WO2022138214A1 - リチウムイオン電池用の負極、リチウムイオン電池、リチウムイオン電池用の負極の製造方法、およびリチウムイオン電池の製造方法 - Google Patents

リチウムイオン電池用の負極、リチウムイオン電池、リチウムイオン電池用の負極の製造方法、およびリチウムイオン電池の製造方法 Download PDF

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WO2022138214A1
WO2022138214A1 PCT/JP2021/045419 JP2021045419W WO2022138214A1 WO 2022138214 A1 WO2022138214 A1 WO 2022138214A1 JP 2021045419 W JP2021045419 W JP 2021045419W WO 2022138214 A1 WO2022138214 A1 WO 2022138214A1
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Prior art keywords
negative electrode
lithium ion
ion battery
binder
cellulose
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PCT/JP2021/045419
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English (en)
French (fr)
Japanese (ja)
Inventor
亮 石黒
諭 中村
右典 九軒
正典 森下
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Japan Steel Works Ltd
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Japan Steel Works Ltd
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Priority to KR1020237021349A priority Critical patent/KR20230124599A/ko
Priority to EP21910363.7A priority patent/EP4270533A4/en
Priority to CN202180079465.9A priority patent/CN116636035A/zh
Priority to US18/269,563 priority patent/US20250015277A1/en
Publication of WO2022138214A1 publication Critical patent/WO2022138214A1/ja
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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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/386—Silicon or alloys based on silicon
    • 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
    • H01M4/134—Electrodes based on metals, Si or alloys
    • 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
    • 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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/058—Construction or 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
    • H01M10/058—Construction or manufacture
    • H01M10/0585—Construction or manufacture of accumulators having only flat construction elements, i.e. flat positive electrodes, flat negative electrodes and flat separators
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • 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
    • 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
    • H01M4/1393—Processes of manufacture of electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • 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
    • H01M4/1395—Processes of manufacture of electrodes based on metals, Si or alloys
    • 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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/364—Composites as mixtures
    • 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
    • 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
    • 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
    • H01M4/623—Binders being polymers fluorinated polymers
    • 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
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • 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
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • 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
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention relates to a negative electrode for a lithium ion battery, a lithium ion battery, a method for manufacturing a negative electrode for a lithium ion battery, and a method for manufacturing a lithium ion battery.
  • secondary batteries which are compact and lightweight and have high energy density, are attracting attention. ing.
  • the negative electrode in the lithium ion battery consists of a current collector and a negative electrode mixture layer provided above the current collector, and the negative electrode mixture layer contains a binder and the like in addition to the negative electrode active material.
  • Patent Document 1 describes a non-aqueous binder in an electrode for a lithium ion battery in which a cellulose nanofiber and a thermoplastic fluororesin are composited, wherein the cellulose nanofiber has a fiber diameter (diameter) of 0.
  • binders of cellulose having a fiber length of 002 ⁇ m or more and 1 ⁇ m or less, a fiber length of 0.5 ⁇ m or more and 10 mm or less, and an aspect ratio (fiber length of cellulose nanofibers / fiber diameter of cellulose nanofibers) of 2 or more and 100,000 or less. ..
  • Si silicon
  • graphite a promising material for a negative electrode active material
  • the negative electrode is formed by adding a negative electrode active material or a binder to a solvent to form a slurry, which is then applied onto a current collector.
  • the surface area of the Si nanoparticles nano-Si
  • the amount of binder for binding the nano-Si to each other becomes large.
  • Si reacts with water, and when an aqueous binder is used, hydrogen gas is generated and the battery characteristics are deteriorated (Problem 1). Further, even when an organic binder is used, the cycle characteristics become low (battery life is short) due to the large amount of the binder (problem 2).
  • an object of the embodiment of the present specification is to provide a negative electrode capable of increasing the capacity of the battery and improving battery characteristics such as cycle characteristics (battery life) and a lithium ion battery using the negative electrode.
  • Another object of the present invention is to provide a method for manufacturing a negative electrode and a method for manufacturing a lithium ion battery, which can improve battery characteristics such as high battery capacity and cycle characteristics (battery life).
  • the negative electrode for a lithium ion battery disclosed in the present application has a negative electrode mixture having a negative electrode active material, a binder, and hydrophobic cellulose, the negative electrode active material contains Si particles, and the binder is
  • the hydrophobic cellulose is an organic solvent-based binder in which a part of the hydrophilic groups of the cellulose is replaced with a hydrophobic group.
  • the lithium ion battery disclosed in the present application is a lithium ion battery including a negative electrode having a current collector and a negative electrode mixture layer formed on the current collector, a positive electrode, and an electrolytic solution.
  • the negative electrode mixture layer contains a negative electrode active material, a binder, and hydrophobic cellulose, the negative electrode active material contains Si particles, the binder is an organic solvent-based binder, and the hydrophobic cellulose. Is a part of the hydrophilic group of cellulose replaced with a hydrophobic group.
  • the method for manufacturing a negative electrode for a lithium ion battery disclosed in the present application comprises (a) a step of mixing a negative electrode active material, a binder, and hydrophobic cellulose to form a negative electrode slurry, and (b) the negative electrode slurry.
  • the negative electrode active material contains Si particles
  • the binder is an organic solvent-based binder
  • the hydrophobic cellulose has a part of the hydrophilic group of the cellulose. , Substituted for a hydrophobic group.
  • the method for manufacturing a lithium ion battery disclosed in the present application is as follows: (a) a step of preparing a slurry for a negative electrode, (b) the slurry for a negative electrode is applied onto a current collector, and the current collector and the negative electrode mixture layer are combined. A step of forming a negative electrode having the above, (c) a step of forming an electrode group in which the negative electrode and the positive electrode are laminated via a separator, (d) a step of accommodating the electrode group in a battery container, (e) the above.
  • step (d) there is a step of injecting an electrolytic solution into the battery container, and in the step (a), a negative electrode active material, a binder and a hydrophobic cellulose are mixed to form a slurry for a negative electrode.
  • the negative electrode active material contains Si particles
  • the binder is an organic solvent-based binder
  • the hydrophobicized cellulose is obtained by substituting a part of the hydrophilic groups of the cellulose with hydrophobic groups. Is.
  • the negative electrode for a lithium ion battery disclosed in one embodiment of the present specification, it is possible to increase the capacity of the battery and improve the battery characteristics such as the cycle characteristics (battery life).
  • the lithium ion battery disclosed in one embodiment of the present specification, it is possible to increase the capacity of the battery and improve the battery characteristics such as the cycle characteristics (battery life).
  • a negative electrode capable of increasing battery capacity and improving battery characteristics such as cycle characteristics (battery life) can be manufactured. can do.
  • a lithium ion battery having a high battery capacity and improved battery characteristics such as cycle characteristics (battery life). can.
  • FIG. It is a figure which shows typically the structure of the positive electrode, the negative electrode, and the lithium ion battery using these of Embodiment 1.
  • FIG. It is a figure which shows typically the structure of the positive electrode, the negative electrode, and the lithium ion battery using these of Embodiment 1.
  • FIG. It is a figure which shows the preparation process of a hydrophobic CeNF (cellulose nanofiber) dispersed in a solvent. It is a figure which shows the example of the preparation process of the slurry for a negative electrode.
  • FIG. It is a perspective view which shows the state of application of the slurry for a negative electrode using a slit die.
  • FIGS. 1 and 2 are diagrams schematically showing the configuration of a negative electrode, a positive electrode, and a lithium ion battery using these of the present embodiment.
  • 1A shows the configuration of the negative electrode
  • FIG. 1B shows the configuration of the positive electrode
  • FIG. 1C shows the internal configuration of the lithium ion battery.
  • the negative electrode is composed of the current collector 1S and the negative electrode mixture layer 1M provided on the current collector 1S
  • the positive electrode is the current collector 2S and It is composed of a positive electrode mixture layer 2M provided on the upper portion thereof.
  • the lithium ion battery has a negative electrode, a positive electrode, and a separator arranged between them, and the negative electrode and the positive electrode are the negative electrode mixture layer 1M and the positive electrode, respectively.
  • the agent layer 2M is arranged so as to be in contact with the separator SP (see also FIG. 2). As shown in FIG.
  • a part of the current collector 1S of the negative electrode becomes a negative electrode terminal 1T
  • a part of the current collector 2S of the positive electrode becomes a positive electrode terminal 2T.
  • the laminated body of the negative electrode, the positive electrode and the separator (also referred to as an electrode group) is housed in a battery container (a bag made of a laminated film, a battery can, etc.) together with an electrolytic solution, and the negative electrode terminal 1T and the positive electrode terminal 2T are projected (exposed). It is sealed in the state of being sealed.
  • each electrode material such as an electrode active material or a binder is added to a solvent (organic solvent, aqueous solvent, etc.) to form a slurry, which is applied onto a current collector and dried. It is formed.
  • a solvent organic solvent, aqueous solvent, etc.
  • nano-Si is used as the negative electrode active material in the negative electrode mixture layer.
  • a binder is used to bind the negative electrode active material and the like.
  • hydrophobic cellulose is used as an additive in the negative electrode mixture layer.
  • the negative electrode (negative electrode plate, negative electrode sheet) has a current collector and a negative electrode mixture layer provided on the current collector.
  • the negative electrode mixture layer is a layer provided on the upper part of the current collector and containing at least the negative electrode active material. Then, in the present embodiment, nano-Si is contained as the negative electrode active material. Further, the negative electrode mixture layer contains a binder for binding the negative electrode active material. Further, the negative electrode mixture layer contains hydrophobicized cellulose as an additive.
  • the negative electrode mixture layer may contain a thickener, a dispersant, a conductive agent (also referred to as a conductive auxiliary agent) and the like as other additives.
  • a metal thin film can be used as the current collector for the negative electrode.
  • the metal material copper, lithium (Li), stainless steel and the like can be used. Further, those having a surface plated with nickel or the like may be used.
  • nano-Si which is a Si (silicon) -based material
  • This nano-Si consists of Si particles on the order of nanometers.
  • SiO SiOx
  • the thickness of the coating layer is preferably about 1 ⁇ m to 10 nm.
  • nano-Si there is no limitation on the method of miniaturizing (nano) Si, but for example, fine particles of Si can be obtained by vaporizing a Si compound and then cooling it.
  • the average particle size (median diameter, D50) of the nano-Si is preferably 10 nm to 500 nm, more preferably 20 nm to 200 nm.
  • the finer the particle size of Si the higher the electrode capacity.
  • the surface area of Si increases, it is necessary to increase the amount of binder in order to prevent peeling due to expansion / contraction during charging / discharging. Therefore, it is preferable to select the particle size according to the battery capacity to be manufactured.
  • the average particle size (median diameter, D50) of nano-Si can be measured by, for example, a laser diffraction / scattering type particle size distribution measuring method. Further, the Si particles can be observed by using an electron microscope such as SEM or TEM, or an atomic force microscope such as AFM or SPM, and the particle size can also be measured by this observation.
  • nano-Si and the following other substances may be used in combination.
  • carbon-based materials such as graphite (graphite), hard carbon (non-graphitizable carbon), and soft carbon (easy graphitizable carbon) can be used.
  • lithium titanate (Li 4 Ti 5 O 12 ) or the like may be used. From the viewpoint of improving cycle characteristics, it is preferable to use a carbon-based material, particularly graphite, in combination.
  • the capacity should theoretically increase, but in the end, the battery capacity does not increase so much, and the cycle characteristics tend to decrease. ..
  • this is due to the increase in the binder due to the increase in the surface area of the particles based on the nanonization of the particles in order to reduce the influence of the volume expansion of Si.
  • the hydrophobic CeNF by adding the hydrophobic CeNF, it is possible to suppress the decrease in the battery capacity even if the binder is increased, and it is possible to bring out the original effect of increasing the battery capacity of Si. It is considered that this is because the volume expansion of Si is suppressed by the compounding of the hydrophobic CeNF and the binder. Further, it is considered that such suppression of volume expansion suppresses peeling of the negative electrode active material and improves cycle characteristics (battery life).
  • the binder has a role of binding the negative electrode materials such as the electrode active material in the negative electrode mixture layer to each other, and binding the negative electrode material to the current collector.
  • the binder for the electrode mixture layer can be divided into an aqueous system and an organic solvent system.
  • aqueous binder examples include styrene-butadiene copolymer rubber (SBR), polyvinyl alcohol, polyacrylic acid, carboxymethyl cellulose and the like, and are used in a state of being dispersed in an aqueous solvent (for example, water).
  • SBR styrene-butadiene copolymer rubber
  • polyvinyl alcohol polyvinyl alcohol
  • polyacrylic acid carboxymethyl cellulose and the like
  • organic solvent-based binder examples include polyvinylidene fluoride (PVdF) and polyimide (PI), which are used in a state of being added to an organic solvent.
  • PVdF polyvinylidene fluoride
  • PI polyimide
  • NMP N-methyl-2-pyrrolidone
  • PI polyimide
  • NMP N-methyl-2-pyrrolidone
  • PI polyimide
  • NMP N-methyl-2-pyrrolidone
  • PI polyimide
  • the PI precursor is used in a state of being dissolved or dispersed in a solvent such as NMP, and is heat-treated to undergo imidization (dehydration reaction and cyclization reaction). A cross-linking reaction can be caused to obtain a tough PI.
  • an organic solvent-based binder is used.
  • an aqueous binder is used as described later, hydrogen gas is generated by the reaction between water and Si, and the electrode characteristics are deteriorated (see FIG. 9).
  • the organic solvent-based binder by using the organic solvent-based binder, the reaction between water and Si can be prevented and the electrode characteristics can be improved.
  • the use of nano-Si has no choice but to increase the amount of the organic solvent-based binder added, which reduces the battery capacity and cycle characteristics (battery life).
  • the addition is performed.
  • the hydrophobic CeNF as an agent, the battery capacity and cycle characteristics (battery life) can be improved even when an organic solvent-based binder is used (see FIGS. 10, 11 and the like).
  • Cellulose (Hydrophobic cellulose) is a carbohydrate represented by (C 12 H 20 O 10 ) n .
  • n indicating the average number of repetitions is a number of 1 or more, preferably 10 to 10000, and more preferably 50 to 2000.
  • a group for example, -CH 2 OH in which a part of a plurality of hydroxyl groups of a carbohydrate represented by (C 12 H 20 O 10 ) n has a hydroxyl group has a hydroxyl group.
  • Cellulose substituted with such -R-OH (R represents a divalent hydrocarbon group) may be used.
  • cellulose has a hydroxyl group (hydrophilic group).
  • This hydroxyl group (hydrophilic group) is treated hydrophobically (lipophilic treatment) using a hydrophobic agent (for example, a carboxylic acid compound). That is, the hydroxyl group ( ⁇ OH) portion of cellulose is replaced with a hydrophobic group.
  • a part of the hydroxyl group of cellulose is esterified with a carboxylic acid compound (R-CO-OH).
  • the hydroxyl group (-OH) portion of cellulose is an ester bond (-O-CO-R, carboxyl group).
  • the hydrophobic agent is not particularly limited as long as it has a composition capable of imparting a hydrophobic group to the hydrophilic group of cellulose, but for example, a carboxylic acid compound can be used. Among them, it is preferable to use an acid anhydride of a compound having two or more carboxyl groups and a compound having two or more carboxyl groups. Among the compounds having two or more carboxyl groups, it is preferable to use a compound having two carboxyl groups (dicarboxylic acid compound).
  • Examples of compounds having two carboxy groups include propanedioic acid (malonic acid), butanedioic acid (succinic acid), pentanedioic acid (glutaric acid), hexanedioic acid (adipic acid), and 2-methylpropanediacid, 2.
  • the acid anhydrides of the compounds having two carboxy groups include maleic anhydride, succinic anhydride, phthalic anhydride, glutaric acid anhydride, adipic acid anhydride, itaconic acid anhydride, pyromellitic acid anhydride, and 1,2-cyclohexanedicarboxylic acid anhydride.
  • Examples thereof include acid anhydrides of dicarboxylic acid compounds such as acids and compounds containing a plurality of carboxy groups.
  • Derivatives of the acid anhydride of the compound having two carboxy groups include at least a part of the acid anhydride of the compound having a carboxy group, such as dimethylmaleic acid anhydride, diethylmaleic acid anhydride, and diphenylmaleic acid anhydride.
  • Examples thereof include those in which a hydrogen atom is substituted with a substituent (for example, an alkyl group, a phenyl group, etc.).
  • a substituent for example, an alkyl group, a phenyl group, etc.
  • maleic anhydride, succinic anhydride, and phthalic anhydride are preferable because they are easy to apply industrially and easily gasified.
  • hydrophilic group of cellulose may be subjected to a hydrophobic treatment (modification of a carboxylic acid compound) and then a treatment for improving the hydrophilicity by adding an alkylene oxide. Further, two or more kinds of the above-mentioned hydrophobic agents may be added.
  • the cellulose may be made finer (nano-sized) by performing a defibration treatment.
  • the defibration treatment includes a chemical treatment method and a mechanical treatment method. A method combining these may be used.
  • CeNF having a fiber length (L) of 3 nm or more and 10 ⁇ m or less and an aspect ratio (length L / diameter D) of 0.005 or more and 10,000 or less can be obtained.
  • Such finely divided cellulose fibers to nanometer size are called cellulose nanofibers (CeNF).
  • Cellulose miniaturization (nano-ization) as described above may be performed before hydrophobization or after hydrophobization.
  • the hydrophobized CeNF is preferably used in a state of being dispersed in a solvent in order to prevent aggregation and enhance dispersibility in the slurry.
  • FIG. 3 is a diagram showing a process of preparing a hydrophobized CeNF dispersed in a solvent.
  • cellulose solid, for example, powder
  • succinic anhydride solid, for example, tablet
  • the weight of cellulose and succinic anhydride is, for example, 90 wt% (% by weight, mass%) and 10 wt%.
  • the produced hydrophobic cellulose is dispersed in an aqueous solvent (water and / or alcohols, etc., here, water ( H2O )), and a micronization treatment (defibration treatment, nanonization) is performed.
  • a micronization treatment defibration treatment, nanonization
  • a miniaturization device starburst
  • a treatment of 245 MPa and 10 Pass is performed to nanonize cellulose. This makes it possible to obtain a hydrophobized CeNF dispersed in an aqueous solvent (for example, water).
  • FIG. 4 is a diagram showing an example of a process for preparing a slurry for a negative electrode. An example of the process of preparing the slurry for the negative electrode will be described with reference to FIG. 4.
  • the mixed solution 1 is prepared by mixing an organic solvent-based binder, an organic solvent, and a hydrophobic CeNF (dispersed in water). At this time, other additives such as a conductive agent and a dispersant may be further added.
  • the mixture 1 is stirred (for example, about 1 minute at 1000 rpm).
  • a high-speed stirrer for example, homodisper
  • graphite and nano-Si are added as negative electrode active materials to the mixed liquid 1, and for example, CNT and acetylene black (AB) are added as conductive agents, and then the mixture is stirred to prepare the mixed liquid 2.
  • a high-speed stirrer for example, homodisper
  • the mixture is stirred at 3000 rpm for about 30 minutes, for example.
  • alcohol is added to the mixture 2 and then stirred to prepare the mixture 3.
  • a high-speed stirrer for example, homodisper
  • the mixture is stirred at 3000 rpm for about 1 minute, for example.
  • the slurry for the negative electrode can be obtained.
  • the viscosity of the negative electrode slurry thus obtained was 6200 mPas (35 ° C.), and bubbles such as the negative electrode slurry 4 described later could not be visually confirmed.
  • the coatability was good.
  • the viscosity of the slurry for the negative electrode is preferably 3000 to 5000 mPas in consideration of coatability.
  • the organic solvent-based binder by using the organic solvent-based binder, it is possible to reduce the bubbles generated in the slurry for the negative electrode and improve the characteristics of the negative electrode mixture layer.
  • Ketjen black, carbon nanofiber and the like can be used as the conductive agent which is the other additive mentioned above.
  • a surfactant can be used as the dispersant.
  • a thickener or the like may be used in addition to the dispersant.
  • the negative electrode slurry is applied and dried on the surface of a current collector (for example, a steel foil) to form a negative electrode mixture layer.
  • a current collector for example, a steel foil
  • a negative electrode mixture layer can be formed (see FIG. 1 (A)).
  • a die coater can be used. Then, by drying the coating layer, a negative electrode mixture layer can be formed on the surface of the base material S. In this way, a negative electrode having a base material (for example, a steel foil which is a current collector) S and a negative electrode mixture layer can be formed.
  • FIG. 5 is a schematic diagram showing the configuration of the negative electrode manufacturing apparatus of the present embodiment.
  • the manufacturing apparatus shown in FIG. 5 has an unwinding unit (unloading unit) UW that unwinds the base material (current collector) S and a winding unit (carrying unit) WD that winds up the base material (current collector) S. Have.
  • the base material (current collector) S is continuously arranged from the unwinding portion UW to the winding portion WD, and the surface of the base material S (the first) between the unwinding portion UW and the winding portion WD.
  • a negative electrode mixture layer (coating layer of slurry SL for negative electrode) 1M is formed on one surface), and the negative electrode is completed.
  • the scroll-shaped (rolled strip-shaped) base material S can be continuously processed, and the negative electrode can be efficiently formed.
  • the unwinding portion UW side may be referred to as upstream, and the winding portion WD may be referred to as downstream.
  • At least one coating unit 20 and a drying unit (drying furnace) 30 are arranged between the unwinding unit UW and the winding unit WD.
  • the base material S is treated in each processing unit while being guided by a plurality of rolls (guide rolls) R, and a negative electrode mixture layer (coating layer of slurry SL for negative electrode) 1M is formed on the surface thereof. This will be described in detail below.
  • the base material S unwound from the unwinding portion UW is guided by a plurality of rolls R and conveyed to the coating portion 20.
  • the coating portion 20 is provided with a coating liquid tank T, a pump P, and a slit die D.
  • a negative electrode slurry SL which is a coating liquid, is supplied from the coating liquid tank T to the slit die D via a pump P.
  • a valve B is provided between the supply pipe of the slurry SL for the negative electrode and the liquid coating tank T.
  • FIG. 6 is a perspective view showing a state of application of the slurry for the negative electrode using the slit die. As shown in FIG. 6, the negative electrode slurry SL is applied onto the base material S from the manifold inside the slit die D via the slit (discharge portion) at the tip of the die, and the coating layer (SL) is formed.
  • the base material S on which the coating layer (SL) is formed is guided by the roll R and conveyed to the drying portion 30.
  • heated air is introduced from a nozzle (not shown).
  • the temperature of the heated air is controlled by a heating unit (heater or the like) (not shown).
  • the temperature of the drying portion 30 is 100 ° C. or lower, for example, about 70 ° C.
  • the liquid component of the coating layer (SL) is vaporized to form a negative electrode mixture layer 1M.
  • the negative electrode slurry SL As described above, by using the negative electrode slurry SL, a highly accurate negative electrode can be efficiently formed.
  • the negative electrode slurry SL has few bubbles and good coatability, and a good negative electrode can be formed even when the carry-in speed of the base material S is 10 m / min or more.
  • a rolled portion may be provided downstream of the drying portion 30.
  • the coating layer can be rolled by passing the laminate of the base material S and the coating layer through a narrow gap between the two rolls.
  • the rolled portion may be provided between the coating portion 20 and the drying portion 30.
  • the negative electrode slurry SL may be applied to both surfaces of the base material S.
  • the negative electrode slurry SL may be sequentially applied to each side of the base material S, or the negative electrode slurry SL may be applied to both sides of the base material S during the process shown in FIG.
  • FIG. 7 shows an example of a process for preparing a slurry for a negative electrode when an aqueous binder is used.
  • the mixed liquid 1 is prepared by mixing the water-based binder and water. At this time, other additives such as a conductive agent and a dispersant may be further added.
  • the mixture 1 is stirred (for example, about 1 minute at 1000 rpm).
  • a high-speed stirrer for example, homodisper
  • graphite, nano-Si, and other negative electrode active materials are added to the mixed solution 1 as the negative electrode active material, and then the mixture is stirred to prepare the mixed solution 2.
  • a high-speed stirrer for example, homodisper
  • the mixture is stirred at 1000 to 4000 rpm for about 30 minutes, for example.
  • alcohol is added to the mixture 2 and then stirred to prepare the mixture 3.
  • a high-speed stirrer for example, homodisper
  • the mixture is stirred at 1000 to 4000 rpm for about 1 minute, for example.
  • the positive electrode (positive electrode plate, positive electrode sheet) has a current collector and a positive electrode mixture layer provided on the current collector.
  • the positive electrode mixture layer is a layer provided on the upper part of the current collector and containing at least the positive electrode active material.
  • the positive electrode active material examples include NCA (lithium-nickel-cobalt-aluminum-based oxide, nickel-cobalt-lithium aluminate (Li (Ni, Co, Al) O 2 )) and NCM (lithium-nickel-cobalt-manganese-based oxide, nickel).
  • -Cobalt-lithium ternary metal such as lithium manganate (Li (Ni, Co, Mn) O 2 )
  • the positive electrode mixture layer contains a binder for binding the positive electrode active material.
  • a plastic fluororesin-based binder such as polyvinylidene fluoride (PVdF) can be used.
  • the positive electrode mixture layer may contain a conductive agent, a thickener, a dispersant and the like.
  • a metal thin film can be used as the current collector for the positive electrode.
  • the metal material aluminum, stainless steel (SUS) and the like can be used. Further, those having a surface plated with nickel or the like may be used. In the examples described later, the evaluation was performed using a half cell (the counter electrode is Li metal) in which the positive electrode was omitted.
  • a resin such as polypropylene (PP), polyethylene (PE), polyethylene terephthalate (PET), glass fiber, a non-woven fabric or the like can be used.
  • the electrolytic solution is composed of an electrolyte salt and an electrolyte solvent.
  • a lithium salt can be used. Among them, lithium hexafluorophosphate (LiPF 6 ), lithium perchlorate (LiClO 4 ), lithium tetrafluoroborate (LiBF 4 ), lithium trifluoromethanesulfonate (LiCF 3 SO 4 ), lithium bistrifluoromethanesulfonylimide (LiCF 3 SO 4).
  • LiN LiN (SO 2 CF 3 ) 2
  • LiN lithium bispentafluoroethanesulfonylimide
  • LiBC 4 O 8 lithium bisoxalate volate
  • the electrolyte solvent include propylene carbonate (PC), ethylene carbonate (EC), dimethyl carbonate (DMC), diethyl carbonate (DEC), ethylmethyl carbonate (EMC), diphenyl carbonate, ⁇ -butyrolactone (GBL), and ⁇ -.
  • a mixture of the cyclic carbonate such as EC and PC and the chain carbonate such as DMC, DEC and EMC are preferable to use.
  • the proportion of cyclic carbonate can be prepared in the range of 10 to 90% by volume.
  • VC or one to which EVC, FEC, or ES is added.
  • binder PI dissolved in NMP, 11 wt%) and hydrophobized CeNF (dispersed in water, solid component concentration 0.5 wt%, acid value: 76.5 mg / g) were applied using a homodisper. , was mixed at a rotation speed of 1000 rpm.
  • hydrophobized CeNF one dispersed in water and having an acid value of 76.5 mg / g was used.
  • addition amount of the hydrophobized CeNF the addition amount of the aqueous dispersion is prepared so that the ratio in the solid component (that is, the portion serving as the negative electrode mixture) in the slurry 1 for the negative electrode is 0.5 wt%. did.
  • the concentration of hydrophobized CeNF in the aqueous dispersion is 4 wt%.
  • the acid value is represented by the number of mg of potassium hydroxide required to neutralize the acidic component contained in 1 g of the sample, and can be prepared in the range of, for example, 30 to 300 mg / g.
  • graphite which is a negative electrode active material
  • nano-Si are added at a weight ratio of 9: 1
  • carbon nanotubes (CNTs) are added as other negative electrode active materials.
  • the amounts of graphite, nano-Si, and CNT added are 78.3 wt%, 8.7 wt%, and 2 wt%, respectively.
  • alcohol was added and the mixture was stirred for 1 minute to obtain a slurry 1 for a negative electrode.
  • Table 1 shows the amount of the negative electrode material added.
  • carbon-coated nano-Si was used as the nano-Si (average particle size 45 nm, coat thickness 2 to 3 nm).
  • graphite graphite having an average particle size of 22 ⁇ m was used.
  • a negative electrode was manufactured in accordance with the above-mentioned “negative electrode forming step”.
  • the negative electrode slurry 1 was applied to a current collector using a die coater and dried in a drying oven at 70 ° C.
  • a Ni-plated steel foil was used as the current collector.
  • a half-cell coin-type battery (sample 1) was prepared by combining the prepared negative electrode 1, the counter electrode Li metal, and a glass fiber (separator) having a thickness of 100 ⁇ m.
  • the positive electrode shown in FIGS. 1 and 2 is Li metal, and the laminate of the Li metal, the negative electrode, and the separator (also referred to as an electrode group) is housed inside a coin-type can, and an electrolytic solution is injected. After that, the lid is closed and sealed.
  • the laminate is arranged so that the Li metal is in contact with the bottom of the can and the negative electrode is in contact with the back surface of the lid.
  • ⁇ Sample 2> (Preparation of slurry 2 for negative electrode)
  • the negative electrode slurry 1 was prepared so that the binder (PI dissolved in NMP) of the above-mentioned negative electrode slurry 1 was 11 wt% to 5 wt% and the difference was 9: 1 between graphite and nano-Si.
  • a slurry 2 for a negative electrode was prepared in the same manner as in 1.
  • the negative electrode 2 was manufactured in the same manner as in the case of the negative electrode 1 described above.
  • Example 3> (Preparation of slurry 3 for negative electrode)
  • the negative electrode slurry 3 was produced in the same manner as the negative electrode slurry 1 except that the ratio of graphite of the negative electrode slurry 1 to the nano-Si was adjusted to 8: 2.
  • the negative electrode 3 was manufactured in the same manner as in the case of the negative electrode 1 described above.
  • the battery 3 was manufactured in the same manner as in the case of the battery 1.
  • ⁇ Sample 4> (Preparation of slurry 4 for negative electrode)
  • the negative electrode slurry 4 was prepared by using an aqueous binder (here, SBR dispersed in water, 11 wt%) of the above-mentioned negative electrode slurry 1 and adding no hydrophobic CeNF.
  • a water-based binder When a water-based binder was used, it was difficult to add a large amount of nano-Si, so a part of the nano-Si was changed to SiO to prepare a slurry 4 for a negative electrode.
  • nano-Si was 4 wt%
  • SiO was 8.5 wt%
  • graphite was 81 wt%
  • acetylene black (AB) was 2 wt% as another negative electrode active material. Bubbles were confirmed in the negative electrode slurry 4.
  • the negative electrode 4 was manufactured in the same manner as in the case of the negative electrode 1 described above.
  • slurry 5 for negative electrode The negative electrode slurry 1 was prepared so that the binder (PI dissolved in NMP) of the above-mentioned negative electrode slurry 1 was 11 wt% to 7 wt%, and the difference was 9: 1 between graphite and nano-Si.
  • a slurry 5 for a negative electrode was prepared in the same manner as in 1.
  • the negative electrode 5 was manufactured in the same manner as in the case of the negative electrode 1 described above.
  • slurry 6 for negative electrode The negative electrode slurry 1 was prepared so that the binder (PI dissolved in NMP) of the above-mentioned negative electrode slurry 1 was 11 wt% to 9 wt%, and the difference was 9: 1 between graphite and nano-Si.
  • a slurry 6 for a negative electrode was prepared in the same manner as in 1.
  • the negative electrode 6 was manufactured in the same manner as in the case of the negative electrode 1 described above.
  • Example 7> (Preparation of slurry 7 for negative electrode) Similar to the negative electrode slurry 1 except that the hydrophobic CeNF (dissolved in water, acid value: 76.5 mg / g) of the negative electrode slurry 1 was changed from 0.5 wt% to 0.3 wt%. A slurry 7 for a negative electrode was prepared. Since the hydrophobized CeNF is 1 wt% or less, it is not counted as a solid component, but the solid component including the hydrophobized CeNF may be calculated as 100 wt%.
  • the negative electrode 7 was manufactured in the same manner as in the case of the negative electrode 1 described above.
  • ⁇ Sample 8> (Preparation of slurry 8 for negative electrode) Same as the negative electrode slurry 1 and 7 except that the hydrophobic CeNF (dissolved in water, acid value: 76.5 mg / g) of the negative electrode slurry 1 was changed from 0.5 wt% to 0.25 wt%. To prepare a slurry 8 for a negative electrode.
  • the negative electrode 8 was manufactured in the same manner as in the case of the negative electrode 1 described above.
  • Example 9 (Preparation of slurry 9 for negative electrode)
  • the negative electrode slurry 9 was produced in the same manner as the negative electrode slurry 2 except that the non-hydrophobicized CeNF (also referred to as untreated CeNF) was used instead of the hydrophobic CeNF of the negative electrode slurry 1 described above.
  • the non-hydrophobicized CeNF also referred to as untreated CeNF
  • the negative electrode 9 was manufactured in the same manner as in the case of the negative electrode 1 described above.
  • the negative electrode 10 was manufactured in the same manner as in the case of the negative electrode 1 described above.
  • the battery 10 was manufactured in the same manner as in the case of the battery 1.
  • Example 11 (Preparation of slurry 11 for negative electrode)
  • the negative electrode slurry 11 was produced in the same manner as the negative electrode slurry 6 except that the ratio of graphite of the negative electrode slurry 1 to the nano-Si was adjusted to 8: 2.
  • the negative electrode 11 was manufactured in the same manner as in the case of the negative electrode 1 described above.
  • the battery 11 was manufactured in the same manner as in the case of the battery 1.
  • FIG. 8 is a graph showing the initial characteristics of the coin-type battery (samples 1, 2, 5, and 6).
  • the horizontal axis is the capacity (Capacity, (mAh / g)), and the vertical axis is the voltage (E, (V)).
  • FIG 9 is a graph showing the initial characteristics of the battery 4 using the aqueous solvent.
  • the battery capacity was lower than that of any of the above samples 1, 2, 5, and 6.
  • a portion having no visual defect in the coating layer was used.
  • FIG. 10 is a graph showing the cycle characteristics of coin-type batteries (samples 1, 2, 5, and 6).
  • the horizontal axis is the number of cycles (Cycle number), and the vertical axis is the discharge capacity (Discharge capacity (mAh / g)).
  • any of the samples (samples 1, 2, 5, and 6), a good discharge capacity was shown even if the number of cycles increased. Moreover, in all the samples (samples 1, 2, 5, and 6), the discharge capacity was better than that of the sample 10 to which CeNF was not added.
  • the amount of binder PI dissolved in NMP
  • the amount of binder added was 11 wt% rather than 9 wt%. The one with better cycle characteristics and the addition amount of 11 wt% had the best cycle characteristics among Samples 1, 2, 5, 6 and 10.
  • FIG. 11 is a graph showing the cycle characteristics of coin-type batteries (samples 2, 7, and 8) having different amounts of hydrophobized CeNF added.
  • the horizontal axis is the number of cycles (Cycle number), and the vertical axis is the discharge capacity (Discharge capacity (mAh / g)).
  • the discharge capacity was better than that of the sample 10 to which CeNF was not added and the sample 9 using the untreated CeNF. Then, as the amount of the hydrophobized CeNF added increased from 0.25 wt% ⁇ 0.3 wt% ⁇ 0.5 wt%, the capacity increased, and the decrease in the discharge capacity with the increase in the number of cycles was also small.
  • the ratio to the nano-Si was set to 10% by weight, but the cycle characteristics of the samples 3 and 11 to which the ratio to the nano-Si was 20% were investigated. rice field.
  • FIG. 12 is a graph showing the cycle characteristics of a coin-type battery (samples 3 and 11) having a ratio of nano Si to 8: 2.
  • the horizontal axis is the number of cycles (Cycle number), and the vertical axis is the discharge capacity (Discharge capacity (mAh / g)).
  • the discharge capacity was better than that of the sample 10 to which CeNF was not added and the sample 9 using the untreated CeNF.
  • the discharge capacity was improved by the larger proportion of nano-Si. It was also confirmed that in the above samples 3 and 11, the volume increased as the amount of the binder (PI dissolved in NMP) increased from 9 wt% to 11 wt%.
  • the slurry for the negative electrode containing nano-Si it is preferable to use a hydrophobic CeNF and an organic solvent-based binder.
  • the amount of hydrophobized CeNF added is preferably 0.25 wt% or more, and good results can be obtained even in the range of 0.25 to 0.5 wt%.
  • this hydrophobized CeNF one dispersed in an aqueous solvent may be used.
  • the nano-Si can react with water, but the amount of the hydrophobized CeNF added is smaller than that of the binder, for example, and the amount of the solvent (dispersion medium) thereof is also small. Therefore, the water in the hydrophobized CeNF of the water dispersion does not have an adverse effect.
  • the concentration of the hydrophobized CeNF in the aqueous dispersion is, for example, 0.05 to 1 wt%.
  • the amount added is about 0.05 to 1 ml with respect to 100 ml of the total amount of the solvent for the negative electrode slurry, and is preferably 1 wt% or less of the total amount of the solvent for the negative electrode slurry.
  • the content of the hydrophobized CeNF in the slurry for the negative electrode is preferably 0.01 wt% or more, more preferably 0.02 wt% or more with respect to the solid component (total amount of the negative electrode active material and the binder). ..
  • a slurry, an electrode and a battery are formed in the atmosphere.
  • an aqueous solvent may be used as long as it is slight, and it is not easily affected by the moisture in the atmosphere. Therefore, in the formation of the slurry, the electrode and the battery of the present embodiment, it is not necessary to use a dry booth in which the humidity and temperature are strictly controlled, and the slurry, the electrode and the battery can be formed in the atmosphere, which is very useful.
  • FIG. 13 is a cross-sectional perspective view showing the configuration of a cylindrical lithium ion battery.
  • the lithium ion battery shown in FIG. 13 has a cylindrical can 106, and the can 106 contains a group of electrodes in which a strip-shaped positive electrode 101 and a negative electrode 103 are wound via a separator SP. ..
  • electrode mixture layers are formed on both sides of the current collector.
  • the positive electrode current collecting tab on the upper end surface of the electrode group is joined to the positive electrode cap.
  • the negative electrode current collecting tab on the lower end surface of the electrode group is joined to the bottom of the can 106.
  • An insulating coating (not shown) is provided on the outer peripheral surface of the can 106.
  • an electrolytic solution (not shown) is injected into the can 106.
  • polyimide (PI) is used as the binder, but another organic solvent-based binder may be used.
  • organic solvent-based binder it is preferable to use the above-mentioned polyimide (PI) or polyvinylidene fluoride (PVdF) from the viewpoint of improving the adhesiveness of nano-Si.
  • the slurry for the negative electrode is prepared by using a stirrer such as a homodisper, but the slurry for the negative electrode may be prepared by using an extruder.
  • FIG. 14 is a cross-sectional view showing a method of preparing a slurry for a negative electrode using an extruder.
  • the extruder has a cylinder 111 and a screw SC arranged inside the cylinder 111.
  • a screw drive unit (not shown) is connected to the screw SC.
  • the cylinder 111 is provided with three supply ports 113a, 113b, 113c from the upstream side of the cylinder 111. Further, a discharge nozzle 119 is provided at the tip of the cylinder 111.
  • a negative electrode active material for example, graphite, nanoSi, or other negative electrode active material
  • a negative electrode active material for example, graphite, nanoSi, or other negative electrode active material
  • the organic solvent-based binder, the organic solvent, and the hydrophobic material are added from the supply port 113b.
  • Chemicalized CeNF dispersed in water
  • alcohol preparation solvent
  • the slurry for the negative electrode is prepared and discharged from the discharge nozzle 119.
  • FIG. 15 is a cross-sectional view showing a method of preparing a slurry for a positive electrode using an extruder.
  • a binder and additives are added from the supply port 113a, and an organic solvent (for example, NMP) is added from the supply port 113b while mixing by rotating the screw SC.
  • an organic solvent for example, NMP
  • the positive electrode active material is further added from the supply port 113c and mixed by rotating the screw SC.
  • the slurry for the positive electrode is prepared and discharged from the discharge nozzle 119.
  • an aqueous solvent water and / or alcohols, etc., here, water ( H2O )
  • an organic solvent may be used.
  • the hydrophobized CeNF is preferably used in a state of being dispersed in a solvent in order to prevent aggregation and enhance dispersibility in the slurry.
  • a method of obtaining a hydrophobic CeNF dispersed in an organic solvent by replacing the aqueous solvent of the hydrophobic CeNF dispersed in the aqueous solvent with an organic solvent will be described.
  • FIG. 16 is a diagram showing a step of preparing a hydrophobized CeNF dispersed in an organic solvent.
  • a method for preparing NMP-dispersed hydrophobicized CeNF will be described when NMP is used as the organic solvent and succinic anhydride is used as the carboxylic acid-based compound which is a hydrophobic agent.
  • cellulose solid, for example, powder
  • succinic anhydride solid, for example, tablet
  • 100 ° C. or higher For example, use a pressurized kneader to mix at 125 ° C. for 20 minutes.
  • the weight ratio of cellulose and succinic anhydride is, for example, 90 wt% and 10 wt%.
  • the produced hydrophobic cellulose is dispersed in an aqueous solvent (water and / or alcohols, etc., here, water ( H2O )), and a micronization treatment (defibration treatment, nanonization) is performed.
  • a micronization treatment defibration treatment, nanonization
  • a miniaturization device starburst
  • a treatment of 245 MPa and 10 Pass is performed to nanonize cellulose.
  • the method is the same as the method for preparing the hydrophobic CeNF dispersed in the aqueous solvent described with reference to FIG. This makes it possible to obtain a hydrophobized CeNF.
  • the hydrophobized CeNF at this stage is in a state of being dispersed in an aqueous solvent, and this aqueous solvent is replaced with NMP (organic solvent).
  • NMP organic solvent
  • an aqueous solvent here, water ( H2O )
  • an organic solvent here, NMP
  • an organic solvent for example, NMP
  • an organic solvent for example, NMP
  • the mixed solution is prepared so that the hydrophobized CeNF (solid content) is 0.1 to 20 wt%.
  • CeNF dispersed in an organic solvent for example, NMP
  • the concentration of the organic solvent here, NMP
  • the aqueous solvent here, water ( H2O )

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PCT/JP2021/045419 2020-12-25 2021-12-09 リチウムイオン電池用の負極、リチウムイオン電池、リチウムイオン電池用の負極の製造方法、およびリチウムイオン電池の製造方法 Ceased WO2022138214A1 (ja)

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EP21910363.7A EP4270533A4 (en) 2020-12-25 2021-12-09 NEGATIVE ELECTRODE FOR LITHIUM-ION BATTERIES, LITHIUM-ION BATTERY, METHOD FOR PRODUCING NEGATIVE ELECTRODE FOR LITHIUM-ION BATTERIES, AND METHOD FOR PRODUCING LITHIUM-ION BATTERY
CN202180079465.9A CN116636035A (zh) 2020-12-25 2021-12-09 锂离子电池用的负极、锂离子电池、锂离子电池用负极的制造方法及锂离子电池的制造方法
US18/269,563 US20250015277A1 (en) 2020-12-25 2021-12-09 Negative electrode for lithium ion cell battery, lithium ion cell battery, method of manufacturing negative electrode for lithium ion cell battery, and method of manufacturing lithium ion cell battery

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