JP2012193088A - Method for manufacturing positive electrode active material for lithium-ion battery - Google Patents
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本発明は、リチウムイオン電池用正極活物質の製造法に関する。 The present invention relates to a method for producing a positive electrode active material for a lithium ion battery.
リチウムイオン電池は、非水電解質電池の１種であり、携帯電話、デジタルカメラ、ノートＰＣ、ハイブリッド自動車、電気自動車等広い分野に利用されている。リチウムイオン電池は、正極材料としてリチウム金属酸化物を用い、負極材料としてグラファイトなどの炭素材を用いるものが主流となっている。 Lithium ion batteries are a type of non-aqueous electrolyte battery and are used in a wide range of fields such as mobile phones, digital cameras, notebook PCs, hybrid cars, and electric cars. Lithium ion batteries mainly use lithium metal oxide as a positive electrode material and a carbon material such as graphite as a negative electrode material.
この正極材料としては、コバルト酸リチウム（ＬｉＣｏＯ2）、マンガン酸リチウム（ＬｉＭｎＯ2）、リン酸鉄リチウム（ＬｉＦｅＰＯ4）、ケイ酸鉄リチウム（Ｌｉ2ＦｅＳｉＯ4）等が知られている。このうち、ＬｉＦｅＰＯ4やＬｉ2ＦｅＳｉＯ4等は、オリビン構造を有し、高容量のリチウムイオン電池用正極材料として有用である。 As this positive electrode material, lithium cobaltate (LiCoO 2 ), lithium manganate (LiMnO 2 ), lithium iron phosphate (LiFePO 4 ), lithium iron silicate (Li 2 FeSiO 4 ) and the like are known. Among these, LiFePO 4 and Li 2 FeSiO 4 have an olivine structure and are useful as a positive electrode material for a high capacity lithium ion battery.
Ｌｉ2ＦｅＳｉＯ4等のケイ酸鉄リチウム系正極材料の製造法としては、Ｌｉ源、鉄源及びケイ酸源の混合物を粉砕し、５００〜９００℃で焼成するという固相法が一般的である（特許文献１、２）。しかし、固相法では、不活性ガス雰囲気での焼成と粉砕を行う必要があり、複雑な操作が必要であるとともに、粒径や結晶度を制御することが困難である。
これに対し、非特許文献１及び２には、Ｌｉ2Ｍｎ1-yＦｅyＳｉＯ4（ｙ＝０〜１）を水熱合成で得られる旨の記載がある。
As a method for producing a lithium iron silicate-based positive electrode material such as Li 2 FeSiO 4, a solid phase method in which a mixture of a Li source, an iron source and a silicate source is pulverized and fired at 500 to 900 ° C. is common. (Patent Documents 1 and 2). However, in the solid phase method, it is necessary to perform firing and pulverization in an inert gas atmosphere, which requires complicated operations and it is difficult to control the particle size and crystallinity.
In contrast, Non-Patent Documents 1 and 2 have a description that Li 2 Mn 1-y Fe y SiO 4 (y = 0 to 1) can be obtained by hydrothermal synthesis.
しかしながら、リチウム源、鉄源及びシリケート源の３者を水に混合し、その混合液をそのまま水熱反応に付してもＬｉ2ＦｅＳｉＯ4の単一相は得られず、Ｆｅ3Ｓｉ2Ｏ4（ＯＨ）4等が副生することが判明した。
また、非特許文献２にいては、Ｆｅ源としてＦｅＣｌ2を用いており、反応装置の腐食等の問題がある。
従って、本発明の課題は、原料として塩化物を使用することなく、水熱反応により、リチウムイオン電池用正極活物質として有用なＬｉ2ＦｅＳｉＯ4等のオリビン型シリケート化合物を製造する方法を提供することにある。
However, even if a lithium source, an iron source, and a silicate source are mixed with water and the mixture is subjected to a hydrothermal reaction as it is, a single phase of Li 2 FeSiO 4 cannot be obtained, and Fe 3 Si 2 O 4 (OH) 4 etc. were found to be by-produced.
In Non-Patent Document 2, FeCl 2 is used as the Fe source, which causes problems such as corrosion of the reactor.
Accordingly, an object of the present invention is to provide a method for producing an olivine-type silicate compound such as Li 2 FeSiO 4 useful as a positive electrode active material for a lithium ion battery by a hydrothermal reaction without using chloride as a raw material. There is.
そこで本発明者は、Ｆｅ源等の遷移金属源として有機酸遷移金属塩を採用し、当該有機酸遷移金属塩と、リチウム源と、ケイ酸源とを塩基性水分散液としておき、次いで水熱反応を行えば、副反応が生じることなく、純度の高い粒径の小さい均一なオリビン型シリケート化合物が得られることを見出した。さらに、得られたオリビン型シリケート化合物をカーボン担持して焼成して得られた材料を正極材料として用いたリチウムイオン電池は優れた電池特性を有することを見出した。 Therefore, the present inventor employs an organic acid transition metal salt as a transition metal source such as an Fe source, leaves the organic acid transition metal salt, a lithium source, and a silicic acid source as a basic aqueous dispersion, It has been found that if the thermal reaction is carried out, a uniform olivine-type silicate compound having a high purity and a small particle size can be obtained without causing side reactions. Furthermore, it has been found that a lithium ion battery using as a positive electrode material a material obtained by carrying and baking the obtained olivine-type silicate compound on carbon has excellent battery characteristics.
すなわち、本発明は、リチウム化合物、ケイ酸化合物及び（Ｒ）2Ｍ（式中、Ｒは有機酸残基を示し、ＭはＦｅ、Ｎｉ、Ｃｏ又はＭｎを示す）で表される有機酸遷移金属塩を含有する塩基性水分散液を水熱反応させることを特徴とする、Ｌｉ2ＭＳｉＯ4（式中、ＭはＦｅ、Ｎｉ、Ｃｏ及びＭｎから選ばれる１種又は２種以上を示す）で表されるオリビン型シリケート化合物の製造法を提供するものである。 That is, the present invention provides an organic acid transition represented by a lithium compound, a silicate compound, and (R) 2 M (wherein R represents an organic acid residue and M represents Fe, Ni, Co, or Mn). Li 2 MSiO 4 (wherein M represents one or more selected from Fe, Ni, Co, and Mn), characterized in that a basic aqueous dispersion containing a metal salt is hydrothermally reacted. The manufacturing method of the olivine type | mold silicate compound represented by these is provided.
また、本発明は、上記の水熱反応で得られたオリビン型シリケート化合物にカーボン担持し、次いで焼成することを特徴とする、Ｌｉ2ＭＳｉＯ4（Ｍは前記と同じ）で表されるオリビン型シリケート化合物を含有するリチウムイオン電池用正極活物質の製造法を提供するものである。 The present invention also relates to an olivine type represented by Li 2 MSiO 4 (M is the same as described above), wherein carbon is supported on the olivine type silicate compound obtained by the above hydrothermal reaction, and then calcined. The present invention provides a method for producing a positive electrode active material for a lithium ion battery containing a silicate compound.
さらに本発明は、上記の正極活物質を含む正極を有するリチウムイオン電池を提供するものである。 Furthermore, this invention provides the lithium ion battery which has a positive electrode containing said positive electrode active material.
本発明方法によれば、水熱反応により微細なオリビン型シリケート化合物が高純度で効率良く得られる。得られたオリビン型シリケート化合物を用いれば、優れた電池特性を有するリチウムイオン電池が得られる。 According to the method of the present invention, a fine olivine-type silicate compound can be efficiently obtained with high purity by a hydrothermal reaction. By using the obtained olivine type silicate compound, a lithium ion battery having excellent battery characteristics can be obtained.
本発明は、Ｌｉ2ＭＳｉＯ4（式中、ＭはＦｅ、Ｎｉ、Ｃｏ又はＭｎから選ばれる１種又は２種以上を示す）で表されるオリビン型シリケート化合物の製造法である。当該オリビン型シリケート化合物の具体例としては、Ｌｉ2ＦｅＳｉＯ4、Ｌｉ2ＮｉＳｉＯ4、Ｌｉ2ＣｏＳｉＯ4、Ｌｉ2ＭｎＳｉＯ4、Ｌｉ2（Ｆｅ）m（Ｍｎ）1-mＳｉＯ4（０＜ｍ＜１である）等が挙げられる。このうち、原料コストの点からＬｉ2ＦｅＳｉＯ4、Ｌｉ2ＭｎＳｉＯ4が好ましく、Ｌｉ2ＦｅＳｉＯ4が特に好ましい。 The present invention is a method for producing an olivine type silicate compound represented by Li 2 MSiO 4 (wherein M represents one or more selected from Fe, Ni, Co, or Mn). Specific examples of the olivine silicate compound include Li 2 FeSiO 4 , Li 2 NiSiO 4 , Li 2 CoSiO 4 , Li 2 MnSiO 4 , Li 2 (Fe) m (Mn) 1-m SiO 4 (0 <m < 1). Among these, Li 2 FeSiO 4 and Li 2 MnSiO 4 are preferable from the viewpoint of raw material cost, and Li 2 FeSiO 4 is particularly preferable.
本発明に用いられるリチウム化合物としては、水酸化リチウム（例えばＬｉＯＨ・Ｈ2Ｏ）、炭酸リチウム（Ｌｉ2ＣＯ3）、硫酸リチウム、酢酸リチウムが挙げられるが、水酸化リチウム、炭酸リチウムが特に好ましい。 Examples of the lithium compound used in the present invention include lithium hydroxide (for example, LiOH.H 2 O), lithium carbonate (Li 2 CO 3 ), lithium sulfate, and lithium acetate, and lithium hydroxide and lithium carbonate are particularly preferable. .
ケイ酸化合物としては、反応性のあるシリカ化合物であれば特に限定されず、非晶質シリカ、Ｎａ4ＳｉＯ4（例えばＮａ4ＳｉＯ4・Ｈ2Ｏ）が好ましい。このうちＮａ4ＳｉＯ4を用いた場合、水分散液が塩基性になるので、より好ましい。 The silicic acid compound is not particularly limited as long as it is a reactive silica compound, and amorphous silica and Na 4 SiO 4 (for example, Na 4 SiO 4 .H 2 O) are preferable. Of these, the use of Na 4 SiO 4 is more preferable because the aqueous dispersion becomes basic.
本発明においては、遷移金属（Ｍ）源として、有機酸遷移金属塩（（Ｒ）2Ｍ）を用いて水熱反応を行う点に特徴がある。通常、有機酸塩は固相法に用いられる原料であり、水熱反応に用いることにより副反応が抑制できることは全く予想外であった。遷移金属としては前記と同じものが用いられる。Ｒで示される有機酸としては、炭素数１〜２０の有機酸が好ましく、炭素数２〜１２の有機酸がより好ましい。より具体的な有機酸としては、シュウ酸、フマル酸等のジカルボン酸、乳酸等のヒドロキシカルボン酸、酢酸等の脂肪酸が挙げられる。 The present invention is characterized in that a hydrothermal reaction is performed using an organic acid transition metal salt ((R) 2 M) as a transition metal (M) source. Usually, an organic acid salt is a raw material used in a solid phase method, and it was completely unexpected that side reactions can be suppressed by using it in a hydrothermal reaction. The same transition metal as described above is used. As the organic acid represented by R, an organic acid having 1 to 20 carbon atoms is preferable, and an organic acid having 2 to 12 carbon atoms is more preferable. More specific organic acids include dicarboxylic acids such as oxalic acid and fumaric acid, hydroxycarboxylic acids such as lactic acid, and fatty acids such as acetic acid.
本発明におけるＳｉ及びＬｉは、遷移金属に対してモル比で２倍以上用いることが好ましく、Ｓｉ：Ｌｉ：Ｍが１：１：２．５〜１：１：３程度がより好ましい。 In the present invention, Si and Li are preferably used in a molar ratio of 2 or more with respect to the transition metal, and Si: Li: M is more preferably about 1: 1: 2.5 to 1: 1: 3.
水分散液中のリチウム化合物の濃度は、０．３０〜３．００ｍｏｌ／ｌが好ましく、さらに１．００〜１．５０ｍｏｌ／ｌが好ましい。また、ケイ酸化合物の濃度は、０．１５〜１.５０ｍｏｌ／ｌが好ましく、さらに０．５０〜０．７５ｍｏｌ／ｌが好ましい。また有機酸遷移金属塩の濃度は０．１５〜１.５０ｍｏｌ／ｌが好ましく、さらに０．５０〜０．７５ｍｏｌ／ｌが好ましい。 The concentration of the lithium compound in the aqueous dispersion is preferably 0.30 to 3.00 mol / l, more preferably 1.00 to 1.50 mol / l. The concentration of the silicate compound is preferably 0.15 to 1.50 mol / l, more preferably 0.50 to 0.75 mol / l. The concentration of the organic acid transition metal salt is preferably 0.15 to 1.50 mol / l, more preferably 0.50 to 0.75 mol / l.
また、水分散液中には、必要により酸化防止剤を添加してもよく、酸化防止剤としては、ハイドロサルファイトナトリウム（Ｎａ2Ｓ2Ｏ4）、アンモニア水、亜硫酸ナトリウム等が使用できる。水分散液中の酸化防止剤の含有量は、多量に添加するとオリビン型シリケート化合物の生成を抑制してしまうため、遷移金属に対して等モル量以下が好ましく、遷移金属に対してモル比で０．５以下がさらに好ましい。 In addition, an antioxidant may be added to the aqueous dispersion as necessary. As the antioxidant, sodium hydrosulfite (Na 2 S 2 O 4 ), aqueous ammonia, sodium sulfite and the like can be used. The content of the antioxidant in the aqueous dispersion is preferably equal to or less than the transition metal in terms of a molar ratio with respect to the transition metal because it suppresses the formation of the olivine-type silicate compound when added in a large amount. 0.5 or less is more preferable.
これらの成分の水分散液は、塩基性とするのが副反応を防止し、ケイ酸化合物を溶解するうえで重要である。水分散液のｐＨは、塩基性であればよいが、１２．０〜１３．５であるのが副反応（Ｆｅ3Ｏ4の生成）の防止、ケイ酸化合物の溶解性及び反応の進行の点で特に好ましい。該水分散液のｐＨの調整は、塩基、例えば、水酸化ナトリウムを添加することにより行ってもよいが、ケイ酸化合物としてＮａ4ＳｉＯ4を用いるのが特に好ましい。 It is important for the aqueous dispersion of these components to be basic in order to prevent side reactions and dissolve the silicate compound. The pH of the aqueous dispersion may be basic, but it is 12.0 to 13.5 to prevent side reaction (formation of Fe 3 O 4 ), solubility of the silicate compound, and progress of the reaction. Particularly preferred in terms. The pH of the aqueous dispersion may be adjusted by adding a base such as sodium hydroxide, but it is particularly preferable to use Na 4 SiO 4 as the silicate compound.
前記リチウム化合物、ケイ酸化合物及び有機酸遷移金属塩の添加順序は特に限定されない。また、大気条件下でもよい。 The order of addition of the lithium compound, silicic acid compound and organic acid transition metal salt is not particularly limited. Moreover, atmospheric conditions may be sufficient.
本発明においては、次に前記水分散液を水熱反応に付す。水熱反応は、１００℃以上であればよく、１３０〜１８０℃が好ましく、さらに１４０〜１６０℃が好ましい。水熱反応は耐圧容器中で行うのが好ましく、１３０〜１８０℃で反応を行う場合この時の圧力は０．３〜０．９ＭＰａとなり、１４０〜１６０℃で反応を行う場合の圧力は０．３〜０．４ＭＰａとなる。水熱反応時間は１〜２４時間が好ましく、さらに３〜１２時間が好ましい。 In the present invention, the aqueous dispersion is then subjected to a hydrothermal reaction. The hydrothermal reaction should just be 100 degreeC or more, 130-180 degreeC is preferable and 140-160 degreeC is more preferable. The hydrothermal reaction is preferably performed in a pressure vessel. When the reaction is performed at 130 to 180 ° C, the pressure at this time is 0.3 to 0.9 MPa, and the pressure when the reaction is performed at 140 to 160 ° C is 0. 3 to 0.4 MPa. The hydrothermal reaction time is preferably 1 to 24 hours, more preferably 3 to 12 hours.
当該水熱反応により、Ｌｉ2ＭＳｉＯ4（Ｍは前記と同じ）が高収率で得られる。また、得られたＬｉＭＳｉＯ4の平均粒径は１０〜１００ｎｍとなり、その結晶度も高い。 By the hydrothermal reaction, Li 2 MSiO 4 (M is the same as above) is obtained in high yield. The obtained LiMSiO 4 has an average particle size of 10 to 100 nm and a high crystallinity.
得られたＬｉ2ＭＳｉＯ4は、ろ過後、乾燥することにより単離できる。乾燥手段は、凍結乾燥、真空乾燥が用いられる。 The obtained Li 2 MSiO 4 can be isolated by drying after filtration. As the drying means, freeze drying or vacuum drying is used.
得られたＬｉ2ＭＳｉＯ4は、カーボン担持し、次いで焼成することにより、リチウムイオン電池用正極活物質とすることができる。カーボン担持は、Ｌｉ2ＭＳｉＯ4に常法により、グルコース、フルクトース、ポリエチレングリコール、ポリビニルアルコール、カルボキシメチルセルロース、サッカロース、デンプン、デキストリン、クエン酸等の炭素源及び水を添加し、次いで焼成すればよい。焼成条件は、不活性ガス雰囲気下又は還元条件下に４００℃以上、好ましくは４００〜８００℃で１０分〜３時間、好ましくは０．５〜１．５時間行うのが好ましい。かかる処理によりＬｉ2ＭＳｉＯ4表面にカーボンが担持された正極活物質とすることができる。炭素源の使用量は、Ｌｉ2ＭＳｉＯ4 １００質量部に対し、炭素源に含まれる炭素として３〜１５質量部が好ましく、炭素源に含まれる炭素として５〜１０質量部がさらに好ましい。 The obtained Li 2 MSiO 4 can be used as a positive electrode active material for a lithium ion battery by carrying carbon and then firing. Carbon support may be obtained by adding a carbon source such as glucose, fructose, polyethylene glycol, polyvinyl alcohol, carboxymethylcellulose, saccharose, starch, dextrin, citric acid, and water to Li 2 MSiO 4 and then baking. The firing conditions are 400 ° C. or higher, preferably 400 to 800 ° C. for 10 minutes to 3 hours, preferably 0.5 to 1.5 hours under an inert gas atmosphere or reducing conditions. By such treatment, a positive electrode active material in which carbon is supported on the surface of Li 2 MSiO 4 can be obtained. The amount of carbon source used is preferably 3 to 15 parts by mass as carbon contained in the carbon source and more preferably 5 to 10 parts by mass as carbon contained in the carbon source with respect to 100 parts by mass of Li 2 MSiO 4 .
得られた正極活物質は、放電容量の点で優れており、リチウムイオン電池の正極材料として有用である。本発明の正極活物質を適用できるリチウムイオン電池としては、リチウムイオン二次電池であればよく、正極と負極と電解液とセパレータを必須構成とするものであれば特に限定されない。 The obtained positive electrode active material is excellent in terms of discharge capacity, and is useful as a positive electrode material for lithium ion batteries. The lithium ion battery to which the positive electrode active material of the present invention can be applied is not particularly limited as long as it is a lithium ion secondary battery and has a positive electrode, a negative electrode, an electrolytic solution, and a separator as essential components.
ここで、負極については、リチウムイオンを充電時には吸蔵し、かつ放電時には放出することができれば、その材料構成で特に限定されるものではなく、公知の材料構成のものを用いることができる。たとえば、リチウム金属、グラファイト又は非晶質炭素等の炭素材料等である。そしてリチウムを電気化学的に吸蔵・放出し得るインターカレート材料で形成された電極、特に炭素材料を用いることが好ましい。 Here, as long as lithium ions can be occluded at the time of charging and released at the time of discharging, the material structure is not particularly limited, and a known material structure can be used. For example, a carbon material such as lithium metal, graphite, or amorphous carbon. It is preferable to use an electrode formed of an intercalating material capable of electrochemically inserting and extracting lithium, particularly a carbon material.
電解液は、有機溶媒に支持塩を溶解させたものである。有機溶媒は、通常リチウム二次電池の電解液の用いられる有機溶媒であれば特に限定されるものではなく、例えば、カーボネート類、ハロゲン化炭化水素、エーテル類、ケトン類、ニトリル類、ラクトン類、オキソラン化合物等を用いることができる。 The electrolytic solution is obtained by dissolving a supporting salt in an organic solvent. The organic solvent is not particularly limited as long as it is an organic solvent that is usually used for an electrolyte solution of a lithium secondary battery. For example, carbonates, halogenated hydrocarbons, ethers, ketones, nitriles, lactones, An oxolane compound or the like can be used.
支持塩は、その種類が特に限定されるものではないが、ＬｉＰＦ6、ＬｉＢＦ4、ＬｉＣｌＯ4及びＬｉＡｓＦ6から選ばれる無機塩、該無機塩の誘導体、ＬｉＳＯ3ＣＦ3、ＬｉＣ（ＳＯ3ＣＦ3）2及びＬｉＮ（ＳＯ3ＣＦ3）2、ＬｉＮ（ＳＯ2Ｃ2Ｆ5）2及びＬｉＮ（ＳＯ2ＣＦ3）（ＳＯ2Ｃ4Ｆ9）から選ばれる有機塩、並びに該有機塩の誘導体の少なくとも１種であることが好ましい。 The type of the supporting salt is not particularly limited, but an inorganic salt selected from LiPF 6 , LiBF 4 , LiClO 4 and LiAsF 6 , a derivative of the inorganic salt, LiSO 3 CF 3 , LiC (SO 3 CF 3 ) 2 and LiN (SO 3 CF 3 ) 2 , LiN (SO 2 C 2 F 5 ) 2 and LiN (SO 2 CF 3 ) (SO 2 C 4 F 9 ), and organic salt derivatives It is preferable that it is at least 1 type of these.
セパレータは、正極及び負極を電気的に絶縁し、電解液を保持する役割を果たすものである。たとえば、多孔性合成樹脂膜、特にポリオレフィン系高分子（ポリエチレン、ポリプロピレン）の多孔膜を用いればよい。 The separator plays a role of electrically insulating the positive electrode and the negative electrode and holding the electrolytic solution. For example, a porous synthetic resin film, particularly a polyolefin polymer (polyethylene, polypropylene) porous film may be used.
次に実施例を挙げて本発明を詳細に説明する。 EXAMPLES Next, an Example is given and this invention is demonstrated in detail.
実施例１
ＬｉＯＨ・Ｈ2Ｏ ４．２０ｇ（０．１ｍｏｌ）、非晶質シリカ１．５０ｇ（０．０２５ｍｏｌ）、シュウ酸鉄（ＦｅＣ2Ｏ4・２Ｈ2Ｏ）５．００ｇ（０．０２５ｍｏｌ）に超純水７５ｃｍ3を加えて混合した（この時のｐＨは約１２）。得られた混合液をオートクレーブに投入し、１４０℃で４８ｈｒ水熱反応を行った。反応液をろ過後、凍結乾燥した。凍結乾燥（約１２時間）して得られた粉末４．２ｇにポリビニルアルコール（炭素濃度として３％）及び超純水１０ｃｍ3を加え、還元雰囲気下で７００℃で１ｈｒ焼成した。
Example 1
LiOH.H 2 O 4.20 g (0.1 mol), amorphous silica 1.50 g (0.025 mol), iron oxalate (FeC 2 O 4 .2H 2 O) 5.00 g (0.025 mol) 75 cm 3 of pure water was added and mixed (the pH at this time was about 12). The obtained liquid mixture was thrown into the autoclave and the hydrothermal reaction was performed at 140 degreeC for 48 hours. The reaction solution was filtered and then lyophilized. Polyvinyl alcohol (carbon concentration: 3%) and 10 cm 3 of ultrapure water were added to 4.2 g of the powder obtained by freeze-drying (about 12 hours), and calcined at 700 ° C. for 1 hr in a reducing atmosphere.
比較例１
ＬｉＯＨ・Ｈ2Ｏ ８．２０ｇ（０．２ｍｏｌ）、非晶質シリカ３．００ｇ（０．０５ｍｏｌ）及び超純水１００ｃｍ3を混合した。一方、ＦｅＣｌ2・４Ｈ2Ｏ ３．９８ｇ（０．２ｍｏｌ）、アスコルビン酸０．５９ｇ（０．００３３ｍｏｌ）及び超純水５０ｃｍ3を混合した。両混合液を混合し、実施例１と同様に水熱反応（１５０℃、１６ｈｒ）を行い、得られた反応液をろ過し、凍結乾燥（１２時間）した。得られた粉末を実施例１と同様にカーボン担持焼成した。
Comparative Example 1
8.20 g (0.2 mol) of LiOH.H 2 O, 3.00 g (0.05 mol) of amorphous silica, and 100 cm 3 of ultrapure water were mixed. Meanwhile, 3.98 g (0.2 mol) of FeCl 2 .4H 2 O, 0.59 g (0.0033 mol) of ascorbic acid and 50 cm 3 of ultrapure water were mixed. Both liquid mixtures were mixed, hydrothermal reaction (150 degreeC, 16 hours) was performed like Example 1, and the obtained reaction liquid was filtered and freeze-dried (12 hours). The obtained powder was calcined with carbon in the same manner as in Example 1.
試験例１
実施例１及び比較例１で得られた凍結乾燥粉末のＸ線回折を行った。得られたＸ線回折図を図１に示す。図１から明らかなように、比較例１で得られた粉末は、Ｆｅ3Ｓｉ2Ｏ5（ＯＨ）4を副生していた。これに対し、実施例１で得られた粉末はＬｉ2ＦｅＳｉＯ4の単一相であり、高純度であることが判明した。
Test example 1
X-ray diffraction of the lyophilized powder obtained in Example 1 and Comparative Example 1 was performed. The obtained X-ray diffraction pattern is shown in FIG. As is clear from FIG. 1, the powder obtained in Comparative Example 1 produced Fe 3 Si 2 O 5 (OH) 4 as a by-product. On the other hand, it was found that the powder obtained in Example 1 was a single phase of Li 2 FeSiO 4 and had high purity.
試験例２
実施例１及び比較例１で得られた焼成物を用い、リチウムイオン二次電池の正極を作製した。実施例１及び比較例１で得られた焼成物、ケッチェンブラック（導電剤）、ポリフッ化ビニリデン（粘結剤）を重量比７５：１５：１０の配合割合で混合し、これにＮ−メチル−２−ピロリドンを加えて充分混練し、正極スラリーを調製した。正極スラリーを厚さ２０μｍのアルミニウム箔からなる集電体に塗工機を用いて塗布し、８０℃で１２時間の真空乾燥を行った。その後、φ１４ｍｍの円盤状に打ち抜いてハンドプレスを用いて１６ＭＰａで２分間プレスし、正極とした。
次いで、上記の正極を用いてコイン型リチウムイオン二次電池を構築した。負極には、φ１５ｍｍに打ち抜いたリチウム箔を用いた。電解液には、エチレンカーボネート及びエチルメチルカーボネートを体積比１：１の割合で混合した混合溶媒に、ＬＩＰＦ6を１ｍｏｌ／ｌの濃度で溶解したものを用いた。セパレータには、ポリプロピレンなどの高分子多孔フィルムなど、公知のものを用いた。これらの電池部品を露点が−５０℃以下の雰囲気で常法により組み込み収容し、コイン型リチウム二次電池（ＣＲ−２０３２）を製造した。
製造したリチウムイオン二次電池を用いて定電流密度での充放電を４サイクル行った。このときの充電条件は電流０．１ＣＡ（３３ｍＡ／ｇ）、電圧４．５Ｖの定電流定電圧充電とし、放電条件は電流０．１ＣＡ、終止電圧１．５Ｖの定電流放電とした。温度は全て３０℃とした。
得られた４サイクル目の放電容量を図２に示す。また、実施例１の正極材で構築した電池の充放電曲線を図２に示す。
図２及び図３より、本発明の正極材料を用いたリチウムイオン電池は優れた電池特性を有することがわかる。
Test example 2
Using the fired product obtained in Example 1 and Comparative Example 1, a positive electrode of a lithium ion secondary battery was produced. The fired product obtained in Example 1 and Comparative Example 1, ketjen black (conductive agent), and polyvinylidene fluoride (binding agent) were mixed at a mixing ratio of 75:15:10, and this was mixed with N-methyl. -2-Pyrrolidone was added and sufficiently kneaded to prepare a positive electrode slurry. The positive electrode slurry was applied to a current collector made of an aluminum foil having a thickness of 20 μm using a coating machine, and vacuum dried at 80 ° C. for 12 hours. Thereafter, it was punched into a disk shape of φ14 mm and pressed at 16 MPa for 2 minutes using a hand press to obtain a positive electrode.
Next, a coin-type lithium ion secondary battery was constructed using the positive electrode. A lithium foil punched to φ15 mm was used for the negative electrode. As the electrolytic solution, a solution obtained by dissolving LIPF 6 at a concentration of 1 mol / l in a mixed solvent in which ethylene carbonate and ethyl methyl carbonate were mixed at a volume ratio of 1: 1 was used. As the separator, a known one such as a polymer porous film such as polypropylene was used. These battery components were assembled and housed in a conventional manner in an atmosphere with a dew point of −50 ° C. or lower to produce a coin-type lithium secondary battery (CR-2032).
Charging / discharging at a constant current density was performed for 4 cycles using the manufactured lithium ion secondary battery. The charging conditions at this time were constant current and constant voltage charging with a current of 0.1 CA (33 mA / g) and a voltage of 4.5 V, and the discharging conditions were constant current discharging with a current of 0.1 CA and a final voltage of 1.5 V. All temperatures were 30 ° C.
The obtained discharge capacity at the fourth cycle is shown in FIG. Moreover, the charging / discharging curve of the battery constructed | assembled with the positive electrode material of Example 1 is shown in FIG.
2 and 3, it can be seen that the lithium ion battery using the positive electrode material of the present invention has excellent battery characteristics.
Claims (7)
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