CN106910933B - Lithium ion secondary battery - Google Patents
Lithium ion secondary battery Download PDFInfo
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- CN106910933B CN106910933B CN201610949356.9A CN201610949356A CN106910933B CN 106910933 B CN106910933 B CN 106910933B CN 201610949356 A CN201610949356 A CN 201610949356A CN 106910933 B CN106910933 B CN 106910933B
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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
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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
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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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
- H01M10/0567—Liquid materials characterised by the additives
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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
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/381—Alkaline or alkaline earth metals elements
- H01M4/382—Lithium
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
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- 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
Abstract
The present invention provides a lithium ion secondary battery, comprising: a positive electrode in which a positive electrode active material layer is disposed on a positive electrode current collector; a negative electrode in which a negative electrode active material layer is disposed on a negative electrode current collector; a diaphragm; and an electrolyte solution, wherein the positive electrode active material layer contains a positive electrode active material containing a lithium nickel-based composite oxide, the electrolyte solution contains an unsaturated cyclic carbonate and/or a halogenated cyclic carbonate as an additive, and the total of the mass of the unsaturated cyclic carbonate and the halogenated cyclic carbonate adsorbed on the positive electrode per unit surface area of the lithium nickel-based composite oxide is 0.2 to 3.5g/m2。
Description
CROSS-REFERENCE TO RELATED APPLICATIONS
This application claims priority from Japanese patent application No. 2015-213798, filed 2015, 10, 30 and to the office, which is hereby incorporated by reference in its entirety.
Technical Field
The present invention relates to a nonaqueous electrolyte battery, and particularly to a lithium ion secondary battery.
Background
Nonaqueous electrolyte batteries have been put to practical use as batteries for automobiles including hybrid automobiles, electric automobiles, and the like. As such a battery for a vehicle-mounted power supply, a lithium ion secondary battery is used. Lithium ion secondary batteries are required to have various characteristics such as output characteristics, energy density, capacity, life, and high-temperature stability at the same time. In particular, various improvements have been made to the electrolytic solution in order to improve the battery life (cycle characteristics and storage characteristics).
For example, japanese patent laid-open publication No. 2012-94454 proposes an electrolyte solution containing a cyclic disulfonate as a nonaqueous electrolyte solution excellent in rate characteristics of a lithium ion secondary battery after storage at high temperature. It is known that cyclic disulfonic acid esters form a coating film on the surface of an electrode (particularly, a negative electrode) by decomposing on the surface of the electrode. The formed coating film can improve the cycle characteristics of the battery. Among them, it is known that methylene methanedisulfonate (hereinafter referred to as "MMDS") has a high protective effect on a negative electrode. In addition, from the viewpoint of improving the cycle life of the battery and the like, it has been conventionally attempted to use a lithium nickel-based composite oxide as a positive electrode active material.
In a battery using a positive electrode active material containing a lithium nickel composite oxide, an electrolyte solution containing a disulfonate compound such as methylene methanedisulfonate as an additive is sometimes used. In this case, it is known that the capacity of the battery tends to decrease. The disulfonate compound reacts with water that may be contained in a slight amount in the battery material to generate a decomposed product (disulfonic acid compound). And the disulfonic acid is adsorbed on the surface of the positive electrode and forms a positive electrode protection covering film. However, if the amount of the adsorbed disulfonic acid is too large, the lithium nickel-based composite oxide is attacked. As a result, it is considered that this causes an increase in the resistance of the battery, and therefore, the output is reduced.
Disclosure of Invention
The object of the invention is therefore: the resistance of a lithium ion secondary battery using a positive electrode active material containing a lithium-nickel composite oxide is inhibited from increasing.
The present invention provides a lithium ion secondary battery, comprising: the method comprises the following steps: a positive electrode in which a positive electrode active material layer is disposed on a positive electrode current collector; a negative electrode in which a negative electrode active material layer is disposed on a negative electrode current collector; a diaphragm; and an electrolyte solution, wherein the positive electrode active material layer contains a positive electrode active material containing a lithium nickel-based composite oxide, the electrolyte solution contains an unsaturated cyclic carbonate and/or a halogenated cyclic carbonate as an additive, and the total of the mass of the unsaturated cyclic carbonate and the halogenated cyclic carbonate adsorbed on the positive electrode per unit surface area of the lithium nickel-based composite oxide is 0.2 to 3.5g/m2。
The invention can inhibit the resistance of the lithium ion secondary battery from increasing after the battery is subjected to charge-discharge cycle or after the battery is stored for a long time.
Drawings
Fig. 1 is a schematic sectional view showing a lithium-ion secondary battery according to an embodiment of the present invention.
Fig. 2 is a graph showing the relationship between the mass of the cyclic carbonate (the cyclic carbonate compound (VC) having an unsaturated bond and the cyclic carbonate compound (FEC) having a halogen) per unit surface area of the composite oxide contained in the positive electrode active material and the dc resistance value of the battery after storage.
Fig. 3 is a graph showing the relationship between the mass of the cyclic carbonate (the cyclic carbonate compound (VC) having an unsaturated bond and the cyclic carbonate compound (FEC) having a halogen) per unit surface area of the composite oxide contained in the positive electrode active material and the dc resistance value of the battery after charge and discharge cycles.
Detailed Description
The following describes embodiments of the present invention. In the present embodiment, the positive electrode is a battery member in a thin plate or sheet shape having a positive electrode active material layer formed by applying or rolling (rolling) a mixture containing a positive electrode active material, a binder, and if necessary, a conductive auxiliary agent on a positive electrode current collector such as a metal foil, and then performing a drying process. The negative electrode is a thin plate-shaped or sheet-shaped battery member having a negative electrode active material layer formed by coating a mixture containing a negative electrode active material, a binder, and, if necessary, a conductive assistant on a negative electrode current collector. The separator is a film-shaped battery member that separates a positive electrode and a negative electrode to ensure lithium ion conductivity between the negative electrode and the positive electrode. The electrolyte is obtained by dissolving an ionic substance in a solvent, and is a conductive solution. In the present embodiment, a nonaqueous electrolytic solution can be particularly used. The power generating element including the positive electrode, the negative electrode, and the separator is one unit of the main constituent member of the battery. The power generating element is generally a laminate including a positive electrode and a negative electrode laminated with a separator interposed therebetween. In the lithium-ion secondary battery according to the embodiment of the invention, the laminate is immersed in an electrolytic solution.
The lithium ion secondary battery of the present embodiment includes a package and the power generating element housed therein. Preferably, the power generating element is housed inside the sealed package. Here, "sealed" means that the power generation element is wrapped with a packaging material so as not to contact the outside air. That is, the package has a bag shape capable of housing the power generating element therein and being sealed.
Here, the positive electrode active material layer preferably contains a positive electrode active material containing a lithium nickel composite oxide. The lithium-nickel complex oxide is represented by the general formula LixNiyMe(1-y)O2(where Me is at least 1 or more metal selected from the group consisting of Al, Mn, Na, Fe, Co, Cr, Cu, Zn, Ca, K, Mg and Pb).
The positive electrode active material layer may further include a positive electrode active material containing a lithium manganese-based composite oxide. An example of the lithium manganese-based composite oxide is lithium manganate (LiMnO) having a zigzag layered structure2) And spinel type lithium manganate (LiMn)2O4). By using the lithium manganese-based composite oxide in combination, the positive electrode can be manufactured at a lower cost. Particularly preferably, spinel-type lithium manganate (LiMn) excellent in stability of crystal structure in an overcharged state is used2O4)。
Examples of a preferable electrolyte solution used in all embodiments of the present invention include a mixture of nonaqueous electrolyte solutions containing: chain carbonates such as dimethyl carbonate (hereinafter referred to as "DMC"), diethyl carbonate (hereinafter referred to as "DEC"), di-n-propyl carbonate, diisopropyl carbonate, di-n-butyl carbonate, diisobutyl carbonate, and di-t-butyl carbonate; and cyclic carbonates that are not contained in unsaturated bonds such as propylene carbonate (hereinafter referred to as "PC") and ethylene carbonate (hereinafter referred to as "EC") and halogens. By mixing lithium hexafluorophosphate (LiPF)6) Lithium tetrafluoroborate (LiBF)4) Or lithium perchlorate (LiClO)4) Dissolving lithium saltObtaining an electrolyte in the carbonate mixture.
The electrolyte solution of the present embodiment may contain an additive. Examples of the additive that can be added to the electrolytic solution include a cyclic carbonate compound having an unsaturated bond (hereinafter, appropriately referred to as "unsaturated cyclic carbonate"). The cyclic carbonate compound having an unsaturated bond is electrochemically decomposed during charge and discharge of the battery. The decomposed additive forms a coating film on the surface of the electrode used in all the embodiments described later. By doing so, the cyclic carbonate compound having an unsaturated bond can function as an additive for stabilizing the electrode structure. Examples of such additives include vinylene carbonate, ethylene carbonate, propylene methacrylate (メタクリル acid プロピレンカーボネート) and propylene acrylate (アクリル acid プロピレンカーボネート). As the cyclic carbonate compound having an unsaturated bond, vinylene carbonate (hereinafter referred to as "VC") is particularly preferably used.
In addition to the above, the electrolyte may contain a cyclic carbonate compound having a halogen (hereinafter, appropriately referred to as "halogenated cyclic carbonate"). The cyclic carbonate compound having a halogen also forms a protective coating film for the positive electrode and the negative electrode during charge and discharge of the battery. In particular, it is possible to prevent the attack of a sulfur-containing compound such as the disulfonic acid compound or disulfonate ester compound on the positive electrode active material containing the lithium nickel composite oxide. Examples of the cyclic carbonate compound having a halogen include fluoroethylene carbonate, difluoroethylene carbonate, trifluoroethylene carbonate, chloroethylene carbonate, dichloroethylene carbonate and trichloroethylene carbonate. Particularly preferably, fluoroethylene carbonate (hereinafter referred to as "FEC") is used as the halogenated cyclic carbonate. Preferably, the total mass of the unsaturated cyclic carbonate and the halogenated cyclic carbonate adsorbed on the positive electrode per unit surface area of the lithium nickel-based composite oxide described above is 0.2 to 3.5g/m2. Here, for example, in the case of composite oxidesIn the case of a particle shape, the "surface area of the lithium nickel-based composite oxide" refers to the surface area of the lithium nickel-based composite oxide particle. That is, in this case, the surface area of the composite oxide is a surface area calculated from the specific surface area of the composite oxide that can be measured by a general method of measuring the specific surface area of particles by the BET method or the like and the weight of the lithium nickel-based composite oxide. The surface area is not meant to refer to the area of the positive plate. In general, the unsaturated cyclic carbonate and the halogenated cyclic carbonate are adsorbed not only on the surface of the positive electrode to form a protective film, but also inside the positive electrode active material, that is, between particles of the positive electrode active material and in the void part of the crystal of the positive electrode active material to form a coating film. Therefore, in the present embodiment, the amounts of the unsaturated bond cyclic carbonate and the halogenated cyclic carbonate present per unit surface area of the lithium nickel composite oxide are defined.
Further, it is preferable that the electrolyte further contains a disulfonic acid compound. The disulfonic acid compound is a compound having two sulfonic acid groups in one molecule. The disulfonic acid compound includes a disulfonate compound which is a salt formed from a sulfonic acid group and a metal ion, and a disulfonate compound having a sulfonic acid group forming an ester bond.
The disulfonic acid compound may be included in the electrolyte as described in chemical formula 1 below.
(chemical formula 1)
(in chemical formula 1, R11Is alkylene, arylene, or a combination of alkylene and arylene).
One or both of the sulfonic acid groups of the disulfonic acid compound may form a salt together with the metal ion or may be in an anionic state. Examples of the disulfonic acid compound include methanedisulfonic acid, 1, 2-ethanedisulfonic acid, 1, 3-propanedisulfonic acid, 1, 4-butanedisulfonic acid, benzenedisulfonic acid, naphthalenedisulfonic acid, biphenyldisulfonic acid, salts thereof (lithium methanedisulfonate, lithium 1, 3-ethanedidisulfonate, and the like), and anions thereof (methanedisulfonate anion, 1, 3-ethanedisulfonate anion, and the like).
A disulfonic acid compound may be added to the electrolyte solution when the battery of the present embodiment is manufactured. Alternatively, a disulfonate compound having a sulfonic acid group forming an ester bond may be added in advance to the electrolyte solution at the time of manufacturing the battery. The disulfonate compound reacts with water that may be present in a trace amount inside the battery to form a disulfonic acid compound in the electrolyte. Here, the disulfonate compound that can be added to the electrolyte solution in the production of the battery means: a compound having one or two sulfonate groups in one molecule. The compound is one of disulfonic acid compounds. The disulfonate ester compound includes a chain compound represented by the following chemical formula 2.
(chemical formula 2)
(in chemical formula 2, R11Is an alkylene group, an arylene group, or a combination of an alkylene group and an arylene group. R12Is an alkyl or aryl group. R13Is an alkyl or aryl group). Alternatively, the disulfonate compound includes a cyclic compound represented by the following chemical formula 3.
(chemical formula 3)
(in chemical formula 3, R1Is an alkylene group, an arylene group, or a combination of an alkylene group and an arylene group. R2Is alkylene, arylene, or a combination of alkylene and arylene).
Examples of the disulfonate compound include chain disulfonate compounds such as methanedisulfonic acid, 1, 2-ethanedisulfonic acid, 1, 3-propanedisulfonic acid, 1, 4-butanedisulfonic acid, benzenedisulfonic acid, naphthalenedisulfonic acid, and alkyl and aryl diesters of biphenyldisulfonic acid. In addition, other examples include cyclic disulfonic acid esters such as methylene methanedisulfonate, vinyl methanedisulfonate, and allyl methanedisulfonate. It is particularly preferable to use methylene methanedisulfonate (hereinafter referred to as "MMDS").
When a cyclic disulfonate compound is added to an electrolyte solution during the production of a battery, the cyclic disulfonate compound reacts with water that may be present in the battery to produce a disulfonic acid compound. The route of the generation of the disulfonic acid compound is described below. As shown in chemical formula 4 below, the cyclic disulfonate compound (1) reacts with water to produce a disulfonic acid compound (2). The acidic disulfonic acid compound (2) is adsorbed on the surface of a basic positive electrode containing a positive electrode active material containing a lithium-nickel composite oxide, thereby forming a positive electrode coating film (3). The coating film formed appropriately on the surface of the positive electrode is preferable because it can suppress the outflow of an element such as manganese in the positive electrode active material.
(chemical formula 4)
(in chemical formula 4, R1Is an alkylene group, an arylene group, or a combination of an alkylene group and an arylene group. R2Is an alkylene group, an arylene group, or a combination of an alkylene group and an arylene group. )
If the amount of the compound of (3) in chemical formula 4 present on the surface of the positive electrode is too large, the compound attacks the lithium nickel-based composite oxide itself. As a result, the internal resistance of the positive electrode may increase and the capacity may decrease. Therefore, it is preferable to set the mass of the disulfonic acid compound per unit surface area of the lithium nickel-based composite oxide described above to a small amount (for example, 1.0 g/m)2Below).
Preferably, the positive electrode active material contained in the positive electrode active material layer contains a positive electrode active material represented by the general formula LixNiyCozMn(1-y-z)O2A lithium nickel manganese cobalt composite oxide represented by (I) and having a layered crystal structure. Here, x in the formula is a number satisfying the condition of 1 ≦ x ≦ 1.2. y and z are positive numbers satisfying the relationship of y + z < 1. The value of y is 0.5 or less. In addition, if the proportion of manganese becomes large, a single phase is formedThe composite oxide of (2) becomes difficult to synthesize. Therefore, it is preferable that the relationship of 1-y-z ≦ 0.4 is satisfied. Further, if the proportion of cobalt becomes large, the cost becomes high, and further, the capacity also becomes small. Therefore, it is preferable that the relationships of z < y and z < 1-y-z are satisfied. In order to obtain a high capacity battery, it is particularly preferable to satisfy the relationships of y > 1-y-z and y > z.
In addition, when the positive electrode active material layer further contains a lithium manganese-based composite oxide as the positive electrode active material, it is preferable that the total mass of the unsaturated cyclic carbonate and the halogenated cyclic carbonate adsorbed on the positive electrode per unit surface area of the lithium manganese-based composite oxide is 0.04 to 0.6g/m2. When the unsaturated cyclic carbonate and/or halogenated cyclic carbonate present in the positive electrode active material contains a sulfur-containing compound such as the disulfonic acid compound or disulfonate compound described above, the sulfur-containing compound can be prevented from attacking the positive electrode active material containing the lithium nickel-based composite oxide. Here, it is preferable to appropriately maintain the total mass of the unsaturated cyclic carbonate and the halogenated cyclic carbonate adsorbed on the positive electrode per unit surface area of the lithium manganese-based composite oxide. Here, the "surface area of the lithium manganese-based composite oxide" refers to the surface area of the lithium manganese-based composite oxide particles. That is, the surface area is calculated from the specific surface area that can be measured by a general method of measuring the specific surface area of particles by the BET method or the like, and the weight of the lithium manganese-based composite oxide. The surface area is not meant to refer to the area of the positive plate. In general, the unsaturated cyclic carbonate and the halogenated cyclic carbonate are adsorbed not only on the surface of the positive electrode to form a coating film, but also in the positive electrode active material, that is, between particles of the positive electrode active material and in the void part of the crystal of the positive electrode active material to form a coating film. Therefore, in the present embodiment, the amount of the unsaturated cyclic carbonate and the halogenated cyclic carbonate present per unit surface area of the lithium manganese-based composite oxide is specified.
In another embodiment, the positive electrode active material layer may include a positive electrode active material containing only a lithium manganese-based composite oxide. In the positive electrode active material layerIn the case of a positive electrode active material containing only a lithium manganese-based composite oxide, for example, lithium manganate (LiMnO) having a zigzag layered structure may be used2) Or spinel type lithium manganate (LiMn)2O4). Particularly preferably, spinel-type lithium manganate (LiMn) is used alone2O4). As described above, the flow of elements such as manganese from the positive electrode can be suppressed by the disulfonic acid compound derived from the electrolyte solution present on the positive electrode active material. In addition, an increase in internal resistance and a decrease in capacity can be prevented. Therefore, when a positive electrode active material containing a lithium-manganese composite oxide is used, it is particularly preferable to appropriately maintain the mass of the disulfonic acid compound adsorbed on the positive electrode per unit surface area. Preferably, the mass of the disulfonic acid compound adsorbed on the positive electrode per unit surface area of the lithium-manganese composite oxide is 0.04 to 0.6g/m2。
In preparing the electrolyte solution, an additive selected from a sulfur-containing compound such as a disulfonic acid compound or a disulfonic acid ester compound, a cyclic carbonate compound having an unsaturated bond, a cyclic carbonate compound having a halogen, and a mixture thereof is added to the electrolyte solution in a proportion of 15 wt% or less, preferably 10 wt% or less, more preferably 5 wt% or less, based on the weight of the entire electrolyte solution.
The negative electrode that can be used in all embodiments includes a negative electrode active material layer that is disposed on a negative electrode current collector and contains a negative electrode active material. Preferably, the negative electrode has a negative electrode active material layer obtained by applying or rolling a mixture containing a negative electrode active material, a binder, and optionally a conductive assistant onto a negative electrode current collector including a metal foil such as a copper foil, and then performing a drying step. In each embodiment, it is preferable that the negative electrode active material contains graphite particles and/or amorphous carbon particles. If a mixed carbon material containing graphite particles and amorphous carbon particles is used, the battery regeneration performance is improved.
Graphite is a carbon material of hexagonal plate crystals of a hexagonal system. Graphite is also sometimes referred to as black lead or the like. Preferably, the graphite has the shape of particles. In addition, the amorphous carbon may locally have a graphite-like structure. Here, amorphous carbon means a carbon material having a structure including crystallites randomly forming a network and being amorphous as a whole. Examples of the amorphous carbon include carbon black, coke, activated carbon, carbon fiber, hard carbon, soft carbon, and mesoporous carbon. Preferably, the amorphous carbon has a particle shape.
Examples of the conductive aid used in the negative electrode active material layer according to circumstances include carbon fibers such as carbon nanofibers, carbon blacks such as acetylene black and ketjen black, and carbon materials such as activated carbon, mesoporous carbon, fullerenes, and carbon nanotubes. In addition, the anode active material layer may also suitably contain additives commonly used for electrode formation, such as a thickener, a dispersant, and a stabilizer.
Examples of the binder used in the negative electrode active material layer include fluorine resins such as polyvinylidene fluoride (PVDF), Polytetrafluoroethylene (PTFE), and polyvinyl fluoride (PVF); conductive polymers such as polyaniline, polythiophene, polyacetylene and polypyrrole; synthetic rubbers such as Styrene Butadiene Rubber (SBR), Butadiene Rubber (BR), Chloroprene Rubber (CR), Isoprene Rubber (IR), and Nitrile Butadiene Rubber (NBR); and polysaccharides such as carboxymethyl cellulose (CMC), xanthan gum, guar gum, and pectin.
The positive electrode usable in all embodiments includes the positive electrode active material layer described above disposed on the positive electrode current collector, and the positive electrode active material layer contains a positive electrode active material. Preferably, the positive electrode has a positive electrode active material layer obtained by applying or rolling a mixture containing a positive electrode active material, a binder, and optionally a conductive auxiliary agent onto a positive electrode current collector including a metal foil such as an aluminum foil, and then performing a drying step.
Examples of the conductive aid used in the positive electrode active material layer in some cases include carbon fibers such as carbon nanofibers, carbon blacks such as acetylene black and ketjen black, activated carbon, graphite, mesoporous carbon, fullerenes, and carbon materials such as carbon nanotubes. In addition, additives generally used for electrode formation, such as a thickener, a dispersant, and a stabilizer, may be appropriately used for the positive electrode active material layer.
Examples of the binder used in the positive electrode active material layer include fluorine resins such as polyvinylidene fluoride (PVDF), Polytetrafluoroethylene (PTFE), and polyvinyl fluoride (PVF); conductive polymers such as polyaniline, polythiophene, polyacetylene and polypyrrole; synthetic rubbers such as Styrene Butadiene Rubber (SBR), Butadiene Rubber (BR), Chloroprene Rubber (CR), Isoprene Rubber (IR), and Nitrile Butadiene Rubber (NBR); and polysaccharides such as carboxymethyl cellulose (CMC), xanthan gum, guar gum, and pectin.
In the present embodiment, it is preferable that the content of water relative to the weight of the lithium nickel composite oxide in the positive electrode active material is as small as possible. The water content is, for example, 400ppm or less. As described above, water that may be contained in the positive electrode active material can promote decomposition of the additive in the electrolyte solution to form a coating film on the positive electrode. Therefore, water is not disadvantageous as long as it is present in an appropriate amount. However, if the amount of water present is too large, the generation of gas from the electrolyte additive may be promoted. Therefore, it is preferable to prepare the positive electrode active material by reducing the water content as much as possible so that the water content becomes an appropriate amount. In the use process of the positive electrode active material and the production process of the positive electrode, water cannot be completely prevented from being mixed into the positive electrode active material due to an accident. However, if the water content is about 400ppm based on the weight of the lithium nickel composite oxide, the gas generation promoting effect can be suppressed.
The separator used in all embodiments includes an olefin-based resin layer including polyolefin obtained by polymerization or copolymerization of α -olefin, and α -olefin includes, as an example of such a α -olefin, ethylene, propylene, butene, pentene, and hexene, in embodiments, it is preferable that the olefin-based resin layer be a layer having a structure including pores that are clogged when the battery temperature rises, that is, a layer including porous or microporous polyolefin, and by having such a structure, the separator is clogged (closed) even if the battery temperature rises, and an ion flow can be cut off.
Here, a configuration example of the lithium-ion secondary battery according to the embodiment will be described with reference to the drawings. Fig. 1 shows an example of a cross-sectional view of a lithium-ion secondary battery. The lithium-ion secondary battery 10 includes, as main constituent elements: a negative electrode current collector 11, a negative electrode active material layer 13, a separator 17, a positive electrode current collector 12, and a positive electrode active material layer 15. In fig. 1, the negative electrode active material layer 13 is provided on both sides of the negative electrode current collector 11. The positive electrode active material layer 15 is provided on both surfaces of the positive electrode current collector 12. However, the active material layer may be formed only on one surface of each current collector. The negative electrode current collector 11, the positive electrode current collector 12, the negative electrode active material layer 13, the positive electrode active material layer 15, and the separator 17 constitute a power generating element (a single cell 19 in the drawing) which is a constituent unit of one battery. A plurality of such single cells 19 are stacked via the separator 17. The extension portions extending from the negative electrode current collectors 11 are connected to the negative electrode lead 25. The extending portions extending from the positive electrode current collectors 12 are connected to the positive electrode lead 27. An aluminum plate is preferably used as the positive electrode lead, and a copper plate is preferably used as the negative electrode lead. The positive electrode lead and the negative electrode lead may have a partial covering layer formed of other metal (e.g., nickel, tin, solder) or polymer material as the case may be. The positive electrode lead and the negative electrode lead are respectively welded with the positive electrode and the negative electrode. A battery including a plurality of stacked unit cells is packaged by a package 29 so that the welded negative electrode lead 25 and positive electrode lead 27 are led to the outside. An electrolyte 31 is injected into the package 29. The package 29 has a shape obtained by heat-welding the peripheral edge portions of two stacked laminated bodies.
The capacity of the lithium-ion secondary battery of the present embodiment is preferably 5Ah to 70Ah, more preferably 30Ah to 60 Ah. The lithium ion battery having a capacity in such a range is particularly suitable for use as a vehicle-mounted battery or a stationary battery. Such batteries are required to have a high capacity retention rate. Therefore, the battery of the present embodiment is particularly suitable for the use.
[ examples ]
< production of negative electrode: examples and comparative examples >
As the negative electrode active material, a negative electrode having a thickness of 3.4m was used2BET specific surface area per g of graphite powder. The graphite powder as conductive additive has a thickness of 62m2Carbon black powder (hereinafter referred to as "CB") having a BET specific surface area,/g, carboxymethyl cellulose (hereinafter referred to as "CMC") as a binder resin, and styrene-butadiene copolymer latex (hereinafter referred to as "SBR") in a solid content mass ratio CB: CMC: SBR ═ 0.3: 1.0: the mixing was carried out at a ratio of 2.0. The resulting mixture was added to ion-exchanged water, and then further stirred together with the ion-exchanged water. Thereby, a slurry comprising the material uniformly dispersed in water was prepared. The obtained slurry was coated on a copper foil having a thickness of 10 μm to be a negative electrode current collector. Subsequently, the water was evaporated by heating the electrode at 125 ℃ for 10 minutes. Thereby, the anode active material layer was formed. Further, the negative electrode active material layer is punched to produce a negative electrode having the negative electrode active material layer coated on one surface of the negative electrode current collector.
< preparation of Positive electrode: examples and comparative examples >
So that the amount of LiOH after firing and Li2CO3Lithium carbonate (Li) in a predetermined molar ratio so that the total amount of the lithium carbonate is 1.0 wt% or less2CO3) Nickel hydroxide (Ni (OH))2) Cobalt hydroxide (Co (OH)2) And manganese hydroxide (Mn (OH)2) Mixing was performed. The resulting mixture was fired at 750 ℃ for 20 hours in a dry atmosphere. The lithium nickel composite oxide was pulverized to obtain a lithium nickel composite oxide having an average particle size of 9 μm (nickel cobalt lithium manganate (NCM523, i.e., nickel: cobalt: manganese: 5: 2: 3, lithium/metal other than lithium ratio: 1.04, BET specific surface area of 22 m)2In,/g)). The lithium nickel-based Composite Oxide (CO); as a conductive aid having a thickness of 62m2CB having a BET specific surface area/g and a particle size of 22m2Graphite powder (GR) with BET specific surface area/g; and polyvinylidene fluoride (PVDF) as a binder resin, the ratio of solid components by mass CO: CB: GR: PVDF became 93: 3: 1: 3, to N-methylpyrrolidone (hereinafter referred to as "NMP") as a solvent. Furthermore, 0.03 parts by mass of oxalic anhydride (molecular weight 90) as an organic moisture scavenger was added to the mixture per 100 parts by mass of the solid content from which NMP was removed. A slurry containing the uniformly dispersed material was prepared by subjecting the mixture containing the oxalic anhydride to 30-minute planetary dispersive mixing. The obtained slurry was applied to an aluminum foil having a thickness of 20 μm as a positive electrode current collector. Then, NMP was evaporated by heating the electrode at 125 ℃ for 10 minutes. Thereby, a positive electrode active material layer was formed. Further, the positive electrode active material layer was punched to produce a positive electrode having the positive electrode active material layer coated on one surface of the positive electrode current collector.
In addition, another positive electrode active material was prepared. The lithium nickel-based composite oxide and lithium manganese-based oxide (LiMn) obtained above were mixed2O4) And (3) adding 70: 30 (by weight ratio) of Mixed Oxide (MO); as a conductive aid having a thickness of 62m2CB having a BET specific surface area/g and a particle size of 22m2Graphite powder (GR) with BET specific surface area/g; and polyvinylidene fluoride (PVDF) as a binder resin, in terms of MO: CB: GR: PVDF became 93: 3: 1: 3, to NM as solventIn P. Further, 0.03 parts by mass of oxalic anhydride (molecular weight: 90) as an organic water scavenger was added to the mixture per 100 parts by mass of the solid content from which NMP was removed. A slurry containing the uniformly dispersed material was prepared by subjecting the mixture containing the oxalic anhydride to 30-minute planetary dispersive mixing. The obtained slurry was applied to an aluminum foil having a thickness of 20 μm as a positive electrode current collector. Then, the electrode was heated at 125 ℃ for 10 minutes to evaporate NMP. Thereby, a positive electrode active material layer was formed. Further, the positive electrode active material layer was punched to produce a positive electrode having the positive electrode active material layer coated on one surface of the positive electrode current collector.
< separator >
A ceramic separator including a heat-resistant fine particle layer using alumina as heat-resistant fine particles and an olefin-based resin layer having a thickness of 25 μm made of polypropylene was used.
< electrolyte solution >
To prepare a nonaqueous electrolytic solution, ethylene carbonate (hereinafter referred to as "EC"), diethyl carbonate (hereinafter referred to as "DEC") and ethyl methyl carbonate (hereinafter referred to as "EMC") were mixed in an amount of EC: DEC: EMC 30: 60: 10 (volume ratio). Lithium hexafluorophosphate (LiPF) as an electrolyte salt6) The resulting solution was dissolved in the obtained nonaqueous solvent so that the concentration of the solution became 0.9 mol/L. An electrolytic solution obtained by dissolving at least one of Methylene Methanedisulfonate (MMDS), fluoroethylene carbonate (FEC), and Vinylene Carbonate (VC) as an additive in the obtained electrolytic solution was used. The amounts of MMDS, FEC, and VC added were adjusted so that the remaining amount of VC on the positive electrode after the initial charge and discharge of the battery became the values shown in table 1.
< Assembly of lithium ion Secondary Battery >
Each of the negative and positive electrodes produced as described above was cut into a rectangle having a predetermined size. Wherein a positive electrode lead terminal made of aluminum is ultrasonically welded to an uncoated portion for connecting the terminals.
Similarly, a negative lead terminal made of nickel having the same size as the positive lead terminal was ultrasonically welded to the uncoated portion of the negative plate. The negative electrode plate and the positive electrode plate were disposed on both surfaces of the polypropylene porous separator so that the two active material layers were overlapped with the separator interposed therebetween, to obtain an electrode plate laminate. A bag-shaped composite package was produced by bonding three sides of two aluminum composite films except for one long side by thermal fusion bonding. Inserting the electrode stack into a composite package. And vacuum-impregnating the electrolyte injected into the composite packaging body into the electrode laminated body. Thereafter, the opening portion was sealed by thermal fusion bonding under reduced pressure. Thus, a laminated lithium ion battery was assembled. The assembly of the laminated lithium ion battery is completed by performing several high-temperature aging processes using the laminated lithium ion battery.
< initial Charge and discharge >
The lithium ion secondary battery assembled as described above was charged from 0% to 100% in residual capacity (hereinafter referred to as "SOC") under conditions of an ambient temperature of 55 ℃, a current of 1C, and an upper limit voltage of 4.15V with a constant current and a constant voltage. Then, until the SOC became 0%, constant current discharge was performed at a current of 1C. Thus, a lithium ion secondary battery according to an embodiment of the present invention was obtained.
< measurement of the Mass of disulfonic acid Compound (MMDS) adsorbed on the Positive electrode >
The lithium ion secondary battery after the initial charge and discharge is decomposed. The amount of disulfonic acid compound adsorbed on the positive electrode was measured by Nuclear Magnetic Resonance (NMR). Mass of MMDS adsorbed on the positive electrode per unit surface area of the lithium nickel-based composite oxide; and the mass of MMDS adsorbed on the positive electrode per unit surface area of the lithium manganese-based composite oxide are shown in table 1.
< measurement of the quality of unsaturated cyclic carbonate (VC) and halogenated cyclic carbonate (FEC) adsorbed on the cathode >
The lithium ion secondary battery after the initial charge and discharge is decomposed. The masses of the unsaturated bond cyclic carbonate and the halogenated cyclic carbonate adsorbed on the positive electrode were measured by Nuclear Magnetic Resonance (NMR). The sum of the mass of VC adsorbed on the positive electrode and the mass of FEC per unit surface area of the lithium nickel-based composite oxide; and the sum of the mass of VC adsorbed on the positive electrode and the mass of FEC per unit surface area of the lithium manganese-based composite oxide are shown in table 1.
< measurement of specific surface area of Complex oxide >
N by using BET method2The gas adsorption method measures the specific surface area of the composite oxide contained in the positive electrode active material.
< calculation of surface area of lithium-nickel composite oxide for Positive electrode >
The surface area of the positive electrode lithium nickel composite oxide was calculated by the following calculation formula.
Surface area (m) of positive electrode lithium-nickel composite oxide2) Specific surface area (m) of positive electrode active material lithium nickel composite oxide2Weight (g) of lithium-nickel composite oxide for positive electrode
< calculation of surface area of lithium manganese-based composite oxide for Positive electrode >
The surface area of the positive electrode lithium manganese complex oxide was calculated by the following calculation.
Surface area (m) of positive electrode lithium manganese complex oxide2) Specific surface area (m) of positive electrode active material lithium manganese composite oxide2Weight (g) of lithium manganese complex oxide for positive electrode
< measurement of moisture content >
The amount of water contained in the positive electrode active material was measured by the karl fischer method.
< test on cycle characteristics >
The lithium ion secondary battery obtained by the above method was repeatedly charged and discharged at a temperature of 45 ℃. That is, charge and discharge cycles were repeated 500 times, and one charge and discharge cycle included constant current and constant voltage charging at a current of 1C and an upper limit voltage of 4.15V and constant current discharging at a current of 1C and a lower limit end voltage of 2.5V which was subsequently performed by the charging. After the cycle test, the dc resistance value of the battery was measured by the following method.
< storage test >
The lithium ion secondary battery obtained by the method was stored at a temperature of 45 ℃ for two weeks. After storage, the dc resistance value of the battery was measured by the following method.
< resistance of Battery >
A battery having a remaining capacity (SOC) of 50% was prepared. A constant current discharge of 10A was carried out at 25 ℃ for 10 seconds. The dc resistance value (DCR) of the battery was obtained by measuring the voltage at the end of discharge. The volume of the cell was measured according to JISZ8807 "measurement method of density and specific gravity of solid-measurement method of density and specific gravity by weighing in liquid".
TABLE 1
The correlation between the amount of each electrolyte additive per unit surface area of the lithium nickel composite oxide contained in the positive electrode active material, the dc resistance value of the battery after the storage test, and the dc resistance value of the battery after the charge and discharge cycles was plotted (fig. 2 and 3). As shown in table 1, by adjusting the amount of the additive added to the electrolyte solution, the adsorption amount of each additive to the positive electrode per unit surface area of the composite oxide contained in the positive electrode active material can be changed. As is clear from fig. 2 and 3, the increase in the dc resistance of the battery can be suppressed by adjusting the mass of the carbonate compound or the mass of the disulfonic acid compound per unit surface area of the lithium nickel-based composite oxide and the lithium manganese-based composite oxide to an appropriate value. As is clear from fig. 2 and 3, the electrolyte additive does not have to be too large or too small to form a coating film on the positive electrode active material. That is, it was concluded that there was an appropriate range of the amount of the cover film formed. By controlling the extent of the electrolyte additive forming a coating film on the positive electrode active material within an appropriate range, it is possible to suppress an increase in the resistance of the battery after storage or after cyclic charge and discharge. That is, a lithium ion secondary battery having high cycle characteristics and a long shelf life can be obtained.
In the above, the embodiments of the present invention have been explained. However, the above-described example is only an example of the embodiment of the present invention. The examples are not intended to limit the technical scope of the present invention to specific embodiments or specific configurations.
The lithium ion secondary battery according to the embodiment of the present invention may be the following first to ninth lithium ion secondary batteries.
The first lithium ion secondary battery includes a power generation element inside a package, the power generation element including: a positive electrode in which a positive electrode active material layer is disposed on a positive electrode current collector; a negative electrode in which a negative electrode active material layer is disposed on a negative electrode current collector; a diaphragm; and an electrolyte solution, wherein the positive electrode active material layer contains a lithium nickel-based composite oxide as a positive electrode active material, the electrolyte solution contains an unsaturated cyclic carbonate and/or a halogenated cyclic carbonate as an additive, and the total mass of the unsaturated cyclic carbonate compound and the halogenated cyclic carbonate compound is 0.2 to 3.5g/m with respect to the surface area of the lithium nickel-based composite oxide2。
The second lithium ion secondary battery is the first lithium ion secondary battery, wherein the positive electrode active material layer further contains a lithium manganese-based composite oxide as a positive electrode active material, the electrolyte contains an unsaturated cyclic carbonate and/or a halogenated cyclic carbonate as an additive, and the total mass of the unsaturated cyclic carbonate and the halogenated cyclic carbonate present on a unit surface area of the lithium manganese-based composite oxide is 0.8 to 5.5g/m2。
The third lithium ion secondary battery is the first lithium ion secondary battery or the second lithium ion secondary battery, wherein the positive electrode active material layer further contains a lithium manganese-based composite oxide as a positive electrode active material, the electrolyte solution further contains a disulfonic acid compound, and the amount of the disulfonic acid compound is 0.04 to 0.6g/m with respect to the surface area of the lithium manganese-based composite oxide2。
The fourth lithium ion secondary battery which is the first lithium ionAny one of the secondary battery to the third lithium ion secondary battery, wherein the lithium nickel-based composite oxide contains a lithium compound represented by the general formula LixNiyCozMe(1-y-z)O2The lithium nickel cobalt complex oxide having a layered crystal structure is shown as a positive electrode active material. Me is at least 1 or more metal selected from Al, Mn, Na, Fe, Cr, Cu, Zn, Ca, K, Mg and Pb.
The fifth lithium ion secondary battery is any one of the first to third lithium ion secondary batteries, wherein the lithium nickel-based composite oxide contains a lithium represented by the general formula LixNiyCozMe(1-y-z)O2The lithium nickel cobalt manganese composite oxide having a layered crystal structure is shown as a positive electrode active material.
The sixth lithium ion secondary battery is any one of the second to fifth lithium ion secondary batteries, wherein the lithium manganese-based composite oxide is LiMn2O4。
The seventh lithium ion secondary battery is any one of the first to sixth lithium ion secondary batteries, wherein the negative electrode active material layer includes a carbon-based negative electrode material as a negative electrode active material.
The eighth lithium ion secondary battery is any one of the first to seventh lithium ion secondary batteries, wherein the unsaturated cyclic carbonate is vinylene carbonate, and the halogenated cyclic carbonate is fluoroethylene carbonate.
The ninth lithium-ion secondary battery is any one of the first to eighth lithium-ion secondary batteries, and has a capacity of 5Ah to 70 Ah.
Claims (10)
1. A lithium ion secondary battery is characterized in that,
the lithium ion secondary battery includes:
a positive electrode in which a positive electrode active material layer is disposed on a positive electrode current collector;
a negative electrode in which a negative electrode active material layer is disposed on a negative electrode current collector;
a diaphragm; and
an electrolyte solution is added to the electrolyte solution,
the positive electrode active material layer contains a positive electrode active material containing a lithium-nickel composite oxide,
the electrolyte contains an unsaturated cyclic carbonate and/or a halogenated cyclic carbonate as an additive,
the total mass of the unsaturated cyclic carbonate and the halogenated cyclic carbonate adsorbed on the positive electrode per unit surface area of the lithium nickel-based composite oxide is 0.2 to 3.5g/m2(ii) a Wherein the content of the first and second substances,
the additive accounts for 15 wt% or less of the total weight of the electrolyte.
2. The lithium-ion secondary battery according to claim 1,
the positive electrode active material layer contains a positive electrode active material containing a lithium manganese-based composite oxide,
the total mass of the unsaturated cyclic carbonate and the halogenated cyclic carbonate adsorbed on the positive electrode per unit surface area of the lithium manganese-based composite oxide is 0.8 to 5.5g/m2。
3. The lithium-ion secondary battery according to claim 1,
the positive electrode active material layer contains a positive electrode active material containing a lithium manganese-based composite oxide,
the electrolyte contains a disulfonic acid compound,
the mass of the disulfonic acid compound adsorbed on the positive electrode per unit surface area of the lithium manganese-based composite oxide is 0.04 to 0.6g/m2。
4. The lithium-ion secondary battery according to claim 2,
the electrolyte contains a disulfonic acid compound,
the mass of the disulfonic acid compound adsorbed on the positive electrode per unit surface area of the lithium manganese-based composite oxide is 0.04 to 0.6g/m2。
5. The lithium ion secondary battery according to any one of claims 1 to 4,
the lithium nickel-based composite oxide is a lithium nickel cobalt composite oxide,
the general formula Li for the lithium nickel cobalt composite oxidexNiyCozMe(1-y-z)O2And has a layered crystal structure, wherein x in the general formula satisfies the condition of 1 ≦ x ≦ 1.2, y and z are positive numbers satisfying the relationship of y + z < 1, the value of y is 0.5 or less, and Me is at least 1 or more metals selected from the group consisting of Al, Mn, Na, Fe, Cr, Cu, Zn, Ca, K, Mg and Pb.
6. The lithium ion secondary battery according to claim 5, wherein Me is Mn.
7. The lithium ion secondary battery according to claim 2, wherein the lithium manganese-based composite oxide is LiMn2O4。
8. The lithium ion secondary battery according to claim 1, wherein the anode active material layer contains an anode active material containing a carbon-based anode material.
9. The lithium ion secondary battery according to claim 1, wherein the unsaturated cyclic carbonate is vinylene carbonate and the halogenated cyclic carbonate is fluoroethylene carbonate.
10. The lithium ion secondary battery according to claim 1, wherein the capacity of the lithium ion secondary battery is 5Ah or more and 70Ah or less.
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