WO2017056449A1 - 非水電解質二次電池 - Google Patents
非水電解質二次電池 Download PDFInfo
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- WO2017056449A1 WO2017056449A1 PCT/JP2016/004273 JP2016004273W WO2017056449A1 WO 2017056449 A1 WO2017056449 A1 WO 2017056449A1 JP 2016004273 W JP2016004273 W JP 2016004273W WO 2017056449 A1 WO2017056449 A1 WO 2017056449A1
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- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
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- Y02T10/00—Road transport of goods or passengers
- Y02T10/60—Other road transportation technologies with climate change mitigation effect
- Y02T10/70—Energy storage systems for electromobility, e.g. batteries
Definitions
- This disclosure relates to a non-aqueous electrolyte secondary battery.
- Non-aqueous electrolyte secondary batteries that charge and discharge by moving lithium ions between positive and negative electrodes have high energy density and high capacity, and are therefore widely used as drive power sources for mobile information terminals.
- non-aqueous electrolyte secondary batteries have attracted attention as power sources for power tools, electric vehicles (EV), hybrid electric vehicles (HEV, PHEV), etc., and further expansion of applications is expected.
- EV electric vehicles
- HEV hybrid electric vehicles
- PHEV PHEV
- Patent Document 1 describes that the use of 1,2-dimethoxyethane as an electrolytic solution improves the low-temperature characteristics, improves the electrical conductivity of the electrolytic solution, and provides a large discharge capacity in an electrochemical cell. Has been.
- Patent Document 2 by using an electrode containing inorganic particles (such as Li 3 PO 4 ) having lithium ion transfer capability, the reaction between the electrode active material and the electrolytic solution on the electrode surface is suppressed, and overcharge occurs. It is described that safety can be improved.
- an electrode containing inorganic particles such as Li 3 PO 4
- An object of the present disclosure is to provide a non-aqueous electrolyte secondary battery with improved normal temperature regeneration.
- the present disclosure is a non-aqueous electrolyte secondary battery including an electrode body having a structure in which a positive electrode plate and a negative electrode plate are laminated via a separator, and a non-aqueous electrolyte, wherein the positive electrode plate is a lithium-containing transition metal oxide A material, an element belonging to Group 5 or Group 6 of the periodic table, and a phosphate compound.
- the non-aqueous electrolyte is characterized by containing 1,2-dimethoxyethane.
- group 5 / group 6 element means “element belonging to group 5 or 6 of the periodic table”.
- the positive electrode plate contains a lithium-containing transition metal oxide, a Group 5 / Group 6 element, a phosphate compound, and the nonaqueous electrolyte is 1,2-
- the resistance of the negative electrode surface is reduced by the Group 5 / Group 6 element eluted from the positive electrode plate and the mobile decomposition product generated by oxidative decomposition of 1,2-dimethoxyethane on the positive electrode surface. It was found that the room temperature regeneration of the nonaqueous electrolyte secondary battery was greatly improved.
- the basic configuration of the nonaqueous electrolyte secondary battery of the present embodiment is the same as that of the prior art, and includes a wound electrode body in which a positive electrode plate and a negative electrode plate are stacked and wound via a separator, and a nonaqueous electrolyte.
- the outermost peripheral surface of the wound electrode body is covered with a separator.
- the nonaqueous electrolyte secondary battery of the present embodiment is not limited to the above configuration as long as it includes an electrode body having a structure in which a positive electrode plate and a negative electrode plate are laminated via a separator, and a nonaqueous electrolyte.
- a positive electrode plate (hereinafter, also simply referred to as “positive electrode”) includes a positive electrode core body and a positive electrode mixture layer formed on both surfaces of the positive electrode core body.
- the positive electrode mixture layer is formed such that a positive electrode core exposed portion in which the positive electrode core body is exposed in a strip shape along the longitudinal direction is formed on both surfaces of the positive electrode core body at an end portion on at least one side in the width direction. Yes.
- the negative electrode plate (hereinafter also simply referred to as “negative electrode”) includes a negative electrode core and a negative electrode mixture layer formed on both surfaces of the negative electrode core.
- the negative electrode mixture layer is formed so that a negative electrode core exposed portion in which the negative electrode core is exposed in a strip shape along the longitudinal direction is formed on both surfaces of the negative electrode core at an end on at least one side in the width direction. Yes.
- positive electrode plate and negative electrode plate are wound through a separator and formed into, for example, a flat shape or a cylindrical shape to produce a flat or cylindrical wound electrode body. At this time, a positive electrode core exposed portion wound around one end of the wound electrode body is formed, and a negative electrode core exposed portion wound around the other end is formed.
- the wound positive electrode core exposed portion is electrically connected to the positive electrode terminal via the positive electrode current collector.
- the wound negative electrode core exposed portion is electrically connected to the negative electrode terminal via the negative electrode current collector.
- the positive terminal is fixed to the sealing body via an insulating member, and the negative terminal is also fixed to the sealing body via an insulating member.
- the wound electrode body is housed in, for example, a rectangular or cylindrical exterior body in a state covered with a resin insulating sheet.
- the sealing body is brought into contact with the opening of the metal exterior body, and the contact portion between the sealing body and the exterior body is laser-welded.
- the sealing body has a non-aqueous electrolyte injection port, the non-aqueous electrolyte is injected from the non-aqueous electrolyte injection port, and then the non-aqueous electrolyte injection port is sealed with a blind rivet or the like.
- a non-aqueous electrolyte secondary battery is an example, and other configurations, for example, a non-aqueous electrolyte secondary battery in which a non-aqueous electrolyte and a wound electrode body are inserted into a laminate outer package may be used.
- a positive electrode plate is comprised with positive electrode core bodies, such as metal foil, for example, and the positive mix layer formed on the positive electrode core body.
- positive electrode core a metal foil that is stable in the positive electrode potential range, a film in which the metal is disposed on the surface layer, and the like can be used.
- the metal used for the positive electrode core is preferably aluminum or an aluminum alloy.
- the positive electrode current collector and the positive electrode terminal are also preferably made of aluminum or an aluminum alloy.
- the positive electrode mixture layer includes a lithium-containing transition metal oxide that is a positive electrode active material, a Group 5 / Group 6 element, and a phosphate compound.
- the positive electrode mixture layer preferably further includes a conductive material and a binder.
- the positive electrode plate is formed by, for example, applying a positive electrode mixture slurry containing a positive electrode active material, a binder, etc. to a positive electrode core body, drying the coating film, and rolling the positive electrode mixture layer on both surfaces of the positive electrode core body. It can be manufactured by forming.
- the Group 5 / Group 6 element is included in any form as long as it is present in the vicinity of the lithium-containing transition metal oxide in the positive electrode mixture layer. It may be.
- a Group 5 / Group 6 element compound may be attached to the surface of the lithium-containing transition metal oxide particles, and a Group 5 / Group 6 element is contained in the lithium-containing transition metal oxide. It may be contained in.
- the case where the Group 5 / Group 6 element is contained in the lithium-containing transition metal oxide is particularly preferable. This is due to the elution of the Group 5 / Group 6 element and the film formed by the decomposition product derived from DME. This is because the ratio of being taken in is optimal, and it is easy to form a low-resistance film.
- the lithium-containing transition metal oxide contained in the positive electrode as a positive electrode active material is a metal oxide containing at least lithium (Li) and a transition metal element.
- the lithium-containing transition metal oxide may contain an additive element other than lithium (Li) and the transition metal element.
- the lithium-containing transition metal oxide can be represented, for example, by the general formula Li x Me y O 2 .
- Me is one or more transition metal elements including at least one selected from the group consisting of nickel (Ni), cobalt (Co), and manganese (Mn).
- x is, for example, not less than 0.8 and not more than 1.2.
- y varies depending on the type of Me and the oxidation number, but is, for example, 0.7 or more and 1.3 or less.
- nickel cobalt lithium manganate containing Ni, Co and Mn as transition metals is particularly preferable.
- Examples of the additive element that may be contained in the lithium-containing transition metal oxide include, for example, alkali metal elements other than lithium, transition metal elements other than Mn, Ni, and Co, alkaline earth metal elements, Group 12 elements, Examples include Group 13 elements and Group 14 elements.
- Specific examples of transition metal elements and additive elements other than Ni, Co, Mn, and Group 5 / Group 6 elements that may be contained in the lithium-containing transition metal oxide include, for example, zirconium (Zr), boron ( B), magnesium (Mg), aluminum (Al), titanium (Ti), iron (Fe), copper (Cu), zinc (Zn), tin (Sn), sodium (Na), potassium (K), barium ( Ba), strontium (Sr), calcium (Ca) and the like.
- the lithium-containing transition metal oxide preferably contains Zr as a transition metal. This is because the amount of decomposition of 1,2-dimethoxyethane (DME) contained in the nonaqueous electrolyte changes by containing Zr, and the amount of decomposition products can be adjusted.
- the content of Zr in the lithium-containing transition metal oxide is preferably 0.05 mol% or more and 10 mol% or less, more preferably 0.1 mol% or more and 5 mol% or less, and more preferably 0.2 mol% with respect to the total amount of metals excluding Li. Above 3 mol% is particularly preferable.
- the particle size of the lithium-containing transition metal oxide is not particularly limited, but is preferably 2 ⁇ m or more and 30 ⁇ m or less.
- the lithium-containing transition metal oxide particles are secondary particles formed by agglomeration of primary particles, the secondary particles preferably have the above-mentioned particle diameter, and the primary particles are, for example, 50 nm or more and 10 ⁇ m or less.
- the particle diameter of the lithium-containing transition metal oxide is, for example, a random extraction of 100 lithium-containing transition metal oxide particles observed with a scanning electron microscope (SEM), and the length of the major axis and the minor axis of each particle.
- the BET specific surface area of the lithium-containing transition metal oxide is not particularly limited, but is preferably 0.1 m 2 / g or more and 6 m 2 / g or less.
- the BET specific surface area of a lithium containing transition metal oxide can be measured with a well-known BET type powder specific surface area measuring apparatus.
- the nonaqueous electrolyte secondary battery of this embodiment includes a Group 5 / Group 6 element in the positive electrode mixture layer of the positive electrode plate.
- Elements belonging to Group 5 of the periodic table are vanadium (V), niobium (Nb), tantalum (Ta) and dobnium (Db), and elements belonging to Group 6 of the periodic table are chromium (Cr). Molybdenum (Mo), tungsten (W), and seaborgium (Sg).
- the Group 5 / Group 6 element is contained in the positive electrode mixture layer of the positive electrode plate at the time of production, but it elutes into the non-aqueous electrolyte when charging the non-aqueous electrolyte secondary battery and migrates to the negative electrode.
- a film is formed on the surface of the negative electrode and a decomposition product of 1,2-dimethoxyethane (DME) which is oxidatively decomposed on the surface of the positive electrode.
- DME 1,2-dimethoxyethane
- the Group 5 / Group 6 element Since the Group 5 / Group 6 element has a common property of being eluted at the time of charging / discharging and being taken into the film by the decomposition product derived from DME to form a low resistance film, the Group 5 / Group 6 element is used. Any of the group elements is considered to form a low-resistance film on the negative electrode surface under the condition that the phosphoric acid compound is present in the positive electrode mixture layer.
- the Group 5 / Group 6 element contained in the positive electrode plate of the nonaqueous electrolyte secondary battery of this embodiment W, Nb, Ta, Cr and Mo are preferable, and tungsten is particularly preferable. This is because tungsten is optimal in elution and the ratio of being taken into the film by the decomposition product derived from DME, and has the property of easily forming a low-resistance film.
- Examples of the Group 5 / Group 6 element compound when the Group 5 / Group 6 element compound adheres to the surface of the lithium-containing transition metal oxide particles include WO 3 and W 2 O 5. And tungsten oxide salts such as lithium tungstate. Of the tungsten oxides, WO 3 is preferable because the oxidation number is the most stable hexavalent.
- the compound of Group 5 / Group 6 element can be mechanically mixed with the positive electrode active material, for example, and adhered to the surface of the active material particles.
- a group 5 / group 6 element compound may be added and mixed with these positive electrode mixture layers.
- a Group 5 / Group 6 element compound is added to the positive electrode mixture layer.
- the group 5 / group 6 element compound can be efficiently present in the vicinity of the surface of the active material particles.
- the content of the Group 5 / Group 6 element in the positive electrode plate in the case of adhering to the lithium-containing transition metal oxide is such that the total amount of the Group 5 or Group 6 element is a metal excluding Li of the lithium-containing transition metal oxide. That is, the amount is preferably 0.05 mol% or more and 10 mol% or less, more preferably 0.1 mol% or more and 5 mol% or less, relative to the total amount of (the transition metal and the additive element). 2 mol% or more and 3 mol% or less are particularly preferable.
- the content of the Group 5 / Group 6 element is within this range, the formation of a low-resistance film with the decomposition product of 1,2-dimethoxyethane on the negative electrode surface is further promoted.
- the particle size of the Group 5 / Group 6 element attached to the lithium-containing transition metal oxide is preferably smaller than the particle size of the lithium-containing transition metal oxide, and is 25% or less of the particle size of the oxide. It is particularly preferred.
- the particle size of the Group 5 / Group 6 element is, for example, 50 nm to 10 ⁇ m. If the particle diameter is within the above range, it is considered that a good dispersion state of the Group 5 / Group 6 element in the positive electrode mixture layer is maintained, and the elution from the positive electrode plate is suitably performed.
- the group 5 / group 6 particle size was randomly extracted from 100 group 5 / group 6 elements observed with a scanning electron microscope (SEM), similar to the lithium-containing transition metal oxide.
- SEM scanning electron microscope
- the average value of the diameters of 100 particles is defined as the average value of the lengths of the major axis and the minor axis of each particle.
- the particle size of the Group 5 / Group 6 element is the particle size of the smallest unit particle (primary particle) that forms the aggregate.
- the Group 5 / Group 6 element may be contained in the lithium-containing transition metal oxide.
- Lithium-containing transition metal oxides containing Group 5 / Group 6 elements have the common property of eluting at the time of charge and discharge, and being taken into the film by decomposition products derived from DME to form a low resistance film. In order to provide, it is preferable.
- the lithium-containing transition metal oxide containing a Group 5 / Group 6 element includes, for example, a composite oxide containing Ni, Co, Mn, or the like, a lithium compound such as lithium hydroxide, and a Group 5 / Group 6 It can synthesize
- the lithium-containing transition metal oxide is added to at least one selected from the group consisting of nickel (Ni), cobalt (Co) and manganese (Mn) in the above general formula Li x Me y O 2 .
- Ni nickel
- Co cobalt
- Mn manganese
- the lithium-containing transition metal oxide contains a Group 5 / Group 6 element
- the lithium-containing transition metal oxide and the Group 5 / Group 6 element are in solid solution.
- a part of the Group 5 / Group 6 element may be deposited on the interface of the primary particles of the positive electrode active material or the surface of the secondary particles.
- the lithium-containing transition metal oxide containing a Group 5 / Group 6 element a lithium-containing transition metal oxide containing Ni, Co, Mn and W as transition metals is particularly preferable.
- the content of the Group 5 / Group 6 element is a metal other than Li in the lithium-containing transition metal oxide (ie, the transition metal and
- the total amount of Group 5 / Group 6 elements is preferably 0.05 mol% to 10 mol% with respect to the total amount of the above additive elements), preferably 0.1 mol% to 5 mol% It is more preferable that it is contained in such an amount.
- the content of the Group 5 / Group 6 element is within this range, the formation of a low-resistance film with the decomposition product of 1,2-dimethoxyethane on the negative electrode surface is further promoted.
- the nonaqueous electrolyte secondary battery of this embodiment contains a phosphoric acid compound in the positive electrode mixture layer of the positive electrode plate.
- the phosphoric acid compound contained in the positive electrode mixture layer is not particularly limited, and examples thereof include phosphoric acid and phosphate. Examples thereof include lithium phosphate, lithium dihydrogen phosphate, cobalt phosphate, nickel phosphate, and phosphoric acid. Mention may be made of manganese, potassium phosphate and ammonium dihydrogen phosphate. Among these, lithium phosphate is particularly preferable.
- the Group 5 / Group 6 element eluted from the positive electrode mixture layer during charging, and the decomposition product of DME that is also oxidatively decomposed on the positive electrode surface during charging.
- a film is formed by mixing the Group 5 / Group 6 element and the decomposition product derived from DME.
- the elution behavior of the Group 5 / Group 6 element at the positive electrode and the decomposition reaction rate of DME change due to the catalytic action of the phosphoric acid compound. .
- the composition of the film formed on the negative electrode changes, so that a film having a lower resistance is formed and the room temperature regeneration is greatly improved as compared with the case where no phosphate compound is present in the positive electrode mixture layer. It is considered to be done.
- the content of the phosphoric acid compound in the positive electrode mixture layer is preferably 0.03% by mass or more and 10% by mass or less, and more preferably 0.1% by mass or more with respect to the total amount of the lithium-containing transition metal oxide as the positive electrode active material 8 mass% or less is more preferable.
- the content is preferably 0.01% by mass or more and 3% by mass or less, and more preferably 0.03% by mass or more and 2% by mass or less with respect to the total amount of the lithium-containing transition metal oxide. If the phosphate compound content is too small, a low-resistance film may not be sufficiently formed on the negative electrode surface. If the phosphate compound content is too high, efficient electron transfer in the positive electrode active material is inhibited. There is a risk.
- the particle size of the phosphoric acid compound is preferably smaller than the particle size of the lithium-containing transition metal oxide, and particularly preferably 25% or less of the particle size of the oxide.
- the particle size of the phosphoric acid compound is, for example, 50 nm to 10 ⁇ m. When the particle size is within the range, a good dispersion state of the phosphoric acid compound in the positive electrode mixture layer is maintained.
- the particle size of the phosphoric acid compound as in the case of the lithium-containing transition metal oxide, 100 particles of the phosphoric acid compound observed with a scanning electron microscope (SEM) were randomly extracted. The average value of the lengths of the diameters is taken as the particle size of each particle, and the average particle size of 100 particles.
- the particle size of the phosphate compound is the particle size of the smallest unit particle (primary particle) that forms the aggregate.
- the phosphoric acid compound can be adhered to the surface of the active material particles by mechanically mixing with, for example, the positive electrode active material.
- the positive electrode mixture layer may be mixed by adding a phosphoric acid compound.
- the phosphoric acid compound is added to the positive electrode mixture layer using the former method. Thereby, the phosphoric acid compound can be efficiently present in the vicinity of the surface of the active material particles.
- the conductive material is used to increase the electrical conductivity of the positive electrode mixture layer.
- Examples of the conductive material include carbon materials such as carbon black, acetylene black, ketjen black, and graphite. These may be used alone or in combination of two or more.
- the binder is used in the positive electrode mixture layer to maintain a good contact state between the positive electrode active material and the conductive material and to increase the binding property of the positive electrode active material and the like to the surface of the positive electrode core.
- the binder include fluorine resins such as polytetrafluoroethylene (PTFE) and polyvinylidene fluoride (PVdF), polyacrylonitrile (PAN), polyimide resins, acrylic resins, and polyolefin resins. It is done.
- these resins, carboxymethyl cellulose (CMC) or a salt thereof (CMC-Na, CMC-K, CMC-NH 4 etc., may be a partially neutralized salt), polyethylene oxide (PEO), etc. May be used in combination. These may be used alone or in combination of two or more.
- the non-aqueous electrolyte includes a non-aqueous solvent and an electrolyte salt dissolved in the non-aqueous solvent, and the non-aqueous solvent includes at least 1,2-dimethoxyethane (DME).
- DME 1,2-dimethoxyethane
- the decomposition product derived from DME decomposed at the positive electrode and the Group 5 / Group 6 element eluted from the positive electrode form a low-resistance film on the surface of the negative electrode. It is done.
- the nonaqueous electrolyte may contain a nonaqueous solvent other than DME.
- a nonaqueous solvent other than DME for example, esters, ethers, nitriles, amides such as dimethylformamide, a mixed solvent of two or more of these, and the like can be used.
- a halogen-substituted product in which at least a part is substituted with a halogen atom such as fluorine can also be used.
- the content of DME contained in the non-aqueous electrolyte is preferably 3% by volume or more and 20% by volume or less with respect to the total amount of the solvent contained in the non-aqueous electrolyte. This is because if the DME content is too small, the film forming effect may not be sufficiently exhibited, and if the DME content is too large, it may be co-inserted into the negative electrode side and the battery characteristics may deteriorate.
- esters contained in the nonaqueous electrolyte include cyclic carbonates, chain carbonates, and carboxylic acid esters.
- cyclic carbonates such as ethylene carbonate (EC), propylene carbonate (PC), butylene carbonate, vinylene carbonate; dimethyl carbonate (DMC), methyl ethyl carbonate (MEC), diethyl carbonate (DEC), methyl propyl carbonate Chain carbonates such as ethyl propyl carbonate and methyl isopropyl carbonate; chain carboxylic acid esters such as methyl propionate (MP), ethyl propionate, methyl acetate, ethyl acetate and propyl acetate; and ⁇ -butyrolactone (GBL) And cyclic carboxylic acid esters such as ⁇ -valerolactone (GVL). and cyclic carboxylic acid esters such as ⁇ -butyrolactone (GBL) and ⁇ -valerolactone (GVL).
- ethers contained in the nonaqueous electrolyte include 1,3-dioxolane, 4-methyl-1,3-dioxolane, tetrahydrofuran, 2-methyltetrahydrofuran, propylene oxide, 1,2-butylene oxide, 1,3-dioxane, Cyclic ethers such as 1,4-dioxane, 1,3,5-trioxane, furan, 2-methylfuran, 1,8-cineol, crown ether; diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, dihexyl ether, Ethyl vinyl ether, butyl vinyl ether, methyl phenyl ether, ethyl phenyl ether, butyl phenyl ether, pentyl phenyl ether, methoxytoluene, benzyl ethyl ether, diphenyl ether, dibenzyl
- nitriles contained in the non-aqueous electrolyte include acetonitrile, propionitrile, butyronitrile, valeronitrile, n-heptanenitrile, succinonitrile, glutaronitrile, adiponitrile, pimelonitrile, 1,2,3-propanetricarboro. Nitriles, 1,3,5-pentanetricarbonitrile and the like can be mentioned.
- halogen-substituted substances contained in the nonaqueous electrolyte include fluorinated cyclic carbonates such as 4-fluoroethylene carbonate (FEC), fluorinated chain carbonates, methyl 3,3,3-trifluoropropionate (FMP). ) And the like.
- fluorinated cyclic carbonates such as 4-fluoroethylene carbonate (FEC), fluorinated chain carbonates, methyl 3,3,3-trifluoropropionate (FMP).
- the nonaqueous electrolyte secondary battery of this embodiment preferably contains a mixed solvent of DME and the above esters, and DME, cyclic carbonates, chain carbonates, and chain carboxylates. It is more preferable to contain a mixed solvent.
- the mixed solvent particularly contains cyclic carbonates, chain carbonates, chain carboxylic esters and DME in a volume ratio of 10 to 50:10 to 80: 1 to 20: 3 to 20. preferable.
- the electrolyte salt used for the non-aqueous electrolyte is preferably a lithium salt.
- the lithium salt LiBF 4, LiClO 4, LiPF 6, LiAsF 6, LiSbF 6, LiAlCl 4, LiSCN, LiCF 3 SO 3, LiC (C 2 F 5 SO 2), LiCF 3 CO 2, Li (P (C 2 O 4 ) F 4 ), Li (P (C 2 O 4 ) F 2 ), LiPF 6-x (C n F 2n + 1 ) x (1 ⁇ x ⁇ 6, n is 1 or 2), LiB 10 Cl 10 , LiCl, LiBr, LiI, chloroborane lithium, lower aliphatic lithium carboxylate, Li 2 B 4 O 7 , Li (B (C 2 O 4 ) 2 ) [lithium-bisoxalate borate (LiBOB)], li (B (C 2 O 4 ) F 2) boric acid salts such as, LiN (FSO 2) 2, LiN (C 1 F 2l +
- lithium salts may be used alone or in combination of two or more.
- at least a fluorine-containing lithium salt from the viewpoints of ion conductivity, electrochemical stability, and the like, and for example, LiPF 6 is preferably used.
- a lithium salt having a fluorine-containing lithium salt and an oxalato complex as an anion for example, LiBOB
- concentration of the lithium salt is preferably 0.8 to 1.8 mol per liter of nonaqueous solvent.
- a known negative electrode plate can be used as the negative electrode plate.
- the negative electrode plate After a negative electrode active material and a binder are dispersed in water or a suitable dispersion medium to prepare a negative electrode mixture slurry, the negative electrode mixture slurry is applied to the negative electrode current collector, and the coating film is dried
- the negative electrode plate can be produced by rolling and forming the negative electrode mixture layer on both surfaces of the negative electrode core.
- the negative electrode core it is preferable to use a conductive thin film, in particular, a metal foil that is stable in the potential range of the negative electrode, a film in which the metal is disposed on the surface layer, and the like.
- the metal used for the negative electrode core is preferably copper or a copper alloy, and the negative electrode current collector and the negative electrode terminal are also preferably made of copper or a copper alloy.
- the negative electrode active material is not particularly limited as long as it can reversibly occlude and release lithium ions.
- carbon materials such as natural graphite and artificial graphite, metals such as Si and Sn, and alloys that form an alloy with lithium A material, a metal composite oxide, or the like can be used. These may be used alone or in combination of two or more.
- a carbon material obtained by coating a graphite material with low crystalline carbon it is preferable to use a carbon material obtained by coating a graphite material with low crystalline carbon.
- binder a known binder can be used, and as in the case of the positive electrode, fluorine resin such as PTFE, PAN, polyimide resin, acrylic resin, and polyolefin resin can be used. it can.
- fluorine resin such as PTFE, PAN, polyimide resin, acrylic resin, and polyolefin resin
- SBR styrene-butadiene rubber
- PAA polyacrylic acid
- PVA polyvinyl alcohol
- the binder used for producing the negative electrode plate it is particularly preferable to use CMC or a salt thereof in combination with a styrene-butadiene copolymer (SBR) or a modified body thereof.
- a porous sheet having ion permeability and insulating properties is used.
- the porous sheet include a microporous thin film, a woven fabric, and a nonwoven fabric.
- olefinic resins such as polyethylene and polypropylene, cellulose and the like are suitable.
- the separator may be a laminate having a cellulose fiber layer and a thermoplastic resin fiber layer such as an olefin resin.
- the multilayer separator containing a polyethylene layer and a polypropylene layer may be sufficient, and what applied resin, such as an aramid resin, to the surface of a separator can also be used.
- lithium transition metal oxide positive electrode active material
- the molar ratio of each element of Ni, Co, Mn, W, and Zr to the entire transition metal was 46.7, 26. 7, 25.6, 0.5 and 0.5.
- lithium transition metal oxide 0.5 mol% of WO 3 with respect to the total amount of metal elements (transition metals) excluding Li of the oxide, and 5 mass with respect to the total amount of the oxide % Lithium phosphate (Li 3 PO 4 ) was mixed to obtain a positive electrode active material in which WO 3 and Li 3 PO 4 were adhered to the particle surface.
- the positive electrode active material, carbon black, and polyvinylidene fluoride (PVDF) were mixed at a mass ratio of 91: 7: 2.
- NMP N-methyl-2-pyrrolidone
- the positive electrode mixture slurry was applied onto the aluminum foil as the positive electrode core, and the coating film was dried to form a positive electrode mixture layer on the aluminum foil.
- the positive electrode core body in which the positive electrode compound material layer was formed was cut out to a predetermined size, rolled, attached with an aluminum tab, and used as a positive electrode.
- the positive electrode obtained as described above was observed with a scanning electron microscope (SEM). As a result, tungsten oxide particles having an average particle diameter of 150 nm and lithium phosphate particles having an average particle diameter of 100 nm were obtained. It was confirmed that it adhered to the surface of the lithium-containing transition metal composite oxide. However, some of tungsten oxide and lithium phosphate may be peeled off from the surface of the positive electrode active material in the step of mixing the conductive agent and the binder. In some cases, part of tungsten oxide and / or lithium phosphate is contained. Moreover, it was confirmed by observation by SEM that lithium phosphate is attached to tungsten oxide or exists in the vicinity of tungsten oxide.
- LiPF 6 is dissolved in the mixed solvent so as to have a concentration of 1.2 mol / L.
- vinylene carbonate is dissolved in a concentration of 0.3% by mass with respect to the LiPF 6- containing mixed solvent.
- LiBOB Li (B (C 2 O 4 ) 2 ) was dissolved in the LiPF 6 -containing mixed solvent so as to have a concentration of 0.05 mol / L.
- An aluminum lead is attached to the positive electrode, a nickel lead is attached to the negative electrode, a microporous membrane made of polyethylene is used as a separator, and the positive electrode and the negative electrode are wound spirally through the separator to form a wound electrode body.
- the electrode body is housed in a bottomed cylindrical battery case body, the nonaqueous electrolyte is injected, the opening of the battery case body is sealed with a gasket and a sealing body, and a cylindrical nonaqueous electrolyte secondary battery (Battery A1) was produced.
- Type non-aqueous electrolyte secondary battery (battery A3) was produced.
- Type non-aqueous electrolyte secondary battery (battery A4) was produced.
- Example 7 A cylindrical nonaqueous electrolyte secondary battery (battery A7) was produced in the same manner as in Experimental Example 2, except that tungsten oxide was not mixed with the lithium-containing transition metal oxide in the step of producing the positive electrode active material. .
- Example 9 A cylindrical nonaqueous electrolyte secondary battery (battery A9) was produced in the same manner as in Experimental Example 6, except that lithium phosphate was not mixed with the lithium-containing transition metal oxide in the production process of the positive electrode active material. did.
- Example 12 A cylindrical nonaqueous electrolyte secondary battery (battery A12) was produced in the same manner as in Experimental Example 1, except that lithium phosphate was not mixed with the lithium-containing transition metal oxide in the production process of the positive electrode active material. did.
- the normal temperature regeneration value at the charging depth (SOC) 50% of each secondary battery is obtained from the following formula from the maximum current value that can be charged for 10 seconds when the end-of-charge voltage is 4.3V. It was.
- batteries A1 to A7 which are positive electrode active materials containing a lithium nickel cobalt manganese composite oxide containing a Group 5 / Group 6 element and lithium phosphate, and a nonaqueous electrolyte containing DME, Compared with batteries A8 to A13, normal temperature regeneration was remarkably superior.
- DME generates a mobile decomposition product by oxidative decomposition at the time of charging on the positive electrode surface. Further, when a Group 5 / Group 6 element is present in the positive electrode, the Group 5 / Group 6 element is eluted into the non-aqueous electrolyte. Then, a film formed by mixing the decomposition product of DME and the Group 5 / Group 6 element is formed on the negative electrode surface. At this time, if both the Group 5 / Group 6 element and the phosphoric acid compound are present in the positive electrode, the elution and deposition form of the Group 5 / Group 6 element changes, and a low resistance film is formed on the surface of the negative electrode. Therefore, it is thought that room temperature regeneration can be greatly improved.
- FIG. 1 is a reaction schematic diagram of a positive electrode and a negative electrode in the nonaqueous electrolyte secondary battery of the present disclosure. It is considered that DME is decomposed on the positive electrode surface to generate a mobile decomposition product, and this decomposition product and the Group 5 / Group 6 element eluted from the positive electrode form a low-resistance negative electrode film on the negative electrode surface. .
- FIG. 2 is a reaction schematic diagram of the positive electrode and the negative electrode in the prior art in which no phosphoric acid compound is present on the positive electrode.
- the phosphoric acid compound is not present in the positive electrode, the elution of the Group 5 / Group 6 element is not adjusted by the phosphoric acid compound. Therefore, even if DME is contained in the nonaqueous electrolyte, a low resistance negative electrode film is not formed. Therefore, even when DME is contained as a nonaqueous electrolyte, the normal temperature regeneration is reduced or hardly changed as compared with the case where DME is not present (battery A9 to battery A12).
- the phosphoric acid compound causes the group 5 / Although the elution of the Group 6 element is promoted, since a decomposition product derived from DME is not formed, a low-resistance film is not formed on the surface of the negative electrode, and improvement in normal temperature regeneration cannot be obtained.
- the elements of Group 5 / Group 6 are dissolved in the lithium transition metal oxide, and the Group 5 / Group 5 element is formed on the surface of the lithium transition metal oxide.
- a positive electrode active material to which a Group 6 element is attached is used, it is possible to greatly improve normal temperature regeneration. This is presumably because a lower resistance film was formed on the negative electrode.
- any of the batteries A1 to A7 of the present disclosure can improve the normal temperature regeneration, and further, the batteries A1 to A5 having a DME content of 5% by volume or more and 20% by volume or less with respect to the total amount of the solvent contained in the nonaqueous electrolyte.
- the improvement effect of normal temperature regeneration was more remarkable. It is considered that when the content of DME is in the above range, co-insertion of DME into the negative electrode can be suppressed and battery characteristics can be improved.
- the positive electrode plate contains a lithium-containing transition metal oxide, a Group 5 / Group 6 element, and a phosphoric acid compound, and the nonaqueous electrolyte contains 1,2-dimethoxyethane. It was confirmed that normal temperature regeneration of the electrolyte secondary battery can be improved.
- This disclosure can be used for non-aqueous electrolyte secondary batteries.
Abstract
Description
本実施形態の非水電解質二次電池の基本的な構成は従来と同様であり、正極板及び負極板がセパレータを介して積層されて巻回された巻回電極体と、非水電解質とを有しており、巻回電極体の最外周面は、セパレータにより覆われている。本実施形態の非水電解質二次電池は、正極板及び負極板がセパレータを介して積層された構造を有する電極体と、非水電解質とを備える限り、上記構成に限定されない。
正極板は、例えば金属箔等の正極芯体と、正極芯体上に形成された正極合材層とで構成される。正極芯体としては、正極の電位範囲で安定な金属の箔、及び、当該金属を表層に配置されているフィルム等を用いることができる。正極芯体に用いられる金属としては、アルミニウム又はアルミニウム合金が好ましい。正極集電体及び正極端子もアルミニウム又はアルミニウム合金製であることが好ましい。
正極に正極活物質として含有されているリチウム含有遷移金属酸化物は、リチウム(Li)及び遷移金属元素を少なくとも含む金属の酸化物である。リチウム含有遷移金属酸化物は、リチウム(Li)及び遷移金属元素以外の添加元素を含有していてもよい。
本実施形態の非水電解質二次電池は、正極板の正極合材層に第5族/第6族元素を含む。周期表の第5族に属する元素とは、バナジウム(V)、ニオブ(Nb)、タンタル(Ta)及びドブニウム(Db)であり、周期表の第6族に属する元素とは、クロム(Cr)、モリブデン(Mo)、タングステン(W)及びシーボーギウム(Sg)である。
本実施形態の非水電解質二次電池は、正極板の正極合材層にリン酸化合物を含む。正極合材層に含まれるリン酸化合物は、特に限定されないが、リン酸及びリン酸塩等が挙げられ、例えば、リン酸リチウム、リン酸二水素リチウム、リン酸コバルト、リン酸ニッケル、リン酸マンガン、リン酸カリウム及びリン酸二水素アンモニウムが挙げられる。これらの中でも、特にリン酸リチウムが好ましい。
導電材は、正極合材層の電気伝導性を高めるために用いられる。導電材の例としては、カーボンブラック、アセチレンブラック、ケッチェンブラック及び黒鉛等の炭素材料等が挙げられる。これらは、単独で用いてもよく、2種類以上を組み合わせて用いてもよい。
結着剤は、正極合材層において、正極活物質及び導電材間の良好な接触状態を維持し、且つ、正極芯体表面に対する正極活物質等の結着性を高めるために用いられる。結着剤の例としては、ポリテトラフルオロエチレン(PTFE)及びポリフッ化ビニリデン(PVdF)等のフッ素系樹脂、ポリアクリロニトリル(PAN)、ポリイミド系樹脂、アクリル系樹脂、並びに、ポリオレフィン系樹脂等が挙げられる。また、これらの樹脂と、カルボキシメチルセルロース(CMC)又はその塩(CMC-Na、CMC-K、CMC-NH4等、また部分中和型の塩であってもよい)、ポリエチレンオキシド(PEO)等が併用されてもよい。これらは、単独で用いてもよく、2種類以上を組み合わせて用いてもよい。
非水電解質は、非水溶媒と、非水溶媒に溶解した電解質塩とを含み、非水溶媒は1,2-ジメトキシエタン(DME)を少なくとも含む。非水電解質二次電池において、非水電解質がDMEを含有すると、正極がリン酸化合物及び第5族/第6族元素を含有することを条件として、非水電解質二次電池の常温回生特性を改善することができる。本実施形態の非水電解質二次電池では、正極で分解したDME由来の分解生成物と正極から溶出した第5族/第6族元素とが負極表面で低抵抗の被膜を形成するためと考えられる。
負極板としては、公知の負極板を用いることができる。例えば、負極活物質と、結着剤とを水あるいは適当な分散媒に分散させて負極合材スラリーを調製し、当該負極合材スラリーを負極集電体に塗布し、塗膜を乾燥した後、圧延して、負極合材層を負極芯体の両面に形成することにより、負極板を作製できる。負極芯体には、導電性を有する薄膜体、特に、負極の電位範囲で安定な金属の箔、及び当該金属が表層に配置されているフィルム等を用いることが好適である。負極芯体に用いられる当該金属は銅又は銅合金が好ましく、負極集電体及び負極端子も銅又は銅合金製であることが好ましい。
結着剤としては、公知の結着剤を用いることができ、正極の場合と同様、PTFE等のフッ素系樹脂、PAN、ポリイミド系樹脂、アクリル系樹脂、並びに、ポリオレフィン系樹脂等を用いることができる。また、水系溶媒を用いて負極合材スラリーを調製する場合は、CMC又はその塩、スチレン-ブタジエンゴム(SBR)、ポリアクリル酸(PAA)又はその塩(PAA-Na、PAA-K等、また部分中和型の塩であってもよい)、ポリビニルアルコール(PVA)等を用いることが好ましい。負極板の作製に用いる結着剤としては、CMC又はその塩と、スチレンーブタジエン共重合体(SBR)又はこの変性体とを併用することが特に好ましい。
セパレータには、イオン透過性及び絶縁性を有する多孔性シートが用いられる。多孔性シートの具体例としては、微多孔薄膜、織布、不織布等が挙げられる。セパレータの材質としては、ポリエチレン、ポリプロピレン等のオレフィン系樹脂、セルロース等が好適である。セパレータは、セルロース繊維層及びオレフィン系樹脂等の熱可塑性樹脂繊維層を有する積層体であってもよい。また、ポリエチレン層及びポリプロピレン層を含む多層セパレータであってもよく、セパレータの表面にアラミド系樹脂等の樹脂が塗布されたものを用いることもできる。
[正極活物質の作製]
NiSO4、CoSO4及びMnSO4を水溶液中で混合して共沈させることで得たニッケルコバルトマンガン複合水酸化物を焼成して、ニッケルコバルトマンガン複合酸化物を作製した。次に、当該複合酸化物と、炭酸リチウムと、酸化タングステン(WO3)と、酸化ジルコニウム(ZrO2)とをらいかい乳鉢を用いて混合した。この混合物における、リチウムと、遷移金属であるニッケルコバルトマンガンと、タングステンと、ジルコニウムとの混合比(モル比)は1.15:1.0:0.005:0.005であった。この混合物を空気中で900℃で10時間焼成した後、粉砕することにより、W及びZrをその中に含有するリチウム遷移金属酸化物(正極活物質)を得た。そして、得られたリチウム遷移金属酸化物の元素分析をICP発光分析法により行ったところ、遷移金属全体に対するNi、Co、Mn、W及びZrの各元素のモル比はそれぞれ46.7、26.7、25.6、0.5及び0.5であった。
上記正極活物質と、カーボンブラックと、ポリフッ化ビニリデン(PVDF)とを、91:7:2の質量比で混合した。当該混合物に分散媒としてN-メチル-2-ピロリドン(NMP)を添加して混練し、正極合材スラリーを調製した。次に、正極芯体であるアルミニウム箔上に正極合材スラリーを塗布し、塗膜を乾燥させて、アルミニウム箔に正極合材層を形成した。このように正極合材層を形成した正極芯体を所定のサイズに切り出し、圧延して、アルミニウムタブを取り付け、正極とした。
黒鉛粉末と、カルボキシメチルセルロース(CMC)と、スチレン-ブタジエンゴム(SBR)とを、98:1:1の質量比で混合し、水を添加した。これを混合機(プライミクス製、T.K.ハイビスミックス)を用いて攪拌し、負極合材スラリーを調製した。次に、負極芯体である銅箔上に負極合材スラリーを塗布し、塗膜を乾燥させた後、圧延ローラにより圧延した。こうして、銅箔の両面に負極合材層が形成された負極を作製した。
エチレンカーボネート(EC)と、メチルエチルカーボネート(MEC)と、ジメチルカーボネート(DMC)と、プロピオン酸メチル(MP)と、1,2-ジメトキシエタン(DME)を、30:15:40:5:10の体積比で混合した。当該混合溶媒に、LiPF6を1.2mol/Lの濃度となるように溶解させ、さらに、ビニレンカーボネートを当該LiPF6含有混合溶媒に対して0.3質量%の濃度となるように、また、LiBOB(Li(B(C2O4)2))を当該LiPF6含有混合溶媒に対して0.05mol/Lの濃度となるように、それぞれ溶解させた。
上記正極にアルミニウムリードを、上記負極にニッケルリードをそれぞれ取り付け、ポリエチレン製の微多孔膜をセパレータとして用い、セパレータを介して正極及び負極を渦巻き状に巻回することにより巻回型の電極体を作製した。この電極体を有底円筒形状の電池ケース本体に収容し、上記非水電解質を注入した後、ガスケット及び封口体により電池ケース本体の開口部を封口して、円筒型の非水電解質二次電池(電池A1)を作製した。
正極活物質の作製工程において、リチウム含有遷移金属酸化物に混合するリン酸リチウムの量を当該酸化物の総量に対して2質量%としたこと、並びに、非水電解質の調製工程において、体積比がEC:MEC:DMC:MP:DME=30:20:40:5:5である混合溶媒を調製したこと以外は、実験例1と同様にして、円筒型の非水電解質二次電池(電池A2)を作製した。
非水電解質の調製工程において、体積比がEC:MEC:DMC:MP:DME=30:10:40:5:15である混合溶媒を調製したこと以外は、実験例2と同様にして、円筒型の非水電解質二次電池(電池A3)を作製した。
非水電解質の調製工程において、体積比がEC:MEC:DMC:MP:DME=30:5:40:5:20である混合溶媒を調製したこと以外は、実験例2と同様にして、円筒型の非水電解質二次電池(電池A4)を作製した。
非水電解質の調製工程において、体積比がEC:DMC:MP:DME=30:35:5:30である混合溶媒を調製したこと以外は、実験例2と同様にして、円筒型の非水電解質二次電池(電池A5)を作製した。
正極活物質の作製工程において、ニッケルコバルトマンガン複合酸化物、炭酸リチウム及び酸化ジルコニウムのみをらいかい乳鉢を用いて混合したこと以外は、実験例2と同様にして、円筒型の非水電解質二次電池(電池A6)を作製した。
正極活物質の作製工程において、酸化タングステンをリチウム含有遷移金属酸化物に混合しなかったこと以外は、実験例2と同様にして、円筒型の非水電解質二次電池(電池A7)を作製した。
正極活物質の作製工程において、ニッケルコバルトマンガン複合酸化物、炭酸リチウム及び酸化ジルコニウムのみをらいかい乳鉢を用いて混合し、タングステンをその中に含有しないリチウム含有遷移金属酸化物を作製したこと、並びに、非水電解質の調製工程において、体積比がEC:MEC:DMC:MP=30:25:40:5である混合溶媒を調製したこと以外は、実験例2と同様にして、円筒型の非水電解質二次電池(電池A8)を作製した。
正極活物質の作製工程において、リン酸リチウムをリチウム含有遷移金属酸化物に混合しなかったこと以外は、実験例6と同様にして、円筒型の非水電解質二次電池(電池A9)を作製した。
正極活物質の作製工程において、ニッケルコバルトマンガン複合酸化物、炭酸リチウム及び酸化ジルコニウムのみをらいかい乳鉢を用いて混合し、タングステンをその中に含有しないリチウム含有遷移金属酸化物を作製したこと、並びに、リン酸リチウムをリチウム含有遷移金属酸化物に混合しなかったこと以外は、実験例1と同様にして、円筒型の非水電解質二次電池(電池A10)を作製した。
正極活物質の作製工程において、リン酸リチウムをリチウム含有遷移金属酸化物に混合しなかったこと、並びに、非水電解質の調製工程において、体積比がEC:MEC:DMC:MP=30:25:40:5である混合溶媒を調製したこと以外は、実験例1と同様にして、円筒型の非水電解質二次電池(電池A11)を作製した。
正極活物質の作製工程において、リン酸リチウムをリチウム含有遷移金属酸化物に混合しなかったこと以外は、実験例1と同様にして、円筒型の非水電解質二次電池(電池A12)を作製した。
正極活物質の作製工程において、リチウム含有遷移金属酸化物に混合するリン酸リチウムの量を当該酸化物の総量に対して2質量%としたこと、並びに、非水電解質の調製工程において、体積比がEC:MEC:DMC:MP=30:25:40:5である混合溶媒を調製したこと以外は、実験例1と同様にして、円筒型の非水電解質二次電池(電池A13)を作製した。
上記で作製した電池A1~A13をそれぞれ用いて、25℃の温度条件下、電流値800mAで4.1Vになるまで定電流充電を行い、次いで、4.1Vで電流値が0.1mAになるまで定電圧充電を行った。その後、800mAで2.5Vになるまで定電流放電を行った。この定電流放電を行ったときの放電容量を、各二次電池の定格容量とした。
実験例7の電池A9の回生特性結果を基準として、電池A1~A13の常温回生特性の比率を算出した。その結果を表1に示す。
Claims (8)
- 正極板及び負極板がセパレータを介して積層された構造を有する電極体と、非水電解質と、を備える非水電解質二次電池であって、
前記正極板は、リチウム含有遷移金属酸化物と、周期表の第5族又は第6族に属する元素と、リン酸化合物とを含み、
前記非水電解質は1,2-ジメトキシエタンを含む
非水電解質二次電池。 - 前記周期表の第5族又は第6族に属する元素が、前記リチウム含有遷移金属酸化物に遷移金属として含有されている、請求項1に記載の非水電解質二次電池。
- 前記リチウム含有遷移金属酸化物と前記周期表の第5族/第6族元素に属する元素が固溶し、かつ、前記周期表の第5族/第6族に属する元素は、前記リチウム含有遷移金属酸化物の表面に付着している、請求項1又は2に記載の非水電解質二次電池。
- 前記周期表の第5族又は第6族に属する元素がタングステンである、請求項1~3のいずれかに記載の非水電解質二次電池。
- 前記リン酸化合物がリン酸リチウムである請求項1~4のいずれか一項に記載の非水電解質二次電池。
- 前記1,2-ジメトキシエタンの含有量が、前記非水電解質に含まれる溶媒の総量に対して3体積%以上20体積%以下である、請求項1~5のいずれか一項に記載の非水電解質二次電池。
- 前記リチウム含有遷移金属酸化物がジルコニウムを含む、請求項1~6のいずれか一項に記載の非水電解質二次電池。
- 前記非水電解質にLi(B(C2O4)2)を含む、請求項1~7のいずれか一項に記載の非水電解質二次電池。
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