JP2021157959A - Positive electrode and lithium ion secondary battery - Google Patents
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- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 49
- 239000007774 positive electrode material Substances 0.000 claims abstract description 39
- 150000001875 compounds Chemical class 0.000 claims abstract description 36
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- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 3
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Images
Classifications
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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、正極、およびリチウムイオン二次電池に関する。 The present invention relates to a positive electrode and a lithium ion secondary battery.
リチウムイオン二次電池は、ニッケルカドミウム電池、ニッケル水素電池等と比べ、軽量、高容量であるため、携帯電子機器用電源として広く応用されている。また、ハイブリッド自動車や、電気自動車用に搭載される電源としても有力な候補となっている。そして、近年の携帯電子機器の小型化、高機能化に伴い、これらの電源となるリチウムイオン二次電池の更なる高容量化が期待されている。 Lithium-ion secondary batteries are lighter and have higher capacity than nickel-cadmium batteries, nickel-metal hydride batteries, and the like, and are therefore widely used as power sources for portable electronic devices. It is also a promising candidate for power sources installed in hybrid vehicles and electric vehicles. With the recent miniaturization and higher functionality of portable electronic devices, it is expected that the capacity of lithium ion secondary batteries, which are the power sources for these devices, will be further increased.
リチウムイオン電池の容量は主に電極の活物質に依存する。負極活物質には、一般に黒鉛などの炭素材料が利用されている。しかし、黒鉛の理論容量は３７２ｍＡｈ／ｇであり、実用化されている電池では、既に約３５０ｍＡｈ／ｇの容量が利用されている。よって、将来の高機能携帯機器のエネルギー源として十分な容量を有するリチウムイオン二次電池を得るためには、さらなる高容量化を実現する必要がある。 The capacity of a lithium-ion battery mainly depends on the active material of the electrode. A carbon material such as graphite is generally used as the negative electrode active material. However, the theoretical capacity of graphite is 372 mAh / g, and a capacity of about 350 mAh / g has already been used in a practical battery. Therefore, in order to obtain a lithium ion secondary battery having a sufficient capacity as an energy source for future high-performance mobile devices, it is necessary to realize a further increase in capacity.
また、近年ではより一層の高容量化に加え、利便性の向上のため急速充電特性や、電動工具やコードレス家電などリチウムイオン二次電池の新規な用途が開拓されたことによる急速放電への要望も高まりつつある。 In recent years, in addition to further increasing the capacity, there is a demand for rapid discharge due to the rapid charging characteristics and the development of new applications for lithium-ion secondary batteries such as power tools and cordless home appliances to improve convenience. Is also increasing.
特許文献１では低空孔率の高エネルギー密度電極を使用したリチウムイオン二次電池において、非水電解質の塩濃度を１．３ｍｏｌ・ｄｍ−３以上にすることで、出力特性を改善している。特許文献２ではリチウムイオン二次電池の非水電解液を、ＬｉＰＦ６及びＬｉＢＦ４を含むリチウム塩；及び（ａ）エチレンカーボネートまたはエチレンカーボネートとプロピレンカーボネートとの混合物からなる環状カーボネートと（ｂ）プロピオネート系エステルのような鎖状エステルとの混合体積比（ａ：ｂ）が約１０：９０〜約７０：３０とすることで、出力特性を改善している。 In Patent Document 1, in a lithium ion secondary battery using a high energy density electrode having a low porosity, the output characteristics are improved by setting the salt concentration of the non-aqueous electrolyte to 1.3 mol · dm -3 or more. In Patent Document 2, the non-aqueous electrolyte solution of a lithium ion secondary battery is a lithium salt containing LiPF 6 and LiBF 4 , and (a) ethylene carbonate or a cyclic carbonate composed of a mixture of ethylene carbonate and propylene carbonate and (b) a propionate system. The output characteristics are improved by setting the mixed volume ratio (a: b) with a chain ester such as an ester to about 10:90 to about 70:30.
しかしながら、従来技術の方法では出力特性は改善するものの、急速充電特性については未だ満足されないという課題があった。 However, although the output characteristics are improved by the method of the prior art, there is a problem that the quick charging characteristics are not yet satisfied.
本発明は上記従来技術の有する課題に鑑みてなされたものであり、急速充電特性に優れる正極、およびリチウムイオン二次電池を提供することを目的とする。 The present invention has been made in view of the above-mentioned problems of the prior art, and an object of the present invention is to provide a positive electrode having excellent quick charging characteristics and a lithium ion secondary battery.
上記課題を解決するため、本発明に係る正極は、リチウム遷移金属酸化物を主体とする正極活物質を含む正極活物質層を有する正極であって、上記正極活物質層は、化学式（１）で表される化合物を含むことを特徴とする。 In order to solve the above problems, the positive electrode according to the present invention is a positive electrode having a positive electrode active material layer containing a positive electrode active material mainly composed of a lithium transition metal oxide, and the positive electrode active material layer is a chemical formula (1). It is characterized by containing a compound represented by.
（Ｘ１およびＸ２はＨまたはＬｉであり、Ｒは炭素数が１〜３のアルキレン基またはハロゲン化アルキレン基を示す。）
(X 1 and X 2 are H or Li, and R represents an alkylene group having 1 to 3 carbon atoms or a halogenated alkylene group.)
本発明に係る正確なメカニズムは不明だが、以下のように考えている。一般的なリチウムイオン電池では、正極活物質表面のリチウムイオンが、電解液中のカーボネート溶媒４分子に配位される（溶媒和される）ことで充電反応が進行する。この正極活物質から電解液への固液界面の溶媒和反応が律速となり、急速充電特性が悪化する。本発明に係る正極は、カルボニル基を４つ有する化学式（１）で表される化合物を正極に含む。これにより、正極活物質表面のリチウムイオンが強く配位され、上記の溶媒和反応が速やかに進行し、急速充電特性が改善する。 Although the exact mechanism according to the present invention is unknown, it is considered as follows. In a general lithium ion battery, the charging reaction proceeds by coordinating (solvating) the lithium ions on the surface of the positive electrode active material with four molecules of the carbonate solvent in the electrolytic solution. The solvation reaction at the solid-liquid interface from the positive electrode active material to the electrolytic solution becomes rate-determining, and the rapid charging characteristics deteriorate. The positive electrode according to the present invention contains a compound represented by the chemical formula (1) having four carbonyl groups in the positive electrode. As a result, the lithium ions on the surface of the positive electrode active material are strongly coordinated, the above solvation reaction proceeds rapidly, and the quick charging characteristics are improved.
本発明に係る正極は更に、上記化学式（１）で表される化合物が、上記正極活物質層の単位質量当たり２．５×１０−５ｍｏｌ／ｇ以上２．５×１０−２ｍｏｌ／ｇ以下含まれることが好ましい。 Further, in the positive electrode according to the present invention, the compound represented by the chemical formula (1) is 2.5 × 10 −5 mol / g or more and 2.5 × 10 −2 mol / g per unit mass of the positive electrode active material layer. It is preferably contained below.
これによれば、化合物の含有量として好適であり、急速充電特性がより改善する。 According to this, it is suitable as the content of the compound, and the quick charging characteristic is further improved.
本発明に係るリチウムイオン二次電池は、上記正極を含むことを特徴とする。 The lithium ion secondary battery according to the present invention is characterized by including the above-mentioned positive electrode.
本発明によれば、急速充電特性に優れる正極、およびリチウムイオン二次電池を提供される。 According to the present invention, a positive electrode having excellent quick charging characteristics and a lithium ion secondary battery are provided.
以下、図面を参照しながら本発明に係る好適な実施形態について説明する。なお、本発明は以下の実施形態に限定されるものではない。また以下に記載した構成要素には、当業者が容易に想到できるもの、実質的に同一のものが含まれる。さらに以下に記載した構成要素は、適宜組み合わせることができる。 Hereinafter, preferred embodiments according to the present invention will be described with reference to the drawings. The present invention is not limited to the following embodiments. In addition, the components described below include those that can be easily conceived by those skilled in the art and those that are substantially the same. Further, the components described below can be combined as appropriate.
＜リチウムイオン二次電池＞
図１に示すように、本実施形態に係るリチウムイオン二次電池１００は、互いに対向する板状の負極２０及び板状の正極１０と、負極２０と正極１０との間に隣接して配置される板状のセパレータ１８と、を備える積層体３０と、リチウムイオンを含む電解質溶液と、これらを密閉した状態で収容するケース５０と、負極２０に一方の端部が電気的に接続されると共に他方の端部がケースの外部に突出されるリード６２と、正極１０に一方の端部が電気的に接続されると共に他方の端部がケースの外部に突出されるリード６０とを備える。
<Lithium-ion secondary battery>
As shown in FIG. 1, the lithium ion
正極１０は、正極集電体１２と、正極集電体１２上に形成された正極活物質層１４と、を有する。また、負極２０は、負極集電体２２と、負極集電体２２上に形成された負極活物質層２４と、を有する。セパレータ１８は、負極活物質層２４と正極活物質層１４との間に位置している。
The
＜正極＞
本実施形態に係る正極は、リチウム遷移金属酸化物を主体とする正極活物質を含む正極活物質層を有する正極であって、上記正極活物質層は、化学式（１）で表される化合物を含むことを特徴とする。
<Positive electrode>
The positive electrode according to the present embodiment is a positive electrode having a positive electrode active material layer containing a positive electrode active material mainly composed of a lithium transition metal oxide, and the positive electrode active material layer is a compound represented by the chemical formula (1). It is characterized by including.
本実施形態に係る正確なメカニズムは不明だが、以下のように考えている。一般的なリチウムイオン電池では、正極活物質表面のリチウムイオンが、電解液中のカーボネート溶媒４分子に配位される（溶媒和される）ことで充電反応が進行する。この正極活物質から電解液への固液界面の溶媒和反応が律速となり、急速充電特性が悪化する。本実施形態に係る正極は、カルボニル基を４つ有する化学式（１）で表される化合物を正極に含む。これにより、正極活物質表面のリチウムイオンが強く配位され、上記の溶媒和反応が速やかに進行し、急速充電特性が改善する。 The exact mechanism according to this embodiment is unknown, but it is considered as follows. In a general lithium ion battery, the charging reaction proceeds by coordinating (solvating) the lithium ions on the surface of the positive electrode active material with four molecules of the carbonate solvent in the electrolytic solution. The solvation reaction at the solid-liquid interface from the positive electrode active material to the electrolytic solution becomes rate-determining, and the rapid charging characteristics deteriorate. The positive electrode according to the present embodiment contains a compound represented by the chemical formula (1) having four carbonyl groups in the positive electrode. As a result, the lithium ions on the surface of the positive electrode active material are strongly coordinated, the above solvation reaction proceeds rapidly, and the quick charging characteristics are improved.
化学式（１）で表される化合物の合成法としては特に限定されるものではないが、例えば次の方法が挙げられる。まず、シュウ酸と、２価アルコールとを適当な溶媒へ溶解させ、この溶液を加熱することで脱水反応を進行させ、Ｘ１およびＸ２がＨである化合物を得る。更に、この化合物と、水酸化リチウムとを適当な溶媒中で中和反応を進行させることで、Ｘ１およびＸ２がＬｉで置換した化合物を得ることが出来る。 The method for synthesizing the compound represented by the chemical formula (1) is not particularly limited, and examples thereof include the following methods. First, oxalic acid and a dihydric alcohol are dissolved in a suitable solvent, and the solution is heated to proceed with a dehydration reaction to obtain a compound in which X 1 and X 2 are H. Further, by proceeding the neutralization reaction of this compound and lithium hydroxide in an appropriate solvent, a compound in which X 1 and X 2 are replaced with Li can be obtained.
化学式（１）で表される化合物の同定法としては、ＮＭＲ、ＩＲ、ＭＳ等、一般的に有機化合物の同定に用いられる解析手法を用いることが出来る。 As a method for identifying the compound represented by the chemical formula (1), an analysis method generally used for identification of an organic compound such as NMR, IR, and MS can be used.
本実施形態に係る正極は更に、上記化学式（１）で表される化合物が、上記正極活物質層の単位質量当たり２．５×１０−５ｍｏｌ／ｇ以上２．５×１０−２ｍｏｌ／ｇ以下含まれることが好ましい。 Further, in the positive electrode according to the present embodiment, the compound represented by the chemical formula (1) is 2.5 × 10 −5 mol / g or more and 2.5 × 10 −2 mol / g per unit mass of the positive electrode active material layer. It is preferably contained in an amount of g or less.
これによれば、化合物の含有量として好適であり、急速充電特性がより改善する。 According to this, it is suitable as the content of the compound, and the quick charging characteristic is further improved.
（正極集電体）
正極集電体１２は、導電性の板材であればよく、例えば、アルミニウム又はそれらの合金、ステンレス等の金属薄板（金属箔）を用いることができる。
(Positive current collector)
The positive electrode
（正極活物質層）
正極活物質層１４は、正極活物質、正極用バインダー、および正極用導電助剤から主に構成されるものである。
(Positive electrode active material layer)
The positive electrode
（正極活物質）
正極活物質としては、リチウムイオンの吸蔵及び放出、リチウムイオンの脱離及び挿入（インターカレーション）、又は、該リチウムイオンのカウンターアニオン（例えば、ＰＦ６ −）のドープ及び脱ドープを可逆的に進行させることが可能であれば特に限定されず、公知の電極活物質を使用できる。例えば、コバルト酸リチウム（ＬｉＣｏＯ２）、ニッケル酸リチウム（ＬｉＮｉＯ２）、リチウムマンガンスピネル（ＬｉＭｎ２Ｏ４）、及び、化学式：ＬｉＮｉｘＣｏｙＭｎｚＭａＯ２（ｘ＋ｙ＋ｚ＋ａ＝１、０≦ｘ≦１、０≦ｙ≦１、０≦ｚ≦１、０≦ａ≦１、ＭはＡｌ、Ｍｇ、Ｎｂ、Ｔｉ、Ｃｕ、Ｚｎ、Ｃｒより選ばれる１種類以上の元素）で表される複合金属酸化物、リチウムバナジウム化合物Ｌｉａ（Ｍ）ｂ（ＰＯ４）ｃ（ただし、Ｍ＝ＶＯまたはＶ、かつ、０．９≦ａ≦３．３、０．９≦ｂ≦２．２、０．９≦ｃ≦３．３）、オリビン型ＬｉＭＰＯ４（ただし、Ｍは、Ｃｏ、Ｎｉ、Ｍｎ、Ｆｅ、Ｍｇ、Ｎｂ、Ｔｉ、Ａｌ、Ｚｒより選ばれる１種類以上の元素を示す）、チタン酸リチウム（Ｌｉ４Ｔｉ５Ｏ１２）、ＬｉＮｉｘＣｏｙＡｌｚＯ２（０．９＜ｘ＋ｙ＋ｚ＜１．１）等の複合金属酸化物が挙げられる。
(Positive electrode active material)
As the positive electrode active material, occlusion of lithium ions and release, desorption and insertion of lithium ions (intercalation), or counter anions of the lithium ions (e.g., PF 6 -) to doping and dedoping of reversibly As long as it can be advanced, it is not particularly limited, and a known electrode active material can be used. For example, lithium cobalt oxide (LiCoO 2), lithium nickel oxide (LiNiO 2), lithium manganese spinel (LiMn 2 O 4), and the chemical formula: LiNi x Co y Mn z M a O 2 (x + y + z + a = 1,0 ≦ x ≦ 1, 0 ≦ y ≦ 1, 0 ≦ z ≦ 1, 0 ≦ a ≦ 1, M is a compound represented by one or more elements selected from Al, Mg, Nb, Ti, Cu, Zn, and Cr). Metal oxide, lithium vanadium compound Li a (M) b (PO 4 ) c (However, M = VO or V, and 0.9 ≦ a ≦ 3.3, 0.9 ≦ b ≦ 2.2, 0 .9 ≤ c ≤ 3.3), olivine type LiMPO 4 (where M indicates one or more elements selected from Co, Ni, Mn, Fe, Mg, Nb, Ti, Al, Zr), titanium lithium acid (Li 4 Ti 5 O 12) , LiNi x Co y Al z O 2 composite metal oxide such as (0.9 <x + y + z <1.1) , and the like.
（正極用バインダー）
正極用バインダーは正極活物質同士を結合すると共に、正極活物質層１４と正極用集電体１２とを結合している。バインダーは、上述の結合が可能なものであればよく、例えば、ポリフッ化ビニリデン（ＰＶＤＦ）、ポリテトラフルオロエチレン（ＰＴＦＥ）等のフッ素樹脂や、セルロース、スチレン・ブタジエンゴム、エチレン・プロピレンゴム、ポリイミド樹脂、ポリアミドイミド樹脂等を用いてもよい。また、バインダーとして電子伝導性の導電性高分子やイオン伝導性の導電性高分子を用いてもよい。電子伝導性の導電性高分子としては、例えば、ポリアセチレン、ポリチオフェン、ポリアニリン等が挙げられる。イオン伝導性の導電性高分子としては、例えば、ポリエチレンオキシド、ポリプロピレンオキシド等のポリエーテル系高分子化合物と、ＬｉＣｌＯ４、ＬｉＢＦ４、ＬｉＰＦ６等のリチウム塩とを複合化させたもの等が挙げられる。
(Binder for positive electrode)
The positive electrode binder binds the positive electrode active materials to each other, and also bonds the positive electrode
正極活物質層１４中のバインダーの含有量は特に限定されないが、添加する場合には正極活物質１００質量部に対して０．５〜５質量部であることが好ましい。
The content of the binder in the positive electrode
（正極用導電助剤）
正極用導電助剤としては、正極活物質層１４の導電性を良好にするものであれば特に限定されず、公知の導電助剤を使用できる。例えば、黒鉛、カーボンブラック等の炭素系材料や、銅、ニッケル、ステンレス、鉄等の金属微粉、ＩＴＯ等の導電性酸化物が挙げられる。
(Conductive aid for positive electrode)
The conductive auxiliary agent for the positive electrode is not particularly limited as long as it improves the conductivity of the positive electrode
＜負極＞
（負極集電体）
負極集電体２２は、導電性の板材であればよく、例えば、銅等の金属薄板（金属箔）を用いることができる。
<Negative electrode>
(Negative electrode current collector)
The negative electrode
（負極活物質層）
負極活物質層２４は、負極活物質、負極用バインダー、および負極用導電助剤から主に構成されるものである。
(Negative electrode active material layer)
The negative electrode active material layer 24 is mainly composed of a negative electrode active material, a negative electrode binder, and a negative electrode conductive auxiliary agent.
（負極活物質）
負極活物質としては、リチウムイオンの吸蔵及び放出、リチウムイオンの脱離及び挿入（インターカレーション）を可逆的に進行させることが可能であれば特に限定されず、公知の電極活物質を使用できる。例えば、グラファイト、ハードカーボン等の炭素系材料、酸化シリコン（ＳｉＯｘ）、金属シリコン（Ｓｉ）等の珪素系材料、チタン酸リチウム（ＬＴＯ）等の金属酸化物、リチウム、スズ、亜鉛等の金属材料が挙げられる。
(Negative electrode active material)
The negative electrode active material is not particularly limited as long as it can reversibly proceed with the occlusion and release of lithium ions and the desorption and insertion (intercalation) of lithium ions, and a known electrode active material can be used. .. For example, carbon-based materials such as graphite and hard carbon , silicon-based materials such as silicon oxide (SiO x ) and metallic silicon (Si), metal oxides such as lithium titanate (LTO), and metals such as lithium, tin and zinc. Materials can be mentioned.
負極活物質として金属材料を用いない場合、負極活物質層２４は更に、負極用バインダーおよび負極用導電助剤を含んでいてもよい。 When no metal material is used as the negative electrode active material, the negative electrode active material layer 24 may further contain a negative electrode binder and a negative electrode conductive auxiliary agent.
（負極用バインダー）
負極用バインダーとしては特に限定は無く、上記で記載した正極用バインダーと同様のものを用いることができる。
(Binder for negative electrode)
The binder for the negative electrode is not particularly limited, and the same binder as the binder for the positive electrode described above can be used.
（負極用導電助剤）
負極用導電助剤としては特に限定は無く、上記で記載した正極用導電助剤と同様のものを用いることができる。
(Conductive auxiliary agent for negative electrode)
The conductive auxiliary agent for the negative electrode is not particularly limited, and the same conductive auxiliary agent for the positive electrode described above can be used.
＜電解液＞
本発明に係る電解液は、溶媒および電解質から主に構成されるものである。
<Electrolytic solution>
The electrolytic solution according to the present invention is mainly composed of a solvent and an electrolyte.
（溶媒）
上記溶媒としては、一般にリチウムイオン二次電池に用いられている溶媒を任意の割合で混合して使用することが出来る。例えば、エチレンカーボネート（ＥＣ）、プロピレンカーボネート（ＰＣ）、ブチレンカーボネート等の環状カーボネート化合物、ジエチルカーボネート（ＤＥＣ）、エチルメチルカーボネート（ＥＭＣ）、ジメチルカーボネート（ＤＭＣ）等の鎖状カーボネート化合物、γ−ブチロラクトン（ＧＢＬ）等の環状エステル化合物、プロピオン酸プロピル（ＰｒＰ）、プロピオン酸エチル（ＰｒＥ）、酢酸エチル等の鎖状エステル化合物が挙げられる。
(solvent)
As the solvent, a solvent generally used for a lithium ion secondary battery can be mixed and used at an arbitrary ratio. For example, cyclic carbonate compounds such as ethylene carbonate (EC), propylene carbonate (PC) and butylene carbonate, chain carbonate compounds such as diethyl carbonate (DEC), ethyl methyl carbonate (EMC) and dimethyl carbonate (DMC), γ-butyrolactone. Cyclic ester compounds such as (GBL), chain ester compounds such as propyl propionate (PrP), ethyl propionate (PrE), and ethyl acetate can be mentioned.
（電解質）
電解質は、リチウムイオン二次電池の電解質として用いられるリチウム塩であれば特に限定は無く、例えば、ＬｉＰＦ６、ＬｉＢＦ４、リチウムビスオキサレートボラート等の無機酸陰イオン塩、ＬｉＣＦ３ＳＯ３、（ＣＦ３ＳＯ２）２ＮＬｉ、（ＦＳＯ２）２ＮＬｉ等の有機酸陰イオン塩等を用いることができる。
(Electrolytes)
The electrolyte is not particularly limited as long as it is a lithium salt used as an electrolyte for a lithium ion secondary battery. For example, an inorganic acid anion salt such as LiPF 6 , LiBF 4 , or lithium bisoxalate boron, LiCF 3 SO 3 , Organic acid anionic salts such as (CF 3 SO 2 ) 2 NLi and (FSO 2 ) 2 NLi can be used.
以上、本発明に係る好適な実施形態について説明したが、本発明は上記実施形態に限定されるものではない。 Although the preferred embodiment of the present invention has been described above, the present invention is not limited to the above embodiment.
以下、実施例及び比較例に基づいて本発明をより具体的に説明するが、本発明は以下の実施例に限定されるものではない。 Hereinafter, the present invention will be described in more detail based on Examples and Comparative Examples, but the present invention is not limited to the following Examples.
［実施例１］
（化学式（１）で表される化合物の合成）
純水１Ｌに対し、シュウ酸１００ｍｍｏｌおよびエチレングリコール１０ｍｍｏｌを溶解させ、攪拌しながら１００℃で８時間還流を行った。溶液を冷却した後、水−ジエチルエーテルで分液を繰り返し、有機相を回収することでｎ＝２，Ｘ１＝Ｘ２＝Ｈ，Ｒ＝ＣＨ２−ＣＨ２である中間体を得た。この中間体５ｍｍｏｌを改めて純水１Ｌへ溶解させ、これに１０ｍｍｏｌの水酸化リチウムを加えて３０分攪拌した。この溶液を水−ジエチルエーテルで分液を繰り返し、水相を回収することでｎ＝２，Ｘ１＝Ｘ２＝Ｌｉ，Ｒ＝ＣＨ２−ＣＨ２である目的物を得た。
[Example 1]
(Synthesis of compound represented by chemical formula (1))
100 mmol of oxalic acid and 10 mmol of ethylene glycol were dissolved in 1 L of pure water, and the mixture was refluxed at 100 ° C. for 8 hours with stirring. After cooling the solution, water - diethyl ether repeating the separation was obtained by collecting the organic phase n = 2, X 1 = X 2 = H, the intermediates are R = CH 2 -CH 2. 5 mmol of this intermediate was dissolved again in 1 L of pure water, 10 mmol of lithium hydroxide was added thereto, and the mixture was stirred for 30 minutes. The solution of water - diethyl ether repeatedly separated, n by recovering the aqueous phase = 2, X 1 = X 2 = Li, to give the desired compound is R = CH 2 -CH 2.
（正極の作製）
正極活物質としてＬｉＣｏＯ２、導電助剤としてカーボンブラック、バインダーとしてＰＶＤＦを用いた。ＬｉＣｏＯ２：カーボンブラック：ＰＶＤＦ＝９０：５：５（質量部）の割合で混合し、この混合粉全体に対して、２．５×１０−３ｍｏｌ／ｇの濃度となるように、上記で作製した化学式（１）で表される化合物を添加した。これを、ハイブリッドミキサーを用いてＮ−メチル−２−ピロリドン（ＮＭＰ）に分散させることで、正極活物質層形成用のスラリーを調整した。このスラリーを、厚さ２０μｍのアルミニウム箔に塗布量１２．０ｍｇ／ｃｍ２となるように塗布し、１００℃で乾燥することで正極活物質層を形成した。その後、これをローラープレス機によって加圧成形し、正極を作製した。
(Preparation of positive electrode)
LiCoO 2 was used as the positive electrode active material, carbon black was used as the conductive auxiliary agent, and PVDF was used as the binder. LiCoO 2 : Carbon black: PVDF = 90: 5: 5 (parts by mass) was mixed, and the concentration was 2.5 × 10 -3 mol / g with respect to the entire mixed powder. The prepared compound represented by the chemical formula (1) was added. This was dispersed in N-methyl-2-pyrrolidone (NMP) using a hybrid mixer to prepare a slurry for forming a positive electrode active material layer. This slurry was applied to an aluminum foil having a thickness of 20 μm so as to have a coating amount of 12.0 mg / cm 2, and dried at 100 ° C. to form a positive electrode active material layer. Then, this was pressure-molded by a roller press to prepare a positive electrode.
（負極の作製）
負極活物質として黒鉛、導電助剤としてカーボンブラック、バインダーとしてＰＶＤＦを用いた。黒鉛：カーボンブラック：ＰＶＤＦ＝９０：５：５（質量部）の割合で混合し、ハイブリッドミキサーを用いてＮ−メチル−２−ピロリドン（ＮＭＰ）に分散させ、負極活物質層形成用のスラリーを調整した。このスラリーを、厚さ２０μｍの銅箔に塗布量８．０ｍｇ／ｃｍ２となるように塗布し、１００℃で乾燥することで負極活物質層を形成した。その後、これをローラープレス機によって加圧成形し、負極を作製した。
(Preparation of negative electrode)
Graphite was used as the negative electrode active material, carbon black was used as the conductive auxiliary agent, and PVDF was used as the binder. Graphite: carbon black: PVDF = 90: 5: 5 (parts by mass) was mixed and dispersed in N-methyl-2-pyrrolidone (NMP) using a hybrid mixer to prepare a slurry for forming the negative electrode active material layer. It was adjusted. This slurry was applied to a copper foil having a thickness of 20 μm so as to have a coating amount of 8.0 mg / cm 2, and dried at 100 ° C. to form a negative electrode active material layer. Then, this was pressure-molded by a roller press to prepare a negative electrode.
（電解液の作製）
溶媒としてエチレンカーボネート（ＥＣ）およびジエチルカーボネート（ＤＥＣ）、支持塩としてヘキサフルオロリン酸リチウム（ＬｉＰＦ６）を用いた。ＥＣ：ＤＥＣ＝５０：５０（体積部）となるように混合し、これに１．０ｍｏｌ／Ｌの濃度となるようにＬｉＰＦ６を溶解させ、電解液を作製した。
(Preparation of electrolytic solution)
Ethylene carbonate (EC) and diethyl carbonate (DEC) were used as the solvent, and lithium hexafluorophosphate (LiPF 6) was used as the supporting salt. The mixture was mixed so that EC: DEC = 50: 50 (volume part), and LiPF 6 was dissolved therein so as to have a concentration of 1.0 mol / L to prepare an electrolytic solution.
（評価用リチウムイオン二次電池の作製）
上記で作製した正極および負極を、ポリエチレンセパレータを介して順次積層した。この積層体にタブリードを超音波溶着した後、アルミラミネートパックで包装した。その後、上記で作製した電解液を注入し、真空シールすることで評価用リチウムイオン二次電池を作製した。
(Manufacturing of lithium-ion secondary battery for evaluation)
The positive electrode and the negative electrode prepared above were sequentially laminated via a polyethylene separator. The tab leads were ultrasonically welded to this laminate and then packaged in an aluminum laminate pack. Then, the electrolytic solution prepared above was injected and vacuum-sealed to prepare a lithium ion secondary battery for evaluation.
（初回充放電）
上記で作製した評価用リチウムイオン二次電池を、２５℃に設定した恒温槽内に入れ、北斗電工株式会社製の充放電試験装置で評価した。まず、電流値０．１Ｃの定電流充電で電池電圧が４．２Ｖとなるまで充電を行い、続けて、電流値０．１Ｃの定電流放電で電池電圧が２．８Ｖとなるまで放電を行った。なお、電流値「Ｘ」Ｃの充電とは、この電池を「１／Ｘ」時間で充電可能な電流値のことを示す。例えば、０．１Ｃは１／０．１時間で充電可能な電流値のことを示す。
(First charge / discharge)
The evaluation lithium ion secondary battery produced above was placed in a constant temperature bath set at 25 ° C. and evaluated with a charge / discharge test device manufactured by Hokuto Denko Co., Ltd. First, the battery is charged until the battery voltage reaches 4.2 V by constant current charging with a current value of 0.1 C, and then discharged until the battery voltage reaches 2.8 V by constant current discharge with a current value of 0.1 C. rice field. The charging of the current value "X" C means the current value at which the battery can be charged in the "1 / X" time. For example, 0.1C indicates a current value that can be charged in 1 / 0.1 hour.
（急速充電特性の測定）
上記と同じ装置を用い、まず、電流値０．１Ｃの定電流充電で電池電圧が４．２Ｖとなるまで充電を行い、０．１Ｃ充電容量を求め、電流値０．１Ｃの定電流放電で電池電圧が２．８Ｖとなるまで放電を行った。続けて、電流値１０Ｃの定電流充電で電池電圧が４．２Ｖとなるまで充電を行い、１０Ｃ充電容量を求め、電流値０．１Ｃの定電流放電で電池電圧が２．８Ｖとなるまで放電を行った。１０Ｃ充電容量維持率＝１０Ｃ充電容量／０．１Ｃ充電容量、と定義し、得られた値を表１に示した。この値が高いほど、急速充電特性に優れることを意味する。
(Measurement of quick charge characteristics)
Using the same device as above, first charge with constant current charging with a current value of 0.1C until the battery voltage reaches 4.2V, determine the 0.1C charging capacity, and with constant current discharge with a current value of 0.1C. The battery was discharged until the battery voltage reached 2.8 V. Subsequently, the battery is charged until the battery voltage reaches 4.2 V by constant current charging with a current value of 10 C, the 10 C charging capacity is obtained, and the battery is discharged until the battery voltage reaches 2.8 V by constant current discharge with a current value of 0.1 C. Was done. 10C charge capacity retention rate = 10C charge capacity / 0.1C charge capacity was defined, and the obtained values are shown in Table 1. The higher this value, the better the quick charging characteristics.
［実施例２］
正極の作製において、スラリーに添加した化学式（１）で表される化合物の量を表１に示した値に変更した。それ以外は実施例１と同様として、実施例２の評価用リチウムイオン二次電池を作製した。
[Example 2]
In the preparation of the positive electrode, the amount of the compound represented by the chemical formula (1) added to the slurry was changed to the value shown in Table 1. A lithium ion secondary battery for evaluation of Example 2 was produced in the same manner as in Example 1 except for the above.
［実施例３］
正極の作製において、スラリーに添加した化学式（１）で表される化合物の量を表１に示した値に変更した。それ以外は実施例１と同様として、実施例３の評価用リチウムイオン二次電池を作製した。
[Example 3]
In the preparation of the positive electrode, the amount of the compound represented by the chemical formula (1) added to the slurry was changed to the value shown in Table 1. A lithium ion secondary battery for evaluation of Example 3 was produced in the same manner as in Example 1 except for the above.
［実施例４］
正極の作製において、スラリーに添加した化学式（１）で表される化合物の量を表１に示した値に変更した。それ以外は実施例１と同様として、実施例４の評価用リチウムイオン二次電池を作製した。
[Example 4]
In the preparation of the positive electrode, the amount of the compound represented by the chemical formula (1) added to the slurry was changed to the value shown in Table 1. A lithium ion secondary battery for evaluation of Example 4 was produced in the same manner as in Example 1 except for the above.
［実施例５］
正極の作製において、スラリーに添加した化学式（１）で表される化合物の量を表１に示した値に変更した。それ以外は実施例１と同様として、実施例５の評価用リチウムイオン二次電池を作製した。
[Example 5]
In the preparation of the positive electrode, the amount of the compound represented by the chemical formula (1) added to the slurry was changed to the value shown in Table 1. A lithium ion secondary battery for evaluation of Example 5 was produced in the same manner as in Example 1 except for the above.
［実施例６］
正極の作製において、スラリーに添加した化学式（１）で表される化合物の量を表１に示した値に変更した。それ以外は実施例１と同様として、実施例６の評価用リチウムイオン二次電池を作製した。
[Example 6]
In the preparation of the positive electrode, the amount of the compound represented by the chemical formula (1) added to the slurry was changed to the value shown in Table 1. A lithium ion secondary battery for evaluation of Example 6 was produced in the same manner as in Example 1 except for the above.
［実施例７］
化学式（１）で表される化合物の合成において、中間体５ｍｍｏｌに対して、５ｍｍｏｌの水酸化リチウムを加えることで、ｎ＝２，Ｘ１＝Ｈ，Ｘ２＝Ｌｉ，Ｒ＝ＣＨ２−ＣＨ２と片側の水酸基のみリチウム化された化合物を得た。それ以外は実施例１と同様として、実施例７のリチウムイオン二次電池を作製した。
[Example 7]
In the synthesis of the compound represented by the chemical formula (1), by adding 5 mmol of lithium hydroxide to 5 mmol of the intermediate, n = 2, X 1 = H, X 2 = Li, R = CH 2-CH. A compound in which only 2 and the hydroxyl group on one side were lithium-ized was obtained. A lithium ion secondary battery of Example 7 was produced in the same manner as in Example 1 except for the above.
［実施例８］
化学式（１）で表される化合物の合成において、中間体をそのまま用いることで、ｎ＝２，Ｘ１＝Ｘ２＝Ｈ，Ｒ＝ＣＨ２−ＣＨ２の化合物を得た。それ以外は実施例１と同様として、実施例８のリチウムイオン二次電池を作製した。
[Example 8]
In the synthesis of the compounds of formula (1), by using the intermediate as to obtain n = 2, X 1 = X 2 = H, the compound of R = CH 2 -CH 2. A lithium ion secondary battery of Example 8 was produced in the same manner as in Example 1 except for the above.
［実施例９］
化学式（１）で表される化合物の合成において、エチレングリコールの代わりにメタンジオールを用いることで、ｎ＝２，Ｘ１＝Ｘ２＝Ｈ，Ｒ＝ＣＨ２の中間体を得た。それ以降の手順は実施例１と同様として、実施例９のリチウムイオン二次電池を作製した。
[Example 9]
By using methanediol instead of ethylene glycol in the synthesis of the compound represented by the chemical formula (1), an intermediate of n = 2, X 1 = X 2 = H, R = CH 2 was obtained. Subsequent procedures were the same as in Example 1, and the lithium ion secondary battery of Example 9 was produced.
［実施例１０］
化学式（１）で表される化合物の合成において、エチレングリコールの代わりにトリメチレングリコールを用いることで、ｎ＝２，Ｘ１＝Ｘ２＝Ｈ，Ｒ＝ＣＨ２−ＣＨ２−ＣＨ２の中間体を得た。それ以降の手順は実施例１と同様として、実施例１０のリチウムイオン二次電池を作製した。
[Example 10]
In the synthesis of the compounds of formula (1), by using trimethylene glycol instead of ethylene glycol, n = 2, X 1 = X 2 = H, the intermediate R = CH 2 -CH 2 -CH 2 I got a body. Subsequent procedures were the same as in Example 1, and the lithium ion secondary battery of Example 10 was produced.
［実施例１１］
化学式（１）で表される化合物の合成において、エチレングリコールの代わりにモノフルオロエチレングリコールを用いることで、ｎ＝２，Ｘ１＝Ｘ２＝Ｈ，Ｒ＝ＣＨ２−ＣＨＦの中間体を得た。それ以降の手順は実施例１と同様として、実施例１１のリチウムイオン二次電池を作製した。
[Example 11]
By using monofluoroethylene glycol instead of ethylene glycol in the synthesis of the compound represented by the chemical formula (1), an intermediate of n = 2, X 1 = X 2 = H, R = CH 2- CHF can be obtained. rice field. Subsequent procedures were the same as in Example 1, and the lithium ion secondary battery of Example 11 was produced.
［比較例１］
正極の作製において、化学式（１）で表される化合物を添加しなかった。それ以外は実施例１と同様として、比較例１の評価用リチウムイオン二次電池を作製した。
[Comparative Example 1]
In the preparation of the positive electrode, the compound represented by the chemical formula (1) was not added. A lithium ion secondary battery for evaluation of Comparative Example 1 was produced in the same manner as in Example 1 except for the above.
実施例２〜１１、および比較例１で作製した評価用リチウムイオン二次電池について、実施例１と同様に、急速充電特性の測定を行った。結果を表１に示す。 The quick charging characteristics of the evaluation lithium ion secondary batteries produced in Examples 2 to 11 and Comparative Example 1 were measured in the same manner as in Example 1. The results are shown in Table 1.
実施例１〜６はいずれも、正極に化学式（１）で表される化合物を添加しなかった比較例１に対し、急速充電特性が改善した。上記化合物が存在することで、正極活物質表面のリチウムイオンが強く配位され、溶媒和反応が速やかに進行したものと考えられる。また、添加量としては、２．５×１０−５ｍｏｌ／ｇ以上２．５×１０−２ｍｏｌ／ｇが最適であることが明らかとなった。 In each of Examples 1 to 6, the quick charging characteristics were improved as compared with Comparative Example 1 in which the compound represented by the chemical formula (1) was not added to the positive electrode. It is considered that the presence of the above compound strongly coordinated the lithium ions on the surface of the positive electrode active material, and the solvation reaction proceeded rapidly. Further, it was clarified that the optimum amount of addition is 2.5 × 10 −5 mol / g or more and 2.5 × 10 −2 mol / g.
Ｘ１およびＸ２を水素で置換した実施例７，８についても、急速充電特性が改善している。このことより、二つのシュウ酸残渣のカルボニル基が、本発明に係る改善効果を示すにあたって重要であることが示唆された。 The quick charging characteristics are also improved in Examples 7 and 8 in which X 1 and X 2 are replaced with hydrogen. This suggests that the carbonyl groups of the two oxalic acid residues are important in exhibiting the improving effect according to the present invention.
また、連結基Ｒの構造を変更した実施例９〜１１においても、急速充電特性が改善しており、このことからもシュウ酸残渣のカルボニル基が重要な役割を担うことが示唆された。 Further, in Examples 9 to 11 in which the structure of the linking group R was changed, the quick charging characteristics were also improved, suggesting that the carbonyl group of the oxalic acid residue plays an important role.
本発明により、急速充電特性に優れる正極、およびリチウムイオン二次電池を提供される。 INDUSTRIAL APPLICABILITY The present invention provides a positive electrode having excellent quick charging characteristics and a lithium ion secondary battery.
１０…正極、１２…正極集電体、１４…正極活物質層、１８…セパレータ、２０…負極、２２…負極集電体、２４…負極活物質層、３０…積層体、５０…ケース、６０，６２…リード、１００…リチウムイオン二次電池。 10 ... Positive electrode, 12 ... Positive electrode current collector, 14 ... Positive electrode active material layer, 18 ... Separator, 20 ... Negative electrode, 22 ... Negative electrode current collector, 24 ... Negative electrode active material layer, 30 ... Laminated body, 50 ... Case, 60 , 62 ... Reed, 100 ... Lithium ion secondary battery.
Claims (3)
前記正極活物質層は、化学式（１）で表される化合物を含むことを特徴とする、正極。
（Ｘ１およびＸ２はＨまたはＬｉであり、Ｒは炭素数が１〜３のアルキレン基またはハロゲン化アルキレン基を示す。）
The positive electrode active material layer is characterized by containing a compound represented by the chemical formula (1).
(X 1 and X 2 are H or Li, and R represents an alkylene group having 1 to 3 carbon atoms or a halogenated alkylene group.)
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JPH11265719A (en) * | 1998-03-17 | 1999-09-28 | Toshiba Corp | Lithium secondary battery |
| JP2004014472A (en) * | 2002-06-11 | 2004-01-15 | Sony Corp | Nonaqueous secondary battery |
| JP2004259680A (en) * | 2003-02-27 | 2004-09-16 | Sanyo Electric Co Ltd | Non-aqueous lithium secondary battery |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JPH11265719A (en) * | 1998-03-17 | 1999-09-28 | Toshiba Corp | Lithium secondary battery |
| JP2004014472A (en) * | 2002-06-11 | 2004-01-15 | Sony Corp | Nonaqueous secondary battery |
| JP2004259680A (en) * | 2003-02-27 | 2004-09-16 | Sanyo Electric Co Ltd | Non-aqueous lithium secondary battery |
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