter, the solvent was distilled off by heating. 20 g of the diallylamine-sulfur dioxide copolymer 0.5% -coated graphite was weighed and diluted as an aqueous solution (0.19.9 g of vinyl sulfonic acid Na manufactured by Tokyo Chemical Industry Co., Ltd.) as compound (B). Was put in a flask and stirred. Then, the solvent was distilled off by heating to obtain a powdery non-aqueous secondary battery negative electrode active material k. Evaluation was carried out in the same manner as in Example 1.

<Example 16>
Spherical natural graphite (average particle size (d50) 17 μm) particles (50 g) are used as the active material (A), and an aqueous polymer solution in which the amine part of polyallylamine is modified to 20 mol% benzyl structure as the graphite and polymer (C). (A solution obtained by diluting 49.7 g of distilled water to 0.25 g of PAA-PT20 manufactured by Nittobo Medical Co., Ltd.) was placed in a flask and stirred. Thereafter, the solvent was distilled off by heating. 20 g of the above-mentioned polyallylamine 20% benzyl modified 0.5% coated graphite was weighed and diluted as an aqueous solution (19.9 g of distilled water to 0.1 g of vinyl sulfonic acid Na manufactured by Tokyo Chemical Industry Co., Ltd.). Was put in a flask and stirred. Thereafter, the solvent was distilled off by heating to obtain a powdery active material 1 for a nonaqueous secondary battery negative electrode, and evaluation was carried out in the same manner as in Example 1.

<Example 17>
PS produced by Tosoh Organic Chemical Co., Ltd. was added to 50 g of polyallylamine 0.2% coated graphite produced in the same manner as in Example 3 using spherical natural graphite (average particle size (d50) 17 μm) particles as the active material (A). -5 Aqueous solution (polystyrene sulfonate Na, molecular weight 50,000 to 100,000 (estimated from viscosity standard value), 21% aqueous solution) 1.19 g of distilled water 48.8 g diluted and put in a flask and stirred . Thereafter, the solvent was distilled off by heating. 20 g of the above polyallylamine-polystyrenesulfonic acid Na-coated graphite was weighed, and an aqueous solution (diluted by adding 19.9 g of distilled water to 0.1 g of sodium vinylsulfonate manufactured by Tokyo Chemical Industry Co., Ltd.) as the compound (B). Stir in a flask. Then, the solvent was distilled off by heating to obtain a powdery non-aqueous secondary battery negative electrode active material m. Evaluation was carried out in the same manner as in Example 1.

<Comparative Example 1>
Conducted using an active material n for a non-aqueous secondary battery negative electrode that does not contain the compound (B) and the polymer (C) and is composed only of spherical natural graphite (average particle size (d50) 17 μm) as the active material (A). Evaluation was carried out in the same manner as in Example 1.

<Comparative Example 2>
Spherical natural graphite (average particle size (d50) 17 μm) particles (20 g) are used as the active material (A), and sodium alginate aqueous solution (0.2 g of sodium alginate manufactured by Wako Pure Chemical Industries, Ltd.) is used as the graphite and polymer (C). (Diluted by adding 19.8 g of distilled water) to a flask immersed in an oil bath. While stirring, the oil bath was heated to 95 ° C. to distill off water, and a powdery non-aqueous secondary battery negative electrode active material o was obtained. Evaluation was performed in the same manner as in Example 1.

<Comparative Example 3>
Spherical natural graphite (average particle diameter (d50) 17 μm) particles (20 g) are used as the active material (A), and the radical scavenging has no radical-polymerizable unsaturated bond group as the graphite and compound (B). An aqueous solution of a polymer compound (oxynitrox (Alfa Aesar)
R) S100, free radical MW2250) 0.1 g diluted with 19.9 g distilled water) was placed in a flask immersed in an oil bath. While stirring, the oil bath was heated to 95 ° C. to distill off water, and a powdery non-aqueous secondary battery negative electrode active material p was obtained and evaluated in the same manner as in Example 1.

<Comparative Example 4>
Spherical natural graphite (average particle size (d50) 17 μm) particles (20 g) are used as the active material (A), and an aqueous solution of a low molecular compound having an unsaturated bond as the graphite and compound (B) (Wako Pure Chemical Industries, Ltd.) Distilled water (19.9 g) diluted with 0.1 g of maleic anhydride manufactured by the company) was placed in a flask immersed in an oil bath. While stirring, the oil bath was heated to 95 ° C. to distill off water, and a powdered active material q for a non-aqueous secondary battery negative electrode was obtained and evaluated in the same manner as in Example 1.

<Comparative Example 5>
Spherical natural graphite (average particle size (d50) 17 μm) particles (20 g) are used as the active material (A), and an aqueous solution of a low molecular compound having an unsaturated bond as the graphite and compound (B) (Tokyo Chemical Industry Co., Ltd.) A solution prepared by adding 19.9 g of distilled water to 0.1 g of sodium vinyl sulfonate and diluting it was placed in a flask immersed in an oil bath. The oil bath was heated to 95 ° C. while stirring to distill off water, and a powdery active material r for a nonaqueous secondary battery negative electrode was obtained. Evaluation was carried out in the same manner as in Example 1.

<Comparative Example 6>
Using spherical natural graphite (average particle diameter (d50) 17 μm) particles as the active material (A), 50 g of polyallylamine-coated graphite prepared in the same manner as in Example 2 was added to 50 g of the graphite and compound (B). As a solution, an aqueous solution of sodium polyvinyl sulfonate (diluted by adding 19.7 g of distilled water to 0.25 g of sodium polyvinyl sulfonate manufactured by Tokyo Chemical Industry Co., Ltd.) was placed in a flask immersed in an oil bath. While stirring, the oil bath was heated to 95 ° C. to distill off water, and a powdery non-aqueous secondary battery negative electrode active material s was obtained. Evaluation was performed in the same manner as in Example 1.
The above evaluation results are shown in Table 1 below.

Non-aqueous system containing active material (A), mixture of radically polymerizable compound (B) having unsaturated bond and polymer (C) hardly soluble in non-aqueous electrolyte, and / or reaction product thereof As for the active material for secondary battery negative electrodes (Examples 1-17), it turned out that the gas generation amount is reduced significantly compared with the comparative example 1 which is only an active material (A). This is presumably because the radically polymerizable unsaturated bond of the compound (B) effectively formed a polymerizable film using radicals on the negative electrode surface at the initial stage of battery conditioning. Similarly, in Examples 1 to 17, it was found that the gas generation amount was greatly reduced even when compared with Comparative Example 3 containing the active material (A) and the radical scavenger. This is because, in a battery that repeats charging and discharging with a radical scavenger, even if the radical is trapped temporarily, the radical is released again by its own oxidation-reduction potential, so there is no effect in suppressing gas generation. In contrast, a mixture of an active material (A), a compound (B) having an unsaturated bond capable of radical polymerization and a polymer (C) which is hardly soluble in a non-aqueous electrolyte, and / or a reaction product thereof In the case of an active material for a negative electrode of a non-aqueous secondary battery containing the compound, the trapped radicals are utilized for polymerization, and the formed coating effectively suppresses the reductive decomposition of the electrolyte solution on the negative electrode surface, and the compound (B This is probably because the radical is consumed in the reaction in which the growth radical is inactivated and stopped in the latter stage of polymerization accompanied by ()).

  Examples 1 to 17 are hardly soluble in Comparative Examples 4 and 5 containing the active material (A) and the compound (B) having an unsaturated bond capable of radical polymerization, and in the active material (A) and the non-aqueous electrolyte. Comparative Example 2 containing the polymer (C), and the polyvinyl sulfone corresponding to the polymer of the active material (A) and the polymer (C) which is hardly soluble in the non-aqueous electrolyte and the compound (B) used in Example 2 It was found that the amount of gas generated was reduced even when compared with each non-aqueous secondary battery negative electrode active material of Comparative Example 6 containing acid. The coexistence of the compound (B) and the polymer (C) forms a stable film that is difficult to peel off even under repeated charging / discharging or heating conditions on the negative electrode surface, and side reaction with the electrolyte. This is thought to be because the reductive decomposition due to sucrose could be suppressed more effectively.

  Further, Examples 5 to 8 are a mixture of the active material (A), the compound (B) having an unsaturated bond capable of radical polymerization, and the polymer (C) which is hardly soluble in a non-aqueous electrolyte solution, and / or them. In general, vinylene carbonate or 1,3-bis (isocyanatomethylcyclohexane), which is a commonly used electrolyte additive, is combined in the battery system with a non-aqueous secondary battery negative electrode active material containing the reaction product of However, it has been found that the gas generation is not adversely affected and the gas generation is effectively suppressed even in a region where the amount of additive is small. This contains in advance a mixture of a compound (B) having an unsaturated bond capable of radical polymerization with a negative electrode active material and a polymer (C) which is hardly soluble in a non-aqueous electrolyte, and / or a reaction product thereof. Therefore, it is considered that the electrolytic solution additive acting on the active sites on the surface of the active material is effective in a smaller amount.

Moreover, it turned out that Example 2-4 and 9-17 have also improved the initial stage charge-and-discharge efficiency compared with Comparative Examples 1-5 (Example 2: 84.6%, Example 3: 85.). 5%, Example 4: 85.
8%, Example 9: 83.6%, Example 10: 85.5%, Example 11: 84.2%, Example 12: 83.3%, Example 13: 82.5%, Example 14: 85.3%, Example 15: 85.0%, Example 16: 83.8%, Example 17: 85.5%, Comparative Example 1: 81.8%, Comparative Example 2: 82.1 %, Comparative Example 3: 82.6%, Comparative Example 4: 76.3%, Comparative Example 5: 82.2%). This is presumably because the film formed on the negative electrode surface derived from the compound (B) described above suppresses side reactions between the negative electrode surface and the non-aqueous electrolyte.

  Examples 2-4 and 9-17 are charge / discharge at the time of initial conditioning compared with the comparative example 1 which is only an active material (A), and the comparative example 3 containing the active material (A) and the radical scavenger. The efficiency was also excellent. The former is thought to be because the formation of a polymer film on the negative electrode surface during the initial conditioning occurs extremely efficiently. In Comparative Example 3, a certain improvement in the initial charge / discharge efficiency can be seen due to the effect of capturing radicals generated in the battery, but Examples 2 to 4 and 9 to 17 are considered to be combined with gas characteristics. I think the effect is great.

Also in Example 11, as compared with Comparative Example 4 which is maleic anhydride alone, a significant improvement in charge and discharge efficiency during initial conditioning was observed. This is because maleic anhydride alone is partly dissolved in the electrolyte in the battery, and maleic anhydride has low homopolymerizability, so that radicals generated in the battery can be used. As the formed film, the graphite surface cannot be covered sufficiently, but when it coexists with the polymer (C), the polymer (C) itself, which is hardly soluble in the electrolyte, sufficiently covers the graphite surface. In addition, by utilizing the radicals generated by the maleic anhydride in the battery, the electrolyte solution reduction product generated by the side reaction is captured on the negative electrode surface, and the effect of suppressing oxidative decomposition at the positive electrode improves the performance. It is thought that it was shown.
As for Examples 2 to 4, 9, 10, and 12 to 17, the charge / discharge efficiency and storage characteristics during initial conditioning were improved due to the same effects as in Example 11 of the combination of maleic anhydride and polyallylamine described above. .

  Moreover, compared with Comparative Example 5, Examples 1 and 13 had improved charge / discharge efficiency characteristics during initial conditioning. This is because Examples 2-12 and 14-17 in which the dissolution of the electrolyte component in the battery is suppressed by the interaction such as the acid-base interaction between the compound (B) and the polymer (C) Unlikely, it is considered that both the compound (B) and the polymer (C) are poorly soluble in the electrolytic solution, so that the effects as described above can be sufficiently obtained.

Claims (12)

A non-aqueous secondary battery negative electrode active material containing an active material (A) capable of inserting and removing lithium ions and an organic compound (D),
A non-aqueous secondary battery, wherein the organic compound (D) is an organic compound containing a compound (B) having an unsaturated bond capable of radical polymerization and a polymer (C) that is hardly soluble in a non-aqueous electrolyte. Active material for negative electrode. The radical polymerizable unsaturated bond of the compound (B) is a carbon-carbon bond, and the bond is at least one unsaturated bond selected from a double bond and a triple bond.
The active material for a non-aqueous secondary battery negative electrode according to claim 1.   The active material for a nonaqueous secondary battery negative electrode according to claim 1 or 2, wherein the compound (B) has an ionic group in water.   The ionic group that the compound (B) has in water is a hydroxy group, a carbamic acid group, a carboxylic acid group, a sulfonic acid group, a sulfinic acid group, a phosphoric acid group, a phosphonic acid group, a boronic acid group, a borinic acid group, The non-aqueous secondary battery negative electrode according to claim 3, wherein the negative electrode is at least one ionic group selected from the group consisting of a primary amino group, a secondary amino group, a tertiary amino group, a quaternary ammonium group, and salts thereof. Active material.   The active material for negative electrodes for nonaqueous secondary batteries according to any one of claims 1 to 4, wherein the compound (B) and / or the polymer (C) has water solubility.   The active material for a nonaqueous secondary battery negative electrode according to any one of claims 1 to 5, wherein the compound (B) is contained in an amount of 0.1 to 5 mass% with respect to the active material (A).   The active material for a nonaqueous secondary battery negative electrode according to any one of claims 1 to 6, wherein the compound (C) is contained in an amount of 0.1 to 5 mass% with respect to the active material (A). The non-active material according to any one of claims 1 to 6, wherein the active material (A) is at least one selected from the group consisting of artificial graphite, natural graphite, amorphous carbon, silicon, and silicon oxide. Active material for negative electrode of water-based secondary battery.   The negative electrode for non-aqueous secondary batteries formed using the active material for non-aqueous secondary battery negative electrodes as described in any one of Claims 1-7.   A non-aqueous secondary battery comprising a positive electrode and a negative electrode capable of inserting and extracting lithium ions, and an electrolyte, wherein the negative electrode is a negative electrode for a non-aqueous secondary battery according to claim 7. .   11. The negative electrode for a non-aqueous secondary battery according to claim 10, wherein the electrolyte contains an electrolyte solution additive (E), and the content thereof is 10% by mass or less based on the whole electrolyte. A non-aqueous secondary battery.   The non-aqueous secondary battery according to claim 11, wherein the electrolytic solution additive (E) is at least one compound selected from the group consisting of a carbonate compound, an alkene sulfide, a sultone compound, an acid anhydride, and an isocyanate compound. A non-aqueous secondary battery that is a negative electrode for use.