Positive electrode additive for non-aqueous electrolyte secondary battery, positive electrode active material composition for non-aqueous electrolyte secondary battery containing the same, positive electrode for non-aqueous electrolyte secondary battery, and non-aqueous electrolyte secondary battery including the same

Abstract

The present invention provides a positive electrode additive that is for a nonaqueous electrolyte secondary battery and that is capable of improving electric conductivity of electrodes, lowering electrode resistance, and enhancing use efficiency of cationic species such as lithium ion, sodium ion, various types of quaternary ammonium salts, and phosphonium salts.　Disclosed is a positive electrode additive that is for a nonaqueous electrolyte secondary battery and that is made from a carbonaceous material having an oxygen content, measured by element analysis, of not less than 0.5 mass% but less than 1.3 mass%, having a micropore volume, measured by a DFT method, of less than 0.60 cm3 / g, and having a specific surface area, measured by a BET method, of 1,000-2,000 m2 / g. <sp / >

Description

Technical Field

[0001] This patent application claims priority under the Paris Convention with respect to Japanese Patent Application No. 2021-017338 (filing date: February 5, 2021), the entire disclosure of which is incorporated herein by reference in its entirety. The present invention relates to a positive electrode additive for a non-aqueous electrolyte secondary battery, a positive electrode active material composition for a non-aqueous electrolyte secondary battery containing the same, a positive electrode for a non-aqueous electrolyte secondary battery, and a non-aqueous electrolyte secondary battery including the same.

Background Art

[0002] Recently, electrochemical elements (non-aqueous electrolyte secondary batteries) such as lithium-ion secondary batteries, which have been in the spotlight as power sources for portable small electronic devices, use an organic electrolyte solution and exhibit a discharge voltage more than twice as high as that of existing batteries using an alkaline aqueous solution, and have a high energy density. As the positive electrode active material of the lithium-ion secondary battery, oxides composed of lithium and transition metals having a structure capable of intercalation of lithium, such as LiCoO2, LiMn2O4, LiNi CoxO2 (0 < X < 1), etc., are mainly used.

[0003] Since this lithium-ion secondary battery uses a non-aqueous electrolyte, water in the battery can cause a loss of safety. In addition, the above metal oxides, which are positive electrode active materials used in lithium-ion secondary batteries, are brittle in water and easily decompose. Furthermore, in recent years, attempts have been made to increase the Ni content in order to improve the battery capacity of the positive electrode, and the influence of the presence of more water on the performance tends to increase. The presence of water promotes the elution of Ni, deposits on the negative electrode side by the shuttle reaction, and significantly reduces the stability of the battery.

[0004] Patent Documents 1 and 2 disclose technologies related to lithium-ion secondary batteries that can reduce the decrease in battery capacity by effectively removing moisture inside the battery. In the technology disclosed in Patent Document 1, zeolite, activated alumina, activated carbon, silica gel, etc., which are moisture adsorbents, are added inside the lithium-ion secondary battery to effectively remove the moisture inside the battery, thereby suppressing the decrease in the capacity of the lithium-ion secondary battery. Patent Document 2 exemplifies a group of zeolites containing lithium.

[0005] Patent Document 3 exemplifies adding activated carbon having an electric double layer capacitance to the positive electrode of a lithium-ion secondary battery. Further, Patent Document 4 discloses a non-aqueous alkali metal type energy storage element using activated carbon as a positive electrode active material. Specifically, when activated carbon is added to the positive electrode active material, and the amount of mesopores derived from pores with a diameter of 20 Å or more and 500 Å or less calculated by the BJH method in the positive electrode active material layer is V1 (cc / g), and the amount of micropores derived from pores with a diameter of less than 20 Å calculated by the MP method is V2 (cc / g), 0.3 < V1 ≤ 0.8 and 0.5 ≤ V2 ≤ 1.0 are satisfied, and the specific surface area measured by the BET method is 1500 m 2 / g or more and 3000 m 2 / g or less.

[0006] Patent Document 5 exemplifies using heat-treated activated carbon with controlled specific surface area and amount of functional groups as an electrode of an electric double layer capacitor.

Prior Art Documents

Patent Documents

[0007]

Patent Document 1

Patent Document 2

Patent Document 3

Patent Document 4

[0008] As explained in the background art, the technology disclosed in Patent Document 1 prevents the capacity of a lithium ion secondary battery from decreasing by adding a moisture adsorbent inside the battery to remove moisture from the battery.

[0009] However, the moisture adsorbent provided inside a lithium-ion secondary battery becomes an unnecessary component after adsorbing moisture. In other words, after adsorbing moisture, the moisture adsorbent itself does not contribute to improving battery characteristics, so the unnecessary component remains inside the battery. The continued presence of such unnecessary components inside the battery is undesirable from the perspective of improving battery characteristics. To address this issue, Patent Document 2 discloses zeolite, which contains Li and contributes to capacity, but it remains a non-conductive substance, and there is still room for improvement in terms of preventing a decrease in positive electrode capacity.

[0010] The electrode for a lithium secondary battery described in Patent Document 3 is required to have a material (activated carbon) with an electric double layer capacity, and a pore volume of 20 Å or more and 0.418 cc / g or more. However, anions are strongly adsorbed to activated carbon with such an excessively large mesopore volume, which reduces the diffusibility of ions, resulting in a decrease in electrical conductivity and an increase in direct current resistance.

[0011] The invention described in Patent Document 4 is used in devices utilizing non-Faraday reactions such as lithium ion capacitors, and essentially uses activated carbon with relatively large mesopore and micropore volumes, and the amount of activated carbon added is large. Furthermore, it is specialized for output, and does not take into consideration suitability as a secondary battery, i.e., the actual capacity and DC current resistance of the positive electrode.

[0012] Patent Document 5 relates to a method for producing activated carbon used in electric double layer capacitors, but makes no mention of non-aqueous electrolyte secondary batteries such as lithium ion secondary batteries. Furthermore, there is no mention of the amount of micropores that contribute to the capacity of electric double layer capacitors, and therefore no mention of suitability for use as a positive electrode in lithium ion batteries.

[0013] In view of the above problems, an object of the present invention is to provide an additive for a positive electrode of a non-aqueous electrolyte secondary battery that can improve electrode conductivity, reduce electrode resistance, and improve the utilization efficiency of cationic species such as lithium ions, sodium ions, various quaternary ammonium salts, and phosphonium salts; a positive electrode active material composition for a non-aqueous electrolyte secondary battery that contains the additive for a positive electrode of a non-aqueous electrolyte secondary battery; a positive electrode including a layer and a collector electrode made of the composition; and a non-aqueous electrolyte secondary battery that includes the positive electrode. In particular, the present invention provides an additive for a positive electrode of a non-aqueous electrolyte secondary battery that can improve electrode conductivity, reduce electrode resistance, and improve the utilization efficiency of cationic species, even when using a positive electrode active material whose performance is significantly affected by the presence of water; a positive electrode active material composition for a non-aqueous electrolyte secondary battery that contains the additive for a positive electrode of a non-aqueous electrolyte secondary battery; a positive electrode including a layer and a collector electrode made of the composition; and a non-aqueous electrolyte secondary battery that includes the positive electrode. [Means for solving the problem]

[0014] That is, the present invention includes the following aspects.

[0015] [1] Specific surface area by BET method is 1000m 2 / g or more 2000m 2 / g or less, and the micropore volume determined by the DFT method is 0.60 cm 3 / g, and the amount of oxygen measured by elemental analysis is 0.5% by mass or more and less than 1.3% by mass. [2] The additive for a positive electrode of a non-aqueous electrolyte secondary battery according to [1], wherein the ratio of the amount of oxygen in a quinone group measured by surface functional group titration using Boehm titration to the amount of oxygen measured by elemental analysis is 30% or more and 70% or less. [3] The additive for a positive electrode of a non-aqueous electrolyte secondary battery according to [1] or [2], wherein the carbonaceous material has an average particle size of 2 μm to 20 μm. [4] The mesopore volume of the carbonaceous material determined by DFT is 0.35 cm 3 The additive for a positive electrode of a non-aqueous electrolyte secondary battery according to any one of [1] to [3], wherein the additive has a value of not more than 1 / g. [5] A positive electrode active material composition for a non-aqueous electrolyte secondary battery, comprising the additive for a positive electrode of a non-aqueous electrolyte secondary battery according to any one of [1] to [4], a positive electrode active material, and a binder. [6] The positive electrode active material composition for a non-aqueous electrolyte secondary battery according to [5], wherein the content of the additive for a positive electrode of a non-aqueous electrolyte secondary battery relative to the total mass of the positive electrode active material composition is 10 mass % or less. [7] A positive electrode for a non-aqueous electrolyte secondary battery, comprising a positive electrode active material layer made of the positive electrode active material composition for a non-aqueous electrolyte secondary battery according to either [5] or [6], and a current collector. [8] A non-aqueous electrolyte secondary battery comprising the positive electrode according to [7]. [9] The nonaqueous electrolyte secondary battery according to [8], which operates at 2 V to 5 V. [Effects of the Invention]

[0016] The present invention provides an additive for a positive electrode of a non-aqueous electrolyte secondary battery that can improve electrode conductivity, reduce electrode resistance, and improve the utilization efficiency of cationic species such as sodium ions, various quaternary ammonium salts, and phosphonium salts; a positive electrode active material composition for a non-aqueous electrolyte secondary battery that contains the additive for a positive electrode of a non-aqueous electrolyte secondary battery; a positive electrode including a layer and a collector electrode made of the composition; and a non-aqueous electrolyte secondary battery that includes the positive electrode. The present invention can improve electrode conductivity, reduce electrode resistance, and improve the utilization efficiency of cationic species, particularly when using a positive electrode active material whose performance is significantly affected by the presence of water. DETAILED DESCRIPTION OF THE INVENTION

[0017] An embodiment of the present invention will now be described in detail, but is given by way of example only and is not intended to limit the scope of the present invention, which is defined by the claims.

[0018] (Additive for positive electrodes of non-aqueous electrolyte secondary batteries) The additive for a positive electrode of a non-aqueous electrolyte secondary battery of the present invention has a specific surface area of ​​1000 m2 by the BET method. 2 / g or more 2000m 2 / g or less, and the micropore volume determined by the DFT method is 0.60 cm 3 / g, and the amount of oxygen measured by elemental analysis is 0.5% by mass or more and 1.3% by mass or less.

[0019] The carbonaceous material used in the present invention has a specific surface area of ​​1000 m2 by the BET method. 2 / g or more 2000m 2 / g or less. If the specific surface area is within the above range, it can sufficiently adsorb the moisture present in the battery, maintain mechanical strength, and suppress deterioration of battery performance such as separation from the electrode and short circuit during charging and discharging due to powdering inside the battery. The specific surface area by the BET method is 1100 m 2 / g or more is preferable, and 1150m 2 / g or more. The specific surface area according to the BET method is 1900 m 2 / g or less, and 1850m 2 It is more preferable that the saturation coefficient is 1 / g or less.

[0020] The carbonaceous material used in the present invention has a micropore volume of 0.60 cm as determined by the DFT method using nitrogen adsorption. 3 / g. Here, micropores refer to pores with a pore diameter of less than 2 nm. Micropore volume is less than 0.60 cm 3 When the micropore volume is less than 0.58 cm3 / g, the moisture adsorbed in the carbonaceous material itself can be reduced, the drying process during battery fabrication can be simplified and shortened, and loss of activity of the battery active material can be suppressed. 3 / g or less, and 3 / g or less is more preferable, and 0.53 cm 3 / g or less is more preferable, and 3The micropore volume is particularly preferably 0.35 cm3 / g or less, since it adsorbs water and electrolyte decomposition products in the battery and contributes to stabilizing the battery behavior. 3 / g or more, and 3 / g or more is more preferable, and 0.40 cm 3 It is more preferable that the saturation coefficient is 1 / g or more.

[0021] The carbonaceous material used in the present invention has a pore volume (mesopore volume) of pores with a diameter of 2 nm or more of 0.35 cm as measured by pore distribution analysis using the DFT method with nitrogen adsorption. 3 / g or less, and 3 / g or less is more preferable, and 0.30 cm 3 / g or less is more preferable, and 0.25 cm 3 It is particularly preferable that the lower limit is 0.02 cm / g or less. 3 / g or more is preferable, and 0.04cm 3 / g or more is more preferable. When the mesopore volume is within this range, the electrolyte retention ability is excellent, and a sufficient electrolyte environment can be maintained around the positive electrode active material in the positive electrode, providing a fast ion transfer environment. This can improve high-rate performance. Furthermore, this electrolyte retention ability prevents electrolyte depletion in the positive electrode during charge-discharge cycles, maintaining an ion transfer environment around the active material, thereby improving cycle life.

[0022] The carbonaceous material used in the present invention has an oxygen content of 0.5% by mass or more and less than 1.3% by mass as measured by elemental analysis. The method for measuring the oxygen content by elemental analysis will be described later in the Examples. When the oxygen content is equal to or greater than the above lower limit, the affinity with the electrolyte is maintained at a suitable level, and the penetration of the electrolyte into the electrode is less likely to be hindered. When the oxygen content is equal to or less than the above upper limit, electrochemical stability is maintained, and affinity with hydrophobic binders such as PVDF is also maintained. Furthermore, when the oxygen content is within the above range, the oxygen on the surface of the carbonaceous material suppresses water attraction and adsorption while maintaining affinity with the electrolyte, thereby preventing electrolysis of the electrolyte, resulting in improved charging efficiency and further contributing to reduced DC resistance by avoiding coating of decomposed products. Furthermore, metals eluted from the positive electrode, particularly nickel-cobalt-manganese co-oxides, have recently been used as positive electrode materials for lithium-ion batteries due to increased battery capacity, and their water resistance is becoming increasingly poor. Nickel, which is easily eluted in coordinating solvents such as N-methylpyrrolidone, may extract fluorine from the binder polyvinylidene fluoride during electrode fabrication, resulting in gelation. Furthermore, there is an increased risk of nickel growing on the negative electrode due to charging and discharging during battery operation. Oxygen present on the surface of the carbonaceous material coordinates with the eluted nickel, thereby reducing these concerns. The oxygen content is preferably 0.52% by mass or more. Furthermore, the oxygen content is preferably 1.25% by mass or less.

[0023] The carbonaceous material used in the present invention preferably has a ratio of the amount of oxygen in quinone groups measured by surface functional group titration using Boehm titration to the amount of oxygen measured by elemental analysis (amount of oxygen in quinone groups measured by surface functional group titration using Boehm titration / amount of oxygen measured by elemental analysis × 100 [%]) of 30% to 70%. The method for measuring Boehm titration will be described later in the Examples. This ratio is more preferably 33% or more, and even more preferably 35% or more. Furthermore, this ratio is more preferably 60% or less, even more preferably 59% or less, and particularly preferably 58% or less. The quinone functional groups on the surface of the carbonaceous material may be formed in various ways, including when quinones present on the surface of the raw material carbonaceous material remain as they are during the production of the carbonaceous material, when they are formed by dehydrogenation of phenolic functional groups during aromatic nucleation in the carbonaceous material, or when they are induced by the elimination of carboxylic acids from the surface of the carbonaceous material. When the quinone functional groups are present in a certain proportion relative to the total oxygen content, it is possible to reduce the amount of carbonyl groups present, which are easily thermally decomposed, without impairing the affinity with the electrolyte or binder, and not only suppress gas generation induced by the decomposition of functional groups within the battery, but also significantly reduce hygroscopicity, which is thought to contribute to simplifying the battery manufacturing process and improving battery stability.

[0024] The carbonaceous material used in the present invention preferably has an ash content of 0.5% by mass or less, more preferably 0.48% by mass or less, and even more preferably 0.46% by mass or less. Because the heavy metal compounds contained in the ash may diffuse within the positive electrode and precipitate during discharge, the nickel content is preferably 100 ppm or less, more preferably 80 ppm or less. Furthermore, the iron content is preferably 100 ppm or less, more preferably 50 ppm or less.

[0025] The carbonaceous material used in the present invention preferably has an average particle size (D50) of 2 μm to 20 μm as determined by a laser scattering method. When the average particle size is equal to or less than the upper limit, electrical conductivity within the positive electrode is easily maintained, while when the average particle size is equal to or greater than the lower limit, the carbonaceous material can be sufficiently bound by a binder or the like, and degradation of battery performance, such as a short circuit caused by carbonaceous material powder being liberated from the electrode, can be prevented.

[0026] The carbon precursor of the carbonaceous material used in the present invention is not particularly limited, but examples include plant materials such as coconut shells, coffee beans, tea leaves, sugarcane, fruits (e.g., mandarin oranges and bananas), straw, rice husks, hardwoods, softwoods, and bamboo; processed plant materials such as lignin and lignocellulose; thermosetting resins such as phenolic resins, furan resins, and melamine resins; and fossil fuels such as coal, coal pitch, and petroleum pitch. These raw materials may be used alone or in combination of two or more. Among these plant raw materials, plant-derived raw materials are preferred, and coconut shells are preferred, because they are easily available and can be used to produce carbonaceous materials with various properties.

[0027] The coconut shell is not particularly limited, but examples thereof include coconut shells from palm trees (oil palm), coconut palm, salak palm, and bay palm. These coconut shells may be used alone or in combination of two or more. Coconut and palm shells are biomass wastes generated in large quantities after coconuts are used as food, detergent raw materials, biodiesel oil raw materials, etc., and are particularly preferred from the viewpoint of easy availability.

[0028] The carbonaceous material used in the present invention can be produced by a method including carbonizing a carbon precursor, subjecting it to primary activation, washing, and optionally subjecting it to secondary activation, and further subjecting it to heat treatment to obtain a carbonaceous material.

[0029] The carbonization and activation methods are not particularly limited, and may be carried out by known methods such as a fixed bed method, a moving bed method, a fluidized bed method, a multi-stage bed method, or a rotary kiln.

[0030] In the method for producing the carbonaceous material used in the present invention, first, a carbon precursor (preferably plant-derived) is prepared. The carbonization method is not particularly limited, but nitrogen, carbon dioxide, Examples of such a method include firing the powder at a temperature of about 400 to 800°C in an atmosphere of an inert gas such as helium, argon, carbon monoxide, or fuel exhaust gas, a mixed gas of these inert gases, or a mixed gas containing these inert gases as the main component and other gases.

[0031] After carbonization of the carbon precursor, primary activation is performed. There are two activation methods: gas activation and chemical activation. In the present invention, gas activation is preferred because it leaves less impurities behind. Gas activation can be performed by reacting the carbonized carbon precursor with an activation gas (e.g., water vapor, carbon dioxide, etc.).

[0032] In the primary activation, from the viewpoint of efficiently proceeding with activation, a mixture of inert gas and water vapor similar to that used in carbonization is preferred, and the partial pressure of the water vapor in this case is preferably in the range of 10 to 60%. When the partial pressure of water vapor is 10% or more, activation can be easily proceeded sufficiently, and when it is 60% or less, a rapid activation reaction can be suppressed, making it easy to control the reaction.

[0033] The total amount of activation gas supplied in the primary activation is preferably 50 to 10,000 parts by mass, more preferably 100 to 5,000 parts by mass, and even more preferably 200 to 3,000 parts by mass, relative to 100 parts by mass of the carbon precursor. When the total amount of activation gas supplied is within the above range, the activation reaction can proceed more efficiently.

[0034] The activation temperature in the primary activation is usually 700 to 1100°C, preferably 800 to 1000°C. The activation time and heating rate are not particularly limited and will, of course, vary depending on the type, shape, size, and desired pore size distribution of the plant-derived carbon precursor selected. Increasing the activation temperature or lengthening the activation time in the primary activation tends to increase the BET specific surface area of ​​the resulting carbonaceous material. Therefore, the activation temperature and activation time are adjusted to obtain a carbonaceous material with a BET specific surface area within the desired range.

[0035] Next, the carbonaceous material obtained after the primary activation is washed to reduce the ash content. Washing can be performed by immersing the carbonaceous material obtained after the primary activation in a washing solution containing an acid. Examples of the washing solution include mineral acids and organic acids. Examples of mineral acids include hydrochloric acid and sulfuric acid. Examples of organic acids include saturated carboxylic acids such as formic acid, acetic acid, propionic acid, oxalic acid, tartaric acid, and citric acid, and aromatic carboxylic acids such as benzoic acid and terephthalic acid. From the viewpoint of washability, the acid used in the washing solution is preferably a mineral acid, and more preferably hydrochloric acid. Note that after washing with the acid, it is preferable to further wash with water or the like to remove excess acid. This operation can reduce the load on the activation equipment during the secondary activation and subsequent steps, which are performed as needed.

[0036] The cleaning solution can usually be prepared by mixing an acid with an aqueous solution. Examples of the aqueous solution include water and a mixture of water and a water-soluble organic solvent. Examples of the water-soluble organic solvent include alcohols such as methanol, ethanol, propylene glycol, and ethylene glycol.

[0037] The concentration of the acid in the cleaning solution is not particularly limited, and may be adjusted appropriately depending on the type of acid used. The acid concentration in the cleaning solution is preferably 0.01 to 3.5 mass%, more preferably 0.02 to 2.2 mass%, and even more preferably 0.03 to 1.6 mass%, based on the total amount of the cleaning solution. It is preferable that the acid concentration in the cleaning solution is within the above range, because impurities contained in the carbonaceous material can be efficiently removed.

[0038] The temperature of the cleaning solution when the carbonaceous material is immersed is not particularly limited, but is preferably 0 to 98° C., more preferably 10 to 95° C., and even more preferably 15 to 90° C. If the temperature of the cleaning solution when the carbonaceous material is immersed is within the above range, cleaning can be carried out for a practical time with reduced load on the device, which is desirable.

[0039] The method for washing the carbonaceous material is not particularly limited as long as it allows the carbonaceous material to be immersed in the cleaning liquid, and may include a method in which the cleaning liquid is continuously added, allowed to remain for a predetermined time, and the immersion is continued while the liquid is removed, or a method in which the carbonaceous material is immersed in the cleaning liquid, allowed to remain for a predetermined time, drained, and then new cleaning liquid is added and the immersion-draining process is repeated. Furthermore, the method may involve refreshing all or part of the cleaning liquid. The time for immersing the carbonaceous material in the cleaning liquid can be adjusted appropriately depending on the acid used, the acid concentration, the treatment temperature, etc.

[0040] The washing time is not particularly limited, but from the viewpoint of the economic efficiency of the reaction equipment and the structural retention of the carbonaceous material, it is preferably 0.05 to 4 hours, more preferably 0.1 to 3 hours.

[0041] When the carbonaceous material is immersed in the cleaning liquid, the mass ratio between the cleaning liquid and the carbonaceous material may be adjusted as appropriate depending on the type, concentration, temperature, etc. of the cleaning liquid used. The mass of the carbonaceous material to be immersed relative to the mass of the cleaning liquid is usually 0.1 to 50 mass%, preferably 1 to 20 mass%, and more preferably 1.5 to 10 mass%. Within the above range, impurities dissolved in the cleaning liquid are less likely to precipitate from the cleaning liquid, and redeposition to the carbonaceous material is easily suppressed, and volume efficiency is also appropriate, which is desirable from the standpoint of economy.

[0042] The atmosphere in which the cleaning is carried out is not particularly limited and may be appropriately selected depending on the cleaning method used. In the present invention, the cleaning is usually carried out in the air atmosphere.

[0043] In the production of the carbonaceous material used in the present invention, secondary activation may be performed on the carbonaceous material obtained after washing following the primary activation. The secondary activation can be performed under the same conditions as those for the primary activation. Similarly, in the secondary activation, increasing the activation temperature or lengthening the activation time tends to increase the BET specific surface area of ​​the resulting carbonaceous material. Therefore, the activation temperature and activation time can be adjusted to obtain a carbonaceous material having a BET specific surface area within the desired range.

[0044] After the secondary activation, a tertiary activation or a higher activation may be carried out. Furthermore, washing may be carried out between each activation after the secondary activation. From the viewpoint of economy, it is preferable to carry out the secondary activation or the tertiary activation. In the present invention, the tertiary activation and the higher activation may be carried out under the same conditions as the primary activation.

[0045] The carbonaceous material obtained after the secondary activation or higher activation may be further washed to remove ash and metal impurities contained in the carbonaceous material.

[0046] The carbonaceous material used in the present invention is obtained by heat-treating the carbonaceous material obtained after primary activation, secondary activation, or even higher activation. This heat treatment can adjust the surface properties of the carbonaceous material. Specifically, moisture and other substances adsorbed on the carbonaceous material can be removed, and newly generated functional groups can be removed by washing or the like, thereby adjusting the amount of micropores. The heat treatment is carried out by heating the carbonaceous material under an inert gas, such as nitrogen, argon, or carbon dioxide. Alternatively, in addition to or instead of the above heat treatment, the carbonaceous material can also be prepared by heat treatment using means such as reduced pressure or reduced pressure heating.

[0047] From the viewpoint of pore adjustment of the carbonaceous material, the heat treatment temperature is preferably 500° C. or higher, more preferably 550° C. or higher, even more preferably 600° C. or higher, even more preferably 700° C. or higher, and particularly preferably 800° C. or higher. The heat treatment temperature is preferably 1200° C. or lower, more preferably 1150° C. or lower, and even more preferably 1100° C. or lower.

[0048] The heat treatment time varies depending on the heat treatment temperature employed, but from the viewpoint of preparation of the carbonaceous material, it is preferably 0.1 hour or more, more preferably 0.5 hour or more, and even more preferably 1 hour or more, and from the viewpoint of economy, it is preferably 24 hours or less, more preferably 18 hours or less, and even more preferably 10 hours or less.

[0049] In the present invention, the carbonaceous material thus obtained may then be pulverized. The pulverization method is not particularly limited, and known pulverization methods such as a ball mill, a roll mill, or a jet mill, or a combination of these, can be used.

[0050] In the present invention, the carbonaceous material obtained by pulverization may be classified. For example, by removing particles having a particle diameter of 1 μm or less, it is possible to obtain carbonaceous material particles having a narrow particle size distribution. By removing such fine particles, it is possible to reduce the amount of binder used in constructing an electrode. The classification method is not particularly limited, and examples thereof include classification using a sieve, wet classification, and dry classification. Examples of wet classifiers include classifiers that utilize the principles of gravity classification, inertia classification, hydraulic classification, centrifugal classification, etc. Examples of dry classifiers include classifiers that utilize the principles of sedimentation classification, mechanical classification, centrifugal classification, etc. From the standpoint of economy, it is preferable to use a dry classifier.

[0051] The carbonaceous material obtained as described above can be preferably used as an additive for the positive electrode of the non-aqueous electrolyte secondary battery of the present invention.

[0052] The positive electrode active material composition for a non-aqueous electrolyte secondary battery of the present invention (also referred to as a non-aqueous electrolyte secondary battery positive electrode composition) contains the above-mentioned additive for a non-aqueous electrolyte secondary battery positive electrode, a positive electrode active material, and a binder. The non-aqueous electrolyte secondary battery positive electrode composition of the present invention may also contain other components in addition to those described above.

[0053] The content of the additive for a positive electrode of a non-aqueous electrolyte secondary battery is preferably 10% by mass or less, more preferably 8% by mass or less, and even more preferably 6% by mass or less, based on the total mass of the solid content of the composition for a positive electrode of a non-aqueous electrolyte secondary battery. The lower limit of the content of the additive for a positive electrode is not particularly limited, but is preferably 0.5% by mass or more, and more preferably 1% by mass or more.

[0054] The mixing ratio of the additive for a positive electrode of a non-aqueous electrolyte secondary battery to the positive electrode active material described below may be 1:99 to 10:90 by mass. When the mixing ratio of the additive for a positive electrode of a non-aqueous electrolyte secondary battery to the positive electrode active material is within this range, excellent output characteristics and capacity characteristics can all be obtained.

[0055] (Cathode active material) As the positive electrode active material contained in the composition for the positive electrode of the non-aqueous electrolyte secondary battery, known positive electrode active materials can be used without particular limitation. For example, lithium-containing cobalt oxide (LiCoO2), lithium manganate (LiMn2O4), lithium-containing nickel oxide (LiNiO2), lithium-containing composite oxide of Co-Ni-Mn, lithium-containing composite oxide of Ni-Mn-Al, lithium-containing composite oxide of Ni-Co-Al, olivine-type lithium iron phosphate (LiFePO4), olivine-type lithium manganese phosphate (LiMnPO4), lithium-excess spinel compound represented by Li 1+x Mn 2-x O4 (0 < X < 2), metal oxides such as Li[Ni 0.17 Li 0.2 Co 0.07 Mn 0.56 O2, LiNi 0.5 Mn1 .5 O4, etc., sulfur, compounds and polymers having nitroxyl radicals, compounds and polymers having oxyl radicals, compounds and polymers having nitrogen radicals, organic radicals such as compounds and polymers having a fulvalene skeleton.

[0056] These can be used alone or in combination of two or more. Among those described above, from the viewpoint of improving the battery capacity of the secondary battery, etc., as the positive electrode active material, lithium-containing cobalt oxide (LiCoO2), lithium-containing nickel oxide (LiNiO2), lithium-containing composite oxide of Co-Ni-Mn, for example, LiNi 1 / 3 Co 1 / 3 Mn 1 / 3 O2, LiNi 0.5 Co 0.2 Mn 0.3 O2, LiNi<00000​​​​​​​​​​​​​​​​​​

[0057] The particle size of the positive electrode active material is not particularly limited and can be the same as that of conventionally used positive electrode active materials, and is usually in the range of 0.1 μm to 40 μm, more preferably 0.5 μm to 20 μm.

[0058] In the positive electrode active material composition according to one embodiment of the present invention, the content of the positive electrode active material may be 99% by weight or less, 95% by weight or less, or 90% by weight or less, or 30% by weight or more, 40% by weight or more, or 50% by weight or more, based on the total weight of the solid content of the composition.

[0059] (binder) The positive electrode composition for a non-aqueous electrolyte secondary battery of the present invention contains a binder to effectively adhere positive electrode active material particles to each other and to effectively adhere the positive electrode active material to a current collector. Examples of binders that may be used include, but are not limited to, polyvinyl alcohol, carboxymethyl cellulose, hydroxypropyl cellulose, diacetyl cellulose, polyvinyl chloride, carboxylated polyvinyl chloride, polyvinyl fluoride, polymers containing ethylene oxide, polyvinylpyrrolidone, polyurethane, polytetrafluoroethylene, polyvinylidene fluoride, polyethylene, polypropylene, styrene-butadiene rubber, acrylated styrene-butadiene rubber, epoxy resin, and nylon. These binders may be used alone or in combination. In the positive electrode composition for a non-aqueous electrolyte secondary battery of the present invention, the content of the binder may be 0.5 to 10 mass % or 1 to 7 mass % based on the total mass of the positive electrode in the composition.

[0060] (Conductive material) The composition for a positive electrode of a non-aqueous electrolyte secondary battery of the present invention may further contain a conductive material to further enhance the conductivity of the positive electrode formed on the current collector. Any electrically conductive material that does not undergo chemical changes in the resulting electrochemical device may be used as the conductive material. Specific examples of the conductive material include natural graphite, artificial graphite, carbon black, acetylene black, ketjen black, carbon fiber, metal powders and fibers of metals such as copper, nickel, aluminum, and silver, and conductive materials such as polyphenylene derivatives may be used alone or in combination. In the composition for a positive electrode of a non-aqueous electrolyte secondary battery of the present invention, the content of the conductive material may be 0.5 to 10 mass % or 1 to 7 mass % based on the total mass of the solid components in the composition.

[0061] (solvent) The composition for a positive electrode of a nonaqueous electrolyte secondary battery of the present invention may contain a solvent. For example, an organic solvent can be used as the solvent, and among these, a polar organic solvent capable of dissolving the binder is preferred. Specifically, the organic solvent may be acetonitrile, N-methylpyrrolidone, acetylpyridine, cyclopentanone, N,N-dimethylacetamide, dimethylformamide, dimethyl sulfoxide, methylformamide, methyl ethyl ketone, furfural, ethylenediamine, or the like. Among these, N-methylpyrrolidone (NMP) is most preferred from the viewpoints of ease of handling, safety, ease of synthesis, and the like. These organic solvents may be used alone or in combination of two or more.

[0062] The amount of the solvent used is such that the solid content concentration in the composition for an electrochemical element positive electrode is preferably 1 to 80 mass %, more preferably 5 to 70 mass %, and even more preferably 10 to 60 mass %. By setting the solid content concentration in the above range, the positive electrode active material, the additive for an electrochemical element positive electrode, and other components contained therein can be uniformly dispersed, which is preferable.

[0063] (Method of manufacturing a composition for a positive electrode of a non-aqueous electrolyte secondary battery) The method for producing the composition for a positive electrode of a non-aqueous electrolyte secondary battery of the present invention involves mixing the additive for a positive electrode of a non-aqueous electrolyte secondary battery, the positive electrode active material, and, if necessary, a solvent and other components. There are no particular limitations on the mixing method, and for example, a general mixing device such as a disperser, mill, or kneader can be used. For example, it is preferable to stir the mixture for 20 minutes to 120 minutes.

[0064] The mixing temperature is not particularly limited either, and is, for example, in the range of 0° C. to 160° C., more preferably in the range of 20° C. to 80° C. A temperature that is too low is undesirable because the viscosity becomes too high and coating becomes impossible, while a temperature that is too high is undesirable from the viewpoints of safety and equipment operability because of the evaporation of the organic solvent and the accompanying viscosity changes.

[0065] [Nonaqueous electrolyte secondary battery] Such a non-aqueous electrolyte positive electrode composition according to one embodiment of the present invention can be usefully used in non-aqueous electrolyte secondary batteries. The present invention also includes an electrochemical device having a positive electrode prepared using the above-described non-aqueous electrolyte secondary battery positive electrode composition. By containing the above-described additive for a non-aqueous electrolyte secondary battery positive electrode, the electrochemical device of the present invention can improve the conductivity of the positive electrode and reduce the electrode resistance. It can also improve lithium utilization efficiency and reduce irreversible capacity. The non-aqueous electrolyte secondary battery of the present invention preferably operates at 2 V to 5 V, and an example of such a battery is a lithium ion secondary battery.

[0066] For example, when the nonaqueous electrolyte secondary battery of the present invention is a lithium ion secondary battery, the lithium ion secondary battery includes a positive electrode, a negative electrode, and an electrolyte.

[0067] (positive electrode) The positive electrode is produced using the positive electrode composition for non-aqueous electrolyte secondary batteries of the present invention and includes a current collector and a positive electrode active material layer. The positive electrode active material layer is formed, for example, by applying the positive electrode composition of the present invention to the current collector. The positive electrode active material layer is often prepared by applying the positive electrode composition for non-aqueous electrolyte secondary batteries to the current collector and drying it, and is usually composed of the solid content of the positive electrode composition for non-aqueous electrolyte secondary batteries.

[0068] The method for applying the nonaqueous electrolyte secondary battery positive electrode composition onto a current collector is not particularly limited, and known methods can be used. Specifically, examples of the application method include a doctor blade method, a dipping method, a reverse roll method, a direct roll method, a gravure method, an extrusion method, and a brush coating method. In this case, the positive electrode composition may be applied to only one side of the current collector, or may be applied to both sides. The thickness of the composition film on the current collector after application and before drying can be appropriately set depending on the thickness of the positive electrode active material layer obtained by drying.

[0069] The current collector to which the positive electrode composition is applied is made of a material that is electrically conductive and electrochemically durable. Specifically, a current collector made of aluminum or an aluminum alloy can be used. In this case, aluminum and an aluminum alloy may be used in combination, or different types of aluminum alloys may be used in combination. Aluminum and aluminum alloys are excellent current collector materials because they are heat resistant and electrochemically stable.

[0070] The method for drying the positive electrode composition on the current collector is not particularly limited and can be a known method, for example, drying with warm air, hot air, or low-humidity air, vacuum drying, or drying by irradiation with infrared rays or electron beams, etc. By drying the positive electrode composition on the current collector in this manner, a positive electrode active material layer can be formed on the current collector, and a positive electrode including the current collector and the positive electrode active material layer can be obtained.

[0071] In particular, in order to maintain the metal capturing ability of the added carbonaceous material, it is preferable to perform a sufficient drying step during positive electrode production, and it is preferable to perform drying within a range that does not affect the current collector (e.g., aluminum foil) and allows water adsorbed on the surfaces of the positive electrode active material and the carbonaceous material to volatilize. Drying is preferably performed at a drying temperature of 100°C to 160°C under atmospheric pressure or under reduced pressure for 1 to 12 hours.

[0072] After the drying step, the positive electrode active material layer may be subjected to pressure treatment using a mold press, a roll press, etc. Pressure treatment can improve the adhesion between the positive electrode active material layer and the current collector.

[0073] The positive electrode for a non-aqueous electrolyte secondary battery produced in this manner has an excellent internal conductive network, and therefore, by using this positive electrode for a non-aqueous electrolyte secondary battery, the internal resistance of the non-aqueous electrolyte secondary battery can be reduced, thereby improving the performance of the secondary battery.

[0074] (Negative electrode) The negative electrode includes a current collector and a negative electrode active material layer formed on the current collector, and the negative electrode active material layer includes a negative electrode active material.

[0075] The negative electrode active material is a material capable of reversibly intercalating / deintercalating lithium ions, and includes lithium metal, a lithium metal alloy, a material capable of being doped with and dedoped from lithium, or a transition metal oxide.

[0076] As substances capable of reversibly intercalating / deintercalating lithium ions, carbon substances can be used, and any carbon-based negative electrode active material generally used in lithium-ion secondary batteries can be used. Representative examples thereof include crystalline carbon and amorphous carbon, and these may be used together. Examples of the crystalline carbon include graphite such as amorphous, plate-like, scaly, spherical or fibrous natural graphite or artificial graphite. Examples of the amorphous carbon include soft carbon or hard carbon, mesophase pitch carbide, fired coke, etc.

[0077] As the alloy of the lithium metal, an alloy of lithium and a metal selected from the group consisting of Na, K, Rb, Cs, Fr, Be, Mg, Ca, Sr, Si, Sb, Pb, In, Zn, Ba, Ra, Ge, Al and Sn may be used.

[0078] As substances capable of doping and undoping lithium, Si, SiOx(0 < x < 2), Si-Q alloy (where Q is an element selected from the group consisting of alkali metals, alkaline earth metals, group 13 elements, group 14 elements, group 15 elements, group 16 elements, transition metals, rare earth elements and combinations thereof, and is not Si), Sn, SnO2, Sn-R (where R is an element selected from the group consisting of alkali metals, alkaline earth metals, group 13 elements, group 14 elements, group 15 elements, group 16 elements, transition metals, rare earth elements and combinations thereof, and is not Sn), etc. may be mentioned, and at least one of these may be mixed with SiO2 and used. As the elements Q and R, those selected from the group consisting of Mg, Ca, Sr, Ba, Ra, Sc, Y, Ti, Zr, Hf, Rf, V, Nb, Ta, Db, Cr, Mo, W, Sg, Tc, Re, Bh, Fe, Pb, Ru, Os, Hs, Rh, Ir, Pd, Pt, Cu, Ag, Au, Zn, Cd, B, Al, Ga, Sn, In, Ti, Ge, P, As, Sb, Bi, S, Se, Te, Po, and combinations thereof may be used.

[0079] Examples of the transition metal oxide include vanadium oxide and lithium vanadium oxide.

[0080] The content of the negative electrode active material in the negative electrode active material layer may be 90% by mass to 100% by mass, or 95% by mass to 99% by mass, based on the total mass of the negative electrode active material layer. The negative electrode active material layer may consist of only the negative electrode.

[0081] The negative electrode active material layer includes a binder and may optionally further include a conductive material. The content of the binder in the negative electrode active material layer may be 1% by mass to 10% by mass based on the total mass of the negative electrode active material layer. When the negative electrode active material layer further includes a conductive material, the negative electrode active material may be used in an amount of 80% by mass (preferably 90% by mass) to 98% by mass, the binder may be used in an amount of 1% by mass to 10% by mass, and the conductive material may be used in an amount of 1% by mass to 10% by mass.

[0082] The binder serves to effectively adhere the negative electrode active material particles to each other and to the current collector. The binder may be a water-insoluble binder, a water-soluble binder, or a combination thereof.

[0083] Examples of the non-water-soluble binder include polyvinyl chloride, carboxylated polyvinyl chloride, polyvinyl fluoride, polymers containing ethylene oxide, polyvinylpyrrolidone, polyurethane, polytetrafluoroethylene, polyvinylidene fluoride, polyethylene, polypropylene, polyamideimide, polyimide, and combinations thereof.

[0084] Examples of the water-soluble binder include styrene-butadiene rubber, acrylated styrene-butadiene rubber, polyvinyl alcohol, sodium polyacrylate, a copolymer of propylene and an olefin having 2 to 8 carbon atoms, a copolymer of (meth)acrylic acid and an alkyl (meth)acrylate ester, and combinations thereof.

[0085] When a water-soluble binder is used as the negative electrode binder, a cellulose-based compound capable of imparting viscosity may be further used as a thickener. Examples of the cellulose-based compound include carboxymethyl cellulose, hydroxypropyl methyl cellulose, methyl cellulose, and alkali metal salts thereof, and two or more of these may be used in combination. The alkali metal may be Na, K, or Li. The amount of such a thickener used may be 0.1 to 150 parts by mass per 100 parts by mass of the binder.

[0086] The conductive material is used to impart conductivity to the electrodes, and any electron-conductive material that does not undergo chemical change in the battery that is constructed can be used. Examples include carbon-based materials such as natural graphite, artificial graphite, carbon black, acetylene black, ketjen black, and carbon fiber; metal-based materials such as metal powders or metal fibers of copper, nickel, aluminum, and silver; conductive polymers such as polyphenylene derivatives; and conductive materials containing mixtures thereof.

[0087] The current collector may be selected from the group consisting of copper foil, nickel foil, stainless steel foil, titanium foil, nickel foam, copper foam, a polymer substrate coated with a conductive metal, and combinations thereof.

[0088] (electrolyte) The electrolyte preferably contains a non-aqueous organic solvent and a lithium salt.

[0089] The non-aqueous organic solvent serves as a medium through which ions involved in the electrochemical reaction of the battery can migrate.

[0090] The non-aqueous organic solvent may be a carbonate, ester, ether, ketone, alcohol, or aprotic solvent. Examples of the carbonate solvent include dimethyl carbonate (DMC), diethyl carbonate (DEC), dipropyl carbonate (DPC), methyl propyl carbonate (MPC), ethyl propyl carbonate (EPC), methyl ethyl carbonate (MEC), ethyl methyl carbonate (EMC), ethylene carbonate (EC), propylene carbonate (PC), and butylene carbonate (BC). Examples of the ester solvent include n-methyl acetate, n-ethyl acetate, n-propyl acetate, dimethyl acetate, methyl propionate, ethyl propionate, γ-butyrolactone, decanolide, valerolactone, mevalonolactone, and caprolactone. Examples of the ether solvents that can be used include dibutyl ether, tetraglyme, diglyme, dimethoxyethane, 2-methyltetrahydrofuran, and tetrahydrofuran. Examples of the ketone solvents that can be used include cyclohexanone. Examples of the alcohol solvents that can be used include ethyl alcohol and isopropyl alcohol. Examples of the aprotic solvents that can be used include nitriles such as R-CN (R is a linear, branched, or cyclic hydrocarbon group having 2 to 20 carbon atoms, which may contain a double bond-oriented ring or an ether bond), amides such as dimethylformamide, dioxolanes such as 1,3-dioxolane, and sulfolanes.

[0091] The non-aqueous organic solvents may be used alone or in combination of two or more. When two or more are used in combination, the mixing ratio may be appropriately adjusted depending on the desired battery performance.

[0092] In addition, in the case of the carbonate-based solvent, it is preferable to use a mixture of a cyclic carbonate and a chain carbonate, and in this case, the cyclic carbonate and the chain carbonate are mixed in a volume ratio of 1:1 to 1:9, which can provide better electrolyte performance.

[0093] The lithium salt is a substance that is dissolved in an organic solvent and acts as a lithium ion supply source in the battery, enabling basic operation of a lithium ion secondary battery, and promoting the movement of lithium ions between the positive electrode and the negative electrode. Representative examples of such lithium salts include LiPF6, LiBF4, LiSbF6, LiAsF6, LiCF3SO3, LiN(SO2C2F5)2, Li(CF3SO2)2N, LiC4F9SO3, LiClO4, LiAlO4, LiAlCl4, and LiN(CxF 2x+1 SO2)(CyF 2y +1 Examples of suitable lithium salts include lithium bis(oxalato)borate (LiBOB), lithium bis(oxalato)borate (LiBOB), and lithium bis(oxalato)borate (LiBOB). These may be used alone or in combination. The lithium salt concentration should be within the range of 0.1 to 2.0 M. If the lithium salt concentration is less than 0.1 M, the conductivity of the electrolyte tends to decrease, resulting in a decrease in electrolyte performance. If the lithium salt concentration is more than 2.0 M, the viscosity of the electrolyte tends to increase, resulting in a decrease in lithium ion mobility.

[0094] The electrolyte may further contain a vinylene carbonate or ethylene carbonate compound as a life-promoting agent to improve the battery life.

[0095] Representative examples of the ethylene carbonate-based compound include difluoroethylene carbonate, chloroethylene carbonate, dichloroethylene carbonate, bromoethylene carbonate, dibromoethylene carbonate, nitroethylene carbonate, cyanoethylene carbonate, fluoroethylene carbonate, etc. When such a lifespan improver is further used, the amount used may be appropriately adjusted.

[0096] In the non-aqueous electrolyte secondary battery of the present invention, a separator may be present between the positive electrode and the negative electrode. Such a separator may be made of polyethylene, polypropylene, polyvinylidene fluoride, or a multilayer film of two or more of these. Alternatively, a mixed multilayer film such as a polyethylene / polypropylene two-layer separator, a polyethylene / polypropylene / polyethylene three-layer separator, or a polypropylene / polyethylene / polypropylene three-layer separator may be used. [Example]

[0097] Examples and comparative examples will be described below. However, the following examples are provided to more specifically explain the present invention, and the concept of the present invention is not limited to the following examples.

[0098] (Specific surface area by nitrogen adsorption BET method, pore volume by NL-DFT method) Below is an approximate formula derived from the BET formula.

number

[0099] Using the above approximate formula (I), we substitute the adsorption amount (v) measured at a given relative pressure (p / p0) by the multipoint method using nitrogen adsorption at liquid nitrogen temperature to obtain v. m Calculate the following formula ( II) to determine the specific surface area (SSA: unit is m 2 / g) was calculated.

[0100]

number

[0101] In the above formulas (I) and (II), v m is the amount of adsorption (cm) required to form a monolayer on the sample surface. 3 / g), and v is the measured adsorption amount (cm 3 / g), p0 is the saturated vapor pressure, p is the absolute pressure, c is a constant (reflecting the heat of adsorption), and N is Avogadro's number 6.022 × 10 23 , a(nm 2 ) is the area occupied by the adsorbate molecule on the sample surface (molecular occupied cross-sectional area).

[0102] Specifically, the amount of nitrogen adsorption onto the carbonaceous material at liquid nitrogen temperature was measured using an "Autosorb-iQ-MP" manufactured by Quantachrome, as follows: The carbonaceous material to be measured was loaded into a sample tube, and the sample tube was cooled to -196°C (77K), and then the pressure was reduced once. Nitrogen (purity 99.999%) was then adsorbed onto the measurement sample at the desired relative pressure. The amount of nitrogen adsorbed onto the sample when equilibrium pressure was reached at each desired relative pressure was defined as the amount of adsorbed gas v. Based on this measured value, the specific surface area was calculated by the BET method using the above formulas (I) and (II).

[0103] Furthermore, the adsorption isotherm obtained from the above-mentioned measurement of the amount of adsorbed nitrogen was analyzed by the DFT method, and the volume of pores with a pore diameter of less than 2 nm was calculated as the micropore volume, and the volume of pores with a pore diameter of 2 nm or more and 50 nm or less was calculated as the mesopore volume.

[0104] (oxygen content measured by elemental analysis) Elemental analysis was performed using an oxygen, nitrogen, and hydrogen analyzer EMGA-930 manufactured by Horiba Ltd. based on the inert gas dissolution method. The detection method of this device is oxygen: inert gas fusion - non-dispersive infrared absorption method (NDIR), and calibration is (oxygen · nitrogen) Ni capsule, TiH2 (H standard sample), SS-3 (N, The test was performed using a carbonaceous material (O standard sample), and as a pretreatment, the moisture content was measured at 250°C for approximately 10 minutes. 20 mg of the carbonaceous material sample was placed in a Ni capsule and degassed for 30 seconds in an elemental analyzer before measurement. Three samples were analyzed, and the average value was taken as the analytical value (oxygen content (mass%) in the carbonaceous material measured by elemental analysis: (A)).

[0105] (Functional group titration by Boehm method) The quantitative determination of the amount of functional groups in carbonaceous materials is generally known, and can be carried out by the method detailed in, for example, Hyomen, 34[2] (1996) Otowa, p. 62 or Catal., 1966

[16] (US), p. 179. Specifically, 2 g of each carbonaceous material sample was placed in a 100 ml Erlenmeyer flask, and 50 ml of each of N / 10 alkaline reagents ((a) sodium bicarbonate, (b) sodium carbonate, (c) caustic soda, (d) sodium ethoxide) was added. After shaking for 24 hours, the mixture was filtered off. The unreacted alkaline reagent was titrated with N / 10 hydrochloric acid. The carboxyl group reacts with all reagents (a) to (d), the lactone group with (b) to (d), the hydroxyl group with (c) to (d), and the quinone group with (d). The amount of each titration was subtracted to determine the amount of functional groups (meq / g).

[0106] (The ratio of the amount of oxygen in the quinone group measured by functional group titration using the Boehm method to the amount of oxygen measured by elemental analysis) The ratio of the amount of oxygen (B) in quinone groups measured by functional group titration using the Boehm method to the amount of oxygen (A) in the carbonaceous material measured by elemental analysis was calculated using the following method. From the amount of quinone groups determined above, the amount of oxygen (mass%) in the quinone groups contained in the carbonaceous material was calculated using the following formula (III). Furthermore, the ratio of the amount of oxygen in quinone groups in the carbonaceous material measured by surface functional group titration using Boehm titration was calculated by dividing the amount of oxygen in the quinone groups contained in the carbonaceous material determined by elemental analysis (formula (IV)).

[0107]

number

[0108]

number

[0109] (Average particle size measured by laser scattering method) The average particle size (particle size distribution) of plant-derived char and carbonaceous materials was measured using the following method. The sample was placed in an aqueous solution containing 5% by mass of a surfactant ("Toriton X100" manufactured by Wako Pure Chemical Industries, Ltd.), treated in an ultrasonic cleaner for at least 10 minutes, and dispersed in the aqueous solution. The particle size distribution was measured using this dispersion. The particle size distribution was measured using a particle size and particle size distribution measuring device ("Microtrac MT3300EXII" manufactured by Microtrac-Bell Corporation). D50 is the particle size at which the cumulative volume is 50%, and this value was used as the average particle size.

[0110] (Method for measuring ash content) The mass of an alumina crucible was measured after baking at 900°C and cooling in a desiccator containing silica gel. After vacuum drying for 8–10 hours in a thermostatic oven adjusted to 120°C, 20 g of activated carbon was placed in a 50 ml alumina crucible. The mass of the crucible plus the mass of the carbonaceous material was accurately weighed to the nearest 0.1 mg. The alumina crucible containing the sample was placed in an electric furnace. Dry air was introduced into the furnace at 20 L / min. The temperature was raised to 200°C over 1 hour, then to 700°C over 2 hours, and held at 700°C for 14 hours for incineration. After incineration, the sample was cooled in a desiccator containing silica gel. The mass of the crucible plus the ash was accurately weighed to the nearest 0.1 mg, and the ash content was calculated using formula (V).

[0111]

number

[0112] (water content) The hygroscopicity of the carbonaceous material was measured by Karl Fischer titration (coulometric titration) using a Karl Fischer moisture analyzer (Mitsubishi Chemical Analytech, CA-200 trace moisture analyzer). 1 g of the carbonaceous material was dried by heating at 120°C and 10 mmHg for 24 hours, and the mass of the residue was measured. The temperature of the Karl Fischer moisture analyzer was then raised to 250°C, and the measurement sample was exposed to this temperature, and the released moisture was measured.

[0113] (Positive electrode composition for lithium secondary batteries) Dissolve 3 parts by mass of polyvinylidene fluoride (KF Polymer 7200, manufactured by Kureha Corporation) in 30 parts by mass of N-methylpyrrolidone solution, LiNi as a positive electrode active material 0.33 Co 0.33 Mn 0. 33 93 parts by mass of O2 (manufactured by Nippon Chemical Industry Co., Ltd., "Cellseed C"), 2 parts by mass of acetylene black (manufactured by Denki Kagaku Kogyo Co., Ltd., "Denka Black") as a conductive additive, and 2 parts by mass of the carbonaceous material prepared in the examples were mixed together, and the mixture was stirred and dispersed in a homomixer (manufactured by Primix Corporation) (4500 rpm) while appropriately adding N-methylpyrrolidone so that the solid content concentration of the positive electrode material became 50% by mass, to obtain a slurry composition for a lithium secondary battery electrode.

[0114] (Positive electrode for lithium secondary batteries) The lithium secondary battery electrode slurry composition was applied to an aluminum foil current collector ("1N30-H" manufactured by Fuji Kakoshi) using a bar coater ("T101" manufactured by Matsuo Sangyo Co., Ltd.). The coating was then dried at 80°C for 30 minutes in a hot air dryer (manufactured by Yamato Scientific Co., Ltd.) and rolled using a roll press (manufactured by Hosen Co., Ltd.). The resulting electrode was punched out into a lithium secondary battery electrode (φ14 mm) and then secondary dried at 120°C for 3 hours under reduced pressure to produce a lithium secondary battery electrode (cathode). The moisture content of the dried electrode (φ14 mm) was measured by heating it to 250°C using a Karl Fischer meter (manufactured by Mitsubishi Chemical Analytech Co., Ltd.) under a nitrogen stream. The moisture content was controlled to be 20 ppm or less, allowing the added carbonaceous material to perform functions other than water absorption.

[0115] (Fabrication of lithium-ion secondary batteries) The lithium ion secondary battery electrode was transferred to a glove box (manufactured by Miwa Seisakusho) under an argon gas atmosphere. This lithium secondary battery electrode was used as the positive electrode. For the negative electrode, a laminate consisting of a metallic lithium foil (0.2 mm thick, φ16 mm) as the negative electrode active material layer and a steel foil (0.2 mm thick, φ17 mm) as the current collector was used. A polypropylene separator (Celgard #2400, manufactured by Polypore) was used as the separator. The electrolyte was a mixed solvent system (1M-LiPF6, EC / EMC = 3 / 7 vol%, VC = 2 mass%) of lithium hexafluorophosphate (LiPF6) in ethylene carbonate (EC) and ethyl methyl carbonate (EMC) with vinylene carbonate (VC) added (1M-LiPF6, EC / EMC = 3 / 7 vol%, VC = 2 mass%). A coin-type lithium secondary battery (2032 type) was fabricated.

[0116] [Example 1] Char made from coconut shells from the Philippines (specific surface area: 370 m 2 / g) The carbonaceous material was then subjected to primary activation at 850°C using propane combustion gas and steam (steam partial pressure: 25%). It was then pickled at 85°C for 30 minutes using hydrochloric acid (concentration: 0.5N, diluted with ion-exchanged water), after which it was thoroughly washed with ion-exchanged water and dried to remove any remaining acid. The specific surface area of ​​the carbonaceous material obtained at this stage was 1685 m 2 The carbonaceous material thus obtained was heat-treated at 900°C under atmospheric pressure in a nitrogen atmosphere for 1 hour, and was then discharged into a nitrogen-flowing container with a purity of 99.99% upon heat treatment. The material was then cooled to 200°C or below in a nitrogen gas atmosphere to obtain a second-washed granular carbonaceous material. This granular carbonaceous material was then pulverized to an average particle size of 6 μm, and the various physical properties of the resulting carbonaceous material were measured. The results are shown in Table 1.

[0117] [Example 2] The granular carbonaceous material before heat treatment, which was obtained by primary activation, acid washing, water washing and drying in the same manner as in Example 1, was further subjected to secondary activation at 970°C using propane combustion gas (water vapor partial pressure 15%) to obtain a granular carbonaceous material. The specific surface area of ​​the carbonaceous material obtained at this stage was 2184 m 2The result was a carbonaceous material with a molecular weight of 10 ...

[0118] [Example 3] The activation time of the primary activation in Example 1 was extended, and the specific surface area was 1810 m 2 A primary activated granular carbonaceous material (carbonaceous material before heat treatment) with a specific surface area of ​​1834 m / g was obtained. This granular carbonaceous material was further subjected to secondary activation at 970°C using propane combustion gas (water vapor partial pressure 15%) to obtain a granular carbonaceous material. 2 / g. The obtained secondarily activated granular carbonaceous material was further pickled at 85°C for 30 minutes, thoroughly washed with ion-exchanged water, dried, and then heat-treated in a nitrogen atmosphere at atmospheric pressure and 900°C for 1 hour to obtain a secondarily washed granular carbonaceous material. This granular carbonaceous material was pulverized to an average particle size of 6 μm, and the various physical properties of the obtained carbonaceous material were measured. The results are shown in Table 1.

[0119] [Comparative Examples 1 to 3] In each of Examples 1 to 3, carbonaceous materials obtained in the same manner as in Examples 1 to 3, except that heat treatment in a nitrogen atmosphere after activation and cleaning was not performed and reduced-pressure drying at 120°C and 1 Torr was performed for 12 hours, were used as additives for positive electrodes of nonaqueous electrolyte secondary batteries in Comparative Examples 1 to 3, respectively. The results are shown in Table 1.

[0120] Comparative Example 4 The carbonaceous material obtained in the same manner as in Example 1 was further heated in an ESPEC high-temperature chamber under atmospheric pressure at 230° C. for 3 hours.

[0121] Comparative Example 5 The same procedures as in Example 1 were carried out except that the heat treatment was carried out at 780° C., and the various physical properties of the resulting carbonaceous material were measured. The results are shown in Table 1.

[0122] [Table 1]

[0123] [Battery characteristics of Examples 1 to 3 and Comparative Examples 1 to 4] Lithium ion secondary batteries were fabricated according to the above-described procedure using the carbonaceous materials obtained in Examples 1 to 3 and Comparative Examples 1 to 4. For the resulting lithium ion secondary batteries, DC resistance was measured before initial charging using a charge / discharge tester ("TOSCAT" manufactured by Toyo Systems Co., Ltd.), and then a charge / discharge test was performed. DC resistance was measured when 0.5 mA was applied for 3 seconds. Lithium doping was performed at a rate of 70 mA / g relative to the active material mass until the potential reached 1 mV relative to the lithium potential. A constant voltage of 1 mV relative to the lithium potential was applied for 8 hours to terminate the doping. The capacity (mAh / g) at this time was recorded as the charge capacity. Next, undoping was performed at a rate of 70 mA / g relative to the active material mass until the potential reached 2.5 V relative to the lithium potential, and the discharged capacity at this time was recorded as the discharge capacity. The percentage of the discharge capacity / charge capacity was recorded as the charge / discharge efficiency (initial charge / discharge efficiency) and was used as an index of the utilization efficiency of lithium ions in the battery. The irreversible capacity was calculated by subtracting the discharge capacity from the charge capacity. The results are shown in Table 2.

[0124] Comparative Example 6 Except for not adding the carbonaceous material, a lithium ion battery was fabricated in the same manner as in Example 1, and the battery characteristics were measured. The results are shown in Table 2.

[0125] [Table 2]

[0126] The above results show that in Examples that satisfy all the requirements of the present invention, the electrode conductivity is improved, the electrode resistance is reduced, and the utilization efficiency of cationic species is improved compared to Comparative Examples that do not satisfy the requirements of the present invention. In particular, even when using a positive electrode active material in which the presence of water has a greater impact on performance (in this case, a positive electrode active material with a relatively low nickel content), the electrode conductivity is improved, the electrode resistance is reduced, and the utilization efficiency of cationic species is improved.

Claims

1. Specific surface area by BET method is 1000m ２ / g or more 2000m ２ / g or less, and the micropore volume determined by the DFT method is 0.60 cm ３ / g and an oxygen content measured by elemental analysis of 0.5 mass % or more and less than 1.3 mass %.

2. 2. The additive for a positive electrode of a non-aqueous electrolyte secondary battery according to claim 1, wherein the ratio of the amount of oxygen in quinone groups measured by surface functional group titration using Boehm titration to the amount of oxygen measured by elemental analysis is 30% or more and 70% or less.

3. 3. The additive for a positive electrode of a non-aqueous electrolyte secondary battery according to claim 1, wherein the carbonaceous material has an average particle size of 2 μm to 20 μm.

4. The mesopore volume of the carbonaceous material determined by the DFT method is 0.35 cm ３ The additive for a positive electrode of a non-aqueous electrolyte secondary battery according to any one of claims 1 to 3, wherein the total weight of the additive is 1000 or less.

5. A positive electrode active material composition for a non-aqueous electrolyte secondary battery, comprising the additive for a positive electrode of a non-aqueous electrolyte secondary battery according to any one of claims 1 to 4, a positive electrode active material, and a binder.

6. 6. The positive electrode active material composition for a non-aqueous electrolyte secondary battery according to claim 5, wherein the content of the additive for a positive electrode of a non-aqueous electrolyte secondary battery is 10 mass % or less relative to the total mass of the positive electrode active material composition.

7. A positive electrode for a non-aqueous electrolyte secondary battery, comprising a positive electrode active material layer made of the positive electrode active material composition for a non-aqueous electrolyte secondary battery according to claim 5 or 6, and a current collector.

8. A non-aqueous electrolyte secondary battery comprising the positive electrode according to claim 7 .

9. 9. The nonaqueous electrolyte secondary battery according to claim 8, which operates at 2 V to 5 V.

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