JP2007287569A - Nonaqueous electrolyte secondary battery - Google Patents
Nonaqueous electrolyte secondary battery Download PDFInfo
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- JP2007287569A JP2007287569A JP2006116026A JP2006116026A JP2007287569A JP 2007287569 A JP2007287569 A JP 2007287569A JP 2006116026 A JP2006116026 A JP 2006116026A JP 2006116026 A JP2006116026 A JP 2006116026A JP 2007287569 A JP2007287569 A JP 2007287569A
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- 239000011255 nonaqueous electrolyte Substances 0.000 title claims abstract description 21
- 239000011572 manganese Substances 0.000 claims abstract description 53
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 40
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 26
- 239000007774 positive electrode material Substances 0.000 claims abstract description 23
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 22
- -1 lithium transition metal Chemical class 0.000 claims abstract description 20
- 239000000203 mixture Substances 0.000 claims abstract description 18
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 18
- 239000002245 particle Substances 0.000 claims abstract description 16
- 229910052796 boron Inorganic materials 0.000 claims abstract description 12
- KLARSDUHONHPRF-UHFFFAOYSA-N [Li].[Mn] Chemical compound [Li].[Mn] KLARSDUHONHPRF-UHFFFAOYSA-N 0.000 claims abstract description 10
- 150000003624 transition metals Chemical class 0.000 claims abstract description 8
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims abstract description 7
- 150000001342 alkaline earth metals Chemical class 0.000 claims abstract description 7
- 229910052596 spinel Inorganic materials 0.000 claims abstract description 7
- 239000011029 spinel Substances 0.000 claims abstract description 7
- 239000002131 composite material Substances 0.000 claims description 18
- 229910052782 aluminium Inorganic materials 0.000 claims description 16
- 239000002905 metal composite material Substances 0.000 claims description 13
- 229910052749 magnesium Inorganic materials 0.000 claims description 5
- 229910052719 titanium Inorganic materials 0.000 claims description 5
- 229910052726 zirconium Inorganic materials 0.000 claims description 5
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 239000000463 material Substances 0.000 abstract description 33
- 238000012423 maintenance Methods 0.000 abstract description 9
- 239000011248 coating agent Substances 0.000 description 27
- 238000000576 coating method Methods 0.000 description 27
- 229910052748 manganese Inorganic materials 0.000 description 26
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 22
- 239000011162 core material Substances 0.000 description 21
- 239000013078 crystal Substances 0.000 description 16
- 238000012360 testing method Methods 0.000 description 15
- 239000010410 layer Substances 0.000 description 13
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- 239000003792 electrolyte Substances 0.000 description 7
- 239000008151 electrolyte solution Substances 0.000 description 7
- 239000007784 solid electrolyte Substances 0.000 description 7
- 238000010828 elution Methods 0.000 description 6
- 238000000034 method Methods 0.000 description 6
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- 229910017052 cobalt Inorganic materials 0.000 description 5
- 239000010941 cobalt Substances 0.000 description 5
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 5
- 230000014759 maintenance of location Effects 0.000 description 5
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 5
- 239000012528 membrane Substances 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- URIIGZKXFBNRAU-UHFFFAOYSA-N lithium;oxonickel Chemical compound [Li].[Ni]=O URIIGZKXFBNRAU-UHFFFAOYSA-N 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
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- 239000000243 solution Substances 0.000 description 4
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- 229910052725 zinc Inorganic materials 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
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- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 2
- 229910013716 LiNi Inorganic materials 0.000 description 2
- 229910013290 LiNiO 2 Inorganic materials 0.000 description 2
- 229910013870 LiPF 6 Inorganic materials 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 239000003125 aqueous solvent Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 150000002484 inorganic compounds Chemical class 0.000 description 2
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- 229910021445 lithium manganese complex oxide Inorganic materials 0.000 description 2
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- 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
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 description 1
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 description 1
- 229910000733 Li alloy Inorganic materials 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
- 229910014689 LiMnO Inorganic materials 0.000 description 1
- 229910013131 LiN Inorganic materials 0.000 description 1
- 229910013528 LiN(SO2 CF3)2 Inorganic materials 0.000 description 1
- 229910013398 LiN(SO2CF2CF3)2 Inorganic materials 0.000 description 1
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
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- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
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- 239000006182 cathode active material Substances 0.000 description 1
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- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 description 1
- 150000002642 lithium compounds Chemical class 0.000 description 1
- 229910002102 lithium manganese oxide Inorganic materials 0.000 description 1
- IDBFBDSKYCUNPW-UHFFFAOYSA-N lithium nitride Chemical compound [Li]N([Li])[Li] IDBFBDSKYCUNPW-UHFFFAOYSA-N 0.000 description 1
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 description 1
- VLXXBCXTUVRROQ-UHFFFAOYSA-N lithium;oxido-oxo-(oxomanganiooxy)manganese Chemical compound [Li+].[O-][Mn](=O)O[Mn]=O VLXXBCXTUVRROQ-UHFFFAOYSA-N 0.000 description 1
- IPJKJLXEVHOKSE-UHFFFAOYSA-L manganese dihydroxide Chemical compound [OH-].[OH-].[Mn+2] IPJKJLXEVHOKSE-UHFFFAOYSA-L 0.000 description 1
- 238000010303 mechanochemical reaction Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
Description
本発明は、非水電解質二次電池に関する。 The present invention relates to a non-aqueous electrolyte secondary battery.
従来、非水電解質二次電池（以下、電池ともいう）の正極活物質としては、リチウムコバルト酸化物、リチウムニッケル酸化物またはリチウムマンガン酸化物などのような、リチウムを含有する複合酸化物（以下、リチウム含有複合酸化物ともいう）が知られている。これらのなかでも、リチウムニッケル酸化物は高容量で比較的安価な正極活物質材料として期待されている。 Conventionally, as a positive electrode active material of a nonaqueous electrolyte secondary battery (hereinafter also referred to as a battery), a lithium-containing composite oxide (hereinafter referred to as lithium cobalt oxide, lithium nickel oxide, lithium manganese oxide, or the like). Also known as lithium-containing composite oxide). Among these, lithium nickel oxide is expected as a positive electrode active material having a high capacity and a relatively low price.
しかし、リチウムニッケル酸化物を正極活物質として用いた電池には、高温環境下において、電解液との反応によってガスが発生したり、被膜が発生することで電池が膨張したり抵抗が増大することがある。それは、他のリチウム含有複合酸化物と比較して、リチウムニッケル酸化物と電解液との反応性が高いことが原因ではないかと考えられる。 However, in batteries using lithium nickel oxide as the positive electrode active material, gas is generated by reaction with the electrolytic solution in a high-temperature environment, and the battery expands and resistance increases due to the formation of a film. There is. It is thought that this is because the reactivity between the lithium nickel oxide and the electrolytic solution is higher than that of other lithium-containing composite oxides.
上記の問題点を解決するために、特許文献１においては、電池の正極用活物質として、ＬｉＮｉＯ２の表面をＬｉＭｎＯ２で被覆したものが提案されている。
上記特許文献１において提案されている正極用活物質を用いた電池においては、ＬｉＮｉＯ２と電解液との接触面が減少することから、抵抗増大という問題は緩和されるが、６０℃を超える高温環境下において、電解液にマンガン（Ｍｎ２＋）が溶出することで放電容量が低下し劣化が進み易いという問題がある。 In the battery using the positive electrode active material proposed in Patent Document 1, since the contact surface between LiNiO 2 and the electrolytic solution is reduced, the problem of increased resistance is alleviated, but the high temperature exceeding 60 ° C. Under the environment, there is a problem that manganese (Mn 2+ ) elutes in the electrolytic solution, so that the discharge capacity is reduced and deterioration is likely to proceed.
本発明は上記のような事情に基づいて完成されたものであって、高温環境下においても抵抗増加が小さく、放電容量の維持率の高い非水電解質二次電池を提供することを目的とする。 The present invention has been completed based on the above circumstances, and an object thereof is to provide a non-aqueous electrolyte secondary battery having a small increase in resistance even under a high temperature environment and a high discharge capacity maintenance rate. .
本発明者らは、上記の目的を達成するために鋭意研究を行った結果、正極活物質としてニッケルを含有するリチウム含有複合酸化物を用いた場合でも、結晶中のマンガンの平均価数が４価に近いリチウムマンガン複合酸化物で被覆することでマンガンの溶出が起こり難くなるという知見を得た。 As a result of intensive studies to achieve the above object, the present inventors have found that the average valence of manganese in the crystal is 4 even when a lithium-containing composite oxide containing nickel is used as the positive electrode active material. It was found that manganese elution is less likely to occur by coating with lithium manganese composite oxide close to the valence.
これは、結晶中に３価のマンガンが多くなると以下の反応式で示すような不均化反応が起こりやすいが、４価のマンガンが多い場合には起こり難いのが一因であると考えられる。
２Ｍｎ３＋→Ｍｎ４＋＋Ｍｎ２＋
This is considered to be caused by the disproportionation reaction as shown in the following reaction formula when trivalent manganese is increased in the crystal, but less likely when tetravalent manganese is large. .
2Mn 3+ → Mn 4+ + Mn 2+
そこで、請求項１の発明は、正極活物質を含有する正極合剤層を集電体上に形成させてなる正極を備えた非水電解質二次電池であって、前記正極活物質は、少なくともニッケルを含むリチウム遷移金属複合酸化物の粒子表面の少なくとも一部が、一般式（１）で示されるスピネル構造を有するリチウムマンガン系複合酸化物で被覆されたものであることを特徴とする非水電解質二次電池である。
Ｌｉｚ（ＬｉｘＭｎ２−ｘ−ｙＭｙ）Ｏ４（１）
（式中０．１２＜ｘ≦０．３３３，０≦ｙ＜０．２，０＜ｚ≦１，ＭはＭｎ以外の遷移金属、アルカリ土類金属、ＢまたはＡｌである。）
なお、上記一般式（１）において、ｚは、このリチウムマンガン系複合酸化物の充放電状態によって変化する値である。
Accordingly, the invention of claim 1 is a nonaqueous electrolyte secondary battery including a positive electrode in which a positive electrode mixture layer containing a positive electrode active material is formed on a current collector, wherein the positive electrode active material includes at least Non-water characterized in that at least a part of the particle surface of a lithium transition metal composite oxide containing nickel is coated with a lithium manganese composite oxide having a spinel structure represented by the general formula (1) It is an electrolyte secondary battery.
Li z (Li x Mn 2- x-y M y) O 4 (1)
(Wherein 0.12 <x ≦ 0.333, 0 ≦ y <0.2, 0 <z ≦ 1, M is a transition metal other than Mn, alkaline earth metal, B or Al.)
In the general formula (1), z is a value that varies depending on the charge / discharge state of the lithium manganese composite oxide.
請求項２の発明は、請求項１に記載のものにおいて、前記リチウム遷移金属複合酸化物は、一般式（２）で示される複合酸化物であるところに特徴を有する。
ＬｉａＮｉｂＣｏｃＭｎｄＯ２（２）
（式中０＜ａ≦１．２，０＜ｂ≦０．８５，０＜ｃ＜１．０，０≦ｄ≦０．５，ｂ＋ｃ＋ｄ＝１である。）
The invention of
Li a Ni b Co c Mn d O 2 (2)
(Where 0 <a ≦ 1.2, 0 <b ≦ 0.85, 0 <c <1.0, 0 ≦ d ≦ 0.5, b + c + d = 1)
請求項３の発明は、請求項１または請求項２に記載のものにおいて、前記一般式（１）において、ＭがＡｌ、Ｂ、Ｍｇ、Ｔｉ、Ｚｒ、ＦｅまたはＺｎであるところに特徴を有する。
The invention of
＜請求項１の発明＞
本発明において正極活物質は、少なくともニッケルを含むリチウム遷移金属複合酸化物の粒子表面の少なくとも一部が、一般式（１）で示される、スピネル構造を有するリチウムマンガン系複合酸化物で被覆されたものである。
Ｌｉｚ（ＬｉｘＭｎ２−ｘ−ｙＭｙ）Ｏ４（１）
（式中０．１２＜ｘ≦０．３３３，０≦ｙ＜０．２，０＜ｚ≦１，ＭはＭｎ以外の遷移金属、アルカリ土類金属、ＢまたはＡｌである。）
<Invention of Claim 1>
In the present invention, at least a part of the particle surface of the lithium transition metal composite oxide containing at least nickel is coated with the lithium manganese composite oxide having a spinel structure represented by the general formula (1). Is.
Li z (Li x Mn 2- x-y M y) O 4 (1)
(Wherein 0.12 <x ≦ 0.333, 0 ≦ y <0.2, 0 <z ≦ 1, M is a transition metal other than Mn, alkaline earth metal, B or Al.)
請求項１に記載の発明によれば、正極活物質の材料としてニッケルを含有するリチウム含有複合酸化物を用い、その表面の少なくとも一部をマンガンの平均価数が３．７〜４．０となるようなリチウムマンガン系複合酸化物で被覆しているから、ニッケルと電解液とが接触して反応するのを防止し、マンガンの溶出が起こりにくく、高温環境下においても抵抗増加を抑えることができ、放電容量の維持率が高い非水電解質二次電池を提供することができる。 According to the first aspect of the present invention, a lithium-containing composite oxide containing nickel is used as a material for the positive electrode active material, and at least a part of the surface has an average manganese valence of 3.7 to 4.0. Because it is coated with a lithium manganese based composite oxide, it prevents nickel and electrolyte from contacting and reacting, makes it difficult for elution of manganese, and suppresses an increase in resistance even in high temperature environments. And a non-aqueous electrolyte secondary battery having a high discharge capacity retention rate can be provided.
＜請求項２の発明＞
本発明においては、充電時の結晶構造が安定し、電池の安全性が向上するという観点から、リチウム遷移金属複合酸化物として、一般式（２）で示される複合酸化物が好適に用いられる。
ＬｉａＮｉｂＣｏｃＭｎｄＯ２（２）
（式中０＜ａ≦１．２，０＜ｂ≦０．８５，０＜ｃ＜１．０，０≦ｄ≦０．５，ｂ＋ｃ＋ｄ＝１である。）
<Invention of
In the present invention, the composite oxide represented by the general formula (2) is preferably used as the lithium transition metal composite oxide from the viewpoint that the crystal structure during charging is stable and the safety of the battery is improved.
Li a Ni b Co c Mn d O 2 (2)
(Where 0 <a ≦ 1.2, 0 <b ≦ 0.85, 0 <c <1.0, 0 ≦ d ≦ 0.5, b + c + d = 1)
＜請求項３の発明＞
リチウムマンガン系複合酸化物として、ＬｉおよびＭｎ以外にＡｌ、Ｂ、Ｍｇ、Ｔｉ、Ｚｒ、ＦｅまたはＺｎを含むものは、これらの元素が結晶構造中で３価以下の価数で安定して存在可能であることから、少量置換するだけで３価のマンガンを減らしてＭｎの平均価数を４．０に近づけることができる。したがって、請求項３に記載の発明によれば、放電容量の維持率がより高い電池を提供することができる。
<Invention of
Lithium-manganese complex oxides that contain Al, B, Mg, Ti, Zr, Fe or Zn in addition to Li and Mn exist stably in the crystal structure with a valence of 3 or less Since it is possible, trivalent manganese can be reduced and the average valence of Mn can be brought close to 4.0 by substituting only a small amount. Therefore, according to the invention described in
＜実施形態１＞
以下、本発明の実施形態について説明する。
図２は、本発明の一実施形態である角形の非水電解質二次電池１の概略断面図である。この非水電解質二次電池１は、アルミニウム箔からなる正極集電体に正極合剤を塗布してなる正極板３と、銅箔からなる負極集電体に負極合剤を塗布してなる負極板４とがセパレータ５を介して渦巻状に巻回された発電要素２と、非水電解液とを電池ケース６に収納してなる。
<Embodiment 1>
Hereinafter, embodiments of the present invention will be described.
FIG. 2 is a schematic cross-sectional view of a prismatic nonaqueous electrolyte secondary battery 1 according to an embodiment of the present invention. The nonaqueous electrolyte secondary battery 1 includes a
電池ケース６には、安全弁８を設けた電池蓋７がレーザー溶接によって取り付けられ、負極板４は負極リード１１を介して電池ケース６の上部にある負極端子９と接続され、正極板３は正極リード１０を介して電池蓋７と接続されている。
A
非水電解液は非水溶媒に電解質塩を溶解してなり、非水溶媒は、エチレンカーボネート、プロピレンカーボネート、γ−ブチロラクトン、ジメチルカーボネート、エチルメチルカーボネート、ジエチルカーボネート、スルホラン、ジメチルスルホキシド、アセトニトリル、ジメチルホルムアミド、ジメチルアセトアミド、１，２−ジメトキシエタン、１，２−ジエトキシエタン、テトラヒドロフラン、２−メチルテトラヒドロフラン、ジオキソラン、メチルアセテート、ビニレンカーボネートなどの極性溶媒を単独でまたは二種以上混合して使用することができる。 The non-aqueous electrolyte solution is obtained by dissolving an electrolyte salt in a non-aqueous solvent. Use polar solvents such as formamide, dimethylacetamide, 1,2-dimethoxyethane, 1,2-diethoxyethane, tetrahydrofuran, 2-methyltetrahydrofuran, dioxolane, methyl acetate, vinylene carbonate alone or in admixture of two or more. be able to.
非水溶媒に溶解する電解質塩は、ＬｉＰＦ６、ＬｉＣｌＯ４、ＬｉＢＦ４、ＬｉＡｓＦ６、ＬｉＣＦ３ＣＯ２、ＬｉＣＦ３（ＣＦ３）３、ＬｉＣＦ３（Ｃ２Ｆ５）３、ＬｉＣＦ３ＳＯ３、ＬｉＮ（ＳＯ２ＣＦ３）２、ＬｉＮ（ＳＯ２ＣＦ２ＣＦ３）２、ＬｉＮ（ＣＯＣＦ３）２、ＬｉＮ（ＣＯＣＦ２ＣＦ３）２、ＬｉＰＦ３（ＣＦ２ＣＦ３）３等の塩を単独でまたは二種以上混合して使用することができる。 The electrolyte salts that dissolve in the non-aqueous solvent are LiPF 6 , LiClO 4 , LiBF 4 , LiAsF 6 , LiCF 3 CO 2 , LiCF 3 (CF 3 ) 3 , LiCF 3 (C 2 F 5 ) 3 , LiCF 3 SO 3 , LiN (SO 2 CF 3 ) 2 , LiN (SO 2 CF 2 CF 3 ) 2 , LiN (COCF 3 ) 2 , LiN (COCF 2 CF 3 ) 2 , LiPF 3 (CF 2 CF 3 ) 3 and the like alone Or a mixture of two or more.
電池ケース６内に収容された発電要素２は、正極板３と負極板４とをセパレータ５を挟んで巻回されて構成されている。
The
セパレータ５としては、織布、不織布、合成樹脂微多孔膜等を用いることができ、特に合成樹脂微多孔膜を好適に用いることができる。なかでも、ポリエチレン及びポリプロピレン製微多孔膜、またはこれらを複合した微多孔膜等のポリオレフィン系微多孔膜が、厚さ、膜強度、膜抵抗等の面で好適に用いることができる。
As the
次に、負極板４について説明する。負極板４は、銅などの金属により形成された厚さ５ないし３０μｍの銅箔からなる負極集電体の両面に、リチウムイオンを吸蔵放出可能な負極活物質を含有する負極合剤層を備えている。負極集電体のうち負極合剤層の形成されていない部分には、負極リード１１が超音波溶着により溶着されている。
Next, the
負極合剤層に含有される負極活物質としては、Ａｌ、Ｓｉ、Ｐｂ、Ｓｎ、Ｚｎ、Ｃｄ等とリチウムとの合金、ＬｉＦｅ２Ｏ３、ＷＯ２、ＭｏＯ２、ＳｉＯ、ＣｕＯ等の金属酸化物、グラファイト、カーボン等の炭素質材料、Ｌｉ５（Ｌｉ３Ｎ）等の窒化リチウム、もしくは金属リチウム、またはこれらの混合物を用いることができる。 Examples of the negative electrode active material contained in the negative electrode mixture layer include alloys of lithium with Al, Si, Pb, Sn, Zn, Cd, and the like, and metal oxides such as LiFe 2 O 3 , WO 2 , MoO 2 , SiO, and CuO. Materials, carbonaceous materials such as graphite and carbon, lithium nitride such as Li 5 (Li 3 N), metallic lithium, or a mixture thereof can be used.
正極板３は、アルミニウムなどの金属により形成された厚さ１０〜５０μｍの正極集電体の両面に、リチウムイオンを吸蔵放出可能な正極活物質（後述する）を含有する正極合剤層を備えている。正極集電体のうち正極合剤層の形成されていない部分には正極リード１０が超音波溶着により溶着されている。
The
さて、正極合剤層に含有される正極活物質としては、少なくともニッケルを含む、空間群Ｒ３−ｍ群に属する層構造のリチウム遷移金属複合酸化物からなる粒子（以下、芯材ともいう）の表面の少なくとも一部を一般式（１）に示すスピネル構造を有するリチウムマンガン複合酸化物（以下、被覆材ともいう）で被覆したものが用いられる。 Now, as the positive electrode active material contained in the positive electrode mixture layer, particles of lithium transition metal composite oxide having a layer structure belonging to the space group R3-m group (hereinafter also referred to as a core material) containing at least nickel. What coat | covered at least one part of the surface with the lithium manganese complex oxide (henceforth a coating | covering material) which has a spinel structure shown in General formula (1) is used.
正極活物質の芯材として用いられるリチウム遷移金属複合酸化物は、コバルトおよびニッケルに加えてマンガンを含むものが、結晶構造を安定化させて電池１の安全性を向上させる観点から好適に用いられる。この複合酸化物にはコバルト、ニッケルおよびマンガン以外の元素（以下、第４元素という）として、遷移金属、アルカリ土類金属、ＢまたはＡｌを含んでいても良い。これらの、リチウム遷移金属複合酸化物は、一般式（３）で示される。
ＬｉａＮｉｂＣｏｃＭｎｄＭｅＯ２（３）
（式中、０＜ａ≦１．２，０＜ｂ≦０．８５，０＜ｃ＜１．０，０≦ｄ≦０．５，０≦ｅ＜０．２，ｂ＋ｃ＋ｄ＋ｅ＝１，ＭはＮｉ，Ｃｏ，Ｍｎ以外の遷移金属、アルカリ土類金属、ＢまたはＡｌである。）
As the lithium transition metal composite oxide used as the core material of the positive electrode active material, one containing manganese in addition to cobalt and nickel is preferably used from the viewpoint of stabilizing the crystal structure and improving the safety of the battery 1. . This composite oxide may contain a transition metal, an alkaline earth metal, B or Al as an element other than cobalt, nickel and manganese (hereinafter referred to as a fourth element). These lithium transition metal composite oxides are represented by the general formula (3).
Li a Ni b Co c Mn d M e O 2 (3)
(Where 0 <a ≦ 1.2, 0 <b ≦ 0.85, 0 <c <1.0, 0 ≦ d ≦ 0.5, 0 ≦ e <0.2, b + c + d + e = 1, M is Transition metals other than Ni, Co and Mn, alkaline earth metals, B or Al.)
第４元素（一般式（３）中のＭ）の置換量ｅは、ニッケル、コバルト、マンガンおよび第４元素の総モル数に対して０．５〜５％であることが好ましい。０．５％未満の場合には第４元素で置換しても結晶構造が安定せず第４元素の置換による効果が現れ難く、５％よりも多いと放電容量が低下する。 The substitution amount e of the fourth element (M in the general formula (3)) is preferably 0.5 to 5% with respect to the total number of moles of nickel, cobalt, manganese, and the fourth element. If it is less than 0.5%, the crystal structure is not stable even if it is substituted with the fourth element, and the effect due to the substitution of the fourth element is difficult to appear.
本発明においては、上記一般式（３）で示されるリチウム遷移金属複合酸化物のうち、特に一般式（２）で示されるものが好適に用いられる。
ＬｉａＮｉｂＣｏｃＭｎｄＯ２（２）
（式中、０＜ａ≦１．２，０＜ｂ≦０．８５，０＜ｃ＜１．０，０≦ｄ≦０．５，ｂ＋ｃ＋ｄ＝１である。）
In the present invention, among the lithium transition metal composite oxides represented by the general formula (3), those represented by the general formula (2) are preferably used.
Li a Ni b Co c Mn d O 2 (2)
(Where 0 <a ≦ 1.2, 0 <b ≦ 0.85, 0 <c <1.0, 0 ≦ d ≦ 0.5, b + c + d = 1)
なお、上記一般式（２）および（３）において、ａはこのリチウム遷移金属複合酸化物の充放電状態によって変化する値である。負極活物質に炭素系材料を用いる非水電解質二次電池では、通常、電池組立時は放電状態にある。したがって、ａが０．９未満では放出するリチウムが不足するために放電容量が低下し、リチウム層に遷移金属が置換されるため充放電時の結晶構造が不安定になることからサイクル寿命特性が低下するおそれがあり、ａが１．２を超えると単一相が得られず放電容量が低下するおそれがある。 In the general formulas (2) and (3), a is a value that varies depending on the charge / discharge state of the lithium transition metal composite oxide. In a non-aqueous electrolyte secondary battery using a carbon-based material as the negative electrode active material, it is usually in a discharged state when the battery is assembled. Therefore, if a is less than 0.9, the discharge capacity is reduced due to the lack of lithium to be released, and the transition metal is substituted into the lithium layer, so that the crystal structure at the time of charge / discharge becomes unstable. If a exceeds 1.2, a single phase cannot be obtained and the discharge capacity may be reduced.
また、ｂが０．８５を超えると充電時の結晶構造が不安定になり、電池１の安全性が低下するおそれがある。
さらに、０＜ｄの場合には、マンガンによって結晶構造が安定化され、充電時の正極活物質の熱安定性に優れるが、ｄが０．５を超えると単一相が得られなくなったり、放電容量及びサイクル寿命特性が低下することがある。
On the other hand, if b exceeds 0.85, the crystal structure during charging becomes unstable, and the safety of the battery 1 may be reduced.
Further, when 0 <d, the crystal structure is stabilized by manganese, and the thermal stability of the positive electrode active material during charging is excellent. However, when d exceeds 0.5, a single phase cannot be obtained, Discharge capacity and cycle life characteristics may be reduced.
なお、酸素量は一般式（２）および（３）に示すように、かならず２である必要はなくある程度の不定比性を有していてもよい。 The oxygen amount is not necessarily 2 as shown in the general formulas (2) and (3), and may have a certain degree of non-stoichiometry.
正極活物質の被覆材としては、一般式（１）で示されるスピネル構造を有するリチウムマンガン系複合酸化物が用いられる。
Ｌｉｚ（ＬｉｘＭｎ２−ｘ−ｙＭｙ）Ｏ４（１）
（式中、０．１２＜ｘ≦０．３３３，０≦ｙ＜０．２，０＜ｚ≦１，ＭはＭｎ以外の遷移金属、アルカリ土類金属、ＢまたはＡｌである。）
As the positive electrode active material coating material, a lithium manganese composite oxide having a spinel structure represented by the general formula (1) is used.
Li z (Li x Mn 2- x-y M y) O 4 (1)
(Wherein 0.12 <x ≦ 0.333, 0 ≦ y <0.2, 0 <z ≦ 1, M is a transition metal other than Mn, alkaline earth metal, B or Al.)
本発明においては、一般式（１）で示されるもののうち、一般式（４）で表されるもの（一般式（１）においてｙ＝０の場合）と、Ｌｉ及びＭｎ以外の元素Ｍ（以下、第３元素ともいう）を含むもの（後述する）とが、好適に用いられる。
Ｌｉｚ（ＬｉｘＭｎ２−ｘ）Ｏ４（４）
In the present invention, among those represented by the general formula (1), those represented by the general formula (4) (when y = 0 in the general formula (1)) and elements M other than Li and Mn (hereinafter referred to as “M”) And those containing a third element) (described later) are preferably used.
Li z (Li x Mn 2-x ) O 4 (4)
一般式（１）および（４）において、ｘの値は０．１５以上０．３３３未満であることが、好ましい。ｘが０．１５未満であるとマンガンの平均価数が小さくなるためマンガンの溶出を効果的に抑え難くなり０．３３３を越えると未反応のリチウム化合物が残るために電池１にしたときにガスを発生して電池特性が低下する可能性がある。 In the general formulas (1) and (4), the value of x is preferably 0.15 or more and less than 0.333. When x is less than 0.15, the average valence of manganese becomes small, so it is difficult to effectively suppress elution of manganese, and when it exceeds 0.333, an unreacted lithium compound remains, so that when the battery 1 is used, May cause battery characteristics to deteriorate.
リチウムマンガン系複合酸化物に含まれるＬｉおよびＭｎ以外の第３元素（一般式（１）におけるＭ）としては、Ａｌ、Ｂ、Ｍｇ、Ｔｉ、Ｚｒ、ＦｅまたはＺｎが好ましい。これらの元素で置換することにより結晶構造が安定化するのでマンガンの溶出を抑制することができる。また、これらの元素は、結晶構造中で３価以下の価数で安定して存在可能であることから、少量置換するだけで３価のマンガンを減らしてＭｎの平均価数を４．０に近づけることができるので好適である。 As the third element (M in the general formula (1)) other than Li and Mn contained in the lithium manganese composite oxide, Al, B, Mg, Ti, Zr, Fe or Zn is preferable. Substitution with these elements stabilizes the crystal structure, so that elution of manganese can be suppressed. In addition, since these elements can stably exist at a valence of 3 or less in the crystal structure, the trivalent manganese can be reduced and the average valence of Mn can be reduced to 4.0 simply by substituting a small amount. Since it can approach, it is suitable.
第３元素の置換量ｙは、０．０１≦ｙ＜０．２であることが好ましい。ｙが０．０１未満であると第３元素で置換することによるマンガン溶出抑制効果が小さくなり、ｙが０．２以上になると被膜層の結晶構造が不安定になりリチウムイオンの拡散が阻害され抵抗が大きくなる傾向にある。 The substitution amount y of the third element is preferably 0.01 ≦ y <0.2. When y is less than 0.01, the effect of suppressing manganese elution by substituting with the third element is reduced, and when y is 0.2 or more, the crystal structure of the coating layer becomes unstable and the diffusion of lithium ions is inhibited. Resistance tends to increase.
本発明における正極活物質は、例えば、以下に例示する方法によって製造することができる。
あらかじめ合成しておいた芯材と被覆材とを使用して正極活物質を製造する場合には、芯材の粒子と被覆材の粒子とを混合して得られる混合粉末を圧縮摩砕して、芯材粒子の表面に被覆材の粒子を付着させ、メカノケミカル反応をおこさせることで一体化する方法、高速気流中に芯材粒子と被覆材粒子の混合物を分散し衝撃操作を繰り返し行って芯材の表面に被覆材粒子を付着させる方法などが用いられる。
The positive electrode active material in this invention can be manufactured by the method illustrated below, for example.
When a positive electrode active material is produced using a core material and a coating material synthesized in advance, the mixed powder obtained by mixing the core material particles and the coating material particles is compressed and ground. , A method of integrating the particles of the coating material on the surface of the core material particles by causing a mechanochemical reaction to occur, a mixture of the core material particles and the coating material particles is dispersed in a high-speed air stream, and the impact operation is repeated. For example, a method of attaching coating material particles to the surface of the core material is used.
別の方法としては、芯材を合成した後、芯材表面に被覆材の前駆体となる材料を被覆した後これらを焼成することで芯材に被覆材を被覆する方法を用いることもできる。具体的には、マンガンを溶解した溶液に芯材を浸漬し、ｐＨを一定に保ちながらアルカリ溶液を滴下することで芯材表面に水酸化マンガンを析出する方法などにより被覆材の前駆体を形成する。次に、この被覆材の前駆体に、炭酸リチウムなどのＬｉ源を加えた後、例えば、空気雰囲気下、７５０℃で１２時間焼成することで芯材に被覆材を被覆することもできる。 As another method, after synthesizing the core material, the core material surface may be coated with a material that becomes a precursor of the coating material, and then fired, and then the core material may be coated with the coating material. Specifically, the precursor of the coating material is formed by immersing the core material in a solution in which manganese is dissolved and dropping the alkali solution while keeping the pH constant to deposit manganese hydroxide on the surface of the core material. To do. Next, after adding a Li source such as lithium carbonate to the precursor of the coating material, the core material can be coated with the coating material, for example, by baking at 750 ° C. for 12 hours in an air atmosphere.
さらなる、別の方法としては、被覆材の分散溶液に芯材を投入して乾燥させ、乾燥品をメタノールなどに分散させて乾燥焼成することで被覆材を芯材に被覆する方法を用いることもできる。 Further, as another method, it is also possible to use a method in which the core material is applied to the dispersion solution of the coating material and dried, and the dried product is dispersed in methanol and dried and fired to coat the coating material on the core material. it can.
正極活物質の結晶構造は、例えば、粉末Ｘ線回折によって確認することができる。具体的には芯材の結晶構造として、空間群Ｒ３−ｍに属する層構造の回折線を確認することができ、被覆材としてスピネル構造の回折線を非常に弱いピークであるが確認することができる。 The crystal structure of the positive electrode active material can be confirmed by, for example, powder X-ray diffraction. Specifically, the diffraction line of the layer structure belonging to the space group R3-m can be confirmed as the crystal structure of the core material, and the diffraction line of the spinel structure as the coating material is confirmed to be a very weak peak. it can.
被覆の状況は、活物質粒子をエポキシ樹脂で含浸した後、ミクロトームで粒子の断面を切りだし、この断面についてＥＰＭＡにて元素分析を行うことで、粒子表面にＭｎ元素の濃度の高い層が確認することができる。 After coating the active material particles with epoxy resin, the cross-section of the particles is cut out with a microtome, and elemental analysis is performed on this cross-section with EPMA to confirm a layer with a high Mn element concentration on the particle surface. can do.
正極活物質には、導電剤、結着剤等を添加することもできる。導電剤としては、無機化合物、有機化合物を用いることができる。無機化合物としては、カーボンブラック、グラファイトなどを用いることができ、有機化合物としては、例えばポリアニリン等の導電性ポリマーなどを用いることができる。結着剤としては、ポリフッ化ビニリデン、フッ化ビニリデン−ヘキサフルオロプロピレン共重合体、スチレン−ブタジエンゴム、ポリアクリロニトリルなどを単独で、あるいは混合して用いることができる。
＜実施例１〜２４および比較例１〜１５＞
A conductive agent, a binder or the like can also be added to the positive electrode active material. As the conductive agent, an inorganic compound or an organic compound can be used. As the inorganic compound, carbon black, graphite and the like can be used, and as the organic compound, for example, a conductive polymer such as polyaniline can be used. As the binder, polyvinylidene fluoride, vinylidene fluoride-hexafluoropropylene copolymer, styrene-butadiene rubber, polyacrylonitrile and the like can be used alone or in combination.
<Examples 1-24 and Comparative Examples 1-15>
以下、本発明の実施例１〜２４および比較例１〜１５を示すが、本発明はこれに限定されるものではない。
１．電池１の作製
（１）正極板３の作製
結着剤のポリフッ化ビニリデン７重量部と、導電剤のアセチレンブラック４重量部と、ＬｉＮｉｂＣｏｃＭｎｄＯ２の粒子（芯材）の表面をＬｉ（ＬｉｘＭｎ２−ｘ−ｙＭｙ）Ｏ４(被覆材）で被覆してなる正極活物質８９重量部とを混合したものに、Ｎ−メチル−２−ピロリドンを加えて分散させ、スラリーを調製した。なお、実施例１〜２４および比較例１〜１５において使用された芯材および被覆材は表１に記載した。
Examples 1 to 24 and Comparative Examples 1 to 15 of the present invention are shown below, but the present invention is not limited thereto.
1. Production of battery 1
(1) Production of
このスラリーを、厚さが２０μｍのアルミニウム製の正極集電体の両面にドクターブレードで均一に塗布し、乾燥させた後、ロールプレスで厚みが１３０μｍ（集電体を含む）になるように圧縮成形して、長さ６４０ｍｍ、幅３０ｍｍの正極板３を作製した。合剤層非形成部には正極リード１０を超音波溶着にて備え付けた。
This slurry is uniformly applied to both sides of an aluminum positive electrode current collector with a thickness of 20 μm with a doctor blade, dried, and then compressed with a roll press to a thickness of 130 μm (including the current collector). The
（２）負極板４の作製
難黒鉛化性炭素９０重量部と、結着剤のポリフッ化ビニリデン１０重量部とを混合したものに、Ｎ−メチル−２−ピロリドンを加えて分散させスラリーを調製した。
(2) Production of negative electrode plate 4 N-methyl-2-pyrrolidone was added to a mixture of 90 parts by weight of non-graphitizable carbon and 10 parts by weight of polyvinylidene fluoride as a binder to prepare a slurry. did.
このスラリーを、厚さが１０μｍの銅箔製の負極集電体の両面にドクターブレードで均一に塗布し、乾燥させた後、ロールプレスで厚みが１４０μｍ（集電体を含む）になるように圧縮成形して、長さ６００ｍｍ、幅３１ｍｍの負極板４を作製した。合剤層非形成部には負極リード１１を超音波溶着にて備え付けた。
The slurry is uniformly applied on both sides of a negative electrode current collector made of copper foil having a thickness of 10 μm with a doctor blade and dried, and then the thickness is adjusted to 140 μm (including the current collector) with a roll press. The
（３）電池１の作製
セパレータ５として長さ１３００ｍｍ、幅３４ｍｍ、厚み２５μｍのポリエチレン微多孔膜を用い、非水電解質としてエチレンカーボネート（ＥＣ）：ジエチルカーボネート（ＤＭＣ）：エチルメチルカーボネート（ＥＭＣ）＝２５：３５：４０（体積比）の混合溶媒にＬｉＰＦ６を１ｍｏｌ／Ｌ溶解した溶液を用いた。
そして、（１）で得られた正極板３と、セパレータ５と、（２）で得られた負極板４とを順に重ね合わせ、これをポリエチレン製の長方形状の巻芯の周囲に長円渦状に巻回して発電要素２とした。
(3) Production of Battery 1 A polyethylene microporous film having a length of 1300 mm, a width of 34 mm, and a thickness of 25 μm was used as the
Then, the
次いで、この発電要素２を角形アルミニウム製の電池ケース６に収納し、正極リード１０を正極集電体から導出して電池蓋７に、負極リード１１を負極集電体から導出して負極端子９に溶接してから、電解液を注液した。次に電池蓋７と電池ケース６をレーザー溶接し電池１内の気密性を保持させ、公称容量が５００ｍＡｈの非水電解質二次電池１を作製した。
Next, the
２．電池性能試験
作製した非水電解質二次電池１について以下の試験を行った。
（１）高温放置試験
実施例１〜２４および比較例１〜１５の電池１について、一時間率（１ＣＡ＝５００ｍＡ）の充電電流で４．２Ｖまで定電流充電した後、引き続き４．２Ｖで合計３時間となるように定電圧充電した。その後、１Ｃの放電電流で２．５Ｖまで放電し、放置試験前の放電容量と電池１の厚さを測定した。次に、１Ｃの充電電流で３０分間充電することにより、５０％の充電状態まで定電流充電し、温度７０℃の恒温槽中で７日間放置した。
2. Battery performance test The following tests were performed on the produced nonaqueous electrolyte secondary battery 1.
(1) High-temperature storage test For the batteries 1 of Examples 1 to 24 and Comparative Examples 1 to 15, the battery 1 was charged at a constant current rate of 4.2 V with a charging current of one hour rate (1 CA = 500 mA), and then continuously at 4.2 V. The battery was charged at a constant voltage to be 3 hours. Thereafter, the battery was discharged to 2.5 V with a discharge current of 1 C, and the discharge capacity before the standing test and the thickness of the battery 1 were measured. Next, the battery was charged at a constant current of 1 C for 30 minutes, so that it was charged at a constant current up to a charge state of 50% and left in a constant temperature bath at a temperature of 70 ° C. for 7 days.
放置後の電池１を１Ｃの放電電流で２．５Ｖまで放電した後、放置前と同様に１Ｃの充電電流で４．２Ｖまで定電流充電し、引き続き４．２Ｖで合計３時間となるように定電圧充電した。その後、１Ｃの放電電流で２．５Ｖまで放電した電池１について、放置試験後の放電容量と電池１の厚さを測定した。 After leaving the battery 1 discharged to 2.5 V with a discharge current of 1 C, it was charged at a constant current to 4.2 V with a charge current of 1 C, as before, and then continued to 4.2 V for a total of 3 hours. Charged at a constant voltage. Thereafter, for the battery 1 discharged to 2.5 V with a discharge current of 1 C, the discharge capacity after the standing test and the thickness of the battery 1 were measured.
放置試験前の放電容量に対する放置試験後の放電容量の割合（％）を算出して容量維持率とした。
放置試験前後における電池１の厚さの差を求め、電池厚さ増加量（ｍｍ）とした。
The ratio (%) of the discharge capacity after the standing test to the discharge capacity before the standing test was calculated as the capacity maintenance rate.
The difference in the thickness of the battery 1 before and after the standing test was determined and used as the battery thickness increase (mm).
（２）直流抵抗測定試験
高温放置試験時の抵抗増加について評価するために、（１）の高温放置試験の前と後においてそれぞれ下記の直流抵抗測定試験を行った。
実施例１〜２４および比較例１〜１５の電池１について、一時間率（１Ｃ）の充電電流で４．２Ｖまで定電流充電した後、引き続き４．２Ｖで合計３時間となるように定電圧充電した。その後、０．２Ｃの放電電流で１０秒間放電して１０秒目の電池電圧を測定した。放電電流が０．５Ｃ、１Ｃの場合についても同様に１０秒間放電して１０秒目の電池電圧を測定した。
(2) DC resistance measurement test In order to evaluate the increase in resistance during the high temperature storage test, the following DC resistance measurement test was performed before and after the high temperature storage test of (1).
The batteries 1 of Examples 1 to 24 and Comparative Examples 1 to 15 were charged at a constant current rate of 4.2V with a charging current of 1 hour rate (1C), and then continuously at 4.2V so that the total voltage would be 3 hours. Charged. Thereafter, the battery was discharged at a discharge current of 0.2 C for 10 seconds, and the battery voltage at 10 seconds was measured. Similarly, when the discharge current was 0.5C or 1C, the battery voltage was measured for 10 seconds after discharging for 10 seconds.
横軸に放電電流、縦軸に１０秒目の電池電圧をとって測定値をプロットし、得られた直線の傾きから直流抵抗を算出した。
次に高温放置試験後の直流抵抗値と高温放置試験前の直流抵抗値との差を算出し、高温放置試験前の直流抵抗値に対する比を求めて直流抵抗増加率(％）とした。
The measured value was plotted with the discharge current on the horizontal axis and the battery voltage at 10 seconds on the vertical axis, and the DC resistance was calculated from the slope of the obtained straight line.
Next, the difference between the DC resistance value after the high-temperature storage test and the DC resistance value before the high-temperature storage test was calculated, and the ratio to the DC resistance value before the high-temperature storage test was determined to obtain the DC resistance increase rate (%).
表１に、使用された正極活物質の芯材と被覆材の組み合わせとともに容量維持率（％）、電池厚さ増加量（ｍｍ）および直流抵抗増加率（％）を記載した。
表１中、ｂ、ｃ、ｄは、式ＬｉＮｉｂＣｏｃＭｎｄＯ２中のｂ、ｃ、ｄにそれぞれ対応しており、ｘ、２−ｘ−ｙ、ｙ、Ｍは、式Ｌｉ（ＬｉｘＭｎ２−ｘ−ｙＭｙ）Ｏ４中のｘ、２−ｘ−ｙ、ｙ、Ｍにそれぞれ対応している。
Table 1 shows the capacity retention rate (%), the battery thickness increase amount (mm), and the DC resistance increase rate (%) as well as the combination of the core material and the covering material of the positive electrode active material used.
In Table 1, b, c, d has the formula LiNi b Co c Mn d O 2 in b, c, respectively correspond to d, x, 2-x- y, y, M has the formula Li ( Li x Mn 2-xy M y ) corresponding to x, 2-xy, y, M in O 4 .
また、実施例１〜６および比較例１〜６の電池における、被覆材に用いた一般式（５）（一般式（１）においてｙ＝０、ｚ＝１のもの）のｘと放電容量維持率との関係を図１に示す。
Ｌｉ（ＬｉｘＭｎ２−ｘ）Ｏ４（５）
図１に示すように、放電容量の維持率は、ｘの値が０から０．１２未満においては緩やかに上昇するが、０．１２以上になると、急激に上昇し、良好な結果（放電容量の維持率が高い）が得られた。上記一般式（３）に示されるリチウムマンガン系複合酸化物におけるマンガンの価数を算出すると、ｘが０．１２の場合、マンガンの平均価数は約３．７であり、ｘが０．３３３の場合、マンガンの平均価数は約４．０になる。すなわちマンガンの平均価数が３．７〜４．０の場合に、放電容量の維持率が急激に上昇することを意味する。
In addition, in the batteries of Examples 1 to 6 and Comparative Examples 1 to 6, x of the general formula (5) used for the coating material (with y = 0 and z = 1 in the general formula (1)) and the discharge capacity maintenance The relationship with the rate is shown in FIG.
Li (Li x Mn 2-x ) O 4 (5)
As shown in FIG. 1, the discharge capacity retention rate rises moderately when the value of x is from 0 to less than 0.12, but rises sharply when the value of x is equal to or greater than 0.12, indicating good results (discharge capacity). Is high). When the valence of manganese in the lithium manganese composite oxide represented by the general formula (3) is calculated, when x is 0.12, the average valence of manganese is about 3.7, and x is 0.333. In this case, the average valence of manganese is about 4.0. That is, when the average valence number of manganese is 3.7 to 4.0, it means that the discharge capacity maintenance rate is rapidly increased.
３．試験結果と考察
（１）本発明の電池１（実施例１〜２４）の全てにおいて、容量維持率が８０％以上で、電池厚さ増加量が１．５ｍｍ以下でかつ直流抵抗増加率が２０％以下であるという良好な結果が得られた。
3. Test Results and Discussion (1) In all of the batteries 1 (Examples 1 to 24) of the present invention, the capacity maintenance rate is 80% or more, the battery thickness increase is 1.5 mm or less, and the DC resistance increase rate is 20 Good results of less than% were obtained.
（２）被覆材により被覆されていない正極活物質を使用したもの（比較例６ないし１５）と比較すると、本発明の電池１は、特に抵抗増加率、電池厚さ増加量において、良好な結果が得られた。また、本発明の電池１の中でも、ｂ値が０．８５未満のもの（実施例１〜１９、実施例２１〜２４）において特に抵抗増加率および電池厚さ増加量に関し良好な結果が得られた。 (2) Compared with those using a positive electrode active material not coated with a coating material (Comparative Examples 6 to 15), the battery 1 of the present invention has good results particularly in the resistance increase rate and the battery thickness increase amount. was gotten. Moreover, among the batteries 1 of the present invention, those having a b value of less than 0.85 (Examples 1 to 19 and Examples 21 to 24), particularly good results are obtained with respect to the resistance increase rate and the battery thickness increase amount. It was.
これは、ニッケルを含有するリチウム遷移金属複合酸化物を、被覆材により被覆したことで、ニッケルと電解液との反応を抑えることができたからではないかと考えられる。また、本発明の電池１の中でも、ｂ値が０．８５未満のものはニッケルの含有量が適量であるから、ニッケルを多く含むもの（ｂ値が０．８５の実施例２０）と比較して、電解液との反応が起こり難く充電時の結晶構造が安定しているので良好な結果が得られたのではないかと考えられる。 This is thought to be because the reaction between nickel and the electrolytic solution could be suppressed by coating the lithium transition metal composite oxide containing nickel with a coating material. Further, among the batteries 1 of the present invention, those having a b value of less than 0.85 have an appropriate nickel content, so that they are compared with those containing a large amount of nickel (Example 20 having a b value of 0.85). Thus, the reaction with the electrolytic solution hardly occurs and the crystal structure at the time of charging is stable, so it is considered that good results have been obtained.
（３）被覆材により被覆されているが、被覆材のｘの値が０．１２以下のものを備えるもの（比較例１ないし比較例５）と比較すると、本発明の電池１は容量維持率が高かった。また、本発明の電池１の中でもｘ値が０．３３３に近いもの（実施例１）ほど容量保持率が良好であった。 (3) The battery 1 of the present invention has a capacity retention rate as compared with the case where the value of x of the covering material is 0.12 or less (Comparative Example 1 to Comparative Example 5). Was expensive. Further, among the batteries 1 of the present invention, the capacity retention was better as the x value was closer to 0.333 (Example 1).
これは、被覆材のマンガンの平均価数を４．０に近づけることで、被覆材に含有されるマンガンの溶出を防ぎ、高温放置による電池容量の低下を抑えることができたからではないかと考えられる。 This is considered to be because the average valence of manganese in the coating material was brought close to 4.0, thereby preventing the elution of manganese contained in the coating material and suppressing the decrease in battery capacity due to standing at high temperatures. .
（４）本発明の電池１の中でも被覆材においてリチウムとマンガン以外の第３元素を含んでいるもの（実施例７〜１５）は、ｘ値が０．３３３に近くなくても、良好な電池特性を示した。 (4) Among the batteries 1 of the present invention, those containing a third element other than lithium and manganese in the covering material (Examples 7 to 15) are good batteries even when the x value is not close to 0.333. The characteristics are shown.
これは、第３元素として含まれている元素は、結晶構造中で３価以下の価数で安定して存在可能であることから、少量置換するだけで３価のマンガンを減らしてＭｎの平均価数を４．０に近づけることができるからではないかと考えられる。 This is because the element contained as the third element can be stably present at a valence of 3 or less in the crystal structure, so the trivalent manganese can be reduced by substituting only a small amount and the average of Mn This is probably because the valence can be brought close to 4.0.
４．まとめ
以上より、本発明によれば、高温環境下においても抵抗増加が小さく、放電容量の維持率の高い非水電解質二次電池１を提供することができる。
4). Summary As described above, according to the present invention, it is possible to provide the nonaqueous electrolyte secondary battery 1 having a small increase in resistance even in a high temperature environment and a high discharge capacity maintenance rate.
＜他の実施形態＞
本発明は上記記述及び図面によって説明した実施形態に限定されるものではなく、例えば次のような実施形態も本発明の技術的範囲に含まれる。
（１）本発明においては、非水電解液のみならず固体電解質を用いてもよく、両者を併用することもできる。固体電解質としては、公知の固体電解質を用いることができ、例えば無機固体電解質、ポリマー固体電解質を用いることができる。また、ゲル状の高分子固体電解質を用いる場合には、ゲルを構成する電解液と、電極板の活物質の細孔中などに含有されている電解液とが異なっていてもよい。また、合成樹脂微多孔膜と高分子固体電解質等を組み合わせて使用することもできる。
<Other embodiments>
The present invention is not limited to the embodiment described with reference to the above description and drawings. For example, the following embodiments are also included in the technical scope of the present invention.
(1) In the present invention, not only a nonaqueous electrolytic solution but also a solid electrolyte may be used, or both may be used in combination. As the solid electrolyte, a known solid electrolyte can be used. For example, an inorganic solid electrolyte or a polymer solid electrolyte can be used. When a gel polymer solid electrolyte is used, the electrolyte constituting the gel may be different from the electrolyte contained in the pores of the active material of the electrode plate. A synthetic resin microporous membrane and a polymer solid electrolyte can also be used in combination.
（２）実施形態１においては角形の電池ケースを使用したが、電池ケースは長円形、円形または袋形のものであってもよいし素材も金属ラミネート樹脂フィルムなどであってもよい。 (2) Although a rectangular battery case is used in Embodiment 1, the battery case may be oval, circular, or bag-shaped, and the material may be a metal laminate resin film.
（３）上記実施例においては、芯材としてニッケル、コバルト、マンガンを含むリチウム遷移金属複合酸化物を使用したが、ニッケル、コバルト、マンガン以外の第四元素を含むもの、例えば、Ａｌ、Ｂ、Ｍｇ、Ｔｉ、Ｚｒなどをふくむものであってもよい。 (3) In the above embodiment, a lithium transition metal composite oxide containing nickel, cobalt, and manganese is used as a core material. However, a material containing a fourth element other than nickel, cobalt, and manganese, such as Al, B, It may contain Mg, Ti, Zr or the like.
１…非水電解質二次電池
３…正極板
４…負極板
５…セパレータ
６…電池ケース
９…負極端子
１０…正極リード
１１…負極リード
DESCRIPTION OF SYMBOLS 1 ... Nonaqueous electrolyte
Claims (3)
前記正極活物質は、少なくともニッケルを含むリチウム遷移金属複合酸化物の粒子表面の少なくとも一部が、一般式（１）で示されるスピネル構造を有するリチウムマンガン系複合酸化物で被覆されたものであることを特徴とする非水電解質二次電池。
Ｌｉｚ（ＬｉｘＭｎ２−ｘ−ｙＭｙ）Ｏ４（１）
（式中０．１２＜ｘ≦０．３３３，０≦ｙ＜０．２，０＜ｚ≦１，ＭはＭｎ以外の遷移金属、アルカリ土類金属、ＢまたはＡｌである。） A non-aqueous electrolyte secondary battery including a positive electrode formed by forming a positive electrode mixture layer containing a positive electrode active material on a current collector,
In the positive electrode active material, at least a part of the particle surface of a lithium transition metal composite oxide containing at least nickel is coated with a lithium manganese composite oxide having a spinel structure represented by the general formula (1). A non-aqueous electrolyte secondary battery.
Li z (Li x Mn 2- x-y M y) O 4 (1)
(Wherein 0.12 <x ≦ 0.333, 0 ≦ y <0.2, 0 <z ≦ 1, M is a transition metal other than Mn, alkaline earth metal, B or Al.)
ＬｉａＮｉｂＣｏｃＭｎｄＯ２（２）
（式中０＜ａ≦１．２，０＜ｂ≦０．８５，０＜ｃ＜１．０，０≦ｄ≦０．５，ｂ＋ｃ＋ｄ＝１である。） The non-aqueous electrolyte secondary battery according to claim 1, wherein the lithium transition metal composite oxide is a composite oxide represented by the general formula (2).
Li a Ni b Co c Mn d O 2 (2)
(Where 0 <a ≦ 1.2, 0 <b ≦ 0.85, 0 <c <1.0, 0 ≦ d ≦ 0.5, b + c + d = 1)
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