WO2015129187A1 - 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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- 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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Definitions
- the present invention relates to a non-aqueous electrolyte secondary battery with high capacity and high durability.
- non-aqueous electrolyte secondary batteries in particular lithium secondary batteries, are expected to be used as power sources for electronic devices, power storage, and electric vehicles because of their high voltage and high energy density. ing.
- the non-aqueous electrolyte secondary battery as described above includes a positive electrode, a negative electrode, and a separator interposed between them.
- a lithium cobalt oxide which has a high potential for lithium and is easy to synthesize
- LiCoO 2 LiCoO 2
- a layered active material mainly composed of nickel or a layered compound composed of three components of nickel cobalt manganese has been used as a positive electrode active material for the purpose of increasing the capacity.
- Various carbon materials such as graphite are used as the negative electrode active material, and a polyolefin microporous film is mainly used as the separator.
- a non-aqueous electrolyte solution in which a lithium salt such as LiBF 4 or LiPF 6 is dissolved in an aprotic organic solvent is used.
- the problem to be solved by the present invention is to provide a non-aqueous electrolyte secondary battery that can suppress an increase in positive electrode resistance during charge and discharge and obtain excellent cycle characteristics.
- a nonaqueous electrolyte secondary battery includes a positive electrode including a positive electrode active material, a negative electrode including a negative electrode active material, a separator interposed between the positive electrode and the negative electrode, a nonaqueous electrolyte,
- the positive electrode active material is a layered lithium-containing transition metal oxide, the crystallite size of the positive electrode active material is 140 nm or less, the negative electrode active material contains at least carbon, and the nonaqueous electrolyte contains fluoroethylene carbonate. It is characterized by containing 2 to 30% by volume.
- non-aqueous electrolyte secondary battery that suppresses an increase in positive electrode resistance during charging and discharging and dramatically improves cycle characteristics.
- FIG. 4 is a diagram showing an XRD pattern of a positive electrode active material of Experimental Example 1.
- FIG. It is a typical sectional view of the cylindrical nonaqueous electrolyte secondary battery of this embodiment.
- Ni 0.5 Co 0.2 Mn 0.3 (OH) 2 obtained by the coprecipitation method was calcined at 540 ° C. for 3 hours while adjusting the oxygen concentration to 23% by volume, and the oxide Ni 0.5 Co 0. 2 Mn 0.3 Ox was obtained. Then, the Li 2 CO 3 were mixed at a predetermined ratio to said oxide, 12 hours at 880 ° C. while adjusting them to the oxygen concentration of 25 vol%, Li 1.08 Ni 0 having a layered structure by firing. 50 Co 0.20 Mn 0.30 O 2 (lithium-containing transition metal composite oxide) was produced.
- the state of the composite varies depending on the hydroxide preparation conditions (coprecipitation temperature and pH), the oxygen concentration during firing, and the firing temperature, and therefore needs to be appropriately adjusted according to the purpose.
- the crystallite size of the positive electrode active material of this experiment example 1 was 71 nm.
- the crystallite size was determined as follows.
- an XRD pattern of the lithium-containing transition metal oxide was obtained using a powder X-ray diffractometer (manufactured by Rigaku Corporation) using CuK ⁇ as an X-ray source.
- the lithium-containing transition metal oxide of this experimental example was hexagonal in all samples from the obtained XRD pattern, and was assigned to the space group R-3m due to its symmetry.
- the XRD pattern of the positive electrode active material of Experimental Example 1 is shown in FIG.
- fluoroethylene carbonate FEC
- EC ethylene carbonate
- PC propylene carbonate
- EMC ethyl methyl carbonate
- DMC dimethyl carbonate
- LiPF 6 lithium hexafluorophosphate
- FIG. 2 is a schematic cross-sectional view showing the produced nonaqueous electrolyte secondary battery.
- the non-aqueous electrolyte secondary battery shown in FIG. 2 includes a battery case 1 made of stainless steel and an electrode plate group accommodated in the battery case 1.
- the electrode plate group includes a positive electrode 5, a negative electrode 6, and a polyethylene separator 7, and the positive electrode 5 and the negative electrode 6 are wound in a spiral shape via the separator 7.
- An upper insulating plate 8a and a lower insulating plate 8b are disposed above and below the electrode plate group.
- the battery case 1 is sealed by caulking the opening plate 2 with a sealing plate 2 through a gasket 3.
- One end of an aluminum positive electrode lead 5a is attached to the positive electrode 5, and the other end of the positive electrode lead 5a is connected to a sealing plate 2 that also serves as a positive electrode terminal.
- One end of a nickel negative electrode lead 6 a is attached to the negative electrode 6, and the other end of the negative electrode lead 6 a is connected to the battery case 1 that also serves as a negative electrode terminal.
- an aluminum positive electrode lead 5a and a nickel negative electrode lead 6a were attached to current collectors of a predetermined positive electrode 5 and negative electrode 6, respectively, and then wound through a separator 7 to constitute an electrode plate group.
- Insulating plates 8a and 8b are arranged on the upper and lower parts of the electrode plate group, the negative electrode lead 6a is welded to the battery case 1, and the positive electrode lead 5a is welded to the sealing plate 2 having an internal pressure actuated safety valve. 1 was stored inside. Thereafter, a non-aqueous electrolyte was injected into the battery case 1 by a reduced pressure method. Finally, the 18650 type nonaqueous electrolyte secondary battery was completed by caulking the opening end of the battery case 1 to the sealing plate 2 via the gasket 3. The battery thus produced is hereinafter referred to as battery A1.
- Example 2 In preparation of the positive electrode active material, Ni 0.5 Co 0.2 Mn 0.3 (OH) 2 was baked at 540 ° C. for 5 hours while adjusting the oxygen concentration to 25% by volume, and the oxide Ni 0.5 Co 0.2 Mn 0.3 Ox was obtained. Subsequently, after mixing Li 2 CO 3 at a predetermined ratio to the oxide, the except for using 900 ° C. firing temperature, to prepare a non-aqueous electrolyte secondary battery in the same manner as in Experimental Example 1. The battery thus produced is hereinafter referred to as battery A2.
- the crystallite size of the positive electrode active material in Experimental Example 2 was 93 nm.
- Example 4 In preparation of the positive electrode active material, Ni 0.5 Co 0.2 Mn 0.3 (OH) 2 was baked at 585 ° C. for 5 hours while adjusting the oxygen concentration to 28% by volume, and the oxide Ni 0.5 Co 0.2 Mn 0.3 Ox was obtained. Subsequently, after mixing Li 2 CO 3 at a predetermined ratio to the oxide, the except for using 950 ° C. firing temperature, to prepare a non-aqueous electrolyte secondary battery in the same manner as in Experimental Example 3. The battery thus produced is hereinafter referred to as battery A4. In addition, the crystallite size of this experimental example 4 was 125 nm.
- Example 5 A nonaqueous electrolyte secondary battery was produced in the same manner as in Experimental Example 4 except that in Example 4 above, a negative electrode in which 2% by mass of SiO was added to the negative electrode active material was used.
- the battery thus produced is hereinafter referred to as battery A5.
- Example 6 In the production of the positive electrode active material, the temperature of the aqueous solution was 45 ° C., Ni 0.5 Co 0.2 Mn 0.3 (OH) 2 and Li 2 CO 3 were mixed at a predetermined ratio, and then the atmosphere (oxygen concentration) A nonaqueous electrolyte secondary battery was fabricated in the same manner as in Experimental Example 1 except that the firing temperature was set to 1000 ° C. The battery thus produced is hereinafter referred to as battery Z1. In addition, the crystallite size of this Experimental Example 6 was 142 nm.
- LiPF Lithium hexafluorophosphate
- EC ethylene carbonate
- PC propylene carbonate
- DMC dimethyl carbonate
- a nonaqueous electrolyte secondary battery was fabricated in the same manner as in Experimental Example 4 except that an electrolytic solution in which 1.2 was dissolved at a rate of 1.2 mol / liter was used. The battery thus produced is hereinafter referred to as battery Z2.
- Example 8 A nonaqueous electrolyte secondary battery was produced in the same manner as in Experimental Example 1 except that the positive electrode active material of Experimental Example 6 and the nonaqueous electrolyte solvent of Experimental Example 7 were used.
- the battery thus produced is hereinafter referred to as battery Z3.
- DC-IR measurement The batteries A1 to A4 and Z1 to Z3 were charged to 50% of the discharge capacity (mAh) of the second and 500th times after charging and discharging were repeated twice and 500 times under the above conditions. After resting for 1 minute, discharging was performed at 1150 mA [0.5 It] for 10 seconds, and DC-IR was calculated using equation (1).
- DC-IR (battery voltage immediately before discharge ⁇ battery voltage after 10 seconds of discharge) / 1150 (1)
- the DC-IR value in Table 1 is an index when battery A2 is 100. ing.
- Capacity maintenance ratio (%) (discharge capacity at 500th cycle / discharge capacity at the first cycle) ⁇ 100 (2)
- the DC-IR values of the batteries Z2 and Z3 are larger than those of the batteries A1 to A4. This is because, in the batteries A1 to A4, the FEC is contained in the electrolytic solution, so that a good film is formed on the surface of the positive electrode active material at the initial stage of the charging / discharging cycle. It is considered that the side reaction was suppressed, and the change in DC-IR was suppressed to be small compared to after 2 cycles.
- the value of the DC-IR is larger as the amount of decrease in the battery voltage before and after the discharge near 50% charge (SOC 50%) is larger. It is an index indicating that it is preferable.
- the capacity maintenance rate after 500 cycles of batteries A1 to A4 is 94 to 96%, whereas the capacity maintenance rate after 500 cycles of batteries Z2 and Z3 is 85 to 87%. However, it can be seen that the cycle characteristics are improved.
- the DC-IR value after 500 cycles is increased compared to the battery Z3 in which the electrolytic solution does not contain FEC.
- the reason for this is that when the crystallite size is larger than 140 nm, even when a film is formed on the surface of the positive electrode active material, it expands and contracts in a specific direction of the crystal of the positive electrode active material, particularly in the c-axis direction, during charging and discharging. This is because the film is destroyed.
- the FEC-derived decomposition products are unevenly distributed on the surface of the positive electrode active material, so that the electron conductivity of the positive electrode active material is reduced, and current is concentrated in a portion where the decomposition products are less deposited and the electronic resistance is low. Therefore, the positive electrode active material is deteriorated and the cycle characteristics are lowered.
- the lattice change in the c-axis direction in the positive electrode active material crystal is preferably suppressed to a range of 0.33 mm or less, more preferably 0.30 mm or less, and particularly preferably 0.26 mm or less. This is because if the lattice change in the c-axis direction exceeds 0.33 mm, the effect of improving the cycle characteristics may be reduced.
- the lattice change is the difference between the c-axis length of the positive electrode in the discharged state and the c-axis length of the positive electrode in the charged state.
- the c-axis length of the positive electrode in the discharged state in the second cycle of the positive electrode is 14.29 mm
- the c-axis length of the positive electrode in the charged state is 14.53 mm.
- the change was 0.24 cm.
- the crystal size of the positive electrode active material needs to be 140 nm or less.
- the suitable range of the crystallite size of a positive electrode active material is 40 nm or more and 140 nm or less, Furthermore, a suitable range is the range of 60 nm or more and 140 nm or less.
- the FEC amount of the electrolytic solution is preferably 2% by volume or more and 30% by volume or less, and more preferably 5% by volume or more and 30% by volume or less. This is because when the FEC is less than 2% by volume, a sufficient film is not formed on the surface of the positive electrode active material, and an increase in resistance of the positive electrode active material after a long-term cycle cannot be suppressed. On the other hand, when the FEC exceeds 30% by volume, if the charge / discharge cycle is repeated, the safety valve of the battery may be activated due to an increase in the amount of gas generated due to decomposition of the electrolytic solution, which is not desirable.
- Table 2 below shows the DC-IR measurement results after 400 cycles of the batteries A4 and A5 of the present invention.
- the DC-IR measurement method was the same as that in the DC-IR measurement method except that the cycle was 400 cycles. Note that DC-IR in Table 2 is expressed as an index when the value of DC-IR of the battery A5 is 100.
- the DC-IR value after 400 cycles is smaller in the battery A5 than in the battery A5 containing SiO in the negative electrode active material and the battery A4 not containing SiO in the negative electrode active material. . It can be considered that by including SiO in the negative electrode active material, the charge / discharge efficiency of the negative electrode can be lowered at the beginning of the cycle, and the lattice change of the positive electrode can be limited to 0.33 mm or less.
- the addition amount of SiO to the negative electrode active material is preferably 1% by mass or more and 20% by mass or less. This is because when the amount of SiO added is less than 1% by mass, the effect of limiting the lattice change of the positive electrode due to SiO is small, and when it exceeds 20% by mass, the battery capacity decreases due to an increase in irreversible capacity.
- addition amounts are preferably 0.1 mol% or more and 5.0 mol% or less with respect to the transition metal in the lithium-containing transition metal composite oxide, and more preferably 0.1 mol% or more and 3.0 mol% or less. preferable. This is because when the amount added exceeds 5.0 mol%, the capacity is lowered and the energy density is lowered. On the other hand, when the added amount is less than 0.1 mol%, the effect on the crystal growth by the added element is reduced.
- the positive electrode active material used in the nonaqueous electrolyte secondary battery of the present invention does not need to be composed of only the positive electrode active material described above, and has a layered structure capable of reversibly inserting and extracting lithium. If it is, it will not specifically limit.
- the lithium-containing transition metal composite oxide include lithium cobaltate, lithium composite oxide of Ni—Mn—Al, lithium composite oxide of Ni—Co—Al, lithium composite oxide of Co—Mn, iron, manganese, and the like. Examples include transition metal oxides.
- the active material and a compound having a spinel structure, a phosphoric acid compound, a boric acid compound, and a silicic acid compound May be used in combination.
- the packing density of the positive electrode used in the nonaqueous electrolyte secondary battery of the present invention is preferably 2.0 g / cm 3 or more and 4.0 g / cm 3 or less, and particularly 2.8 g / cm 3 or more and 3.7 g / cm 3. More preferably, it is 3 or less.
- the packing density of the positive electrode exceeds 4.0 g / cm 3 , the amount of the electrolytic solution in the positive electrode is reduced, and the cycle characteristics are deteriorated due to a heterogeneous reaction.
- the packing density of the positive electrode is less than 2.0 g / cm 3 , not only the energy density is decreased, but also the electron conductivity in the positive electrode is decreased, resulting in a decrease in capacity and cycle characteristics due to a heterogeneous reaction. Because.
- Examples of the negative electrode active material for the non-aqueous electrolyte secondary battery of the present invention include carbon materials such as various natural graphites, cokes, graphitized carbon, carbon fibers, spherical carbon, various artificial graphites, amorphous carbon, and metals, Two or more kinds of metal fibers, oxides, nitrides, tin compounds, silicon compounds, various alloy materials and the like can be used in combination.
- a material used together with the carbon material a simple substance such as silicon (Si) or tin (Sn), or a silicon compound or tin compound such as an alloy, a compound, or a solid solution is preferable from the viewpoint of a large capacity density.
- SiO x (0.05 ⁇ x ⁇ 1.95), or any one of these may be B, Mg, Ni, Ti, Mo, Co, Ca, Cr, Cu, Fe, Mn, Nb, An alloy, a compound, a solid solution, or the like in which a part of Si is substituted with at least one element selected from the group consisting of Ta, V, W, Zn, C, N, and Sn can be used. More preferably, the silicon oxide has a ratio of oxygen atom to silicon atom (O / Si) of 0.5 to 1.5.
- Ni 2 Sn 4 , Mg 2 Sn, SnO x (0 ⁇ x ⁇ 2), SnO 2 , SnSiO 3 or the like can be applied.
- a material having a higher charge / discharge potential with respect to lithium metal such as lithium titanate than a carbon material can be used.
- positive electrode or negative electrode binder examples include polyvinylidene fluoride, polytetrafluoroethylene, polyethylene, polypropylene, aramid resin, polyamide, polyimide, polyamideimide, polyacrylonitrile, polyacrylic acid, polyacrylic acid methyl ester, and polyacrylic.
- Acid ethyl ester polyacrylic acid hexyl ester, polymethacrylic acid, polymethacrylic acid methyl ester, polymethacrylic acid ethyl ester, polymethacrylic acid hexyl ester, polyvinyl acetate, polyvinylpyrrolidone, polyether, polyethersulfone, hexafluoropolypropylene Styrene butadiene rubber, carboxymethyl cellulose, etc. can be used.
- a copolymer of the above materials may be used. Two or more selected from these may be mixed and used.
- Examples of the conductive agent included in the electrode include natural graphite and artificial graphite graphite, acetylene black, ketjen black, channel black, furnace black, lamp black, thermal black, carbon nanotubes, and other carbon blacks, gas phase Conductive fibers such as carbon fibers and metal fibers such as growth carbon fiber (VGCF), metal powders such as carbon fluoride and aluminum, conductive whiskers such as zinc oxide and potassium titanate, and conductivity such as titanium oxide
- VGCF growth carbon fiber
- conductive whiskers such as zinc oxide and potassium titanate
- conductivity such as titanium oxide
- Organic conductive materials such as metal oxides and phenylene derivatives can be used.
- the mixing ratio of the positive electrode active material, the conductive agent, and the binder is within the range of 80 to 99% by mass of the positive electrode active material, 0.5 to 20% by mass of the conductive agent, and 0.5 to 20% by mass of the binder, respectively. It is desirable. This is because when the positive electrode active material is less than 80% by mass, the energy density decreases, and when it exceeds 99% by mass, the electron conductivity in the positive electrode decreases, resulting in a decrease in capacity and cycle characteristics due to a heterogeneous reaction. .
- the blending ratio of the negative electrode active material and the binder is preferably in the range of 93 to 99% by mass of the negative electrode active material and 1 to 10% by mass of the binder, respectively. This is because if the negative electrode active material is less than 93% by mass, the energy density decreases, and if it exceeds 99% by mass, the binder is insufficient and the active material collapses.
- the current collector a long porous conductive substrate or a non-porous conductive substrate is used.
- a material used for the conductive substrate for example, stainless steel, aluminum, titanium, or the like is used.
- the negative electrode current collector for example, stainless steel, nickel, copper, or the like is used.
- the thickness of these current collectors is not particularly limited, but is preferably 1 to 500 ⁇ m, and more preferably 5 to 20 ⁇ m. By setting the thickness of the current collector within the above range, it is possible to reduce the weight while maintaining the strength of the electrode plate.
- a microporous thin film, a woven fabric, a non-woven fabric or the like having a large ion permeability and having a predetermined mechanical strength and an insulating property is used.
- a material of the separator for example, polyolefin such as polypropylene and polyethylene is preferable from the viewpoint of safety of the nonaqueous electrolyte secondary battery because it has excellent durability and has a shutdown function.
- the thickness of the separator is generally 6 to 300 ⁇ m, but is desirably 40 ⁇ m or less. Further, the range of 10 to 30 ⁇ m is more preferable, and the more preferable range of the separator thickness is 10 to 25 ⁇ m.
- the microporous film may be a single layer film made of one kind of material, or a composite film or a multilayer film made of one kind or two or more kinds of materials.
- the porosity of the separator is preferably in the range of 30 to 70%.
- the porosity indicates the volume ratio of the pores to the separator volume.
- a more preferable range of the porosity of the separator is 35 to 60%.
- the solute of the non-aqueous electrolyte used in the present invention is not limited, and solutes conventionally used for non-aqueous electrolyte secondary batteries can be used.
- a lithium salt a lithium salt containing one or more elements among P, B, F, O, S, N, and Cl can be used.
- a lithium salt having an oxalato complex as an anion can also be used.
- the lithium salt having the oxalato complex as an anion include LiBOB [lithium-bisoxalate borate] and a lithium salt having an anion in which C 2 O 4 2 ⁇ is coordinated to the central atom, for example, Li [M (C 2 O 4 ) x R y ] (wherein M is a transition metal, an element selected from groups IIIb, IVb, and Vb of the periodic table, R is selected from a halogen, an alkyl group, and a halogen-substituted alkyl group) Group, x is a positive integer, and y is 0 or a positive integer).
- the said solute may be used not only independently but in mixture of 2 or more types.
- the concentration of the solute is not particularly limited, but is preferably 0.8 to 1.7 mol per liter of the electrolyte.
- the solvent of the nonaqueous electrolyte used in the present invention can be used by mixing FEC and the following solvents.
- cyclic carbonates such as ethylene carbonate, propylene carbonate, butylene carbonate, vinylene carbonate, chain carbonates such as dimethyl carbonate, methyl ethyl carbonate, diethyl carbonate, methyl acetate, ethyl acetate, propyl acetate, methyl propionate, propionic acid
- esters such as ethyl and ⁇ -butyrolactone
- compounds containing sulfone groups such as propane sultone, 1,2-dimethoxyethane, 1,2-diethoxyethane, tetrahydrofuran, 1,2-dioxane, 1,4 -Compounds containing ethers such as dioxane and 2-methyltetrahydrofuran, butyronitrile, valeronitrile, n-heptanenitrile, succinon
- a solvent in which some or all of these H are substituted with F can be used. Further, these can be used alone or in combination, and a solvent in which a cyclic carbonate and a chain carbonate are combined, and a solvent in which a compound containing a small amount of nitrile or an ether is further combined with these is preferable. .
- the non-aqueous electrolyte may contain a known benzene derivative that decomposes during overcharge to form a film on the electrode and inactivate the battery.
- the benzene derivative those having a phenyl group and a cyclic compound group adjacent to the phenyl group are preferable.
- the cyclic compound group a phenyl group, a cyclic ether group, a cyclic ester group, a cycloalkyl group, a phenoxy group, and the like are preferable.
- Specific examples of the benzene derivative include cyclohexylbenzene, biphenyl, diphenyl ether, and tertiary amylbenzene. These may be used alone or in combination of two or more. However, the content of the benzene derivative is preferably 10% by volume or less of the entire non-aqueous solvent.
- a layer made of an inorganic filler that has been conventionally used can be formed.
- the filler it is possible to use oxides or phosphate compounds using titanium, aluminum, silicon, magnesium, etc., which have been used conventionally, or those whose surfaces are treated with hydroxide or the like.
- the filler layer can be formed by directly applying a filler-containing slurry to a positive electrode, a negative electrode, or a separator, or by attaching a sheet formed of a filler to the positive electrode, the negative electrode, or the separator. it can.
- a cylindrical battery may be an easily deformable one such as an aluminum laminate and a stainless steel can, as well as an aluminum laminate.
- the non-aqueous electrolyte secondary battery according to one aspect of the present invention can be applied to applications that require a particularly high capacity and a long life, such as a mobile phone, a notebook computer, a smartphone, and a tablet terminal.
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Abstract
Description
このような観点から、非水電解質二次電池、特に、リチウム二次電池が、高電圧であり、かつ高エネルギー密度を有するため、電子機器用、または電力貯蔵用、電気自動車の電源として期待されている。
また、近年高容量化を目的としてニッケルを主体とする層状活物質やニッケルコバルトマンガンの三成分からなる層状化合物が正極活物質として用いられている。負極活物質としては、黒鉛などの種々の炭素材料が用いられ、セパレータには、主としてポリオレフィン製の微多孔膜が用いられている。非水電解質には、LiBF4、LiPF6等のリチウム塩を非プロトン性の有機溶媒に溶解した非水電解液が用いられている。
[正極活物質の作製]
先ず、反応槽に、硫酸コバルト、硫酸ニッケル、硫酸マンガンから調整したコバルトイオン、ニッケルイオン、マンガンイオンを含有する水溶液を用意し、水溶液中のコバルトと、ニッケルと、マンガンとのモル比(ニッケル:コバルト:マンガン)が、5:2:3となるように調整した。次に、水溶液の温度を30℃、pH=9に保持しつつ、2時間かけて水酸化ナトリウム水溶液を滴下した。これにより、コバルト、ニッケル、及びマンガンを含む沈殿物を得た後、その沈殿物をろ過、水洗後に乾燥することにより、Ni0.5Co0.2Mn0.3(OH)2を得た。
尚、本実験例1の正極活物質の結晶子サイズは71nmであった。ここで、結晶子サイズは、次のように求めた。
先ず、正極活物質としての上記Li1.08Ni0.50Co0.20Mn0.30O2と、導電剤としてのアセチレンブラックと、結着剤としてのポリフッ化ビニリデンとを、質量比で95:2.5:2.5となるように混合した後、N-メチル-2-ピロリドン(NMP)を適量加えて、正極スラリーを調製した。次に、この正極合剤スラリーを、アルミニウム箔から成る正極集電体の両面に塗布、乾燥した後、圧延ローラにより圧延することにより、正極集電体の両面に正極合剤層が形成された正極を作製した。
尚、正極の充填密度は、3.5g/cm3とした。
負極活物質としての人造黒鉛と、分散剤としてのCMC(カルボキシメチルセルロースナトリウム)と、結着剤としてのSBR(スチレン-ブタジエンゴム)とを、98:1:1の質量比で水溶液中において混合し、負極合剤スラリーを調製した。次に、この負極合剤スラリーを銅箔から成る負極集電体の両面に均一に塗布した後、乾燥させ、更に、圧延ローラにより圧延した。これにより、負極集電体の両面に負極合剤層が形成された負極を得た。尚、この負極における負極活物質の充填密度は1.63g/cm3であった。
フルオロエチレンカーボネート(FEC)とエチレンカーボネート(EC)とプロピレンカーボネート(PC)とエチルメチルカーボネート(EMC)ジメチルカーボネート(DMC)とを、10:10:5:45:30の体積比で混合した混合溶媒に対し、六フッ化リン酸リチウム(LiPF6)を1.4モル/リットルの割合で溶解させて、非水電解液を調製した。
上記の正極、負極、非水電解液、及びポリエチレン微多孔膜からなるセパレータを用いて、公称容量2300mAhの18650円筒型の非水電解質二次電池を作製した。図2は、作製した非水電解質二次電池を示す模式的断面図である。
前記正極活物質の作製において、Ni0.5Co0.2Mn0.3(OH)2を酸素濃度25体積%に調整しながら540℃で5時間焼成し、酸化物のNi0.5Co0.2Mn0.3Oxを得た。次いで、前記酸化物にLi2CO3を所定の割合で混合した後、焼成温度を900℃とした以外は、上記実験例1と同様にして非水電解質二次電池を作製した。このようにして作製した電池を、以下、電池A2と称する。尚、本実験例2の正極活物質の結晶子サイズは93nmであった。
前記正極活物質の作製において、コバルト、ニッケル及びマンガンを含む沈殿物を得る工程で水溶液の温度を40℃、pH=10となるように調整し、Ni0.5Co0.2Mn0.3(OH)2を酸素濃度26体積%に調整しながら570℃で5時間焼成し、酸化物のNi0.5Co0.2Mn0.3Oxを得た。次いで、前記酸化物にLi2CO3を所定の割合で混合した後、酸素濃度28体積%に調整しながら、焼成温度を920℃とした以外は、上記実験例1と同様にして非水電解質二次電池を作製した。このようにして作製した電池を、以下、電池A3と称する。尚、本実験例3の正極活物質の結晶子サイズは103nmであった。
前記正極活物質の作製において、Ni0.5Co0.2Mn0.3(OH)2を酸素濃度28体積%に調整しながら585℃で5時間焼成し、酸化物のNi0.5Co0.2Mn0.3Oxを得た。次いで、前記酸化物にLi2CO3を所定の割合で混合した後、焼成温度を950℃とした以外は、上記実験例3と同様にして非水電解質二次電池を作製した。このようにして作製した電池を、以下、電池A4と称する。尚、本実験例4の結晶子サイズは125nmであった。
上記実験例4において、負極活物質にSiOを2質量%添加した負極を用いたこと以外は、上記実験例4と同様にして非水電解質二次電池を作製した。このように作製した電池を、以下、電池A5と称する。
前記正極活物質の作製において、水溶液の温度を45℃、Ni0.5Co0.2Mn0.3(OH)2とLi2CO3を所定の割合で混合した後、大気中(酸素濃度約21体積%)で、焼成温度を1000℃とした以外は、上記実験例1と同様にして非水電解質二次電池を作製した。このようにして作製した電池を、以下、電池Z1と称する。尚、本実験例6の結晶子サイズは142nmであった。
非水電解質溶媒を、エチレンカーボネート(EC)とプロピレンカーボネート(PC)とジメチルカーボネート(DMC)とを、25:5:70の体積比で混合した混合溶媒に対し、六フッ化リン酸リチウム(LiPF6)を1.2モル/リットルの割合で溶解した電解液を用いたこと以外は、上記実験例4と同様にして非水電解質二次電池を作製した。このようにして作製した電池を、以下、電池Z2と称する。
実験例6の正極活物質と、実験例7の非水電解質溶媒を用いたこと以外は、上記実験例1と同様にして非水電解質二次電池を作製した。このようにして作製した電池を、以下、電池Z3と称する。
以上のようにして得られた電池A1~A4、Z1~Z3を用いて下記に示す方法でDC-IR、サイクル容量維持率を測定し、下記表1にその結果を示す。
1150mA[0.5It]で電池電圧4.10Vとなるまで定電流充電を行いさらに4.10Vの電圧で電流値が46mAとなるまで定電圧充電を行い、10分間休止した後、1150mA[0.5It]で電池電圧3.0Vまで放電し、その後20分間休止した。尚、充放電時の温度は25℃である。
上記電池A1~A4、Z1~Z3を、上記条件で充放電を2回及び500回繰り返した後に、2回目及び500回目の放電容量(mAh)の50%まで充電させ、20分の休止を行った後、1150mA[0.5It]で10秒間放電を行い、(1)式を用いてDC-IRを各々算出した。
DC-IR=(放電直前の電池電圧-放電10秒後の電池電圧)/1150・・・(1)尚、表1におけるDC-IRの値は、電池A2を100としたときの指数で表している。
上記充放電条件で500回充放電を繰り返し、下記(2)式を用いて容量維持率を算出した。
容量維持率(%)=(500サイクル目の放電容量/1サイクル目の放電容量)×100・・・(2)
一方、FECが30体積%を超える場合においては、充放電サイクルを繰り返すと、電解液の分解に伴うガス生成量の増加により電池の安全弁が作動してしまう恐れがあるため望ましくない。
本発明の非水電解質二次電池の正極活物質としては、ホウ素(B)、フッ素(F)、マグネシウム(Mg)、アルミニウム(Al)、クロム(Cr)、バナジウム(V)、鉄(Fe)、銅(Cu)、亜鉛(Zn)、モリブデン(Mo)、ジルコニウム(Zr)、錫(Sn)、タングステン(W)、チタン(Ti)、ニオブ(Nb)、タンタル(Ta)、ナトリウム(Na)、カリウム(K)、希土類からなる群から選択される少なくとも一種が含まれていても良い。これらの添加量は、リチウム含有遷移金属複合酸化物中の遷移金属に対して0.1mol%以上5.0mol%以下が好ましく、特に、0.1mol%以上3.0mol%以下であることがより好ましい。これは、添加量が5.0mol%を超えると、容量が低下してエネルギー密度の低下が生じる。一方、添加量が0.1mol%未満になると、添加元素による結晶成長への影響の低下が生じるからである。
尚、上記溶質は、単独で用いるのみならず、2種以上を混合して用いても良い。また、溶質の濃度は特に限定されないが、電解液1リットル当り0.8~1.7モルであることが望ましい。
上記フィラー層の形成は、正極、負極、或いはセパレータに、フィラー含有スラリーを直接塗布して形成する方法や、フィラーで形成したシートを、正極、負極、或いはセパレータに貼り付ける方法等を用いることができる。
Claims (6)
- 正極活物質を含む正極と、負極活物質を含む負極と、前記正極と前記負極との間に介在するセパレータと、非水電解質とを備え、前記正極活物質が層状リチウム含有遷移金属酸化物であり、且つ前記正極活物質の結晶子サイズが140nm以下であり、負極活物質に少なくとも炭素を含み、非水電解質にフルオロエチレンカーボネートを2~30体積%含むことを特徴とする非水電解質二次電池。
- 前記正極活物質の結晶子サイズが40nm以上140nm以下の範囲であることを特徴とする請求項1に記載の非水電解質二次電池。
- 前記正極活物質において、充放電時のc軸方向の格子変化が0.33Å以下の範囲であることを特徴とする請求項1または請求項2に記載の非水電解質二次電池。
- 前記負極活物質として、ケイ素酸化物と炭素とを備えたことを特徴とする請求項1~請求項3の何れか1項に記載の非水電解質二次電池。
- 前記ケイ素酸化物と前記炭素との質量の和に対する前記ケイ素酸化物の質量が1質量%以上20質量%以下であることを特徴とする請求項1~請求項4の何れか1項に記載の非水電解質二次電池。
- 前記ケイ素酸化物の酸素原子とケイ素原子との比(O/Si)が0.5以上1.5以下であることを特徴とする請求項1~5の何れか1項に記載の非水電解質二次電池。
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
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CN201580007993.8A CN105981210B (zh) | 2014-02-28 | 2015-02-13 | 非水电解质二次电池 |
JP2016505032A JP6443437B2 (ja) | 2014-02-28 | 2015-02-13 | 非水電解質二次電池 |
US15/119,617 US10340521B2 (en) | 2014-02-28 | 2015-02-13 | Non-aqueous electrolyte secondary battery |
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Cited By (6)
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---|---|---|---|---|
JPWO2019103046A1 (ja) * | 2017-11-21 | 2020-05-28 | 日立金属株式会社 | リチウムイオン二次電池用正極活物質の製造方法及び熱処理装置 |
KR20210058959A (ko) * | 2018-09-21 | 2021-05-24 | 가부시끼가이샤 다나까 가가꾸 겡뀨쇼 | 이차 전지용 양극 활물질 및 그 제조방법 |
US20210159541A1 (en) * | 2017-08-03 | 2021-05-27 | Samsung Sdi Co., Ltd. | Electrolyte for lithium battery and lithium battery comprising same |
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JP2022548260A (ja) * | 2019-09-13 | 2022-11-17 | ユミコア | 充電式リチウムイオン電池用の正極材料の調製方法 |
Families Citing this family (4)
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Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2003346809A (ja) * | 1997-03-07 | 2003-12-05 | Nichia Chem Ind Ltd | リチウムイオン二次電池用正極活物質及びその製造方法 |
JP2008210618A (ja) * | 2007-02-26 | 2008-09-11 | Hitachi Maxell Ltd | 非水電解質二次電池 |
WO2011108464A1 (ja) * | 2010-03-01 | 2011-09-09 | 古河電気工業株式会社 | 正極活物質材料、正極、2次電池及びこれらの製造方法 |
JP2012227154A (ja) * | 2010-09-14 | 2012-11-15 | Hitachi Maxell Energy Ltd | 非水二次電池 |
EP2565965A1 (en) * | 2011-08-31 | 2013-03-06 | Samsung SDI Co., Ltd. | Lithium secondary battery |
WO2013042176A1 (ja) * | 2011-09-20 | 2013-03-28 | 日立ビークルエナジー株式会社 | リチウムイオン電池 |
JP2014013659A (ja) * | 2012-07-03 | 2014-01-23 | Mitsubishi Chemicals Corp | 非水系電解質、およびそれを用いた非水系電解質二次電池 |
Family Cites Families (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR100653170B1 (ko) * | 1999-07-07 | 2006-12-04 | 쇼와 덴코 가부시키가이샤 | 정극활물질, 그 제조방법 및 2차전지 |
US6699618B2 (en) | 2000-04-26 | 2004-03-02 | Showa Denko K.K. | Cathode electroactive material, production method therefor and secondary cell |
US6960335B1 (en) * | 2001-09-20 | 2005-11-01 | Nanopowder Enterprises Inc | Nanostructured and layered lithium manganese oxide and method of manufacturing the same |
CN100414743C (zh) * | 2002-05-08 | 2008-08-27 | 株式会社杰士汤浅 | 一种非水电解质二次电池 |
JP4976715B2 (ja) | 2006-03-17 | 2012-07-18 | 三井化学株式会社 | 非水電解液及びそれを用いたリチウム二次電池 |
KR101084068B1 (ko) * | 2009-11-25 | 2011-11-16 | 삼성에스디아이 주식회사 | 리튬 이차 전지 |
JP2011243558A (ja) | 2010-04-22 | 2011-12-01 | Hitachi Maxell Energy Ltd | リチウム二次電池用正極およびリチウム二次電池 |
JP6024457B2 (ja) | 2010-09-02 | 2016-11-16 | 日本電気株式会社 | 二次電池およびそれに用いる二次電池用電解液 |
JP2012134082A (ja) * | 2010-12-24 | 2012-07-12 | Hitachi Ltd | 二次電池用正極活物質及びこれを用いたマグネシウム二次電池 |
JP2013062164A (ja) * | 2011-09-14 | 2013-04-04 | Hitachi Maxell Energy Ltd | 電気化学素子用非水電解液および電気化学素子 |
JP5263416B1 (ja) | 2012-03-02 | 2013-08-14 | 株式会社豊田自動織機 | 二次電池およびそれを搭載した車両 |
JP5846040B2 (ja) | 2012-05-14 | 2016-01-20 | 株式会社豊田自動織機 | 電解液およびそれを備えるリチウムイオン二次電池 |
-
2015
- 2015-02-13 CN CN201580007993.8A patent/CN105981210B/zh active Active
- 2015-02-13 WO PCT/JP2015/000656 patent/WO2015129187A1/ja active Application Filing
- 2015-02-13 JP JP2016505032A patent/JP6443437B2/ja active Active
- 2015-02-13 US US15/119,617 patent/US10340521B2/en active Active
Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2003346809A (ja) * | 1997-03-07 | 2003-12-05 | Nichia Chem Ind Ltd | リチウムイオン二次電池用正極活物質及びその製造方法 |
JP2008210618A (ja) * | 2007-02-26 | 2008-09-11 | Hitachi Maxell Ltd | 非水電解質二次電池 |
WO2011108464A1 (ja) * | 2010-03-01 | 2011-09-09 | 古河電気工業株式会社 | 正極活物質材料、正極、2次電池及びこれらの製造方法 |
JP2012227154A (ja) * | 2010-09-14 | 2012-11-15 | Hitachi Maxell Energy Ltd | 非水二次電池 |
EP2565965A1 (en) * | 2011-08-31 | 2013-03-06 | Samsung SDI Co., Ltd. | Lithium secondary battery |
WO2013042176A1 (ja) * | 2011-09-20 | 2013-03-28 | 日立ビークルエナジー株式会社 | リチウムイオン電池 |
JP2014013659A (ja) * | 2012-07-03 | 2014-01-23 | Mitsubishi Chemicals Corp | 非水系電解質、およびそれを用いた非水系電解質二次電池 |
Cited By (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20210159541A1 (en) * | 2017-08-03 | 2021-05-27 | Samsung Sdi Co., Ltd. | Electrolyte for lithium battery and lithium battery comprising same |
JPWO2019103046A1 (ja) * | 2017-11-21 | 2020-05-28 | 日立金属株式会社 | リチウムイオン二次電池用正極活物質の製造方法及び熱処理装置 |
KR20210058959A (ko) * | 2018-09-21 | 2021-05-24 | 가부시끼가이샤 다나까 가가꾸 겡뀨쇼 | 이차 전지용 양극 활물질 및 그 제조방법 |
KR102648286B1 (ko) | 2018-09-21 | 2024-03-15 | 가부시끼가이샤 다나까 가가꾸 겡뀨쇼 | 이차 전지용 양극 활물질 및 그 제조방법 |
JP2022548260A (ja) * | 2019-09-13 | 2022-11-17 | ユミコア | 充電式リチウムイオン電池用の正極材料の調製方法 |
KR20220064394A (ko) * | 2019-12-24 | 2022-05-18 | 컨템포러리 엠퍼렉스 테크놀로지 씨오., 리미티드 | 이차 전지 및 이를 포함하는 장치 |
JP2022553518A (ja) * | 2019-12-24 | 2022-12-23 | 寧徳時代新能源科技股▲分▼有限公司 | 二次電池及び該二次電池を備える装置 |
US11777134B2 (en) | 2019-12-24 | 2023-10-03 | Contemporary Amperex Technology Co., Limited | Secondary battery and device including the same |
KR102648175B1 (ko) * | 2019-12-24 | 2024-03-19 | 컨템포러리 엠퍼렉스 테크놀로지 씨오., 리미티드 | 이차 전지 및 이를 포함하는 장치 |
JP7460765B2 (ja) | 2019-12-24 | 2024-04-02 | 寧徳時代新能源科技股▲分▼有限公司 | 二次電池及び該二次電池を備える装置 |
KR20220035220A (ko) | 2020-05-28 | 2022-03-21 | 아사히 가세이 가부시키가이샤 | 비수계 이차 전지 및 비수계 전해액 |
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JPWO2015129187A1 (ja) | 2017-03-30 |
US20170062818A1 (en) | 2017-03-02 |
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CN105981210A (zh) | 2016-09-28 |
US10340521B2 (en) | 2019-07-02 |
CN105981210B (zh) | 2020-09-18 |
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