JP2013131366A - Anode active material for metal ion battery - Google Patents
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Abstract
Description
本発明は、金属イオン電池用の負極活物質に関し、さらに詳しくはＭｇＨ２と炭素材料とを含有する電池の過電圧を低減し得る金属イオン電池用の負極活物質に関する。 The present invention relates to a negative electrode active material for a metal ion battery, and more particularly to a negative electrode active material for a metal ion battery that can reduce overvoltage of a battery containing MgH 2 and a carbon material.
近年、高電圧および高エネルギー密度を有する電池としてリチウム二次電池が実用化されている。リチウム二次電池の用途が広い分野に拡大していることおよび高性能の要求から、電池の更なる性能向上のために種々の研究が行われている。
例えば、負極についても種々の材料が検討され、炭素材料やアルミニウム合金等が実用電池の負極活物質として実用化されている。しかし、炭素材料は高容量を与え得ることから広く用いられているが、比重が小さいため電池内部での占有体積の割合が大きくなる。また、炭素材料については既にこれ以上の改善が困難なレベルにまで性能の向上が図られていることが知られている。このため、電池の性能向上には炭素材料やアルミニウム合金等以外の負極活物質による高容量化が不可欠であり、炭素以外の負極活物質についての検討がなされている。
In recent years, lithium secondary batteries have been put into practical use as batteries having high voltage and high energy density. Due to the expansion of the use of lithium secondary batteries in a wide range of fields and the demand for high performance, various studies have been conducted to further improve battery performance.
For example, various materials have been studied for the negative electrode, and carbon materials, aluminum alloys and the like have been put into practical use as negative electrode active materials for practical batteries. However, although carbon materials are widely used because they can provide high capacity, the ratio of occupied volume inside the battery increases because the specific gravity is small. Further, it is known that the performance of carbon materials has already been improved to a level where further improvement is difficult. For this reason, in order to improve the performance of the battery, it is indispensable to increase the capacity by using a negative electrode active material other than a carbon material or an aluminum alloy, and negative electrode active materials other than carbon have been studied.
リチウム電池に用いられる負極活物質として、金属水素化物（ＭＨＸ）であるコンバージョン系の負極活物質およびそれを用いた負極材料が知られている。
例えば、特許文献１には、リチウム以外の金属水素化物、例えばＭｇＨ２と導電性炭素材料とを含むリチウムイオン電池用の負極活物質が記載されており、具体例としてボールミルされたＭｇＨ２と導電性炭素材料であるバルカンとを混合して得た負極活物質が示されている。
As a negative electrode active material used for a lithium battery, a conversion-type negative electrode active material which is a metal hydride (MH X ) and a negative electrode material using the same are known.
For example, Patent Document 1 describes a negative electrode active material for a lithium ion battery including a metal hydride other than lithium, for example, MgH 2 and a conductive carbon material. As a specific example, a ball milled MgH 2 and a conductive material are disclosed. A negative electrode active material obtained by mixing a vulcanized carbon material is shown.
また、非特許文献１には、リチウム電池用の金属水素化物、例えばＭｇＨ２およびリチウムの以下に示すコンバージョン反応：
ＭｇＨ２＋２Ｌｉ＋＋２ｅ−→Ｍｇ＋２ＬｉＨ
が記載されており、具体例としてボールミルされたＭｇと微細化したＭＣＭＢとの混合物を水素化した後、ボールミル化して得た負極活物質が示されている。
Non-Patent Document 1 discloses the following conversion reaction of metal hydrides for lithium batteries, such as MgH 2 and lithium:
MgH 2 + 2Li + + 2e − → Mg + 2LiH
A negative electrode active material obtained by hydrogenating a mixture of ball milled Mg and refined MCMB and then ball milling is shown as a specific example.
しかし、上記公知技術に基づいて得られる負極活物質は、リチウムイオン電池に適用した場合に過電圧（理論電位−電極電位）が高く、急速充放電時の電池特性であるレート特性に問題がある。
従って、本発明の目的は、金属イオン電池の過電圧を低減し得る金属イオン電池用の負極活物質を提供することである。
However, the negative electrode active material obtained based on the above known technique has a high overvoltage (theoretical potential-electrode potential) when applied to a lithium ion battery, and has a problem in rate characteristics which are battery characteristics at the time of rapid charge / discharge.
Therefore, the objective of this invention is providing the negative electrode active material for metal ion batteries which can reduce the overvoltage of a metal ion battery.
このため、本発明者等は、前記のＭｇＨ２と導電性炭素とを含む金属イオン電池用の負極活物質を用いた金属イオン電池の過電圧を低減することを目的に検討を行った結果、金属イオン電池用の負極活物質による過電圧には負極活物質の粉末表面の特性が影響していることを見出しさらに検討を行った結果、本発明を完成した。
すなわち、本発明は、ＭｇＨ２と炭素材料とを含む粉末混合物からなる金属イオン電池用の負極活物質であって、前記粉末混合物の表面におけるＯとＭｇとの比（Ｏ／Ｍｇ原子比）が１．０５以下である、前記物質に関する。
本発明における粉末混合物の表面におけるＯとＭｇとの比（Ｏ／Ｍｇ、原子比）は、通常粉末混合物に対して深さ方向にＳｉＯ２基準で２ｎｍ／分の速度でアルゴンによりエッチング処理する間のＯおよびＭｇの濃度をＸＰＳ（X-ray Photoelectron Spectroscopy、Ｘ線光電子分光法）により測定して求められる値の最初の５分間の平均値として求められる値である。
For this reason, the present inventors have conducted studies for the purpose of reducing the overvoltage of the metal ion battery using the negative electrode active material for metal ion batteries containing MgH 2 and conductive carbon, and as a result, As a result of further finding out that the characteristics of the powder surface of the negative electrode active material had an influence on the overvoltage due to the negative electrode active material for the ion battery, the present invention was completed.
That is, the present invention is a negative electrode active material for a metal ion battery comprising a powder mixture containing MgH 2 and a carbon material, wherein the ratio of O and Mg (O / Mg atomic ratio) on the surface of the powder mixture is It relates to said substance which is 1.05 or less.
The ratio of O to Mg (O / Mg, atomic ratio) on the surface of the powder mixture in the present invention is usually determined by etching with argon at a rate of 2 nm / min on the basis of SiO 2 in the depth direction with respect to the powder mixture. This is a value obtained as an average value for the first 5 minutes of a value obtained by measuring the O and Mg concentrations in XPS (X-ray Photoelectron Spectroscopy, X-ray photoelectron spectroscopy).
本発明によれば、従来公知のＭｇＨ２と炭素材料とからなる負極活物質に比べて金属イオン電池の過電圧を低減し得る金属イオン電池用の負極活物質を得ることができる。 According to the present invention, it is possible to obtain a negative electrode active material for a metal ion batteries capable of reducing the overvoltage of the metal ion battery than the negative electrode active material comprising a conventional MgH 2 and a carbon material.
本発明においては、ＭｇＨ２と炭素材料とを含む粉末混合物からなり、粉末混合物に対して深さ方向にアルゴンでエッチング処理する５分間の平均値として求められる前記粉末混合物の表面におけるＯとＭｇとの比（Ｏ／Ｍｇ原子比）が１．０５以下である金属イオン電池用の負極活物質であることが必要であり、これによって電池の過電圧を低減化し得る。
本明細書において、過電圧とは、ＭｇＨ２負極活物質についての理論電圧と電極電位の差（過電圧＝理論電圧−電極電位）として求められる（但し、理論電圧＝０．５４Ｖ：Ｎａｔｕｒｅ ｍａｔｅｒｉａｌｓ ７、９１６（２００８）より）。
In the present invention, it is composed of a powder mixture containing MgH 2 and a carbon material, and O and Mg on the surface of the powder mixture obtained as an average value for 5 minutes when the powder mixture is etched with argon in the depth direction. The ratio (O / Mg atomic ratio) must be a negative electrode active material for a metal ion battery having a ratio of 1.05 or less, which can reduce the overvoltage of the battery.
In this specification, the overvoltage is obtained as a difference between the theoretical voltage and the electrode potential (overvoltage = theoretical voltage−electrode potential) for the MgH 2 negative electrode active material (however, the theoretical voltage = 0.54 V: Nature materials 7, 916). (From 2008)).
本発明の負極活物質により、電池の過電圧が低減される理論的な解明は十分にはなされていないが、次のように推定される。すなわち、従来は水素がヒドリド（Ｈ−）状態でＭｇＨ２内に存在しているので、金属イオン電池における金属イオン（例えば、Ｌｉ＋）と反応するためはＭｇＨ２の結晶内から外に出る必要があるが、ＭｇＨ２表面に形成された層を通過する必要があり、Ｏ２−がＨ−の移動を阻害すると考えられる。しかし、Ｏ／Ｍｇ原子比が１．０５以下であることによってＭｇＨ２と金属イオン、例えば、Ｌｉ＋との間で水素移動が容易になり、下記式
２Ｌｉ＋＋ＭｇＨ２＋２ｅ−→２ＬｉＨ＋Ｍｇ
で示されるコンバージョン反応が促進され、その結果、過電圧を低くすることが可能となると推定される。
Although the theoretical elucidation that the overvoltage of the battery is reduced by the negative electrode active material of the present invention has not been sufficiently made, it is presumed as follows. That is, conventionally, hydrogen is present in MgH 2 in a hydride (H − ) state, and therefore it is necessary to move out of the MgH 2 crystal in order to react with metal ions (for example, Li + ) in a metal ion battery. However, it is necessary to pass through a layer formed on the surface of MgH 2 , and it is considered that O 2− inhibits the movement of H − . However, when the O / Mg atomic ratio is 1.05 or less, hydrogen transfer between MgH 2 and a metal ion, for example, Li + is facilitated, and the following formula 2Li ++ MgH 2 + 2e − → 2LiH + Mg
It is presumed that the conversion reaction indicated by is promoted, and as a result, the overvoltage can be lowered.
本発明の負極活物質は、ＭｇＨ２と炭素材料とを含む粉末混合物からなり、粉末混合物に対して深さ方向にアルゴンでエッチング処理する５分間の平均値として求められる前記粉末混合物の表面におけるＯとＭｇとの比（Ｏ／Ｍｇ原子比）が１．０５以下、通常は０．７５以上１．０５以下である。 The negative electrode active material of the present invention is composed of a powder mixture containing MgH 2 and a carbon material, and O on the surface of the powder mixture obtained as an average value for 5 minutes by etching with argon in the depth direction of the powder mixture. The ratio of Mg to Mg (O / Mg atomic ratio) is 1.05 or less, usually 0.75 or more and 1.05 or less.
本発明の負極活物質は、好適には前記粉末混合物中のＭｇＨ２と炭素材料との割合（ＭｇＨ２：炭素材料）が、質量比で９９：１〜８０：２０、特に９５：５〜８５：１５の範囲であり得る。炭素材料の割合がＭｇＨ２と炭素材料との合計量１００質量部に対して１質量部を下回ると、十分な導電性を得ることが難しくなる場合があり、ＭｇＨ２と炭素材料との合計量１００質量部に対して２０質量部を越えると、電池性能の１つの放電容量が低下する等の問題が発生する場合がある。 In the negative electrode active material of the present invention, the ratio of MgH 2 to the carbon material (MgH 2 : carbon material) in the powder mixture is preferably 99: 1 to 80:20, particularly 95: 5 to 85 in mass ratio. : 15 range. When the proportion of the carbon material is less than 1 part by mass with respect to 100 parts by mass of the total amount of MgH 2 and the carbon material, it may be difficult to obtain sufficient conductivity, and the total amount of MgH 2 and the carbon material. When it exceeds 20 parts by mass with respect to 100 parts by mass, there may be a problem that one discharge capacity of the battery performance is lowered.
本発明の負極活物質は、好適にはＭｇＨ２と導電助剤としての炭素材料とを混合および微粉化して得ることができる。
前記の混合および微細化は、例えばメカニカルミリングにより行い得る。前記のメカニカルミリングは、ＭｇＨ２粒子と炭素材料粉末との原料を機械的エネルギーを付与しながら粉砕する方法であり、メカニカルミリングで微細化することにより原料に含まれる両材料の粒子が激しく接触し、単なる微細化（例えば、乳鉢を用いた微細化）に比べて格段に微細化される。また、メカニカルミリングで微細化することにより、炭素材料がＭｇＨ２粒子の表面に均一に分散され得る。
前記のメカニカルミリングとして、例えば、ボールミル、振動ミル、ターボミル、ディスクミル等を挙げることができ、特にボールミル、その中でも特に遊星型ボールミルが好適である。
The negative electrode active material of the present invention can be preferably obtained by mixing and pulverizing MgH 2 and a carbon material as a conductive additive.
Said mixing and refinement | miniaturization can be performed by mechanical milling, for example. The mechanical milling is a method in which the raw material of MgH 2 particles and carbon material powder is pulverized while applying mechanical energy, and the particles of both materials contained in the raw material are in intense contact with each other by refining by mechanical milling. , Compared to simple miniaturization (for example, miniaturization using a mortar). Moreover, the carbon material can be uniformly dispersed on the surface of the MgH 2 particles by miniaturization by mechanical milling.
Examples of the mechanical milling include a ball mill, a vibration mill, a turbo mill, and a disk mill. Particularly, a ball mill, among which a planetary ball mill is particularly preferable.
また、前記混合および微細化、特にメカニカルミリングの条件としては、例えば遊星型ボールミルにより負極活物質を製造する場合、ポット内に原料のＭｇＨ２と炭素材料と粉砕用ボールを加え、所定の回転数および時間で処理を行い得る。遊星型ボールミルを行う際の回転数としては例えば１００〜１０００ｒｐｍの範囲内、例えば２００〜６００ｒｐｍの範囲内であって、処理時間としては例えば２〜１０時間の範囲内であり得る。 In addition, as a condition of the mixing and refinement, particularly mechanical milling, for example, when producing a negative electrode active material by a planetary ball mill, raw material MgH 2 , a carbon material, and grinding balls are added to a pot, and a predetermined rotational speed is obtained. And processing can be done in time. The number of rotations when performing the planetary ball mill may be, for example, in the range of 100 to 1000 rpm, for example, in the range of 200 to 600 rpm, and the processing time may be in the range of, for example, 2 to 10 hours.
前記導電助剤としての炭素材料としては、水分を除く揮発分が０．７質量％以下であるものが好適である。前記の水分を除く揮発分は例えばＪＩＳ Ｋ６２２１により、るつぼの中に炭素材料を規定量入れ、９５０℃で７分間加熱した後の揮発減量を測定することによって求められる。
このような炭素材料として、アセチレンブラックあるいはケッチェンブラックが挙げられる。バルカンなどの炭素材料は、前記の水分を除く揮発分が０．７質量％より多いことが知られており好適ではない。
As the carbon material as the conductive assistant, those having a volatile content excluding moisture of 0.7% by mass or less are suitable. The volatile content excluding moisture is determined by, for example, measuring the loss of volatility after putting a specified amount of carbon material in a crucible and heating at 950 ° C. for 7 minutes according to JIS K6221.
Examples of such a carbon material include acetylene black and ketjen black. It is known that a carbon material such as Vulcan has a volatile content excluding the moisture described above of more than 0.7% by mass, and is not suitable.
前記のようにして得られる負極活物質は、好適には前記ＭｇＨ２の粒径が１００〜５００ｎｍの範囲であって、前記炭素材料の粒径が２０ｎｍ以下、例えば１〜１０ｎｍの範囲、例えば５〜１０ｎｍの範囲である。前記炭素材料の粒径が１０ｎｍ以下であることによって、負極活物質中のＭｇＨ２の割合が高くなり得て、このような負極活物質を用いた電池の特性が向上し得る。
前記のＭｇＨ２の粒径および炭素材料の粒径は、ＳＥＭ（走査型電子顕微鏡）によって求めることが出来る。
The negative electrode active material obtained as described above preferably has a MgH 2 particle size in the range of 100 to 500 nm, and the carbon material has a particle size of 20 nm or less, for example, 1 to 10 nm, for example, 5 It is in the range of -10 nm. When the particle size of the carbon material is 10 nm or less, the ratio of MgH 2 in the negative electrode active material can be increased, and the characteristics of a battery using such a negative electrode active material can be improved.
The particle diameter of the MgH 2 and the particle diameter of the carbon material can be obtained by SEM (scanning electron microscope).
前記のようにして得られるＭｇＨ２と炭素材料とを含む粉末混合物からなる金属イオン電池用の負極活物質から、一般的に用いられる導電助剤および／又はバインダーおよび必要であればさらに分散媒を組み合わせて、負極を作製し得る。
前記導電助剤としては、炭素材料、導電性高分子材料等が挙げられ、炭素材料が好適である。前記炭素材料としては、グラファイト、カーボンブラック、カーボンナノチューブ、カーボンナノファイバー、フラーレン等を単独で又は２種以上の組み合わせが挙げられ、好適には負極活物質の作製に用いられるもの、特にアセチレンブラックあるいはケッチェンブラックが挙げられる。
前記バインダーとしては、スチレンブタジエンゴム（ＳＢＲ）、ポリアクリレート、ポリフッ化ビニリデン（ＰＶｄＦ）等が挙げられる。
From a negative electrode active material for a metal ion battery comprising a powder mixture containing MgH 2 and a carbon material obtained as described above, a commonly used conductive additive and / or binder and, if necessary, further a dispersion medium In combination, a negative electrode can be produced.
Examples of the conductive aid include carbon materials and conductive polymer materials, and carbon materials are preferred. Examples of the carbon material include graphite, carbon black, carbon nanotube, carbon nanofiber, fullerene, etc., alone or in combination of two or more, preferably those used for the production of a negative electrode active material, particularly acetylene black or Ketjen black is an example.
Examples of the binder include styrene butadiene rubber (SBR), polyacrylate, polyvinylidene fluoride (PVdF), and the like.
また、前記の分散媒としては、アルコール、グリコール、セロソルブ、アミノアルコール、アミン、ケトン、カルボン酸アミド、リン酸アミド、スルホキシド、カルボン酸エステル、リン酸エステル、エーテル、ニトリル等が挙げられる。具体例としては、メチルアルコール、エチルアルコール、２−プロパノール、１−ブタノール、１，２−エタンジオール、１，２−プロパンジオール、１，３−プロパンジオール、１，４−ブタンジオール、ジエチレングリコール、２−メトキシエタノール、２−エトキシエタノール、２−アミノエタノール、アセトン、メチルエチルケトン、ホルムアミド、Ｎ−メチルホルムアミド、Ｎ，Ｎ−ジメチルホルムアミド、Ｎ−メチルアセトアミド、Ｎ，Ｎ−ジメチルホルムアミド、Ｎ−メチルアセトアミド、Ｎ，Ｎ−ジメチルアセトアミド、Ｎ−メチルプロピオンアミド、Ｎ−メチルピロリドン、ヘキサメチルリン酸トリアミド、ジメチルスルホキシド、スルホラン、アセトニトリル、プロピオニトリルが挙げられる。 Examples of the dispersion medium include alcohol, glycol, cellosolve, amino alcohol, amine, ketone, carboxylic acid amide, phosphoric acid amide, sulfoxide, carboxylic acid ester, phosphoric acid ester, ether, and nitrile. Specific examples include methyl alcohol, ethyl alcohol, 2-propanol, 1-butanol, 1,2-ethanediol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, diethylene glycol, 2 -Methoxyethanol, 2-ethoxyethanol, 2-aminoethanol, acetone, methyl ethyl ketone, formamide, N-methylformamide, N, N-dimethylformamide, N-methylacetamide, N, N-dimethylformamide, N-methylacetamide, N , N-dimethylacetamide, N-methylpropionamide, N-methylpyrrolidone, hexamethylphosphoric triamide, dimethyl sulfoxide, sulfolane, acetonitrile, propionitrile.
前記の負極中の総固形分に占めるバインダーの割合は、通常１質量％以上で２０質量％以下であることが好適である。
前記バインダーの割合が１質量％を下回ると、結着性が低下するため集電体から負極活物質や炭素材料等が脱離しやすくなる場合があり、２０質量％を越えると、ＭｇＨ２および導電助剤の割合が低下するため、電池性能の低下をもたらす可能性がある。
The proportion of the binder in the total solid content in the negative electrode is preferably 1% by mass or more and 20% by mass or less.
If the proportion of the binder is less than 1 mass%, there are cases where such a negative electrode active material and a carbon material from a current collector for binding property is lowered easily desorbed exceeds 20 wt%, MgH 2 and conductive Since the ratio of the auxiliary agent is lowered, there is a possibility that the battery performance is lowered.
本発明の前記負極活物質を用いて負極を得る方法として、負極活物質、導電助剤および／又はバインダーおよび必要であればさらに分散材を含むペースト又はこのペーストにさらに溶剤を加えたスラリーを負極集電体上に塗布した後、乾燥し、圧延（プレス）して、集電体上に負極活物質層を形成する塗布法が挙げられる。前記溶剤として、前記の分散媒として挙げたものが用いられ得る。 As a method for obtaining a negative electrode using the negative electrode active material of the present invention, a negative electrode active material, a conductive additive and / or a binder, and if necessary, a paste further containing a dispersing agent or a slurry obtained by further adding a solvent to this paste An application method may be mentioned in which a negative electrode active material layer is formed on a current collector by drying and rolling (pressing) after applying on the current collector. As the solvent, those mentioned as the dispersion medium can be used.
本発明の前記負極活物質を用いて得られた負極、他の構成材、例えば正極、セパレータおよび電解質を用いて金属イオン電池が構成され得る。
金属イオン電池としては、リチウム二次電池、ナトリウム二次電池、カリウム二次電池、マグネシウム二次電池、カルシウム二次電池など、好適にはリチウム二次電池、ナトリウム二次電池、カリウム二次電池、特にリチウム二次電池が挙げられる。
前記正極は、正極集電体およびその少なくとも一面に設けられた正極活物質層を有し得る。
前記正極集電体は、例えば、アルミニウム、ニッケル又はステンレスなどの金属材料によって構成されている。
A metal ion battery can be formed using a negative electrode obtained using the negative electrode active material of the present invention, other constituent materials such as a positive electrode, a separator and an electrolyte.
As the metal ion battery, lithium secondary battery, sodium secondary battery, potassium secondary battery, magnesium secondary battery, calcium secondary battery, etc., preferably lithium secondary battery, sodium secondary battery, potassium secondary battery, In particular, a lithium secondary battery can be mentioned.
The positive electrode may have a positive electrode current collector and a positive electrode active material layer provided on at least one surface thereof.
The positive electrode current collector is made of, for example, a metal material such as aluminum, nickel, or stainless steel.
前記正極活物質層としては、リチウム、リチウム酸化物、特にリチウムと遷移金属とを含む複合酸化物、リチウム硫化物、リチウムを含む層間化合物、リチウムリン酸化合物などの正極材料が含まれる。正極活物質層には高分子材料、例えば、ポリアニリン、ポリチオフェンや、導電剤、例えば、黒鉛、カーボンブラック、アセチレンブラック又はケッチェンブラック、カーボンナノチューブ、カーボンナノファイバー、フラーレン等を単独で又は２種以上を組み合わせた炭素材料が含まれていてもよい。 Examples of the positive electrode active material layer include positive electrode materials such as lithium, lithium oxide, in particular, a composite oxide containing lithium and a transition metal, lithium sulfide, an intercalation compound containing lithium, and a lithium phosphate compound. The positive electrode active material layer may be a polymer material such as polyaniline, polythiophene, or a conductive agent such as graphite, carbon black, acetylene black or ketjen black, carbon nanotube, carbon nanofiber, fullerene, etc. The carbon material which combined these may be contained.
前記セパレータとしては、ポリプロピレン（ＰＰ）、ポリエチレン（ＰＥ）などのポリオレフィン製の多孔質膜、セラミック製の多孔質膜が挙げられる。特に、多層構造、例えばＰＥ／ＰＰ／ＰＥの３層構造のポリオレフィン製の多孔質膜が好適に用いられる。 Examples of the separator include a porous film made of polyolefin such as polypropylene (PP) and polyethylene (PE), and a porous film made of ceramic. In particular, a porous film made of polyolefin having a multilayer structure, for example, a three-layer structure of PE / PP / PE is preferably used.
前記電解質としては電解液、ゲル状あるいは固体の電解質、好適には電解液が挙げられる。電解液は溶剤と電解質塩とを含んでいて、溶剤としては、エチレンカーボネート（ＥＣ）、プロピレンカーボネート、ジメチルカーボネート（ＤＭＣ）、ジエチルカーボネートおよびエチルメチルカーボネート（ＥＭＣ）が好適に挙げられる。その中でも、エチレンカーボネートあるいはプロピレンカーボネートなどの高粘度溶剤と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、エチルメチルカーボネートなどの低粘度溶剤の少なくとも１種又は２種以上とを混合した混合溶剤が好適である。この溶剤にはビニレンカーボネートやビニルエチレンカーボネートなどの不飽和結合を有する環状カーボネートや、ビス（フルオロメチル）カーボネートなどのハロゲンを有する環状カーボネートを含有させてもよい。 Examples of the electrolyte include an electrolytic solution, a gel-like or solid electrolyte, and preferably an electrolytic solution. The electrolytic solution contains a solvent and an electrolyte salt, and preferred examples of the solvent include ethylene carbonate (EC), propylene carbonate, dimethyl carbonate (DMC), diethyl carbonate, and ethyl methyl carbonate (EMC). Among them, a mixed solvent obtained by mixing a high-viscosity solvent such as ethylene carbonate or propylene carbonate and at least one or two or more low-viscosity solvents such as dimethyl carbonate, ethyl methyl carbonate, diethyl carbonate, or ethyl methyl carbonate is preferable. . This solvent may contain a cyclic carbonate having an unsaturated bond such as vinylene carbonate or vinylethylene carbonate, or a cyclic carbonate having a halogen such as bis (fluoromethyl) carbonate.
前記電解液には、一般的に電解質塩が支持塩として含有されている。この電解質塩としては、例えば、六フッ化リン酸リチウム（ＬｉＰＦ6 ）、四フッ化ホウ酸リチウム（ＬｉＢＦ4 ）、過塩素酸リチウム（ＬｉＣｌＯ4 ）、六フッ化ヒ酸リチウム（ＬｉＡｓＦ6 ）、ビス（ペンタフルオロエタンスルホニル）イミドリチウム（ＬｉＮ（Ｃ2 Ｆ5 ＳＯ2 ）2 ）、トリフルオロメタンスルホン酸リチウム（ＬｉＣＦ3 ＳＯ3 ）、ビス（トリフルオロメタンスルホニル）イミドリチウム（ＬｉＮ（ＣＦ3 ＳＯ2 ）2 ）、リチウムトリス（トリフルオロメタンスルホニル）メチド（ＬｉＣ（ＣＦ3 ＳＯ2 ）3 ）、塩化リチウム（ＬｉＣｌ）あるいは臭化リチウム（ＬｉＢｒ）など、好適には六フッ化リン酸リチウム（ＬｉＰＦ6 ）が挙げられる。 The electrolytic solution generally contains an electrolyte salt as a supporting salt. Examples of the electrolyte salt include lithium hexafluorophosphate (LiPF 6 ), lithium tetrafluoroborate (LiBF 4 ), lithium perchlorate (LiClO 4 ), lithium hexafluoroarsenate (LiAsF 6 ), Bis (pentafluoroethanesulfonyl) imidolithium (LiN (C 2 F 5 SO 2 ) 2 ), lithium trifluoromethanesulfonate (LiCF 3 SO 3 ), bis (trifluoromethanesulfonyl) imide lithium (LiN (CF 3 SO 2 ) 2 ), lithium tris (trifluoromethanesulfonyl) methide (LiC (CF 3 SO 2 ) 3 ), lithium chloride (LiCl) or lithium bromide (LiBr), preferably lithium hexafluorophosphate (LiPF 6 ) Can be mentioned.
前記ゲル状の電解質は、例えば正極および負極を作製し、これらに溶剤と電解質塩とを含む電解液を塗布した後に溶剤を揮発させて形成し得る。 The gel electrolyte can be formed, for example, by preparing a positive electrode and a negative electrode, applying an electrolytic solution containing a solvent and an electrolyte salt thereto, and then volatilizing the solvent.
前記正極活物質を用いて正極を得る方法としてはそれ自体公知の方法、例えば蒸着又はスパッタもしくはＣＶＤにより正極集電体、例えば銅箔上に正極活物質層を形成する方法が挙げられる。
または、前記正極活物質を用いて正極を得る方法として、前記正極活物質を含むペースト又はスラリーを正極集電体上に塗布した後、乾燥させて正極集電体上に正極活物質層を形成する塗布法が挙げられる。前記正極活物質を含むペースト又はこのペーストにさらに溶剤、例えば前記の負極作製用の溶剤を加えたスラリーを正極集電体上に塗布した後、乾燥し、プレスすることによって得ることができる。
また、本発明の負極活物質を用いて得られる負極、正極、セパレータおよび電解質を用いることによって、過電圧が低減された金属イオン電池を得ることが可能となる。
前記金属イオン電池としては任意の形状を有するものが挙げられる。
Examples of a method for obtaining a positive electrode using the positive electrode active material include a method known per se, for example, a method of forming a positive electrode active material layer on a positive electrode current collector, for example, a copper foil, by vapor deposition, sputtering, or CVD.
Alternatively, as a method of obtaining a positive electrode using the positive electrode active material, a paste or slurry containing the positive electrode active material is applied on a positive electrode current collector and then dried to form a positive electrode active material layer on the positive electrode current collector The coating method to do is mentioned. The paste containing the positive electrode active material or a slurry obtained by adding a solvent, for example, the above-mentioned negative electrode preparation solvent, to the paste is applied onto the positive electrode current collector, and then dried and pressed.
Further, by using a negative electrode, a positive electrode, a separator and an electrolyte obtained by using the negative electrode active material of the present invention, a metal ion battery with reduced overvoltage can be obtained.
Examples of the metal ion battery include those having an arbitrary shape.
以下、本発明の実施例を示す。
以下の実施例は単に説明するためのものであり、本発明を限定するものではない。
以下の各例において、粉末混合物の表面におけるＯとＭｇとの比（Ｏ／Ｍｇ、原子比）を、粉末混合物に対して深さ方向にＳｉＯ２基準で２ｎｍ／分の速度でアルゴンによりエッチング処理する間のＯおよびＭｇの濃度をＸＰＳ（X-ray Photoelectron Spectroscopy、Ｘ線光電子分光法）により測定した。なお、アルゴンによりエッチング処理する際の条件は下記の通りである。
アルゴンガスによるエッチングの条件：試料をステンレス台座の上に置き、常温で、試料の上方から試料にアルゴンガスに吹き付けてエッチィングを行った。
測定試料の量：０．０１〜０．１ｇ
Examples of the present invention will be described below.
The following examples are for illustrative purposes only and are not intended to limit the invention.
In each of the following examples, the O / Mg ratio (O / Mg, atomic ratio) on the surface of the powder mixture is etched with argon at a rate of 2 nm / min on the basis of SiO 2 in the depth direction with respect to the powder mixture. During this time, the concentrations of O and Mg were measured by XPS (X-ray Photoelectron Spectroscopy). The conditions for etching with argon are as follows.
Etching conditions with argon gas: A sample was placed on a stainless steel pedestal, and etching was performed by spraying argon gas onto the sample from above the sample at room temperature.
Amount of measurement sample: 0.01 to 0.1 g
実施例１
［負極活物質の調製］
ＭｇＨ２（活物質）とアセチレンブラック（電気化学工業社、水分を除く揮発分０．４質量％）とを質量比９０：１０の割合で、遊星ボールミル（Ｆｒｉｔｓｃｈ製、ＰｒｅｍｉｕｍＬｉｎｅ Ｐ−７）による混合および微細化処理を、アルゴン雰囲気、４００ｒｐｍ、５時間の処理条件で行って負極活物質を得た。
Example 1
[Preparation of negative electrode active material]
Mixing MgH 2 (active material) and acetylene black (Electrochemical Co., Ltd., 0.4% by mass of volatile matter excluding moisture) at a mass ratio of 90:10 using a planetary ball mill (made by Fritsch, PremiumLine P-7) And the refinement | miniaturization process was performed on argon atmosphere and the process conditions of 400 rpm and 5 hours, and the negative electrode active material was obtained.
［負極活物質の分析］
調製した負極活物質について、粉末混合物に対して深さ方向にアルゴンによりエッチング処理する間のＯおよびＭｇの濃度をＸＰＳ分析装置により測定した。
得られた結果を図２に示す。また、エッチング処理した最初の５分間の平均値のＯ／Ｍｇ（原子比）は０．８９であった。他の結果と比較して図１に示す。
得られた結果を図２に示す。
また、粉末混合物についてＳＥＭによりＭｇＨ２粒子および炭素材料の粒径の測定を行ったところ、ＭｇＨ２粒子の粒径は３００〜４００ｎｍ、炭素材料の粒径は５〜１０ｎｍであった。
［試験用負極作製］
調製した負極活物質、導電助剤としてのアセチレンブラックおよびバインダーとしてのＰＶｄＦパウダーを質量比で４５：４０：１５の割合で加え、分散材としてＮ−メチルピロリドンを用いて混練してスラリーを作製し、負極集電体として銅箔上に塗布し、乾燥、そして圧延して、膜厚１０μｍの電極を作製した。
[Analysis of negative electrode active material]
About the prepared negative electrode active material, the density | concentration of O and Mg was measured with the XPS analyzer during the etching process with argon in the depth direction with respect to the powder mixture.
The obtained results are shown in FIG. The average value of O / Mg (atomic ratio) for the first 5 minutes after the etching treatment was 0.89. It shows in FIG. 1 compared with another result.
The obtained results are shown in FIG.
Also was measured for the particle size of MgH 2 particles and the carbon material by SEM for powder mixtures, the particle size of MgH 2 particles 300 to 400 nm, the particle size of the carbon material was 5 to 10 nm.
[Preparation of test anode]
The prepared negative electrode active material, acetylene black as a conductive additive, and PVdF powder as a binder are added at a mass ratio of 45:40:15, and kneaded using N-methylpyrrolidone as a dispersing agent to prepare a slurry. Then, it was applied on a copper foil as a negative electrode current collector, dried and rolled to prepare an electrode having a thickness of 10 μm.
［電池の作製］
使用セル：ＣＲ２０３２型コインセル、試験極：塗工電極、対極：Ｌｉ金属箔、セパレータ：多孔質ポリオレフィン製セパレータ（ＰＥ／ＰＰ／ＰＥ）、電解液：ＥＣ（エチレンカーボネート）とＤＭＣ（ジメチルカーボネート）とＥＭＣ（エチルメチルカーボネート）とを体積比３：３：４で混合した混合溶剤に、支持塩としてＬｉＰＦ６を濃度１ｍｏｌ／Ｌで溶解した電解液で、電池を作製した。
[Production of battery]
Use cell: CR2032-type coin cell, test electrode: coated electrode, counter electrode: Li metal foil, separator: separator made of porous polyolefin (PE / PP / PE), electrolyte: EC (ethylene carbonate) and DMC (dimethyl carbonate) A battery was fabricated using an electrolytic solution obtained by dissolving LiPF 6 as a supporting salt in a concentration of 1 mol / L in a mixed solvent in which EMC (ethyl methyl carbonate) was mixed at a volume ratio of 3: 3: 4.
［電気化学特性評価］
電池評価環境温度２５℃、電流レート１／１０Ｃ、上下限電圧３．０Ｖ〜０．０１Ｖにて評価を行った。それぞれの充電量に対して規格化し、ＳＯＣとして横軸に表示した。得られた結果を他の結果とまとめて図５に示す。
また、電池評価によって得られた結果より、図５において今回の反応と考えられる部位（落ち込んだ後のふくらみ部分）での電極電位（測定された電位）と理論電位（０．５４Ｖ）との差から過電圧を算出したところ、過電圧は０．２３Ｖであった。他の結果と比較して図１に示す。
[Electrochemical characteristics evaluation]
Battery evaluation was evaluated at an environmental temperature of 25 ° C., a current rate of 1/10 C, and an upper and lower limit voltage of 3.0 V to 0.01 V. It normalized with respect to each charge amount, and displayed on the horizontal axis as SOC. The obtained results are shown together with other results in FIG.
Further, from the results obtained by the battery evaluation, the difference between the electrode potential (measured potential) and the theoretical potential (0.54 V) at the site considered to be the current reaction in FIG. From the above, the overvoltage was calculated to be 0.23V. It shows in FIG. 1 compared with another result.
実施例２
アセチレンブラックに代えてケッチェンブラック（ライオン社、水分を除く揮発分０．７質量％）を用いた他は実施例１と同様にして、負極活物質および試験用負極を得た。
負極活物質について、粉末混合物に対して深さ方向にＳｉＯ２基準で２ｎｍ／分の速度でアルゴンによりエッチング処理する間のＯおよびＭｇの濃度をＸＰＳ分析装置により測定した。結果を図３に示す。また、エッチング処理した最初の５分間の平均値のＯ／Ｍｇ（原子比）は１．０２であった。他の結果と比較して図１に示す。
また、粉末混合物についてＳＥＭによりＭｇＨ２粒子および炭素材料の粒径の測定を行ったところ、ＭｇＨ２粒子の粒径は３００〜４００ｎｍ、炭素材料の粒径は５〜１０ｎｍであった。
また、電気化学特性評価を行った結果を他の結果とまとめて図５に示す。
また、上記電池評価によって得られた結果より算出した過電圧は０．３６Ｖであった。他の結果と比較して図１に示す。
Example 2
A negative electrode active material and a test negative electrode were obtained in the same manner as in Example 1 except that ketjen black (Lion Corporation, volatile content excluding moisture 0.7 mass%) was used instead of acetylene black.
Regarding the negative electrode active material, the concentration of O and Mg was measured with an XPS analyzer during etching with argon at a rate of 2 nm / min on the basis of SiO 2 in the depth direction with respect to the powder mixture. The results are shown in FIG. The average value of O / Mg (atomic ratio) for the first 5 minutes after the etching treatment was 1.02. It shows in FIG. 1 compared with another result.
Also was measured for the particle size of MgH 2 particle and a carbon material by SEM for powder mixtures, the particle size of MgH 2 particle 300 to 400 nm, the particle size of the carbon material was 5 to 10 nm.
In addition, the results of electrochemical property evaluation are shown in FIG. 5 together with other results.
The overvoltage calculated from the results obtained by the battery evaluation was 0.36V. It shows in FIG. 1 compared with another result.
比較例１
アセチレンブラックに代えてＭＣＭＢ（大阪ガスケミカル社、水分を除く揮発分８．５質量％）を用いた他は実施例１と同様にして、負極活物質および試験用負極を得た。
負極活物質について、粉末混合物に対して深さ方向にＳｉＯ２基準で２ｎｍ／分の速度でアルゴンによりエッチング処理する間のＯおよびＭｇの濃度をＸＰＳ分析装置により測定した。結果を図４に示す。また、エッチング処理した最初の５分間の平均値のＯ／Ｍｇ（原子比）は１．１６であった。他の結果と比較して図１に示す。
また、粉末混合物についてＳＥＭによりＭｇＨ２粒子および炭素材料の粒径の測定を行ったところ、ＭｇＨ２粒子の粒径は３００〜４００ｎｍ、炭素材料の粒径は５〜１０ｎｍであった。
また、電気化学特性評価を行った結果を他の結果とまとめて図５に示す。
また、上記電池評価によって得られた結果より算出した過電圧は０．３７Ｖであった。他の結果と比較して図１に示す。
Comparative Example 1
A negative electrode active material and a test negative electrode were obtained in the same manner as in Example 1 except that MCMB (Osaka Gas Chemical Co., Ltd., volatile content excluding moisture 8.5% by mass) was used instead of acetylene black.
Regarding the negative electrode active material, the concentration of O and Mg was measured with an XPS analyzer during etching with argon at a rate of 2 nm / min on the basis of SiO 2 in the depth direction with respect to the powder mixture. The results are shown in FIG. The average O / Mg (atomic ratio) for the first 5 minutes after the etching treatment was 1.16. It shows in FIG. 1 compared with another result.
Also was measured for the particle size of MgH 2 particles and the carbon material by SEM for powder mixtures, the particle size of MgH 2 particles 300 to 400 nm, the particle size of the carbon material was 5 to 10 nm.
In addition, the results of electrochemical property evaluation are shown in FIG. 5 together with other results.
The overvoltage calculated from the results obtained by the battery evaluation was 0.37V. It shows in FIG. 1 compared with another result.
図１から、実施例１、実施例２、比較例１の順に過電圧が低い（過電圧：実施例１＜実施例２＜比較例１）ことが示され、Ｏ／Ｍｇが小さいほど電池の過電圧が減少していることが理解される。
また、図２〜４から、実施例１の負極活物質は表面でわずかに酸素が増えた後に深さ方向で一定化しておること、実施例２の負極活物質は表面でわずかに酸素が増えた後に深さ方向で一定化していて少し酸素量が多いこと、比較例１の負極活物質は一定化した状態と比較して表面での酸素量が多いことが示されている。
FIG. 1 shows that the overvoltage is low in the order of Example 1, Example 2, and Comparative Example 1 (overvoltage: Example 1 <Example 2 <Comparative Example 1). The smaller the O / Mg, the more the overvoltage of the battery. It is understood that it is decreasing.
2 to 4, the negative electrode active material of Example 1 is constant in the depth direction after a slight increase in oxygen on the surface, and the negative electrode active material of Example 2 has a slight increase in oxygen on the surface. After that, it is shown that the amount of oxygen is slightly increased after being constant in the depth direction, and that the amount of oxygen on the surface of the negative electrode active material of Comparative Example 1 is large compared to the state of being constant.
本発明によれば、従来公知のＭｇＨ２である負極活物質に比べて電池の過電圧を低減し得る金属イオン電池用の負極活物質を得ることができる。 According to the present invention, it is possible to obtain a negative electrode active material for a metal ion batteries capable of reducing the overvoltage of the battery than the negative electrode active material are known MgH 2.
Claims (7)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2011279517A JP2013131366A (en) | 2011-12-21 | 2011-12-21 | Anode active material for metal ion battery |
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