JP2005339886A - Nonaqueous electrolyte secondary battery - Google Patents
Nonaqueous electrolyte secondary battery Download PDFInfo
- Publication number
- JP2005339886A JP2005339886A JP2004154787A JP2004154787A JP2005339886A JP 2005339886 A JP2005339886 A JP 2005339886A JP 2004154787 A JP2004154787 A JP 2004154787A JP 2004154787 A JP2004154787 A JP 2004154787A JP 2005339886 A JP2005339886 A JP 2005339886A
- Authority
- JP
- Japan
- Prior art keywords
- composite oxide
- active material
- lithium
- transition metal
- metal composite
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000011255 nonaqueous electrolyte Substances 0.000 title claims abstract description 22
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 46
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 38
- 239000002905 metal composite material Substances 0.000 claims abstract description 36
- -1 lithium transition metal Chemical class 0.000 claims abstract description 34
- 239000010419 fine particle Substances 0.000 claims abstract description 24
- 239000007774 positive electrode material Substances 0.000 claims abstract description 23
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000007773 negative electrode material Substances 0.000 claims abstract description 5
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 3
- 239000002131 composite material Substances 0.000 claims description 9
- KLARSDUHONHPRF-UHFFFAOYSA-N [Li].[Mn] Chemical compound [Li].[Mn] KLARSDUHONHPRF-UHFFFAOYSA-N 0.000 claims description 8
- 229910052596 spinel Inorganic materials 0.000 claims description 5
- 239000011029 spinel Substances 0.000 claims description 5
- 239000011572 manganese Substances 0.000 claims description 4
- 150000003624 transition metals Chemical class 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims 1
- 230000003247 decreasing effect Effects 0.000 abstract 1
- 238000003860 storage Methods 0.000 description 11
- 239000008151 electrolyte solution Substances 0.000 description 7
- 239000002245 particle Substances 0.000 description 7
- 239000011248 coating agent Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 239000003792 electrolyte Substances 0.000 description 5
- 239000011230 binding agent Substances 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 3
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 3
- 239000011149 active material Substances 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 239000003575 carbonaceous material Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 150000005676 cyclic carbonates Chemical class 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 2
- 229910012529 LiNi0.4Co0.3Mn0.3O2 Inorganic materials 0.000 description 2
- 229910013870 LiPF 6 Inorganic materials 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- 150000005678 chain carbonates Chemical class 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000006258 conductive agent Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 239000011267 electrode slurry Substances 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 229910052758 niobium Inorganic materials 0.000 description 2
- 239000011164 primary particle Substances 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000002562 thickening agent Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- 229910052727 yttrium Inorganic materials 0.000 description 2
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- ZZXUZKXVROWEIF-UHFFFAOYSA-N 1,2-butylene carbonate Chemical compound CCC1COC(=O)O1 ZZXUZKXVROWEIF-UHFFFAOYSA-N 0.000 description 1
- LZDKZFUFMNSQCJ-UHFFFAOYSA-N 1,2-diethoxyethane Chemical compound CCOCCOCC LZDKZFUFMNSQCJ-UHFFFAOYSA-N 0.000 description 1
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910015015 LiAsF 6 Inorganic materials 0.000 description 1
- 229910013063 LiBF 4 Inorganic materials 0.000 description 1
- 229910013684 LiClO 4 Inorganic materials 0.000 description 1
- 229910016476 Ni0.4Co0.3Mn0.3 Inorganic materials 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 239000004210 ether based solvent Substances 0.000 description 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 239000007770 graphite material Substances 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- ACFSQHQYDZIPRL-UHFFFAOYSA-N lithium;bis(1,1,2,2,2-pentafluoroethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)C(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)C(F)(F)F ACFSQHQYDZIPRL-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000006864 oxidative decomposition reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 239000011163 secondary particle Substances 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
Images
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
Description
本発明は、リチウム二次電池などの非水電解質二次電池に関するものである。 The present invention relates to a non-aqueous electrolyte secondary battery such as a lithium secondary battery.
コバルト酸リチウム及びニッケル酸リチウムなどの層状構造を有するリチウム遷移金属複合酸化物を正極活物質として用いた非水電解質二次電池は、電圧が４Ｖ程度と高く、また大きな容量が得られるため、高いエネルギー密度を有する電池とすることができる。しかしながら、これらの正極活物質を用いた場合、充電状態において高温環境下に放置すると電池容量が低下するという問題があった。 A non-aqueous electrolyte secondary battery using a lithium transition metal composite oxide having a layered structure such as lithium cobaltate and lithium nickelate as a positive electrode active material has a high voltage of about 4 V and a high capacity, and thus is high. A battery having an energy density can be obtained. However, when these positive electrode active materials are used, there is a problem in that the battery capacity decreases when left in a high temperature environment in a charged state.
この問題を解決するため、リチウム遷移金属複合酸化物中の遷移金属のサイトを異種の元素により置換したり、あるいは酸素のサイトをフッ素により置換するなどの技術が提案されている。例えば、ＬｉＣｏＯ2の表面上における電解液の酸化分解を抑制し、結晶構造を安定化するために、ＬｉＣｏＯ2にイットリウムを添加する技術が提案されている（特許文献１）。 In order to solve this problem, a technique has been proposed in which the transition metal site in the lithium transition metal composite oxide is replaced with a different element, or the oxygen site is replaced with fluorine. For example, a technique for adding yttrium to LiCoO 2 has been proposed in order to suppress oxidative decomposition of the electrolyte solution on the surface of LiCoO 2 and stabilize the crystal structure (Patent Document 1).
しかしながら、上記のように正極活物質にイットリウムなどの異種元素を添加し遷移金属サイトを置換する場合には、電池容量が低下するという問題があった。
本発明の目的は、層状構造を有するリチウム遷移金属複合酸化物を正極活物質として用いた非水電解質二次電池において、電池容量を低下させることなく、高温耐久性を高めた非水電解質二次電池を提供することにある。 An object of the present invention is to provide a non-aqueous electrolyte secondary battery using a lithium transition metal composite oxide having a layered structure as a positive electrode active material, the non-aqueous electrolyte secondary having improved high-temperature durability without reducing the battery capacity. To provide a battery.
本発明は、リチウムの吸蔵・放出が可能な正極活物質を含む正極と、リチウムの吸蔵・放出が可能な負極活物質を含む負極と、リチウムイオン伝導性を有する非水電解液とを備えた非水電解質二次電池であり、正極活物質として、Ｙ2Ｏ3の微粒子で表面が被覆された、層状構造を有するリチウム遷移金属複合酸化物を用いることを特徴としている。 The present invention includes a positive electrode including a positive electrode active material capable of occluding and releasing lithium, a negative electrode including a negative electrode active material capable of occluding and releasing lithium, and a non-aqueous electrolyte having lithium ion conductivity. A non-aqueous electrolyte secondary battery is characterized in that a lithium transition metal composite oxide having a layered structure, the surface of which is coated with fine particles of Y 2 O 3 , is used as a positive electrode active material.
本発明においては、正極活物質として、Ｙ2Ｏ3の微粒子で表面が被覆された、層状構造を有するリチウム遷移金属複合酸化物を用いている。本発明において、「被覆」とは、層状構造を有するリチウム遷移金属複合酸化物の表面にＹ2Ｏ3の微粒子が付着した状態を意味している。従って、Ｙ2Ｏ3の微粒子は、リチウム遷移金属複合酸化物の表面を完全に被覆している必要はなく、少なくとも一部の表面が被覆されていればよい。 In the present invention, a lithium transition metal composite oxide having a layered structure whose surface is coated with fine particles of Y 2 O 3 is used as the positive electrode active material. In the present invention, “coating” means a state in which fine particles of Y 2 O 3 are adhered to the surface of a lithium transition metal composite oxide having a layered structure. Therefore, it is not necessary for the Y 2 O 3 fine particles to completely cover the surface of the lithium transition metal composite oxide, as long as at least a part of the surface is covered.
本発明に従い、Ｙ2Ｏ3の微粒子で表面が被覆された層状構造を有するリチウム遷移金属複合酸化物を用いることにより、電池容量を低下させることなく、高温耐久性、すなわち高温保存特性を高めることができる。高温耐久性を高めることができる理由の詳細については明らかではないが、正極活物質がＹ2Ｏ3の微粒子で被覆されていることにより、正極活物質と非水電解液とが直接接触することにより生じる活物質表面の劣化が抑制されるためであると思われる。 According to the present invention, by using a lithium transition metal composite oxide having a layered structure whose surface is coated with fine particles of Y 2 O 3 , high temperature durability, that is, high temperature storage characteristics, is improved without reducing battery capacity. Can do. Although the details of the reason why the high temperature durability can be improved are not clear, the positive electrode active material and the nonaqueous electrolyte solution are in direct contact with each other because the positive electrode active material is coated with the fine particles of Y 2 O 3. This is thought to be due to the suppression of the deterioration of the active material surface caused by.
本発明において、Ｙ2Ｏ3の微粒子でリチウム遷移金属複合酸化物の表面を被覆する方法としては、例えば、リチウム遷移金属複合酸化物とＹ2Ｏ3の微粒子とを大きな剪断力がかかる混合装置等を用いて混合し、リチウム遷移金属複合酸化物の表面にＹ2Ｏ3の微粒子を物理的に付着させる方法が挙げられる。 In the present invention, Y 2 as a method for coating the surface of particles of lithium transition metal composite oxide of O 3, for example, a large shearing force is applied mixing apparatus and a particle of the lithium-transition metal composite oxide and Y 2 O 3 And the like, and the fine particles of Y 2 O 3 are physically attached to the surface of the lithium transition metal composite oxide.
本発明において、層状構造を有するリチウム遷移金属複合酸化物に対するＹ2Ｏ3の微粒子の被覆量は、該複合酸化物に対して０．１〜３．０モル％の範囲であることが好ましく、０．３〜１．０モル％の範囲であることがさらに好ましい。Ｙ2Ｏ3の微粒子の被覆量が０．１モル％未満であると、高温耐久性（高温保存特性）が十分に得られない場合があり、３．０モル％を超えると、高温耐久性（高温保存特性）は向上するものの、レート特性等が低下する場合がある。 In the present invention, the coating amount of the fine particles of Y 2 O 3 on the lithium transition metal composite oxide having a layered structure is preferably in the range of 0.1 to 3.0 mol% with respect to the composite oxide, More preferably, it is in the range of 0.3 to 1.0 mol%. When the coating amount of the fine particles of Y 2 O 3 is less than 0.1 mol%, high temperature durability (high temperature storage characteristics) may not be sufficiently obtained. Although (high temperature storage characteristics) are improved, rate characteristics and the like may be deteriorated.
被覆するＹ2Ｏ3粒子の平均粒子径は、０．３μｍ以下であることが好ましく、さらに好ましくは０．２μｍ以下である。Ｙ2Ｏ3粒子の平均粒子径を０．３μｍ以下にすることにより、より均一にリチウム遷移金属複合酸化物の表面を被覆することができる。リチウム遷移金属複合酸化物の平均一次粒子径は、一般に１〜３μｍ程度である。 The average particle diameter of the Y 2 O 3 particles to be coated is preferably 0.3 μm or less, more preferably 0.2 μm or less. By making the average particle diameter of Y 2 O 3 particles 0.3 μm or less, the surface of the lithium transition metal composite oxide can be coated more uniformly. The average primary particle diameter of the lithium transition metal composite oxide is generally about 1 to 3 μm.
本発明に用いる層状構造を有するリチウム遷移金属複合酸化物は、電池容量を大きくするためにＮｉを含んでいることが好ましい。さらに構造安定性を高めるためにＭｎを含んでいることが好ましく、さらにはＣｏを含んでいることがより好ましい。 The lithium transition metal composite oxide having a layered structure used in the present invention preferably contains Ni in order to increase the battery capacity. Further, in order to enhance the structural stability, it is preferable that Mn is contained, and further that Co is more preferably contained.
本発明に用いる層状構造を有するリチウム遷移金属複合酸化物としては、一般式ＬｉaＭｎxＮｉyＣｏzＯ2（ａ，ｘ，ｙ及びｚは、０≦ａ≦１．２、ｘ＋ｙ＋ｚ＝１、０≦ｘ≦０．５、０≦ｙ≦０．５、ｚ≧０を満足する。）で表わされるものが好ましい。また、上記リチウム遷移金属複合酸化物には、Ｂ，Ｆ，Ｍｇ，Ａｌ，Ｔｉ，Ｃｒ，Ｖ，Ｆｅ，Ｃｕ，Ｚｎ，Ｎｂ，Ｚｒ，及びＳｎから選択される少なくとも１種類の元素がさらに含まれていてもよい。 As the lithium transition metal composite oxide having a layered structure used in the present invention, the general formula Li a Mn x Ni y Co z O 2 (a, x, y and z are 0 ≦ a ≦ 1.2, x + y + z = 1). And 0 ≦ x ≦ 0.5, 0 ≦ y ≦ 0.5, and z ≧ 0) are preferable. The lithium transition metal composite oxide further includes at least one element selected from B, F, Mg, Al, Ti, Cr, V, Fe, Cu, Zn, Nb, Zr, and Sn. It may be.
また、本発明においては、上記のＹ2Ｏ3の微粒子で被覆された層状構造を有するリチウム遷移金属複合酸化物に、スピネル構造を有するリチウムマンガン複合酸化物を混合して正極活物質として用いてもよい。スピネル構造を有するリチウムマンガン複合酸化物には、Ｂ，Ｆ，Ｍｇ，Ａｌ，Ｔｉ，Ｃｒ，Ｖ，Ｆｅ，Ｃｏ，Ｎｉ，Ｃｕ，Ｚｎ，Ｎｂ，及びＺｒから選択される少なくとも１種類の元素がさらに含まれていてもよい。 In the present invention, the lithium transition metal composite oxide having a layered structure coated with the Y 2 O 3 fine particles is mixed with a lithium manganese composite oxide having a spinel structure and used as a positive electrode active material. Also good. The lithium manganese composite oxide having a spinel structure includes at least one element selected from B, F, Mg, Al, Ti, Cr, V, Fe, Co, Ni, Cu, Zn, Nb, and Zr. Further, it may be included.
Ｙ2Ｏ3の微粒子で被覆された、層状構造を有するリチウム遷移金属複合酸化物と、スピネル構造を有するリチウムマンガン複合酸化物とを混合して正極活物質として用いる場合、その混合割合（リチウム遷移金属複合酸化物：リチウムマンガン複合酸化物）は、重量比率で１：９〜９：１の範囲であることが好ましく、さらに好ましくは６：４〜９：１の範囲である。これらの範囲でリチウムマンガン複合酸化物をリチウム遷移金属複合酸化物に混合することにより、高温耐久性をさらに向上させることができる。 When a lithium transition metal composite oxide having a layered structure covered with fine particles of Y 2 O 3 and a lithium manganese composite oxide having a spinel structure are mixed and used as a positive electrode active material, the mixing ratio (lithium transition The metal composite oxide: lithium manganese composite oxide) is preferably in the range of 1: 9 to 9: 1 by weight ratio, more preferably in the range of 6: 4 to 9: 1. By mixing the lithium manganese composite oxide with the lithium transition metal composite oxide within these ranges, the high temperature durability can be further improved.
本発明において負極に用いる負極活物質は特に限定されるものではなく、非水電解質二次電池に用いることができるものであればよいが、好ましくは炭素材料が用いられる。炭素材料の中でも、特に黒鉛材料が好ましく用いられる。 The negative electrode active material used for the negative electrode in the present invention is not particularly limited as long as it can be used for a non-aqueous electrolyte secondary battery, but a carbon material is preferably used. Among carbon materials, graphite material is particularly preferably used.
非水電解質としては、非水電解質二次電池に用いられる電解質を制限なく用いることができる。電解質の溶媒としては、特に限定されるものではないが、エチレンカーボネート、プロピレンカーボネート、ブチレンカーボネート、ビニレンカーボネートなどの環状カーボネート、ジメチルカーボネート、メチルエチルカーボネート、ジエチルカーボネートなどの鎖状カーボネートなどを用いることができる。特に、環状カーボネートと鎖状カーボネートの混合溶媒が好ましく用いられる。また、上記環状カーボネートと、１，２−ジメトキシエタン、１，２−ジエトキシエタンなどのエーテル系溶媒との混合溶媒も例示される。 As the non-aqueous electrolyte, an electrolyte used for a non-aqueous electrolyte secondary battery can be used without limitation. The electrolyte solvent is not particularly limited, but cyclic carbonates such as ethylene carbonate, propylene carbonate, butylene carbonate, and vinylene carbonate, and chain carbonates such as dimethyl carbonate, methyl ethyl carbonate, and diethyl carbonate may be used. it can. In particular, a mixed solvent of a cyclic carbonate and a chain carbonate is preferably used. Moreover, the mixed solvent of the said cyclic carbonate and ether solvents, such as 1, 2- dimethoxyethane and 1, 2- diethoxyethane, is also illustrated.
また、電解質の溶質としては、特に限定されるものではないが、ＬｉＰＦ6、ＬｉＢＦ4、ＬｉＣＦ3ＳＯ3、ＬｉＮ（ＣＦ3ＳＯ2)2、ＬｉＮ（Ｃ2Ｆ5ＳＯ2)2、ＬｉＮ（ＣＦ3ＳＯ2)(Ｃ4Ｆ9ＳＯ2)、ＬｉＣ（ＣＦ3ＳＯ2)3、ＬｉＣ（Ｃ2Ｆ5ＳＯ2)3、ＬｉＡｓＦ6、ＬｉＣｌＯ4、Ｌｉ2Ｂ10Ｃｌ10、Ｌｉ2Ｂ12Ｃｌ12など及びそれらの混合物が挙げられる。 Moreover, the electrolyte solute is not particularly limited, but LiPF 6 , LiBF 4 , LiCF 3 SO 3 , LiN (CF 3 SO 2 ) 2 , LiN (C 2 F 5 SO 2 ) 2 , LiN ( CF 3 SO 2 ) (C 4 F 9 SO 2 ), LiC (CF 3 SO 2 ) 3 , LiC (C 2 F 5 SO 2 ) 3 , LiAsF 6 , LiClO 4 , Li 2 B 10 Cl 10 , Li 2 B And 12 Cl 12 and mixtures thereof.
本発明に従い、正極活物質として、Ｙ2Ｏ3の微粒子で表面が被覆された層状構造を有するリチウム遷移金属複合酸化物を用いることにより、電池容量を低下させることなく、高温耐久性を高めることができる。 According to the present invention, by using a lithium transition metal composite oxide having a layered structure whose surface is coated with fine particles of Y 2 O 3 as the positive electrode active material, the high temperature durability is improved without reducing the battery capacity. Can do.
以下、本発明を実施例に基づいてさらに詳細に説明するが、本発明は以下の実施例に何ら限定されるものではなく、その要旨を変更しない範囲において適宜変更して実施することが可能なものである。 Hereinafter, the present invention will be described in more detail based on examples. However, the present invention is not limited to the following examples, and can be implemented with appropriate modifications within a range not changing the gist thereof. Is.
（実施例１）
〔Ｙ2Ｏ3の微粒子で被覆したリチウム遷移金属複合酸化物の作製〕
平均二次粒子径１０μｍのＬｉＮｉ0.4Ｃｏ0.3Ｍｎ0.3Ｏ2：１５０ｇと、平均粒子径０．１μｍのＹ2Ｏ3：１．７７ｇ（遷移金属Ｎｉ0.4Ｃｏ0.3Ｍｎ0.3に対して０．５モル％）とをホソカワミクロン（株）製メカノフュージョンＡＭ−２０ＦＳに充填し、１５００ｒｐｍで５分間混合した。混合後の粉末状態を走査型電子顕微鏡（ＳＥＭ）で観察した結果、一次粒子径約１μｍのリチウム遷移金属複合酸化物の表面に、Ｙ2Ｏ3の微粒子が均一に付着していることを確認した。
(Example 1)
[Preparation of lithium transition metal composite oxide coated with fine particles of Y 2 O 3 ]
LiNi 0.4 Co 0.3 Mn 0.3 O 2 with an average secondary particle diameter of 10 μm: 150 g and Y 2 O 3 with an average particle diameter of 0.1 μm: 1.77 g (0.5 mol with respect to the transition metal Ni 0.4 Co 0.3 Mn 0.3 %) Was loaded into Mechanofusion AM-20FS manufactured by Hosokawa Micron Corporation and mixed at 1500 rpm for 5 minutes. As a result of observing the powder state after mixing with a scanning electron microscope (SEM), it was confirmed that fine particles of Y 2 O 3 were uniformly attached to the surface of the lithium transition metal composite oxide having a primary particle diameter of about 1 μm. did.
〔正極の作製〕
上記のように作製した、Ｙ2Ｏ3の微粒子で表面を被覆したリチウム遷移金属複合酸化物と、スピネル構造を有するリチウムマンガン複合酸化物（Ｌｉ1.1Ｍｎ1.9Ｏ4）とを重量比（リチウム遷移金属複合酸化物：リチウムマンガン複合酸化物）で７：３となるように混合して、この混合物を正極活物質として用いた。この混合物（正極活物質）と、導電剤としての炭素材料と、結着剤としてのポリフッ化ビニリデンを溶解したＮ−メチル−２−ピロリドン溶液を、活物質と導電剤と結着剤の重量比が９０：５：５となるように混合して正極スラリーを作製した。作製したスラリーを集電体としてのアルミニウム箔上に塗布した後、乾燥し、その後圧延ローラーを用いて圧延し、集電体タブを取り付けることにより正極を作製した。
[Production of positive electrode]
The weight ratio (lithium transition) of the lithium transition metal composite oxide whose surface was coated with the fine particles of Y 2 O 3 and the lithium manganese composite oxide (Li 1.1 Mn 1.9 O 4 ) having a spinel structure prepared as described above. Metal composite oxide: lithium manganese composite oxide) was mixed so as to be 7: 3, and this mixture was used as a positive electrode active material. This mixture (positive electrode active material), a carbon material as a conductive agent, and an N-methyl-2-pyrrolidone solution in which polyvinylidene fluoride as a binder is dissolved are mixed in a weight ratio of the active material, the conductive agent, and the binder. Was mixed to be 90: 5: 5 to prepare a positive electrode slurry. The prepared slurry was applied onto an aluminum foil as a current collector, dried, then rolled using a rolling roller, and a current collector tab was attached to produce a positive electrode.
〔負極の作製〕
負極活物質としての黒鉛と、結着剤としてのＳＢＲと、増粘剤としてのカルボキシメチルセルロースを溶かした水溶液を、活物質と結着剤と増粘剤の重量比が９８：１：１になるように混練して負極スラリーを作製した。作製したスラリーを集電体としての銅箔上に塗布した後、乾燥し、その後圧延ローラーを用いて圧延し、集電タブを取り付けて負極を作製した。
(Production of negative electrode)
An aqueous solution in which graphite as a negative electrode active material, SBR as a binder, and carboxymethyl cellulose as a thickener are dissolved has a weight ratio of 98: 1: 1 between the active material, the binder, and the thickener. The negative electrode slurry was prepared by kneading as described above. After apply | coating the produced slurry on the copper foil as a collector, it dried and then rolled using the rolling roller, the collector tab was attached, and the negative electrode was produced.
〔電解液の作製〕
エチレンカーボネート（ＥＣ）と、ジエチルカーボネート（ＤＥＣ）とを体積比３：７で混合した溶媒に、溶質としてのＬｉＰＦ6を１モル／リットルとなるように溶解し、電解液を作製した。
(Preparation of electrolyte)
LiPF 6 as a solute was dissolved in a solvent in which ethylene carbonate (EC) and diethyl carbonate (DEC) were mixed at a volume ratio of 3: 7 so as to be 1 mol / liter to prepare an electrolytic solution.
〔三電極式ビーカーセルの作製〕
上記で作製した正極を作用極として用い、対極及び参照極としてリチウム金属を用い、図１に示す三電極式ビーカーセルＡ１を作製した。図１に示すように、ビーカーセルの容器中には電解液４が入れられており、この電解液４に、作用極１、対極２、及び参照極３が浸漬されている。また、電解液４としては、上記で作製した電解液を用いている。
[Production of three-electrode beaker cell]
A three-electrode beaker cell A1 shown in FIG. 1 was prepared using the positive electrode prepared above as a working electrode and lithium metal as a counter electrode and a reference electrode. As shown in FIG. 1, an electrolyte solution 4 is placed in a beaker cell container, and a working
〔非水電解質二次電池の作製〕
上記で作製した正極及び負極を、ポリエチレン製のセパレータを介して対向するように巻取って巻取り体を作製し、アルゴン雰囲気下のグローボックス中にて、この巻取り体を電解液とともに電池缶に封入することにより、定格容量１．４Ａｈの円筒型１８６５０サイズの非水電解質二次電池Ａ２を作製した。
[Preparation of non-aqueous electrolyte secondary battery]
The positive electrode and the negative electrode prepared above are wound so as to face each other with a polyethylene separator therebetween, and a wound body is produced. In a glow box under an argon atmosphere, the wound body is combined with an electrolytic solution into a battery can. Was sealed to produce a cylindrical 18650 size non-aqueous electrolyte secondary battery A2 having a rated capacity of 1.4 Ah.
（比較例１）
実施例１において、Ｙ2Ｏ3の微粒子で表面が被覆されたリチウム遷移金属複合酸化物に代えて、Ｙ2Ｏ3の微粒子で表面を被覆していない、すなわちＹ2Ｏ3の微粒子と混合処理していないリチウム遷移金属複合酸化物（ＬｉＮｉ0.4Ｃｏ0.3Ｍｎ0.3Ｏ2）を用いる以外は、実施例１と同様にして、三電極式ビーカーセルＢ１と、定格容量１．４Ａｈの円筒型１８６５０サイズの非水電解質二次電池Ｂ２を作製した。
(Comparative Example 1)
Mixed in Example 1, in place of the lithium-transition metal composite oxide whose surface is coated with fine particles of Y 2 O 3, no surface coating of fine particles of Y 2 O 3, namely the fine particles of Y 2 O 3 A three-electrode beaker cell B1 and a cylindrical 18650 with a rated capacity of 1.4 Ah are used in the same manner as in Example 1 except that an untreated lithium transition metal composite oxide (LiNi 0.4 Co 0.3 Mn 0.3 O 2 ) is used. A non-aqueous electrolyte secondary battery B2 having a size was produced.
〔三電極式ビーカーセルの放電容量の測定〕
三電極式ビーカーセルＡ１及びＢ１について、放電容量を測定した。放電容量の測定は、９．３ｍＡと３．１ｍＡの２段階充電で４．３Ｖまで充電した後、放電終止電圧を３．１Ｖに設定し、９．３ｍＡで３．１Ｖまで放電したときの容量を測定し、これを放電容量とした。測定結果を表１に示す。
[Measurement of discharge capacity of three-electrode beaker cell]
The discharge capacity was measured for the three-electrode beaker cells A1 and B1. The discharge capacity is measured after charging to 4.3V by two-step charging at 9.3 mA and 3.1 mA, then setting the discharge end voltage to 3.1 V, and discharging to 3.1 V at 9.3 mA. Was measured and used as the discharge capacity. The measurement results are shown in Table 1.
電池Ａ２及びＢ２について、定格容量を測定した。電池の定格容量は、１４００ｍＡの定電流−定電圧（７０ｍＡカット）で４．２Ｖまで充電した後、放電終止電圧を３．０Ｖに設定し、４７０ｍＡで３．０Ｖまで放電したときの電池容量を定格容量とした。
The rated capacities of the batteries A2 and B2 were measured. The battery has a rated capacity of 1400 mA constant current-constant voltage (70 mA cut) after charging to 4.2 V, then set the discharge end voltage to 3.0 V, and the battery capacity when discharged to 3.0 V at 470 mA. Rated capacity.
〔電池のＩＶ抵抗の測定〕
電池Ａ２及びＢ２について、ＩＶ抵抗を測定した。１４００ｍＡでＳＯＣ５０％まで充電した後、ＳＯＣ５０％を中心として２８０ｍＡ、７００ｍＡ、２１００ｍＡ、及び４２００ｍＡで１０秒間充電と放電をそれぞれ行い、それぞれの場合における１０秒後の電池電圧を電流値に対してプロットし、その傾きをＩＶ抵抗とした。
[Measurement of battery IV resistance]
IV resistance was measured about battery A2 and B2. After charging to SOC 50% at 1400 mA, charging and discharging are performed for 10 seconds at 280 mA, 700 mA, 2100 mA and 4200 mA centering on SOC 50%, respectively, and the battery voltage after 10 seconds in each case is plotted against the current value. The slope was defined as IV resistance.
〔保存特性試験〕
電池Ａ２及びＢ２について、１４００ｍＡでＳＯＣ５０％まで充電した後、温度を６５℃に保持した恒温槽内で３０日間保存試験を行った。保存後、上記と同様にして定格容量を測定し、容量復帰率を求めた。容量復帰率は、保存試験後の電池定格容量を保存試験前の電池定格容量で割って算出した。また、定格容量を測定した後、上記と同様にしてＩＶ抵抗測定を行った。この結果から、保存試験前後のＩＶ抵抗の増加を算出した。電池Ａ２及びＢ２についての容量復帰率及び保存前後のＩＶ抵抗の増加を表２に示す。
[Storage characteristics test]
Regarding batteries A2 and B2, after being charged to SOC 50% at 1400 mA, a storage test was performed for 30 days in a thermostatic bath maintained at 65 ° C. After storage, the rated capacity was measured in the same manner as described above to determine the capacity recovery rate. The capacity recovery rate was calculated by dividing the battery rated capacity after the storage test by the battery rated capacity before the storage test. Further, after measuring the rated capacity, the IV resistance was measured in the same manner as described above. From this result, the increase in IV resistance before and after the storage test was calculated. Table 2 shows the capacity recovery rate and the increase in IV resistance before and after storage for batteries A2 and B2.
１…正極
２…対極（リチウム金属）
３…参照極（リチウム金属）
４…電解液
DESCRIPTION OF
3. Reference electrode (lithium metal)
4 ... Electrolyte
Claims (3)
前記正極活物質として、Ｙ2Ｏ3の微粒子で表面が被覆された、層状構造を有するリチウム遷移金属複合酸化物を用いることを特徴とする非水電解質二次電池。 A non-aqueous electrolyte comprising a positive electrode including a positive electrode active material capable of inserting and extracting lithium, a negative electrode including a negative electrode active material capable of inserting and extracting lithium, and a non-aqueous electrolyte having lithium ion conductivity In the next battery,
A non-aqueous electrolyte secondary battery using a lithium transition metal composite oxide having a layered structure, the surface of which is coated with fine particles of Y 2 O 3 as the positive electrode active material.
2. The positive electrode active material, wherein the lithium transition metal composite oxide whose surface is coated with fine particles of Y 2 O 3 and a lithium manganese composite oxide having a spinel structure are mixed and used. Or the nonaqueous electrolyte secondary battery of 2.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2004154787A JP2005339886A (en) | 2004-05-25 | 2004-05-25 | Nonaqueous electrolyte secondary battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2004154787A JP2005339886A (en) | 2004-05-25 | 2004-05-25 | Nonaqueous electrolyte secondary battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2005339886A true JP2005339886A (en) | 2005-12-08 |
Family
ID=35493220
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2004154787A Pending JP2005339886A (en) | 2004-05-25 | 2004-05-25 | Nonaqueous electrolyte secondary battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2005339886A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009038021A (en) * | 2007-07-11 | 2009-02-19 | Toda Kogyo Corp | Manufacturing method of composite cathode active substance for nonaqueous electrolyte secondary batteries |
| JPWO2012086277A1 (en) * | 2010-12-20 | 2014-05-22 | 三洋電機株式会社 | Non-aqueous electrolyte secondary battery positive electrode and non-aqueous electrolyte secondary battery using the positive electrode |
| WO2024048564A1 (en) * | 2022-08-30 | 2024-03-07 | 三井金属鉱業株式会社 | Active material, method for producing recycled active material, method for tracking valuable element recovered from battery, and compound for tracking |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2002019449A1 (en) * | 2000-08-29 | 2002-03-07 | Santoku Corporation | Positive active material for non-aqueous electrolyte secondary cell, method for preparation thereof and non-aqueous electrolyte secondary cell |
| JP2002075361A (en) * | 2000-08-30 | 2002-03-15 | Denso Corp | Lithium ion secondary battery |
| JP2003500318A (en) * | 1999-05-15 | 2003-01-07 | メルク パテント ゲゼルシャフト ミット ベシュレンクテル ハフトング | Lithium mixed oxide particles coated with metal oxide |
| JP2004006094A (en) * | 2002-05-31 | 2004-01-08 | Nec Corp | Nonaqueous electrolyte secondary battery |
-
2004
- 2004-05-25 JP JP2004154787A patent/JP2005339886A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003500318A (en) * | 1999-05-15 | 2003-01-07 | メルク パテント ゲゼルシャフト ミット ベシュレンクテル ハフトング | Lithium mixed oxide particles coated with metal oxide |
| WO2002019449A1 (en) * | 2000-08-29 | 2002-03-07 | Santoku Corporation | Positive active material for non-aqueous electrolyte secondary cell, method for preparation thereof and non-aqueous electrolyte secondary cell |
| JP2002075361A (en) * | 2000-08-30 | 2002-03-15 | Denso Corp | Lithium ion secondary battery |
| JP2004006094A (en) * | 2002-05-31 | 2004-01-08 | Nec Corp | Nonaqueous electrolyte secondary battery |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009038021A (en) * | 2007-07-11 | 2009-02-19 | Toda Kogyo Corp | Manufacturing method of composite cathode active substance for nonaqueous electrolyte secondary batteries |
| JPWO2012086277A1 (en) * | 2010-12-20 | 2014-05-22 | 三洋電機株式会社 | Non-aqueous electrolyte secondary battery positive electrode and non-aqueous electrolyte secondary battery using the positive electrode |
| US9437869B2 (en) | 2010-12-20 | 2016-09-06 | Sanyo Electric Co., Ltd. | Positive electrode for nonaqueous electrolyte secondary battery and nonaqueous electrolyte secondary battery using the positive electrode |
| WO2024048564A1 (en) * | 2022-08-30 | 2024-03-07 | 三井金属鉱業株式会社 | Active material, method for producing recycled active material, method for tracking valuable element recovered from battery, and compound for tracking |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP4841116B2 (en) | Nonaqueous electrolyte secondary battery | |
| JP4798964B2 (en) | Nonaqueous electrolyte secondary battery | |
| JP4660164B2 (en) | Nonaqueous electrolyte secondary battery | |
| KR101772754B1 (en) | Method for producing positive electrode active material layer for lithium ion battery, and positive electrode active material layer for lithium ion battery | |
| JP4841133B2 (en) | Nonaqueous electrolyte secondary battery | |
| JP5874430B2 (en) | Non-aqueous electrolyte secondary battery and method for producing the same, and method for producing lithium transition metal composite oxide for non-aqueous electrolyte secondary battery | |
| JP2007234565A (en) | Nonaqueous electrolyte secondary battery | |
| JP2008300180A (en) | Nonaqueous electrolyte secondary battery | |
| JP5036121B2 (en) | Nonaqueous electrolyte secondary battery | |
| JP2007123251A (en) | Nonaqueous electrolyte secondary battery | |
| JP2011138621A (en) | Manufacturing method of positive electrode of nonaqueous electrolyte secondary battery | |
| JP2008091236A (en) | Nonaqueous electrolyte secondary battery | |
| CN105580171A (en) | Negative electrode active material for nonaqueous electrolyte secondary batteries and nonaqueous electrolyte secondary battery using same | |
| JP2005050779A (en) | Nonaqueous electrolytic solution secondary battery | |
| JP2008091041A (en) | Nonaqueous secondary battery | |
| JP2011181427A (en) | Lithium secondary battery | |
| JP4297709B2 (en) | Nonaqueous electrolyte secondary battery | |
| JP4297704B2 (en) | Nonaqueous electrolyte secondary battery | |
| JP2009277395A (en) | Nonaqueous secondary battery, and nonaqueous secondary battery system | |
| US10177370B2 (en) | Positive electrode for lithium ion secondary battery and lithium ion secondary battery using the same | |
| JP2009266791A (en) | Nonaqueous electrolyte secondary battery | |
| WO2016103592A1 (en) | Positive electrode active material and nonaqueous electrolyte secondary battery | |
| JP2004296181A (en) | Lithium secondary battery | |
| JP5089097B2 (en) | Non-aqueous electrolyte secondary battery and charging / discharging method thereof | |
| JP2005339887A (en) | Nonaqueous electrolyte secondary battery |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20070427 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20100521 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20100706 |
|
| A02 | Decision of refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A02 Effective date: 20101109 |