JP5862622B2 - Method for producing active material for lithium ion secondary battery - Google Patents

Method for producing active material for lithium ion secondary battery Download PDF

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JP5862622B2
JP5862622B2 JP2013161122A JP2013161122A JP5862622B2 JP 5862622 B2 JP5862622 B2 JP 5862622B2 JP 2013161122 A JP2013161122 A JP 2013161122A JP 2013161122 A JP2013161122 A JP 2013161122A JP 5862622 B2 JP5862622 B2 JP 5862622B2
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active material
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JP2014044949A (en
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正則 原田
正則 原田
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Toyota Industries Corp
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/364—Composites as mixtures
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • C01G53/40—Nickelates
    • C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
    • C01G53/44—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese
    • C01G53/50—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese of the type [MnO2]n-, e.g. Li(NixMn1-x)O2, Li(MyNixMn1-x-y)O2
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
    • 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

Description

本発明は、活物質、活物質の製造方法、及び、リチウムイオン二次電池に関する。   The present invention relates to an active material, a method for producing the active material, and a lithium ion secondary battery.

従来より、リチウムイオン二次電池用の種々の正極活物質が知られている。例えば、特許文献１には、ＭＸＯkの化学式で表される化合物を含む表面処理層を活物質の表面に有してなる活物質が開示されている。ここで、Ｍはアルカリ金属、アルカリ土類金属、１３族元素、１４族元素、遷移金属及び希土類元素からなる群より選択される少なくとも一つの元素であり、Ｘは酸素と二重結合を形成することができる元素であり、ｋは２乃至４の範囲の数である。 Conventionally, various positive electrode active materials for lithium ion secondary batteries are known. For example, Patent Document 1 discloses an active material having a surface treatment layer containing a compound represented by the chemical formula MXO k on the surface of the active material. Here, M is at least one element selected from the group consisting of alkali metals, alkaline earth metals, Group 13 elements, Group 14 elements, transition metals, and rare earth elements, and X forms a double bond with oxygen. Where k is a number in the range of 2-4.

特開２００３−７２９９号公報JP 2003-7299 A 特開平１０−１５４５３２号公報JP-A-10-154532 特開２００１−２５６９７９号公報Japanese Patent Laid-Open No. 2001-256969 特開２０１１−１３８７１８号公報JP 2011-138718 A 特開平１０−２４１６８１号公報Japanese Patent Laid-Open No. 10-241681

リチウムイオン二次電池の出力特性は未だ十分ではなく、より一層出力特性を向上させることのできる活物質が求められている。本発明は上記課題に鑑みてなされたものであり、出力特性に優れたリチウムイオン二次電池を実現可能な活物質等を提供することを目的とする。   The output characteristics of the lithium ion secondary battery are not yet sufficient, and an active material that can further improve the output characteristics is demanded. This invention is made | formed in view of the said subject, and it aims at providing the active material etc. which can implement | achieve the lithium ion secondary battery excellent in the output characteristic.

本発明に係る活物質は、Ｎｉ、Ｍｎ及びＣｏから成る群から選択される少なくとも１つの元素及びＬｉを含む複合酸化物と、Ｍｇ２Ｐ２Ｏ７と、を含み、１００質量部の前記複合酸化物に対して、Ｍｇ２Ｐ２Ｏ７を０．２〜７．０質量部含む。 The active material according to the present invention includes a composite oxide containing at least one element selected from the group consisting of Ni, Mn, and Co and Li, and Mg 2 P 2 O 7, and 100 parts by mass of the composite the oxide comprises Mg 2 P 2 O 7 0.2~7.0 parts by mass.

本発明によれば、出力特性に優れたリチウムイオン二次電池が実現可能となる。   According to the present invention, a lithium ion secondary battery excellent in output characteristics can be realized.

ここで、前記複合酸化物は、ＬｉＣｏｐＮｉｑＭｎｒＯ２（ｐ＋ｑ＋ｒ＝１、０＜ｐ＜１、０＜ｑ＜１、０＜ｒ＜１）であることが好ましい。 Here, the composite oxide is preferably LiCo p Ni q Mn r O 2 (p + q + r = 1, 0 <p <1, 0 <q <1, 0 <r <1).

本発明にかかるリチウムイオン二次電池は、上記活物質を含む正極と、負極とを備える。   The lithium ion secondary battery concerning this invention is equipped with the positive electrode containing the said active material, and a negative electrode.

また、本発明に係るリチウムイオン二次電池は、０．１Ｈｚにおけるインピーダンスが１０Ω以下であることが好ましい。   In addition, the lithium ion secondary battery according to the present invention preferably has an impedance at 0.1 Hz of 10Ω or less.

本発明に係る活物質の製造方法は、Ｎｉ、Ｍｎ及びＣｏから成る群から選択される少なくとも１つの元素及びＬｉを含む複合酸化物と、ＭｇＮＨ４ＰＯ４・Ｈ２Ｏとを含む混合物を焼成する工程を備え、前記混合物は、１００質量部の前記複合酸化物に対して、ＭｇＮＨ４ＰＯ４・Ｈ２Ｏを０．３〜９．０質量部含む。 In the method for producing an active material according to the present invention, a mixture containing at least one element selected from the group consisting of Ni, Mn, and Co and Li, and MgNH 4 PO 4 .H 2 O is fired. The mixture includes 0.3 to 9.0 parts by mass of MgNH 4 PO 4 .H 2 O with respect to 100 parts by mass of the composite oxide.

前記焼成の温度は５００℃〜８００℃であることが好ましい。   The firing temperature is preferably 500 ° C to 800 ° C.

本発明によれば、出力特性に優れたリチウムイオン二次電池を提供可能な活物質が提供される。   ADVANTAGE OF THE INVENTION According to this invention, the active material which can provide the lithium ion secondary battery excellent in the output characteristic is provided.

図１（ａ）は本発明の１実施形態に係る正極の概略断面図、図１（ｂ）は本発明の１実施形態にかかるリチウムイオン二次電池の概略断面図である。FIG. 1A is a schematic sectional view of a positive electrode according to one embodiment of the present invention, and FIG. 1B is a schematic sectional view of a lithium ion secondary battery according to one embodiment of the present invention.

（活物質）
本発明の実施形態に係る活物質は、Ｎｉ、Ｍｎ及びＣｏから成る群から選択される少なくとも１つの元素及びＬｉを含む複合酸化物と、Ｍｇ２Ｐ２Ｏ７とを含む。 (Active material)
The active material according to the embodiment of the present invention includes Mg 2 P 2 O 7 and a composite oxide containing Li and at least one element selected from the group consisting of Ni, Mn, and Co.

上記複合酸化物の例は、リチウムコバルト複合酸化物ＬｉＣｏＯ２、リチウムニッケル複合酸化物ＬｉＮｉＯ２、リチウムマンガン複合酸化物ＬｉＭｎＯ２，ＬｉＭｎ２Ｏ４、リチウムニッケルコバルト複合酸化物ＬｉＮｉａＣｏｂＯ２（ａ＋ｂ＝１、０＜ａ＜１、０＜ｂ＜１）、リチウムマンガンコバルト複合酸化物ＬｉＭｎａＣｏｂＯ２（ａ＋ｂ＝１、０＜ａ＜１、０＜ｂ＜１）、リチウムコバルトニッケルマンガン複合酸化物ＬｉＣｏｐＮｉｑＭｎｒＯ２（ｐ＋ｑ＋ｒ＝１、０＜ｐ＜１、０＜ｑ＜１、０＜ｒ＜１）である。 Examples of the composite oxide include lithium cobalt composite oxide LiCoO 2 , lithium nickel composite oxide LiNiO 2 , lithium manganese composite oxide LiMnO 2 , LiMn 2 O 4 , lithium nickel cobalt composite oxide LiNi a Co b O 2 (a + b = 1,0 <a <1,0 <b <1), lithium-manganese-cobalt composite oxide LiMn a Co b O 2 (a + b = 1,0 <a <1,0 <b <1), lithium cobalt nickel manganese a composite oxide LiCo p Ni q Mn r O 2 (p + q + r = 1,0 <p <1,0 <q <1,0 <r <1).

中でも、上記複合酸化物は、ＬｉＣｏｐＮｉｑＭｎｒＯ２（ｐ＋ｑ＋ｒ＝１、０＜ｐ＜１、０＜ｑ＜１、０＜ｒ＜１）であることが好ましい。このような複合酸化物の例はＬｉＣｏ１／３Ｎｉ１／３Ｍｎ１／３Ｏ２である。また、別の例は、ｐ＝０．２、ｑ＝０．６、ｒ＝０．２の組み合わせや、ｐ＝０．２、ｑ＝０．５、ｒ＝０．３の組み合わせである。 Among them, the composite oxide is preferably LiCo p Ni q Mn r O 2 (p + q + r = 1,0 <p <1,0 <q <1,0 <r <1). An example of such a composite oxide is LiCo 1/3 Ni 1/3 Mn 1/3 O 2 . Another example is a combination of p = 0.2, q = 0.6, r = 0.2, or a combination of p = 0.2, q = 0.5, r = 0.3.

この活物質は、１００質量部の前記酸化物に対して、Ｍｇ２Ｐ２Ｏ７を０．２〜７．０質量部、好ましくは０．４〜６．０質量部、さらに好ましくは０．５〜５．０質量部含む。０．２質量部未満及び７．０質量部超では出力特性の改善効果が低い。 This active material is 0.2 to 7.0 parts by mass, preferably 0.4 to 6.0 parts by mass, and more preferably 0.002 parts by mass of Mg 2 P 2 O 7 with respect to 100 parts by mass of the oxide. 5 to 5.0 parts by mass are included. If it is less than 0.2 parts by mass or more than 7.0 parts by mass, the effect of improving output characteristics is low.

（活物質の製造方法）
続いて、本発明に係る活物質の製造方法の１例について説明する。 (Method for producing active material)
Then, an example of the manufacturing method of the active material which concerns on this invention is demonstrated.

まず、ＭｇＮＨ４ＰＯ４・Ｈ２Ｏを用意する。ＭｇＮＨ４ＰＯ４・Ｈ２Ｏは例えば以下のようにして得ることができる。まず、Ｍｇ（ＮＯ３）２水溶液と、（ＮＨ４）２ＨＰＯ４水溶液とを混合する。これにより、水中にＭｇＮＨ４ＰＯ４・６Ｈ２Ｏが生成し、沈殿する。えられた沈殿物をろ過により回収し、沈殿物を乾燥すると、ＭｇＮＨ４ＰＯ４・Ｈ２Ｏが得られる。乾燥温度は特に限定されないが１００℃〜３００℃が好ましい。乾燥時間も特に限定されないが、６〜１２時間が好ましい。 First, MgNH 4 PO 4 .H 2 O is prepared. MgNH 4 PO 4 .H 2 O can be obtained, for example, as follows. First, the Mg (NO 3 ) 2 aqueous solution and the (NH 4 ) 2 HPO 4 aqueous solution are mixed. Thereby, MgNH 4 PO 4 .6H 2 O is generated and precipitated in water. The obtained precipitate is collected by filtration, and the precipitate is dried to obtain MgNH 4 PO 4 .H 2 O. Although a drying temperature is not specifically limited, 100 to 300 degreeC is preferable. The drying time is not particularly limited, but is preferably 6 to 12 hours.

次に、得られたＭｇＮＨ４ＰＯ４・Ｈ２Ｏと、前述の複合酸化物と、を混合し、混合物を得る。混合方法は特に限定されないが、例えば、ボールミル等で行うことができる。混合物の組成は、得られる焼成物において、１００質量部の複合酸化物に対して、Ｍｇ２Ｐ２Ｏ７が０．２〜７．０質量部含まれるように、１００質量部の複合酸化物に対して、ＭｇＮＨ４ＰＯ４・Ｈ２Ｏを０．３〜９．０質量部含む。１００質量部の複合酸化物に対して、ＭｇＮＨ４ＰＯ４・Ｈ２Ｏは０．５〜８．０質量部含むことがより好ましく、０．７〜７．０質量部含むことがさらに好ましい。 Next, the obtained MgNH 4 PO 4 .H 2 O and the above-described composite oxide are mixed to obtain a mixture. The mixing method is not particularly limited, but can be performed by, for example, a ball mill. The composition of the mixture is 100 parts by mass of the composite oxide so that 0.2 to 7.0 parts by mass of Mg 2 P 2 O 7 is contained with respect to 100 parts by mass of the composite oxide in the obtained fired product. In contrast, 0.3 to 9.0 parts by mass of MgNH 4 PO 4 .H 2 O are included. MgNH 4 PO 4 .H 2 O is more preferably contained in an amount of 0.5 to 8.0 parts by mass, more preferably 0.7 to 7.0 parts by mass with respect to 100 parts by mass of the composite oxide.

混合により混合物を得た後に、混合物を焼成する。焼成温度は、ＭｇＮＨ４ＰＯ４・Ｈ２Ｏが分解してＭｇ２Ｐ２Ｏ７が生成しうる温度であれば良く、５００〜８００℃が好ましい。これにより、ＭｇＮＨ４ＰＯ４・Ｈ２Ｏが、Ｍｇ２Ｐ２Ｏ７に転化し、上述の活物質が得られる。焼成時間は特に限定されないが、例えば、１〜６時間とすることができる。 After obtaining the mixture by mixing, the mixture is fired. The firing temperature may be a temperature at which MgNH 4 PO 4 .H 2 O can be decomposed to produce Mg 2 P 2 O 7 , and is preferably 500 to 800 ° C. Thus, MgNH 4 PO 4 · H 2 O is converted to Mg 2 P 2 O 7, the active material described above can be obtained. Although baking time is not specifically limited, For example, it can be set as 1 to 6 hours.

（正極）
続いて、本実施形態に係る正極１０について図１（ａ）を参照して説明する。正極１０は、正極集電体１２、及び、正極集電体１２上に設けられた正極活物質層１４を有する。なお、正極活物質層１４は正極集電体１２において活物質（正極活物質）が塗工された領域を指す。正極活物質層１４は、正極集電体１２の一方面のみにあっても良いし、図１（ａ）に点線で示すように正極集電体１２の両面に設けられていても良い。 (Positive electrode)
Subsequently, the positive electrode 10 according to the present embodiment will be described with reference to FIG. The positive electrode 10 includes a positive electrode current collector 12 and a positive electrode active material layer 14 provided on the positive electrode current collector 12. The positive electrode active material layer 14 refers to a region where the active material (positive electrode active material) is coated on the positive electrode current collector 12. The positive electrode active material layer 14 may be provided only on one surface of the positive electrode current collector 12 or may be provided on both surfaces of the positive electrode current collector 12 as indicated by a dotted line in FIG.

正極集電体１２は導電材料からなる。正極集電体１２の材料の例は、ステンレス鋼、チタン、ニッケル、アルミニウム、銅などの金属材料または導電性樹脂である。特に、正極集電体１２の材料として、アルミニウムが好適である。正極集電体１２の厚みは特に限定されないが、例えば、１５〜２０μｍとすることができる。   The positive electrode current collector 12 is made of a conductive material. An example of the material of the positive electrode current collector 12 is a metal material such as stainless steel, titanium, nickel, aluminum, or copper, or a conductive resin. In particular, aluminum is suitable as a material for the positive electrode current collector 12. The thickness of the positive electrode current collector 12 is not particularly limited, but can be, for example, 15 to 20 μm.

正極活物質層１４は、前述した活物質、及び、バインダーを含む。活物質の粒径は、１０〜１５μｍであることが好ましい。   The positive electrode active material layer 14 includes the active material described above and a binder. The particle size of the active material is preferably 10 to 15 μm.

バインダーは、活物質を集電体に固定する。バインダーの例は、ポリフッ化ビニリデン、ポリテトラフルオロエチレン、フッ素ゴム等の含フッ素樹脂、ポリプロピレン、ポリエチレン等の熱可塑性樹脂、ポリイミド、ポリアミドイミド等のイミド系樹脂、アルコキシシリノレ基含有樹脂である。バインダーの量は、活物質１００質量部に対して、１〜３０質量部とすることができる。   The binder fixes the active material to the current collector. Examples of the binder are fluorine-containing resins such as polyvinylidene fluoride, polytetrafluoroethylene, and fluororubber, thermoplastic resins such as polypropylene and polyethylene, imide resins such as polyimide and polyamideimide, and alkoxysilanol group-containing resins. The quantity of a binder can be 1-30 mass parts with respect to 100 mass parts of active materials.

正極活物質層１４は、必用に応じて、さらに導電助剤を含むことができる。導電助剤の例は、カーボンブラック、黒鉛、アセチレンブラック(ＡＢ)、ケッチェンブラック(登録商標)(ＫＢ) 、気相法炭素繊維(ＶａｐｏｒＧｒｏｗｎ Ｃａｒｂｏｎ Ｆｉｂｅｒ : ＶＧＣＦ)等の炭素系粒子である。これらは、単独で、または２種以上組み合わせて添加することができる。導電助剤の使用量については、特に限定されないが、例えば、１００質量部の活物質に対して、１〜３０質量部とすることができる。   The positive electrode active material layer 14 can further contain a conductive additive as necessary. Examples of the conductive auxiliary agent are carbon-based particles such as carbon black, graphite, acetylene black (AB), ketjen black (registered trademark) (KB), vapor grown carbon fiber (Vapor Carbon Carbon Fiber: VGCF). These can be added alone or in combination of two or more. Although it does not specifically limit about the usage-amount of a conductive support agent, For example, it can be set as 1-30 mass parts with respect to 100 mass parts active material.

このような正極は、活物質、バインダー、及び、必用に応じて添加される導電助剤を含むスラリーを、集電体に塗布し、乾燥させることにより得ることができる。スラリーの溶媒の例は、Ｎ−メチル−２−ピロリドン(ＮＭＰ)、メタノール、メチルイソブチルケトン(ＭＩＢＫ)である。乾燥後、活物質層をプレスしても良い。   Such a positive electrode can be obtained by applying a slurry containing an active material, a binder, and a conductive additive added as necessary to a current collector and drying it. Examples of the solvent for the slurry are N-methyl-2-pyrrolidone (NMP), methanol, methyl isobutyl ketone (MIBK). After drying, the active material layer may be pressed.

正極集電体１２はその端部に、正極活物質層１４が形成されていないタブ部１２ｔを有する。タブ部１２ｔには、後述するリード１６が電気的に接続される。   The positive electrode current collector 12 has a tab portion 12t at the end thereof where the positive electrode active material layer 14 is not formed. A lead 16 described later is electrically connected to the tab portion 12t.

（リチウムイオン二次電池）
続いて、本発明の実施形態にかかるリチウムイオン二次電池１００の１例を、図１（ｂ）を参照して説明する。 (Lithium ion secondary battery)
Next, an example of the lithium ion secondary battery 100 according to the embodiment of the present invention will be described with reference to FIG.

リチウムイオン二次電池１００は、正極１０、セパレータ２０、負極３０、及び、ケース７０、及び、電解液を主として備える。   The lithium ion secondary battery 100 mainly includes a positive electrode 10, a separator 20, a negative electrode 30, a case 70, and an electrolytic solution.

負極３０は、負極集電体３２、及び、負極集電体３２上に設けられた負極活物質層３４を備える。なお、負極活物質層３４は負極集電体３２において負極活物質が塗工された領域を指す。負極集電体３２は導電材料からなる。負極集電体３２の材料の例は、銅などの金属である。   The negative electrode 30 includes a negative electrode current collector 32 and a negative electrode active material layer 34 provided on the negative electrode current collector 32. The negative electrode active material layer 34 refers to a region of the negative electrode current collector 32 where the negative electrode active material is applied. The negative electrode current collector 32 is made of a conductive material. An example of the material of the negative electrode current collector 32 is a metal such as copper.

負極活物質層３４は、負極活物質、及び、バインダーを有する。負極活物質層３４は、必用に応じて導電助剤を含んでも良い。バインダーや導電助剤の例及び配合量は、正極１０で記載したのと同様とすることができる。   The negative electrode active material layer 34 has a negative electrode active material and a binder. The negative electrode active material layer 34 may contain a conductive additive as necessary. Examples and blending amounts of the binder and the conductive auxiliary agent can be the same as those described for the positive electrode 10.

負極活物質は、リチウムを吸蔵、放出可能な炭素系材料、リチウムと合金化可能な元素、リチウムと合金化可能な元素を有する元素化合物、あるいは高分子材料などを用いることができる。   As the negative electrode active material, a carbon-based material that can occlude and release lithium, an element that can be alloyed with lithium, an elemental compound that has an element that can be alloyed with lithium, a polymer material, or the like can be used.

炭素系材料の例は、難黒鉛化性炭素、人造黒鉛、コークス類、グラファイト類、ガラス状炭素類、有機高分子化合物焼成体、炭素繊維、活性炭あるいはカーボンブラック類である。ここで、有機高分子化合物焼成体とは、フェノール類やフラン類などの高分子材料を適当な温度で焼成して炭素化したものをいう。   Examples of the carbon-based material are non-graphitizable carbon, artificial graphite, coke, graphite, glassy carbon, organic polymer compound fired body, carbon fiber, activated carbon, or carbon black. Here, the organic polymer compound fired body refers to a material obtained by firing and carbonizing a polymer material such as phenols and furans at an appropriate temperature.

リチウムと合金化可能な元素の例は、Ｎａ、Ｋ、Ｒｂ、Ｃｓ、Ｆｒ、Ｂｅ、Ｍｇ、Ｃａ、Ｓｒ、Ｂａ、Ｒａ、Ｔｉ、Ａｇ、Ｚｎ、Ｃｄ、Ａｌ、Ｇａ、１ｎ、Ｓｉ、Ｇｅ、Ｓｎ、Ｐｂ、Ｓｂ、Ｂｉの少なくとも１種である。中でも、リチウムと合金化可能な元素は、珪素（Ｓｉ）または錫（Ｓｎ）であるとよい。   Examples of elements that can be alloyed with lithium are Na, K, Rb, Cs, Fr, Be, Mg, Ca, Sr, Ba, Ra, Ti, Ag, Zn, Cd, Al, Ga, 1n, Si, Ge. , Sn, Pb, Sb, Bi. Among them, the element that can be alloyed with lithium is preferably silicon (Si) or tin (Sn).

リチウムと合金化可能な元素を有する元素化合物の例は、ＺｎＬｉＡｌ、ＡｌＳｂ、ＳｉＢ４、ＳｉＢ６、Ｍｇ２Ｓｉ、Ｍｇ２Ｓｎ、Ｎｉ２Ｓｉ、ＴｉＳｉ２、ＭｏＳｉ２、ＣｏＳｉ２、ＮｉＳｉ２、ＣａＳｉ２、ＣｒＳｉ２、Ｃｕ５Ｓｉ、ＦｅＳｉ２、ＭｎＳｉ２、ＮｂＳｉ２、ＴａＳｉ２、ＶＳｉ２、ＷＳｉ２、ＺｎＳｉ２、ＳｉＣ、Ｓｉ３Ｎ４、Ｓｉ２Ｎ２Ｏ、ＳｉＯｖ（０＜ｖ≦２）、ＳｎＯｗ（０＜ｗ≦２）、ＳｎＳｉＯ３、ＬｉＳｉＯあるいはＬｉＳｎＯなどが使用できる。 Examples of element compound having lithium can be alloyed elements, ZnLiAl, AlSb, SiB 4, SiB 6, Mg 2 Si, Mg 2 Sn, Ni 2 Si, TiSi 2, MoSi 2, CoSi 2, NiSi 2, CaSi 2, CrSi 2, Cu 5 Si , FeSi 2, MnSi 2, NbSi 2, TaSi 2, VSi 2, WSi 2, ZnSi 2, SiC, Si 3 N 4, Si 2 N 2 O, SiO v (0 <v ≦ 2), SnO w (0 <w ≦ 2), SnSiO 3 , LiSiO or LiSnO can be used.

リチウムと合金化反応可能な元素を有する元素化合物の例は、珪素化合物または錫化合物であることがよい。珪素化合物は、ＳｉＯｘ（０．５≦ｘ≦１．５）であることがよい。錫化合物は、例えば、スズ合金（Ｃｕ−Ｓｎ合金、Ｃｏ−Ｓｎ合金等）などが使用できる。 An example of the elemental compound having an element capable of alloying with lithium is preferably a silicon compound or a tin compound. The silicon compound is preferably SiO x (0.5 ≦ x ≦ 1.5). As the tin compound, for example, a tin alloy (Cu-Sn alloy, Co-Sn alloy, or the like) can be used.

高分子材料の例は、ポリアセチレン、ポリピロールである。   Examples of the polymer material are polyacetylene and polypyrrole.

負極の製造方法は、活物質が異なる以外は正極と同様である。   The manufacturing method of the negative electrode is the same as that of the positive electrode except that the active material is different.

負極集電体３２はその端部に、負極活物質層３４が形成されていないタブ部３２ｔを有する。タブ部３２ｔには、後述するリード３６が電気的に接続される。   The negative electrode current collector 32 has a tab portion 32t at the end thereof where the negative electrode active material layer 34 is not formed. A lead 36 described later is electrically connected to the tab portion 32t.

（セパレータ）
セパレータ２０は、正極１０と負極３０とを隔離し、両極の接触による電流の短絡を防止しつつ、リチウムイオンを通過させるものである。セパレータ２０は、例えばポリテトラフルオロエチレン、ポリプロピレン、あるいはポリエチレンなどの合成樹脂製の多孔質膜、またはセラミックス製の多孔質膜が使用できる。正極１０の正極活物質層１４と、負極３０の負極活物質層３４とがセパレータ２０の各面に接触している。 (Separator)
The separator 20 separates the positive electrode 10 and the negative electrode 30 and allows lithium ions to pass through while preventing a short circuit of current due to contact between both electrodes. As the separator 20, for example, a porous film made of a synthetic resin such as polytetrafluoroethylene, polypropylene, or polyethylene, or a porous film made of ceramics can be used. The positive electrode active material layer 14 of the positive electrode 10 and the negative electrode active material layer 34 of the negative electrode 30 are in contact with each surface of the separator 20.

（電解液）
電解液は、電解質と、この電解質を溶解する溶媒とを含む。電解質は、正極活物質層１４、セパレータ２０、負極活物質層３４内に含浸されている。 (Electrolyte)
The electrolytic solution includes an electrolyte and a solvent that dissolves the electrolyte. The electrolyte is impregnated in the positive electrode active material layer 14, the separator 20, and the negative electrode active material layer 34.

電解質の例は、ＬｉＢＦ４、ＬｉＰＦ６、ＬｉＣｌＯ４、ＬｉＡｓＦ６、ＬｉＣＦ３ＳＯ３、ＬｉＮ（ＣＦ３ＳＯ２）２等のリチウム塩である。 Examples of the electrolyte are lithium salts such as LiBF 4 , LiPF 6 , LiClO 4 , LiAsF 6 , LiCF 3 SO 3 , and LiN (CF 3 SO 2 ) 2 .

溶媒の例は、環状エステル類、鎖状エステル類、エーテル類である。これらの溶媒を２種以上混合することもできる。   Examples of the solvent are cyclic esters, chain esters, and ethers. Two or more of these solvents can be mixed.

環状エステル類の例は、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、ガンマブチロラクトン、ビニレンカーボネート、２−メチル−ガンマブチロラクトン、アセチル−ガンマブチロラクトン、ガンマバレロラクトンである。鎖状エステル類の例は、メチルカーボネート、ジエチルカーボネート、ジブチルカーボネート、ジプロピルカーボネート、メチルエチルカーボネート、プロピオン酸アルキルエステル、マロン酸ジアルキルエステル、酢酸アルキルエステルである。エーテル類の例は、テトラヒドロフラン、２−メチルテトラヒドロフラン、１，４−ジオキサン、１，２−ジメトキシエタン、１，２−ジエトキシエタン、１，２−ジブトキシエタンである。   Examples of cyclic esters are ethylene carbonate, propylene carbonate, butylene carbonate, gamma butyrolactone, vinylene carbonate, 2-methyl-gamma butyrolactone, acetyl-gamma butyrolactone, gamma valerolactone. Examples of the chain esters are methyl carbonate, diethyl carbonate, dibutyl carbonate, dipropyl carbonate, methyl ethyl carbonate, propionic acid alkyl ester, malonic acid dialkyl ester, and acetic acid alkyl ester. Examples of ethers are tetrahydrofuran, 2-methyltetrahydrofuran, 1,4-dioxane, 1,2-dimethoxyethane, 1,2-diethoxyethane, 1,2-dibutoxyethane.

電解液における電解質の濃度は、例えば、０．５〜１．７ｍｏｌ／Ｌとすることができる。電解液は、ゲル化剤を含んでいても良い。   The density | concentration of the electrolyte in electrolyte solution can be 0.5-1.7 mol / L, for example. The electrolytic solution may contain a gelling agent.

（ケース）
ケース７０は、正極１０、セパレータ２０、負極３０、及び、電解液を収容する。ケースの材料や形態は特に限定されず、樹脂、金属など公知の種々の物を使用できる。 (Case)
The case 70 accommodates the positive electrode 10, the separator 20, the negative electrode 30, and the electrolytic solution. The material and form of the case are not particularly limited, and various known materials such as resins and metals can be used.

正極集電体１２のタブ部１２ｔ、及び、負極集電体３２のタブ部３２ｔには、それぞれ、リード１６、３６が接続されている。リード１６、３６の一端は、ケース７０の外に出ている。   Leads 16 and 36 are connected to the tab portion 12t of the positive electrode current collector 12 and the tab portion 32t of the negative electrode current collector 32, respectively. One ends of the leads 16 and 36 are out of the case 70.

このようなリチウムイオン二次電池１００は、出力特性に優れる。具体的には、このリチウムイオン二次電池１００は、Ｍｇ２Ｐ２Ｏ７を含まず、濃度が０である以外は構造及び材料が同じリチウムイオン二次電池１００に対して、０．１Ｈｚインピーダンスが低減されることができる。 Such a lithium ion secondary battery 100 is excellent in output characteristics. Specifically, the lithium ion secondary battery 100 does not contain Mg 2 P 2 O 7 and has a 0.1 Hz impedance relative to the lithium ion secondary battery 100 having the same structure and material except that the concentration is 0. Can be reduced.

なお、本発明に係るリチウムイオン二次電池１００は、上記実施形態に限られず様々な変形態様が可能である。例えば、正極、負極、及び、セパレータを複数有し、正極及び負極が交互に配置され、かつ、各正極及び負極の間にセパレータが配置されるように積層されているものでもよい。   In addition, the lithium ion secondary battery 100 which concerns on this invention is not restricted to the said embodiment, A various deformation | transformation aspect is possible. For example, a plurality of positive electrodes, negative electrodes, and separators may be provided, the positive electrodes and the negative electrodes may be alternately disposed, and the separators may be disposed between the positive electrodes and the negative electrodes.

（実施例１）
３質量％のＭｇ（ＮＯ３）２水溶液と、１質量％の（ＮＨ４）２ＨＰＯ４の水溶液を調製した。次に、これらの水溶液を混合し、沈殿物をろ過により回収した。沈殿物（ＭｇＮＨ４ＰＯ４・６Ｈ２Ｏ）を１２０℃で６時間乾燥し、ＭｇＮＨ４ＰＯ４・Ｈ２Ｏ粒子を得た。 Example 1
A 3% by mass Mg (NO 3 ) 2 aqueous solution and a 1% by mass (NH 4 ) 2 HPO 4 aqueous solution were prepared. Next, these aqueous solutions were mixed, and the precipitate was collected by filtration. The precipitate (MgNH 4 PO 4 .6H 2 O) was dried at 120 ° C. for 6 hours to obtain MgNH 4 PO 4 .H 2 O particles.

ＭｇＮＨ４ＰＯ４・Ｈ２Ｏ粒子と、ＬｉＣｏ１／３Ｎｉ１／３Ｍｎ１／３Ｏ２粒子とを、質量比で２：１００となるように混合し、混合物を７００℃で５時間焼成し、１００質量部のＬｉＣｏ１／３Ｎｉ１／３Ｍｎ１／３Ｏ２に対してＭｇ２Ｐ２Ｏ７を１．４質量部含む活物質粒子を得た。 MgNH 4 PO 4 .H 2 O particles and LiCo 1/3 Ni 1/3 Mn 1/3 O 2 particles are mixed at a mass ratio of 2: 100, and the mixture is fired at 700 ° C. for 5 hours. Then, active material particles containing 1.4 parts by mass of Mg 2 P 2 O 7 with respect to 100 parts by mass of LiCo 1/3 Ni 1/3 Mn 1/3 O 2 were obtained.

得られた活物質粒子、アセチレンブラック、及び、ポリフッ化ビニリデン（ＰＶＤＦ）を、質量比で８８：６：６となるように混合し、さらに、Ｎ−メチル−２−ピロリドン（ＮＭＰ）を加えてスラリーとし、アルミニウム箔上に塗布し、１２０℃で６時間乾燥させ、その後、プレスし、正極１０（２５ｍｍ×３０ｍｍ）を得た。   The obtained active material particles, acetylene black, and polyvinylidene fluoride (PVDF) were mixed at a mass ratio of 88: 6: 6, and N-methyl-2-pyrrolidone (NMP) was further added. A slurry was applied, applied onto an aluminum foil, dried at 120 ° C. for 6 hours, and then pressed to obtain a positive electrode 10 (25 mm × 30 mm).

また、黒鉛粉末と、アセチレンブラックと、スチレンブタジエンゴムと、カルボキシメチルセルロースとを、９７：１：１：１となるように混合した。この混合物をイオン交換水に分散させてスラリーを得て、銅箔上に塗布し、乾燥させ、その後プレスし、負極３０（２５ｍｍ×３０ｍｍ）を得た。   Further, graphite powder, acetylene black, styrene butadiene rubber, and carboxymethyl cellulose were mixed so as to be 97: 1: 1: 1. This mixture was dispersed in ion-exchanged water to obtain a slurry, which was applied onto a copper foil, dried, and then pressed to obtain a negative electrode 30 (25 mm × 30 mm).

正極１０及び負極３０のタブ部１２ｔ、３２ｔにそれぞれリード１６、３６を接続した後、得られた正極１０の正極活物質層１４と負極３０の負極活物質層３４とを、セパレータ２０としてのポリプロピレン多孔膜（２７ｍｍ×３２ｍｍ）を介して重ね合わせ、樹脂製のケース７０に収容し、電解液を注入し、リチウムイオン二次電池を得た。   After connecting the leads 16 and 36 to the tab portions 12t and 32t of the positive electrode 10 and the negative electrode 30, respectively, the positive electrode active material layer 14 of the positive electrode 10 and the negative electrode active material layer 34 of the negative electrode 30 thus obtained are polypropylene as the separator 20. They were overlapped via a porous film (27 mm × 32 mm), accommodated in a resin case 70, and an electrolyte was injected to obtain a lithium ion secondary battery.

電解液は、エチレンカーボネート及びジエチルカーボネートを、３：７の体積比で含有する溶媒と、１ｍｏｌ／Ｌの濃度で含有されたＬｉＰＦ６を含むものであった。 The electrolytic solution contained a solvent containing ethylene carbonate and diethyl carbonate in a volume ratio of 3: 7 and LiPF 6 contained at a concentration of 1 mol / L.

（実施例２）
ＭｇＮＨ４ＰＯ４・Ｈ２Ｏ粒子と、ＬｉＣｏ１／３Ｎｉ１／３Ｍｎ１／３Ｏ２粒子とを、質量比で５：１００となるように混合し、１００質量部のＬｉＣｏ１／３Ｎｉ１／３Ｍｎ１／３Ｏ２に対してＭｇ２Ｐ２Ｏ７を３．６質量部含む正極活物質粒子を得た以外は実施例１と同様にした。 (Example 2)
MgNH 4 PO 4 .H 2 O particles and LiCo 1/3 Ni 1/3 Mn 1/3 O 2 particles are mixed at a mass ratio of 5: 100, and 100 parts by mass of LiCo 1/3. The same procedure as in Example 1 was performed except that positive electrode active material particles containing 3.6 parts by mass of Mg 2 P 2 O 7 with respect to Ni 1/3 Mn 1/3 O 2 were obtained.

（実施例３）
ＭｇＮＨ４ＰＯ４・Ｈ２Ｏ粒子と、ＬｉＣｏ１／３Ｎｉ１／３Ｍｎ１／３Ｏ２粒子とを、質量比で０．５：１００となるように混合し、１００質量部のＬｉＣｏ１／３Ｎｉ１／３Ｍｎ１／３Ｏ２に対してＭｇ２Ｐ２Ｏ７を０．４質量部含む正極活物質粒子を得た以外は実施例１と同様にした。 (Example 3)
MgNH 4 PO 4 .H 2 O particles and LiCo 1/3 Ni 1/3 Mn 1/3 O 2 particles are mixed at a mass ratio of 0.5: 100, and 100 parts by mass of LiCo 1 / 3 The same procedure as in Example 1 was conducted except that positive electrode active material particles containing 0.4 parts by mass of Mg 2 P 2 O 7 with respect to Ni 1/3 Mn 1/3 O 2 were obtained.

（比較例１）
活物質粒子としてＬｉＣｏ１／３Ｎｉ１／３Ｍｎ１／３Ｏ２粒子を用いた以外は実施例１と同様にした。 (Comparative Example 1)
The same operation as in Example 1 was performed except that LiCo 1/3 Ni 1/3 Mn 1/3 O 2 particles were used as the active material particles.

（比較例２）
ＭｇＮＨ４ＰＯ４・Ｈ２Ｏ粒子と、ＬｉＣｏ１／３Ｎｉ１／３Ｍｎ１／３Ｏ２粒子とを、質量比で１０：１００となるように混合し、１００質量部のＬｉＣｏ１／３Ｎｉ１／３Ｍｎ１／３Ｏ２に対してＭｇ２Ｐ２Ｏ７を７．２質量部含む活物質粒子を得た以外は実施例１と同様にした。 (Comparative Example 2)
MgNH 4 PO 4 .H 2 O particles and LiCo 1/3 Ni 1/3 Mn 1/3 O 2 particles are mixed at a mass ratio of 10: 100, and 100 parts by mass of LiCo 1/3. The same operation as in Example 1 was performed except that active material particles containing 7.2 parts by mass of Mg 2 P 2 O 7 with respect to Ni 1/3 Mn 1/3 O 2 were obtained.

（評価）
得られたリチウムイオン二次電池それぞれについて、インピーダンスをマルチポテンショスタット１４７０Ｅ型（Ｓｏｌａｒｔｒｏｎ社製）にて以下のように測定した。インピーダンスは、セルをＳＯＣ２０％の電圧に調整した後、１ＭＨｚ〜０．０５Ｈｚの範囲でインピーダンス測定したときに得られた０．１Ｈｚにおけるインピーダンスの値である。
結果を表１に示す。
実施例１〜３では、１０Ω以下の０．１Ｈｚインピーダンスが達成されたが、比較例１、２では、１０Ω以下の０．１Ｈｚインピーダンスは達成されなかった。

Figure 0005862622
(Evaluation)
For each of the obtained lithium ion secondary batteries, the impedance was measured with a multipotentiostat 1470E type (manufactured by Solartron) as follows. The impedance is a value of impedance at 0.1 Hz obtained when impedance is measured in the range of 1 MHz to 0.05 Hz after the cell is adjusted to a voltage of SOC 20%.
The results are shown in Table 1.
In Examples 1 to 3, a 0.1 Hz impedance of 10Ω or less was achieved, but in Comparative Examples 1 and 2, a 0.1 Hz impedance of 10Ω or less was not achieved.
Figure 0005862622

１０…正極、２０…セパレータ、３０…負極、１００…リチウムイオン二次電池。   DESCRIPTION OF SYMBOLS 10 ... Positive electrode, 20 ... Separator, 30 ... Negative electrode, 100 ... Lithium ion secondary battery.

Claims (6)

Ｎｉ、Ｍｎ及びＣｏから成る群から選択される少なくとも１つの元素及びＬｉを含む複合酸化物と、ＭｇＮＨ４ＰＯ４・Ｈ２Ｏとを含む混合物を焼成する工程を備え、
前記混合物は、１００質量部の前記複合酸化物に対して、ＭｇＮＨ４ＰＯ４・Ｈ２Ｏを０．３〜９．０質量部含み、
前記焼成の温度が５００〜８００℃である、リチウムイオン二次電池用活物質の製造方法。 Firing a mixture containing a composite oxide containing Li and at least one element selected from the group consisting of Ni, Mn, and Co, and MgNH 4 PO 4 .H 2 O;
Said mixture relative to the composite oxide of 100 parts by weight, the MgNH 4 PO 4 · H 2 O viewed from 0.3 to 9.0 parts by weight containing,
The manufacturing method of the active material for lithium ion secondary batteries whose temperature of the said baking is 500-800 degreeC . 前記混合物が、１００質量部の前記複合酸化物に対して、ＭｇＮＨThe mixture is MgNH with respect to 100 parts by mass of the composite oxide. ４4 ＰＯPO ４4 ・Ｈ・ H ２2 Ｏを０．５〜８．０質量部含む、請求項１に記載の方法。The method of Claim 1 which contains 0.5-8.0 mass parts of O. 前記混合物が、１００質量部の前記複合酸化物に対して、ＭｇＮＨThe mixture is MgNH with respect to 100 parts by mass of the composite oxide. ４4 ＰＯPO ４4 ・Ｈ・ H ２2 Ｏを０．７〜７．０質量部含む、請求項１に記載の方法。The method according to claim 1, comprising 0.7 to 7.0 parts by mass of O. 前記焼成の温度が７００℃である、請求項１〜３のいずれか一項に記載の方法。The method as described in any one of Claims 1-3 whose temperature of the said baking is 700 degreeC. 前記焼成の時間が５時間である、請求項１〜４のいずれか一項に記載の方法。The method as described in any one of Claims 1-4 whose time of the said baking is 5 hours. 前記ＭｇＮＨMgNH ４4 ＰＯPO ４4 ・Ｈ・ H ２2 Ｏが、Ｍｇ（ＮＯO is Mg (NO ３3 ）) ２2 水溶液と（ＮＨAqueous solution and (NH ４4 ）) ２2 ＨＰＯHPO ４4 水溶液とを混合し、ろ過することによって得られる、請求項１〜５のいずれか一項に記載の方法。The method as described in any one of Claims 1-5 obtained by mixing and filtering with aqueous solution.
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