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WO2017221677A1 - Batterie rechargeable au lithium - Google Patents

Batterie rechargeable au lithium Download PDF

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Publication number
WO2017221677A1
WO2017221677A1 PCT/JP2017/020787 JP2017020787W WO2017221677A1 WO 2017221677 A1 WO2017221677 A1 WO 2017221677A1 JP 2017020787 W JP2017020787 W JP 2017020787W WO 2017221677 A1 WO2017221677 A1 WO 2017221677A1
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Prior art keywords
positive electrode
negative electrode
particles
ceramic
battery
Prior art date
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Ceased
Application number
PCT/JP2017/020787
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English (en)
Japanese (ja)
Inventor
西村　悦子
和明 直江
新平 尼崎
野家　明彦
鈴木　修一
千恵子 荒木
繁貴 坪内
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Hitachi Ltd
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Hitachi Ltd
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Priority to KR1020187032829A priority Critical patent/KR20180132138A/ko
Priority to JP2018523665A priority patent/JPWO2017221677A1/ja
Priority to CN201780032421.4A priority patent/CN109155384A/zh
Publication of WO2017221677A1 publication Critical patent/WO2017221677A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
    • H01M50/491—Porosity
    • 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
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/431—Inorganic material
    • H01M50/434—Ceramics
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/443—Particulate material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/463—Separators, membranes or diaphragms characterised by their shape
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G23/00—Compounds of titanium
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2220/00—Batteries for particular applications
    • H01M2220/20—Batteries in motive systems, e.g. vehicle, ship, plane
    • 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
    • Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
    • Y02T10/00—Road transport of goods or passengers
    • Y02T10/60—Other road transportation technologies with climate change mitigation effect
    • Y02T10/70—Energy storage systems for electromobility, e.g. batteries

Definitions

  • the present invention relates to a lithium secondary battery having excellent output characteristics.
  • Lithium secondary batteries have high energy density and are attracting attention as batteries for electric vehicles and power storage.
  • electric vehicles include zero-emission electric vehicles that are not equipped with an engine, hybrid electric vehicles that are equipped with both an engine and a secondary battery, and plug-in electric vehicles that are charged from a system power source.
  • output characteristics at a large current are required for a lithium secondary battery.
  • there are various means as conventional techniques for improving the output characteristics of the lithium secondary battery and in particular, there are the following prior arts as means for promoting the reaction of insertion / extraction of lithium ions.
  • Patent Document 1 in an all-solid lithium secondary battery, a modifier having a relative dielectric constant higher than that of the solid electrolyte material is arranged at the interface between the positive electrode active material and the solid electrolyte material, and the positive electrode and the solid electrolyte A technique for reducing the interfacial resistance is disclosed.
  • Patent Document 2 discloses a technique in which a ferroelectric substance is added to a positive electrode to improve ion conductivity and reduce resistance.
  • Patent Document 3 a modifier having a relative dielectric constant higher than that of the electrolyte material is disposed at an interface between at least one of the positive electrode active material and the negative electrode active material and the electrolyte material. A technique for reducing the interface resistance is disclosed.
  • Patent Document 4 an inorganic particle layer containing a binder and inorganic particles exists between a positive electrode plate and a separator and / or a negative electrode plate and a separator, and LiPF 2 O 2 is used as the nonaqueous electrolyte.
  • a technique for adding (lithium difluorophosphate) is disclosed.
  • Patent Documents 1, 2, and 3 relate to all-solid lithium secondary batteries, and attempt to reduce the interface resistance between an active material and an electrolyte. In a lithium ion battery using an electrolytic solution, this interfacial resistance is remarkably small, and technical problems are different. Therefore, these techniques cannot be applied.
  • Patent Document 4 is an invention related to an increase in the output of a lithium ion battery using an electrolytic solution.
  • inorganic particles are as small as 300 nm, the pores of the inorganic particle layer become too small, and lithium ion permeability (that is, electrolysis). (Liquid resistance) may deteriorate.
  • An object of the present invention is to reduce resistance between a positive electrode and a negative electrode in a lithium ion secondary battery in which an inorganic particle layer (for example, a ceramic layer) is provided between the positive electrode and the negative electrode and an electrolytic solution is used. .
  • an inorganic particle layer for example, a ceramic layer
  • the means for solving the above problems are, for example, as follows.
  • the relationship between the average particle diameter (Da) of the ceramic particles and the average particle diameter (Db) of the dielectric particles is 30 ⁇ m or less, and Db / Da is in the range of Db / Da ⁇ 0.2.
  • a volume ratio of the dielectric to the sum of the volumes of the dielectric is in the range of 1 to 40 vol%.
  • the resistance between the positive electrode and the negative electrode can be reduced.
  • FIG. 1 is a diagram schematically showing the internal structure of the lithium secondary battery 101.
  • the lithium secondary battery 101 is an electrochemical device that can store or use electric energy by occlusion / release of lithium ions to and from an electrode in a non-aqueous electrolyte.
  • the lithium secondary battery 101 has a configuration in which an electrode group composed of a positive electrode 107, a negative electrode 108, and a ceramic layer 109 is housed in a battery container 102 in a sealed state.
  • the ceramic layer 109 is formed at least on the surface of the positive electrode 107 or the negative electrode 108.
  • the ceramic layer 109 has a function of a layer that allows lithium ions to permeate by electrically insulating the positive electrode 107 and the negative electrode 108 and holding an electrolyte solution described later.
  • the electrode group can employ various configurations such as a configuration in which strip-shaped electrodes are stacked, a configuration in which strip-shaped electrodes are wound and formed into a cylindrical shape or a flat shape.
  • the battery container 102 can be selected from an arbitrary shape such as a cylindrical shape, a flat oval shape, and a square shape in accordance with the shape of the electrode group.
  • the battery case 102 accommodates the electrode group from the opening provided in the upper part, and then the opening is closed and sealed by the lid 103.
  • the lid 103 is joined to the opening of the battery case 102 by, for example, welding, caulking, adhesion, or the like, and the outer edge of the lid 103 is hermetically sealed.
  • the lid 103 has a liquid injection port for injecting the electrolyte L into the battery container 102 after sealing the opening of the battery container 102.
  • the liquid injection port is sealed with a liquid injection stopper 106 after the electrolyte L is injected into the battery container 102.
  • a safety mechanism to the liquid filling plug 106.
  • a pressure valve for releasing the pressure inside the battery container 102 may be provided.
  • the positive electrode external terminal 104 and the negative electrode external terminal 105 are fixed to the lid 103 via an insulating seal member 112, and a short circuit between both terminals 104 and 105 is prevented by the insulating seal member 112.
  • the positive external terminal 104 is connected to the positive electrode 107 via the positive lead 110 and the negative external terminal 105 is connected to the negative 108 via the negative lead 111.
  • the material of the lead wire insulating seal member 112 can be selected from fluorine resin, thermosetting resin, glass hermetic seal, etc., and any insulating material that does not react with the electrolyte L and has excellent airtightness is used. can do.
  • the insulating sheet 113 is also inserted between the electrode group and the battery container 102 so that the positive electrode 107 and the negative electrode 108 are not short-circuited through the battery container 102.
  • the positive electrode 107 a positive electrode current collector in which a positive electrode mixture layer is formed can be used.
  • the positive electrode mixture includes, for example, a positive electrode active material, a conductive agent, a binder, and a current collector.
  • Typical examples of the positive electrode active material include LiCoO 2 , LiNiO 2 , and LiMn 2 O 4 .
  • Fe (MoO 4) 3, FeF 3, LiFePO 4, LiMnPO 4 , etc. can be used.
  • LiNi 1/3 Mn 1/3 Co 1/3 O 2 was selected as the positive electrode active material.
  • LiNi 1/3 Co 1/3 Mn 1/3 O 2 was used as the active material, but a higher capacity Li 2 MnO 3 —LiMnO 2 solid solution positive electrode can also be used.
  • a high power 5V positive electrode (such as LiNi 0.5 Mn 1.5 O 4 ) may be used.
  • these high-capacity materials or high-power materials are used, the above-mentioned mixture thickness can be reduced, and the electrode area that can be stored in the battery can be increased. As a result, the resistance of the battery can be reduced to enable high output, and at the same time, the capacity of the battery can be increased as compared with the case of using a LiNi 1/3 Co 1/3 Mn 1/3 O 2 positive electrode.
  • a powder of secondary particles (granulated primary particles) of the positive electrode active material is collected.
  • some lithium primary phosphates can be used without granulating the primary particle powder.
  • the presence or absence of granulation varies depending on the type of the positive electrode active material, but any can be used as long as an inorganic particle layer can be provided on the surface of the positive electrode mixture.
  • the particle size of the positive electrode active material is specified to be equal to or less than the thickness of the mixture layer.
  • the coarse particles are removed in advance by sieving classification, wind classification or the like to produce particles having a thickness of the mixture layer or less.
  • the positive electrode active material may be used as primary particles that are not granulated, or may be granulated to use secondary particles.
  • a method for producing a positive electrode will be described assuming that secondary particles are used.
  • the average particle diameter (D 50 ) of the positive electrode active material was measured by a laser scattering method.
  • the average particle diameter D 50 is a sample of the positive electrode active material was suspended in water, a laser scattering type particle size measuring apparatus (for example, Microtrac) are measured using a.
  • D 50 is defined as the particle size when the ratio (volume fraction) to the volume of the entire sample is 50%. If the range is 3 to 20 ⁇ m, it is applicable to the present invention. When D 50 is set to a small range of 3 to 8 ⁇ m, the output characteristics are improved, which is more preferable.
  • the positive electrode active material of this example is LiNi 1/3 Co 1/3 Mn 1/3 O 2 having a D 50 of 3 to 8 ⁇ m.
  • the positive electrode slurry is applied to the positive electrode current collector and then becomes a positive electrode mixture layer by drying or the like.
  • the positive electrode active material was 88 parts by weight
  • the conductive agent was 5 parts by weight
  • the PVDF (polyvinylidene fluoride) binder was 7 parts by weight.
  • the conductive agent was a mixture of acetylene black and carbon nanotubes (CNT), and the weight composition of each was 4.7: 0.3. In addition, it changes according to the kind of material, a specific surface area, a particle size distribution, etc., and is not limited to the illustrated composition.
  • the solvent used to prepare the positive electrode slurry may be any solvent that can dissolve the binder, and 1-methyl-2-pyrrolidone was used for PVDF. Depending on the type of binder, the solvent is selected. A known kneader or disperser was used for the dispersion treatment of the positive electrode material.
  • a positive electrode slurry in which a positive electrode active material, a conductive agent, a binder, and an organic solvent are mixed is attached to a current collector by a doctor blade method, a dipping method, a spray method, etc., and then the organic solvent is dried and the positive electrode is removed by a roll press.
  • a positive electrode can be produced by pressure molding. It is also possible to stack a plurality of mixture layers on a current collector by repeating a plurality of times from application to drying.
  • the mixture density of the positive electrode mixture layer is preferably 3 g / cm 3 or more, and the conductive agent and the positive electrode active material are preferably adhered to each other. By adjusting the density, the electronic resistance of the mixture layer can be reduced.
  • an aluminum foil having a thickness of 10 to 100 ⁇ m, or an aluminum perforated foil having a thickness of 10 to 100 ⁇ m and a hole diameter of 0.1 to 10 mm, an expanded metal, a foam metal plate, or the like is used.
  • aluminum, stainless steel, titanium, and the like are also applicable.
  • any material can be used for the current collector without being limited by the material, shape, manufacturing method, or the like as long as it does not change during the use of the battery, such as dissolution and oxidation.
  • the thickness of the positive electrode mixture layer is desirably equal to or greater than the average particle diameter.
  • the average particle diameter (D 50 ) of the positive electrode active material of the present invention is measured by a laser scattering method, and the range thereof is preferably 3 to 20 ⁇ m, particularly preferably 3 to 8 ⁇ m.
  • the resistance can be reduced by setting the mixture thickness to 10 ⁇ m or more.
  • the upper limit of the thickness of the positive electrode mixture is 40 ⁇ m or less, and particularly preferably 30 ⁇ m or less.
  • the positive electrode mixture layer has a thickness of 50 ⁇ m or more, unless the conductive agent is added in a large amount to the positive electrode mixture, the charge level of the positive electrode active material near the surface of the mixture and the current collector surface is uneven and uneven. This is because charging / discharging occurs.
  • the amount of the conductive agent is increased, the positive electrode volume becomes bulky, and the energy density of the battery may decrease.
  • a negative electrode current collector in which a negative electrode mixture layer is formed can be used.
  • the negative electrode mixture has a negative electrode active material, a binder, and a current collector.
  • the negative electrode active material for example, natural graphite coated with amorphous carbon can be used. In this example, natural graphite coated with amorphous carbon was used.
  • a method of forming amorphous carbon on the surface of natural graphite there is a method of depositing pyrolytic carbon on the negative electrode active material powder.
  • low molecular hydrocarbons such as ethane, propane and butane
  • an inert gas such as argon
  • hydrogen is desorbed from the hydrocarbons on the surface of the negative electrode active material particles, and the negative electrode active Carbon is deposited on the surface of the material particles.
  • Carbon is an amorphous form.
  • heat treatment is performed at 300 to 1000 ° C. in an inert gas atmosphere, so that hydrogen and oxygen are desorbed in the form of hydrogen, carbon monoxide, and carbon dioxide. Only carbon can be deposited on the surface of the negative electrode active material.
  • a gas in which 1% propane and 99% argon were mixed was brought into contact with the negative electrode active material at 1000 ° C. to deposit carbon.
  • the amount of carbon deposited is desirably in the range of 1 to 30% by weight. In this example, 2% by weight of carbon was deposited on the surface of the negative electrode active material. Carbon coating not only increases the discharge capacity at the first cycle, but is also effective for increasing cycle life characteristics and rate characteristics.
  • the negative electrode 112 In order to produce the negative electrode 112, it is necessary to prepare a negative electrode slurry. After the negative electrode slurry is applied to the negative electrode current collector, it becomes a negative electrode mixture layer by drying or the like.
  • the addition amount of the conductive agent was x
  • the negative electrode active material was 96-x parts by weight
  • the conductive agent was x parts by weight
  • the PVDF (polyvinylidene fluoride) binder was 4 parts by weight.
  • x is the amount of the fibrous conductive agent added.
  • carbon nanotubes (CNT) were used as the fibrous carbon, and the addition amount x was 0.1.
  • conductive agents such as acetylene black may be mixed in the same manner as the positive electrode.
  • a styrene butadiene rubber and carboxymethyl cellulose binder may be used instead of PVDF.
  • fluorine rubber, ethylene / propylene rubber, polyacrylic acid, polyimide, polyamide and the like can be used, and there is no restriction in the present invention. Any binder that does not decompose on the surface of the negative electrode and does not dissolve in the electrolyte can be used in the present invention.
  • the solvent used for preparing the negative electrode slurry may be any solvent that can dissolve the binder, and 1-methyl-2-pyrrolidone was used for PVDF. Depending on the type of binder, the solvent is selected. For example, when using a styrene butadiene rubber and carboxymethyl cellulose binder, water is used as a solvent. A known kneader and disperser were used for the dispersion treatment of the negative electrode material.
  • a known technique such as a doctor blade method, a dipping method, or a spray method can be applied to apply the negative electrode slurry to the negative electrode current collector. It is also possible to form a multilayer mixture layer on the current collector by performing a plurality of times from application to drying. In this example, the coating was performed once on the copper foil by the doctor blade method.
  • the thickness of the negative electrode mixture layer is desirably equal to or greater than the average particle diameter. When the thickness is equal to or less than the average particle size, the electron conductivity between adjacent particles may be deteriorated.
  • the mixture thickness is preferably 10 ⁇ m or more, more preferably 15 ⁇ m or more. Further, the upper limit of the negative electrode mixture thickness is desirably 50 ⁇ m or less. If the thickness is more than that, unless the conductive agent is added in a large amount to the negative electrode mixture, the charge level of the negative electrode active material near the surface of the mixture and the current collector surface varies, and uneven charge and discharge occur. When the amount of the conductive agent is increased, the negative electrode volume becomes bulky, and the energy density of the battery decreases.
  • graphite is used as the negative electrode active material, but silicon, tin, or a compound thereof (oxide, nitride, and alloy with other metals) may be used as the negative electrode active material.
  • These active materials are larger than the theoretical capacity of graphite (372 Ah / kg), and a capacity of 500 to 3600 Ah / kg is obtained.
  • the above-mentioned mixture thickness can be reduced, and the electrode area that can be accommodated in the battery can be increased.
  • the resistance of the battery can be reduced to enable high output, and at the same time, the capacity of the battery can be increased as compared with the case where a graphite negative electrode is used.
  • Examples of the negative electrode current collector that can be used in the present invention include a copper foil having a thickness of 10 to 100 ⁇ m, a copper perforated foil having a thickness of 10 to 100 ⁇ m and a pore diameter of 0.1 to 10 mm, an expanded metal, and a foam metal plate.
  • a copper foil having a thickness of 10 to 100 ⁇ m a copper perforated foil having a thickness of 10 to 100 ⁇ m and a pore diameter of 0.1 to 10 mm
  • an expanded metal and a foam metal plate.
  • An arbitrary current collector can be used without being limited by the material, shape, manufacturing method, and the like. In this example and comparative example, a rolled copper foil having a thickness of 10 ⁇ m was used.
  • a ceramic layer 109 is provided as an inorganic particle layer. Thereby, it will be in the state by which the ceramic layer was provided between the positive mix layer and the negative mix layer.
  • a method for producing a ceramic layer on both electrodes will be described. In Example 1, the ceramic layer is formed only on the positive electrode mixture layer.
  • the ceramic layer 109 has ceramic particles and dielectric particles. Ceramic particles and dielectric particles are oxides containing a metal element, and both must be insoluble in the electrolytic solution.
  • the ceramic particles and the dielectric particles are selected to have an optimal average particle size (D 50 ) ratio.
  • D 50 represents a D 50 of the ceramic particles and Da, denoted the D 50 of the dielectric particles and Db.
  • Da is preferably 1 ⁇ m or more and 30 ⁇ m or less. This is because the thickness of the ceramic layer is 30 ⁇ m or less. If the ceramic layer becomes too thick, the movement distance of lithium ions that permeate through the pores inside the ceramic layer becomes too long, and the electrolyte resistance may increase. Further, when considering the case where the same battery container is filled with the electrode and the ceramic layer, the increase in the thickness of the ceramic layer relatively decreases the amount of the battery active material and decreases the battery capacity. Therefore, if the insulation between the positive electrode and the negative electrode can be ensured, it can serve as a ceramic layer. Therefore, the thickness of the ceramic layer is preferably 30 ⁇ m or less.
  • the thickness of the ceramic layer may be further reduced to 2 ⁇ m. Since Da is 1 ⁇ m, the insulation between the positive electrode and the negative electrode can be ensured if at least a thickness equivalent to two ceramic particles can be ensured. When the thickness is equivalent to one ceramic particle (1 ⁇ m), a part of the electrode surface is exposed due to dropping of the ceramic particles, and there is a risk of short circuit between the positive electrode and the negative electrode. Moreover, in order to prevent the positive electrode and the negative electrode from being short-circuited due to the mixing of metal foreign matters during production, the thickness of the ceramic layer is desirably 5 ⁇ m or more. Considering that the thickness unevenness (unevenness on the surface) between the positive electrode and the negative electrode is 1 to 2 ⁇ m, it is more preferable that the thickness of the ceramic layer is 10 ⁇ m or more.
  • the pores of the ceramic layer are determined by the size of the ceramic particles. As D 50 is large, the pore size is increased, the pore size becomes smaller as D 50 is reduced.
  • the lower limit value 1 ⁇ m of Da is a limit value at which the pore diameter becomes too small to deteriorate the lithium ion permeability.
  • the ceramic particles not only function as an insulator for the positive electrode and the negative electrode, but also function as a medium for forming pores that allow lithium ions to pass therethrough.
  • the dielectric particles have a function of promoting the dissociation of the electrolyte in the ceramic layer and reducing the electrolyte resistance of the ceramic layer.
  • Db of the dielectric particles is preferably controlled so as to satisfy Db / Da ⁇ 0.2. That is, small Db dielectric particles that are 1/5 or less of the average particle diameter Da of the ceramic particles are used.
  • the dielectric particles are added so as to be incorporated into the ceramic particles. It is undesirable for this to block the pores formed in the gaps between the ceramic particles. In order to avoid clogging of the pores, it is preferable to use dielectric particles having a smaller particle size than ceramic particles.
  • the volume ratio of the dielectric to the volume of the ceramic layer is preferably in the range of 1 to 40 vol%.
  • the volume ratio of the dielectric particles is less than 1 vol%, it is difficult to obtain the effect of dissociating the electrolyte.
  • it exceeds 40 vol% the ratio of the ceramic particles becomes too small, and the insulating properties of the ceramic layer may be deteriorated. This is because the dielectric has a lower electronic resistance than the ceramic particles, so that the excessively added dielectric particles come into contact with each other, and the electric resistance of the ceramic layer is reduced.
  • the ceramic layer is formed on the positive electrode or the negative electrode.
  • ceramic particles and dielectric particles are stirred and mixed thoroughly.
  • NMP 1-methyl-2-pyrrolidone
  • This processing method is the same as the method for producing the positive electrode slurry.
  • the prepared ceramic layer slurry is applied to the surface of the positive electrode or the negative electrode, and the NMP is removed by drying to obtain a ceramic layer. After forming the ceramic layer, it may be compressed by a roll press or may be omitted.
  • an electrolyte solution that can be used in the present invention, a solvent obtained by mixing dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, and the like with ethylene carbonate, lithium hexafluorophosphate (LiPF 6 ), or lithium borofluoride (Li There is a solution in which LiBF 4 ) is dissolved.
  • the present invention is not limited to the type of solvent and electrolyte, and the mixing ratio of solvents, and other electrolytes can be used.
  • the electrolyte can also be used in a state of being contained in an ion conductive polymer such as polyvinylidene fluoride and polyethylene oxide. Since the ceramic layer 109 of the present invention prevents the positive electrode 107 and the negative electrode 108 from being short-circuited, a conventional resin separator can be dispensed with.
  • Solvents that can be used for the electrolyte are propylene carbonate, ethylene carbonate, butylene carbonate, vinylene carbonate, ⁇ -butyrolactone, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, 1, 2-dimethoxyethane, 2-methyltetrahydrofuran, dimethyl Sulfoxide, 1, 3-dioxolane, formamide, dimethylformamide, methyl propionate, ethyl propionate, phosphate triester, trimethoxymethane, dioxolane, diethyl ether, sulfolane, 3-methyl-2-oxazolidinone, tetrahydrofuran, 1 ,
  • Non-aqueous solvents such as 2-diethoxyethane, chloroethylene carbonate, and chloropropylene carbonate. Other solvents may be used as long as they do not decompose on the positive electrode or negative electrode incorporated in the battery of the present invention.
  • the electrolyte the chemical formula LiPF 6, LiBF 4, LiClO 4 , LiCF 3 SO 3, LiCF 3 CO 2, LiAsF 6, LiSbF 6, or multi such imide lithium salts represented by lithium trifluoromethane sulfonimide
  • LiPF 6, LiBF 4, LiClO 4 , LiCF 3 SO 3, LiCF 3 CO 2, LiAsF 6, LiSbF 6, or multi such imide lithium salts represented by lithium trifluoromethane sulfonimide There are different types of lithium salts.
  • a non-aqueous electrolytic solution obtained by dissolving these salts in the above-described solvent can be used as a battery electrolytic solution.
  • An electrolyte other than this may be used as long as it does not decompose on the positive electrode or the negative electrode incorporated in the battery of the present invention.
  • an electrolytic solution and a solid polymer electrolyte (polymer electrolyte)
  • an ion conductive polymer such as ethylene oxide, acrylonitrile, polyvinylidene fluoride, methyl methacrylate, or hexafluoropropylene polyethylene oxide may be used as the polymer electrolyte. it can.
  • These solid polymer electrolytes can be used by impregnating the ceramic layer 109.
  • an ionic liquid can be used.
  • EMI-BF 4 1-ethyl-3-methylimidazole tetrafluoroborate
  • LiTFSI lithium salt LiN
  • triglyme and tetraglyme a mixed complex of lithium salt LiN (SO 2 CF 3 ) 2 (LiTFSI), triglyme and tetraglyme, a cyclic quaternary ammonium cation (N—
  • the combination of methyl-N-propylpyrrolidinium and imide anion (exemplified by bis (fluorosulfonyl) imide) that does not decompose at the positive electrode and the negative electrode is selected to provide the lithium secondary battery of the present invention.
  • a solid polymer electrolyte (polymer electrolyte) or a gel electrolyte can be used.
  • a known polymer electrolyte such as polyethylene oxide or a mixture (gel electrolyte) of polyvinylidene fluoride and a nonaqueous electrolytic solution can be used.
  • An ionic liquid may be used.
  • an electrolytic solution in which 1 mol concentration (1M 1 mol / dm 3 ) of LiPF 6 was dissolved in a mixed solvent of ethylene carbonate (denoted as EC) and ethyl methyl carbonate (denoted as EMC) was used. .
  • the mixing ratio of EC and EMC was 1: 2.
  • the electrolyte concentration was 1 molar as a reference value.
  • 1% vinylene carbonate was added to the electrolytic solution.
  • Electrolytic solution L is held on the surface of ceramic layer 109 and electrodes 107 and 108 and in the pores.
  • the positive electrode 107 and the negative electrode 108 on which the ceramic layer 109 is formed are stacked.
  • the ceramic layer 109 may be formed on either surface of the positive electrode 107 and the negative electrode 108, or may be formed on both surfaces. The ceramic layer 109 prevents a short circuit between the positive electrode 107 and the negative electrode 108.
  • the ceramic layer 109 needs to allow lithium ions to permeate during charging and discharging of the battery, it can be used if the pore diameter is generally 0.01 to 10 ⁇ m and the porosity is 20 to 90%.
  • the thickness is 2 ⁇ m to 30 ⁇ m, desirably 5 ⁇ m to 30 ⁇ m, and more preferably 10 ⁇ m to 30 ⁇ m.
  • the porosity of the ceramic layer is 30% or more and 90% or less.
  • An insulating sheet 113 is inserted between the electrode disposed at the end of the electrode group and the battery container 102 so that the positive electrode 107 and the negative electrode 108 are not short-circuited through the battery container 102.
  • the upper part of the laminate is electrically connected to an external terminal via a lead wire.
  • the positive electrode 107 is connected to the positive electrode external terminal 104 of the lid 103 via the positive electrode lead wire 110.
  • the negative electrode 108 is connected to the negative electrode external terminal 105 of the lid 103 via the negative electrode lead wire 111.
  • the lead wires 110 and 111 can take any shape such as a wire shape or a plate shape.
  • the lead wires 110 and 111 may have any shape and material depending on the structure of the battery can 113 as long as the structure can reduce the ohmic loss when an electric current is applied and does not react with the electrolyte. You can choose.
  • the material of the battery container 102 is selected from materials that are corrosion resistant to non-aqueous electrolytes, such as aluminum, stainless steel, steel, and nickel-plated steel.
  • the lid 103 is brought into close contact with the battery container 102 and the whole battery is sealed.
  • the lid 103 is attached to the battery container 102 by caulking.
  • a known technique such as welding or adhesion may be applied to the method for sealing the battery.
  • the rated capacity (calculated value) of the battery manufactured as an example is 3 Ah.
  • each numerical value, compound and the like in each example are shown in Table 1. From the left side of the table, the type and composition of ceramic particles used in the ceramic layer and the average particle size Da, the type and composition of dielectric particles and the average particle size Db, the ratio of Db / Da, the volume of the ceramic particles and the dielectric particles. The volume ratio of dielectric particles to the sum, the type and composition of the binder, the type of electrode on which the ceramic layer was formed and the thickness of the ceramic layer, and finally the initial value of the DC resistance (DCR) of the lithium secondary battery and 1 at 50 ° C. The DCR measured after standing for a week is shown.
  • DCR DC resistance
  • the reference value of DCR is the initial DCR value of Comparative Example 1 (Table 2), and this is taken as 100%, and the ratios of all other measured values are expressed as percentages.
  • Example 2 In Example 1, the volume ratio of the dielectric particles was changed from 1.1 to 40%, and the influence of the addition amount of the dielectric particles on the DCR was evaluated. From these examples, the volume ratio of the dielectric particles to the sum of the volume of the ceramic particles and the dielectric particles is in the range of 1 to 40%, and the initial DCR is smaller than 100% (reference value of Comparative Example 1). became. That is, in these examples, it can be seen that the electrolyte resistance in the ceramic layer was reduced. Even when left at 50 ° C. for one week, the increase rate of DCR was as small as 8% or less. Compared with the results of Comparative Examples 1 to 3 (Table 2), which will be described later, these Examples were superior in durability at the initial stage and after standing at high temperature.
  • Example 6 Example 10
  • Example 6 DCR when the ceramic particles were changed to SiO 2 , ZrO 2 , TiO 2 , MgO, AlO (OH) was evaluated.
  • the initial DCR was smaller than 100%, and the DCR increase rate after being left at 50 ° C. was as small as 1%.
  • a single dielectric was used, but similar results were obtained even when two or more kinds of mixtures were used, and the DCR substantially coincided with the average value when added alone.
  • Example 11 In Example 1, the DCR when the Ba element of the dielectric particle BaTiO 3 was replaced with La and Sr was evaluated. Compared with Example 1, it was found that the initial DCR was further reduced, and the electrolyte resistance of the ceramic layer was reduced. Also, the DCR increase rate after leaving at 50 ° C. was small.
  • Example 13 In Example 1, the average particle diameter Db of the dielectric was changed to 0.3 ⁇ m and 0.1 ⁇ m, and Db / Da was examined up to a small value of 0.03. There was a tendency for the initial DCR to decrease as Db / Da decreased. It is presumed that the DCR decreased because the void volume between the ceramic particles increased due to the decrease in the dielectric particle size.
  • Example 15 In Example 15, the ceramic layer formed on the positive electrode in Example 2 was provided on the negative electrode. In Example 16, the ceramic layer formed on the positive electrode in Example 3 was provided on the negative electrode. The same results as in Example 2 and Example 3 were obtained, and it was shown that even when a ceramic layer was formed on the negative electrode, the electrolyte resistance of the ceramic layer was reduced and the DCR was reduced.
  • Example 17 In Example 3, ceramic layers were formed on both the positive electrode and the negative electrode. 1/2 of the thickness of the ceramic layer described in the table was prepared on each surface of the positive electrode and the negative electrode. In Example 17, a 10 ⁇ m ceramic layer was formed on the positive electrode and the negative electrode. In Example 18, a 15 ⁇ m ceramic layer was formed on the positive electrode and the negative electrode.
  • the initial DCR was as low as 84 to 87%, and the DCR increase rate after being left at 50 ° C. was as small as 1%.
  • electrolyte solution resistance increases with the increase in the thickness of a ceramic layer, since electrode resistance occupies most of DCR rather than electrolyte solution resistance, the increase in DCR by increase in electrolyte solution resistance was only 1%.
  • Example 19 The average particle diameter of Al 2 O 3 used in Example 18 was 30 ⁇ m, and a ceramic layer having a thickness of 30 ⁇ m was formed only on the negative electrode.
  • Other manufacturing conditions were the same as those in Example 18.
  • the initial DCR was 80%, which was slightly larger than Example 17, but the DCR increase after being left at 50 ° C. could be suppressed to 1%.
  • FIG. 2 are the batteries of Example 14, and FIG. 2 is the battery system of the present invention in which these are connected in series.
  • Each of the lithium ion batteries 201a and 201b has an electrode group having the same specifications including a positive electrode 207, a negative electrode 208, and a ceramic layer 209, and a positive external terminal 204 and a negative external terminal 205 are provided on the upper part.
  • An insulating seal member 212 is inserted between each external terminal and the battery container so that the external terminals are not short-circuited.
  • components corresponding to the positive electrode lead wire 110 and the negative electrode lead wire 111 in FIG. 1 are omitted, but the internal structure of the lithium ion batteries 201a and 201b is the same as that in FIG.
  • the negative external terminal 205 of the lithium ion battery 201a is connected to the negative input terminal of the charge controller 216 by the power cable 213.
  • the positive external terminal 204 of the lithium ion battery 201a is connected to the negative external terminal 205 of the lithium ion battery 201b via the power cable 214.
  • a positive external terminal 204 of the lithium ion battery 201 b is connected to a positive input terminal of the charge controller 216 by a power cable 215.
  • the charge / discharge controller 216 exchanges power with an externally installed device (hereinafter referred to as an external device) 219 via the power cables 217 and 218.
  • the external device 219 includes various electric devices such as an external power source and a regenerative motor for supplying power to the charge / discharge controller 216, and an inverter, a converter, and a load that supply power from the system.
  • An inverter or the like may be provided depending on the type of AC and DC that the external device supports. As these devices, known devices can be arbitrarily applied.
  • a power generation device 222 that simulates the operating conditions of a wind power generator was installed as a device that generates renewable energy, and was connected to the charge / discharge controller 216 via the power cables 220 and 221.
  • the charge / discharge controller 216 shifts to the charging mode, supplies power to the external device 219, and charges surplus power to the lithium ion batteries 201a and 212b.
  • the charge / discharge controller 216 operates to discharge the lithium ion batteries 201a and 212b.
  • the power generation device 222 can be replaced with another power generation device, that is, any device such as a solar cell, a geothermal power generation device, a fuel cell, or a gas turbine generator.
  • the charge / discharge controller 216 stores a program that can be automatically operated so as to perform the above-described operation.
  • the lithium ion batteries 201a and 201b are normally charged so that a rated capacity can be obtained. For example, 2.8V constant voltage charging can be performed for 0.5 hour at a charging current of 1 hour rate. Since the charging conditions are determined by the design of the material and amount of use of the lithium ion battery, the conditions are optimal for each battery specification.
  • the charge / discharge controller 216 After charging the lithium ion batteries 201a and 201b, the charge / discharge controller 216 is switched to the discharge mode to discharge each battery. Normally, the discharge is stopped when a certain lower limit voltage is reached.
  • the external device 219 supplies power during charging and consumes power during discharging.
  • charging is performed at a 2-hour rate, and discharging is performed at a 1-hour rate (1C).
  • the initial discharge capacity was determined.
  • a capacity of 99.5 to 100% of the design capacity 3Ah of each battery 201a, 201b was obtained.
  • a charge / discharge cycle test described below was conducted under the condition of an environmental temperature of 20 to 30 ° C.
  • Comparative Example 1 is a result obtained when no dielectric particles were used in Example 1.
  • the initial DCR was set to 100%, which was the reference value for all examples and comparative examples. Based on this, the DCR after standing at 50 ° C. increased to 130%.
  • Comparative Example 2 is a DCR measurement result when the volume ratio of the dielectric to the sum of the ceramic particles and the dielectric is 0.1%. Compared with Example 1, it can be seen that the DCR is large.
  • Comparative Example 3 shows the battery specifications and DCR measurement results when the amount of dielectric added is increased and the volume ratio (composition) is 40% in Example 1.
  • the initial DCR is low, the dielectric particles are connected to each other, and the battery voltage after being left at 50 ° C. is 1 V or less due to a minute leakage current. That is, overdischarge occurred and the electrode deteriorated. As a result, the DCR significantly increased after standing at 50 ° C.
  • Comparative Example 4 is a DCR measurement result when Db / Da is increased to 0.33 in Example 1.
  • Db approaches Da
  • the dielectric particles close the pores formed by the ceramic particles, and the diffusion of lithium ions is easily inhibited.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Inorganic Chemistry (AREA)
  • Ceramic Engineering (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Secondary Cells (AREA)
  • Cell Separators (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)

Abstract

L'objectif de la présente invention est de réduire la résistance entre une électrode positive et une électrode négative. Une batterie rechargeable au ion lithium qui comprend une électrode positive ayant une couche de mixture d'électrode positive, une électrode négative ayant une couche de mixture d'électrode négative et une couche céramique disposée entre la couche de mixture d'électrode positive et la couche mixture d'électrode négative, et où la couche céramique contient des particules céramiques et diélectriques représentées par Ba1-xMxTiO3(où M est une molécule de La ou Sr et x est dans la plage de 0 à 0.1);les particules céramiques ont environ un diamètre (Da) allant de 1 μm à 30 μm(inclue);la relation entre le diamètre(Da) approximatif des particules céramiques et le diamètre (Db) approximatif des particules diélectriques, appelé Db/Da satisfait Db/Da ≤ 0.2; et le ration volume des particules diélectriques relatif à la somme du volume de particules céramiques et le volume des particules diélectriques est à l'intérieure de la plage de 1-40 vol%.
PCT/JP2017/020787 2016-06-23 2017-06-05 Batterie rechargeable au lithium Ceased WO2017221677A1 (fr)

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