CN115812260A - Nonaqueous electrolyte electricity storage element - Google Patents

Nonaqueous electrolyte electricity storage element Download PDF

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Publication number
CN115812260A
CN115812260A CN202180038917.9A CN202180038917A CN115812260A CN 115812260 A CN115812260 A CN 115812260A CN 202180038917 A CN202180038917 A CN 202180038917A CN 115812260 A CN115812260 A CN 115812260A
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positive electrode
fluorinated
nonaqueous electrolyte
carbonate
solvent
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原田谅
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GS Yuasa International Ltd
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GS Yuasa International Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/54—Electrolytes
    • H01G11/58—Liquid electrolytes
    • H01G11/60—Liquid electrolytes characterised by the solvent
    • 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
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • 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

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  • Engineering & Computer Science (AREA)
  • Electrochemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
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  • Inorganic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • General Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Physics & Mathematics (AREA)
  • Secondary Cells (AREA)

Abstract

A nonaqueous electrolyte electricity storage element according to one aspect of the present invention includes a positive electrode having a positive electrode mixture layer containing a positive electrode active material and an acrylic resin, a negative electrode containing sulfur, and a nonaqueous electrolyte solution containing a fluorinated carbonate, a fluorinated carboxylate, or a combination thereof as a main component as a solvent.

Description

Nonaqueous electrolyte electricity storage element
Technical Field
The present invention relates to a nonaqueous electrolyte electricity storage device.
Background
Nonaqueous electrolyte secondary batteries typified by lithium ion nonaqueous electrolyte secondary batteries have high energy density and are therefore used in many applications such as electronic devices including personal computers and communication terminals, automobiles, and the like. In general, the nonaqueous electrolyte secondary battery is configured to have an electrode body including a pair of electrodes electrically separated by a separator and a nonaqueous electrolyte interposed between the electrodes, and to be charged and discharged by ion exchange between the electrodes. Further, as an electric storage element other than the nonaqueous electrolyte secondary battery, a capacitor such as a lithium ion capacitor or an electric double layer capacitor has been widely used.
In recent years, a positive electrode active material having a high energy density has been demanded for increasing the capacity of a nonaqueous electrolyte storage element. Sulfur is known as such a positive electrode active material. As a nonaqueous electrolyte storage element using a sulfur positive electrode active material, for example, patent document 1 provides a technique capable of improving capacity by suppressing diffusion of sulfide or the like eluted from the positive electrode active material into the nonaqueous electrolyte to the negative electrode side by providing a separator made of a porous insulating inorganic material containing sulfur and a positive electrode of the positive electrode active material and pores (see japanese patent application laid-open No. 2010-257689).
Documents of the prior art
Patent literature
Patent document 1: japanese patent laid-open No. 2010-257689.
Disclosure of Invention
However, if a sulfur-containing positive electrode active material is used for the purpose of increasing the capacity of a nonaqueous electrolyte battery element, there is a problem that a sufficient capacity retention rate after charge and discharge cycles cannot be obtained. Further, the present inventors have found that a sufficient initial discharge capacity cannot be obtained when a combination of a sulfur-containing positive electrode active material and a nonaqueous electrolytic solution containing a solvent containing a fluorinated carbonate or a fluorinated carboxylic acid ester as a main component is used. Therefore, an energy storage device is desired which can achieve an improvement in initial discharge capacity and capacity retention rate after charge-discharge cycles even when a sulfur-containing positive electrode active material is combined with a nonaqueous electrolytic solution containing a solvent containing a fluorinated carbonate or a fluorinated carboxylic acid ester as a main component for the purpose of increasing capacity.
The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a nonaqueous electrolyte electricity storage element capable of improving the initial discharge capacity and the capacity retention rate after charge and discharge cycles in the case of using a nonaqueous electrolyte containing a sulfur-containing positive electrode active material and a solvent mainly containing a fluorinated carbonate, a fluorinated carboxylate, or a combination thereof.
A nonaqueous electrolyte electricity storage element according to one aspect of the present invention includes a positive electrode having a positive electrode active material and a positive electrode mixture layer containing an acrylic resin, a negative electrode, and a nonaqueous electrolyte, wherein the positive electrode active material contains sulfur, and a solvent of the nonaqueous electrolyte contains fluorinated carbonate, fluorinated carboxylate, or a combination thereof as a main component.
In the nonaqueous electrolyte storage device according to one aspect of the present invention, when a sulfur-containing positive electrode active material and a nonaqueous electrolyte containing a solvent containing fluorinated carbonate, fluorinated carboxylate, or a combination thereof as a main component are used, the initial discharge capacity and the capacity retention rate after charge and discharge cycles can be improved.
Drawings
Fig. 1 is an external perspective view showing a nonaqueous electrolyte electricity storage element according to an embodiment of the present invention.
Fig. 2 is a schematic diagram showing an electricity storage device in which a plurality of nonaqueous electrolyte electricity storage elements according to an embodiment of the present invention are assembled.
Detailed Description
A nonaqueous electrolyte electricity storage device according to one aspect of the present invention includes a positive electrode including a positive electrode active material and a positive electrode mixture layer containing an acrylic resin, a negative electrode, and a nonaqueous electrolyte, wherein the positive electrode active material contains sulfur, and a solvent of the nonaqueous electrolyte contains fluorinated carbonate, fluorinated carboxylate, or a combination thereof as a main component.
In this nonaqueous electrolyte electricity storage device, by providing the positive electrode with the positive electrode mixture layer containing the acrylic resin, it is possible to improve the initial discharge capacity and the capacity retention rate after charge-discharge cycles even when a nonaqueous electrolyte solution is used which contains a sulfur-containing positive electrode active material and a solvent containing fluorinated carbonate, fluorinated carboxylate, or a combination thereof as a main component. The reason is not clear, but is presumed as follows. When sulfur is used as the positive electrode active material, it is difficult to stably maintain the structure of the positive electrode mixture layer due to expansion and contraction of the positive electrode active material, and the initial discharge capacity and the capacity retention rate after charge-discharge cycle performance are liable to decrease. In this nonaqueous electrolyte electricity storage element, since the positive electrode active material can be relatively firmly held by using the acrylic resin as the positive electrode binder, expansion and contraction of the positive electrode active material can be suppressed. Further, since the solvent of the nonaqueous electrolytic solution contains a fluorinated carbonate, a fluorinated carboxylate, or a combination thereof as a main component, a large number of excellent films are formed on the surface of the positive electrode active material. As a result, it is considered that the capacity retention rate after the charge/discharge cycle of the nonaqueous electrolyte electricity storage element is improved. Here, the "main component" means that the content ratio of the fluorinated carbonate, the fluorinated carboxylate, or the combination thereof in the entire solvent of the nonaqueous electrolytic solution in terms of volume is, for example, 50% by volume or more, preferably 70% by volume or more, and more preferably 80% by volume or more.
The total content of the main component in the entire solvent of the nonaqueous electrolytic solution is preferably 80 vol% or more. When the content of the fluorinated carbonate, the fluorinated carboxylate, or the combination thereof, which is a main component in the entire solvent of the nonaqueous electrolytic solution, is within the above range, the capacity retention rate after charge and discharge cycles of the nonaqueous electrolytic solution storage element can be further improved.
The solvent of the nonaqueous electrolytic solution preferably contains a fluorinated cyclic carbonate and a fluorinated chain carbonate or a fluorinated chain carboxylic acid ester as main components. When the solvent of the nonaqueous electrolyte contains a fluorinated cyclic carbonate and a fluorinated chain carbonate or a fluorinated chain carboxylic acid ester as main components, the capacity retention rate of the nonaqueous electrolyte electricity storage element after charge-discharge cycles can be further improved.
The content of the non-fluorine solvent in the entire solvent of the nonaqueous electrolytic solution is preferably more than 0 vol% and 40 vol% or less. When the content of the non-fluorinated solvent in the entire solvent of the nonaqueous electrolytic solution is more than 0 vol% and 40 vol% or less, the capacity retention rate after charge and discharge cycles can be further improved.
Hereinafter, a nonaqueous electrolyte electricity storage element according to an embodiment of the present invention will be described in detail.
< nonaqueous electrolyte storage element >
A nonaqueous electrolyte electricity storage element according to one embodiment of the present invention includes a positive electrode, a negative electrode, and a nonaqueous electrolyte. Hereinafter, a nonaqueous electrolyte secondary battery will be described as an example of a nonaqueous electrolyte electricity storage element. The positive electrode and the negative electrode are usually stacked or wound via a separator to form an alternately stacked electrode body. The electrode body is housed in a container, and the container is filled with a nonaqueous electrolytic solution. The nonaqueous electrolytic solution is sandwiched between the positive electrode and the negative electrode. As the container, a known metal container, a known resin container, or the like generally used as a secondary battery container can be used.
[ Positive electrode ]
The positive electrode has a positive electrode base material and a positive electrode mixture layer. The positive electrode mixture layer contains a positive electrode active material. The positive electrode mixture layer is laminated along at least one surface of the positive electrode substrate directly or via an intermediate layer.
(Positive electrode substrate)
The positive electrode substrate is a substrate having conductivity. As a material of the positive electrode base material, a metal such as aluminum, titanium, tantalum, and stainless steel, or an alloy thereof can be used. Among them, aluminum and aluminum alloys are preferable in terms of balance among potential resistance, high conductivity, and cost. The form of the positive electrode base material includes foil, vapor-deposited film, and the like, and foil is preferable from the viewpoint of cost. That is, aluminum foil is preferable as the positive electrode substrate. Examples of the aluminum or aluminum alloy include a1085, a3003, and the like defined in JIS-H4160 (2006).
(Positive electrode mixture layer)
The positive electrode mixture layer is formed of a so-called positive electrode mixture containing a positive electrode active material. The positive electrode active material contains sulfur. The positive electrode active material contains sulfur, and thus the capacity of the nonaqueous electrolyte electricity storage element can be increased.
As the positive electrode active material, a composite material of sulfur and carbon is preferable, and a composite material of sulfur and a porous carbon material is more preferable, from the viewpoints of suppressing elution of sulfide from the positive electrode active material into the nonaqueous electrolyte solution and improving the capacity retention rate of the nonaqueous electrolyte solution electricity storage element after charge and discharge cycles. Examples of the composite material of sulfur and the porous carbon material include a composite material of sulfur and mesoporous carbon, a composite material of sulfur and microporous carbon, and a composite material of sulfur and macroporous carbon. Among them, a composite material of sulfur and mesoporous carbon or a composite material of sulfur and microporous carbon is preferable, and a composite material of sulfur and mesoporous carbon is more preferable. Here, "mesoporous carbon" refers to a porous carbon material having an average pore size (diameter) in the range of 2nm to 50nm, "microporous carbon" refers to a porous carbon material having an average pore size (diameter) of less than 2nm, and "macroporous carbon" refers to a porous carbon material having an average pore size (diameter) of more than 50 nm. In addition, the composite material may be coated with a metal layer, a conductive polymer, or the like. The above-mentioned composite material of sulfur and mesoporous carbon (hereinafter referred to as a sulfur-mesoporous carbon composite material) is a composite material in which sulfur is filled in pores of mesoporous carbon.
The content of sulfur in the sulfur/carbon composite material (the mass ratio of sulfur atoms to the composite material of sulfur and carbon) is preferably 50 to 90 mass%, more preferably 60 to 80 mass%. By setting the sulfur content in the composite material of sulfur and carbon within the above range, both high capacity and good conductivity can be achieved.
The content of the positive electrode active material in the positive electrode mixture layer is not particularly limited, and the lower limit thereof is preferably 50 mass%, more preferably 80 mass%, and still more preferably 90 mass%. On the other hand, the upper limit of the content is preferably 99% by mass, more preferably 98% by mass, and still more preferably 97% by mass.
(Binder)
The positive electrode mixture layer of the nonaqueous electrolyte electricity storage element contains an acrylic resin as a binder. By using an acrylic resin as a binder of the positive electrode mixture layer of the sulfur-containing positive electrode active material, the positive electrode active material can be stabilized, and the stability of the structure of the positive electrode mixture layer can be achieved. In addition, the use of an acrylic resin as a binder can improve the conductivity of lithium ions as charge carriers. The "acrylic resin" refers to a resin formed from a monomer containing acrylic acid or methacrylic acid or a derivative thereof as a main component. Examples of the acrylic resin include polyacrylic acid, polymethyl acrylate, polyacrylamide, acrylic acid-containing copolymer, and alkali metal salt of polyacrylic acid.
In the positive electrode mixture layer, as other binders, there may be mentioned thermoplastic resins such as fluororesins (polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF), etc.), polyethylene, polypropylene, polyimide, etc.; elastomers such as ethylene-propylene-diene rubber (EPDM), sulfonated EPDM, styrene Butadiene Rubber (SBR), and fluororubber; polysaccharide polymers such as carboxymethyl cellulose (CMC) and methyl cellulose. From the viewpoint of improving injectability, the binder is preferably a resin having a small amount of butadiene-derived structural units, such as Styrene Butadiene Rubber (SBR), and more preferably a resin substantially not containing butadiene-derived structural units. Specifically, the upper limit of the mass ratio of the resin derived from a butadiene structural unit to the acrylic resin is preferably 2.3, more preferably 1.5, still more preferably 1.0, and particularly preferably 0.5. In addition, in the copolymer of the acrylic monomer and butadiene, it is also preferable that the content ratio of the structural unit derived from butadiene is small.
The content of the acrylic resin in the binder is preferably 50% by mass or more, more preferably 70% by mass, still more preferably 80% by mass, still more preferably 90% by mass, particularly preferably 99% by mass, and may be 100% by mass.
The lower limit of the binder content in the positive electrode mixture layer is preferably 0.2 mass%, more preferably 0.5 mass%, and still more preferably 1 mass%. On the other hand, the upper limit of the content is preferably 10% by mass, more preferably 8% by mass, and still more preferably 5% by mass. By setting the content of the binder within the above range, the active material can be stably held.
(other optional ingredients)
The positive electrode mixture layer contains optional components such as a conductive agent, a thickener, and a filler, as necessary.
The conductive agent is not particularly limited as long as it is a material having conductivity. Examples of such a conductive agent include carbonaceous materials, metals, conductive ceramics, and the like. Examples of the carbonaceous material include graphitized carbon, non-graphitized carbon, graphene-based carbon, and the like. Examples of the non-graphitizing carbon include carbon nanofibers, pitch-based carbon fibers, and carbon black. Examples of the carbon black include furnace black, acetylene black, and ketjen black. Examples of the graphene-based carbon include graphene, carbon Nanotubes (CNTs), fullerene, and the like. Examples of the shape of the conductive agent include a powder shape and a fiber shape. As the conductive agent, one of these materials may be used alone, or two or more of them may be used in combination. In addition, a composite material of these may also be used. For example, carbon black and CNT composites may be used. Among these, carbon black is preferable from the viewpoint of conductivity and coatability, and among them, acetylene black is preferable.
The content of the conductive agent (carbon in the composite material excluding sulfur and carbon) in the positive electrode mixture layer is preferably 1 to 20 mass%, and more preferably 3 to 15 mass%. By setting the content of the conductive agent to the above range, the energy density of the nonaqueous electrolyte electricity storage element can be improved.
Examples of the thickener include polysaccharide polymers such as carboxymethyl cellulose (CMC) and methyl cellulose. In addition, when the thickener has a functional group that reacts with lithium, the functional group is preferably inactivated in advance by methylation or the like.
The filler is not particularly limited. Examples of the main component of the filler include polyolefins such as polypropylene and polyethylene, silica, alumina, zeolite, and glass. The content of the filler in the positive electrode mixture layer is, for example, preferably 0.1 to 10 mass%. In one embodiment of the present invention, the positive electrode mixture layer may not contain a filler.
(intermediate layer)
The intermediate layer is a coating layer on the surface of the positive electrode base material, and contains conductive particles such as carbon particles, thereby reducing the contact resistance between the positive electrode base material and the positive electrode mixture layer. The intermediate layer is not particularly limited in its constitution, and may be formed, for example, from a composition containing a resin binder and conductive particles.
[ negative electrode ]
The negative electrode has a negative electrode base material and a negative electrode mixture layer. The negative electrode mixture layer contains a negative electrode active material. The negative electrode mixture layer is laminated along at least one surface of the negative electrode base material directly or via an intermediate layer.
(negative electrode substrate)
The negative electrode substrate has conductivity. Material for negative electrode base materialMetals such as copper, nickel, stainless steel, nickel-plated steel, and alloys thereof can be used. Among them, copper or copper alloys are preferable. Examples of the form of the negative electrode base include foil and vapor-deposited film, and foil is preferred from the viewpoint of cost. Therefore, a copper foil or a copper alloy foil is preferable as the negative electrode base material. Examples of the copper foil include rolled copper foil and electrolytic copper foil. The term "electrically conductive" means that the volume resistivity measured in accordance with JIS-H0505 (1975) is 1X 10 7 Omega. Cm or less, and "non-conductive" means that the volume resistivity is more than 1X 10 7 Ω·cm。
(negative electrode mixture layer)
The negative electrode mixture layer is laminated along at least one surface of the negative electrode base material directly or via an intermediate layer. The negative electrode mixture layer is formed of a so-called negative electrode mixture containing a negative electrode active material.
As the negative electrode active material, a material capable of occluding and releasing lithium ions is generally used. Specific examples of the negative electrode active material include carbonaceous materials such as Li metal, li alloy, metal or semimetal such as Si, sn, and Sb, metal oxide or semimetal oxide such as Si oxide, ti oxide, and Sn oxide, polyphosphate compound, silicon carbide, graphite (graphite), and non-graphitizable carbon (graphitizable carbon or graphitizable carbon). Among them, li metal, li alloy, si, sn, si oxide, sn oxide, and the like having a high capacity are preferable, and Li metal, li alloy, and the like are more preferable. In the negative electrode mixture layer, these materials may be used alone or in combination of two or more.
The content of the negative electrode active material in the negative electrode mixture layer is not particularly limited, and the lower limit thereof is preferably 50 mass%, more preferably 80 mass%, and still more preferably 90 mass%. On the other hand, the upper limit of the content is preferably 99% by mass, more preferably 98% by mass. When the negative electrode active material is a metal or semimetal such as Li metal, li alloy, si, sn, or Sb, the upper limit of the content may be 100 mass%.
(other optional Components)
The negative electrode mixture forming the negative electrode mixture layer may contain any component such as a binder, a conductive agent, a thickener, and a filler, as required.
Examples of the binder include thermoplastic resins such as fluororesins (polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF), etc.), polyethylene, polypropylene, polyimide, etc., elastomers such as ethylene-propylene-diene rubber (EPDM), sulfonated EPDM, styrene Butadiene Rubber (SBR), fluororubber, etc.; polysaccharide polymers, and the like.
The conductive agent, the thickener, and the filler may be selected from the materials exemplified in the above-mentioned positive electrode.
(intermediate layer)
The intermediate layer is a coating layer on the surface of the negative electrode base material, and contains conductive particles such as carbon particles to reduce the contact resistance between the negative electrode base material and the negative electrode mixture layer. The intermediate layer is not particularly limited in its structure, and may be formed of a composition containing a resin binder and conductive particles, for example, as in the positive electrode.
[ nonaqueous electrolytic solution ]
The nonaqueous electrolytic solution generally contains a solvent (nonaqueous solvent) and an electrolyte salt dissolved in the nonaqueous solvent.
(non-aqueous solvent)
In the nonaqueous electrolyte electricity storage element, the nonaqueous solvent of the nonaqueous electrolyte is mainly composed of a fluorinated carbonate, a fluorinated carboxylate, or a combination thereof.
Examples of the fluorinated carbonate include fluorinated cyclic carbonates and fluorinated chain carbonates. Examples of the fluorinated cyclic carbonate include Fluorinated Ethylene Carbonate (FEC) such as fluorinated ethylene carbonate and difluoroethylene carbonate, fluorinated propylene carbonate such as fluorinated methyl ethylene carbonate, and fluorinated butylene carbonate such as trifluoroethyl ethylene carbonate. Further, examples of the fluorinated chain carbonate include trifluoroethylmethyl carbonate (TFEMC) and bis (trifluoroethyl) carbonate (FDEC). The fluorinated carbonates may be used singly or in combination.
The fluorinated carboxylic acid ester is preferably a fluorinated chain carboxylic acid ester. Examples of the fluorinated carboxylic acid ester include fluorinated acetate and fluorinated propionate. Examples of the fluorinated acetate ester include methyl 2, 2-difluoroacetate, methyl 2, 2-trifluoroacetate, ethyl 2, 2-difluoroacetate and ethyl 2, 2-trifluoroacetate. Examples of the fluorinated propionate include methyl 3,3, 3-trifluoropropionate and ethyl 3,3, 3-trifluoropropionate. As the fluorinated carboxylic acid ester, fluorinated acetic acid esters are preferred. These fluorinated carboxylic acid esters may be used alone or in combination of two or more.
The solvent of the nonaqueous electrolytic solution preferably contains a fluorinated cyclic carbonate and a fluorinated chain carbonate or a fluorinated chain carboxylic acid ester as main components. The capacity retention rate after charge and discharge cycles of the nonaqueous electrolyte electricity storage element can be further improved by using the fluorinated cyclic carbonate and the fluorinated chain carbonate or the fluorinated chain carboxylic acid ester as the main components as the solvent of the nonaqueous electrolyte.
The lower limit of the proportion of the fluorinated cyclic carbonate in the entire solvent of the nonaqueous electrolytic solution is preferably 35 vol%, and more preferably 37 vol%. The upper limit of the proportion of the fluorinated cyclic carbonate is preferably 55 vol%, and more preferably 53 vol%. When the proportion of the fluorinated cyclic carbonate is within the above range, the capacity retention rate of the nonaqueous electrolyte electricity storage element after charge/discharge cycles can be further improved.
The lower limit of the proportion of the fluorinated chain carbonate or the fluorinated chain carboxylate (hereinafter, collectively referred to as fluorinated chain solvent) in the entire solvent of the nonaqueous electrolytic solution is preferably 35% by volume, and more preferably 37% by volume. The upper limit of the proportion of the fluorinated chain solvent is preferably 55 vol%, and more preferably 53 vol%. By setting the proportion of the fluorinated chain solvent in the above range, the capacity retention rate of the nonaqueous electrolyte electricity storage element after charge and discharge cycles can be further improved.
The lower limit of the volume ratio of the fluorinated chain solvent to the fluorinated cyclic carbonate (fluorinated chain solvent/fluorinated cyclic carbonate) in the nonaqueous electrolytic solution is preferably 40/60, and more preferably 45/55. The upper limit of the volume ratio of the fluorinated chain solvent to the fluorinated cyclic carbonate is preferably 60/40 or less, and more preferably 55/45 or less. When the volume ratio of the fluorinated chain solvent to the fluorinated cyclic carbonate is in the above range, the capacity retention rate after charge and discharge cycles of the nonaqueous electrolyte electricity storage element can be further improved.
The solvent of the nonaqueous electrolytic solution preferably contains a nonaqueous solvent (hereinafter referred to as a non-fluorinated solvent) other than the fluorinated carbonate and the fluorinated carboxylate. By adding a non-fluorinated solvent to the solvent of the nonaqueous electrolyte solution, the initial discharge capacity of the nonaqueous electrolyte solution storage element and the capacity retention rate after charge and discharge cycles can be further improved. As the non-fluorinated solvent, a carbonate other than fluorinated carbonate and a carboxylate other than fluorinated carboxylate are preferable. The proportion of the non-fluorinated solvent in the entire solvent of the non-aqueous electrolyte solution is preferably more than 0 vol% and 10 vol% or less.
Examples of the carbonate other than the fluorinated carbonate include cyclic carbonates and chain carbonates.
Examples of the cyclic carbonate include Ethylene Carbonate (EC), propylene Carbonate (PC), butylene Carbonate (BC), ethylene carbonate (VEC), vinylene carbonate chloride, styrene carbonate, 1-phenylenevinylene carbonate, and 1, 2-diphenylvinylene carbonate. Among them, EC is preferable.
Examples of the chain carbonate include diethyl carbonate (DEC), dimethyl carbonate (DMC), ethyl Methyl Carbonate (EMC), and diphenyl carbonate. Among them, EMC is preferable.
When the cyclic carbonate and the chain carbonate are used together, the volume ratio of the cyclic carbonate to the chain carbonate (cyclic carbonate: chain carbonate) is, for example, preferably in the range of 5: 95 to 50: 50.
Examples of the carboxylic acid ester other than the fluorinated carboxylic acid ester include a cyclic carboxylic acid ester and a chain carboxylic acid ester. Examples of the cyclic carboxylic acid ester include γ -butyrolactone, γ -valerolactone, γ -caprolactone, and ∈ -caprolactone. Examples of the chain carboxylic acid ester include methyl acetate, ethyl acetate, methyl propionate, and ethyl propionate.
The lower limit of the total content of the above-described main components, i.e., the fluorinated carbonate, the fluorinated carboxylate, or the combination thereof, in the entire solvent of the nonaqueous electrolytic solution is preferably 70 vol%, and more preferably 80 vol%. On the other hand, the upper limit of the total content of the main components may be 100% by volume, preferably 90% by volume. By setting the total content of the main components in all the solvents of the nonaqueous electrolyte to the above range, the capacity retention rate after charge and discharge cycles of the nonaqueous electrolyte electricity storage element can be further improved.
The content of the non-fluorinated solvent in the entire solvent of the nonaqueous electrolytic solution is preferably more than 0 vol% and 40 vol% or less, and more preferably 1 vol% to 10 vol%. By setting the content of the non-fluorinated solvent in the entire solvent of the non-aqueous electrolyte solution to the above range, the capacity retention rate after the charge-discharge cycle can be further improved.
(electrolyte salt)
As the electrolyte salt, generally known electrolyte salts used for nonaqueous electrolytic solutions in general electric storage elements can be used. Examples of the electrolyte salt include lithium salt, sodium salt, potassium salt, magnesium salt,
Figure BDA0003969708520000101
Salts and the like, preferably lithium salts.
The lithium salt may be LiPF 6 、LiPO 2 F 2 、LiBF 4 、LiClO 4 Isoinorganic lithium salt, liSO 3 CF 3 、LiC(SO 2 CF 3 ) 3 、LiC(SO 2 C 2 F 5 ) 3 And lithium salts having halogenated hydrocarbon groups, lithium imines, and the like. Among them, lithium imide salts are preferable, lithium sulfonylimide salts are more preferable, and lithium bis (fluorosulfonyl) imide (LiFSI) and lithium bis (trifluoromethanesulfonyl) imide (LiTFSI) are even more preferable.
The lower limit of the content of the electrolyte salt in the nonaqueous solution is preferably 0.1mol dm -3 More preferably 0.3 mol/dm -3 More preferably 0.5 mol/dm -3 Particularly preferably 0.7mol dm -3 . On the other hand, the upper limit is not particularly limited, but is preferably 2.5mol dm -3 More preferably 2mol dm -3 More preferably 1.5mol·dm -3 . The nonaqueous solution means a state in which the electrolyte salt is dissolved in a nonaqueous solvent, and also means a state before the additive is dissolved.
The nonaqueous electrolytic solution may contain an additive. Examples of the additive include aromatic compounds such as biphenyl, alkylbiphenyl, terphenyl, partially hydrogenated product of terphenyl, cyclohexylbenzene, tert-butylbenzene, tert-amylbenzene, diphenyl ether, and dibenzofuran; partial halides of the above aromatic compounds such as 2-fluorobiphenyl, o-cyclohexylfluorobenzene and p-cyclohexylfluorobenzene; halogenated anisole compounds such as 2, 4-difluoroanisole, 2, 5-difluoroanisole, 2, 6-difluoroanisole and 3, 5-difluoroanisole; succinic anhydride, glutaric anhydride, maleic anhydride, citraconic anhydride, glutaconic anhydride, itaconic anhydride, cyclohexane dicarboxylic anhydride; ethylene sulfite, propylene sulfite, dimethyl sulfate, vinyl sulfate, sulfolane, dimethyl sulfone, diethyl sulfone, dimethyl sulfoxide, diethyl sulfoxide, tetramethylene sulfoxide, diphenyl sulfide, 4' -bis (2, 2-dioxo-1, 3, 2-dioxothiapentane), 4-methylsulfonyloxymethyl-2, 2-dioxo-1, 3, 2-dioxothiapentane, thioanisole, diphenyl disulfide, bipyridine
Figure BDA0003969708520000102
Disulfide, perfluorooctane, tris (trimethylsilyl) borate, tris (trimethylsilyl) phosphate, tetrakis (trimethylsilyl) titanate, and the like. These additives may be used singly or in combination of two or more.
The content of the additive contained in the nonaqueous electrolytic solution is preferably 0.01 to 10% by mass, more preferably 0.1 to 7% by mass, even more preferably 0.2 to 5% by mass, and particularly preferably 0.3 to 3% by mass, based on the entire nonaqueous electrolytic solution. By setting the content of the additive within the above range, the capacity retention performance or the charge-discharge cycle performance after high-temperature storage can be improved, or the safety can be further improved.
[ spacers ]
As the separator, woven fabric, nonwoven fabric, porous resin film, or the like can be used. Among these, a porous resin film is preferable from the viewpoint of strength, and a nonwoven fabric is preferable from the viewpoint of liquid retention of the nonaqueous electrolytic solution. As the main component of the separator, for example, polyolefin such as polyethylene and polypropylene is preferable from the viewpoint of strength, and for example, polyimide, aromatic amide and the like are preferable from the viewpoint of oxidation decomposition resistance. Further, a material obtained by compounding these resins can be used.
An inorganic layer may be provided between the separator and the electrode (typically, the positive electrode). The inorganic layer is a porous layer which may be referred to as a heat-resistant layer or the like. In addition, a separator in which an inorganic layer is formed on one surface of a porous resin film may be used. The inorganic layer is generally composed of inorganic particles and a binder, and may contain other components.
[ concrete Structure of Electrical storage element ]
The shape of the nonaqueous electrolyte electricity storage element of the present embodiment is not particularly limited, and examples thereof include a cylindrical battery, a pouch battery, a rectangular battery, a flat battery, a coin battery, and a button battery.
Fig. 1 shows a nonaqueous electrolyte electricity storage element 1 as an example of a rectangular battery. Note that this figure is an internal perspective view of the container 3. An electrode body 2 having a positive electrode and a negative electrode wound with a separator interposed therebetween is housed in a rectangular container 3. The positive electrode is electrically connected to the positive electrode terminal 4 via a positive electrode lead wire 41. The negative electrode is electrically connected to the negative electrode terminal 5 via a negative electrode lead 51. Further, a nonaqueous electrolytic solution is injected into the container 3.
[ method for producing nonaqueous electrolyte Battery element ]
The method for producing the nonaqueous electrolyte electricity storage element according to the present embodiment can be selected from known methods. The method for producing the electrode assembly includes, for example, a step of preparing the electrode assembly, a step of preparing the nonaqueous electrolytic solution, and a step of housing the electrode assembly and the nonaqueous electrolytic solution in a container. The preparation step of the electrode body includes a preparation step of the positive electrode and the negative electrode and a step of forming the electrode body by laminating or winding the positive electrode and the negative electrode with the separator interposed therebetween.
The step of storing the nonaqueous electrolytic solution in the container may be selected from known methods. For example, when a liquid nonaqueous electrolytic solution is used, the nonaqueous electrolytic solution may be injected from an inlet formed on the container, and then the inlet may be sealed. The details of each element of the power storage device obtained by this manufacturing method are as described above.
[ other embodiments ]
The nonaqueous electrolyte storage element according to the present invention is not limited to the above-described embodiment, and various modifications may be made without departing from the scope of the present invention. For example, the configuration of another embodiment may be added to the configuration of one embodiment, or a part of the configuration of one embodiment may be replaced with the configuration of another embodiment or a known technique. Further, a part of the configuration of one embodiment may be deleted. In addition, a known technique may be added to the configuration of one embodiment.
The above embodiment has been described mainly with respect to a nonaqueous electrolyte storage element in a nonaqueous electrolyte secondary battery, but may be another nonaqueous electrolyte storage element. Examples of other nonaqueous electrolyte electricity storage elements include capacitors (electric double layer capacitors, lithium particle capacitors), and the like. Examples of the nonaqueous electrolyte secondary battery include a lithium ion nonaqueous electrolyte secondary battery.
The present invention can also realize an electric storage device including a plurality of the nonaqueous electrolyte electric storage elements. Further, an electric storage unit may be constituted by using one or more nonaqueous electrolyte electric storage elements (cells) of the present invention, and an electric storage device may be constituted by using the electric storage unit. The power storage device can be used as a power source for automobiles such as Electric Vehicles (EV), hybrid Electric Vehicles (HEV), plug-in hybrid electric vehicles (PHEV), and the like. The power storage device can be used in various power supply devices such as an engine start power supply device, an auxiliary power supply device, and an Uninterruptible Power Supply (UPS).
Fig. 2 shows an example of a power storage device 30 in which power storage cells 20 in which two or more electrically connected nonaqueous electrolyte power storage elements 1 are combined are further combined. Power storage device 30 may include a bus bar (not shown) that electrically connects two or more nonaqueous electrolyte battery elements 1, a bus bar (not shown) that electrically connects two or more power storage cells 20, and the like. The power storage unit 20 or the power storage device 30 may include a state monitoring device (not shown) that monitors the state of one or more nonaqueous electrolyte power storage elements.
Examples
The present invention will be specifically described below with reference to examples, but the present invention is not limited to the following examples.
[ example 1]
(preparation of nonaqueous electrolyte solution)
A dissolution concentration of 1mol dm in a mixed solvent of Fluorinated Ethylene Carbonate (FEC) and trifluoroethylmethyl 2, 2-carbonate (TFEMC) in a volume ratio of FEC: TFEMC = 50: 50 -3 Lithium bis (trifluoromethanesulfonyl) imide (LiTFSI) to prepare a nonaqueous electrolytic solution.
(preparation of Positive electrode)
As the positive electrode active material, a composite material of sulfur and mesoporous carbon is used. First, sulfur and mesoporous carbon were mixed in a mass ratio of 72: 28. The mesoporous carbon used had an average pore diameter (diameter) of 5nm and a micropore volume of 0.34cc g -1 The mesoporous volume is 1.02cc g -1 The total pore volume was 1.7cc g -1 Specific surface area of 1500m 2 g -1 . The mixture was placed in a sealed electric furnace. Introducing argon for 1 hour, heating to 150 ℃ at the heating rate of 5 ℃/minute, preserving heat for 5 hours, cooling to the solidification temperature of sulfur of 80 ℃, heating to 300 ℃ at the heating rate of 5 ℃/minute, keeping for 2 hours, and cooling to room temperature to prepare the composite material of sulfur and mesoporous carbon.
A positive electrode paste was prepared by using ion-exchanged water as a dispersion solvent, the positive electrode active material, acetylene Black (AB) as a conductive agent, and polyacrylic acid as a binder in a mass ratio of 80: 10. The positive electrode paste was applied to one surface of an aluminum foil having a thickness of 15 μm of a positive electrode substrate, dried, pressed, and cut to obtain a positive electrode in which a positive electrode mixture layer was arranged in a rectangular shape having a width of 20mm and a length of 20 mm. The positive electrode mixture layer had a thickness of 80 μm and contained 6mg/cm per unit area 2 Positive electrode mixture of. Before use, the positive electrode was dried under reduced pressure at 80 ℃ for 12 hours or more.
(preparation of cathode)
A lithium metal plate having a width of 30mm, a length of 40mm and a thickness of 500 μm was used as the negative electrode plate.
(production of non-aqueous electrolyte Electrical storage device)
A microporous polypropylene film having a thickness of 25 μm was used to fabricate a pouch-shaped separator having two pouch parts. The negative electrode is inserted into the pocket portion on one side of the pouch separator, and the positive electrode is inserted into the pocket portion on the other side such that the surface on which the positive electrode mixture layer is disposed faces the negative electrode. Thus, an electrode body was produced.
In the case of the metal resin composite film, the open ends of the lead terminals connected to the positive electrode and the negative electrode are exposed to the outside in advance, the electrode body is housed therein, the portion outside the liquid injection hole is sealed, the nonaqueous electrolytic solution is injected, and the liquid injection hole is sealed. Thus, a nonaqueous electrolyte electricity storage element was obtained.
Example 2, comparative example 1 and comparative example 2
Except that the types and volume ratios of the active material and the nonaqueous electrolyte solvent, and the binder of the positive electrode mixture layer were as shown in table 1, the nonaqueous electrolyte electrical storage elements of example 2, comparative example 1, and comparative example 2 were obtained in the same manner as in example 1. As the solvents of the nonaqueous electrolytic solution of comparative example 2, fluorinated Ethylene Carbonate (FEC) and 1, 2-tetrafluoroethyl ester-2, 3-tetrafluoropropyl ether (TFETFPE) were used.
[ evaluation ]
(initial Charge and discharge)
Each of the obtained nonaqueous electrolyte electricity storage elements was subjected to charge-discharge cycles twice at 25 ℃. The charging is performed by using a Constant Current (CC) of a charging current of 0.1C and a charging end voltage of 3V, and the discharging is performed by using a Constant Current (CC) of a discharging current of 0.1C and a discharging end voltage of 1V. 10 minute intermittent times were set after charging and after discharging, respectively. The discharge capacity at 1 cycle was set as "initial discharge capacity [ mAh/g ]".
(Charge-discharge cycle test)
Next, each nonaqueous electrolyte electricity storage element after initial charge and discharge was subjected to a charge and discharge cycle test of 10 cycles at 25 ℃. The charging is carried out by using a Constant Current (CC) with a charging current of 0.2C and a charging termination voltage of 3V, and the discharging is carried out by using a Constant Current (CC) with a discharging current of 0.1C and a discharging termination voltage of 1V. After charge and after discharge, 10 minute intermittent times were set. At this time, the discharge capacity after 1 cycle test and the discharge capacity after 10 cycle test were measured. The percentage of the discharge capacity [ mAh/g ] after 10 cycles of the test and the discharge capacity [ mAh/g ] after 1 cycle of the test was defined as "capacity maintenance rate (%) after charge and discharge cycles".
Table 1 shows the initial discharge capacity and the capacity retention rate after charge and discharge cycles.
[ Table 1]
Figure BDA0003969708520000141
As shown in table 1, examples 1 and 2 in which the positive electrode mixture layer contained an acrylic resin as a binder and the solvent of the nonaqueous electrolytic solution contained a fluorinated carbonate as a main component exhibited good initial discharge capacity and good capacity retention rate after charge and discharge cycles. In example 2 in which the solvent of the nonaqueous electrolytic solution contained 10 vol% of the non-fluorinated solvent, that is, the total content of the fluorinated carbonate was 90 vol%, the initial discharge capacity and the capacity retention rate after the charge-discharge cycle were significantly improved as compared with example 1.
On the other hand, comparative example 1, in which carboxymethyl cellulose (CMC) and Styrene Butadiene Rubber (SBR) were used as binders in the positive electrode mixture layer, had a very small initial discharge capacity. This is considered to be because when the positive electrode active material contains sulfur, the expansion and contraction of the positive electrode active material become large, but when carboxymethyl cellulose and styrene-butadiene rubber are used as a binder, the fixing force thereof is weaker than that of an acrylic resin, and thus the inhibition of the expansion and contraction of the positive electrode active material is low. In addition, in comparative example 2 in which acrylic acid was used as a binder in the positive electrode mixture layer and the solvent of the nonaqueous electrolytic solution contained fluorinated carbonate and fluorinated ether, it was found that the initial discharge capacity was large, but the capacity retention rate after charge-discharge cycles was very low. This is considered to be because the initial discharge capacity is increased by the decomposition of the fluorinated ether having a low resistance to reduction, and the capacity retention rate after charge and discharge cycles is decreased by the resistance layer formed by the decomposition product of the fluorinated ether.
As described above, when the nonaqueous electrolyte storage element uses a sulfur-containing positive electrode active material and a nonaqueous electrolyte containing a solvent mainly composed of a fluorinated carbonate, a fluorinated carboxylate, or a combination thereof, it is possible to improve the initial discharge capacity and the capacity retention rate after a discharge cycle.
Industrial applicability
The present invention is applicable to a nonaqueous electrolyte electricity storage element used as a power source for electronic devices such as personal computers and communication terminals, automobiles, and the like.
Description of the symbols
1. Nonaqueous electrolyte electricity storage element
2. Electrode body
3. Container with a lid
4. Positive terminal
41. Positive electrode lead
5. Negative terminal
51. Negative electrode lead
20. Electricity storage unit
30. Electricity storage device

Claims (4)

1. A non-aqueous electrolyte electricity storage element is provided with: a positive electrode, a negative electrode and a nonaqueous electrolytic solution,
the positive electrode has a positive electrode mixture layer containing a positive electrode active material and an acrylic resin,
the positive electrode active material contains sulfur,
the solvent of the nonaqueous electrolytic solution contains a fluorinated carbonate, a fluorinated carboxylate, or a combination thereof as a main component.
2. The nonaqueous electrolyte electricity storage element according to claim 1, wherein a total content of the main component in all solvents of the nonaqueous electrolyte is 80 vol% or more.
3. The nonaqueous electrolyte electricity storage element according to claim 1 or 2, wherein the solvent of the nonaqueous electrolyte contains a fluorinated cyclic carbonate and a fluorinated chain carbonate or a fluorinated chain carboxylic ester as main components.
4. The nonaqueous electrolyte electricity storage element according to claim 1,2, or 3, wherein a content of the non-fluorinated solvent in all the solvents of the nonaqueous electrolyte is greater than 0% by volume and equal to or less than 40% by volume.
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JP2005108724A (en) * 2003-09-30 2005-04-21 Sanyo Electric Co Ltd Nonaqueous electrolyte secondary battery
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US11862765B2 (en) * 2017-03-08 2024-01-02 The School Corporation Kansai University Electrolyte solution for alkali metal-sulfur-based secondary battery, and alkali metal-sulfur-based secondary battery
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