WO2014038356A1 - リチウム二次電池およびその製造方法 - Google Patents
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- WO2014038356A1 WO2014038356A1 PCT/JP2013/071809 JP2013071809W WO2014038356A1 WO 2014038356 A1 WO2014038356 A1 WO 2014038356A1 JP 2013071809 W JP2013071809 W JP 2013071809W WO 2014038356 A1 WO2014038356 A1 WO 2014038356A1
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
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- 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
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- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
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- 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
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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- 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
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- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
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- Y10T29/49108—Electric battery cell making
Definitions
- the present invention relates to a lithium secondary battery and a method for manufacturing the same.
- This application claims priority based on Japanese Patent Application No. 2012-195246 filed on Sep. 5, 2012, the entire contents of which are hereby incorporated by reference.
- Lithium secondary batteries are lightweight and can obtain a high energy density, and are therefore preferably used as so-called portable power sources such as personal computers and portable terminals and vehicle power sources. In particular, it is highly important as a high-output power source for driving vehicles such as electric vehicles and hybrid vehicles. In such a lithium secondary battery, it has been proposed to add a cyclic siloxane to the non-aqueous electrolyte for the purpose of improving cycle characteristics and the like. Patent documents 1 to 4 are cited as documents disclosing this kind of technology.
- a part of components (for example, a supporting electrolyte and a non-aqueous solvent) contained in the non-aqueous electrolyte is decomposed at the time of charging, and the decomposition product is included.
- a film Solid Electrolyte Interphase film; hereinafter also referred to as “SEI film”
- SEI film Solid Electrolyte Interphase film
- Such SEI film tends to be further formed by being stored in a state where the battery is charged, or by repeating charge and discharge. Accordingly, when the SEI film is formed excessively, the resistance of the negative electrode is increased, and the battery performance such as the capacity retention rate may be lowered.
- a part of lithium in the battery can be taken in and fixed to the SEI film as a lithium compound such as LiF or Li 2 O. This can also be a factor in reducing the battery capacity of the lithium secondary battery due to excessive formation of the SEI film.
- Patent Document 1 hexamethylcyclotrisiloxane, 1,3,5-trimethyl-1,3,5-trivinylcyclotrisiloxane or 1,3,5-trimethyl-1,3,5-trimethyl is used as a cyclic siloxane. It is described that the use of an electrolytic solution containing phenylcyclotrisiloxane improved the initial output and the output after a high-temperature charge / discharge cycle compared to a lithium secondary battery using an electrolytic solution containing no cyclic siloxane. Has been. In Patent Document 2, an electrolytic solution having a composition containing hexamethylcyclotrisiloxane or hexamethyldisiloxane (chain siloxane) is used.
- these cyclic siloxanes or chain siloxanes do not provide an effect of suppressing a decrease in battery capacity due to repeated charge / discharge (for example, an effect of improving the capacity retention rate). Or the effect was insufficient.
- the present invention has been made in view of such circumstances, and an object of the present invention is to provide a lithium secondary battery with improved performance for maintaining capacity against repeated charge and discharge. Another object is to provide a method for manufacturing a lithium secondary battery having such improved performance.
- the present invention provides a lithium secondary battery including a positive electrode, a negative electrode, and a nonaqueous electrolyte.
- Cyclic siloxane and / or reaction products thereof are present on the surface of the negative electrode constituting the lithium secondary battery.
- the cyclic siloxane may be a siloxy side chain-containing cyclic siloxane having at least one dimethylsiloxy group in the side chain.
- cyclic siloxane a siloxy side chain-containing cyclic siloxane represented by the following formula (1) can be preferably used.
- R 1 and R 2 are the same or different and are each selected from a hydrogen atom and an organic group having 1 to 12 carbon atoms, and at least one of R 1 and R 2 includes a dimethylsiloxy group.
- N is an integer from 3 to 10.
- the lithium secondary battery disclosed herein may be constructed using, for example, a nonaqueous electrolyte containing 0.01 to 20% by mass of the above siloxy side chain-containing cyclic siloxane. According to such a lithium secondary battery, the effect of the presence of the siloxy side chain-containing cyclic siloxane and / or the reaction product thereof on the negative electrode surface can be suitably exhibited.
- a method for manufacturing a lithium secondary battery includes providing a positive electrode, preparing a negative electrode, and supplying cyclic siloxane to at least the negative electrode.
- the cyclic siloxane may be a siloxy side chain-containing cyclic siloxane having at least one dimethylsiloxy group in the side chain.
- the lithium secondary battery obtained by using the siloxy side chain-containing cyclic siloxane is, for example, a lithium secondary battery using a cyclic siloxane whose side chain is only an alkyl group instead of the siloxy side chain-containing cyclic siloxane.
- the capacity retention rate may be higher than that of a lithium secondary battery using a chain siloxane instead of the siloxy side chain-containing cyclic siloxane.
- the compound represented by said Formula (1) can be employ
- the supply of the cyclic siloxane includes preparing a non-aqueous electrolyte containing the cyclic siloxane and supplying the prepared non-aqueous electrolyte to the negative electrode. Include.
- the cyclic siloxane contained in the non-aqueous electrolyte can be supplied to the negative electrode, and a lithium secondary battery in which the siloxy side chain-containing cyclic siloxane and / or the reaction product thereof are appropriately arranged on the negative electrode surface is realized. Can be done.
- the production method disclosed herein can be preferably carried out in a mode in which a nonaqueous electrolyte containing 0.01 to 20% by mass of the siloxy side chain-containing cyclic siloxane is used as the nonaqueous electrolyte.
- a nonaqueous electrolyte containing 0.01 to 20% by mass of the siloxy side chain-containing cyclic siloxane is used as the nonaqueous electrolyte.
- the lithium secondary battery disclosed herein is excellent in performance (capacity maintenance) for maintaining battery capacity against repeated charge and discharge. Therefore, taking advantage of this feature, it can be suitably used as a drive power source for vehicles such as hybrid vehicles (HV), plug-in hybrid vehicles (PHV), electric vehicles (EV) and the like. According to the present invention, there is provided a vehicle equipped with any of the lithium secondary batteries disclosed herein (which may be in the form of an assembled battery in which a plurality of batteries are connected).
- FIG. 1 is a perspective view schematically showing the outer shape of a lithium secondary battery according to an embodiment.
- FIG. 2 is a cross-sectional view taken along the line II-II in FIG.
- FIG. 3 is a perspective view schematically showing a state in which the electrode body according to the embodiment is wound and manufactured.
- FIG. 4 is a graph showing the relationship between the content of cyclic siloxane and the capacity retention rate in the nonaqueous electrolyte.
- FIG. 5 is a side view schematically showing a vehicle (automobile) including the lithium secondary battery according to the embodiment.
- secondary battery generally refers to a battery that can be repeatedly charged and discharged.
- a storage battery ie, a chemical battery
- a capacitor ie, a physical battery
- an electric double layer capacitor ie, a battery that uses lithium ions (Li ions) as electrolyte ions and is charged and discharged by the movement of charges associated with Li ions between the positive and negative electrodes.
- a secondary battery using a metal ion other than Li ion (for example, sodium ion) as a charge carrier can be included in the “lithium secondary battery” in this specification.
- a battery generally called a lithium ion secondary battery is a typical example included in the lithium secondary battery in this specification.
- the lithium secondary battery 100 includes a rectangular box-shaped battery case 10 and a wound electrode body 20 accommodated in the battery case 10.
- the battery case 10 has an opening 12 on the upper surface.
- the opening 12 is sealed by the lid 14 after the wound electrode body 20 is accommodated in the battery case 10 from the opening 12.
- the battery case 10 also contains a nonaqueous electrolyte (nonaqueous electrolyte solution) 25.
- the lid body 14 is provided with an external positive terminal 38 and an external negative terminal 48 for external connection, and a part of the terminals 38 and 48 protrudes to the surface side of the lid body 14.
- a part of the external positive terminal 38 is connected to the internal positive terminal 37 inside the battery case 10, and a part of the external negative terminal 48 is connected to the internal negative terminal 47 inside the battery case 10.
- the wound electrode body 20 includes a long sheet-like positive electrode (positive electrode sheet) 30 and a long sheet-like negative electrode (negative electrode sheet) 40.
- the positive electrode sheet 30 includes a long positive electrode current collector 32 and a positive electrode active material layer 34 formed on at least one surface (typically both surfaces) thereof.
- the negative electrode sheet 40 includes a long negative electrode current collector 42 and a negative electrode active material layer 44 formed on at least one surface (typically both surfaces) thereof.
- the wound electrode body 20 also includes two long sheet-like separators (separator sheets) 50A and 50B.
- the positive electrode sheet 30 and the negative electrode sheet 40 are laminated via two separator sheets 50A and 50B, and the positive electrode sheet 30, the separator sheet 50A, the negative electrode sheet 40, and the separator sheet 50B are laminated in this order.
- the laminated body is formed into a wound body by being wound in the longitudinal direction, and is further formed into a flat shape by pressing the wound body from the side direction and causing it to be ablated.
- the form of the electrode body is not limited to the wound electrode body as described above, and an appropriate shape and configuration such as a laminate type (stacked type), for example, is appropriately employed depending on the shape of the battery, the purpose of use, and the like. be able to.
- a positive electrode active material layer 34 formed on the surface of the positive electrode current collector 32 and a surface of the negative electrode current collector 42 are formed at the center in the width direction of the wound electrode body 20 (direction orthogonal to the winding direction).
- the negative electrode active material layer 44 thus formed is overlapped and densely stacked. Further, at one end in the width direction of the positive electrode sheet 30, a portion where the positive electrode current collector 32 is exposed without forming the positive electrode active material layer 34 (positive electrode active material layer non-forming portion 36) is provided. .
- the positive electrode active material layer non-forming portion 36 protrudes from the separator sheets 50 ⁇ / b> A and 50 ⁇ / b> B and the negative electrode sheet 40.
- a positive electrode current collector laminated portion 35 in which the positive electrode active material layer non-forming portion 36 of the positive electrode current collector 32 overlaps is formed.
- a portion 45 is formed.
- the separator sheets 50 ⁇ / b> A and 50 ⁇ / b> B have a width that is larger than the width of the laminated portion of the positive electrode active material layer 34 and the negative electrode active material layer 44 and smaller than the width of the wound electrode body 20.
- the positive electrode active material layer 34 and the negative electrode active material layer 44 are prevented from contacting each other and causing an internal short circuit. .
- a positive electrode current collector constituting a positive electrode (typically, a positive electrode sheet) of a lithium secondary battery a conductive member made of a metal having good conductivity is preferably used.
- a conductive member for example, aluminum or an alloy containing aluminum as a main component can be used.
- the shape of the positive electrode current collector can be different depending on the shape of the battery and is not particularly limited, and may be various forms such as a rod shape, a plate shape, a sheet shape, a foil shape, and a mesh shape.
- the thickness of the positive electrode current collector is not particularly limited, and can be, for example, 5 ⁇ m to 30 ⁇ m.
- the positive electrode active material layer is one or two kinds of known additives that can be blended in the positive electrode active material layer of a general lithium secondary battery, such as a conductive material and a binder, in addition to the positive electrode active material.
- a general lithium secondary battery such as a conductive material and a binder, in addition to the positive electrode active material.
- the above can be contained as needed.
- the positive electrode active material one or more of various materials known to be usable as a positive electrode active material for lithium secondary batteries can be used without particular limitation.
- a lithium transition metal compound typically an oxide
- a polyanion type for example, olivine type
- a lithium transition metal compound or the like can be used.
- a positive electrode active material can be used individually by 1 type or in combination of 2 or more types as appropriate. More specifically, for example, the following compounds can be used as the positive electrode active material.
- M includes at least one transition metal element such as Ni, Co, and Mn, and may further include another metal element or a nonmetal element.
- Specific examples of the compound represented by the general formula (A1) include LiNiO 2 and LiNi 1/3 Co 1/3 Mn 1/3 O 2 .
- x is 0 ⁇ x ⁇ 2, and typically 0 ⁇ x ⁇ 1.
- M can be any metallic or nonmetallic element other than Mn.
- a composition in which M contains at least one transition metal element is preferred.
- Specific examples of the compound represented by the general formula (B1) include LiMn 2 O 4 , LiNi 0.5 Mn 1.5 O 4 , LiCrMnO 4 and the like.
- M includes at least one transition metal element such as Mn, Fe, and Co, and may further include another metal element or a nonmetal element.
- Specific examples of the compound represented by the general formula (C1) include Li 2 MnO 3 and Li 2 PtO 3 .
- M includes at least one transition metal element such as Mn, Fe, Ni, and Co, and may further include another metal element or a nonmetal element.
- Specific examples of the compound represented by the general formula (D1) include LiMnPO 4 and LiFePO 4 .
- M includes at least one transition metal element such as Mn, Ni, and Co, and may further include another metal element or a nonmetal element.
- Specific examples of the compound represented by the general formula (E1) include LiMnPO 4 F.
- Li 1 + ⁇ MO 2 refers to the composition represented by the general formula (A1) described in the above (1)
- Li 2 + ⁇ MO 3 represents the composition represented by the general formula (C1) described in the above (3).
- a solid solution represented by 0.5LiNi 1/3 Mn 1/3 Co 1/3 O 2 —0.5Li 2 MnO 3 can be given.
- ⁇ in each of the composition formulas in the above (1) to (6) is 0 ⁇ ⁇ ⁇ 0.5, and typically 0 ⁇ ⁇ ⁇ 0.3 (for example, 0 ⁇ ⁇ ⁇ 0.2). Is appropriate.
- a lithium secondary battery is a lithium transition metal oxide having a layered crystal structure (typically a layered rock salt structure belonging to a hexagonal system) as a positive electrode active material.
- a lithium transition metal oxide having a layered crystal structure typically a layered rock salt structure belonging to a hexagonal system
- a configuration in which 90% by mass or more of the positive electrode active material is a lithium transition metal oxide having a layered crystal structure can be preferably employed.
- the layered lithium transition metal oxide may be substantially 100% by mass of the positive electrode active material.
- the layered lithium transition metal oxide preferably contains at least one of Ni, Co and Mn.
- Preferable examples include lithium nickel oxide, lithium cobalt oxide, and lithium manganese oxide.
- the lithium nickel oxide is an oxide containing lithium (Li), nickel (Ni), and oxygen as constituent elements, and at least one other element in addition to lithium, nickel, and oxygen. It is meant to include oxides contained as constituent elements at a rate equivalent to nickel or less than nickel in terms of conversion.
- the metal elements other than Li and Ni include, for example, Co, Mn, W, Cr, Mo, Ti, Zr, Nb, V, Al, Mg, Ca, Na, Fe, Cu, Zn, Si, Ga, In, It may be one or more elements selected from Sn, La, Ce, B and F. The same meaning applies to lithium cobalt oxide and lithium manganese oxide.
- a positive electrode active material containing a layered lithium transition metal oxide (Ni-containing layered lithium transition metal oxide) having a composition containing at least Ni can be preferably used.
- a positive electrode active material containing a layered lithium transition metal oxide containing Ni in an amount of 10 mol% or more (more preferably 20 mol% or more) with the total amount of metal elements other than lithium being 100 mol% is preferable.
- a preferred example of such a Ni-containing layered lithium transition metal oxide is a layered lithium transition metal oxide containing all of Ni, Co and Mn (hereinafter also referred to as “LiNiCoMn oxide”).
- LiNiCoMn oxide a layered lithium transition metal oxide containing all of Ni, Co and Mn
- the total amount of Ni, Co, and Mn is 1, and the amounts of Ni, Co, and Mn are both greater than 0 and less than or equal to 0.7 (more preferably greater than 0.1 and
- a LiNiCoMn oxide that is typically more than 0.3 and 0.5 or less is preferable.
- a LiNiCoMn oxide for example, LiNi 1/3 Co 1/3 Mn 1/3 O 2 ) having substantially the same amount of Ni, Co, and Mn is preferable.
- the layered lithium transition metal oxide may contain at least one of Ni, Co, and Mn, and may further contain one or more other elements as additional constituent elements (additive elements).
- additive elements include W, Cr, Mo, Ti, Zr, Nb, V, Al, Mg, Ca, Na, Fe, Cu, Zn, Si, Ga, In, Sn, La, Ce, B, and F is exemplified.
- a layered lithium transition metal oxide for example, LiNiCoMn oxide having a composition containing at least one metal element selected from W, Cr, and Mo as the additive element can be preferably used.
- the additive amount of such an additive element is, for example, about 0.001 to 5 mol% (typically about 0.001 to 5 mol%) when the total amount of elements other than lithium and oxygen contained in the layered lithium transition metal oxide is 100 mol%. 005 to 1 mol%).
- a composition containing at least W as the additive element is preferable.
- a battery using a positive electrode active material containing such a layered lithium transition metal oxide can have reduced reaction resistance and excellent input / output characteristics. Or the layered lithium transition metal oxide which does not contain the above additive elements may be sufficient.
- a lithium secondary battery according to another preferred embodiment of the technology disclosed herein includes a compound represented by the general formula (B1) as a positive electrode active material.
- a configuration in which 90% by mass or more (for example, substantially 100% by mass) of the positive electrode active material is a compound represented by the general formula (B1) can be preferably adopted.
- a compound in which M in the general formula (B1) contains at least Ni for example, the following general formula (B2): LiNi p M 1 q Mn 2-p And a lithium transition metal oxide having a spinel structure represented by —q O 4 ; (hereinafter also referred to as “LiNiMn composite oxide”).
- the charge of LiNiMn composite oxide having a spinel structure (for example, LiNi 0.5 Mn 1.5 O 4 ) at the end of charging
- the positive electrode potential can be increased (typically higher than 4.5 V (vs. Li / Li + ) or more), and a 5 V-class lithium secondary battery can be constructed.
- M 1 is one or more of any metal element or non-metal element other than Ni and Mn (for example, Ti, Fe, Co, Cu, 1 type or 2 types or more selected from Cr, Zn and Al). It is preferable that M 1 contains at least one of trivalent Fe and Co. Moreover, it is preferable that 0 ⁇ q ⁇ 0.3 and 1 ⁇ 2p + q.
- the lithium transition metal oxide used as the positive electrode active material is, based on the number of atoms, the total amount m Mall of all metal elements other than Li contained in the lithium transition metal oxide. It may be a composition containing an excessive amount of Li. That is, the composition may satisfy 1.00 ⁇ (m Li / m Mall ). Thus, according to the lithium transition metal oxide having a composition containing excess Li against M all, higher performance (e.g., good output performance) lithium secondary battery can be realized.
- (m Li / m Mall ) is 1.05 or more, more preferably 1.10 or more (that is, 1.10 ⁇ (m Li / m Mall )).
- the upper limit of m Li / m Mall is not particularly limited. Usually, it is preferable that mLi / m Mall is 1.4 or less (preferably 1.3 or less, for example, 1.2 or less).
- the shape of the positive electrode active material is usually preferably a particle shape having an average particle diameter of about 1 ⁇ m to 20 ⁇ m (eg, 2 ⁇ m to 10 ⁇ m).
- the “average particle size” means a particle size at an integrated value of 50% in a particle size distribution measured based on a particle size distribution measuring apparatus based on a laser scattering / diffraction method, that is, 50%. It shall mean the volume average particle diameter.
- a conductive powder material such as carbon powder or carbon fiber is preferably used.
- carbon powder various carbon blacks such as acetylene black, furnace black, ketjen black, and graphite powder are preferable.
- conductive fibers such as carbon fibers and metal fibers, metal powders such as copper and nickel, and organic conductive materials such as polyphenylene derivatives can be used singly or as a mixture of two or more. .
- the binder various polymer materials may be mentioned.
- the positive electrode active material layer is formed using an aqueous composition (a composition using water or a mixed solvent containing water as a main component as a dispersion medium for active material particles), it is water-soluble or water-dispersible.
- these polymer materials can be preferably employed as the binder.
- water-soluble or water-dispersible polymer materials include cellulose polymers such as carboxymethyl cellulose (CMC); polyvinyl alcohol (PVA); fluorine resins such as polytetrafluoroethylene (PTFE); vinyl acetate polymers; styrene butadiene rubber Rubbers such as (SBR) and acrylic acid-modified SBR resin (SBR latex);
- cellulose polymers such as carboxymethyl cellulose (CMC); polyvinyl alcohol (PVA); fluorine resins such as polytetrafluoroethylene (PTFE); vinyl acetate polymers; styrene butadiene rubber Rubbers such as (SBR) and acrylic acid-modified SBR resin (SBR latex);
- a positive electrode active material layer is formed using a solvent-based composition (a composition in which the dispersion medium of active material particles is mainly an organic solvent), polyvinylidene fluoride (PVDF), polyvinylidene chloride (PVDC)
- PVDF poly
- Such a binder can be used individually by 1 type or in combination of 2 or more types.
- the polymer material illustrated above may be used as a thickener and other additives in the composition for forming a positive electrode active material layer, in addition to being used as a binder.
- the proportion of the positive electrode active material in the positive electrode active material layer is preferably more than about 50% by mass and about 70% by mass to 97% by mass (eg, 75% by mass to 95% by mass).
- the ratio of the additive in the positive electrode active material layer is not particularly limited, but the ratio of the conductive material is about 1 to 20 parts by mass (for example, 2 to 10 parts by mass with respect to 100 parts by mass of the positive electrode active material). (Typically 3 to 7 parts by mass).
- the ratio of the binder is about 0.8 to 10 parts by mass (for example, 1 to 7 parts by mass, typically 2 to 5 parts by mass) with respect to 100 parts by mass of the positive electrode active material. It is preferable.
- the method for producing the positive electrode as described above is not particularly limited, and a conventional method can be appropriately employed. For example, it can be produced by the following method.
- a composition is prepared.
- the mixing operation can be performed using, for example, a suitable kneader (planetary mixer, homodisper, clear mix, fill mix, etc.).
- a solvent used for preparing the composition both an aqueous solvent and a non-aqueous solvent can be used.
- the aqueous solvent is not particularly limited as long as it is water-based as a whole, and water or a mixed solvent mainly composed of water can be preferably used.
- Preferable examples of the non-aqueous solvent include N-methyl-2-pyrrolidone (NMP), methyl ethyl ketone, toluene and the like.
- the composition prepared in this manner is applied to the positive electrode current collector, the solvent is volatilized by drying, and then compressed (pressed) as necessary.
- a method for applying the composition to the positive electrode current collector a technique similar to a conventionally known method can be appropriately employed.
- the composition can be suitably applied to the positive electrode current collector by using an appropriate application device such as a slit coater, a die coater, a gravure coater, or a comma coater.
- it can dry favorably by using natural drying, a hot air, low-humidity air, a vacuum, infrared rays, far infrared rays, and an electron beam individually or in combination.
- a compression method a conventionally known compression method such as a roll press method or a flat plate press method can be employed.
- the thickness may be measured with a film thickness measuring instrument, and the press pressure may be adjusted to compress the film a plurality of times until a desired thickness is obtained. In this way, a positive electrode in which the positive electrode active material layer is formed on the positive electrode current collector is obtained.
- the basis weight per unit area of the positive electrode active material layer on the positive electrode current collector (the coating amount in terms of solid content of the composition for forming the positive electrode active material layer) is not particularly limited, but a sufficient conductive path From the viewpoint of securing the (conductive path), it is 3 mg / cm 2 or more (for example, 5 mg / cm 2 or more, typically 6 mg / cm 2 or more) per side of the positive electrode current collector, and 45 mg / cm 2 or less (for example, 28 mg / cm 2 or less, typically 15 mg / cm 2 or less).
- the negative electrode current collector constituting the negative electrode typically, the negative electrode sheet
- a conductive member made of a metal having good conductivity is preferably used as in the conventional lithium secondary battery.
- a conductive member for example, copper or an alloy containing copper as a main component can be used.
- the shape of the negative electrode current collector can be different depending on the shape of the battery and is not particularly limited, and may be various forms such as a rod shape, a plate shape, a sheet shape, a foil shape, and a mesh shape.
- the thickness of the negative electrode current collector is not particularly limited, and can be, for example, about 5 ⁇ m to 30 ⁇ m.
- the negative electrode active material layer includes a negative electrode active material that can occlude and release Li ions serving as charge carriers.
- a negative electrode active material that can occlude and release Li ions serving as charge carriers.
- the 1 type (s) or 2 or more types of the material conventionally used for a lithium secondary battery can be used.
- Examples of such a negative electrode active material include carbon materials that are generally used in lithium secondary batteries.
- Representative examples of the carbon material include graphite carbon (graphite) and amorphous carbon.
- the natural graphite may be a spheroidized graphite.
- a carbonaceous powder having a graphite surface coated with amorphous carbon may be used.
- a negative electrode active material it is also possible to use a single material, an alloy, a compound, or a composite material using the above materials in combination, such as an oxide such as lithium titanate, a silicon material, or a tin material.
- Metal lithium may be used as the negative electrode active material.
- the proportion of the negative electrode active material in the negative electrode active material layer exceeds approximately 50% by mass, and approximately 90% by mass to 99% by mass (eg, 95% by mass to 99% by mass, typically 97% by mass to 99% by mass). It is preferable that
- the negative electrode active material layer requires one or more binders, thickeners, and other additives that can be blended in the negative electrode active material layer of a typical lithium secondary battery. It can be contained accordingly.
- the binder include various polymer materials.
- the same thing as what can be contained in a positive electrode active material layer can be preferably used with respect to an aqueous composition or a solvent-type composition.
- Such a binder can be used as a thickener and other additives in the composition for forming a negative electrode active material layer, in addition to being used as a binder.
- the ratio of these additives in the negative electrode active material layer is not particularly limited, but is approximately 0.8% to 10% by mass (for example, approximately 1% to 5% by mass, typically 1% to 3% by mass). It is preferable that
- the method for producing the negative electrode is not particularly limited, and a conventional method can be adopted.
- a negative electrode active material is mixed with a binder or the like in the appropriate solvent (aqueous solvent, organic solvent, or mixed solvent thereof) to prepare a paste-form or slurry-form composition for forming a negative electrode active material layer.
- the composition thus prepared is applied to the negative electrode current collector, the solvent is volatilized by drying, and then compressed (pressed) as necessary.
- a negative electrode active material layer can be formed on a negative electrode current collector using the composition, and a negative electrode including the negative electrode active material layer can be obtained.
- a method of mixing, coating, drying, and compression the same means as the above-described production of the positive electrode can be employed.
- the basis weight per unit area of the negative electrode active material layer on the negative electrode current collector (the coating amount in terms of solid content of the composition for forming the negative electrode active material layer) is not particularly limited, but a sufficient conductive path From the viewpoint of securing a (conduction path), it is 2 mg / cm 2 or more (for example, 3 mg / cm 2 or more, typically 4 mg / cm 2 or more) per side of the negative electrode current collector, and 40 mg / cm 2 or less (for example, 22 mg / cm 2 or less, typically 10 mg / cm 2 or less).
- a predetermined cyclic siloxane and / or a reaction product thereof is present at least on the surface of the negative electrode (which may be the surface of the negative electrode active material particles).
- the cyclic siloxane is a siloxy side chain-containing cyclic siloxane having at least one siloxy group (—OSi group) in the side chain.
- the cyclic siloxane “having at least one siloxy group in the side chain” means that at least one of silicon atoms constituting the siloxane ring (hereinafter also referred to as “ring-constituting Si atom”) contains a siloxy group. Having a side chain of structure (siloxy side chain) as a substituent.
- the cyclic siloxane in the technology disclosed herein typically has at least one siloxy side chain having a structure containing a dimethylsiloxy group (—OSi (CH 3 ) 2 H).
- Such a cyclic siloxane (siloxy side chain-containing cyclic siloxane) has a three-dimensional structure including a cyclic structure and a siloxy side chain extending from the ring.
- the cyclic siloxane having a steric structure and / or a reaction product thereof can act to effectively inhibit the formation of the SEI film on the negative electrode surface due to the steric effect.
- a decrease in battery performance due to excessive formation of the SEI film is suppressed, and, for example, an effect of improving battery capacity maintainability (capacity maintenance ratio) against repeated charge and discharge can be realized.
- the present inventors have confirmed that such an effect of improving the capacity retention rate is not realized by a chain siloxane or a cyclic siloxane having only an alkyl group in the side chain (that is, a cyclic siloxane having no siloxy side chain).
- a chain siloxane or a cyclic siloxane having only an alkyl group in the side chain that is, a cyclic siloxane having no siloxy side chain.
- the mechanism is unknown, it is speculated that the cyclic siloxane and the siloxy side chain play an important role in improving the capacity retention rate.
- cyclic siloxane and / or reaction product thereof means a component (typically a precipitate) derived from the cyclic siloxane as described above. It can be interpreted as including at least one of the reaction products.
- the reaction product can be, for example, a reduction decomposition product of the cyclic siloxane, a reaction product of the cyclic siloxane or the reduction decomposition product thereof with a nonaqueous solvent, and the like. Presence or absence of precipitates derived from cyclic siloxane can be confirmed by, for example, collecting a sample from the electrode surface and applying a known analysis means such as ICP (High Frequency Inductively Coupled Plasma) emission analysis.
- ICP High Frequency Inductively Coupled Plasma
- the above-mentioned cyclic siloxane is a compound having a ring (siloxane ring) in which Si and O are alternately continuous.
- the number of atoms constituting the siloxane ring is not particularly limited, but it is usually 4 to 20 in view of film-forming properties, etc., and 4 to 12 (for example, It is preferably 4 to 10, typically 6 or 8).
- the number of siloxy side chains is not particularly limited as long as it is 1 or more, but 2 or more is preferable and 3 or more is more preferable from the viewpoint of obtaining a larger steric effect.
- the number of siloxy side chains can be 2 times or less of the number of ring-constituting Si atoms, and it is usually appropriate to be 0.5 to 1.5 times the number of ring-constituting Si atoms.
- a cyclic siloxane having a structure in which one siloxy side chain is bonded to all ring-constituting Si atoms can be preferably used.
- the siloxy side chain in the technology disclosed herein may be an organic group having 1 to 12 carbon atoms (typically 2 to 12, for example 2 to 10), including at least one siloxy group.
- it may be a siloxy side chain having a structure in which a saturated or unsaturated hydrocarbon group, a saturated or unsaturated fluorine-substituted hydrocarbon group, a hydrogen atom, a halogen atom or the like is bonded to a siloxy group.
- the hydrocarbon group include an alkyl group, an alkenyl group, a vinyl group, an allyl group, an aryl group (for example, a phenyl group), an alkylaryl group, and the like.
- the fluorine-substituted hydrocarbon group may be a group having a structure in which part or all of the hydrogen atoms in the saturated or unsaturated hydrocarbon group are replaced with fluorine.
- it may be a fluorinated alkyl group such as a monofluoromethyl group, a difluoromethyl group, and a perfluoromethyl group.
- the number of siloxy groups contained in one siloxy side chain may be 2 or more (for example, about 2 to 5), but is usually preferably 1.
- the siloxy group contained in the siloxy side chain may be bonded to the ring-constituting Si atom via another structural part (for example, an alkylene group such as a methylene group or an oxyalkylene group such as an oxyethylene group).
- a siloxy group (—OSi group) may be directly bonded to the ring-constituting Si atom.
- a cyclic siloxane having at least one siloxy side chain in which a siloxy group is directly bonded to a ring-constituting Si atom is preferable.
- Preferable examples of the siloxy side chain in a structure in which a siloxy group is directly bonded to a ring-constituting Si atom include an alkylsiloxy group.
- R 31 is an alkyl group, preferably an alkyl group having 1 to 12 carbon atoms (more preferably 1 to 6, for example 1 to 3).
- R 32 and R 33 are each independently selected from a hydrogen atom and an alkyl group.
- the alkyl group preferably has 1 to 12 carbon atoms, more preferably 1 to 6, for example 1 to 3.
- the siloxy side chain in the technology disclosed herein may be a dialkylsiloxy group in which R 32 is an alkyl group and R 33 is a hydrogen atom, and a trialkylsiloxy in which R 32 and R 33 are both alkyl groups.
- the group may be a monoalkylsiloxy group in which R 32 and R 33 are both hydrogen atoms. From the viewpoint of steric effects and the like, a dialkylsiloxy group or a trialkylsiloxy group is preferable. In addition, a dialkylsiloxy group is particularly preferable from the viewpoint of film formability and the like.
- dialkylsiloxy group examples include a dialkylsiloxy group represented by the following formula: —OSiR 41 R 42 H; R 41 and R 42 may each independently be an alkyl group having 1 to 12 carbon atoms (preferably 1 to 6, more preferably 1 to 3).
- dimethylsiloxy group diethylsiloxy group, di- (n-propyl) siloxy group, di- (isopropyl) siloxy group, dibutylsiloxy group, dipentylsiloxy group, diheptylsiloxy group, dicyclohexylsiloxy group, methylethyl
- examples include a siloxy group, a methylpropylsiloxy group, a methylbutylsiloxy group, an ethylpropylsiloxy group, an ethylbutylsiloxy group, a propylbutylsiloxy group, and the like.
- a dialkylsiloxy group in which R 41 and R 42 are the same group is preferred.
- R 1 and R 2 are the same or different and are each selected from a hydrogen atom and an organic group having 1 to 12 carbon atoms, and at least one of R 1 and R 2 includes a dimethylsiloxy group.
- n is an integer of 3 to 10.
- groups other than the dimethylsiloxy group in R 1 and R 2 can be independently selected from a hydrogen atom and an organic group having 1 to 12 carbon atoms.
- the organic group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group, n-pentyl group, 1-methylbutyl group, Chain alkyl groups such as 2-methylbutyl group, 3-methylbutyl group, 1-methyl-2-methylpropyl group, 2,2-dimethylpropyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group; cyclohexyl Groups, cyclic alkyl groups such as norbornanyl group; alkenyl groups such as vinyl group, 1-propenyl group, allyl group, butenyl group, 1,3-buta
- the group other than the dimethylsiloxy group is preferably a hydrogen atom or an organic group having 1 to 10 carbon atoms (for example, 1 to 6).
- Preferable examples include a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 4 carbon atoms, an aryl group having 6 to 8 carbon atoms, and the like.
- a hydrogen atom or an alkyl group having 1 to 4 carbon atoms is preferable.
- At least one of R 1 and R 2 contains a dimethylsiloxy group.
- all of at least one of R 1 and R 2 (typically only one of R 1 and R 2 ) is a dimethylsiloxy group.
- N in the above formula (1) is an integer of 3 to 10.
- n is preferably an integer of 3 to 6, more preferably an integer of 3 to 5, and particularly preferably 3 or 4 (for example, 4).
- cyclic siloxane having a dimethylsiloxy group in the side chain examples include dimethylsiloxy side chain-containing cyclotrisiloxane, dimethylsiloxy side chain-containing cyclotetrasiloxane, dimethylsiloxy side chain-containing cyclopentasiloxane, and dimethylsiloxy side chain-containing.
- Examples include cyclohexasiloxane, dimethylsiloxy side chain-containing cycloheptasiloxane, dimethylsiloxy side chain-containing cyclooctasiloxane, dimethylsiloxy side chain-containing cyclononasiloxane, and dimethylsiloxy side chain-containing cyclodecasiloxane.
- dimethylsiloxy side chain-containing cyclotrisiloxane, dimethylsiloxy side chain-containing cyclotetrasiloxane, dimethylsiloxy side chain-containing cyclopentasiloxane, and dimethylsiloxy side chain-containing cyclohexasiloxane are preferable from the viewpoint of improving capacity retention.
- Siloxy side chain containing cyclotetrasiloxane is particularly preferred.
- a cyclic siloxane in which at least one of R 1 and R 2 in the formula (1) is fixed to one type is advantageous.
- Specific examples of such cyclic siloxanes include one in which R 1 is one kind of alkyl such as 2,4,6,8-tetraisobutyl-2,4,6,8-tetra (dimethylsiloxy) cyclotetrasiloxane.
- R 1 is one kind of alkyl
- R 2 is one type of siloxy group
- 2,4-dimethyl-6,8-diethyl-2,4,6,8-tetra dimethylsiloxy
- the separator (separator sheet) disposed so as to separate the positive electrode and the negative electrode may be a member that insulates the positive electrode active material layer and the negative electrode active material layer and allows the electrolyte to move.
- the separator include those made of a porous polyolefin resin.
- a porous separator sheet made of a synthetic resin for example, made of polyethylene, polypropylene, or a polyolefin having a structure of two or more layers combining these
- This separator sheet may be provided with a heat-resistant layer.
- the electrolyte itself can function as a separator, so that a separator is not necessary. There can be.
- a non-aqueous electrolyte (typically, an electrolyte that exhibits a liquid state at a room temperature of about 25 ° C., ie, an electrolytic solution) injected into a lithium secondary battery can include at least a non-aqueous solvent and a supporting salt.
- a typical example is an electrolytic solution having a composition in which a supporting salt is contained in a suitable non-aqueous solvent.
- the non-aqueous solvent various carbonates, ethers, esters, nitriles, sulfones, lactones, and the like can be used in the same manner as the electrolyte solution of a general lithium secondary battery.
- the carbonates mean to include cyclic carbonates and chain carbonates.
- the ethers mean to include cyclic ethers and chain ethers.
- Specific examples of the compound that can be used as the non-aqueous solvent include ethylene carbonate (EC), propylene carbonate (PC), diethyl carbonate (DEC), dimethyl carbonate (DMC), ethyl methyl carbonate (EMC), and vinylene carbonate (VC).
- a non-aqueous solvent mainly composed of carbonates can be mentioned.
- one or more carbonates are included as the non-aqueous solvent, and the total mass of these carbonates is 60% by mass or more (more preferably 75% by mass or more, more preferably 90% by mass) of the total mass of the non-aqueous solvent. % Or more and may be substantially 100% by mass).
- Preferable specific examples include a mixed solvent of EC and EMC, a mixed solvent of EC, DMC and EMC.
- non-aqueous solvent in the technology disclosed herein include a non-aqueous solvent containing one or more fluorinated carbonates (for example, fluorinated products of carbonates as described above).
- fluorinated carbonates for example, fluorinated products of carbonates as described above.
- Either a fluorinated cyclic carbonate or a fluorinated chain carbonate can be preferably used.
- a fluorinated carbonate having one carbonate structure in one molecule it is preferable to use a fluorinated carbonate having one carbonate structure in one molecule.
- the fluorine substitution rate of the fluorinated carbonate is usually suitably 10% or more, and can be, for example, 20% or more (typically 20% or more and 100% or less, such as 20% or more and 80% or less).
- the supporting salt examples include LiPF 6 , LiBF 4 , LiClO 4 , LiAsF 6 , LiCF 3 SO 3 , LiC 4 F 9 SO 3 , LiN (CF 3 SO 2 ) 2 , LiC (CF 3 SO 2 ) 3 , LiI. 1 type, or 2 or more types of lithium compounds (lithium salt), such as these, can be used.
- the concentration of the supporting salt is not particularly limited, but is about 0.1 mol / L to 5 mol / L (for example, 0.5 mol / L to 3 mol / L, typically 0.8 mol / L to 1.5 mol / L). Concentration.
- the non-aqueous electrolyte may contain an optional additive as necessary as long as the object of the present invention is not significantly impaired.
- the additive is used for one or more purposes such as, for example, improving battery output performance, improving storage stability (suppressing capacity reduction during storage, etc.), improving cycle characteristics, improving initial charge / discharge efficiency, etc. Can be done.
- preferable additives include fluorophosphate (preferably difluorophosphate, for example, lithium difluorophosphate represented by LiPO 2 F 2 ), lithium bisoxalate borate (LiBOB), and the like.
- additives such as cyclohexylbenzene and biphenyl which can be used for overcharge countermeasures may be used.
- the method for manufacturing a secondary battery includes preparing a positive electrode and a negative electrode and supplying the cyclic siloxane to at least the negative electrode.
- the manufacturing method can include other steps such as, for example, constructing a positive electrode, constructing a negative electrode, and constructing a lithium secondary battery using the positive electrode and the negative electrode. Since it can be performed by appropriately adopting the above-described explanation and the conventionally used technique, it will not be particularly described here.
- the production method disclosed herein includes supplying a siloxy side chain-containing cyclic siloxane to at least the negative electrode. At least a part of the siloxy side chain-containing cyclic siloxane supplied to the negative electrode is present on the negative electrode surface as a siloxy side chain-containing cyclic siloxane and / or its reaction product (for example, adhering to the negative electrode by adsorption, deposition, precipitation, etc.) However, it can act to suppress the formation of the SEI film on the negative electrode surface.
- the siloxy side chain containing cyclic siloxane the above-mentioned thing can be used preferably.
- the said siloxy side chain containing cyclic siloxane should just be supplied to a negative electrode at least, and may be supplied also to battery components other than negative electrodes, such as a positive electrode.
- the siloxy side chain-containing cyclic siloxane is supplied to the negative electrode through a nonaqueous electrolyte.
- a lithium secondary battery may be constructed by preparing (preparing) a non-aqueous electrolyte containing the siloxy side chain-containing cyclic siloxane and placing the non-aqueous electrolyte in contact with the positive electrode and the negative electrode. According to this supply method, the siloxy side chain-containing cyclic siloxane can be accurately supplied to each part of the negative electrode surface.
- the content (% by mass) of the siloxy side chain-containing cyclic siloxane in the non-aqueous electrolyte is not particularly limited. From the viewpoint of obtaining a sufficient capacity retention rate improvement effect, it is usually preferably 0.005% by mass or more (eg, 0.01% by mass or more, typically 0.05% by mass or more). Further, from the viewpoint of suppressing a decrease in battery characteristics (for example, an increase in resistance) due to excessive addition, the content is preferably less than 25% by mass (more preferably 20% by mass or less, for example, 15% by mass or less).
- the content rate of the siloxy side chain containing cyclic siloxane in a nonaqueous electrolyte can be 10 mass% or less, for example, even if it is 5 mass% or less. It may be 1% by mass or less.
- the supply method of the said siloxy side chain containing cyclic siloxane to a negative electrode is not limited to the inclusion to the above nonaqueous electrolytes.
- a method in which a liquid in which a siloxy side chain-containing cyclic siloxane is dissolved or dispersed in an appropriate liquid medium (typically water or an organic solvent) is applied to the surface of the negative electrode and dried as necessary can be mentioned.
- an appropriate liquid medium typically water or an organic solvent
- the lithium secondary battery disclosed herein has an improved capacity retention rate, it can be used as a secondary battery for various applications.
- the lithium secondary battery 100 is mounted on a vehicle 1 such as an automobile and can be suitably used as a power source for a drive source such as a motor that drives the vehicle 1. Therefore, the present invention provides a vehicle (typically an automobile, particularly a hybrid automobile) provided with the lithium secondary battery (typically, a battery pack formed by connecting a plurality of lithium secondary batteries in series) 100 as a power source.
- HV plug-in hybrid vehicle
- EV electric vehicle equipped with an electric motor such as a fuel cell vehicle
- the compound (a1) was blended as a siloxane compound, and the compounds (a1) were each prepared so that the content of the compound (a1) was the value (% by mass) shown in Table 1.
- the electrolytic solution prepared by mixing the electrolytic solution having the above basic composition and the compound (a1) at a mass ratio of 85:15 (the content of the compound (a1) is 15% by mass). Electrolyte) was used.
- the electrolyte solution of the said basic composition was used for construction of cell A5 as it was.
- the cells B1 to B10 were subjected to the same test as the capacity retention rate measurement test after 50 cycles. The obtained results are shown in Table 2. Table 2 also shows the results of the capacity retention rate measurement test of the cells A3 and A5 obtained in Experimental Example 1.
- the siloxy side chain-containing cyclic siloxane suppressed the formation of the SEI film on the negative electrode (here, the metal lithium electrode as the counter electrode), thereby maintaining the low occlusion resistance of lithium ions to the negative electrode.
- the capacity retention improvement effect obtained by the siloxy side chain-containing cyclic siloxane in these cells is, for example, a lithium ion secondary battery having a general configuration (for example, a lithium transition metal oxide such as LiNiCoMn oxide as a positive electrode). It is understood that the present invention can be similarly applied to a lithium ion secondary battery including a positive electrode including an active material and a negative electrode including a carbon material as a negative electrode active material.
- the effect of greatly improving the capacity retention rate as described above was confirmed at least in the range where the content of the compound (a1) was 20% by mass or less. Moreover, even if the content rate of the compound (a1) was 0.1 mass%, the sufficient capacity maintenance rate improvement effect was exhibited.
- the capacity retention rate effect described above can be obtained both when R 11 to R 14 are a hydrocarbon group having 1 to 10 carbon atoms (for example, an alkyl group, an alkenyl group, an aryl group) or a hydrogen atom. It was.
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Abstract
Description
上記シロキシ側鎖含有環状シロキサンとしては、例えば、上記式(1)で表される化合物を好ましく採用し得る。
リチウム二次電池の正極(典型的には正極シート)を構成する正極集電体としては、導電性の良好な金属からなる導電性部材が好ましく用いられる。そのような導電性部材としては、例えば、アルミニウムまたはアルミニウムを主成分とする合金を用いることができる。正極集電体の形状は、電池の形状等に応じて異なり得るため、特に制限はなく、棒状、板状、シート状、箔状、メッシュ状等の種々の形態であり得る。正極集電体の厚さも特に限定されず、例えば5μm~30μmとすることができる。正極活物質層は、正極活物質の他、導電材や結着剤(バインダ)等の、一般的なリチウム二次電池の正極活物質層に配合され得る公知の添加剤の1種または2種以上を必要に応じて含有し得る。
(2)次の一般式(B1):Li1+αMn2-xMxO4;で表される、典型的にはスピネル構造のリチウム遷移金属酸化物。ここで、xは0≦x<2であり、典型的には0≦x≦1である。xが0より大きい場合、Mは、Mn以外の任意の金属元素または非金属元素であり得る。Mが遷移金属元素の少なくとも1種を含む組成のものが好ましい。一般式(B1)で表される化合物の具体例としては、LiMn2O4,LiNi0.5Mn1.5O4,LiCrMnO4等が挙げられる。
(3)次の一般式(C1):Li2+αMO3;で表されるリチウム遷移金属酸化物。ここで、Mは、Mn,Fe,Co等の遷移金属元素の少なくとも1種を含み、他の金属元素または非金属元素をさらに含み得る。一般式(C1)で表される化合物の具体例としては、Li2MnO3,Li2PtO3等が挙げられる。
(4)次の一般式(D1):Li1+αMPO4;で表されるリチウム遷移金属化合物(リン酸塩)。ここで、Mは、Mn,Fe,Ni,Co等の遷移金属元素の少なくとも1種を含み、他の金属元素または非金属元素をさらに含み得る。一般式(D1)で表される化合物の具体例としては、LiMnPO4,LiFePO4等が挙げられる。
(5)次の一般式(E1):Li2+αMPO4F;で表されるリチウム遷移金属化合物(リン酸塩)。ここで、Mは、Mn,Ni,Co等の遷移金属元素の少なくとも1種を含み、他の金属元素または非金属元素をさらに含み得る。一般式(E1)で表される化合物の具体例としては、LiMnPO4F等が挙げられる。
(6)Li1+αMO2とLi2+αMO3との固溶体。ここで、Li1+αMO2は上記(1)に記載の一般式(A1)で表される組成を指し、Li2+αMO3は上記(3)に記載の一般式(C1)で表される組成を指す。具体例としては、0.5LiNi1/3Mn1/3Co1/3O2-0.5Li2MnO3で表される固溶体が挙げられる。
なお、上記(1)~(6)中の各組成式におけるαは、0≦α≦0.5であり、典型的には0≦α≦0.3(例えば0≦α≦0.2)が適当である。
上記一般式(B1)で表される化合物の好適例として、該一般式(B1)におけるMが少なくともNiを含む化合物、例えば、次の一般式(B2):LiNipM1 qMn2-p-qO4;で表されるスピネル構造のリチウム遷移金属酸化物(以下「LiNiMn複合酸化物」ともいう。)が挙げられる。ここで、0<pであり、0≦qであり、p+q<2(典型的にはp+q≦1)である。好ましい一態様では、q=0であり、0.2≦p≦0.6である。上記の含有割合(上記一般式(B2)のpで示す割合)のNiを含有させることによって、スピネル構造のLiNiMn複合酸化物(例えばLiNi0.5Mn1.5O4)の充電終止時の正極電位を高電位化(典型的には4.5V(対Li/Li+)以上に高電位化)させることができ、5V級のリチウム二次電池を構築することが可能になる。上記一般式(B2)において、0<qである場合、M1は、Ni,Mn以外の任意の金属元素または非金属元素の1種または2種以上(例えば、Ti,Fe,Co,Cu,Cr,ZnおよびAlから選択される1種または2種以上)であり得る。M1が3価のFeおよびCoの少なくとも一方を含むことが好ましい。また、0<q≦0.3であり、1≦2p+qであることが好ましい。
1つのシロキシ側鎖に含まれるシロキシ基の数は、2以上(例えば2~5程度)であってもよいが、通常は1であることが好ましい。
[シロキシ側鎖含有環状シロキサン]
化合物(a1):下記式(2)におけるR11,R12,R13およびR14がいずれもイソブチル基(-CH2CH(CH3)2)である環状シロキサン(2,4,6,8-テトライソブチル-2,4,6,8-テトラ(ジメチルシロキシ)シクロテトラシロキサン)
化合物(a2):下記式(2)におけるR11,R12,R13およびR14がいずれもメチル基(-CH3)である環状シロキサン
化合物(a3):下記式(2)におけるR11,R12,R13およびR14がいずれもエチル基(-CH2CH3)である環状シロキサン
化合物(a4):下記式(2)におけるR11,R12,R13およびR14がいずれもn-ノニル基(-(CH2)8CH3)である環状シロキサン
化合物(a5):下記式(2)におけるR11,R12,R13およびR14がいずれもアリル基(-CH2CH=CH2)である環状シロキサン
化合物(a6):下記式(2)におけるR11,R12,R13およびR14がいずれもフェニル基(-C6H5)である環状シロキサン
化合物(a7):下記式(2)におけるR11,R12,R13およびR14がいずれもビニル基(-CH=CH2)である環状シロキサン
化合物(a8):下記式(2)におけるR11,R12,R13およびR14がいずれも水素原子(H)である環状シロキサン
化合物(a9):下記式(2)におけるR11,R12,R13およびR14のうち2つがメチル基であり、他の2つがエチル基である環状シロキサン
化合物(b1):ヘキサメチルシクロトリシロキサン
[鎖状シロキサン]
化合物(c1):ヘキサメチルジシロキサン
[コインセルの作製]
ステンレス鋼を作用極、金属リチウムを対極とし、これらをセパレータおよび非水電解液とともにステンレス鋼製の容器に組み込んで、直径20mm、厚さ3.2mm(2032型)のコインセル(性能評価用のハーフセル)A1~A7を構築した。セパレータとしては多孔質ポリオレフィンシートを使用した。非水電解液としては、エチレンカーボネート(EC)とエチルメチルカーボネート(EMC)との3:7(質量比)混合溶媒中に支持塩として約1mol/LのLiPF6を含む基本組成の電解液に、シロキサン化合物として化合物(a1)を配合し、該化合物(a1)の含有率がそれぞれ表1に示す値(質量%)となるように調製したものをそれぞれ使用した。例えば、セルA3の構築には、上記基本組成の電解液と化合物(a1)とを85:15の質量比で混合して調製した電解液(化合物(a1)の含有率が15質量%である電解液)を使用した。なお、セルA5の構築には上記基本組成の電解液をそのまま使用した。
セルA1~A7に対して、温度60℃にて、0.5mA/cm2の電流密度で、カット電圧-2.0V~1.5V(E/V vs.(Li+/Li))の範囲で50サイクルの充放電を行った。そして、1サイクル目の充電容量(リチウムイオンをステンレス鋼にLi金属として充電した充電容量)を100%として、50サイクル目の充電容量の維持率(%)を求めた。得られた結果を表1および図4に示す。
上記基本組成の電解液と化合物(a2)~(a9)とをそれぞれ85:15の質量比で混合して調製した電解液(すなわち、各シロキサン化合物を15質量%の含有率で含む電解液)を用いた点以外は実験例1と同様にして、コインセルB1~B8を構築した。また、上記基本組成の電解液と化合物(b1)または(c1)とをそれぞれ85:15の質量比で混合して調製した電解液を用いた点以外は実験例1と同様にして、コインセルB9およびB10を構築した。
10 電池ケース
12 開口部
14 蓋体
20 捲回電極体
25 非水電解質(非水電解液)
30 正極(正極シート)
32 正極集電体
34 正極活物質層
35 正極集電体積層部
36 正極活物質層非形成部
37 内部正極端子
38 外部正極端子
40 負極(負極シート)
42 負極集電体
44 負極活物質層
45 負極集電体積層部
46 負極活物質層非形成部
47 内部負極端子
48 外部負極端子
50A,50B セパレータ(セパレータシート)
100 リチウム二次電池
Claims (7)
- 正極と負極と非水電解質とを備えたリチウム二次電池であって、
前記負極の表面には、環状シロキサンおよび/またはその反応生成物が存在しており、
前記環状シロキサンは、少なくとも1つのジメチルシロキシ基を側鎖に有するシロキシ側鎖含有環状シロキサンである、リチウム二次電池。 - 正極と負極とを用意すること、および
少なくとも前記負極に環状シロキサンを供給すること、を包含し、
前記環状シロキサンは、少なくとも1つのジメチルシロキシ基を側鎖に有するシロキシ側鎖含有環状シロキサンである、リチウム二次電池製造方法。 - 前記環状シロキサンを供給することは、
前記環状シロキサンを含む非水電解質を用意すること、および
その用意した非水電解質を前記負極に供給すること、を包含する、請求項3または4に記載のリチウム二次電池製造方法。 - 前記非水電解質として、前記環状シロキサンを0.01~20質量%含む非水電解質を用いる、請求項5に記載のリチウム二次電池製造方法。
- 請求項1または2に記載のリチウム二次電池を搭載した、車両。
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CN106458636B (zh) * | 2014-05-30 | 2019-01-04 | 住友金属矿山株式会社 | 带覆膜的锂-镍复合氧化物粒子和带覆膜的锂-镍复合氧化物粒子的制造方法 |
EP3353844B1 (en) | 2015-03-27 | 2022-05-11 | Mason K. Harrup | All-inorganic solvents for electrolytes |
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US10707531B1 (en) | 2016-09-27 | 2020-07-07 | New Dominion Enterprises Inc. | All-inorganic solvents for electrolytes |
CN107910591B (zh) * | 2017-11-14 | 2019-12-10 | 石家庄圣泰化工有限公司 | 一种耐高温锂电池电解液 |
KR20200141119A (ko) | 2019-06-10 | 2020-12-18 | 주식회사 엘지화학 | 리튬 이차전지용 전극 보호층 및 이의 제조방법 |
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