JP5031192B2 - Method for producing positive electrode active material for non-aqueous electrolyte sodium secondary battery - Google Patents
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Description
本発明は、非水電解質二次電池用の正極活物質に関する。 The present invention relates to a positive electrode active material for a non-aqueous electrolyte secondary battery.
ポータブル電子機器用の二次電池として、非水電解質リチウム二次電池が実用化されており、広く用いられている。しかし、その正極活物質としては、資源としての埋蔵量が少なく高価なＣｏの化合物であるＬｉＣｏＯ2が用いられており、資源として豊富な元素を主に含有する化合物からなる非水電解質二次電池用正極活物質が求められている。 As secondary batteries for portable electronic devices, non-aqueous electrolyte lithium secondary batteries have been put into practical use and are widely used. However, as the positive electrode active material, LiCoO 2 , which is an expensive Co compound with a small reserve as a resource, is used, and a non-aqueous electrolyte secondary battery comprising a compound mainly containing abundant elements as a resource There is a need for positive electrode active materials.
そこで、資源として豊富な元素である鉄とナトリウムとの複合酸化物であるＮａＦｅＯ2が非水電解質二次電池用の正極活物質として提案され、このものは、Ｎａ2Ｏ2とＦｅ3Ｏ4を混合して空気中において６００〜７００℃で焼成することにより得られることも知られている（例えば、非特許文献１参照。）。 Therefore, NaFeO 2 , which is a complex oxide of iron and sodium, which is an abundant element as a resource, has been proposed as a positive electrode active material for non-aqueous electrolyte secondary batteries, which is Na 2 O 2 and Fe 3 O 4. It is also known that it can be obtained by mixing and baking in air at 600 to 700 ° C. (see, for example, Non-Patent Document 1).
上記のＮａＦｅＯ2は、Ｘ線回折における面間隔２．２０Åのピーク強度を、面間隔５．３６Åのピーク強度で除した値が２．３であり、このものからなる正極活物質を用いてなる非水電解質二次電池は、放電電圧が放電とともに急速に低下するという問題点があった（例えば、非特許文献１参照。）。 The above-mentioned NaFeO 2 has a value obtained by dividing the peak intensity of 2.20 面 plane spacing in X-ray diffraction by the peak intensity of 5.36 面 plane spacing, using a positive electrode active material made of this. The non-aqueous electrolyte secondary battery has a problem that the discharge voltage decreases rapidly with discharge (for example, see Non-Patent Document 1).
そこで本発明の目的は、放電電圧が放電とともに急速に低下することのない非水電解質二次電池を与え、主に鉄とナトリウムとの複合酸化物からなる非水電解質二次電池用正極活物質およびその製造方法を提供することにある。 Accordingly, an object of the present invention is to provide a nonaqueous electrolyte secondary battery in which the discharge voltage does not rapidly decrease with discharge, and is mainly a positive electrode active material for a nonaqueous electrolyte secondary battery composed of a complex oxide of iron and sodium. And providing a manufacturing method thereof.
本発明者らは、主に鉄とナトリウムとを含有する複合酸化物からなる正極活物質について鋭意検討した結果、六方晶の結晶構造を有し、Ｘ線回折分析において特定の二つの回折ピークの強度比が一定の範囲である前記複合酸化物を正極活物質として用いることにより、放電電圧が放電とともに急速に低下することのない非水電解質二次電池が得られることを見出した。さらに、本発明者らは、そのような正極活物質が、主にナトリウム化合物と鉄化合物とを含有する金属化合物混合物を加熱するにあたり、一定温度未満での温度上昇中において特定の雰囲気中で加熱することにより得られることを見出し、本発明を完成するに到った。 As a result of intensive studies on a positive electrode active material mainly composed of a composite oxide containing iron and sodium, the present inventors have a hexagonal crystal structure, and have two specific diffraction peaks in X-ray diffraction analysis. It has been found that a nonaqueous electrolyte secondary battery in which the discharge voltage does not rapidly decrease with discharge can be obtained by using the composite oxide having a certain strength ratio as a positive electrode active material. Furthermore, the present inventors have heated such a positive electrode active material in a specific atmosphere during a temperature rise below a certain temperature when heating a metal compound mixture mainly containing a sodium compound and an iron compound. As a result, the inventors have found out that it can be obtained and have completed the present invention.
すなわち本発明は、主に鉄とナトリウムとを含有する複合酸化物であって、六方晶の結晶構造を有し、かつ該複合酸化物のＸ線回折分析において、面間隔２．２０Åのピークの強度を面間隔５．３６Åのピークの強度で除した値が２以下である複合酸化物からなることを特徴とする非水電解質二次電池用正極活物質を提供する。また本発明は、ナトリウム化合物と鉄化合物とを含有する金属化合物混合物を、４００℃以上９００℃以下の温度範囲で加熱するにあたり、温度上昇中の１００℃未満の温度範囲においては雰囲気を不活性雰囲気として加熱することを特徴とする非水電解質二次電池用正極活物質の製造方法を提供する。さらに本発明は、前記記載の非水電解質二次電池用正極活物質を含んでなることを特徴とする非水電解質ナトリウム二次電池を提供する。 That is, the present invention is a composite oxide mainly containing iron and sodium, has a hexagonal crystal structure, and has a peak with an interplanar spacing of 2.20 mm in X-ray diffraction analysis of the composite oxide. Provided is a positive electrode active material for a non-aqueous electrolyte secondary battery, characterized in that it comprises a composite oxide having a value obtained by dividing the strength by the peak strength with an interplanar spacing of 5.36 Å. Further, in the present invention, when a metal compound mixture containing a sodium compound and an iron compound is heated in a temperature range of 400 ° C. or more and 900 ° C. or less, the atmosphere is inert in the temperature range of less than 100 ° C. during the temperature increase. A method for producing a positive electrode active material for a non-aqueous electrolyte secondary battery is provided. Furthermore, the present invention provides a nonaqueous electrolyte sodium secondary battery comprising the positive electrode active material for a nonaqueous electrolyte secondary battery described above.
本発明の正極活物質を用いれば、放電電圧が放電とともに急速に低下することがなく、さらに放電平坦部の放電電圧が３Ｖ以上と高く、二次電池としての特性が優れた非水電解質二次電池を製造することができ、そして、本発明の製造方法によれば、本発明の正極活物質を製造することができるので、本発明は工業的に極めて有用である。 When the positive electrode active material of the present invention is used, the discharge voltage does not rapidly decrease with discharge, the discharge voltage of the flat discharge portion is as high as 3 V or more, and the nonaqueous electrolyte secondary battery has excellent characteristics as a secondary battery. Since the battery can be manufactured and the positive electrode active material of the present invention can be manufactured according to the manufacturing method of the present invention, the present invention is extremely useful industrially.
本発明の非水電解質二次電池用正極活物質は、主にナトリウムと鉄とを含有する複合酸化物からなる。
この複合酸化物としては、具体的には、式（１）
ＮａＦｅ1-xＭxＯ2 （１）
（ただし、Ｍは１種以上の３価金属である。）で示される化合物が挙げられる。
The positive electrode active material for a non-aqueous electrolyte secondary battery of the present invention is composed of a composite oxide mainly containing sodium and iron.
As this complex oxide, specifically, the formula (1)
NaFe 1-x M x O 2 (1)
(Wherein M is one or more trivalent metals).
ここで、Ｍとしては、Ａｌ、Ｇａ、Ｉｎ、Ｓｃ、Ｔｉ、Ｖ、Ｃｒ、Ｍｎ、Ｃｏ、Ｎｉ、Ｙ、Ｎｂ、Ｍｏ、Ｌａ、Ｃｅ、Ｐｒ、Ｎｄ、Ｓｍ、Ｅｕ、Ｇｄ、Ｔｂ、Ｄｙ、Ｈｏ、Ｅｒ、Ｔｍ、ＹｂおよびＬｕからなる群より選ばれる１種以上が挙げられ、これらのうち、放電電圧が高くなる傾向があるので、Ａｌ、Ｇａ、Ｖ、Ｍｎ、Ｃｏ、Ｎｉ、ＹおよびＬａからなる群より選ばれる１種以上が好ましく、資源的に埋蔵量が豊富であるＡｌ、ＭｎおよびＮｉからなる群より選ばれる１種以上が特に好ましい。ｘの値は六方晶の結晶構造が維持される０≦ｘ＜０．５の範囲で選ぶことができるが、放電容量が大きくなる傾向があるので、０≦ｘ≦０．１の範囲が好ましく、Ｍが含まれていないｘ＝０の場合が特に好ましい。なお、Ｆｅの係数の１−ｘが０．５より大きいので、式（１）で示される化合物は、主に鉄とナトリウムとを含有する複合酸化物である。 Here, as M, Al, Ga, In, Sc, Ti, V, Cr, Mn, Co, Ni, Y, Nb, Mo, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy , Ho, Er, Tm, Yb, and Lu. Among these, since the discharge voltage tends to increase, Al, Ga, V, Mn, Co, Ni, Y And at least one selected from the group consisting of La and La, and at least one selected from the group consisting of Al, Mn and Ni, which are rich in resources, are particularly preferable. The value of x can be selected in the range of 0 ≦ x <0.5 where the hexagonal crystal structure is maintained. However, since the discharge capacity tends to increase, the range of 0 ≦ x ≦ 0.1 is preferable. , M in which x = 0 is particularly preferable. In addition, since 1-x of the coefficient of Fe is larger than 0.5, the compound represented by the formula (1) is a complex oxide mainly containing iron and sodium.
そして、本発明において、この複合酸化物は、六方晶の結晶構造を有し、かつ該複合酸化物のＸ線回折分析において、面間隔２．２０Åのピークの強度を面間隔５．３６Åのピークの強度で除した値が２以下である。従来の複合酸化物ＮａＦｅＯ2は、面間隔２．２０Åのピークの強度を面間隔５．３６Åのピークの強度で除した値は２より大きく、例えば、特許文献１に記載されたＮａＦｅＯ2は、特許文献１のＸ線回折チャートから読み取れるように、面間隔２．２０Åのピークの強度を面間隔５．３６Åのピークの強度で除した値は２．３であった。
In the present invention, the composite oxide has a hexagonal crystal structure, and in the X-ray diffraction analysis of the composite oxide, the intensity of the peak with a plane spacing of 2.20 mm is the peak with a plane spacing of 5.36 mm. The value divided by the intensity is 2 or less. In the conventional composite oxide NaFeO 2 , the value obtained by dividing the intensity of the peak with an interplanar spacing of 2.20 で by the intensity of the peak with an interplanar spacing of 5.36 大 き く is greater than 2, for example, NaFeO 2 described in
これらの面間隔２．２０Åと面間隔５．３６Åの回折ピークは、それぞれα−ＮａＦｅＯ2型構造の（１０４）面および（００３）面のからの回折ピークに相当する。そして、この結晶格子の面間隔には、複合酸化物に含まれるＮａとＦｅ以外の金属元素により、および製造方法等により、若干の変動があり、２．２０Åのピークは±０．０２Åの幅で変動があるので面間隔は２．２０±０．０２Åであり、面間隔５．３６Åのピークは±０．０４Åの幅で変動があるので、面間隔は５．３６±０．０４Åである。この、２．２０±０．０２Åのピークの強度を面間隔５．３６±０．０４Åのピークの強度で除した値ｒが２以下となる場合に、理由は明らかではないが、この主に鉄とナトリウムとを含有する複合酸化物は、放電電圧が放電とともに急速に低下することのない非水電解質二次電池を与える非水電解質二次電池用正極活物質となる。ｒは１．７以下が好ましく１．５以下がさらに好ましい。 These diffraction peaks with a plane spacing of 2.20 mm and a plane spacing of 5.36 mm correspond to diffraction peaks from the (104) plane and (003) plane of the α-NaFeO 2 type structure, respectively. The interplanar spacing of this crystal lattice varies slightly depending on the metal elements other than Na and Fe contained in the composite oxide and the manufacturing method, and the 2.20Å peak has a width of ± 0.02Å. Since there is a fluctuation, the plane spacing is 2.20 ± 0.02 mm, and since the peak of the plane spacing 5.36 mm varies with a width of ± 0.04 mm, the plane spacing is 5.36 ± 0.04 mm. . When the value r obtained by dividing the intensity of the peak of 2.20 ± 0.02Å by the intensity of the peak having an interplanar spacing of 5.36 ± 0.04Å is 2 or less, the reason is not clear. The composite oxide containing iron and sodium becomes a positive electrode active material for a non-aqueous electrolyte secondary battery that gives a non-aqueous electrolyte secondary battery in which the discharge voltage does not rapidly decrease with discharge. r is preferably 1.7 or less, and more preferably 1.5 or less.
次に、本発明の正極活物質の製造方法について説明する。
本発明の正極活物質は、主にナトリウム化合物と鉄化合物とを含有する金属化合物混合物を、４００℃以上９００℃以下の温度範囲で加熱するにあたり、温度上昇中の１００℃未満の温度範囲においては雰囲気を不活性雰囲気として加熱することにより製造することができる。
Next, the manufacturing method of the positive electrode active material of this invention is demonstrated.
When the positive electrode active material of the present invention heats a metal compound mixture mainly containing a sodium compound and an iron compound in a temperature range of 400 ° C. or more and 900 ° C. or less, in a temperature range of less than 100 ° C. during temperature rise. It can be manufactured by heating the atmosphere as an inert atmosphere.
ナトリウム化合物、鉄化合物、式（１）のＭの化合物としては、酸化物、水酸化物、炭酸塩、硝酸塩、硫酸塩、酢酸塩、シュウ酸塩、ハロゲン化物等を用いることができ、ナトリウム化合物としてはＮａ2Ｏ2が特に好ましく、鉄化合物としてはＦｅ3Ｏ4が特に好ましい。 Sodium compounds, iron compounds, M compounds of formula (1) can be used oxides, hydroxides, carbonates, nitrates, sulfates, acetates, oxalates, halides, etc., sodium compounds Is particularly preferably Na 2 O 2 and the iron compound is particularly preferably Fe 3 O 4 .
主にナトリウム化合物と鉄化合物とを含有する金属化合物混合物は、金属化合物を所定のモル比となるように秤量し、乾式または湿式混合により混合して得ることができる。乾式混合が簡便であり好ましく、工業的に通常用いられる乳鉢、回転撹拌機、Ｖ型混合機、Ｗ型混合機、リボン混合機、ドラムミキサー、ボールミル等の装置により混合を行うことができる。 The metal compound mixture mainly containing a sodium compound and an iron compound can be obtained by weighing the metal compounds so as to have a predetermined molar ratio and mixing them by dry or wet mixing. Dry mixing is simple and preferable, and the mixing can be performed by an apparatus such as a mortar, a rotary stirrer, a V-type mixer, a W-type mixer, a ribbon mixer, a drum mixer, or a ball mill, which are usually used industrially.
得られた金属化合物混合物を加熱することにより、本発明の正極活物質を得ることができるが、この加熱において、温度上昇中の１００℃未満の温度では不活性雰囲気中で加熱する。不活性雰囲気としては、具体的には、アルゴン、ヘリウム、ネオン、窒素、二酸化炭素等が挙げられ、アルゴンと窒素が好ましい。この不活性雰囲気中には、１体積％程度までの酸素や水素は含有されてもよいが、水蒸気が多く混入すると、得られる正極活物質が、放電電圧が放電とともに急速に低下することのない非水電解質二次電池を与える正極活物質とはならないことがあり、本発明の製造方法における不活性雰囲気の露点は０℃以下が好ましい。なお、加熱温度に達した後、温度下降中の１００℃未満においては、不活性雰囲気を用いなくてもよい。 By heating the obtained metal compound mixture, the positive electrode active material of the present invention can be obtained. In this heating, heating is performed in an inert atmosphere at a temperature of less than 100 ° C. during the temperature increase. Specific examples of the inert atmosphere include argon, helium, neon, nitrogen, carbon dioxide and the like, and argon and nitrogen are preferable. In this inert atmosphere, oxygen and hydrogen up to about 1% by volume may be contained, but when a large amount of water vapor is mixed, the obtained positive electrode active material does not rapidly decrease with discharge. It may not be a positive electrode active material that gives a nonaqueous electrolyte secondary battery, and the dew point of the inert atmosphere in the production method of the present invention is preferably 0 ° C. or less. After reaching the heating temperature, the inert atmosphere may not be used at a temperature lower than 100 ° C. during the temperature decrease.
１００℃以上の温度においては、雰囲気は特に限定されず、上記不活性雰囲気；酸素を１体積％以上含有した不活性雰囲気や酸素等の酸化性雰囲気；水素および／または一酸化炭素を含有した不活性雰囲気、水素、一酸化炭素等の還元雰囲気のいずれでもよく、また、ハロゲンが含有されてもよい。好ましくは酸化性雰囲気であり、空気および酸素がより好ましい。 At a temperature of 100 ° C. or higher, the atmosphere is not particularly limited, and the above inert atmosphere; an inert atmosphere containing 1% by volume of oxygen or an oxidizing atmosphere such as oxygen; an inert atmosphere containing hydrogen and / or carbon monoxide. The atmosphere may be any of an active atmosphere, a reducing atmosphere such as hydrogen and carbon monoxide, and may contain a halogen. An oxidizing atmosphere is preferable, and air and oxygen are more preferable.
加熱温度は４００℃以上９００℃以下の温度範囲が好ましく、より好ましくは６００℃以上７６０℃以下の温度範囲であり、その温度範囲における保持時間は、通常は２時間から３０時間である。なお、混合物は、加熱の前にペレット状に圧縮成形してもよい。また、加熱温度に達するまでの温度上昇速度は、特に限定されるものではないが、通常、６００℃／時間以下である。また加熱後、室温に達するまでの温度下降速度は特に限定されるものではないが、通常、６００℃／時間以下である。温度下降速度が小さいと、放電容量が大きくなることもある。 The heating temperature is preferably in the temperature range of 400 ° C. or more and 900 ° C. or less, more preferably in the temperature range of 600 ° C. or more and 760 ° C. or less. The holding time in the temperature range is usually 2 hours to 30 hours. The mixture may be compression molded into a pellet before heating. Further, the rate of temperature rise until reaching the heating temperature is not particularly limited, but is usually 600 ° C./hour or less. Further, the rate of temperature decrease until it reaches room temperature after heating is not particularly limited, but is usually 600 ° C./hour or less. If the rate of temperature decrease is low, the discharge capacity may increase.
加熱に用いる炉は、雰囲気置換が可能であることが必要である。真空置換（炉内の雰囲気を真空ポンプを用いて排気した後、所定のガスを炉内に入れる操作のこと。）ができるものが好ましいが、例えば管状炉のように、雰囲気ガスを効率的に流通させられる形式のものであってもよい。 The furnace used for heating needs to be able to replace the atmosphere. It is preferable to be able to perform vacuum substitution (the operation of putting a predetermined gas into the furnace after exhausting the atmosphere in the furnace using a vacuum pump). It may be in a form that can be distributed.
また、加熱することにより得られる正極活物質を、振動ミル、ジェットミル、乾式ボールミル等の工業的に通常行われる公知の方法によって、所定の粒度に調整することができる。 Moreover, the positive electrode active material obtained by heating can be adjusted to a predetermined particle size by a publicly known method such as a vibration mill, a jet mill, or a dry ball mill.
次に、本発明の正極活物質を有してなる非水電解質ナトリウム二次電池について説明する。 Next, a nonaqueous electrolyte sodium secondary battery having the positive electrode active material of the present invention will be described.
ここで、従来のＮａＦｅＯ2からなる正極活物質を正極に用い、ナトリウムイオンを主な電荷担体とした非水電解質二次電池は、二次電池としての特性が十分ではないことが知られている。そのため、従来のＮａＦｅＯ2からなる正極活物質を正極に用いた非水電解質二次電池としては、過塩素酸リチウムを含有する非水電解質を用い、金属リチウムからなる負極を用いてなり、電荷担体がナトリウムイオンではなく主にリチウムイオンである非水電解質二次電池が提案されている（例えば、非特許文献１参照）。しかし、本発明者らは、本発明者が見出した本発明の正極活物質を用いて非水電解質ナトリウム二次電池を製造すると、驚くべきことに、その非水電解質ナトリウム二次電池は、放電電圧が放電とともに急速に低下することがなく、放電平坦部の放電電圧が３Ｖ以上と高く、高い特性を示す非水電解質二次電池となるのである。 Here, it is known that a non-aqueous electrolyte secondary battery using a conventional positive electrode active material made of NaFeO 2 as a positive electrode and using sodium ions as a main charge carrier does not have sufficient characteristics as a secondary battery. . Therefore, as a non-aqueous electrolyte secondary battery using a positive electrode active material made of conventional NaFeO 2 as a positive electrode, a non-aqueous electrolyte containing lithium perchlorate is used, and a negative electrode made of metallic lithium is used. A non-aqueous electrolyte secondary battery in which is not sodium ions but mainly lithium ions has been proposed (for example, see Non-Patent Document 1). However, when the present inventors manufactured a non-aqueous electrolyte sodium secondary battery using the positive electrode active material of the present invention found by the present inventors, surprisingly, the non-aqueous electrolyte sodium secondary battery was discharged. The voltage does not drop rapidly with the discharge, and the discharge voltage of the flat discharge portion is as high as 3 V or higher, resulting in a nonaqueous electrolyte secondary battery exhibiting high characteristics.
まず、本発明の正極活物質を有してなる本発明の非水電解質ナトリウム二次電池の正極は、本発明の正極活物質の他に、さらに導電材としての炭素質材料、バインダーなどを含む正極合剤を正極集電体に担持させて製造することができる。該炭素質材料としては、天然黒鉛、人造黒鉛、コークス類、カーボンブラックなどが挙げられる。導電材として、それぞれ単独で用いてもよいし、例えば人造黒鉛とカーボンブラックとを混合して用いてもよい。 First, the positive electrode of the nonaqueous electrolyte sodium secondary battery of the present invention having the positive electrode active material of the present invention further includes a carbonaceous material, a binder, etc. as a conductive material in addition to the positive electrode active material of the present invention. It can be produced by supporting the positive electrode mixture on the positive electrode current collector. Examples of the carbonaceous material include natural graphite, artificial graphite, cokes, and carbon black. As the conductive material, each may be used alone, for example, artificial graphite and carbon black may be mixed and used.
ここで、バインダーとしては通常は熱可塑性樹脂が用いられ、具体的には、ポリフッ化ビニリデン（以下、ＰＶＤＦということがある。）、ポリテトラフルオロエチレン（以下、ＰＴＦＥということがある。）、四フッ化エチレン・六フッ化プロピレン・フッ化ビニリデン系共重合体、六フッ化プロピレン・フッ化ビニリデン系共重合体、四フッ化エチレン・パーフルオロビニルエーテル系共重合体などが挙げられる。これらをそれぞれ単独で用いてもよいし、二種以上を混合して用いてもよい。 Here, a thermoplastic resin is usually used as the binder, and specifically, polyvinylidene fluoride (hereinafter sometimes referred to as PVDF), polytetrafluoroethylene (hereinafter sometimes referred to as PTFE), and four. Examples thereof include a fluorinated ethylene / hexafluoropropylene / vinylidene fluoride copolymer, a hexafluoropropylene / vinylidene fluoride copolymer, and a tetrafluoroethylene / perfluorovinyl ether copolymer. These may be used alone or in combination of two or more.
また、正極集電体としては、Ａｌ、Ｎｉ、ステンレスなどを用いることができるが、薄膜に加工しやすく、安価であるという点でＡｌが好ましい。正極集電体に正極合剤を担持させる方法としては、加圧成型する方法、または溶媒などを用いてペースト化し、正極集電体上に塗布し乾燥した後プレスするなどして固着する方法が挙げられる。また、必要に応じ、本発明の非水二次電池用活物質以外の活物質を正極に混合してもよい。 As the positive electrode current collector, Al, Ni, stainless steel, or the like can be used, but Al is preferable in that it is easily processed into a thin film and is inexpensive. As a method of supporting the positive electrode mixture on the positive electrode current collector, there is a method of pressure molding, or a method of fixing by pasting into a paste using a solvent, etc., applying to the positive electrode current collector, drying, and pressing. Can be mentioned. Moreover, you may mix active materials other than the active material for non-aqueous secondary batteries of this invention with a positive electrode as needed.
次に、本発明の非水電解質ナトリウム二次電池の負極としては、例えばナトリウム金属、ナトリウム合金またはナトリウムイオンをドープ・脱ドープ可能な材料などを用いることができる。ナトリウムイオンをドープ・脱ドープ可能な材料としては、炭素質材料、正極よりも低い電位でナトリウムイオンのドープ・脱ドープが行える酸化物、硫化物等のカルコゲン化合物、ホウ酸塩等が挙げられる。 Next, as the negative electrode of the non-aqueous electrolyte sodium secondary battery of the present invention, for example, sodium metal, a sodium alloy, or a material that can be doped / undoped with sodium ions can be used. Examples of materials that can be doped / undoped with sodium ions include carbonaceous materials, oxides that can be doped / undoped with sodium ions at a potential lower than that of the positive electrode, chalcogen compounds such as sulfides, borates, and the like.
ここで、必要に応じてバインダーとして熱可塑性樹脂を負極に加えることができる。熱可塑性樹脂としては、ＰＶＤＦ、ポリエチレン、ポリプロピレンなどが挙げられる。 Here, if necessary, a thermoplastic resin can be added to the negative electrode as a binder. Examples of the thermoplastic resin include PVDF, polyethylene, and polypropylene.
また、負極集電体としては、Ｃｕ、Ｎｉ、ステンレスなどを用いることができるが、特にナトリウムと合金を作り難く、かつ薄膜に加工しやすいという点でＣｕが好ましい。該負極集電体に負極活物質を含む合剤を担持させる方法としては、加圧成型する方法、または溶媒などを用いてペースト化し、負極集電体上に塗布し、乾燥した後プレスするなどして固着させる方法が挙げられる。 As the negative electrode current collector, Cu, Ni, stainless steel or the like can be used, and Cu is particularly preferable because it is difficult to make an alloy with sodium and it is easy to process into a thin film. As a method of supporting the mixture containing the negative electrode active material on the negative electrode current collector, a method of pressure molding, or pasting using a solvent or the like, coating on the negative electrode current collector, drying and pressing, etc. And fixing it.
次に、本発明の非水電解質ナトリウム二次電池で用いるセパレータとしては、例えば、ポリエチレン、ポリプロピレンなどのポリオレフィン樹脂、フッ素樹脂、ナイロン、芳香族アラミドなどの材質からなり多孔質膜、不織布、織布などの形態を有する材料を用いることができる。該セパレータの厚みは、通常は１０〜２００μｍ程度である。 Next, the separator used in the nonaqueous electrolyte sodium secondary battery of the present invention is made of a material such as polyolefin resin such as polyethylene or polypropylene, fluororesin, nylon, aromatic aramid, etc. A material having such a form can be used. The thickness of the separator is usually about 10 to 200 μm.
次に、本発明の非水電解質ナトリウム二次電池で用いる非水電解質に用いる溶媒としては、例えばプロピレンカーボネート、エチレンカーボネート、ビニレンカーボネート、ジ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、４−トリフルオロメチル−１，３−ジオキソラン−２−オン、１，２−ジ（メトキシカルボニルオキシ）エタンなどのカーボネート類；１，２−ジメトキシエタン、１，３−ジメトキシプロパン、ペンタフルオロプロピルメチルエーテル、２，２，３，３−テトラフルオロプロピルジフルオロメチルエーテル、テトラヒドロフラン、２−メチルテトラヒドロフランなどのエーテル類；ギ酸メチル、酢酸メチル、γ−ブチロラクトンなどのエステル類；アセトニトリル、ブチロニトリルなどのニトリル類；Ｎ，Ｎ−ジメチルホルムアミド、Ｎ，Ｎ−ジメチルアセトアミドなどのアミド類；３−メチル−２−オキサゾリドンなどのカーバメート類；スルホラン、ジメチルスルホキシド、１，３−プロパンサルトン、エチレンサルファイト、プロピレンサルファイト、ジメチルサルファイト、ジエチルサルファイトなどの含硫黄化合物、または上記の有機溶媒にさらにフッ素置換基を導入したものを用いることができるが、通常はこれらのうちの二種以上を混合して用いる。中でもカーボネート類を含む混合溶媒が好ましく、環状カーボネートと非環状カーボネート、または環状カーボネートとエーテル類の混合溶媒がさらに好ましい。 Next, as a solvent used for the nonaqueous electrolyte used in the nonaqueous electrolyte sodium secondary battery of the present invention, for example, propylene carbonate, ethylene carbonate, vinylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, 4-trifluoromethyl- Carbonates such as 1,3-dioxolan-2-one and 1,2-di (methoxycarbonyloxy) ethane; 1,2-dimethoxyethane, 1,3-dimethoxypropane, pentafluoropropyl methyl ether, 2,2, Ethers such as 3,3-tetrafluoropropyldifluoromethyl ether, tetrahydrofuran, 2-methyltetrahydrofuran; esters such as methyl formate, methyl acetate, γ-butyrolactone; acetonitrile, butyronitrile, etc. Toryls; amides such as N, N-dimethylformamide and N, N-dimethylacetamide; carbamates such as 3-methyl-2-oxazolidone; sulfolane, dimethyl sulfoxide, 1,3-propane sultone, ethylene sulfite, Sulfur-containing compounds such as propylene sulfite, dimethyl sulfite and diethyl sulfite, or those obtained by further introducing a fluorine substituent into the above organic solvent can be used, but usually two or more of these are mixed. Use. Among these, a mixed solvent containing carbonates is preferable, and a mixed solvent of cyclic carbonate and acyclic carbonate or cyclic carbonate and ether is more preferable.
ここで、環状カーボネートと非環状カーボネートの混合溶媒としては、動作温度範囲が広く、負荷特性に優れるという点で、エチレンカーボネート、ジメチルカーボネートおよびエチルメチルカーボネートを含む混合溶媒が好ましい。 Here, the mixed solvent of cyclic carbonate and acyclic carbonate is preferably a mixed solvent containing ethylene carbonate, dimethyl carbonate and ethyl methyl carbonate in that the operating temperature range is wide and the load characteristics are excellent.
なお、非水電解質として固体電解質を用いてもよく、固体電解質としては、例えばポリエチレンオキサイド系の高分子化合物、ポリオルガノシロキサン鎖もしくはポリオキシアルキレン鎖の少なくとも一種以上を含む高分子化合物などからなる電解質を用いることができる。また、高分子に非水電解質溶液を保持させた、いわゆるゲルタイプのものを用いることもできる。また、無機化合物からなる電解質を用いると、安全性を高めることができることがある。 A solid electrolyte may be used as the non-aqueous electrolyte. Examples of the solid electrolyte include an electrolyte made of a polyethylene oxide polymer compound, a polymer compound containing at least one polyorganosiloxane chain or polyoxyalkylene chain, and the like. Can be used. Moreover, what is called a gel type which hold | maintained the nonaqueous electrolyte solution in the polymer | macromolecule can also be used. In addition, when an electrolyte made of an inorganic compound is used, safety may be improved.
次に、本発明の非水二次電池の形状は特に限定されず、ペーパー型、コイン型、円筒型、角型などのいずれであってもよい。
また、外装として負極または正極端子を兼ねる金属製ハードケースを用いずに、アルミニウムを含む積層シート等からなる袋状パッケージを用いてもよい。
Next, the shape of the non-aqueous secondary battery of the present invention is not particularly limited, and may be any of a paper type, a coin type, a cylindrical type, and a square type.
Moreover, you may use the bag-shaped package which consists of a laminated sheet etc. which contain aluminum, without using the metal hard case which serves as a negative electrode or a positive electrode terminal as an exterior.
このようにして、本発明の正極活物質を用いて製造された非水電解質ナトリウム二次電池は、従来の二次電池としての特性の良くない非水電解質ナトリウム二次電池とは異なり、放電電圧が放電とともに急速に低下することのない非水電解質二次電池となる。 In this way, the non-aqueous electrolyte sodium secondary battery manufactured using the positive electrode active material of the present invention is different from the non-aqueous electrolyte sodium secondary battery having poor characteristics as a conventional secondary battery. Becomes a non-aqueous electrolyte secondary battery that does not rapidly decrease with discharge.
また、本発明の正極活物質を用いて製造された非水電解質ナトリウム二次電池は、放電平坦部の放電電圧も高い。放電平坦部は、放電曲線において、放電開始後に放電初期の電圧低下を過ぎ、電圧が放電の進行とともに大きくは変化しない部分である。ここで、放電平坦部の放電電圧は、正極の面積を基準として０．１ｍＡ／ｃｍ2以下の電流密度で放電した際の電圧（電流密度が大き過ぎると低く測定されることがある。）であり、例えば、次のような条件で測定することができる。
電解液：プロピレンカーボネート（以下、ＰＣということがある。）にＮａＣｌＯ4を１モル／リットルとなるように溶かしたもの（以下、１Ｍ ＮａＣｌＯ4／ＰＣと表すことがある。）
負極：金属ナトリウム
放電電流密度：０．１ｍＡ／ｃｍ2
この放電平坦部の放電電圧が、本発明の正極活物質を用いて製造された非水電解質ナトリウム二次電池においては、３．０Ｖ以上となる。
Moreover, the nonaqueous electrolyte sodium secondary battery manufactured using the positive electrode active material of the present invention also has a high discharge voltage at the discharge flat portion. The discharge flat portion is a portion in the discharge curve that has passed a voltage drop in the initial stage of discharge after the start of discharge and the voltage does not change greatly as the discharge progresses. Here, the discharge voltage of the flat discharge portion is a voltage when discharged at a current density of 0.1 mA / cm 2 or less with respect to the area of the positive electrode (may be measured as low if the current density is too high). Yes, for example, it can be measured under the following conditions.
Electrolytic solution: a solution obtained by dissolving NaClO 4 in propylene carbonate (hereinafter sometimes referred to as PC) so as to be 1 mol / liter (hereinafter sometimes referred to as 1M NaClO 4 / PC).
Negative electrode: Sodium metal Discharge current density: 0.1 mA / cm 2
In the non-aqueous electrolyte sodium secondary battery manufactured using the positive electrode active material of the present invention, the discharge voltage at the flat discharge portion is 3.0 V or higher.
さらに、本発明の正極活物質を用いて製造された非水電解質ナトリウム二次電池は、高い放電容量と優れたサイクル特性（充放電を繰り返しても放電電圧の低下が少ないこと。）を示す。 Furthermore, the nonaqueous electrolyte sodium secondary battery manufactured using the positive electrode active material of the present invention exhibits a high discharge capacity and excellent cycle characteristics (a decrease in discharge voltage is small even after repeated charge and discharge).
以下、本発明を実施例によりさらに詳細に説明するが、本発明はこれらによって何ら限定されるものではない。なお、特に断らない限り、充放電試験用の電極と試験電池の作製、粉末Ｘ線回折測定は下記の方法により実施した。 EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited at all by these. In addition, unless otherwise indicated, the production of electrodes for charge / discharge tests and test batteries, and powder X-ray diffraction measurement were performed by the following methods.
（１）充放電試験用の試験電池の作製
正極活物質と導電材のアセチレンブラック（電気化学工業株式会社製、５０％プレス品）、バインダーのＰＴＦＥ（ダイキン工業株式会社製、Ｐｏｌｙｆｌｏｎ ＴＦＥ Ｆ−２０１Ｌ（商品名））を、活物質：導電材：バインダー＝７０：２５：５（重量比）の組成となるように秤量し、まず活物質と導電材をメノウ乳鉢で十分に混合した後、バインダーを加えて引き続き均一になるように混合したものを均一な厚みの正方形になるように成形し、直径１．５ｃｍのコルクボーラーでくり抜いて円形ペレットとした。該ペレットを正極集電体となるチタンエクスパンドメタルに乗せ、メノウ乳棒で軽く押さえた後、ハンドプレスにて十分に圧着し、正極ペレットを得た。
(1) Preparation of test battery for charge / discharge test Positive electrode active material and conductive material acetylene black (manufactured by Denki Kagaku Kogyo Co., Ltd., 50% press product), binder PTFE (Daikin Kogyo Co., Ltd., Polyflon TFE F-201L) (Trade name)) was weighed so that the composition of active material: conductive material: binder = 70: 25: 5 (weight ratio) was obtained, and the active material and conductive material were first thoroughly mixed in an agate mortar, Then, the mixture was mixed so as to be uniform, and formed into a square having a uniform thickness, which was cut out with a cork borer having a diameter of 1.5 cm to obtain a circular pellet. The pellet was placed on a titanium expanded metal serving as a positive electrode current collector, lightly pressed with an agate pestle, and then sufficiently pressed by a hand press to obtain a positive electrode pellet.
ＨＳセル（宝泉株式会社製）の下側パーツの窪みに、チタンメッシュを下に向けて正極ペレットを置き、電解液として１Ｍ ＮａＣｌＯ4／ＰＣ（富山薬品工業株式会社製、導電率５．４２ｍＳ／ｃｍ）、２枚のポリプロピレン多孔質膜（セルガード株式会社製、セルガード３５０１（商品名））の間にグラスフィルター（東洋濾紙株式会社製、ＧＡ−１００（商品名））をはさんだものをセパレータとし、また金属ナトリウム（和光純薬工業株式会社製）を負極とし、それらを組み合わせて試験電池を作製した。なお、試験電池の組み立てはアルゴン雰囲気のグローブボックス内で行った。 In the lower part of the HS cell (manufactured by Hosen Co., Ltd.), a positive electrode pellet is placed with the titanium mesh facing down, and 1M NaClO 4 / PC (manufactured by Toyama Pharmaceutical Co., Ltd., conductivity: 5.42 mS) is used as the electrolyte. / Cm) A separator in which a glass filter (manufactured by Toyo Roshi Kaisha, Ltd., GA-100 (trade name)) is sandwiched between two polypropylene porous membranes (manufactured by Celgard, Celgard 3501 (trade name)) In addition, metallic sodium (manufactured by Wako Pure Chemical Industries, Ltd.) was used as the negative electrode, and these were combined to produce a test battery. The test battery was assembled in a glove box in an argon atmosphere.
（２）粉末Ｘ線回折測定
測定は、株式会社リガク製ＲＩＮＴ２１００ＨＬＲ／ＰＣ型を使用し、以下の条件で行った。
Ｘ線 ：ＣｕＫα
電圧−電流 ：５０ｋＶ−３００ｍＡ
測定角度範囲：２θ＝１０〜８０°
ステップ ：０．０１°
スキャンスピード：２°／分
(2) Powder X-ray diffraction measurement The measurement was performed using the RINT2100HLR / PC type manufactured by Rigaku Corporation under the following conditions.
X-ray: CuKα
Voltage-current: 50 kV-300 mA
Measurement angle range: 2θ = 10-80 °
Step: 0.01 °
Scanning speed: 2 ° / min
実施例１
（１）正極活物質の合成
アルゴン雰囲気のグローブボッックス内で、Ｎａ2Ｏ2（Ｆｌｕｋａ Ｃｈｅｍｉｅ ＡＧ製）とＦｅ3Ｏ4（Ａｌｄｒｉｃｈ Ｃｈｅｍｉｃａｌ Ｃｏｍｐａｎｙ，Ｉｎｃ．製）をＮａとＦｅがＮａＦｅＯ2の化学量論比となるように秤取した後、メノウ乳鉢でよく混合した。得られた混合物をアルミナ製ルツボにいれ、あらかじめ真空ポンプで雰囲気を排気した後にアルゴンを導入して置換したグローブボックスに連結された電気炉に入れて、炉内の雰囲気をアルゴンにして昇温を開始した。１００℃に達する直前に電気炉内を空気中に開放し、その後は空気雰囲気で加熱を行い、６５０℃で１２時間保持し、取り出すことで、非水電解質ナトリウム二次電池用正極活物質Ｅ１を得た。Ｅ１の粉末Ｘ線回折測定結果を図１に示した。Ｅ１は六方晶の結晶構造を有しており、２．２０Åのピーク強度を面間隔５．３６Åのピーク強度で除した値は１．５であった。
Example 1
(1) Synthesis of positive electrode active material In a glove box in an argon atmosphere, Na 2 O 2 (manufactured by Fluka Chemie AG) and Fe 3 O 4 (manufactured by Aldrich Chemical Company, Inc.) were mixed with NaFeFe of NaFeO 2 . After weighing to a stoichiometric ratio, the mixture was mixed well in an agate mortar. The obtained mixture is put in an alumina crucible, and after evacuating the atmosphere with a vacuum pump in advance, it is put into an electric furnace connected to a glove box replaced with argon, and the atmosphere in the furnace is increased to argon. Started. Immediately before reaching 100 ° C., the inside of the electric furnace is opened to the air, and thereafter heated in an air atmosphere, held at 650 ° C. for 12 hours, and taken out to obtain the positive electrode active material E1 for a non-aqueous electrolyte sodium secondary battery. Obtained. The powder X-ray diffraction measurement result of E1 is shown in FIG. E1 has a hexagonal crystal structure, and the value obtained by dividing the peak intensity of 2.20Å by the peak intensity of 5.36Å between the planes was 1.5.
（２）ナトリウム二次電池の正極活物質とした場合の充放電性能評価
Ｅ１を用いて試験電池を作製し、以下の条件で定電流充放電試験を実施した。
電流密度：０．１ｍＡ／ｃｍ2
走査電位範囲：１．５Ｖ−３．５Ｖ
得られた充放電曲線を図２に示した。約０．３６Ｎａの充電後、約０．３Ｎａの放電に対応する、３．３Ｖ（ｖｓ．Ｎａ／Ｎａ+）の放電平坦部が確認された。
(2) Evaluation of charge / discharge performance when used as positive electrode active material of sodium secondary battery A test battery was prepared using E1, and a constant current charge / discharge test was performed under the following conditions.
Current density: 0.1 mA / cm 2
Scanning potential range: 1.5V-3.5V
The obtained charge / discharge curve is shown in FIG. After charging of about 0.36 Na, a discharge flat portion of 3.3 V (vs. Na / Na + ) corresponding to about 0.3 Na discharge was confirmed.
実施例２
（１）正極活物質の合成
アルゴン雰囲気のグローブボッックス内で、Ｎａ2Ｏ2（Ｆｌｕｋａ Ｃｈｅｍｉｅ ＡＧ製）とＦｅ3Ｏ4（Ａｌｄｒｉｃｈ Ｃｈｅｍｉｃａｌ Ｃｏｍｐａｎｙ，Ｉｎｃ．製）をＮａとＦｅがＮａＦｅＯ2の化学量論比となるように秤取した後、メノウ乳鉢でよく混合した。得られた混合物をアルミナ製ルツボにいれ、あらかじめ真空ポンプで雰囲気を排気した後にアルゴンを導入して置換したグローブボックスに連結された電気炉に入れて、炉内の雰囲気をアルゴンにして昇温を開始した。１００℃に達する直前に電気炉内を空気中に開放し、その後は空気雰囲気で加熱を行い、６５０℃で１２時間保持後、室温まで温度下降速度３０℃／時間で降温し、電気炉から取り出すことで、非水電解質ナトリウム二次電池用正極活物質Ｅ２を得た。Ｅ２は六方晶の結晶構造を有しており、２．２０Åのピーク強度を面間隔５．３６Åのピーク強度で除した値は１．３であった。
Example 2
(1) Synthesis of positive electrode active material In a glove box in an argon atmosphere, Na 2 O 2 (manufactured by Fluka Chemie AG) and Fe 3 O 4 (manufactured by Aldrich Chemical Company, Inc.) were mixed with NaFeFe of NaFeO 2 . After weighing to a stoichiometric ratio, the mixture was mixed well in an agate mortar. The obtained mixture is put in an alumina crucible, and after evacuating the atmosphere with a vacuum pump in advance, it is put into an electric furnace connected to a glove box replaced with argon, and the atmosphere in the furnace is increased to argon. Started. Just before reaching 100 ° C, the inside of the electric furnace is opened to the air, and then heated in an air atmosphere. After holding at 650 ° C for 12 hours, the temperature is lowered to room temperature at a rate of temperature drop of 30 ° C / hour and taken out from the electric furnace. Thus, a positive electrode active material E2 for a non-aqueous electrolyte sodium secondary battery was obtained. E2 has a hexagonal crystal structure, and the value obtained by dividing the peak intensity of 2.20% by the peak intensity of the interplanar spacing of 5.36% was 1.3.
（２）ナトリウム二次電池の正極活物質とした場合の充放電性能評価
Ｅ２を用いて試験電池を作製し、以下の条件で定電流充放電試験を実施した。
電流密度：０．２ｍＡ／ｃｍ2
走査電位範囲：１．５Ｖ−３．６Ｖ
約０．４４Ｎａの充電後、約０．３４Ｎａの放電に対応する、３．２Ｖ（ｖｓ．Ｎａ／Ｎａ+）の放電平坦部が確認された。
(2) Evaluation of charge / discharge performance when used as positive electrode active material of sodium secondary battery A test battery was prepared using E2, and a constant current charge / discharge test was performed under the following conditions.
Current density: 0.2 mA / cm 2
Scanning potential range: 1.5V-3.6V
After charging of about 0.44 Na, a discharge flat portion of 3.2 V (vs. Na / Na + ) corresponding to about 0.34 Na discharge was confirmed.
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| JP5085032B2 (en) * | 2004-11-26 | 2012-11-28 | 国立大学法人九州大学 | Cathode active material for non-aqueous electrolyte secondary battery |
| EP1826845A4 (en) | 2004-11-26 | 2010-12-15 | Sumitomo Chemical Co | Positive electrode active material for nonaqueous electrolyte secondary battery |
| JP5100069B2 (en) * | 2006-09-15 | 2012-12-19 | 三洋電機株式会社 | Non-aqueous electrolyte secondary battery and manufacturing method thereof |
| JP2009135092A (en) | 2007-11-09 | 2009-06-18 | Sumitomo Chemical Co Ltd | Compound metal oxide and sodium secondary battery |
| JP2009259601A (en) * | 2008-04-16 | 2009-11-05 | Sumitomo Chemical Co Ltd | Electrode active material for sodium ion secondary battery and its method for manufacturing |
| JP5493301B2 (en) * | 2008-06-30 | 2014-05-14 | 住友化学株式会社 | Sodium secondary battery |
| WO2010002012A1 (en) * | 2008-06-30 | 2010-01-07 | 住友化学株式会社 | Sodium secondary battery |
| JP2010080424A (en) | 2008-08-27 | 2010-04-08 | Sumitomo Chemical Co Ltd | Electrode active material and method for manufacturing the same |
| JP5375580B2 (en) * | 2008-12-18 | 2013-12-25 | 株式会社エクォス・リサーチ | Electrolyte for sodium ion battery |
| JP5625390B2 (en) | 2009-03-13 | 2014-11-19 | 住友化学株式会社 | Composite metal oxide, electrode and sodium secondary battery |
| WO2011129419A1 (en) * | 2010-04-16 | 2011-10-20 | 住友化学株式会社 | Composite metal oxide, positive electrode active material, positive electrode, and sodium secondary battery |
| WO2012032956A1 (en) * | 2010-09-07 | 2012-03-15 | 住友化学株式会社 | Battery assembly |
| JP2013203565A (en) * | 2012-03-27 | 2013-10-07 | Tokyo Univ Of Science | Complex metal oxide, positive electrode active material for sodium secondary battery, positive electrode for sodium secondary battery, and sodium secondary battery |
| JP6083556B2 (en) * | 2012-10-24 | 2017-02-22 | 国立研究開発法人産業技術総合研究所 | Cathode active material for sodium ion secondary battery |
| JP6427921B2 (en) | 2013-06-28 | 2018-11-28 | 日亜化学工業株式会社 | Cathode active material for non-aqueous secondary battery and method for producing the same |
| US20170187039A1 (en) | 2014-02-12 | 2017-06-29 | Industry-University Cooperation Foundation Hanyang University | Positive electrode active material for sodium secondary battery, and method for preparing same |
| JP6466074B2 (en) * | 2014-03-13 | 2019-02-06 | 国立研究開発法人産業技術総合研究所 | Cathode active material for sodium ion secondary battery |
| JP6383188B2 (en) * | 2014-06-16 | 2018-08-29 | 国立大学法人埼玉大学 | Method for producing α-sodium ferrites |
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| JP3439082B2 (en) * | 1997-07-16 | 2003-08-25 | 三洋電機株式会社 | Non-aqueous electrolyte secondary battery |
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