WO2022118443A1 - Électrolyte et batterie à deux ions - Google Patents

Électrolyte et batterie à deux ions Download PDF

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WO2022118443A1
WO2022118443A1 PCT/JP2020/045107 JP2020045107W WO2022118443A1 WO 2022118443 A1 WO2022118443 A1 WO 2022118443A1 JP 2020045107 W JP2020045107 W JP 2020045107W WO 2022118443 A1 WO2022118443 A1 WO 2022118443A1
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negative electrode
positive electrode
active material
electrode active
mass
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PCT/JP2020/045107
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Japanese (ja)
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由磨 五行
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昭和電工マテリアルズ株式会社
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Priority to JP2022566588A priority Critical patent/JPWO2022118443A1/ja
Priority to PCT/JP2020/045107 priority patent/WO2022118443A1/fr
Publication of WO2022118443A1 publication Critical patent/WO2022118443A1/fr

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0568—Liquid materials characterised by the solutes
    • 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
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0569—Liquid materials characterised by the solvents

Definitions

  • the present invention relates to an electrolyte and a dual ion battery.
  • Dual-ion batteries are attracting attention as secondary batteries with excellent input / output characteristics.
  • the dual ion battery is a secondary battery in which charging and discharging proceed by inserting and desorbing an anion in an electrolyte into a positive electrode and inserting and desorbing a cation in an electrolyte into a negative electrode.
  • DIBs a battery in which a carbon material is used for the positive electrode and the negative electrode is called a dual carbon battery (DCB).
  • Patent Document 1 describes a positive electrode containing a positive electrode active material into which an anion can be inserted or removed, a negative electrode containing a negative electrode active material, a non-aqueous solvent, an electrolyte salt containing a halogen atom, and an anion containing a halogen atom.
  • a non-aqueous electrolyte storage element having a compound having a possible moiety and a non-aqueous electrolytic solution containing a cyclic sulfonic acid ester has been proposed.
  • the charge / discharge efficiency, the discharge capacity, and the cycle characteristics can be improved by preventing the decomposition of the non-aqueous electrolyte.
  • Patent Document 1 discloses the use of a non-aqueous solvent such as dimethyl carbonate.
  • the present inventors have focused on the fact that the ionic liquid is non-volatile and has high stability as compared with a non-aqueous solvent such as dimethyl carbonate, and considered applying the ionic liquid to the electrolyte of the dual ion battery. did.
  • One form of the present disclosure is made in view of the above-mentioned conventional circumstances, and is an electrolyte capable of producing a dual ion battery capable of reversibly performing an electrochemical reaction and functioning as a secondary battery. , And a dual ion battery capable of reversibly performing an electrochemical reaction.
  • a positive electrode containing a positive electrode active material containing a lithium salt, a heterocyclic non-aromatic cation containing a nitrogen element in its structure, and a bis (trifluoromethanesulfonyl) imide anion, and an anion can be inserted and removed, and a negative electrode active material.
  • the heterocyclic non-aromatic cation contains at least one cation of a Helicobacter pylori cation and a piperidinium cation.
  • ⁇ 3> The electrolyte according to ⁇ 1> or ⁇ 2>, further comprising at least one compound selected from the group consisting of a sulfite compound, an organic borane compound, a cyclic sulfonic acid ester, and a dinitrile compound.
  • ⁇ 4> The electrolyte according to any one of ⁇ 1> to ⁇ 3>, wherein the heterocyclic non-aromatic cation contains a Helicobacter pyloridinium cation.
  • a dual ion battery comprising a positive electrode containing a positive electrode active material capable of inserting and removing anions, a negative electrode containing a negative electrode active material, and an electrolyte of any one of ⁇ 1> to ⁇ 4>.
  • the negative electrode active material contains at least one of graphite, lithium titanate, aluminum metal, and lithium metal.
  • an electrochemical reaction can be reversibly carried out, an electrolyte capable of producing a dual ion battery capable of functioning as a secondary battery, and an electrochemical reaction can be carried out reversibly. It is possible to provide a dual ion battery capable of being capable.
  • FIG. 1 It is a perspective view which shows an example of the dual ion battery of this disclosure. It is a perspective view which shows the positive electrode plate, the negative electrode plate, a separator and a gas storage member which make up an electrode group. It is a graph which shows the result of the charge / discharge test in Example 1.
  • FIG. 2 It is a graph which shows the result of the charge / discharge test in Example 2.
  • the present invention is not limited to the following embodiments.
  • the components including element steps and the like are not essential unless otherwise specified.
  • various changes and modifications by those skilled in the art are possible within the scope of the technical idea disclosed in the present disclosure.
  • the term "process” includes, in addition to a process independent of other processes, the process as long as the purpose of the process is achieved even if it cannot be clearly distinguished from the other process. ..
  • the numerical range indicated by using "-" includes the numerical values before and after "-" as the minimum value and the maximum value, respectively.
  • each component may contain a plurality of applicable substances.
  • the content rate of each component means the total content rate of the plurality of substances unless otherwise specified.
  • a plurality of types of particles corresponding to each component may be contained.
  • the particle size of each component means a value for a mixture of the plurality of types of particles unless otherwise specified.
  • the term "layer” or “membrane” is used only in a part of the region, in addition to the case where the layer or the membrane is formed in the entire region when the region is observed. The case where it is formed is also included.
  • the "solid content" of the positive electrode mixture or the negative electrode mixture means the remaining components obtained by removing volatile components such as organic solvents from the slurry of the positive electrode mixture or the slurry of the negative electrode mixture.
  • the "positive electrode active material capable of inserting and removing anions” means a positive electrode active material capable of reversibly inserting and removing anions into the crystals of the positive electrode active material.
  • the "negative electrode active material capable of inserting and removing a cation” means a negative electrode active material capable of reversibly inserting and removing a cation into a crystallite of the negative electrode active material. Therefore, a negative electrode active material that repeatedly precipitates lithium ions and dissolves the precipitated lithium metal, such as lithium metal, is not included in the negative electrode active material capable of inserting and removing the cation of the present disclosure.
  • the electrolytes of the present disclosure include a lithium salt, a heterocyclic non-aromatic cation containing a nitrogen element in the structure, and a bis (trifluoromethanesulfonyl) imide anion, and a positive electrode containing a positive electrode active material capable of inserting and removing the anion.
  • An electrolyte for use in a dual ion battery comprising a negative electrode containing a negative electrode active material.
  • the electrolyte of the present disclosure it is possible to reversibly carry out an electrochemical reaction, and it is possible to manufacture a dual ion battery that can function as a secondary battery. Since the positive electrode of the dual ion battery undergoes the reaction at a high potential of 4.5 V or more, the electrolytic solution is required to have oxidation resistance. Since the ionic liquid containing a heterocyclic non-aromatic cation such as a pyrrolidinium cation and a bis (trifluoromethanesulfonyl) imide anion has excellent electrochemical stability, it is considered that the reaction proceeds reversibly.
  • a heterocyclic non-aromatic cation such as a pyrrolidinium cation and a bis (trifluoromethanesulfonyl) imide anion
  • Lithium salt The electrolytes of the present disclosure include lithium salts.
  • Lithium salts include LiPF 6 , LiBF 4 , LiFSI (lithium bis (fluorosulfonyl) imide), LiTFSI (lithium bis (trifluoromethanesulfonyl) imide), LiClO 4 , LiB (C 6 H 5 ) 4 , LiCH 3 SO 3 , LiCF 3 SO 3 , LiN (SO 2 CF 2 CF 3 ) 2 , and the like.
  • the lithium salt one kind may be used alone, or two or more kinds may be used in combination.
  • the concentration of the lithium salt in the electrolyte is preferably 0.5 mol / L or more, and more preferably 1.5 mol / L or more.
  • the upper limit of the concentration of the lithium salt is not particularly limited and may be 3.0 mol / L or less, or 2.5 mol / L or less.
  • the electrolyte of the present disclosure includes a heterocyclic non-aromatic cation (hereinafter, also referred to as “specific cation”) containing a nitrogen element in the structure.
  • specific cation a heterocyclic non-aromatic cation
  • the heterocyclic non-aromatic cation is not particularly limited as long as it is a cation containing a heterocycle having no aromaticity, and it is preferable that the skeleton contains a cyclic structure such as a 5-membered ring or a 6-membered ring.
  • the heterocyclic non-aromatic cation may be one kind or two or more kinds.
  • cyclic structure such as a 5-membered ring or a 6-membered ring
  • a structure derived from a complex monocyclic compound such as pyrrolidine or piperidine is preferable.
  • heterocyclic non-aromatic cation examples include a pyrrolidinium cation such as 1-butyl-1-methylpyrrolidinium cation and a 1-methyl-1-propylpyrrolidinium cation, and 1-butyl-1-methylpiperidinium.
  • a pyrrolidinium cation such as 1-butyl-1-methylpyrrolidinium cation and a 1-methyl-1-propylpyrrolidinium cation
  • 1-butyl-1-methylpiperidinium examples thereof include cations, piperidinium cations such as 1-methyl-1-propylpiperidinium cations, and the like.
  • pyrrolidinium cations such as 1-butyl-1-methylpyrrolidinium cation and 1-methyl-1-propylpyrrolidinium cation are preferable from the viewpoint of electrochemical stability.
  • the electrolytes of the present disclosure include bis (trifluoromethanesulfonyl) imide anions ((CF 3 SO 2 ) 2 N- ) . Certain cations and bis (trifluoromethanesulfonyl) imide anions contained in the electrolytes of the present disclosure can serve as solvents for lithium salts.
  • the electrolyte of the present disclosure may contain cations other than specific cations (hereinafter, also referred to as “other cations”), and anions other than bis (trifluoromethanesulfonyl) imide anions (hereinafter, “other anions”). Also referred to as)).
  • other cations and the other anions may be one kind or two or more kinds independently of each other.
  • the other cations are not particularly limited as long as they are cations that do not contain a heterocyclic ring having no aromaticity, and for example, at least one element selected from the group consisting of an element of nitrogen, an element of phosphorus, an element of sulfur and an element of oxygen.
  • a cation containing a chain structure, a cyclic structure such as a 5-membered ring, a 6-membered ring, or the like in the skeleton can be mentioned.
  • the cyclic structure such as a 5-membered ring or a 6-membered ring includes furan, thiophene, pyrrole, pyridine, oxazole, isooxazole, thiazole, isothiazole, frazane, imidazole, pyrazole, pyrazine, pyrimidine, pyridazine and the like.
  • Examples thereof include a structure derived from a heterocyclic compound, a structure derived from a fused heterocyclic compound such as benzofuran, isobenzofuran, indole, isoindole, indridin, and carbazole.
  • the other cations are not particularly limited, and examples thereof include alkylammonium cations such as triethylammonium cations, imidazolium cations such as ethylmethylimidazolium cations and butylmethylimidazolium cations, and pyridinium cations such as 1-ethylpyridinium cations. ..
  • the other anions are not particularly limited, and are, for example, bis (fluorosulfonyl) imide anions ([N (SO2 F) 2 ] - ), BF 4- , PF 6- , AsF 6- , ClO 4 , NO 3 - , CF 3 SO 3- , CF 3 CO 2- and CH 3 CO 2- .
  • the content of the specific cation with respect to the total of the specific cation and other cations is preferably 50 mol% to 100 mol%, more preferably 70 mol% to 100 mol%. , 90 mol% to 100 mol% is more preferable.
  • the content of the bis (trifluoromethanesulfonyl) imide anion with respect to the total of the bis (trifluoromethanesulfonyl) imide anion and other anions is preferably 50 mol% to 100 mol%, preferably 70 mol%. It is more preferably from ⁇ 100 mol%, still more preferably from 90 mol% to 100 mol%.
  • the electrolyte of the present disclosure is at least one selected from the group consisting of a sulfite compound, an organic borane compound, a cyclic sulfonic acid ester and a dinitrile compound from the viewpoint of improving the cycle characteristics of the dual ion battery and from the viewpoint of preferably maintaining the capacity. It is preferable that the compound of the species (hereinafter, also referred to as “specific compound”) is further contained.
  • the specific compound may be used alone or in combination of two or more.
  • the sulphite compound is not particularly limited, and examples thereof include ethylene sulphite, propylene sulphite, butylene sulphite, pentenesulfite, dimethylsulfite, and dipropargyl sulphite.
  • ethylene sulphite is preferable from the viewpoint of being able to suppress side reactions while maintaining a suitable capacity.
  • the organic borane compound is not particularly limited, and is limited to tris (pentafluorophenyl) borane, tris (hexafluoroisopropyl) borate, trimesityl borane, tris (1,2 dimethylpropyl) borane, tris (parafluorophenyl) borane, and the like.
  • Tris (parachlorophenyl) borane (CH 3 O) 3 B, (C 3 F 7 CH 2 O) 3 B, [(CF 3 ) 2 CHO] 3 B, [(CF 3 ) 2 C (C 6 H 5 ) ) O] 3 B, (C 6 H 5 O) 3 B, (FC 6 H 4 O) 3 B, (F 2 C 6 H 3 O) 3 B, (F 4 C 6 HO) 3 B, (C) 6 F 5 O) 3 B, (CF 3 C 6 H 4 O) 3 B, [(CF 3 ) 2 C 6 H 3 O] 3 B, [(CF 3 ) 2 CHO] 3 B, [CF 3 CH] 2 O] 3 B, (CF 3 O) 3 B and the like.
  • tris (pentafluorophenyl) borane is preferable.
  • the cyclic sulfonic acid ester is not particularly limited, and is a monosulfonic acid ester such as 1,3-propane sulton, 1,4-butane sulton, 1,3-butane sulton, and 2,4-butan sulton; methylenemethanedisulfonic acid ester, ethylene.
  • examples thereof include disulfonic acid esters such as methane disulfonic acid ester. Of these, 1,3-propanesulton is preferable.
  • the dinitrile compound is not particularly limited, and examples thereof include malononitrile, succinonitrile, glutaronitrile, adiponitrile, pimeronitrile, suberonitrile, azelanitrile, sebaconitrile, undecanenitrile, and dodecanenitrile.
  • the content of the specific compound is preferably 0.1% by mass to 5.0% by mass, preferably 0.3% by mass to 4.0% by mass, based on the total amount of the electrolyte. More preferably, it is more preferably 0.5% by mass to 3.0% by mass.
  • the content of a specific compound is 0.1% by mass or more, it tends to be possible to manufacture a dual ion battery having better cycle characteristics, and the content of a specific compound is 5.0% by mass or less. As a result, side reactions tend to be suppressed.
  • the electrolyte of the present disclosure may contain a cyclic carbonate.
  • cyclic carbonate examples include vinylene carbonate (VC), propylene carbonate (PC), ethylene carbonate (EC), butylene carbonate (BC) and fluoroethylene carbonate (FEC). Cyclic carbonate may be used alone or in combination of two or more.
  • the content of the cyclic carbonate may be 0.05% by mass to 3% by mass, 0.2% by mass to 1.5% by mass, or 0.3% by mass or more, based on the total amount of the electrolyte. It may be 1.2% by mass, or 0.4% by mass to 0.9% by mass.
  • the electrolyte of the present disclosure may contain a non-aqueous solvent.
  • the non-aqueous solvent is not particularly limited, and a chain carbonate is preferable from the viewpoint of the solubility of the lithium salt.
  • chain carbonate examples include dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, methyl propionate and the like. Of these, ethylmethyl carbonate is preferable from the viewpoint of oxidation resistance and reduction resistance.
  • the dual ion battery of the present disclosure includes a positive electrode containing a positive electrode active material capable of inserting and removing anions, a negative electrode containing a negative electrode active material, and an electrolyte of the present disclosure.
  • the dual ion battery of the present disclosure is excellent in energy density by providing the above-mentioned electrolyte of the present disclosure.
  • the dual ion battery of the present disclosure comprises a positive electrode containing a positive electrode active material capable of inserting and removing anions.
  • the positive electrode may be configured to be arranged on the positive electrode current collector and its surface and to have a positive electrode mixture layer containing a positive electrode active material.
  • the positive electrode active material is not particularly limited as long as it is an active material capable of inserting and removing anions.
  • Examples of the positive electrode active material include carbon materials such as graphite, carbon nanotubes, graphene, nanocarbon, graphite oxide, graphene oxide, hard carbon, and soft carbon.
  • One type of positive electrode active material may be used alone, or two or more types may be used in combination.
  • the average particle size of the carbon material is preferably 2 ⁇ m to 30 ⁇ m, more preferably 2.5 ⁇ m to 25 ⁇ m, and more preferably 3 ⁇ m to 20 ⁇ m. It is more preferably 5 ⁇ m to 20 ⁇ m, and particularly preferably 5 ⁇ m to 20 ⁇ m.
  • the average particle size is 30 ⁇ m or less, the discharge capacity and the discharge characteristics tend to be improved.
  • the average particle size is 2 ⁇ m or more, the initial charge / discharge efficiency tends to improve.
  • the average particle size (d50) of the particles is determined by measuring the volume-based particle size distribution using, for example, a particle size distribution measuring device (SALD-3000, Shimadzu Corporation) using a laser light scattering method, and d50 (median size). ) Is the volume average particle size.
  • the range of the specific surface area of the carbon material, preferably graphite, is preferably 0.5 m 2 / g to 10 m 2 / g, more preferably 0.8 m 2 / g to 8 m 2 / g, and 1 m 2 It is more preferably / g to 7 m 2 / g, and particularly preferably 1.5 m 2 / g to 6 m 2 / g.
  • the specific surface area is 0.5 m 2 / g or more, excellent battery performance tends to be obtained.
  • the specific surface area is 10 m 2 / g or less, the tap density tends to increase, and the mixing property with other materials such as a binder and a conductive agent tends to be good.
  • the specific surface area can be measured from the nitrogen adsorption capacity according to JIS Z 8830: 2013.
  • the measurement cell containing 0.05 g of the measurement sample is depressurized to 10 Pa or less with a vacuum pump, heated at 110 ° C., held for 3 hours or more, and then kept at room temperature (reduced pressure). Naturally cool to 25 ° C).
  • the evaluation temperature is set to 77K, and the evaluation pressure range is measured as a relative pressure (equilibrium pressure with respect to saturated vapor pressure) of less than 1.
  • Nitrogen adsorption is measured by the multipoint method, and the specific surface area is calculated by the BET method.
  • the positive electrode may be configured to have a positive electrode current collector and a positive electrode mixture layer arranged on the surface thereof and containing a positive electrode active material.
  • the content of the positive electrode active material is preferably 80% by mass or more, preferably 85% by mass, based on the total amount of the positive electrode mixture layer from the viewpoint of increasing the capacity of the battery.
  • the above is more preferable, and 90% by mass or more is further preferable.
  • the positive electrode mixture layer contains a positive electrode active material, a binder, and the like, and is arranged on the positive electrode current collector.
  • the positive electrode mixture layer is formed as follows, for example. By mixing the positive electrode active material, the binder and other materials such as the conductive agent and the thickener used as needed in a dry method to form a sheet, and crimping this to the positive electrode current collector (dry method).
  • a positive electrode mixture layer can be formed.
  • a positive electrode mixture layer can be formed by applying and drying (wet method).
  • Examples of the conductive agent for the positive electrode include metal materials such as copper and nickel; graphite such as natural graphite and artificial graphite (graphite); carbon black such as acetylene black; and carbon materials such as amorphous carbon such as needle coke. ..
  • metal materials such as copper and nickel
  • graphite such as natural graphite and artificial graphite (graphite)
  • carbon black such as acetylene black
  • carbon materials such as amorphous carbon such as needle coke. ..
  • the conductive agent for the positive electrode one type may be used alone, or two or more types may be used in combination.
  • the content of the conductive agent with respect to the mass of the positive electrode mixture layer may be 0.01% by mass to 10% by mass, 0.1% by mass to 5% by mass, or 1% by mass to 3% by mass. May be%.
  • the content of the conductive agent is 0.01% by mass or more, sufficient conductivity tends to be easily obtained.
  • the content of the conductive agent is 10% by mass or less, the decrease in battery capacity tends to be suppressed.
  • the binder for the positive electrode is not particularly limited, and when the positive electrode mixture layer is formed by the wet method, a material having good solubility or dispersibility in the dispersion solvent is selected.
  • resin-based polymers such as polyethylene, polypropylene, polyethylene terephthalate, polyimide, and cellulose
  • rubber-like polymers such as SBR (styrene-butadiene rubber) and NBR (acrylonitrile-butadiene rubber), polyvinylidene fluoride (PVdF).
  • Polytetrafluoroethylene Polytetrafluoroethylene-vinylidene fluoride copolymer, polyvinylidene fluoride and other fluoropolymers, polyacrylonitrile skeleton with acrylic acid and linear ether group added; alkali metal Examples thereof include polymer compositions having ionic conductivity of ions (particularly lithium ions).
  • the binder for the positive electrode one type may be used alone, or two or more types may be used in combination.
  • the binder includes fluoropolymers such as polyvinylidene fluoride (PVdF) and polyvinylidene fluoride-vinylidene fluoride copolymer, copolymers having a polyacrylonitrile skeleton, cellulose and the like. It is preferable to use.
  • PVdF polyvinylidene fluoride
  • PVdF polyvinylidene fluoride-vinylidene fluoride copolymer
  • the content of the binder with respect to the mass of the positive electrode mixture layer is preferably 0.1% by mass to 10% by mass, more preferably 0.5% by mass to 5% by mass, and 1% by mass to It is more preferably 3% by mass.
  • the content of the binder is 0.1% by mass or more, the positive electrode active material can be sufficiently bound, sufficient mechanical strength of the positive electrode mixture layer is obtained, and battery performance such as cycle characteristics is improved. There is a tendency.
  • the content of the binder is 10% by mass or less, sufficient battery capacity and conductivity tend to be obtained.
  • the positive electrode mixture layer formed on the positive electrode current collector by the wet method or the dry method is preferably consolidated by a hand press or a roller press in order to improve the packing density of the positive electrode active material.
  • the density of the compacted positive mixture layer is preferably 0.7 g / cm 3 to 2 g / cm 3 and 0.8 g / cm 3 to 1.9 g / cm from the viewpoint of further improving the input / output characteristics. 3 is more preferable, and 0.9 g / cm 3 to 1.8 g / cm 3 is even more preferable.
  • the amount of the positive electrode mixture slurry applied to the positive electrode current collector on one side when forming the positive electrode mixture layer is 20 g / m 2 as the solid content of the positive electrode mixture from the viewpoint of energy density and input / output characteristics. It is preferably ⁇ 100 g / m 2 , more preferably 30 g / m 2 to 80 g / m 2 , and even more preferably 40 g / m 2 to 60 g / m 2 .
  • the material of the positive electrode current collector is not particularly limited, and among them, a metal material is preferable, and stainless steel coated with aluminum, molybdenum, and titanium nitride is more preferable.
  • the shape of the positive electrode current collector is not particularly limited, and materials processed into various shapes can be used. Examples of the metal material include a metal foil, a metal plate, a metal thin film, an expanded metal, and the like, and among them, it is preferable to use a metal thin film. The thin film may be formed in a mesh shape as appropriate.
  • the average thickness of the positive electrode current collector is not particularly limited, and is preferably 1 ⁇ m to 1 mm, preferably 3 ⁇ m to 100 ⁇ m, from the viewpoint of obtaining the strength required for the positive electrode current collector and good flexibility. It is more preferably present, and even more preferably 5 ⁇ m to 100 ⁇ m.
  • the dual ion battery of the present disclosure includes a negative electrode containing a negative electrode active material.
  • the negative electrode may be configured to be arranged on the negative electrode current collector and its surface and to have a negative electrode mixture layer containing a negative electrode active material.
  • the negative electrode active material is not particularly limited and preferably contains at least one of a carbon material, a metal and a metal compound, more preferably contains at least one of graphite, lithium titanate, an aluminum metal and a lithium metal, and graphite. And at least one of lithium titanate is more preferably contained.
  • the negative electrode active material may be a negative electrode active material capable of inserting and removing a cation, or may be at least one of a carbon material and a metal compound.
  • One type of negative electrode active material may be used alone, or two or more types may be used in combination.
  • carbon materials include graphite, carbon nanotubes, graphene, nanocarbon, graphite oxide, graphene oxide, hard carbon, soft carbon and the like.
  • the metal compound examples include lithium titanium composite oxides such as Li 4 Ti 5 O 12 , molybdenum oxide, niobium pentoxide, iron sulfide, titanium sulfide, titanium dioxide, titanium niobium oxide (TiNb 2 O 7 ), and iron oxide (Fe 2 ).
  • Li 4 Ti 5 O 12 molybdenum oxide, niobium pentoxide, iron sulfide, titanium sulfide, titanium dioxide, titanium niobium oxide (TiNb 2 O 7 ), and iron oxide (Fe 2 ).
  • Li 3 VO 4 lithium vanadium acid
  • WO 3 tungsten oxide
  • manganese oxide Mn 2 O 3
  • Y 2 Ti 2 O 5 S 2 Y 2 Ti 2 O 5 S 2 .
  • lithium titanium composite oxide (LTO) is preferable.
  • the lithium-titanium composite oxide examples include lithium titanate.
  • the negative electrode active material is a carbon material, preferably graphite
  • the conditions such as the average particle size and the specific surface area of the carbon material are the same as when the above-mentioned positive electrode active material is a carbon material, preferably graphite.
  • the content of the negative electrode active material is preferably 80% by mass or more, preferably 85% by mass, based on the total amount of the negative electrode mixture layer from the viewpoint of increasing the capacity of the battery.
  • the above is more preferable, and 90% by mass or more is further preferable.
  • the negative electrode mixture layer contains a negative electrode active material, a binder, and the like, and is arranged on the negative electrode current collector.
  • the negative electrode mixture layer is formed as follows, for example. Negative electrode active material, binder and other materials such as conductive agent and thickener used as needed are dissolved or dispersed in a dispersion solvent to form a slurry of negative electrode mixture, which is applied to the negative electrode current collector.
  • the negative electrode mixture layer can be formed by drying (wet method).
  • the conductive agent for the negative electrode carbon black such as acetylene black, amorphous carbon such as needle coke, etc. can be used.
  • the conductive agent for the negative electrode one type may be used alone, or two or more types may be used in combination. As described above, by adding the conductive agent to the negative electrode mixture, the effect of reducing the resistance of the electrode tends to be obtained.
  • the content of the conductive agent with respect to the mass of the negative electrode mixture layer is preferably 1% by mass to 10% by mass, preferably 2% by mass to 7% by mass, from the viewpoint of improving the conductivity and reducing the initial irreversible capacity. More preferably, it is more preferably 3% by mass to 5% by mass.
  • the content of the conductive agent is 1% by mass or more, it tends to be easy to obtain sufficient conductivity.
  • the content of the conductive agent is 10% by mass or less, the decrease in battery capacity tends to be suppressed.
  • the binder for the negative electrode is not particularly limited as long as it is a non-aqueous electrolytic solution or a material stable to the dispersion solvent used when forming the electrode.
  • resin-based polymers such as polyethylene, polypropylene, polyethylene terephthalate, cellulose, and nitrocellulose; rubber-like polymers such as SBR (styrene-butadiene rubber) and NBR (acrylonitrile-butadiene rubber); polyvinylidene fluoride (PVdF).
  • PVdF polyvinylidene fluoride
  • Polytetrafluoroethylene, polyvinylidene fluoride and the like examples thereof include polymer compositions having ionic conductivity of alkali metal ions (particularly lithium ions).
  • binder for the negative electrode one type may be used alone, or two or more types may be used in combination. Among these, it is preferable to use a fluoropolymer represented by cellulose, SBR, polyvinylidene fluoride and the like.
  • the content of the binder with respect to the mass of the negative electrode mixture layer is preferably 0.1% by mass to 20% by mass, more preferably 0.5% by mass to 15% by mass, and 0.6% by mass. It is more preferably% to 10% by mass.
  • the content of the binder is 0.1% by mass or more, the negative electrode active material can be sufficiently bound, and a sufficient mechanical strength of the negative electrode mixture layer tends to be obtained.
  • the content of the binder is 20% by mass or less, sufficient battery capacity and conductivity tend to be obtained.
  • the content of the binder with respect to the mass of the negative electrode mixture layer is 1% by mass to 15% by mass. It is preferable, it is more preferably 2% by mass to 10% by mass, and further preferably 3% by mass to 8% by mass.
  • Thickeners are used to adjust the viscosity of the slurry.
  • the thickener is not particularly limited, and specific examples thereof include carboxymethyl cellulose, methyl cellulose, hydroxymethyl cellulose, ethyl cellulose, polyvinyl alcohol, oxidized starch, phosphorylated starch, casein, and salts thereof.
  • the thickener may be used alone or in combination of two or more.
  • the content of the thickener with respect to the mass of the negative electrode mixture layer is preferably 0.1% by mass to 5% by mass, preferably 0.5% by mass to 3% by mass, from the viewpoint of input / output characteristics and battery capacity. It is more preferably present, and further preferably 0.6% by mass to 2% by mass.
  • any solvent can be used as long as it can dissolve or disperse the negative electrode active material, the binder, and the conductive agent, thickener, etc. used as needed.
  • an aqueous solvent or an organic solvent may be used.
  • the aqueous solvent include water, alcohol, a mixed solvent of water and alcohol, and the like.
  • organic solvents examples include N-methyl-2-pyrrolidone (NMP), dimethylformamide, dimethylacetamide, methylethylketone, cyclohexanone, methyl acetate, methyl acrylate, tetrahydrofuran (THF), toluene, acetone, diethyl ether, dimethyl sulfoxide. , Benzene, xylene, hexane and the like. In particular, when an aqueous solvent is used, it is preferable to use a thickener.
  • the density of the negative electrode mixture layer is preferably 0.7 g / cm 3 to 2 g / cm 3 , more preferably 0.8 g / cm 3 to 1.9 g / cm 3 , and more preferably 0.9 g / cm. It is more preferably 3 to 1.8 g / cm 3 .
  • the density of the negative electrode mixture layer is 0.7 g / cm 3 or more, the conductivity between the negative electrode active materials can be improved, the increase in battery resistance can be suppressed, and the capacity per unit volume tends to be improved. ..
  • the density of the negative electrode mixture layer is 2 g / cm 3 or less, the initial irreversible capacity increases and the discharge characteristics deteriorate due to the decrease in the permeability of the non-aqueous electrolyte solution near the interface between the negative electrode current collector and the negative electrode active material. There is a tendency that the risk of inviting is reduced.
  • the amount of the negative electrode mixture slurry applied to the negative electrode current collector on one side when forming the negative electrode mixture layer is 20 g / m 2 as the solid content of the negative electrode mixture from the viewpoint of energy density and input / output characteristics. It is preferably ⁇ 100 g / m 2 , more preferably 30 g / m 2 to 80 g / m 2 , and even more preferably 40 g / m 2 to 60 g / m 2 .
  • the material of the negative electrode current collector is not particularly limited, and specific examples thereof include metal materials such as copper, nickel, stainless steel, and nickel-plated steel. Of these, copper is preferable from the viewpoint of ease of processing and cost.
  • the shape of the negative electrode current collector is not particularly limited, and materials processed into various shapes can be used. Specific examples include metal foil, metal plate, metal thin film, expanded metal and the like. Among them, metal foil is preferable, and copper foil is more preferable.
  • the copper foil includes a rolled copper foil formed by a rolling method and an electrolytic copper foil formed by an electrolytic method, both of which are suitable as a negative electrode current collector.
  • the average thickness of the negative electrode current collector is not particularly limited. For example, it is preferably 5 ⁇ m to 50 ⁇ m, more preferably 8 ⁇ m to 40 ⁇ m, and even more preferably 9 ⁇ m to 30 ⁇ m. When the average thickness of the negative electrode current collector is less than 25 ⁇ m, the strength should be improved by using a strong copper alloy (phosphor bronze, titanium copper, Corson alloy, Cu—Cr—Zr alloy, etc.) rather than pure copper. Can be done.
  • a strong copper alloy phosphor bronze, titanium copper, Corson alloy, Cu—Cr—Zr
  • the dual ion battery of the present disclosure may include a separator that insulates between the positive electrode and the negative electrode between the positive electrode and the negative electrode.
  • the separator is not particularly limited as long as it insulates between the positive electrode and the negative electrode, has ion permeability, and has resistance to oxidizing property on the positive electrode side and reducing property on the negative electrode side.
  • a resin, an inorganic substance, or the like is used.
  • the resin an olefin polymer, a fluorine polymer, a cellulosic polymer, a polyimide, nylon and the like are used.
  • a porous sheet or a non-woven fabric made of polyolefin such as polyethylene or polypropylene as a raw material.
  • oxides such as alumina and silicon dioxide, nitrides such as aluminum nitride and silicon nitride, and glass are used.
  • a fiber-shaped or particle-shaped inorganic substance attached to a thin-film-shaped base material such as a non-woven fabric, a woven fabric, or a microporous film can be used as a separator.
  • the thin film-shaped substrate those having a pore diameter of 0.01 ⁇ m to 1 ⁇ m and an average thickness of 5 ⁇ m to 50 ⁇ m are preferably used.
  • a fiber-shaped or particle-shaped inorganic substance formed into a composite porous layer by using a binder such as a resin can also be used as a separator.
  • the composite porous layer may be formed on the surface of another separator to form a multilayer separator. Further, this composite porous layer may be formed on the surface of the positive electrode or the negative electrode to serve as a separator.
  • the method for manufacturing a dual ion battery of the present disclosure is a step of accommodating a positive electrode containing a positive electrode active material capable of inserting and removing anions, a negative electrode containing a negative electrode active material, and the above-mentioned electrolyte of the present disclosure in a battery container ( Containment process).
  • the manufacturing method of the present disclosure includes a step (accommodation step) of accommodating a positive electrode, a negative electrode, and the above-mentioned electrolyte of the present disclosure in a battery container.
  • each component of the dual ion battery is housed in a battery container.
  • the separator may be housed in the battery container so that the separator that insulates between the positive electrode and the negative electrode is arranged between the positive electrode and the negative electrode.
  • the above-mentioned electrolyte of the present disclosure may be supplied into the battery container in a state where the separator is arranged in the battery container between the positive electrode and the negative electrode and, if necessary, the positive electrode and the negative electrode.
  • Example 1 An electrolyte, a positive electrode and a negative electrode were prepared as follows, and a dual ion battery was prepared using each of them.
  • a mixture was obtained by mixing 98 parts by mass of graphite (Showa Denko Materials Co., Ltd.) as a positive electrode active material and 2 parts by mass of carboxymethyl cellulose (# 2200, Daicel Co., Ltd.) as a binder. An appropriate amount of water was added to the mixture and kneaded to obtain a paste-like positive electrode mixture slurry.
  • the positive electrode mixture slurry was applied to one side of an aluminum foil having a thickness of 15 ⁇ m, which is a current collector for the positive electrode, so that the solid content of the positive electrode mixture was 45 g / m 2 . Then, it was dried and a dry coating film was obtained on the current collector.
  • This dried coating film was consolidated by pressing until the solid content density of the positive electrode mixture reached 1.6 g / cm 3 , to prepare a positive electrode laminate having a positive electrode active material layer formed on the current collector.
  • the total thickness of the current collector and the positive electrode active material layer was 30 ⁇ m.
  • the produced positive electrode laminate was cut into a width of 30 mm and a length of 45 mm to obtain a positive electrode plate, and a positive electrode was produced by attaching a positive electrode current collecting tab to the positive electrode plate.
  • the negative electrode mixture slurry was applied to one side of a copper foil having a thickness of 10 ⁇ m, which is a current collector for the negative electrode, so that the solid content of the negative electrode mixture was 45 g / m 2 . Then, it was subjected to a drying treatment, and a dry coating film was obtained. This dried coating film was consolidated by pressing until the solid content density of the negative electrode mixture reached 1.6 g / cm 3 , to prepare a negative electrode laminate having a negative electrode active material layer formed on the current collector. The total thickness of the current collector and the negative electrode active material layer was 30 ⁇ m.
  • the produced negative electrode laminate was cut into a width of 31 mm and a length of 46 mm to form a negative electrode plate, and a negative electrode was produced by attaching a negative electrode current collecting tab to the negative electrode plate.
  • the prepared positive electrode and the negative electrode were opposed to each other via a glass fiber filter paper (Whatman, GF / D) having a thickness of 680 ⁇ m, a width of 35 mm, and a length of 50 mm, which was a separator, to prepare a laminated electrode group.
  • a glass fiber filter paper (Whatman, GF / D) having a thickness of 680 ⁇ m, a width of 35 mm, and a length of 50 mm, which was a separator, to prepare a laminated electrode group.
  • LiTFSI Lithium bis (trifluoromethanesulfonyl) imide
  • Pyr13TFSI 1-methyl-1-propylpyrrolidinium bis (trifluoromethanesulfonyl) imide
  • ES ethylene sulfate
  • the laminated electrode group was housed in a battery exterior made of an aluminum laminated film, and 1.3 mL of the prepared electrolytic solution was injected. Then, the dual ion battery of Example 1 was produced by closing the opening of the battery container with the positive electrode current collecting tab and the negative electrode current collecting tab taken out from the opening.
  • the aluminum laminated film was a laminated body of polyethylene terephthalate (PET) film / aluminum foil / sealant layer (polypropylene).
  • the configurations of the manufactured dual ion battery and the electrode group are shown in FIGS. 1 and 2, respectively.
  • the dual ion battery 10 shown in FIG. 1 contains the electrode group 20 and the electrolytic solution in the battery exterior body 6, and the positive electrode current collecting tab 2 and the negative electrode current collecting tab 4 are taken out of the battery exterior body 6. It is configured to be.
  • the electrode group 20 shown in FIG. 2 is a stack of a positive electrode plate 1 to which a positive electrode current collector tab 2 is attached, a separator 5, and a negative electrode plate 3 to which a negative electrode current collector tab 4 is attached.
  • Example 2 An electrolytic solution was prepared and prepared in the same manner as in Example 1 except that 1-butyl-1-methylpyrrolidinium bis (trifluoromethanesulfonyl) imide (Pyr14TFSI) was used instead of Pyr13TFSI in Example 1.
  • the dual ion battery of Example 2 was produced in the same manner as in Example 1 using the electrolytic solution.
  • Comparative Example 1 An electrolytic solution was prepared in the same manner as in Example 1 except that 1-ethyl-3-methylimidazole bis (trifluoromethanesulfonyl) imide was used instead of Pyr13TFSI in Example 1, and the prepared electrolytic solution was used. A dual ion battery of Comparative Example 1 was produced in the same manner as in Example 1.
  • Example 2 lithium bis (fluorosulfonyl) imide was used instead of lithium bis (trifluoromethanesulfonyl) imide, and 1-ethyl-3-methylimidazole bis (fluorosulfonyl) imide was used instead of Pyr13TFSI.
  • An electrolytic solution was prepared in the same manner as in Example 1, and a dual ion battery of Comparative Example 2 was prepared in the same manner as in Example 1 using the prepared electrolytic solution.
  • the dual ion secondary batteries manufactured in Examples 1 and 2 are charged in the first cycle (1 cyc), the second cycle (2 cyc), and the third cycle (3 cyc). There was no significant difference in the discharge test results and the capacity was maintained.
  • FIGS. 5 and 6 in the dual ion secondary batteries manufactured in Comparative Examples 1 and 2, there is a large difference in the charge / discharge test results between the first cycle and the second cycle. , The capacity could not be maintained either.
  • FIG. 7 in the dual ion secondary battery manufactured in Comparative Example 3 there is a difference in the charge / discharge test results between the first cycle and the third cycle, and the capacity increases with each cycle. It was declining.

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Abstract

L'invention concerne un électrolyte qui contient un sel de lithium, des cations non aromatiques hétérocycliques contenant de l'azote élémentaire dans sa structure, ainsi que des anions bis(trifluorométhanesulfonyle)imide, et qui est utilisée dans une batterie à deux ions comprenant une électrode positive contenant un matériau actif d'électrode positive qui peut insérer/désorber des anions et une électrode négative contenant un matériau actif d'électrode négative.
PCT/JP2020/045107 2020-12-03 2020-12-03 Électrolyte et batterie à deux ions WO2022118443A1 (fr)

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Citations (8)

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Publication number Priority date Publication date Assignee Title
JP2005026091A (ja) * 2003-07-03 2005-01-27 Yuasa Corp 非水電解質電池
JP2012009158A (ja) * 2010-06-22 2012-01-12 Nippon Synthetic Chem Ind Co Ltd:The 電解質及びそれを用いたリチウム二次電池
JP2015153700A (ja) * 2014-02-18 2015-08-24 住友電気工業株式会社 蓄電デバイス
JP2015526890A (ja) * 2012-06-22 2015-09-10 コミッサリア ア レネルジー アトミーク エ オ ゼネルジ ザルタナテイヴ 特定のイオン液体を含んでなる組成物
CN108183261A (zh) * 2017-12-26 2018-06-19 深圳先进技术研究院 电解液和锂离子二次电池及其制备方法
JP2018152519A (ja) * 2017-03-14 2018-09-27 株式会社リコー 非水系蓄電素子
JP2018537831A (ja) * 2015-12-17 2018-12-20 上海交通大学Ｓｈａｎｇｈａｉ Ｊｉａｏ Ｔｏｎｇ Ｕｎｉｖｅｒｓｉｔｙ 固体電解質、固体電解質膜及びその製造方法、並びに二次電池
JP2019029077A (ja) * 2017-07-26 2019-02-21 トヨタ自動車株式会社 水系デュアルイオン二次電池

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005026091A (ja) * 2003-07-03 2005-01-27 Yuasa Corp 非水電解質電池
JP2012009158A (ja) * 2010-06-22 2012-01-12 Nippon Synthetic Chem Ind Co Ltd:The 電解質及びそれを用いたリチウム二次電池
JP2015526890A (ja) * 2012-06-22 2015-09-10 コミッサリア ア レネルジー アトミーク エ オ ゼネルジ ザルタナテイヴ 特定のイオン液体を含んでなる組成物
JP2015153700A (ja) * 2014-02-18 2015-08-24 住友電気工業株式会社 蓄電デバイス
JP2018537831A (ja) * 2015-12-17 2018-12-20 上海交通大学Ｓｈａｎｇｈａｉ Ｊｉａｏ Ｔｏｎｇ Ｕｎｉｖｅｒｓｉｔｙ 固体電解質、固体電解質膜及びその製造方法、並びに二次電池
JP2018152519A (ja) * 2017-03-14 2018-09-27 株式会社リコー 非水系蓄電素子
JP2019029077A (ja) * 2017-07-26 2019-02-21 トヨタ自動車株式会社 水系デュアルイオン二次電池
CN108183261A (zh) * 2017-12-26 2018-06-19 深圳先进技术研究院 电解液和锂离子二次电池及其制备方法

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