JP3983745B2 - Lithium transition metal oxides for lithium batteries - Google Patents
Lithium transition metal oxides for lithium batteries Download PDFInfo
- Publication number
- JP3983745B2 JP3983745B2 JP2004104962A JP2004104962A JP3983745B2 JP 3983745 B2 JP3983745 B2 JP 3983745B2 JP 2004104962 A JP2004104962 A JP 2004104962A JP 2004104962 A JP2004104962 A JP 2004104962A JP 3983745 B2 JP3983745 B2 JP 3983745B2
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- JP
- Japan
- Prior art keywords
- lithium
- transition metal
- metal oxide
- positive electrode
- manganese
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 229910052744 lithium Inorganic materials 0.000 title claims description 48
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims description 47
- 229910021437 lithium-transition metal oxide Inorganic materials 0.000 title claims description 47
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 30
- 239000011572 manganese Substances 0.000 claims description 25
- 239000007774 positive electrode material Substances 0.000 claims description 25
- 229910052748 manganese Inorganic materials 0.000 claims description 19
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- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 7
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- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 claims 1
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims 1
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- 229910001290 LiPF6 Inorganic materials 0.000 description 2
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Images
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Inorganic Compounds Of Heavy Metals (AREA)
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Description
本発明は、リチウム一次電池、リチウム二次電池、リチウムイオン二次電池、リチウムポリマー電池などのリチウム電池の正極活物質として用いるリチウム遷移金属酸化物、特にレート特性に優れたリチウム電池を実現できるリチウム遷移金属酸化物に関する。 The present invention relates to a lithium transition metal oxide used as a positive electrode active material of a lithium battery such as a lithium primary battery, a lithium secondary battery, a lithium ion secondary battery, or a lithium polymer battery, and in particular, a lithium battery that is excellent in rate characteristics. It relates to a transition metal oxide.
リチウム電池、特にリチウム二次電池は、単位電気量当たりの重量が小さく、エネルギー密度が高いため、ビデオカメラ、ノート型パソコン、携帯電話機などの携帯型電子機器や電気自動車などに搭載する駆動用電源として急速に普及しつつある。 Lithium batteries, especially lithium secondary batteries, have a low weight per unit of electricity and high energy density, so they are used as power sources for driving in portable electronic devices such as video cameras, laptop computers, and mobile phones, and electric vehicles. As it is rapidly spreading.
リチウム二次電池の高いエネルギー密度は主に正極材料の電位に起因しており、この種の正極活物質としては、スピネル構造をもつリチウムマンガン酸化物（ＬｉＭｎ2Ｏ4）のほか、層状構造をもつＬｉＣｏＯ2、ＬｉＮｉＯ2、ＬｉＭｎＯ2など、リチウム複合酸化物（ＬｉＭxＯy）が知られている。
これらの中でも、現在市販されているリチウム二次電池の大半は、正極活物質として４Ｖの高電圧を有する層構造のＬｉＣｏＯ2であるが、Ｃｏが極めて高価であるためＬｉＣｏＯ2の代替材料として、例えば同様の層構造を有するリチウム複合酸化物（ＬｉＭxＯy）の研究開発が盛んに進められている。
The high energy density of the lithium secondary battery is mainly due to the potential of the positive electrode material. This type of positive electrode active material includes a spinel-structure lithium manganese oxide (LiMn 2 O 4 ) and a layered structure. Lithium composite oxides (LiM x O y ) such as LiCoO 2 , LiNiO 2 and LiMnO 2 are known.
Among these, most of the lithium secondary batteries are currently commercially available is the LiCoO 2 layer structure having a high voltage of 4V as the positive electrode active material, as a substitute material for LiCoO 2 for Co is very expensive, For example, research and development of a lithium composite oxide (LiM x O y ) having a similar layer structure has been actively promoted.
具体的には、特許文献１には、マンガンとニッケルの混合水溶液中にアルカリ溶液を加えてマンガンとニッケルを共沈させ、水酸化リチウムを加え、ついで焼成することによって式：ＬｉＮｉxＭｎ1-xＯ2（式中、０．７≦x≦０．９５）で示される活物質を得る方法が開示され、
特許文献２には、式：ＬｉＮｉxＭ1-xＯ2（式中、ＭはＣｏ、Ｍｎ、Ｃｒ、Ｆｅ、ＶおよびＡｌの少なくとも一種、１＞x≧０．５）で示される組成を有する好ましい粒子状活物質が開示され、ＮｉおよびＭｎを含む活物質としてx＝０．１５のものが示されている。
また、特許文献３には、共沈合成法で合成された式：Ｌｉy-x1Ｎｉ1-xＭxＯ2（式中、ＭはＣｏ、Ａｌ、Ｍｇ、Ｆｅ、ＭｇまたはＭｎ、０＜x2≦０．５、０≦x1＜０．２、x＝x1＋x2、０．９≦y≦１．３）で示される活物質が開示され、
特許文献４には、３種の遷移金属を含む酸化物の結晶粒子からなり、前記結晶粒子の結晶構造が層構造であり、前記酸化物を構成する酸素原子の配列が立方最密充填である、Ｌｉ［Ｌｉx（ＡPＢQＣR）1-x］Ｏ2（式中、Ａ、ＢおよびＣはそれぞれ異なる３種の遷移金属元素、−０．１≦x≦０．３、０．２≦Ｐ≦０．４、０．２≦Ｑ≦０．４、０．２≦Ｒ≦０．４）で表される正極活物質が開示されている。
Patent Document 2 discloses a composition represented by the formula: LiNi x M 1-x O 2 (wherein M is at least one of Co, Mn, Cr, Fe, V, and Al, 1> x ≧ 0.5). A preferred particulate active material is disclosed, with x = 0.15 being shown as the active material containing Ni and Mn.
近年、携帯情報電子機器などの高性能化に伴い、より一層高い出力パワーを取り出せるリチウム電池が求められるようになり、正極活物質にもレート特性（大電流放電可能という特性）の向上が強く要求されている。
そこで本発明の目的は、層構造を有するリチウム遷移金属酸化物において、レート特性がより一層優れたものを開発することにある。
In recent years, with the improvement in performance of portable information electronic devices and the like, there has been a demand for lithium batteries that can extract even higher output power, and positive electrode active materials are also strongly required to improve rate characteristics (characteristics capable of discharging large currents). Has been.
Accordingly, an object of the present invention is to develop a lithium transition metal oxide having a layer structure that has even better rate characteristics.
本発明は、組成式Ｌｉ1+x（Ｍｎ(1-x)/3Ｃｏ(1-x)/3Ｎｉ(1-x)/3）Ｏ2（x＝０．０１〜０．５）で表される層構造を有するリチウム遷移金属酸化物、すなわち組成式Ｌｉ1+xＭ1-xＯ2で表される層構造を有するリチウム遷移金属酸化物であって、当該組成式中のＭが、Ｍｎ、Ｃｏ及びＮｉをほぼ１：１：１の原子比で含む遷移金属からなり、かつxの値が０．０１〜０．５であることを特徴とするリチウム遷移金属酸化物の中で、赤外線吸収スペクトル（ＦＴ−ＩＲ）において、５７０〜５９５ｃｍ-1付近に出現するピーク（「ピークＡ」と言う）と、５２０〜５５０ｃｍ-1付近に出現するピーク（「ピークＢ」と言う）との差Δが５０ｃｍ-1以下となる結合構造を有するリチウム遷移金属酸化物を提案するものである。 The present invention has the composition formula Li 1 + x (Mn (1-x) / 3 Co (1-x) / 3 Ni (1-x) / 3 ) O 2 (x = 0.01 to 0.5). Lithium transition metal oxide having a layer structure represented, that is, a lithium transition metal oxide having a layer structure represented by a composition formula Li 1 + x M 1-x O 2 , wherein M in the composition formula is Among the lithium transition metal oxides, characterized in that they are made of a transition metal containing an atomic ratio of approximately 1: 1: 1, Mn, Co and Ni, and the value of x is 0.01 to 0.5 In the infrared absorption spectrum (FT-IR), a peak appearing in the vicinity of 570 to 595 cm −1 (referred to as “peak A”) and a peak appearing in the vicinity of 520 to 550 cm −1 (referred to as “peak B”) A lithium transition metal oxide having a bond structure in which the difference Δ is 50 cm −1 or less is proposed.
本発明者が、層構造を有するリチウム遷移金属酸化物のレート特性について様々な観点から調査した中で、赤外線吸収スペクトル（ＦＴ−ＩＲ）において、５７０〜５９５ｃｍ-1付近に出現するピークＡと、５２０〜５５０ｃｍ-1付近に出現するピークＢとのピーク間距離（差Δ）に着目してレート特性との相関を調べたところ、その差Δが５０ｃｍ-1付近を境にレート特性の傾向が変化し、その差Δが５０ｃｍ-1以下である場合にレート特性が顕著に優れることを見出した。
５７０〜５９５ｃｍ-1付近に出現するピークＡ及び５２０〜５５０ｃｍ-1付近に出現するピークＢそれぞれ、どのような化学結合のシグナルに相当するか同定できている訳ではないが、おそらくＬｉ−ＯまたはＭ−Ｏの結合エネルギーがそれぞれ均質であることがレート特性が高まる一因になっているものと考えられる。つまり、ピーク間距離が小さいほど充放電の際のＬｉイオンの挿入脱離がスムースになるものと考えられるから、ピーク間距離が大きいもの、つまり結合エネルギーが不均質なものは充放電の際のＬｉイオンの挿入脱離に抵抗の大きい部分が存在することになり、特にハイレート充放電において容量劣化が著しくなるものと推定することができる。
While the present inventors investigated the rate characteristics of the lithium transition metal oxide having a layer structure from various viewpoints, in the infrared absorption spectrum (FT-IR), a peak A that appears in the vicinity of 570 to 595 cm −1 , Examination of the correlation between the rate characteristics by paying attention to the distance between peaks (the difference delta) between the peak B appeared in the vicinity 520~550cm -1, the difference delta is prone rate characteristic as a boundary around 50 cm -1 It has been found that rate characteristics are remarkably excellent when the difference Δ is 50 cm −1 or less.
Although it has not been possible to identify what kind of chemical bond signals peak A appearing near 570 to 595 cm −1 and peak B appearing near 520 to 550 cm −1 , it is probably Li—O or It is considered that the fact that the bond energy of M-O is uniform is one of the factors that increase the rate characteristics. In other words, it is thought that the smaller the distance between peaks, the smoother the insertion / desorption of Li ions during charging / discharging. A portion having a large resistance exists in insertion and desorption of Li ions, and it can be presumed that the capacity deterioration becomes remarkable especially in high-rate charge / discharge.
中でも、本発明のリチウム遷移金属酸化物は、当該リチウム遷移金属酸化物をリチウム電池の正極活物質として用い、負極にはリチウムを用いて充放電を行った時、充放電電圧範囲３．０〜４．３Ｖにおける充放電レートに対する容量の劣化が−６．７（ｍＡｈ／（ｇ・Ｃ）よりも小さくなる電池特性を実現できるものが好ましい。 Among these, when the lithium transition metal oxide of the present invention is charged and discharged using lithium as the positive electrode active material of the lithium battery and lithium as the negative electrode, the charge / discharge voltage range is 3.0 to What can implement | achieve the battery characteristic in which the capacity | capacitance deterioration with respect to the charging / discharging rate in 4.3V becomes smaller than -6.7 (mAh / (g * C) is preferable.
本発明で特定されるリチウム遷移金属酸化物を選別或いは製造し、このリチウム遷移金属酸化物を正極活物質として使用することにより、レート特性に優れたリチウム電池を実現することができる。 By selecting or producing the lithium transition metal oxide specified in the present invention and using this lithium transition metal oxide as the positive electrode active material, a lithium battery having excellent rate characteristics can be realized.
なお、本発明において「リチウム電池」とは、リチウム一次電池、リチウム二次電池、リチウムイオン二次電池、リチウムポリマー電池など、電池内にリチウムを含有する電池を全て包含する。
また、本発明が特定する数値範囲の上限値及び下限値は、特定する数値範囲から僅かに外れる場合であっても、当該数値範囲内と同様の作用効果を備えている限り本発明の範囲に含まる意を包含する。特に、ピークＡとピークＢとの差が５０ｃｍ-1以下の「５０ｃｍ-1」の値は、実施例１の結果が「５０．１ｃｍ-1」であることからも分かるように、少なくとも四捨五入して「５０ｃｍ-1」となる場合を包含する意である。
In the present invention, the “lithium battery” includes all batteries containing lithium in the battery, such as a lithium primary battery, a lithium secondary battery, a lithium ion secondary battery, and a lithium polymer battery.
Further, the upper and lower limits of the numerical range specified by the present invention are within the scope of the present invention as long as they have the same operational effects as those within the numerical range, even when slightly deviating from the specified numerical range. Includes intent to include. In particular, the peak value of the "50 cm -1" difference 50 cm -1 or less of A and peak B, as evidenced by the results of Example 1 are "50.1Cm -1", and at least rounded It is meant to encompass the case of “50 cm −1 ”.
本発明のリチウム遷移金属酸化物は、遷移金属としてＮｉ、Ｃｏ、Ｍｎをほぼ１：１：１の比率で含む層構造を有し、組成式Ｌｉ1+x（Ｍｎ(1-x)/3Ｃｏ(1-x)/3Ｎｉ(1-x)/3）Ｏ2で表されるリチウム遷移金属酸化物であり、その中でも、赤外線吸収スペクトル（ＦＴ−ＩＲ）において、５７０〜５９５ｃｍ-1付近に出現するピークＡと、５２０〜５５０ｃｍ-1付近に出現するピークＢとの差Δが５０ｃｍ-1以下となる結合構造を有するリチウム遷移金属酸化物である。 The lithium transition metal oxide of the present invention has a layer structure containing Ni, Co, and Mn as transition metals in a ratio of approximately 1: 1: 1, and has the composition formula Li 1 + x (Mn (1-x) / 3 It is a lithium transition metal oxide represented by Co (1-x) / 3 Ni (1-x) / 3 ) O 2 , and among them, in the infrared absorption spectrum (FT-IR), around 570 to 595 cm −1 a peak a appearing in the difference between the peak B appeared in the vicinity 520~550cm -1 Δ is a lithium transition metal oxide having a bonded structure comprising a 50 cm -1 or less.
本発明のリチウム遷移金属酸化物は、遷移金属に対するＬｉの比率、すなわちＬｉ／Ｍｆ定比組成よりも大きいことが必要であり、中でも当該比率が１．０１〜１．５０、特に１．０３〜１．３０が好ましい。
遷移金属Ｍは、Ｍｎ、Ｃｏ及びＮｉの３元素を含み、Ｍｎ、Ｃｏ及びＮｉをほぼ１：１：１の原子比で含むことを特徴とする。なお、Ｎｉ、Ｃｏ及びＭｎの比率が１：１：１から多少ズレた場合も、ピークＡ、ピークＢ間の差Δとレート特性との間には同様の相関があるものと考えられるから、本発明における「ほぼ１：１：１の原子比」とは四捨五入して１：１：１となる原子比を包含する意である。また、現段階では、Ｎｉ、Ｃｏ及びＭｎをほぼ１：１：１の比率で含むリチウム遷移金属酸化物についての知見しか得られていないが、Ｎｉ、Ｃｏ及びＭｎの比率がズレても同様の結果が得られるものと考えられるから、現在調査中である。
The lithium transition metal oxide of the present invention needs to be larger than the ratio of Li to the transition metal, that is, the Li / Mf stoichiometric composition, among which the ratio is 1.01 to 1.50, particularly 1.03 to 3. 1.30 is preferred.
The transition metal M includes three elements of Mn, Co, and Ni, and is characterized by including Mn, Co, and Ni in an atomic ratio of approximately 1: 1: 1. Even when the ratio of Ni, Co and Mn is slightly deviated from 1: 1: 1, it is considered that there is a similar correlation between the difference Δ between peak A and peak B and the rate characteristics. The “substantially 1: 1: 1 atomic ratio” in the present invention is meant to include an atomic ratio rounded to 1: 1: 1. At the present stage, only knowledge about lithium transition metal oxides containing Ni, Co and Mn at a ratio of approximately 1: 1: 1 has been obtained, but the same is true even if the ratio of Ni, Co and Mn is shifted. We are currently investigating because the results are expected.
赤外線吸収スペクトル（ＦＴ−ＩＲ）言い換えればフーリエ変換赤外分光分析は、フーリエ変換を利用して赤外光の各波長における強度分布を調べる分析法である。分子内の原子の結合はそれぞれ赤外線領域に固有の振動数を持っているため、或る物質に赤外線を照射すると、ある振動数（波長）の光が選択的に吸収を受け、この振動数（波長）は赤外線吸収スペクトルにより測定され、分子内の原子の結合に関する情報を得ることができる。
本発明のリチウム遷移金属酸化物、すなわち遷移金属としてＮｉ、Ｃｏ、Ｍｎをほぼ１：１：１の比率で含む層構造を有し、組成式Ｌｉ1+x（Ｍｎ(1-x)/3Ｃｏ(1-x)/3Ｎｉ(1-x)/3）Ｏ2で表されるリチウム遷移金属酸化物について赤外線吸収スペクトル（ＦＴ−ＩＲ）を測定すると、図１に示すように、５７０〜５９５ｃｍ-1付近にピークＡが出現し、５２０〜５５０ｃｍ-1付近にピークＢが出現すること、並びに、同様の組成を示すリチウム遷移金属酸化物であっても、同一物でなければピークＡ及びピークＢの出現する位置がずれてピークＡ、ピークＢ間の差Δ、すなわちピーク間距離が変化することが判明した。また、後述する試験では、同様の組成を有するリチウム遷移金属酸化物において、ピークＡ、ピークＢ間の差Δ（すなわちＩＲピーク間距離）が異なる複数のサンプルを作製し、差Δとレート特性との関係を調べたところ、差Δが５０ｃｍ-1付近を境にレート特性の傾向が顕著に変化すること、すなわち差Δ５０ｃｍ-1付近に変曲点があり、差Δが５０ｃｍ-1以下である場合にレート特性が顕著に優れることを見出すに至った。
Infrared absorption spectrum (FT-IR), in other words, Fourier transform infrared spectroscopic analysis is an analysis method for examining the intensity distribution at each wavelength of infrared light using Fourier transform. Since each atomic bond in the molecule has a specific frequency in the infrared region, when a certain substance is irradiated with infrared light, light of a certain frequency (wavelength) is selectively absorbed, and this frequency ( (Wavelength) is measured by an infrared absorption spectrum, and information on the bonding of atoms in the molecule can be obtained.
The lithium transition metal oxide of the present invention, that is, has a layer structure containing Ni, Co, and Mn as transition metals in a ratio of approximately 1: 1: 1, and has the composition formula Li 1 + x (Mn (1-x) / 3 When an infrared absorption spectrum (FT-IR) of the lithium transition metal oxide represented by Co (1-x) / 3 Ni (1-x) / 3 ) O 2 is measured, as shown in FIG. 595cm peak a appeared around -1, it 520~550cm peak around -1 B appears, and even the lithium transition metal oxide having the same composition, peaks a and to be identical product It was found that the position where peak B appears shifted and the difference Δ between peak A and peak B, that is, the distance between peaks changed. Further, in the test described later, in a lithium transition metal oxide having a similar composition, a plurality of samples having different differences Δ between peaks A and B (that is, the distance between IR peaks) were prepared. Examination of the relationship, the difference Δ is 50cm near the boundary -1 tendency of rate characteristics change significantly, i.e. there is an inflection point in the vicinity of the difference Deruta50cm -1, the difference Δ is a 50cm -1 or less In some cases, it has been found that the rate characteristics are remarkably excellent.
また、本発明のリチウム遷移金属酸化物は、当該リチウム遷移金属酸化物をリチウム電池の正極活物質として用い、負極にはリチウムを用いて充放電を行った時、充放電電圧範囲３．０〜４．３Ｖにおける充放電レートに対する容量の劣化が−６．７（ｍＡｈ／（ｇ・Ｃ）よりも小さくなる電池特性を実現できるものが好ましい。また、充放電電圧範囲３．０〜４．３Ｖで充放電レート０．３Ｃでの初期放電容量が１２０ｍＡｈ／ｇ以上の電池特性を発揮するものが好ましい。
なお、この際の電池構成の詳細及び充放電条件等の試験条件については下記実施例に記載する。
Moreover, when the lithium transition metal oxide of the present invention is charged and discharged using lithium as the positive electrode active material of the lithium battery and lithium as the negative electrode, the charge / discharge voltage range is 3.0 to What can implement | achieve the battery characteristic in which the deterioration of the capacity | capacitance with respect to the charge / discharge rate in 4.3V becomes smaller than -6.7 (mAh / (g * C) is preferable. It is preferable to exhibit battery characteristics with an initial discharge capacity of 120 mAh / g or more at a charge / discharge rate of 0.3 C.
Details of the battery configuration and test conditions such as charge / discharge conditions are described in the following examples.
（製造方法）
本発明のリチウム遷移金属酸化物の製造方法は特に限定されるものではない。例えば公知の製造方法（例えば特開２００３−１７０５２の[００２２]〜[００３０]に記載された方法）によって、所定の組成を有するリチウム遷移金属酸化物を製造し、その中から、赤外線吸収スペクトル（ＦＴ−ＩＲ）において、５７０〜５９５ｃｍ-1付近に出現するピークＡと、５２０〜５５０ｃｍ-1付近に出現するピークＢとの差Δが５０ｃｍ-1以下であるものを選別して得ることができる。
上述したリチウム遷移金属酸化物を製造するための公知の方法とは、例えばリチウム塩化合物、ニッケル塩化合物、コバルト塩化合物及びマンガン塩化合物を所定比率で乾式混合して焼成する方法、金属塩と場合によってはＬｉ塩とを湿式で混合分散したスラリーをスプレードライヤーなどで乾燥して焼成する方法、特開２００３-１８１６３９で示されているような連続式に湿式合成し、これを乾燥後焼成する方法、ニッケルイオン、コバルトイオン及びマンガンイオンを含む混合水溶液中にキレート剤を加えてこれらの遷移金属を共沈させ、この共沈で得られた遷移金属塩化合物とリチウム塩化合物とを混合して焼成する方法などを挙げることができるが、中でも３種類の遷移金属を均質に存在させられる点で共沈法を採用するのが好ましい。
(Production method)
The method for producing the lithium transition metal oxide of the present invention is not particularly limited. For example, a lithium transition metal oxide having a predetermined composition is produced by a known production method (for example, the method described in [0022] to [0030] of JP-A-2003-17052), and an infrared absorption spectrum ( in FT-IR), can be a peak a appeared in the vicinity 570~595cm -1, the difference between the peak B appeared in the vicinity 520~550cm -1 Δ is obtained by selecting not more 50 cm -1 or less .
Examples of the known method for producing the above-mentioned lithium transition metal oxide include a method in which a lithium salt compound, a nickel salt compound, a cobalt salt compound and a manganese salt compound are dry-mixed at a predetermined ratio and fired. Depending on the method, a slurry in which Li salt is mixed and dispersed in a wet process is dried and fired with a spray dryer, etc., or a wet synthesis is performed continuously as shown in Japanese Patent Application Laid-Open No. 2003-181039, followed by drying and firing. Then, a chelating agent is added to a mixed aqueous solution containing nickel ion, cobalt ion and manganese ion to coprecipitate these transition metals, and the transition metal salt compound and lithium salt compound obtained by this coprecipitation are mixed and fired. However, it is preferable to use the coprecipitation method because three kinds of transition metals can exist uniformly. Yes.
本発明のリチウム遷移金属酸化物の製造方法として好ましいのは、製造されたリチウム遷移金属酸化物の全てが差Δ５０ｃｍ-1以下となり、赤外線吸収スペクトル（ＦＴ−ＩＲ）測定して選別する必要のない製造方法である。そこで以下、共沈法を利用してそのようなリチウム遷移金属酸化物を製造する方法について説明する。但し、本発明のリチウム遷移金属酸化物の製造方法を以下の方法に限定する意ではない。 A preferable method for producing the lithium transition metal oxide of the present invention is that all of the produced lithium transition metal oxides have a difference of Δ50 cm −1 or less, and there is no need to select them by measuring an infrared absorption spectrum (FT-IR). It is a manufacturing method. Accordingly, a method for producing such a lithium transition metal oxide using a coprecipitation method will be described below. However, the production method of the lithium transition metal oxide of the present invention is not limited to the following method.
共沈法とは、水溶液中で中和反応を利用して複数元素を同時に沈殿させて複合酸化物を得る方法であり、本発明のリチウム遷移金属酸化物の製造においては、例えば、ニッケルイオン、コバルトイオン及びマンガンイオンを所定量含む混合水溶液中にキレート剤とアルカリ溶液とを混合し、この混合溶液のｐＨを調整することによってニッケルイオン、コバルトイオン及びマンガンイオンを共沈させて遷移金属塩化合物を得、得られた遷移金属塩化合物とリチウム塩化合物とを混合して所定の条件下で焼成する。この際、例えば混合溶液のｐＨ及び焼成温度を調整することによってピークＡとピークＢとの差Δ（ＩＲピーク間距離）を調整することができ、例えば反応溶液（母液）のｐＨを１１．０〜１３．０に調整し、かつ８００℃以上で焼成することにより、ピークＡとピークＢとの差が５０ｃｍ-1以下のリチウム遷移金属酸化物を製造することができる。
以下、さらに詳細に説明する。
The coprecipitation method is a method of obtaining a composite oxide by simultaneously precipitating multiple elements in an aqueous solution using a neutralization reaction. In the production of the lithium transition metal oxide of the present invention, for example, nickel ions, A transition metal salt compound by coprecipitation of nickel ions, cobalt ions and manganese ions by mixing a chelating agent and an alkaline solution in a mixed aqueous solution containing a predetermined amount of cobalt ions and manganese ions, and adjusting the pH of the mixed solution The obtained transition metal salt compound and the lithium salt compound are mixed and fired under predetermined conditions. At this time, for example, the difference Δ (the distance between IR peaks) between the peak A and the peak B can be adjusted by adjusting the pH of the mixed solution and the baking temperature. For example, the pH of the reaction solution (mother liquid) is 11.0. By adjusting to ˜13.0 and firing at 800 ° C. or higher, a lithium transition metal oxide having a difference between the peak A and the peak B of 50 cm −1 or less can be produced.
This will be described in more detail below.
先ず、マンガン、ニッケル及びコバルトの原子比が実質的に１：１：１となる遷移金属塩化合物を得るため、マンガン、ニッケル及びコバルトの原子比が実質的に１：１：１となるように秤量したマンガン塩化合物、ニッケル塩化合物及びコバルト塩化合物を水に添加し、キレート剤溶液（錯化剤）を加え、アルカリ溶液を加えてこの反応溶液のｐＨを調整しながら反応させ、ニッケルイオン、コバルトイオン及びマンガンイオンを共沈させて遷移金属塩化合物粒子を得る。 First, in order to obtain a transition metal salt compound in which the atomic ratio of manganese, nickel and cobalt is substantially 1: 1: 1, the atomic ratio of manganese, nickel and cobalt is substantially 1: 1: 1. Weighed manganese salt compound, nickel salt compound and cobalt salt compound are added to water, chelating agent solution (complexing agent) is added, alkali solution is added and reacted while adjusting pH of this reaction solution, nickel ions, Cobalt ions and manganese ions are coprecipitated to obtain transition metal salt compound particles.
この際、マンガン塩化合物の種類は特に制限はなく、例えば硫酸マンガン、硝酸マンガン、塩化マンガンなどを用いることができ、中でも硫酸マンガン水和物が好ましい。
ニッケル塩化合物の種類も特に制限はなく、例えば硫酸ニッケル、硝酸ニッケル、塩化ニッケルなどを用いることができ、中でも硫酸ニッケル水和物が好ましい。
コバルト塩化合物の種類も特に制限はなく、例えば硫酸コバルト、硝酸コバルト、塩化コバルトなどを用いることができ、中でも硫酸コバルト水和物が好ましい。
In this case, the type of the manganese salt compound is not particularly limited, and for example, manganese sulfate, manganese nitrate, manganese chloride, etc. can be used, and manganese sulfate hydrate is particularly preferable.
The kind of the nickel salt compound is not particularly limited, and for example, nickel sulfate, nickel nitrate, nickel chloride and the like can be used. Among these, nickel sulfate hydrate is preferable.
The type of the cobalt salt compound is not particularly limited, and for example, cobalt sulfate, cobalt nitrate, cobalt chloride and the like can be used, and among these, cobalt sulfate hydrate is preferable.
キレート剤の溶液としては、例えばアンモニウムイオン供給体（塩化アンモニウム、炭酸アンモニウム、弗化アンモニウム、硫酸アンモニウム、硝酸アンモニウム、アンモニア水、アンモニアガスなど）、ヒドラジン、グリシン、グルタミン酸、エチレンジアミン四酢酸、ニトリト三酢酸、ウラシル二酢酸などのアミノカルボン酸またはそれらの塩、シュウ酸・リンゴ酸・クエン酸・サリチル酸などのオキシカルボン酸またはそれらの塩が挙げられ、中でもアンモニア水溶液が好ましい。
アルカリ溶液としては、例えばアルカリ金属水酸化物、例えば水酸化リチウム 、水酸化ナトリウム、水酸化カリウムが挙げられ、中でも水酸化ナトリウム水溶液が好ましい。
Examples of the chelating agent solution include ammonium ion suppliers (ammonium chloride, ammonium carbonate, ammonium fluoride, ammonium sulfate, ammonium nitrate, ammonia water, ammonia gas, etc.), hydrazine, glycine, glutamic acid, ethylenediaminetetraacetic acid, nitritotriacetic acid, uracil. Examples thereof include aminocarboxylic acids such as diacetic acid or salts thereof, and oxycarboxylic acids such as oxalic acid, malic acid, citric acid, and salicylic acid, or salts thereof. Among them, an aqueous ammonia solution is preferable.
Examples of the alkali solution include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, and potassium hydroxide. Among these, an aqueous sodium hydroxide solution is preferable.
このような共沈法によって遷移金属塩化合物を製造する場合に、ピークＡとピークＢとの差Δが５０ｃｍ-1以下となるようにするためには、反応溶液（母液）のｐＨを１１．０〜１３．０に厳格に調整することが大切である。中でもｐＨを１３．０に近付けるほどΔを小さくすることができるから、ｐＨ１２．０〜１３．０に調整するのが特に好ましい。
但し、ｐＨ１１．０を下回ると溶液中のＮｉイオンが沈降しづらくなり、水酸化物の組成ずれを引起こし易くなり、ｐＨ１３．０を上回ると沈殿した水酸化物が微粒となり、洗浄、回収が著しく困難になる。
In the case of producing a transition metal salt compound by such a coprecipitation method, the pH of the reaction solution (mother liquor) is set to 11.1 so that the difference Δ between the peak A and the peak B is 50 cm −1 or less. It is important to strictly adjust to 0 to 13.0. Among them, it is particularly preferable to adjust the pH to 12.0 to 13.0 because Δ can be reduced as the pH is brought closer to 13.0.
However, if the pH is lower than 11.0, Ni ions in the solution are difficult to settle, and it is easy to cause a shift in the composition of the hydroxide. If the pH is higher than 13.0, the precipitated hydroxide becomes fine particles, which can be washed and recovered. It becomes extremely difficult.
次に、このようにして得られた遷移金属塩化合物粒子を乾燥後、リチウム塩化合物と所定比率で混合し、焼成する。 Next, the transition metal salt compound particles thus obtained are dried, mixed with a lithium salt compound at a predetermined ratio, and fired.
リチウム塩化合物としては、例えば水酸化リチウム（ＬｉＯＨ）、炭酸リチウム（Ｌｉ2ＣＯ3）、硝酸リチウム（ＬｉＮＯ3）、ＬｉＯＨ・Ｈ2Ｏ、酸化リチウム（Ｌｉ2Ｏ）、その他脂肪酸リチウムやリチウムハロゲン化物等が挙げられる。中でもリチウムの水酸化物塩、炭酸塩、硝酸塩が好ましい。
リチウム塩化合物と遷移金属塩化合物とのモル比は理想的には１：１であるが、１．０１〜１．５：０．９９〜０．９５範囲であれば同様の効果を得られることが期待できる。
Examples of the lithium salt compound include lithium hydroxide (LiOH), lithium carbonate (Li 2 CO 3 ), lithium nitrate (LiNO 3 ), LiOH · H 2 O, lithium oxide (Li 2 O), other fatty acid lithium and lithium halogen. And the like. Of these, lithium hydroxide salts, carbonates and nitrates are preferred.
The molar ratio of the lithium salt compound to the transition metal salt compound is ideally 1: 1, but the same effect can be obtained if it is in the range of 1.01 to 1.5: 0.99 to 0.95. Can be expected.
混合方法は、均一に混合できれば、その方法を特に限定するものではない。例えばミキサー等の公知の混合機を用いて各原料を同時又は適当な順序で加えて乾式で攪拌混合すればよい。
また、必要に応じて、焼成前に、混合した原料を所定の大きさに造粒するようにしてもよい。造粒方法は、湿式でも乾式でもよく、押し出し造粒、転動造粒、流動造粒、混合造粒、噴霧乾燥造粒、加圧成型造粒、或いはロール等を用いたフレーク造粒でもよい。但し、湿式造粒した場合には、焼成前に充分に乾燥させることが必要である。乾燥方法としては、噴霧熱乾燥、熱風乾燥、真空乾燥、フリーズドライなどの公知の乾燥方法によって乾燥させればよい。
The mixing method is not particularly limited as long as it can be uniformly mixed. For example, using a known mixer such as a mixer, the respective raw materials may be added simultaneously or in an appropriate order, followed by dry stirring and mixing.
If necessary, the mixed raw materials may be granulated to a predetermined size before firing. The granulation method may be wet or dry, and may be extrusion granulation, rolling granulation, fluid granulation, mixed granulation, spray drying granulation, pressure molding granulation, or flake granulation using a roll or the like. . However, when wet granulation is performed, it is necessary to sufficiently dry before firing. As a drying method, it may be dried by a known drying method such as spray heat drying, hot air drying, vacuum drying or freeze drying.
焼成は、大気雰囲気中で行うのが好ましく、８００℃以上１０００℃以下、好ましくは８５０℃以上９５０℃以下で、１時間〜３０時間、好ましくは５時間〜２５時間保持するように焼成する。なお、ここでの焼成温度は焼成炉内の品温を意味する。
焼成炉としては、ロータリーキルン或いは静置炉等を用いることができる。
焼成雰囲気は、大気雰囲気下のほか、酸化性雰囲気を採用することも可能である。
また、焼成に続いて特定の温度でアニーリング（熱処理）するようにしてもよい。
Firing is preferably performed in an air atmosphere, and is performed at 800 ° C. to 1000 ° C., preferably 850 ° C. to 950 ° C. for 1 hour to 30 hours, preferably 5 hours to 25 hours. Here, the firing temperature means the product temperature in the firing furnace.
As the baking furnace, a rotary kiln or a stationary furnace can be used.
The firing atmosphere may be an atmospheric atmosphere or an oxidizing atmosphere.
Further, annealing (heat treatment) may be performed at a specific temperature following firing.
このようにして得られたリチウム遷移金属酸化物は、Ｌｉ1+x（Ｍｎ(1-x)/3Ｃｏ(1-x)/3Ｎｉ(1-x)/3）Ｏ2で表され、遷移金属としてＮｉ、Ｃｏ、Ｍｎをほぼ１：１：１の比率で含む層構造を有するリチウム遷移金属酸化物であり、赤外線吸収スペクトル（ＦＴ−ＩＲ）を測定すると、５７０〜５９５ｃｍ-1付近に出現するピークＡと、５２０〜５５０ｃｍ-1付近に出現するピークＢとの差Δが５０ｃｍ-1以下を示すものとなる。 The lithium transition metal oxide thus obtained is represented by Li 1 + x (Mn (1-x) / 3 Co (1-x) / 3 Ni (1-x) / 3 ) O 2 , It is a lithium transition metal oxide having a layer structure containing Ni, Co, and Mn as a transition metal in a ratio of approximately 1: 1: 1. When an infrared absorption spectrum (FT-IR) is measured, it is around 570 to 595 cm −1 . a peak a appearing, the difference between the peak B appeared in the vicinity 520~550cm -1 Δ may be indicators of 50 cm -1 or less.
以上のように焼成して得られたリチウム遷移金属酸化物は、必要に応じて解砕・分級した後、リチウム電池の正極活物質として有効に利用することができる。例えば、リチウム遷移金属酸化物と、カーボンブラック等からなる導電材と、テフロン（登録商標）バインダー等からなる結着剤とを混合して正極合剤を製造することができる。
そしてそのような正極合剤を正極に用い、負極にはリチウム、カーボン、黒鉛等のリチウムを吸蔵、脱蔵できる材料を用い、非水系電解質には六フッ化リン酸リチウム（ＬｉＰＦ６）等のリチウム塩をエチレンカーボネート−ジメチルカーボネート等の混合溶媒に溶解したものを用いてリチウム電池を構成することができる。
The lithium transition metal oxide obtained by firing as described above can be effectively used as a positive electrode active material of a lithium battery after being crushed and classified as necessary. For example, a positive electrode mixture can be produced by mixing a lithium transition metal oxide, a conductive material made of carbon black or the like, and a binder made of Teflon (registered trademark) binder or the like.
Such a positive electrode mixture is used for the positive electrode, a material that can occlude and desorb lithium, such as lithium, carbon, and graphite, is used for the negative electrode, and lithium such as lithium hexafluorophosphate (LiPF6) is used for the non-aqueous electrolyte. A lithium battery can be formed using a salt dissolved in a mixed solvent such as ethylene carbonate-dimethyl carbonate.
このように構成したリチウム電池は、例えばノート型パソコン、携帯電話、コードレスフォン子機、ビデオムービー、液晶テレビ、電気シェーバー、携帯ラジオ、ヘッドホンステレオ、バックアップ電源、メモリーカード等の電子機器、ペースメーカー、補聴器等の医療機器、電気自動車搭載用の駆動電源に使用することができる。中でも、優れたレート特性が要求される携帯電話機、ＰＤＡ（携帯情報端末）やノート型パソコンなどの各種携帯型コンピュータ、電気自動車（ハイブリッド自動車を含む）、電力貯蔵用電源などの駆動用電源として特に有効である。 Lithium batteries configured in this way are, for example, notebook computers, mobile phones, cordless phones, video movies, LCD TVs, electric shavers, portable radios, headphone stereos, backup power supplies, memory cards, and other electronic devices, pacemakers, hearing aids It can be used as a drive power source for medical equipment such as electric vehicles. Among them, mobile phones that require excellent rate characteristics, various portable computers such as PDAs (personal digital assistants) and notebook computers, electric vehicles (including hybrid vehicles), and power sources for driving power storages It is valid.
なお、後述する試験結果が示すように、Δ５０ｃｍ-1以下のリチウム遷移金属酸化物粉末を正極活物質として用いてリチウム電池を作成し、充放電を繰り返し行った後、当該リチウム電池を解体してその正極活物質の赤外線吸収スペクトルを測定してみると、リチウム遷移金属酸化物粉末の場合より差Δが低下することが確認された。例えばΔ約５０ｃｍ-1のリチウム遷移金属酸化物粉末の場合、充放電後Δ４６ｃｍ-1となった。このことから、使用後の電池を解体してその正極活物質の赤外線吸収スペクトルを測定してその差Δが４６ｃｍ-1以下であれば、電池製造時の正極活物質及びその原料としてのリチウム遷移金属酸化物粉末のΔは５０ｃｍ-1以下であったことが分かる。 As shown in the test results to be described later, a lithium battery was prepared using a lithium transition metal oxide powder of Δ50 cm −1 or less as a positive electrode active material, charged and discharged repeatedly, and then the lithium battery was disassembled. When the infrared absorption spectrum of the positive electrode active material was measured, it was confirmed that the difference Δ was lower than that of the lithium transition metal oxide powder. For example, in the case of a lithium transition metal oxide powder having Δ of about 50 cm −1 , it became Δ46 cm −1 after charge and discharge. From this, the battery after use is disassembled, the infrared absorption spectrum of the positive electrode active material is measured, and if the difference Δ is 46 cm −1 or less, the positive electrode active material at the time of battery production and the lithium transition as its raw material It can be seen that Δ of the metal oxide powder was 50 cm −1 or less.
次に、実際に製造した実施例及び比較例に基づいて説明するが、本発明が以下に示す実施例に限定されるものではない。 Next, although it demonstrates based on the Example and comparative example which were actually manufactured, this invention is not limited to the Example shown below.
（電池評価の方法）
Ｌｉ電池評価は以下の方法で行った。
正極活物質１０．４ｇとアセチレンブッラク（電気化学工業社製）０．８６ｇおよびＮＭＰ（Ｎ-メチルピロリドン）中にＰＶｄＦ（ダイキン工業社製）１０ｗｔ％溶解した液８．６ｇを正確に計り取り、そこにＮＭＰを１０．８ｇ加え十分に混合し、ペーストを作成した。このペーストを集電体であるアルミ箔上にのせ１５０μｍのギャップに調整したアプリケーターで塗膜化し、１２０℃で１２０ｍｉｎ乾燥した後、５０μｍのギャップに調整したロールプレスで厚密した。その後φ１３ｍｍに打ち抜き正極とした。電池作成直前に１２０℃で１２ｈｒ以上乾燥し水分を十分に除去し電池に組み込んだ。また予めφ１３ｍｍのアルミ箔の重さの平均を求めておき、正極の重さからアルミ箔の重さを差し引き正極合材の重さを求め、また正極活物質とアセチレンブラックおよびＰＶｄＦの混合割合から正極活物質の含有量を求めた。負極はφ１６ｍｍ×厚さ０．６ｍｍの金属Ｌｉとし、これらの材料を使用して図２に示す２０３２型コイン電池を作製した。
(Method of battery evaluation)
Li battery evaluation was performed by the following method.
Accurately measure 10.6 g of the positive electrode active material, 0.86 g of acetylene black (manufactured by Denki Kagaku Kogyo) and 8.6 g of a solution of 10 wt% of PVdF (manufactured by Daikin Kogyo) in NMP (N-methylpyrrolidone), There, 10.8 g of NMP was added and mixed well to prepare a paste. This paste was placed on an aluminum foil as a current collector and formed into a coating film with an applicator adjusted to a gap of 150 μm, dried at 120 ° C. for 120 minutes, and then thickened with a roll press adjusted to a gap of 50 μm. Thereafter, a positive electrode was punched into φ13 mm. Immediately before the battery was made, it was dried at 120 ° C. for 12 hours or more to remove water sufficiently and incorporated into the battery. In addition, the average weight of the aluminum foil having a diameter of 13 mm is obtained in advance, the weight of the positive electrode mixture is obtained by subtracting the weight of the aluminum foil from the weight of the positive electrode, and from the mixing ratio of the positive electrode active material, acetylene black and PVdF. The content of the positive electrode active material was determined. The negative electrode was made of metal Li of φ16 mm × thickness 0.6 mm, and these materials were used to produce a 2032 type coin battery shown in FIG.
図２のコイン電池は、耐有機電解液性のステンレンス鋼製の正極ケース１１の内側に、同じくステンレス鋼製の集電体１３がスポット溶接されている。この集電体１３の上面には前記正極合材からなる正極１５が圧着されている。この正極１５の上面には、電解液を含浸した微孔性のポリプロピレン樹脂製のセパレータ１６が配置されている。前記正極ケース１１の開口部には、下方に金属Ｌｉからなる負極１４を接合した封口板１２がポリプロピレン製のガスケット１７をはさんで配置され、これにより電池は密封されている。前記封口板１２は負極端子をかね、正極ケースと同様ステンレス製である。
電池の直径は２０ｍｍ、電池の総高は１．６ｍｍとした。電解液は、エチレンカーボネートと１，３−ジメトキシカーボネートを等体積混合したものを溶媒とし、これに溶質としてＬｉＰＦ6を１ｍｏＬ／Ｌ溶解させたものを用いた。
In the coin battery of FIG. 2, a
The battery diameter was 20 mm and the total battery height was 1.6 mm. As the electrolytic solution, a mixture of ethylene carbonate and 1,3-dimethoxy carbonate in an equal volume was used as a solvent, and a solution obtained by dissolving 1 mol / L of LiPF6 as a solute was used.
このようにして準備したコインセルを下記に記述する方法で充放電試験しレート特性を求めた。
充放電範囲は３．０〜４．３Ｖとし、正極中の正極活物質の含有量から０．３Ｃ、１．０Ｃ、１．５Ｃ、２．０Ｃ、３．０Ｃの充放電レートになるよう電流値を算出し、それぞれのレートでの最大放電容量が観測されるまでサイクルを行なった。このときＸ軸に放電レートを取り、Ｙ軸に最大放電容量（ｍＡｈ／ｇ）をプロットし、最小二乗法で一次近似式を求めた。この近似式の傾き（ｍＡｈ／ｇＣ）が大きなものほど、放電レートに対する容量劣化率が小さいことを示し、この傾きをレート特性値と定義した。
The coin cell thus prepared was subjected to a charge / discharge test by the method described below to obtain rate characteristics.
The charge / discharge range is 3.0 to 4.3 V, and the current is set so that the charge / discharge rate is 0.3 C, 1.0 C, 1.5 C, 2.0 C, and 3.0 C based on the content of the positive electrode active material in the positive electrode. The value was calculated and cycled until the maximum discharge capacity at each rate was observed. At this time, the discharge rate was taken on the X-axis, the maximum discharge capacity (mAh / g) was plotted on the Y-axis, and a first order approximate expression was obtained by the least square method. The larger the slope (mAh / gC) of this approximate expression, the smaller the capacity deterioration rate with respect to the discharge rate, and this slope was defined as the rate characteristic value.
（ＦＴ−ＩＲの測定方法）
正極活物質および正極のＦＴ−ＩＲは、次に記述する方法により測定した。
正極活物質０．２〜１．０ｍｇとＫＢｒ０．２ｇを計り取り、乳鉢で手早く混合し、この混合粉全量をφ１３ｍｍのプレス冶具に入れ、８ｔｏｎのプレス圧で成型した。これを測定冶具に装着し、透過法で、積算測定回数は１００回としてＦＴ−ＩＲ測定を行った。今回の測定には、島津製作所社製ＦＴＩＲ-８３００を用いた。例として下記実施例１に示す正極活物質粉末をＦＴ−ＩＲ測定したときのチャートを図１に示す。このチャートから読み取ることができる５７０〜５９５ｃｍ-1付近に出現するＰｅａｋＡのＴｏｐ位置と５２０〜５５０ｃｍ-1付近に出現するＰｅａｋＢのＴｏｐ位置の差ΔをＩＲ特性値として用いた。
正極または充放電後の正極中の活物質のＦＴ−ＩＲ測定を行う際は、正極から正極活物質とアセチレンブラックおよびＰＶｄＦが混合され塗膜された部位のみをピンセットでわずかにかきとり、ＫＢｒと混合して上記と同様の方法にて測定を実施した。
(Measurement method of FT-IR)
The FT-IR of the positive electrode active material and the positive electrode was measured by the method described below.
0.2 to 1.0 mg of the positive electrode active material and 0.2 g of KBr were weighed and quickly mixed in a mortar, and the total amount of the mixed powder was put in a φ13 mm press jig and molded with a press pressure of 8 ton. This was mounted on a measurement jig, and the FT-IR measurement was performed by the transmission method with the total number of measurements being 100 times. For this measurement, FTIR-8300 manufactured by Shimadzu Corporation was used. As an example, FIG. 1 shows a chart when the FT-IR measurement is performed on the positive electrode active material powder shown in Example 1 below. The difference Δ between the Peak position of Peak A that appears near 570 to 595 cm −1 and the Peak position of Peak B that appears near 520 to 550 cm −1 that can be read from this chart was used as the IR characteristic value.
When performing the FT-IR measurement of the active material in the positive electrode or the positive electrode after charging / discharging, only the portion coated with the positive electrode active material, acetylene black and PVdF from the positive electrode is slightly scraped with tweezers and mixed with KBr. Then, the measurement was carried out by the same method as described above.
（実施例１）
攪拌機付きの１０Ｌの密閉容器（オイルジャケット付き）に市水を２．５Ｌ量入れ、硫酸マンガン・５水和物（柳島製薬社製）５８８ｇ、硫酸コバルト・６水和物（関西触媒社製）７０３ｇおよび硫酸ニッケル・６水和物（三井金属社製）７６２ｇを溶解し、４Ｌになるよう水を加え調整した。その中に２５ｗｔ％のアンモニア水（アガタ薬品工業社製）３００ｍＬを加え、この溶液を攪拌しながら６ｍｏＬ／Ｌの苛性ソーダ水溶液を加え、市販のｐＨ計（横川電機（株）製モデルｐＨ８１）を用いてｐＨ１１．４に調整した。浴温は４５℃に保ち１２時間攪拌した。攪拌後の沈殿物を上澄みの導電率が１ｍS以下となるまでデカンテーション洗浄を繰り返し、その後反応溶液をろ過により固液分離し、固形物を１２０℃で１０ｈｒ乾燥し、金属水酸化物原料（上記「遷移金属塩化合物」に相当）を得た。
この金属水酸化物原料の金属元素のみのモル数をＸモルとし、炭酸リチウム中のＬｉ元素のモル数Ｙが、Ｙ/Ｘ＝１．１０となるように金属水酸化物原料と炭酸リチウム（ＳＱＭ社製）を計り取り、ボールミルで十分に混合し、原料混合粉を得、この原料混合粉を大気中で８５０℃２０時間焼成した。
Example 1
2.5L of city water is put in a 10L sealed container (with oil jacket) with a stirrer, 588g of manganese sulfate pentahydrate (manufactured by Yanagishima Pharmaceutical), cobalt sulfate hexahydrate (manufactured by Kansai Catalysts) 703 g and 762 g of nickel sulfate hexahydrate (manufactured by Mitsui Kinzoku Co., Ltd.) were dissolved, and water was added to adjust to 4 L. Into this, 300 mL of 25 wt% aqueous ammonia (Agata Pharmaceutical Co., Ltd.) was added, and 6 mol / L of aqueous caustic soda solution was added while stirring this solution, and a commercially available pH meter (model pH 81 manufactured by Yokogawa Electric Corporation) was used. To pH 11.4. The bath temperature was kept at 45 ° C. and stirred for 12 hours. The precipitate after stirring is repeatedly decanted and washed until the conductivity of the supernatant becomes 1 mS or less, and then the reaction solution is solid-liquid separated by filtration, and the solid is dried at 120 ° C. for 10 hours to obtain a metal hydroxide raw material (above Corresponding to “transition metal salt compound”).
The number of moles of only the metal element of the metal hydroxide raw material is X mole, and the number of moles of Li element in the lithium carbonate is Y / X = 1.10, so that the metal hydroxide raw material and the lithium carbonate ( SQM) was weighed and thoroughly mixed with a ball mill to obtain a raw material mixed powder, and this raw material mixed powder was fired in the atmosphere at 850 ° C. for 20 hours.
焼成して得られた粉末を乳鉢で解砕後、目開き７５μｍの篩で分級し、その粒度をレーザー散乱式の粒度分布計で測定したところ、体積平均粒子径Ｄ50は１２μｍであり、Ｎ2吸着法による比表面積は０．６ｍ2／ｇであった。また、化学分析結果とＸＲＤ測定結果で、目的物ができていることを確認した。 The powder obtained by firing was crushed in a mortar, classified with a sieve having an opening of 75 μm, and the particle size was measured with a laser scattering particle size distribution meter. The volume average particle size D 50 was 12 μm, and N The specific surface area by the 2 adsorption method was 0.6 m 2 / g. Moreover, it was confirmed from the chemical analysis results and the XRD measurement results that the target product was formed.
焼成して得られた粉末（乳鉢解砕及び分級済）をＩＲ測定し、ピークトップ間距離（Δ）を算出したところ５０.１ｃｍ-1であった（以下「粉末ＩＲ特性値」と呼ぶ）。
また、前述した方法で作製した正極のＩＲ測定を行なったところピーク間距離は、４６．３ｃｍ-1であった（以下「正極ＩＲ特性値」と呼ぶ）。
また、０．３Ｃで３サイクル充放電し、放電で終了した正極をコインセルから取り出しＥＣ中でよく洗浄し、ＩＲ測定を行なったところ４６．１ｃｍ-1であった（以下「充放電後ＩＲ特性値」と呼ぶ）。
レート特性値は−６．６であった。
以上の結果をまとめたものを表１に示し、ＩＲ測定結果をそれぞれプロットしたものを図３，４，５に示した。
It was 50.1 cm < -1 > when IR measurement was carried out and the peak top distance ((DELTA)) was calculated for the powder (mortar crushed and classified) obtained by baking (it is called "powder IR characteristic value" hereafter). .
Further, when IR measurement was performed on the positive electrode manufactured by the above-described method, the peak-to-peak distance was 46.3 cm −1 (hereinafter referred to as “positive electrode IR characteristic value”).
The positive electrode which was charged and discharged at 0.3 C for 3 cycles and was discharged was taken out from the coin cell, washed thoroughly in EC, and subjected to IR measurement, which was 46.1 cm −1 (hereinafter referred to as “IR characteristics after charge and discharge”). Called "value").
The rate characteristic value was −6.6.
The summary of the above results is shown in Table 1, and the IR measurement results are plotted in FIGS.
（実施例２）
実施例１と同じ原料混合粉を大気中で８８０℃２０時間焼成した。
焼成して得られた粉末を、実施例１と同様に解砕及び分級し、その粒度を測定したところ、体積平均粒子径Ｄ50は１０μｍであり、比表面積は０．４ｍ2／ｇであった。
また、焼成して得られた粉末（乳鉢解砕及び分級済）のレート特性値とそれぞれのＩＲ測定値を表１にまとめ、プロットした結果を図３、図４、図５に示した。
(Example 2)
The same raw material mixed powder as in Example 1 was baked in the air at 880 ° C. for 20 hours.
The powder obtained by firing was crushed and classified in the same manner as in Example 1, and the particle size was measured. As a result, the volume average particle diameter D 50 was 10 μm, and the specific surface area was 0.4 m 2 / g. It was.
Moreover, the rate characteristic value of each powder (mortar crushed and classified) obtained by firing and the respective IR measurement values are summarized in Table 1, and the plotted results are shown in FIG. 3, FIG. 4, and FIG.
（実施例３）
実施例１と同じ原料混合粉を大気中で９２０℃２０時間焼成した。
焼成して得られた粉末を、実施例１と同様に解砕及び分級し、その粒度を測定したところ、体積平均粒子径Ｄ50は９μｍであり、比表面積は０．３ｍ2／ｇであった。
また、焼成して得られた粉末（乳鉢解砕及び分級済）のレート特性値とそれぞれのＩＲ測定値を表１にまとめ、プロットした結果を図３、図４、図５に示した。
(Example 3)
The same raw material mixed powder as in Example 1 was fired in the atmosphere at 920 ° C. for 20 hours.
The powder obtained by firing was crushed and classified in the same manner as in Example 1, and the particle size was measured. As a result, the volume average particle diameter D 50 was 9 μm, and the specific surface area was 0.3 m 2 / g. It was.
Moreover, the rate characteristic value of each powder (mortar crushed and classified) obtained by firing and the respective IR measurement values are summarized in Table 1, and the plotted results are shown in FIG. 3, FIG. 4, and FIG.
（実施例４）
攪拌機付きの１０Ｌの密閉容器（オイルジャケット付き）に市水を２．５Ｌ量入れ、硫酸マンガン・５水和物（柳島製薬社製）５８８ｇ、硫酸コバルト・６水和物（関西触媒社製）７０３ｇおよび硫酸ニッケル・６水和物（三井金属社製）７６２ｇを溶解し、４Ｌになるよう水を加え調整した。その中に２５ｗｔ％のアンモニア水（アガタ薬品工業社製）３００ｍＬを加え、この溶液を攪拌しながら６ｍｏｌ／Ｌの苛性ソーダ水溶液を加え、実施例１と同じｐＨ計を用いてｐＨ１２．６に調整した。浴温は４５℃に保ち１２時間攪拌した。攪拌後の沈殿物を上澄みの導電率が１ｍＳ以下となるまでデカンテーション洗浄を繰り返し、その後反応溶液をろ過により固液分離し、固形物を１２０℃で１０ｈｒ乾燥し、金属水酸化物原料を得た。
この金属水酸化物原料の金属元素のみのモル数をＸモルとし、炭酸リチウム中のＬｉ元素のモル数Ｙが、Ｙ/Ｘ＝１．１０となるように金属水酸化物原料と炭酸リチウム（ＳＱＭ社製）を計り取り、ボールミルで十分に混合し、原料混合粉を得、この原料混合粉を大気中で８８０℃２０時間焼成した。
焼成して得られた粉末を、実施例１と同様に解砕及び分級し、その粒度を測定したところ、体積平均粒子径Ｄ50は５μｍであり、比表面積は２．２ｍ2／ｇであった。
また、焼成して得られた粉末（乳鉢解砕及び分級済）のレート特性値とそれぞれのＩＲ測定値を表１にまとめ、プロットした結果を図３，４，５に示した。
(Example 4)
2.5L of city water is put in a 10L sealed container (with oil jacket) with a stirrer, 588g of manganese sulfate pentahydrate (manufactured by Yanagishima Pharmaceutical), cobalt sulfate hexahydrate (manufactured by Kansai Catalysts) 703 g and 762 g of nickel sulfate hexahydrate (manufactured by Mitsui Kinzoku Co., Ltd.) were dissolved, and water was added to adjust to 4 L. Into this, 300 mL of 25 wt% aqueous ammonia (manufactured by Agata Pharmaceutical Co., Ltd.) was added, and a 6 mol / L aqueous caustic soda solution was added while stirring this solution, and the pH was adjusted to 12.6 using the same pH meter as in Example 1. . The bath temperature was kept at 45 ° C. and stirred for 12 hours. The precipitate after stirring is repeatedly decanted and washed until the conductivity of the supernatant is 1 mS or less, and then the reaction solution is solid-liquid separated by filtration, and the solid is dried at 120 ° C. for 10 hours to obtain a metal hydroxide raw material. It was.
The number of moles of only the metal element of the metal hydroxide raw material is X mole, and the number of moles of Li element in the lithium carbonate is Y / X = 1.10, so that the metal hydroxide raw material and the lithium carbonate ( SQM) was weighed and thoroughly mixed with a ball mill to obtain a raw material mixed powder, and this raw material mixed powder was baked in the atmosphere at 880 ° C. for 20 hours.
The powder obtained by firing was crushed and classified in the same manner as in Example 1, and the particle size was measured. As a result, the volume average particle diameter D 50 was 5 μm, and the specific surface area was 2.2 m 2 / g. It was.
Moreover, the rate characteristic value of each powder (mortar crushed and classified) obtained by baking and the respective IR measured values are summarized in Table 1, and the plotted results are shown in FIGS.
（実施例５）
実施例４と同じ原料混合粉を大気中で９２０℃２０時間焼成した。
焼成して得られた粉末を、実施例１と同様に解砕及び分級し、その粒度を測定したところ、体積平均粒子径Ｄ50は７μｍであり、比表面積は１．９ｍ2／ｇであった。
また、焼成して得られた粉末（乳鉢解砕及び分級済）のレート特性値とそれぞれのＩＲ測定値を表１にまとめ、プロットした結果を図３、図４、図５に示した。
(Example 5)
The same raw material mixed powder as in Example 4 was fired in the atmosphere at 920 ° C. for 20 hours.
The powder obtained by firing was crushed and classified in the same manner as in Example 1, and the particle size was measured. As a result, the volume average particle diameter D 50 was 7 μm, and the specific surface area was 1.9 m 2 / g. It was.
Moreover, the rate characteristic value of each powder (mortar crushed and classified) obtained by firing and the respective IR measurement values are summarized in Table 1, and the plotted results are shown in FIG. 3, FIG. 4, and FIG.
（比較例１）
攪拌機付きの１０Ｌの密閉容器（オイルジャケット付き）に市水を２．５Ｌ量入れ、硫酸マンガン・５水和物（柳島製薬社製）５８８ｇ、硫酸コバルト・６水和物（関西触媒社製）７０３ｇおよび硫酸ニッケル・６水和物（三井金属社製）７６２ｇを溶解し、４Ｌになるよう水を加え調整した。その中に２５ｗｔ％のアンモニア水（アガタ薬品工業社製）６００ｍＬを加え、この溶液を攪拌しながら６ｍｏｌ／Ｌの苛性ソーダ水溶液を加え、実施例１と同じｐＨ計を用いてｐＨ１０．９に調整した。浴温は４５℃に保ち１２時間攪拌した。攪拌後の沈殿物を上澄みの導電率が１ｍS以下となるまでデカンテーション洗浄を繰り返し、その後反応溶液をろ過により固液分離し、固形物を１２０℃で１０ｈｒ乾燥し、金属水酸化物原料を得た。
この金属水酸化物原料の金属元素のみのモル数をＸモルとし、炭酸リチウム中のＬｉ元素のモル数Ｙが、Ｙ/Ｘ＝１．１０となるように金属水酸化物原料と炭酸リチウム（ＳＱＭ社製）を計り取り、ボールミルで十分に混合し、原料混合粉を得、この原料混合粉を大気中で８５０℃２０時間焼成した。
焼成して得られた粉末を、実施例１と同様に解砕及び分級し、その粒度を測定したところ、体積平均粒子径Ｄ50は１８μｍであり、比表面積は０．１ｍ2／ｇであった。
また、焼成して得られた粉末（乳鉢解砕及び分級済）のレート特性値とそれぞれのＩＲ測定値を表１にまとめ、プロットした結果を図３、図４、図５に示した。
(Comparative Example 1)
2.5L of city water is put in a 10L sealed container (with oil jacket) with a stirrer, 588g of manganese sulfate pentahydrate (manufactured by Yanagishima Pharmaceutical), cobalt sulfate hexahydrate (manufactured by Kansai Catalysts) 703 g and 762 g of nickel sulfate hexahydrate (manufactured by Mitsui Kinzoku Co., Ltd.) were dissolved, and water was added to adjust to 4 L. Into this, 600 mL of 25 wt% aqueous ammonia (manufactured by Agata Pharmaceutical Co., Ltd.) was added, and a 6 mol / L aqueous caustic soda solution was added while stirring this solution, and the pH was adjusted to 10.9 using the same pH meter as in Example 1. . The bath temperature was kept at 45 ° C. and stirred for 12 hours. The precipitate after stirring is repeatedly decanted and washed until the conductivity of the supernatant is 1 mS or less, and then the reaction solution is solid-liquid separated by filtration, and the solid is dried at 120 ° C. for 10 hours to obtain a metal hydroxide raw material. It was.
The number of moles of only the metal element of the metal hydroxide raw material is X mole, and the number of moles of Li element in the lithium carbonate is Y / X = 1.10, so that the metal hydroxide raw material and the lithium carbonate ( SQM) was weighed and thoroughly mixed with a ball mill to obtain a raw material mixed powder, and this raw material mixed powder was fired in the atmosphere at 850 ° C. for 20 hours.
The powder obtained by firing was crushed and classified in the same manner as in Example 1, and the particle size was measured. As a result, the volume average particle size D 50 was 18 μm, and the specific surface area was 0.1 m 2 / g. It was.
Moreover, the rate characteristic value of each powder (mortar crushed and classified) obtained by firing and the respective IR measurement values are summarized in Table 1, and the plotted results are shown in FIG. 3, FIG. 4, and FIG.
（比較例２）
比較例１と同じ原料混合粉を大気中で８８０℃２０時間焼成した。
焼成して得られた粉末を、実施例１と同様に解砕及び分級し、その粒度を測定したところ、体積平均粒子径Ｄ50は１９μｍであり、比表面積は０．１ｍ2／ｇであった。
また、焼成して得られた粉末（乳鉢解砕及び分級済）のレート特性値とそれぞれのＩＲ測定値を表１にまとめ、プロットした結果を図３、図４、図５に示した。
(Comparative Example 2)
The same raw material mixed powder as in Comparative Example 1 was baked in the air at 880 ° C. for 20 hours.
The powder obtained by firing was crushed and classified in the same manner as in Example 1, and the particle size was measured. As a result, the volume average particle diameter D 50 was 19 μm, and the specific surface area was 0.1 m 2 / g. It was.
Moreover, the rate characteristic value of each powder (mortar crushed and classified) obtained by firing and the respective IR measurement values are summarized in Table 1, and the plotted results are shown in FIG. 3, FIG. 4, and FIG.
（比較例３）
比較例１と同じ原料混合粉を大気中で９２０℃２０時間焼成した。
焼成して得られた粉末を、実施例１と同様に解砕及び分級し、その粒度を測定したところ、体積平均粒子径Ｄ50は２２μｍであり、比表面積は０．１ｍ2／ｇであった。
また、焼成して得られた粉末（乳鉢解砕及び分級済）のレート特性値とそれぞれのＩＲ測定値を表１にまとめ、プロットした結果を図３、図４、図５に示した。
(Comparative Example 3)
The same raw material mixed powder as in Comparative Example 1 was baked in the atmosphere at 920 ° C. for 20 hours.
The powder obtained by firing was crushed and classified in the same manner as in Example 1, and the particle size was measured. As a result, the volume average particle diameter D 50 was 22 μm, and the specific surface area was 0.1 m 2 / g. It was.
Moreover, the rate characteristic value of each powder (mortar crushed and classified) obtained by firing and the respective IR measurement values are summarized in Table 1, and the plotted results are shown in FIG. 3, FIG. 4, and FIG.
１１ 正極ケース
１２ 封口板
１３ 集電体
１５ 正極
１６ セパレータ
１４ 負極
１７ ガスケット
DESCRIPTION OF
Claims (9)
Layer represented by the composition formula Li 1 + x (Mn (1-x) / 3 Co (1-x) / 3 Ni (1-x) / 3 ) O 2 (x = 0.01 to 0.5) A lithium transition metal oxide having a structure, and a difference between a peak appearing near 570 to 595 cm −1 and a peak appearing near 520 to 550 cm −1 in an infrared absorption spectrum (FT-IR) is 50 cm −1 or less lithium transition metal oxide (nickel: manganese: cobalt = 1: 1: 1 sulfate aqueous solution, 13 mol / L ammonia aqueous solution, and 6 mol / L water adjusted to 75 mol / L) A sodium oxide aqueous solution is prepared, nitrogen gas is bubbled into the tank at 1 liter per minute to a dissolved oxygen amount of 0.2 mg / L, a nickel-manganese-cobalt salt aqueous solution at a rate of 10 ml per minute and ammonia at a rate of 1 ml per minute. Keep at 30 ° C The mixture was stirred and maintained, and a 6 mol / L sodium hydroxide aqueous solution was maintained at a rate of 6.2 ml / min. The resulting manganese-containing composite hydroxide was continuously taken out by overflowing from the upper part of the reaction vessel, collected after being continuously operated for 7 hours with a residence time of 7 hours, filtered with water, 80 Dry at 12 ° C. for 12 hours to obtain a manganese-containing composite hydroxide, and the resulting manganese-containing composite hydroxide and lithium hydroxide have a lithium / (nickel + manganese + cobalt) molar ratio of 1.25. And a lithium transition metal oxide obtained by baking at 800 ° C. for 20 hours in a box furnace .
A power storage power source using the lithium battery according to claim 5 as a driving power source.
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