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WO2015115089A1 - Composition de type coulis pour électrodes de batteries rechargeables au lithium-ion, électrode pour batteries rechargeables au lithium-ion et batterie rechargeable au lithium-ion - Google Patents

Composition de type coulis pour électrodes de batteries rechargeables au lithium-ion, électrode pour batteries rechargeables au lithium-ion et batterie rechargeable au lithium-ion Download PDF

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Publication number
WO2015115089A1
WO2015115089A1 PCT/JP2015/000353 JP2015000353W WO2015115089A1 WO 2015115089 A1 WO2015115089 A1 WO 2015115089A1 JP 2015000353 W JP2015000353 W JP 2015000353W WO 2015115089 A1 WO2015115089 A1 WO 2015115089A1
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Prior art keywords
lithium ion
ion secondary
secondary battery
electrode
particulate binder
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English (en)
Japanese (ja)
Inventor
健太郎 早坂
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Zeon Corp
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Zeon Corp
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Priority to KR1020167016417A priority Critical patent/KR102355810B1/ko
Priority to CN201580003265.XA priority patent/CN105849943B/zh
Priority to JP2015559820A priority patent/JP6477503B2/ja
Publication of WO2015115089A1 publication Critical patent/WO2015115089A1/fr
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H01M4/0402—Methods of deposition of the material
    • H01M4/0404—Methods of deposition of the material by coating on electrode collectors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/621—Binders
    • H01M4/622—Binders being polymers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to a slurry composition for a lithium ion secondary battery electrode, an electrode for a lithium ion secondary battery, and a lithium ion secondary battery.
  • Lithium ion secondary batteries are small and light, have high energy density, and can be repeatedly charged and discharged, and are used in a wide range of applications. Therefore, in recent years, improvement of battery members such as electrodes has been studied for the purpose of further improving the performance of lithium ion secondary batteries.
  • an electrode for a lithium ion secondary battery usually includes a current collector and an electrode mixture layer formed on the current collector.
  • the electrode mixture layer is formed on a current collector with a slurry composition obtained by dispersing an electrode active material and a binder (binder) and a conductive material blended as necessary in a dispersion medium. It is formed by applying and drying. Therefore, in recent years, attempts have been made to improve the slurry composition used for forming the electrode mixture layer in order to achieve further performance improvement of the lithium ion secondary battery.
  • the binding property between the components constituting the electrode mixture layer such as the electrode active material and the binding property between the electrode mixture layer and the current collector are improved. It has been proposed to improve the dust resistance and peel strength of lithium ion secondary battery electrodes and the cycle characteristics of lithium ion secondary batteries.
  • Patent Document 1 a particulate polymer having a primary particle mode diameter of 0.01 ⁇ m or more and less than 0.25 ⁇ m, and a primary particle mode particle diameter of 0.25 ⁇ m or more and less than 3 ⁇ m.
  • the binding property of the components constituting the electrode mixture layer and the binding of the electrode mixture layer and the current collector It has been proposed to increase the nature.
  • the number average particle diameter is 50 to 300 nm, and the ratio of the weight average particle diameter to the number average particle diameter (weight average particle diameter / number average particle diameter) is 1.05 or more.
  • the abundance ratio of particles having a particle diameter of 0.01 ⁇ m or more and less than 0.25 ⁇ m is 2 to 60% by volume, and the abundance ratio of particles having a particle diameter of 0.25 ⁇ m or more and 0.5 ⁇ m or less is present.
  • 40 to 98% by volume of polymer particles as a binder it is possible to improve the binding between components constituting the electrode mixture layer and the binding between the electrode mixture layer and the current collector. Proposed.
  • the above conventional technique only focuses on the relationship between the particle size of the particulate polymer used as the binder and the binding property, and is formed using the slurry composition and the slurry composition. No attention has been paid to other components contained in the electrode mixture layer, such as an electrode active material.
  • the present invention has excellent binding properties between components constituting the electrode mixture layer, binding properties between the electrode mixture layer and the current collector, and cycle characteristics and rate characteristics of the lithium ion secondary battery. It aims at providing the slurry composition for lithium ion secondary battery electrodes which can be used. In addition, the present invention is excellent in binding property between components constituting the electrode mixture layer and binding property between the electrode mixture layer and the current collector, and has excellent cycle characteristics and rate characteristics for the lithium ion secondary battery. It aims at providing the electrode for lithium ion secondary batteries which can be exhibited. Furthermore, an object of the present invention is to provide a lithium ion secondary battery excellent in cycle characteristics and rate characteristics.
  • the present inventors have intensively studied for the purpose of solving the above problems. Then, the present inventors use a combination of an electrode active material having a predetermined pore volume and a particulate binder having a predetermined particle diameter, thereby binding the components constituting the electrode mixture layer. The present inventors have found that the adhesion property and the binding property between the electrode mixture layer and the current collector and the cycle characteristics and rate characteristics of the lithium ion secondary battery can be made excellent, and the present invention has been completed.
  • the present invention aims to advantageously solve the above-mentioned problems, and the slurry composition for lithium ion secondary battery electrodes of the present invention has a mercury intrusion pore volume of 0.1 cm 3 / g or more. It contains an electrode active material having a size of 2.0 cm 3 / g or less, a particulate binder having a number average particle diameter of 200 nm to 600 nm, and water. In this way, if a combination of an electrode active material having a mercury intrusion pore volume of a predetermined size and a particulate binder having a number average particle size of a predetermined size is used, a slurry composition can be used.
  • the components constituting the electrode mixture layer and the electrode mixture layer and the current collector can be satisfactorily bound, and excellent Thus, a lithium ion secondary battery having cycle characteristics and rate characteristics can be obtained.
  • the surface acid amount of the particulate binder is preferably 0.01 mmol / g or more and 0.5 mmol / g or less. If the surface acid amount of the particulate binder is 0.01 mmol / g or more and 0.5 mmol / g or less, the binding property of the particulate binder can be improved and the slurry containing the particulate binder This is because the stability of the composition can be increased.
  • the gel content of the particulate binder is preferably 30% by mass or more and 99% by mass or less.
  • the swelling of the electrode is suppressed while ensuring the flexibility of the electrode for the lithium ion secondary battery produced using the slurry composition. Because it can be done.
  • the electrode for lithium ion secondary batteries of this invention is either of the slurry composition for lithium ion secondary battery electrodes mentioned above. It has the electrode compound-material layer obtained by using, It is characterized by the above-mentioned. Thus, if an electrode compound-material layer is formed using the slurry composition for lithium ion secondary battery electrodes mentioned above, the binding property of the components which comprise an electrode compound-material layer, an electrode compound-material layer, and an electrical power collector Thus, an electrode for a lithium ion secondary battery that can exhibit excellent cycle characteristics and rate characteristics in a lithium ion secondary battery is obtained.
  • the present invention aims to advantageously solve the above-mentioned problems, and the lithium ion secondary battery of the present invention includes a positive electrode, a negative electrode, a separator, and an electrolytic solution, and includes at least the positive electrode and the negative electrode.
  • One of the electrodes is the above-described electrode for a lithium ion secondary battery.
  • the positive electrode and the negative electrode is constituted by the above-described electrode for a lithium ion secondary battery, a lithium ion secondary battery having excellent cycle characteristics and rate characteristics can be obtained.
  • the binding property between the components constituting the electrode mixture layer, the binding property between the electrode mixture layer and the current collector, and the cycle characteristics and rate characteristics of the lithium ion secondary battery are excellent.
  • a slurry composition for a lithium ion secondary battery electrode that can be obtained is obtained.
  • the binding property between the components constituting the electrode mixture layer and the binding property between the electrode mixture layer and the current collector are excellent, and the cycle characteristics excellent in the lithium ion secondary battery And the electrode for lithium ion secondary batteries which can exhibit a rate characteristic is obtained.
  • a lithium ion secondary battery having excellent cycle characteristics and rate characteristics can be obtained.
  • FIG. 4 is a graph showing a hydrochloric acid addition amount-electric conductivity curve created when calculating the surface acid amount of a particulate binder.
  • the slurry composition for a lithium ion secondary battery electrode of the present invention is used for forming an electrode of a lithium ion secondary battery.
  • the electrode for lithium ion secondary batteries of this invention can be manufactured using the slurry composition for lithium ion secondary battery electrodes of this invention.
  • the lithium ion secondary battery of the present invention is characterized by using the electrode for a lithium ion secondary battery of the present invention.
  • the slurry composition for a lithium ion secondary battery electrode of the present invention comprises an electrode active material having a mercury intrusion pore volume of 0.1 cm 3 / g or more and 2.0 cm 3 / g or less, and a number average particle size of 200 nm or more and 600 nm.
  • An aqueous slurry composition containing the following particulate binder and water.
  • the slurry composition for lithium ion secondary battery electrodes of the present invention may contain other components such as a conductive material and a viscosity modifier as necessary in addition to the electrode active material and the particulate binder. Good.
  • the electrode active material is a substance that transfers electrons in the electrodes (positive electrode and negative electrode) of the lithium ion secondary battery.
  • As the electrode active material (positive electrode active material, negative electrode active material) of the lithium ion secondary battery a material that can occlude and release lithium is usually used.
  • a compound containing a transition metal for example, a transition metal oxide, a transition metal sulfide, a composite metal oxide of lithium and a transition metal, or the like can be used.
  • a transition metal Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Mo etc. are mentioned, for example.
  • transition metal oxide for example, MnO, MnO 2 , V 2 O 5 , V 6 O 13 , TiO 2 , Cu 2 V 2 O 3 , amorphous V 2 O—P 2 O 5 , amorphous Examples include MoO 3 , amorphous V 2 O 5 , and amorphous V 6 O 13 .
  • the composite metal oxide of lithium and transition metal include a lithium-containing composite metal oxide having a layered structure, a lithium-containing composite metal oxide having a spinel structure, and a lithium-containing composite metal oxide having an olivine structure. It is done.
  • lithium-containing composite metal oxide having a layered structure examples include lithium-containing cobalt oxide (LiCoO 2 ), lithium-containing nickel oxide (LiNiO 2 ), and Co—Ni—Mn lithium-containing composite oxide (Li (Co Mn Ni) O 2 ), Ni—Mn—Al lithium-containing composite oxide, Ni—Co—Al lithium-containing composite oxide, and solid solution of LiMaO 2 and Li 2 MbO 3 .
  • examples of the Co—Ni—Mn lithium-containing composite oxide include Li [Ni 0.5 Co 0.2 Mn 0.3 ] O 2 and Li [Ni 1/3 Co 1/3 Mn 1/3 ] O 2 .
  • Examples of the solid solution of LiMaO 2 and Li 2 MbO 3 include xLiMaO 2. (1-x) Li 2 MbO 3 .
  • x represents a number satisfying 0 ⁇ x ⁇ 1
  • Ma represents one or more transition metals having an average oxidation state of 3+
  • Mb represents one or more transition metals having an average oxidation state of 4+.
  • Examples of such a solid solution include Li [Ni 0.17 Li 0.2 Co 0.07 Mn 0.56 ] O 2 .
  • the “average oxidation state” indicates an average oxidation state of the “one or more transition metals”, and is calculated from the molar amount and valence of the transition metal.
  • lithium-containing composite metal oxide having a spinel structure examples include lithium manganate (LiMn 2 O 4 ) and compounds in which a part of Mn of lithium manganate (LiMn 2 O 4 ) is substituted with another transition metal.
  • LiMn 2 O 4 lithium manganate
  • Specific examples include Li s [Mn 2-t Mc t] O 4 , such as LiNi 0.5 Mn 1.5 O 4.
  • Mc represents one or more transition metals having an average oxidation state of 4+.
  • Mc include Ni, Co, Fe, Cu, and Cr.
  • T represents a number satisfying 0 ⁇ t ⁇ 1, and s represents a number satisfying 0 ⁇ s ⁇ 1.
  • a lithium-excess spinel compound represented by Li 1 + x Mn 2 ⁇ x O 4 (0 ⁇ X ⁇ 2) can also be used.
  • Examples of the lithium-containing composite metal oxide having an olivine type structure include olivine type phosphorus represented by Li y MdPO 4 such as olivine type lithium iron phosphate (LiFePO 4 ) and olivine type lithium manganese phosphate (LiMnPO 4 ).
  • An acid lithium compound is mentioned.
  • Md represents one or more transition metals having an average oxidation state of 3+, and examples thereof include Mn, Fe, and Co.
  • Y represents a number satisfying 0 ⁇ y ⁇ 2.
  • Md may be partially substituted with another metal. Examples of the metal that can be substituted include Cu, Mg, Zn, V, Ca, Sr, Ba, Ti, Al, Si, B, and Mo.
  • examples of the negative electrode active material include a carbon-based negative electrode active material, a metal-based negative electrode active material, and a negative electrode active material obtained by combining these.
  • the carbon-based negative electrode active material is an active material having carbon as a main skeleton, into which lithium can be inserted (also referred to as “dope”).
  • examples of the carbon-based negative electrode active material include a carbonaceous material and a graphite material.
  • the carbonaceous material is a material having a low degree of graphitization (ie, low crystallinity) obtained by carbonizing a carbon precursor by heat treatment at 2000 ° C. or lower.
  • the minimum of the heat processing temperature at the time of carbonizing is not specifically limited, For example, it can be 500 degreeC or more.
  • the carbonaceous material include graphitizable carbon that easily changes the carbon structure depending on the heat treatment temperature, and non-graphitizable carbon having a structure close to an amorphous structure typified by glassy carbon.
  • the graphitizable carbon for example, a carbon material using tar pitch obtained from petroleum or coal as a raw material can be mentioned.
  • examples of the non-graphitizable carbon include a phenol resin fired body, polyacrylonitrile-based carbon fiber, pseudo-isotropic carbon, furfuryl alcohol resin fired body (PFA), and hard carbon.
  • the graphite material is a material having high crystallinity close to that of graphite obtained by heat-treating graphitizable carbon at 2000 ° C. or higher.
  • the upper limit of heat processing temperature is not specifically limited, For example, it can be 5000 degrees C or less.
  • the graphite material include natural graphite and artificial graphite.
  • the artificial graphite for example, artificial graphite obtained by heat-treating carbon containing graphitizable carbon mainly at 2800 ° C. or higher, graphitized MCMB heat-treated at 2000 ° C. or higher, and mesophase pitch-based carbon fiber at 2000 ° C. Examples thereof include graphitized mesophase pitch-based carbon fibers that have been heat-treated.
  • the metal-based negative electrode active material is an active material containing a metal, and usually includes an element capable of inserting lithium in the structure, and the theoretical electric capacity per unit mass when lithium is inserted is 500 mAh /
  • the active material which is more than g.
  • the metal active material include lithium metal and a single metal capable of forming a lithium alloy (for example, Ag, Al, Ba, Bi, Cu, Ga, Ge, In, Ni, P, Pb, Sb, Si, Sn). , Sr, Zn, Ti, etc.) and alloys thereof, and oxides, sulfides, nitrides, silicides, carbides, phosphides, and the like thereof.
  • an active material containing silicon is preferable as the metal-based negative electrode active material. This is because the capacity of the lithium ion secondary battery can be increased by using the silicon-based negative electrode active material.
  • silicon-based negative electrode active materials examples include silicon (Si), alloys containing silicon, SiO, SiO x , and a composite of a Si-containing material obtained by coating or combining a Si-containing material with conductive carbon and conductive carbon. Etc.
  • silicon type negative electrode active materials may be used individually by 1 type, and may be used in combination of 2 types.
  • the alloy containing silicon examples include an alloy composition containing silicon, aluminum, and a transition metal such as iron, and further containing a rare earth element such as tin and yttrium.
  • SiO x is a compound containing at least one of SiO and SiO 2 and Si, and x is usually 0.01 or more and less than 2. Then, SiO x, for example, can be formed by using a disproportionation reaction of silicon monoxide (SiO). Specifically, SiO x can be prepared by heat-treating SiO, optionally in the presence of a polymer such as polyvinyl alcohol, to produce silicon and silicon dioxide. The heat treatment can be performed at a temperature of 900 ° C. or higher, preferably 1000 ° C. or higher, in an atmosphere containing an organic gas and / or steam after grinding and mixing SiO and optionally a polymer.
  • SiO x can be prepared by heat-treating SiO, optionally in the presence of a polymer such as polyvinyl alcohol, to produce silicon and silicon dioxide. The heat treatment can be performed at a temperature of 900 ° C. or higher, preferably 1000 ° C. or higher, in an atmosphere containing an organic gas and / or steam
  • a composite of Si-containing material and conductive carbon for example, a pulverized mixture of SiO, a polymer such as polyvinyl alcohol, and optionally a carbon material is heat-treated in an atmosphere containing, for example, an organic gas and / or steam.
  • an organic gas and / or steam can be mentioned.
  • a method of coating the surface of the SiO particles by a chemical vapor deposition method using an organic gas a method of forming composite particles (granulation) of the SiO particles and graphite or artificial graphite by a mechanochemical method, etc. It can also be obtained by a known method.
  • the electrode active material used for the slurry composition for lithium ion secondary battery electrodes of this invention has a pore.
  • the electrode active material must have a mercury intrusion pore volume of 0.1 cm 3 / g or more and 2.0 cm 3 / g or less, preferably 0.4 cm 3 / g or more, more preferably .9cm 3 / g or more, is preferably 1.5 cm 3 / g or less, and more preferably less 1.1 cm 3 / g.
  • the rate characteristics of a lithium ion secondary battery fabricated using a slurry composition using the pores of the electrode active material This is because it can be improved.
  • an electrode active material having a mercury intrusion pore volume of 2.0 cm 3 / g or less a particulate binder described later is prevented from entering the pores of the electrode active material.
  • the components constituting the layers and the electrode mixture layer and the current collector can be satisfactorily bound, and the rate characteristics of the lithium ion secondary battery produced using the slurry composition are prevented from deteriorating. Because it can.
  • the “mercury intrusion pore volume” can be obtained from a mercury intrusion curve measured by a mercury intrusion method, and the amount of mercury intrusion when the pressure is increased from 4 kPa to 400 MPa (ie, when the pressure is 400 MPa). Of mercury and the amount of mercury intrusion at a pressure of 4 kPa).
  • the mercury intrusion pore volume of the electrode active material can be adjusted using, for example, known methods such as changes in the production conditions of the electrode active material and pulverization, firing and CVD of the electrode active material. .
  • the particulate binder is composed of each component in the electrode mixture layer or each of the components.
  • the component and the current collector are bound together.
  • a polymer that can be dispersed in an aqueous medium such as water can be used.
  • the particulate binder used in the slurry composition for a lithium ion secondary battery electrode of the present invention needs to have a number average particle diameter of 200 nm or more and 600 nm or less, preferably 250 nm or more, It is more preferably 270 nm or more, preferably 400 nm or less, and more preferably 380 nm or less.
  • the particulate binder is prevented from entering the pores of the electrode active material described above, and the components constituting the electrode mixture layer and This is because the electrode mixture layer and the current collector can be satisfactorily bound together and the rate characteristics of the lithium ion secondary battery produced using the slurry composition can be prevented from deteriorating.
  • a particulate binder having a number average particle diameter of 600 nm or less the contact area between the particulate binder and a component or current collector bound through the particulate binder. This is because the components of the electrode mixture layer and the electrode mixture layer and the current collector can be satisfactorily bound to each other by suppressing the decrease in the thickness.
  • the “number average particle diameter” means a particle diameter at which the value of the integrated distribution is 50% in the particle diameter-number integrated distribution measured using a laser diffraction / scattering particle size distribution measuring apparatus. Point to.
  • the number average particle diameter of the particulate binder can be adjusted by changing the production conditions of the polymer used as the particulate binder. Specifically, for example, when a polymer used as a particulate binder is prepared by seed polymerization, the number average of the particulate binder is adjusted by adjusting the number of seed particles and the particle diameter used for the polymerization. The particle size can be controlled.
  • the ratio of the number average particle diameter of the particulate binder to the mercury intrusion pore volume of the electrode active material is preferably 1.5 ⁇ 10 ⁇ 5 g / cm 2 or more, more preferably 2.3 ⁇ 10 ⁇ 5 g / cm 2 or more. More preferably, it is 5 ⁇ 10 ⁇ 5 g / cm 2 or more.
  • the number average of the particulate binder with respect to the mercury intrusion pore volume of the electrode active material is preferably 6.4 ⁇ 10 ⁇ 5 g / cm 2 or less, and is preferably 5.5 ⁇ 10 ⁇ 5 g / cm 2 or less. More preferably, it is 4.0 ⁇ 10 ⁇ 5 g / cm 2 or less.
  • the particulate binder preferably has a surface acid amount of 0.01 mmol / g or more, more preferably 0.02 mmol / g or more, and 0.03 mmol / g or more. More preferably, it is preferably 0.5 mmol / g or less, more preferably 0.4 mmol / g or less, and still more preferably 0.2 mmol / g or less.
  • the surface acid amount of the particulate binder is 0.01 mmol / g or more, the wettability of the particulate binder with respect to water is improved, and thereby the particulate binder is suitably dispersed in water. This is because the storage stability of the slurry composition is improved.
  • the particulate binder when the surface acid amount of the particulate binder is 0.5 mmol / g or less, the particulate binder is used even when the particulate binder having a relatively large particle diameter is used as in the present invention. This is because the binding force of the adhesive becomes sufficiently high, and the components constituting the electrode composite layer and the electrode composite layer and the current collector can be satisfactorily bound.
  • the “surface acid amount” refers to the surface acid amount per 1 g of the solid content of the particulate binder, and can be calculated by the following method.
  • the electrical conductivity is measured. This value is the electrical conductivity at the start of measurement. Further, 0.5 mL of 0.1 N hydrochloric acid is added to the aqueous dispersion containing the particulate binder, and the electrical conductivity is measured after 30 seconds. Thereafter, 0.5 mL of 0.1 N hydrochloric acid is added again, and the electrical conductivity is measured after 30 seconds. This operation is repeated at 30-second intervals until the electrical conductivity of the aqueous dispersion containing the particulate binder becomes equal to or higher than the electrical conductivity at the start of measurement.
  • the obtained electrical conductivity data is plotted with the electrical conductivity (unit “mS”) on the vertical axis (Y coordinate axis) and the cumulative amount of added hydrochloric acid (unit “mmol”) on the horizontal axis (X coordinate axis). Plot to.
  • a hydrochloric acid addition amount-electric conductivity curve having three inflection points is obtained as shown in FIG.
  • the X coordinate of the three inflection points and the X coordinate at the end of the addition of hydrochloric acid are P1, P2, P3, and P4 in order from the smallest value.
  • the approximate straight line L1 For the data in the four sections of the X coordinate from zero to the coordinate P1, from the coordinate P1 to the coordinate P2, from the coordinate P2 to the coordinate P3, and from the coordinate P3 to the coordinate P4, the approximate straight line L1 by the least square method, respectively. , L2, L3, and L4.
  • the X coordinate of the intersection of the approximate line L1 and the approximate line L2 is A1 (mmol)
  • the X coordinate of the intersection of the approximate line L2 and the approximate line L3 is A2 (mmol)
  • the X point of the intersection of the approximate line L3 and the approximate line L4 The coordinates are A3 (mmol).
  • the surface acid amount per 1 g of the particulate binder is given as a value (mmol / g) converted to hydrochloric acid from the following formula (a).
  • the amount of acid in the aqueous phase per gram of the particulate binder (the amount of acid present in the aqueous phase in the aqueous dispersion containing the particulate binder and per gram of the solid content of the particulate binder)
  • the acid amount of (hereinafter also referred to as “the acid amount in the aqueous phase of the particulate binder”) is given as a value (mmol / g) in terms of hydrochloric acid from the following formula (b).
  • the total acid amount per 1 g of the particulate binder dispersed in water is the sum of the formula (a) and the formula (b) as represented by the following formula (c).
  • (A) Surface acid amount per gram of particulate binder (A2-A1) / Solid content of particulate binder in aqueous dispersion
  • (b) Acid in aqueous phase per gram of particulate binder Amount (A3-A2) / Solid content of particulate binder in aqueous dispersion
  • Total acid amount per gram of particulate binder dispersed in water (A3-A1) / in aqueous dispersion Solid content of particulate binder
  • the surface acid amount of the particulate binder can be adjusted by changing the type and amount of the monomer used for producing the polymer used as the particulate binder. Specifically, for example, the amount of surface acid can be increased by increasing the amount of an acidic group-containing monomer such as a monomer containing a carboxylic acid group.
  • the particulate binder preferably has a gel content of 30% by mass or more, more preferably 50% by mass or more, still more preferably 60% by mass or more, and 99% by mass. % Or less, more preferably 95% by mass or less, and still more preferably 92% by mass or less. This is because if the gel content of the particulate binder is 30% by mass or more, the strength of the particulate binder can be increased and the swelling of the electrode can be suppressed.
  • the particulate binder is prevented from losing toughness and becoming brittle, and the components constituting the electrode mixture layer and the electrode mixture This is because the layer and the current collector can be favorably bound.
  • gel content can be measured using the measuring method as described in the Example of this specification.
  • the gel content of the particulate binder can be adjusted by changing the polymerization conditions of the polymer used as the particulate binder.
  • the chain transfer agent used during polymerization for example, t- If the amount of dodecyl mercaptan or the like is reduced, the gel content can be increased, and if the amount of chain transfer agent used during polymerization is increased, the gel content can be reduced.
  • polymer type examples of the polymer used as the particulate binder include known polymers such as diene polymers, acrylic polymers, fluoropolymers, and silicon polymers. These polymers may be used individually by 1 type, and may be used combining two or more types by arbitrary ratios.
  • the polymer when the slurry composition for a lithium ion secondary battery electrode is a slurry composition for a negative electrode, the polymer may be a diene polymer, particularly an aliphatic conjugated diene monomer unit and an aromatic. It is preferable to use a copolymer having a vinyl monomer unit or a hydrogenated product thereof.
  • a copolymer having an aromatic vinyl monomer unit capable of enhancing the stability of the binder can satisfactorily function as a particulate binder.
  • “comprising a monomer unit” means “a monomer-derived structural unit is contained in a polymer obtained using the monomer”.
  • the monomer is not particularly limited, and 1,3-butadiene, 2-methyl-1,3-butadiene, 2,3-dimethyl-1,3-butadiene, 2-chloro-1,3-butadiene Substituted linear conjugated pentadienes, substituted and side chain conjugated hexadienes, and the like can be used.
  • an aliphatic conjugated diene monomer may be used individually by 1 type, and may be used combining two or more types by arbitrary ratios.
  • the content of the aliphatic conjugated diene monomer unit is preferably 20% by mass or more, more preferably 30% by mass or more, preferably 70% by mass or less, more preferably 60% by mass. % Or less. It is because the flexibility of the electrode formed using a slurry composition can be improved because the content rate of an aliphatic conjugated diene monomer unit is 20 mass% or more. In addition, since the content of the aliphatic conjugated diene monomer unit is 70% by mass or less, the binding force of the particulate binder made of the copolymer is sufficiently high, and the component constituting the electrode mixture layer This is because the electrode material layer and the current collector can be favorably bound to each other.
  • aromatic vinyl monomer that can form an aromatic vinyl monomer unit is not particularly limited, and styrene, ⁇ -methylstyrene, vinyl toluene, divinylbenzene, and the like can be used.
  • an aromatic vinyl monomer may be used individually by 1 type, and may be used combining two or more types by arbitrary ratios.
  • the content of the aromatic vinyl monomer unit is preferably 30% by mass or more, more preferably 40% by mass or more, preferably 80% by mass or less, more preferably 70% by mass. It is as follows. It is because the electrolyte solution resistance of the electrode formed using a slurry composition can be improved because the content rate of an aromatic vinyl monomer unit is 30 mass% or more. Further, when the content ratio of the aromatic vinyl monomer unit is 80% by mass or less, the binding force of the particulate binder made of the copolymer is sufficiently increased, and the components constituting the electrode mixture layer are This is because the electrode mixture layer and the current collector can be bound well.
  • the copolymer having an aliphatic conjugated diene monomer unit and an aromatic vinyl monomer unit includes a 1,3-butadiene unit as the aliphatic conjugated diene monomer unit, and the aromatic vinyl monomer unit. It preferably contains a styrene unit (that is, a styrene-butadiene copolymer or a hydrogenated styrene-butadiene copolymer).
  • the copolymer having the aliphatic conjugated diene monomer unit and the aromatic vinyl monomer unit described above includes an ethylenically unsaturated carboxylic acid monomer unit, an unsaturated monomer unit having a hydroxyl group, and a sulfonic acid. It is preferable to include at least one selected from the group consisting of unsaturated monomer units having groups. Especially, it is preferable that a copolymer contains an ethylenically unsaturated carboxylic acid monomer unit.
  • the ethylenically unsaturated carboxylic acid monomer capable of forming an ethylenically unsaturated carboxylic acid monomer unit includes ethylenically unsaturated monocarboxylic acid and derivatives thereof, ethylenically unsaturated dicarboxylic acid and acid anhydrides thereof. Products and derivatives thereof.
  • the ethylenically unsaturated monocarboxylic acid include acrylic acid, methacrylic acid, crotonic acid and the like.
  • Examples of the ethylenically unsaturated monocarboxylic acid derivatives include 2-ethylacrylic acid, isocrotonic acid, ⁇ -acetoxyacrylic acid, ⁇ -trans-aryloxyacrylic acid, ⁇ -chloro- ⁇ -E-methoxyacrylic. Acid, ⁇ -diaminoacrylic acid and the like.
  • Examples of the ethylenically unsaturated dicarboxylic acid include maleic acid, fumaric acid, itaconic acid and the like.
  • Examples of acid anhydrides of ethylenically unsaturated dicarboxylic acids include maleic anhydride, diacrylic anhydride, methyl maleic anhydride, dimethyl maleic anhydride, and the like.
  • examples of ethylenically unsaturated dicarboxylic acid derivatives include methylmaleic acid, dimethylmaleic acid, phenylmaleic acid, chloromaleic acid, dichloromaleic acid, fluoromaleic acid, diphenyl maleate, nonyl maleate, decyl maleate , Dodecyl maleate, octadecyl maleate, fluoroalkyl maleate and the like. One of these may be used alone, or two or more of these may be used in combination at any ratio.
  • the content ratio of the ethylenically unsaturated carboxylic acid monomer unit is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, and preferably 5% by mass or less. More preferably, it is 1 mass% or less. It is because the storage stability of the slurry composition containing the particulate binder is ensured when the content ratio of the ethylenically unsaturated carboxylic acid monomer unit is 0.1% by mass or more. On the other hand, when the content of the ethylenically unsaturated carboxylic acid monomer unit is 5% by mass or less, the binding force of the particulate binder made of the copolymer is sufficiently high, and the electrode mixture layer is formed. This is because the components to be combined and the electrode mixture layer and the current collector can be favorably bound.
  • Examples of the unsaturated monomer having a hydroxyl group that can form an unsaturated monomer unit having a hydroxyl group include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, and hydroxybutyl. Acrylate, hydroxybutyl methacrylate, 3-chloro-2-hydroxypropyl methacrylate, di- (ethylene glycol) maleate, di- (ethylene glycol) itaconate, 2-hydroxyethyl maleate, bis (2-hydroxyethyl) maleate, 2- Examples thereof include hydroxyethyl methyl fumarate. One of these may be used alone, or two or more of these may be used in combination at any ratio.
  • the content ratio of the unsaturated monomer unit having a hydroxyl group is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, and preferably 5% by mass or less. More preferably, it is 1 mass% or less. It is because the storage stability of the slurry composition containing the particulate binder is ensured when the content ratio of the unsaturated monomer unit having a hydroxyl group is 0.1% by mass or more. On the other hand, when the content ratio of the unsaturated monomer unit having a hydroxyl group is 5% by mass or less, the binding force of the particulate binder made of the copolymer is sufficiently high, and the electrode mixture layer is formed. This is because the components, the electrode mixture layer, and the current collector can be favorably bound.
  • examples of the unsaturated monomer having a sulfonic acid group capable of forming an unsaturated monomer unit having a sulfonic acid group include vinyl sulfonic acid, methyl vinyl sulfonic acid, (meth) acryl sulfonic acid, and styrene sulfone.
  • examples include acids, ethyl (meth) acrylic acid-2-sulfonate, 2-acrylamido-2-methylpropanesulfonic acid, 3-allyloxy-2-hydroxypropanesulfonic acid, and the like. One of these may be used alone, or two or more of these may be used in combination at any ratio.
  • “(meth) acryl” means acryl and / or methacryl.
  • the content ratio of the unsaturated monomer unit having a sulfonic acid group is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, and preferably 5% by mass. Hereinafter, it is more preferably 1% by mass or less. It is because the storage stability of the slurry composition containing the particulate binder is ensured when the content ratio of the unsaturated monomer unit having a sulfonic acid group is 0.1% by mass or more. On the other hand, when the content ratio of the unsaturated monomer unit having a sulfonic acid group is 5% by mass or less, the binding force of the particulate binder made of the copolymer becomes sufficiently high, and the electrode mixture layer is formed. This is because the constituent components and the electrode mixture layer and the current collector can be favorably bound.
  • the copolymer having the above-described aliphatic conjugated diene monomer unit and aromatic vinyl monomer unit may contain a (meth) acrylic acid ester monomer unit in addition to the monomer unit described above. preferable.
  • (meth) acrylic acid ester monomers that can form a (meth) acrylic acid ester monomer unit include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, t- Acrylic acid alkyl esters such as butyl acrylate, pentyl acrylate, hexyl acrylate, heptyl acrylate, octyl acrylate, 2-ethylhexyl acrylate; methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, t-butyl Methacrylate, pentyl methacrylate, hexyl methacrylate, heptyl methacrylate, octyl methacrylate, 2-ethylhexyl methacrylate Me
  • the content rate of a (meth) acrylic acid ester monomer unit becomes like this.
  • it is 1 mass% or more, More preferably, it is 3 mass% or more, Preferably it is 10 mass% or less, More preferably 7% by mass or less.
  • the copolymer having the aliphatic conjugated diene monomer unit and the aromatic vinyl monomer unit described above contains any repeating unit other than those described above unless the effects of the present invention are significantly impaired. Also good.
  • the content rate of arbitrary repeating units is not particularly limited, the upper limit is preferably 6% by mass or less, more preferably 4% by mass or less, and particularly preferably 2% by mass or less in total.
  • the method for producing the polymer used as the particulate binder is not particularly limited, and any method such as a solution polymerization method, a suspension polymerization method, a bulk polymerization method, and an emulsion polymerization method may be used.
  • a solution polymerization method a suspension polymerization method, a bulk polymerization method, and an emulsion polymerization method
  • the polymerization reaction any method such as ionic polymerization, radical polymerization, and living radical polymerization can be used. Among these, it is easy to obtain a high molecular weight substance, and since the polymer is obtained in a state of being dispersed in water as it is, no redispersion treatment is required, and it can be used for production of the slurry composition of the present invention as it is.
  • seed polymerization may be performed using seed particles.
  • any seed particle can be used. That is, for example, when a copolymer having the above-described aliphatic conjugated diene monomer unit and aromatic vinyl monomer unit is prepared by seed polymerization, the polymer that forms the surface portion of the particulate copolymer If it is a copolymer mentioned above, polymer particles of arbitrary composition can be used as seed particles.
  • polymerization conditions can also be arbitrarily selected depending on the polymerization method and the type of polymerization initiator.
  • the amount of the particulate binder in the slurry composition for lithium ion secondary battery electrodes of the present invention is preferably 0.5 parts by mass or more per 100 parts by mass of the electrode active material described above, It is preferably 5.0 parts by mass or less.
  • the amount of the particulate binder is 5.0 parts by mass or less per 100 parts by mass of the electrode active material. This is because it is possible to suppress the movement of lithium ions by the binder and to reduce the internal resistance of the lithium ion secondary battery.
  • the slurry composition for lithium ion secondary battery electrodes of the present invention is a particulate binder other than the above-described particulate binder (hereinafter sometimes referred to as “other particulate binder”). That is, a particulate binder having a number average particle diameter of less than 200 nm or a particulate binder having a number average particle diameter of more than 600 nm may be further included.
  • the ratio of the other particulate binder in the total particulate binder is 50% by mass or less. It is preferable that it is 40% by mass or less, and it is more preferable that no other particulate binder is included (that is, only one kind of particulate binder is included).
  • the slurry composition for a lithium ion secondary battery electrode of the present invention may contain components such as a conductive material, a viscosity modifier, a reinforcing material, a leveling agent, and an electrolytic solution additive in addition to the above components.
  • a conductive material such as a conductive material, a viscosity modifier, a reinforcing material, a leveling agent, and an electrolytic solution additive in addition to the above components.
  • this slurry composition contains electrically conductive materials, such as acetylene black.
  • These other components are not particularly limited as long as they do not affect the battery reaction, and known ones such as those described in International Publication Nos. 2012/115096 and 2012-204303 may be used. it can.
  • the viscosity modifier is not particularly limited, and carboxymethyl cellulose or a salt thereof can be suitably used. And the quantity of the carboxymethylcellulose or its salt mix
  • the slurry composition for lithium ion secondary battery electrodes of the present invention can be prepared by dispersing each of the above components in an aqueous medium as a dispersion medium. Specifically, the above components and the aqueous medium are mixed using a mixer such as a ball mill, a sand mill, a bead mill, a pigment disperser, a grinder, an ultrasonic disperser, a homogenizer, a planetary mixer, or a fill mix. Thus, a slurry composition can be prepared.
  • a mixer such as a ball mill, a sand mill, a bead mill, a pigment disperser, a grinder, an ultrasonic disperser, a homogenizer, a planetary mixer, or a fill mix.
  • water is usually used as the aqueous medium, but an aqueous solution of an arbitrary compound or a mixed solution of a small amount of an organic medium and water may be used.
  • the solid content concentration of the slurry composition can be set to a concentration at which each component can be uniformly dispersed, for example, 30% by mass to 90% by mass.
  • the mixing of each of the above components and the aqueous medium can be usually performed at a temperature range of room temperature to 80 ° C. for 10 minutes to several hours.
  • the electrode for lithium ion secondary batteries of this invention can be manufactured using the slurry composition for lithium ion secondary battery electrodes of this invention.
  • the electrode for a lithium ion secondary battery of the present invention includes a current collector and an electrode mixture layer formed on the current collector, and the electrode mixture layer is a lithium ion secondary battery of the present invention. Obtained from the slurry composition for electrodes.
  • each component contained in the electrode mixture layer was contained in the slurry composition for lithium ion secondary battery electrodes of the present invention. It is the same as the suitable abundance ratio of each component in the slurry composition for use.
  • the lithium ion secondary battery electrode of the present invention is excellent in the binding property between the components constituting the electrode mixture layer and in the binding property between the electrode mixture layer and the current collector. The battery can exhibit excellent cycle characteristics and rate characteristics.
  • the electrode for a lithium ion secondary battery of the present invention includes, for example, a step of applying the above-described slurry composition for a lithium ion secondary battery electrode on a current collector (application step), and a lithium applied on the current collector.
  • the slurry composition for an ion secondary battery electrode is dried to produce an electrode mixture layer on the current collector (drying step).
  • the electrode for a lithium ion secondary battery of the present invention is prepared by dry granulating the slurry composition for a lithium ion secondary battery electrode described above to prepare composite particles, and using the composite particles, an electrode is formed on the current collector. It can also be manufactured by a method of forming a composite material layer.
  • a method of apply coating the said slurry composition for lithium ion secondary battery electrodes on a collector
  • a doctor blade method a dip method, a reverse roll method, a direct roll method, a gravure method, an extrusion method, a brush coating method, or the like
  • the slurry composition may be applied to only one side of the current collector or may be applied to both sides.
  • the thickness of the slurry film on the current collector after application and before drying can be appropriately set according to the desired thickness, density, basis weight, etc. of the electrode mixture layer obtained by drying.
  • an electrically conductive and electrochemically durable material is used as the current collector to which the slurry composition is applied.
  • a current collector for example, a current collector made of iron, copper, aluminum, nickel, stainless steel, titanium, tantalum, gold, platinum, or the like can be used.
  • a collector used for a positive electrode an aluminum foil (aluminum) is particularly preferable.
  • a collector used for a negative electrode copper foil is particularly preferable.
  • the said material may be used individually by 1 type, and may be used combining two or more types by arbitrary ratios.
  • the method for drying the slurry composition on the current collector is not particularly limited, and a known method can be used. For example, a drying method using hot air, hot air, low-humidity air, vacuum drying method, infrared ray, electron beam, etc. The drying method by irradiation is mentioned. Thus, by drying the slurry composition on the current collector, an electrode mixture layer is formed on the current collector, and a lithium ion secondary battery electrode including the current collector and the electrode mixture layer is obtained. be able to.
  • the electrode mixture layer may be subjected to pressure treatment using a die press or a roll press.
  • pressure treatment the adhesion between the electrode mixture layer and the current collector can be improved.
  • the electrode for a lithium ion secondary battery formed by forming an electrode mixture layer on the current collector as described above preferably has the following properties.
  • the basis weight of the electrode mixture layer (the mass of the electrode mixture layer per unit area) is preferably 7.0 mg / cm 2 or more, and 8.0 mg / cm more preferably 2 or more, further preferably 10.0 mg / cm 2 or more, preferably 18.0 mg / cm 2 or less, more preferably 17.0 mg / cm 2 or less.
  • the basis weight is increased and the thickness of the electrode mixture layer is increased, the binding property of the electrode mixture layer to the current collector is reduced, but in the electrode for the lithium ion secondary battery of the present invention, the particle size is reduced. Since a large particulate binder is used, it is possible to suppress a decrease in peel strength even with the basis weight.
  • the density of the electrode mixture layer is preferably 1.4 g / cm 3 or more, more preferably 1.5 g / cm 3 or more, and 1.9 g / cm 3. preferably cm 3 or less, more preferably 1.8 g / cm 3 or less.
  • the density of the electrode mixture layer is within the above range, the binding property between the current collector and the electrode mixture layer is good, and an electrode having excellent dust resistance and electrical characteristics can be obtained.
  • the lithium ion secondary battery of the present invention includes a positive electrode, a negative electrode, an electrolytic solution, and a separator, and uses the electrode for the lithium ion secondary battery of the present invention as at least one of the positive electrode and the negative electrode. And since the lithium ion secondary battery of this invention is equipped with the electrode for lithium ion secondary batteries of this invention, it is excellent in electrical characteristics, such as a rate characteristic and cycling characteristics.
  • the electrode for a lithium ion secondary battery of the present invention is used as at least one of a positive electrode and a negative electrode. That is, the positive electrode of the lithium ion secondary battery of the present invention may be the electrode of the present invention and the negative electrode may be another known negative electrode, and the negative electrode of the secondary battery of the present invention is the electrode of the present invention and the positive electrode may be other. And both the positive electrode and the negative electrode of the lithium ion secondary battery of the present invention may be the electrode of the present invention.
  • an electrolytic solution in which an electrolyte is dissolved in a solvent can be used.
  • the solvent an organic solvent capable of dissolving the electrolyte can be used.
  • the solvent include alkyl carbonate solvents such as ethylene carbonate, propylene carbonate, and ⁇ -butyrolactone, 2,5-dimethyltetrahydrofuran, tetrahydrofuran, diethyl carbonate, ethyl methyl carbonate, dimethyl carbonate, methyl acetate, dimethoxyethane. , Dioxolane, methyl propionate, methyl formate and the like can be used.
  • a lithium salt can be used as the electrolyte.
  • the lithium salt for example, those described in JP 2012-204303 A can be used.
  • LiPF 6 , LiClO 4 , and CF 3 SO 3 Li are preferable as the electrolyte because they are easily dissolved in an organic solvent and exhibit a high degree of dissociation.
  • ⁇ Separator> As the separator, for example, those described in JP 2012-204303 A can be used. Among these, the thickness of the entire separator can be reduced, thereby increasing the ratio of the electrode active material in the lithium ion secondary battery and increasing the capacity per volume.
  • a microporous film made of a series resin polyethylene, polypropylene, polybutene, polyvinyl chloride is preferred.
  • a positive electrode and a negative electrode are overlapped via a separator, and this is wound into a battery container according to the battery shape as necessary, and put into a battery container. It can manufacture by inject
  • an overcurrent prevention element such as a fuse or a PTC element, an expanded metal, a lead plate, etc. may be provided as necessary.
  • the shape of the lithium ion secondary battery may be any of, for example, a coin shape, a button shape, a sheet shape, a cylindrical shape, a square shape, a flat shape, and the like.
  • the mercury intrusion pore volume of the electrode active material was measured using a mercury porosimeter (manufactured by Micromeritics, Autopore IV9510 type). Specifically, 0.2 g of an electrode active material is injected into a powder cell, pretreated by degassing at room temperature and under vacuum for 10 minutes, mercury is introduced under reduced pressure, and then the pressure is changed. The amount of mercury intrusion was measured. From the obtained mercury intrusion curve, the amount of mercury intrusion when the pressure was increased from 4 kPa to 400 MPa was calculated as the mercury intrusion pore volume.
  • aqueous dispersion containing the particulate binder 50 g was placed in a 150 mL glass container washed with distilled water, and a solution conductivity meter was set and stirred. Stirring was continued until the addition of hydrochloric acid described later was completed. Add 0.1 N sodium hydroxide aqueous solution to the aqueous dispersion containing the particulate binder so that the electrical conductivity of the aqueous dispersion containing the particulate binder is 2.5-3.0 mS. did. Thereafter, after 6 minutes, the electrical conductivity was measured. This value was taken as the electrical conductivity at the start of measurement.
  • the obtained electric conductivity data is plotted on a graph with the electric conductivity (unit “mS”) on the vertical axis (Y coordinate axis) and the cumulative amount of added hydrochloric acid (unit “mmol”) on the horizontal axis (X coordinate axis). Plotted.
  • a hydrochloric acid addition amount-electric conductivity curve having three inflection points as shown in FIG. 1 was obtained.
  • the X coordinates of the three inflection points were P1, P2, and P3 in order from the smallest value.
  • Approximate straight lines L1, L2, and L3 were obtained by the least square method for the data in the three sections of the X coordinate from zero to coordinate P1, from coordinate P1 to coordinate P2, and from coordinate P2 to coordinate P3, respectively. .
  • the X coordinate of the intersection of the approximate straight line L1 and the approximate straight line L2 was A1 (mmol), and the X coordinate of the intersection of the approximate straight line L2 and the approximate straight line L3 was A2 (mmol).
  • the surface acid amount per 1 g of the particulate binder was determined as a value (mmol / g) converted to hydrochloric acid from the following formula.
  • Surface acid amount per gram of particulate binder A2-A1 ⁇ Gel content>
  • An aqueous dispersion containing a particulate binder was prepared, and the aqueous dispersion was dried in an environment of 50% humidity and a temperature of 23 to 25 ° C. to form a film having a thickness of 1 ⁇ 0.3 mm.
  • This film was dried with a vacuum dryer at a temperature of 60 ° C. for 10 hours. Thereafter, the dried film was cut into 3 to 5 mm square, and about 1 g was precisely weighed. The mass of the film piece obtained by cutting is defined as w0.
  • This film piece was immersed in 50 g of tetrahydrofuran (THF) for 24 hours. Then, the film piece pulled up from THF was vacuum-dried at 105 degreeC for 3 hours, and the mass w1 of insoluble matter was measured. And gel content (mass%) was computed according to the following formula.
  • a viscosity change rate represented by ⁇ ⁇ ( ⁇ 1 ⁇ 0) / ⁇ 0 ⁇ ⁇ 100 (%) was determined from the measured initial viscosity ⁇ 0 and post-standing viscosity ⁇ 1, and evaluated according to the following criteria. A smaller value of the viscosity change rate ⁇ indicates that the slurry composition is more excellent in storage stability.
  • C: ⁇ is 30% or more ⁇ Peel Strength> The produced electrode was cut into a rectangle having a width of 1.0 cm and a length of 10 cm to obtain a test piece. And it fixed with the surface of the electrode mixture layer side of a test piece facing up, and the cellophane tape was affixed on the surface of the electrode mixture layer side of the test piece. At this time, the cellophane tape defined in JIS Z1522 was used. Thereafter, the stress was measured when the cellophane tape was peeled from the one end of the test piece in the 180 ° direction (the other end side of the test piece) at a speed of 50 mm / min.
  • the measurement was performed 10 times, the average value of the stress was determined, and this was defined as the peel strength (N / m). It shows that the binding property of the electrode compound material layer with respect to a collector is excellent, so that peel strength is large.
  • the thickness of 10 points was measured with a thickness meter for the negative electrode, and the average value d0 ( ⁇ m) was calculated.
  • the assembled lithium ion secondary battery was allowed to stand for 24 hours in an environment at a temperature of 25 ° C., and then charged to 4.2 V at a constant current of 1 C in an environment at a temperature of 25 ° C. to 3.0 V. The charging / discharging operation was performed.
  • the smaller the swelling ratio ⁇ d the better the negative electrode has better swelling resistance and the better the life characteristics of the lithium ion secondary battery.
  • required 1C discharge capacity. This measurement was performed on 10 cells of the lithium ion secondary battery, and the average value of each measurement value was set to 0.1 C discharge capacity a and 1 C discharge capacity b. Then, a capacity retention ratio ( (b / a) ⁇ 100 (%)) represented by a ratio of 1 C discharge capacity b to 0.1 C discharge capacity a was obtained and evaluated according to the following criteria. The higher the capacity retention rate, the better the rate characteristics.
  • Capacity retention is 93% or more A: Capacity retention is 90% or more and less than 93% B: Capacity retention is 80% or more and less than 90% C: Capacity retention is 50% or more and less than 80% D: Capacity retention Is less than 50%
  • Example 1 Preparation of seed particles A> In a reactor equipped with a stirrer, 60.0 parts of 1,3-butadiene as an aliphatic conjugated diene monomer, 38.0 parts of styrene as an aromatic vinyl monomer, and an ethylenically unsaturated carboxylic acid monomer 2.0 parts of methacrylic acid as a body, 4.0 parts of sodium dodecylbenzenesulfonate as an emulsifier, 260 parts of ion-exchanged water, and 0.3 part of potassium persulfate as a polymerization initiator were added at a temperature of 60 ° C. Polymerized for hours.
  • an aqueous dispersion of seed particles A made of a polymer having a number average particle diameter of 58 nm was obtained.
  • ⁇ Preparation of seed particles B In a reactor equipped with a stirrer, 2.5 parts of an aqueous dispersion of seed particles A on a solid basis (that is, a mass basis of seed particles A), 0.2 parts of sodium dodecylbenzenesulfonate as an emulsifier, 0.5 parts of potassium persulfate as a polymerization initiator and 100 parts of ion exchange water were added and mixed to obtain a mixture A. Then, the mixture A was heated to a temperature of 80 ° C.
  • the dispersion of the monomer mixture A was continuously added to the mixture A and polymerized over 4 hours.
  • the temperature of the reaction system during the continuous addition of the dispersion of the monomer mixture A was maintained at 80 ° C. to carry out the reaction.
  • the reaction was further continued at a temperature of 90 ° C. for 3 hours.
  • an aqueous dispersion of seed particles B made of a polymer having a number average particle diameter of 175 nm was obtained.
  • ⁇ Preparation of particulate binder A> In a reactor equipped with a stirrer, 25.0 parts of an aqueous dispersion of seed particles B (based on the mass of seed particles B), 0.2 parts of sodium dodecylbenzenesulfonate as an emulsifier, 0.5 parts of potassium persulfate as a polymerization initiator and 100 parts of ion exchange water were added and mixed to obtain a mixture B. Then, the temperature of the mixture B was raised to 80 ° C.
  • the dispersion of the monomer mixture B was continuously added to the mixture B and polymerized over 4 hours.
  • the temperature of the reaction system during the continuous addition of the dispersion of the monomer mixture B was maintained at 70 ° C. to carry out the reaction.
  • 1 part of 2-hydroxyethyl acrylate as an unsaturated monomer having a hydroxyl group was further added.
  • the reaction was stopped by cooling. Thereby, an aqueous dispersion of the particulate binder A made of a polymer having a number average particle diameter of 300 nm was obtained.
  • the slurry composition for a negative electrode of a lithium ion secondary battery was applied with a comma coater to the surface of a copper foil having a thickness of 20 ⁇ m as a current collector so that the film thickness after drying was about 150 ⁇ m.
  • the copper foil coated with the lithium ion secondary battery negative electrode slurry composition was applied at a speed of 0.5 m / min in an oven at a temperature of 60 ° C. for 2 minutes and further in an oven at a temperature of 120 ° C. for 2 minutes. By carrying, the slurry composition on copper foil was dried and the negative electrode original fabric was obtained.
  • the obtained negative electrode original fabric was pressed with the roll press machine, and the negative electrode for lithium ion secondary batteries whose thickness of a negative electrode compound-material layer is 75 micrometers was obtained.
  • the density of the negative electrode mixture layer of the obtained negative electrode was 1.6 g / cm 3 , and the basis weight was 12.0 mg / cm 2 .
  • the peel strength and swell resistance of the negative electrode were evaluated. The results are shown in Table 1.
  • the aluminum foil coated with the slurry composition for a positive electrode of a lithium ion secondary battery was dried by conveying it in an oven at a temperature of 60 ° C. at a rate of 0.5 m / min for 2 minutes. Thereafter, heat treatment was performed at 120 ° C. for 2 minutes to obtain a positive electrode raw material.
  • the obtained positive electrode original fabric was pressed with a roll press machine to obtain a positive electrode for a lithium ion secondary battery.
  • a single-layer polypropylene separator (width 65 mm, length 500 mm, thickness 25 ⁇ m; manufactured by a dry method; porosity 55%) was prepared and cut into a 5 cm ⁇ 5 cm square.
  • the aluminum packaging material exterior was prepared as a battery exterior.
  • the produced positive electrode was cut out into a 4 cm x 4 cm square, and it has arrange
  • the above-described square separator was disposed on the surface of the positive electrode mixture layer of the positive electrode.
  • the produced negative electrode was cut out into a square of 4.2 cm ⁇ 4.2 cm, and this was arranged on the separator so that the surface on the negative electrode mixture layer side faces the separator.
  • Example 2 A slurry composition for a lithium ion secondary battery negative electrode, a lithium ion secondary battery, in the same manner as in Example 1, except that the particulate binder B prepared by the following method was used instead of the particulate binder A
  • a negative electrode for a battery, a positive electrode for a lithium ion secondary battery, and a lithium ion secondary battery were prepared and evaluated. The results are shown in Table 1.
  • a particulate binder B was prepared in the same manner as the particulate binder A except that the amount of acid was 0.1 part and the amount of t-dodecyl mercaptan as a chain transfer agent was 0.16 part.
  • Example 3 A slurry composition for a lithium ion secondary battery negative electrode, a lithium ion secondary battery, in the same manner as in Example 1, except that the particulate binder C prepared by the following method was used in place of the particulate binder A
  • a negative electrode for a battery, a positive electrode for a lithium ion secondary battery, and a lithium ion secondary battery were prepared and evaluated. The results are shown in Table 1.
  • a particulate binder C was prepared in the same manner as the particulate binder A except that the amount of t-dodecyl mercaptan as a chain transfer agent was 0.16 part.
  • Example 4 A slurry composition for a lithium ion secondary battery negative electrode, a lithium ion secondary battery, in the same manner as in Example 1, except that the particulate binder D prepared by the following method was used instead of the particulate binder A
  • a negative electrode for a battery, a positive electrode for a lithium ion secondary battery, and a lithium ion secondary battery were prepared and evaluated. The results are shown in Table 1.
  • ⁇ Preparation of particulate binder D> The amount of the aqueous dispersion of seed particles B is 50.0 parts on a solid basis, the amount of styrene as the aromatic vinyl monomer is 62.0 parts, and acrylic acid is used as the ethylenically unsaturated carboxylic acid monomer.
  • a particulate binder D was prepared in the same manner as the adhesive A.
  • Example 5 A particulate binder E prepared by the following method was used in place of the particulate binder A, and the artificial graphite used in Example 1 was pulverized as a negative electrode active material (pulverizer: Crypto manufactured by Earth Technica) (Lon KTM0 type, rotation speed: 2000 rpm, grinding speed: 20 kg / hr)
  • pulverizer Crypto manufactured by Earth Technica
  • LiNaO LiN-phenyl-N-N-phenyl-N-phenyl-N-phenyl-N-phenyl-N-phenyl-N-phenyl
  • Li ion secondary battery negative electrode slurry composition lithium ions
  • a negative electrode for a secondary battery, a positive electrode for a lithium ion secondary battery, and a lithium ion secondary battery were prepared and evaluated. The results are shown in Table 1.
  • Preparation of particulate binder E> A particulate binder E was prepared in the same manner as the particulate binder A except that the amount of the
  • Example 6 A slurry composition for a negative electrode of a lithium ion secondary battery, lithium as in Example 5 except that the negative electrode active material obtained by firing and CVD treatment of the artificial graphite used in Example 1 was used as the negative electrode active material.
  • a negative electrode for an ion secondary battery, a positive electrode for a lithium ion secondary battery, and a lithium ion secondary battery were prepared and evaluated. Firing was carried out at a temperature of 900 ° C. for 1 hour while maintaining a fluid state while supplying a nitrogen gas at a rate of 1 L / min in a fluid reaction reactor under a nitrogen atmosphere using a fluid reaction furnace. Further, the CVD treatment after firing is carried out at a temperature of 900 ° C. while introducing fired particles by introducing nitrogen gas containing benzene (benzene concentration: 1 g / L) into the fluidized reactor at a rate of 1 L / min. For a minute. The results are shown in Table 1.
  • Example 7 A slurry composition for a lithium ion secondary battery negative electrode, a lithium ion secondary battery, in the same manner as in Example 1, except that the particulate binder F prepared by the following method was used instead of the particulate binder A
  • a negative electrode for a battery, a positive electrode for a lithium ion secondary battery, and a lithium ion secondary battery were prepared and evaluated. The results are shown in Table 1.
  • a particulate binder F was prepared in the same manner as the particulate binder A except that the amount of acid was 0.4 parts and the amount of t-dodecyl mercaptan as a chain transfer agent was 0.14 parts.
  • Example 8 A slurry composition for a lithium ion secondary battery negative electrode, a lithium ion secondary battery, in the same manner as in Example 1, except that the particulate binder G prepared by the following method was used instead of the particulate binder A
  • a negative electrode for a battery, a positive electrode for a lithium ion secondary battery, and a lithium ion secondary battery were prepared and evaluated. The results are shown in Table 1.
  • ⁇ Preparation of particulate binder G> The amount of the aqueous dispersion of seed particles B is 30.0 parts on a solid basis, the amount of styrene as the aromatic vinyl monomer is 59.8 parts, and the acrylic resin as the ethylenically unsaturated carboxylic acid monomer is used.
  • a particulate binder G was prepared in the same manner as the particulate binder A except that the amount of acid was 1.0 part and the amount of t-dodecyl mercaptan as a chain transfer agent was 0.14 part.
  • Example 9 A slurry composition for a negative electrode of a lithium ion secondary battery, a lithium ion secondary battery, in the same manner as in Example 1, except that the particulate binder H prepared by the following method was used instead of the particulate binder A
  • a negative electrode for a battery, a positive electrode for a lithium ion secondary battery, and a lithium ion secondary battery were prepared and evaluated. The results are shown in Table 1.
  • a particulate binder H was prepared in the same manner as the particulate binder A except that the amount was 1.5 parts.
  • Example 10 A slurry composition for a lithium ion secondary battery negative electrode, a lithium ion secondary battery, in the same manner as in Example 1, except that the particulate binder I prepared by the following method was used instead of the particulate binder A
  • a negative electrode for a battery, a positive electrode for a lithium ion secondary battery, and a lithium ion secondary battery were prepared and evaluated. The results are shown in Table 1.
  • particulate binder I The amount of styrene as the aromatic vinyl monomer was 60.4 parts, the amount of acrylic acid as the ethylenically unsaturated carboxylic acid monomer was 0.4 parts, and t-dodecyl mercaptan as a chain transfer agent was used. A particulate binder I was prepared in the same manner as the particulate binder A except that the amount was 0.10 parts.
  • Example 11 When manufacturing the negative electrode for lithium ion secondary batteries, the amount of the slurry composition for lithium ion secondary battery negative electrode applied to the surface of the copper foil was changed, the thickness of the negative electrode mixture layer was 94 ⁇ m, and the density was 1.7 g / A slurry composition for a negative electrode of a lithium ion secondary battery, a negative electrode for a lithium ion secondary battery, and a positive electrode for a lithium ion secondary battery, except that cm 3 and the basis weight were 16.0 mg / cm 2 A lithium ion secondary battery was prepared and evaluated. The results are shown in Table 1.
  • Example 1 A slurry composition for a lithium ion secondary battery negative electrode, a lithium ion secondary battery, in the same manner as in Example 1, except that the particulate binder J prepared by the following method was used instead of the particulate binder A
  • a negative electrode for a battery, a positive electrode for a lithium ion secondary battery, and a lithium ion secondary battery were prepared and evaluated. The results are shown in Table 1.
  • a particulate binder J was prepared in the same manner as the particulate binder A except that the amount of acid was 0.8 parts and the amount of t-dodecyl mercaptan as a chain transfer agent was 0.45 parts.
  • Example 2 A slurry composition for a lithium ion secondary battery negative electrode, a lithium ion secondary battery, in the same manner as in Example 1, except that the particulate binder K prepared by the following method was used instead of the particulate binder A
  • a negative electrode for a battery, a positive electrode for a lithium ion secondary battery, and a lithium ion secondary battery were prepared and evaluated.
  • the results are shown in Table 1.
  • ⁇ Preparation of particulate binder K> Without using seed particles B, the amount of styrene as the aromatic vinyl monomer was 62.0 parts, and 3.8 parts of itaconic acid was used instead of acrylic acid as the ethylenically unsaturated carboxylic acid monomer.
  • the particulate binder is the same as the particulate binder A except that no (meth) acrylic acid ester monomer is used and the amount of t-dodecyl mercaptan as a chain transfer agent is 0.40 part. K was prepared.
  • Example 3 A particulate binder L prepared by the following method was used in place of the particulate binder A, and the artificial graphite used in Example 1 was pulverized as a negative electrode active material (pulverizer: Crypto manufactured by Earth Technica) Ron KTM0 type, rotation speed: 6000 rpm, pulverization speed: 20 kg / hr)
  • pulverizer Crypto manufactured by Earth Technica
  • Ron KTM0 type rotation speed: 6000 rpm
  • pulverization speed 20 kg / hr
  • ⁇ Preparation of particulate binder L> The amount of the aqueous dispersion of seed particles B is 30.0 parts on a solid basis, the amount of styrene as the aromatic vinyl monomer is 60.0 parts, and the acrylic resin as the ethylenically unsaturated carboxylic acid monomer is used.
  • a particulate binder L was prepared in the same manner as the particulate binder A except that the amount of acid was 0.8 parts and the amount of t-dodecyl mercaptan as a chain transfer agent was 0.90 parts.
  • Example 4 A negative electrode obtained by using the particulate binder M prepared by the following method in place of the particulate binder A, and baking and CVD the artificial graphite used in Example 1 as the negative electrode active material
  • a slurry composition for a lithium ion secondary battery negative electrode, a negative electrode for a lithium ion secondary battery, a positive electrode for a lithium ion secondary battery, and a lithium ion secondary battery were prepared in the same manner as in Example 1 except that the active material was used. And evaluated. Firing was carried out at a temperature of 900 ° C. for 1 hour while maintaining a fluid state while supplying a nitrogen gas at a rate of 1 L / min in a fluid reaction reactor under a nitrogen atmosphere using a fluid reaction furnace.
  • the CVD process after firing is performed at a temperature of 900 ° C. while introducing the nitrogen gas containing benzene (benzene concentration: 1 g / L) into the fluidized reaction furnace at a rate of 1 L / min to flow the fired particles. Done for hours.
  • the results are shown in Table 1.
  • ⁇ Preparation of particulate binder M> The amount of the aqueous dispersion of seed particles B is 30.0 parts on a solid basis, the amount of styrene as the aromatic vinyl monomer is 55.8 parts, and the acrylic resin as the ethylenically unsaturated carboxylic acid monomer is used.
  • Example 5 the number average particle size of the particulate binder was small, and the surface acid amount per unit surface area of the particulate binder was reduced, so that it was inferred that the stability of the slurry composition was lowered. Is done. Furthermore, Examples 1 and 9 to 10 show that the gel content of the particulate binder affects the peel strength, swell resistance and cycle characteristics. Moreover, from Examples 1 and 11, it can be seen that the density and basis weight of the negative electrode mixture layer affect the peel strength.
  • the binding property between the components constituting the electrode mixture layer, the binding property between the electrode mixture layer and the current collector, and the cycle characteristics and rate characteristics of the lithium ion secondary battery are excellent.
  • a slurry composition for a lithium ion secondary battery electrode that can be obtained is obtained.
  • the binding property between the components constituting the electrode mixture layer and the binding property between the electrode mixture layer and the current collector are excellent, and the cycle characteristics excellent in the lithium ion secondary battery And the electrode for lithium ion secondary batteries which can exhibit a rate characteristic is obtained.
  • a lithium ion secondary battery having excellent cycle characteristics and rate characteristics can be obtained.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Secondary Cells (AREA)

Abstract

Cette invention concerne une composition de type coulis pour électrodes de batteries rechargeables au lithium-ion, assurant une excellente adhésion entre composants constituant une couche de mélange d'électrode et entre la couche de mélange d'électrode et un collecteur, et assurant d'excellentes caractéristiques de cycle et de régime à une batterie rechargeable au lithium-ion. Ladite composition de type coulis pour électrodes de batteries rechargeables au lithium-ion contient : un matériau actif d'électrode présentant une porosité telle que déterminée par intrusion au mercure allant de 0,1 cm3/g à 2,0 cm3/g (inclus) ; un liant particulaire présentant un diamètre des particules moyen en nombre allant de 200 à 600 nm (inclus) ; et de l'eau.
PCT/JP2015/000353 2014-01-29 2015-01-27 Composition de type coulis pour électrodes de batteries rechargeables au lithium-ion, électrode pour batteries rechargeables au lithium-ion et batterie rechargeable au lithium-ion Ceased WO2015115089A1 (fr)

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KR1020167016417A KR102355810B1 (ko) 2014-01-29 2015-01-27 리튬 이온 이차 전지 전극용 슬러리 조성물, 리튬 이온 이차 전지용 전극 및 리튬 이온 이차 전지
CN201580003265.XA CN105849943B (zh) 2014-01-29 2015-01-27 锂离子二次电池电极用浆料组合物、锂离子二次电池用电极及锂离子二次电池
JP2015559820A JP6477503B2 (ja) 2014-01-29 2015-01-27 リチウムイオン二次電池電極用スラリー組成物、リチウムイオン二次電池用電極およびリチウムイオン二次電池

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WO2019107229A1 (fr) * 2017-11-30 2019-06-06 日本ゼオン株式会社 Composition de liant pour batterie secondaire non aqueuse, composition de bouillie pour couche fonctionnelle de batterie secondaire non aqueuse, couche fonctionnelle de batterie secondaire non aqueuse, élément de batterie pour batterie secondaire non aqueuse, et batterie secondaire non aqueuse
JP2021128918A (ja) * 2020-02-17 2021-09-02 トヨタ自動車株式会社 リチウムイオン二次電池の負極およびその製造方法
WO2023008100A1 (fr) * 2021-07-27 2023-02-02 日本ゼオン株式会社 Composition de liant pour électrode négative de batterie secondaire à électrolyte non aqueux, composition de suspension épaisse pour électrode négative de batterie secondaire à électrolyte non aqueux, électrode négative pour batterie secondaire à électrolyte non aqueux, et batterie secondaire à électrolyte non aqueux

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JP7125891B2 (ja) * 2018-10-30 2022-08-25 三洋電機株式会社 二次電池及び二次電池の製造方法
WO2020175025A1 (fr) * 2019-02-26 2020-09-03 日本ゼオン株式会社 Composition de bouillie pour couches fonctionnelles de batterie secondaire non aqueuse, séparateur pour batteries secondaires non aqueuses et batterie secondaire non aqueuse
CN115050960B (zh) * 2022-06-15 2024-01-12 天津力神电池股份有限公司 负极加速传质和改善膨胀的物料及应用

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WO2023008100A1 (fr) * 2021-07-27 2023-02-02 日本ゼオン株式会社 Composition de liant pour électrode négative de batterie secondaire à électrolyte non aqueux, composition de suspension épaisse pour électrode négative de batterie secondaire à électrolyte non aqueux, électrode négative pour batterie secondaire à électrolyte non aqueux, et batterie secondaire à électrolyte non aqueux

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