JP4343618B2 - Method for producing polyanion type lithium iron composite oxide and battery using the same - Google Patents
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Description
本発明はリチウム二次電池の正極活物質に用いることのできるポリアニオン型リチウム鉄複合酸化物の製造方法及びそれを用いた電池に関する。 The present invention relates to a method for producing a polyanion-type lithium iron composite oxide that can be used as a positive electrode active material of a lithium secondary battery, and a battery using the same.
リチウム二次電池は、情報通信機器などの電源として広く普及しており、近年ではさらに、エネルギー、環境問題の観点からも、自動車などの動力源として応用が検討され、実用化もされるようになってきた。このため、これまで用いられてきたコバルト等に代えて、資源量が豊富な鉄を構成元素として含む、リチウム鉄複合酸化物を正極材料とすることが試みられている。 Lithium secondary batteries are widely used as a power source for information and communication equipment, and in recent years, in view of energy and environmental issues, their application as a power source for automobiles is being studied and put into practical use. It has become. For this reason, it has been attempted to use a lithium iron composite oxide containing, as a constituent element, iron having abundant resources as a positive electrode material instead of cobalt or the like that has been used so far.
その試みの一つとして、例えば、特開平9−134725号公報(特許文献1)に、オリビン構造を有するLiFePO4、LiFeVO4等を正極活物質として用いたリチウム二次電池が示されている。これらのリチウム鉄複合酸化物は、ポリアニオン型と総称されるもので、リン、バナジウム、硫黄などの元素を酸素格子の中に導入することで、鉄の+2価と+3価の間の酸化還元電位が高くなり、優れたエネルギー密度を達成できると言われている(非特許文献1)。 As one of the attempts, for example, Japanese Patent Laid-Open No. 9-134725 (Patent Document 1) discloses a lithium secondary battery using LiFePO 4 , LiFeVO 4, or the like having an olivine structure as a positive electrode active material. These lithium iron composite oxides are collectively referred to as polyanion type, and by introducing elements such as phosphorus, vanadium, and sulfur into the oxygen lattice, an oxidation-reduction potential between +2 and +3 valences of iron. It is said that the high energy density can be achieved (Non-patent Document 1).
ポリアニオン型リチウム鉄複合酸化物は、放電状態ではリチウムを吸蔵しており、鉄は、+2の原子価を有する。従来はこれを合成するために、シュウ酸鉄二水和物(FeC2O4・2H2O)や酢酸鉄(Fe(CH3CO2)2)などの、原子価が+2価の鉄化合物を鉄源に用いていた(特許文献2)。しかし、+2価の鉄化合物は安定性に乏しく、高価である。また、合成の際に雰囲気や共存化合物の影響で酸化や還元を受けやすい。さらに、これらの鉄源は焼成時に多量のガスを発生し、それに伴ってかさ密度も低下するため、合成がしにくいという問題もある。 The polyanion-type lithium iron composite oxide occludes lithium in a discharged state, and iron has a valence of +2. Conventionally, in order to synthesize this, an iron compound having a valence of +2 such as iron oxalate dihydrate (FeC 2 O 4 .2H 2 O) or iron acetate (Fe (CH 3 CO 2 ) 2 ) is used. It was used as an iron source (Patent Document 2). However, + 2-valent iron compounds have poor stability and are expensive. Further, it is susceptible to oxidation and reduction due to the influence of the atmosphere and coexisting compounds during synthesis. In addition, these iron sources generate a large amount of gas during firing, and the bulk density is reduced accordingly, which makes it difficult to synthesize.
一方、+3価の鉄化合物を原料に用いて前駆体を合成した後にこれを還元するという方法も報告されているが、工程が複雑になるという問題がある(非特許文献2、3)。また、金属鉄を用いてFePO4(+3価の鉄化合物)を合成する方法(非特許文献4)も報告されているが、LiFePO4を直接合成する方法はこれまでなかった。
本発明者らは鋭意検討を重ねた結果、+2価より原子価の低い鉄含有物質を酸化することで酸化・還元状態を制御しながらポリアニオン型リチウム鉄複合酸化物を容易に合成できることを見出し本発明に到達した。 As a result of intensive studies, the present inventors have found that a polyanion-type lithium iron composite oxide can be easily synthesized by controlling an oxidation / reduction state by oxidizing an iron-containing substance having a valence lower than +2. The invention has been reached.
すなわち本発明は、少なくとも、リチウム含有物質と、+2価より原子価の低い鉄含有物質と、ポリアニオン形成元素がリンであるポリアニオン形成元素含有物質と、+2価より原子価の高い鉄含有物質である酸化剤とを混合し、300〜1000℃の温度範囲で焼成することを特徴とし、特に、この酸化剤として、Fe3O4を用いることを特徴とするポリアニオン型リチウム鉄複合酸化物の製造方法を提供するものである。 That is, the present invention is at least a lithium-containing material, an iron-containing material having a valence lower than +2 , a polyanion-forming element-containing material in which the polyanion-forming element is phosphorus, and an iron-containing material having a valence higher than +2. an oxidizing agent are mixed, characterized by firing at a temperature range of 300 to 1000 ° C., in particular, the production method as the oxidizing agent, polyanionic lithium-iron composite oxide which comprises using a Fe 3 O 4 Is to provide.
以下、本発明を詳細に説明する。 Hereinafter, the present invention will be described in detail.
本発明において、ポリアニオン型リチウム鉄複合酸化物とは、基本的にリチウムと鉄とポリアニオン形成元素を酸素格子の空隙に有し、充電によってリチウムの脱離と鉄の+2価から+3価への酸化が起こり、放電によってリチウムの挿入と鉄の+3価から+2価への還元が起こるような複合酸化物である。一例としては、LiFePO4が挙げられる。ポリアニオン形成元素としては、Pが挙げられる。なお、ここで「基本的に」とは、これらの構成元素の一部を他の元素で置換した化合物も含むことを意味する。 In the present invention, the polyanion-type lithium iron composite oxide basically has lithium, iron, and a polyanion-forming element in the void of the oxygen lattice, and is desorbed from lithium and oxidized from +2 to +3 by charging. This is a composite oxide in which lithium insertion and iron reduction from +3 to +2 occur due to electric discharge. An example is LiFePO 4 . An example of the polyanion-forming element is P. Here, “basically” means that a compound in which some of these constituent elements are substituted with other elements is included.
本発明のポリアニオン型リチウム鉄複合酸化物の製造方法は、少なくとも、リチウム含有物質と、+2価より原子価の低い鉄含有物質と、ポリアニオン形成元素がリンであるポリアニオン形成元素含有物質と、+2価より原子価の高い鉄含有物質である酸化剤とを混合して混合物を得る原料混合工程と、該混合物を焼成する焼成工程とを含んでなることを特徴とする。また、この酸化剤として+2価より原子価の高い鉄含有物質を用いれば、酸化剤が鉄源の一部にもなり、目的のリチウム鉄複合酸化物を安価で簡単に製造することが可能になる。 The method for producing a polyanion-type lithium iron composite oxide of the present invention includes at least a lithium-containing material, an iron-containing material having a valence lower than +2 , a polyanion-forming element-containing material in which the polyanion-forming element is phosphorus, It is characterized by comprising a raw material mixing step of mixing an oxidizing agent that is an iron-containing substance having a higher valence and a baking step of baking the mixture. In addition, if an iron-containing substance having a valence higher than +2 is used as the oxidant, the oxidant becomes a part of the iron source, and the target lithium iron composite oxide can be easily manufactured at low cost. Become.
本発明で用いる+2価より原子価の低い鉄含有物質としては、金属鉄、Fe(CO)5等が挙げられる。特に、金属鉄は、安価で取り扱いやすいため好ましい。 Examples of the iron-containing substance having a lower valence than +2 used in the present invention include metallic iron and Fe (CO) 5 . In particular, metallic iron is preferable because it is inexpensive and easy to handle.
本発明で用いるリチウム化合物としては、Li2CO3、Li(OH)、Li(OH)・H2O、LiNO3、LiH2PO4等が挙げられる。 Examples of the lithium compound used in the present invention include Li 2 CO 3 , Li (OH), Li (OH) · H 2 O, LiNO 3 , LiH 2 PO 4 and the like.
ポリアニオン形成元素としては、リンが挙げられる。ポリアニオン形成元素がリンの場合、その原料となる物質としては、NH4H2PO4、(NH4)2HPO4、P4O10等、あるいは亜リン酸塩などを用いることができる。また、リチウム源とリン源を兼ねた化合物として、Li:Pが1:1で含まれるような、LiH2PO4等の化合物を用いることもできる。さらに、FePO4・2H2Oのような、リン源と鉄源と酸化剤を兼ねた化合物も用いることができる。 An example of the polyanion-forming element is phosphorus . When the polyanion-forming element is phosphorus, NH 4 H 2 PO 4 , (NH 4 ) 2 HPO 4 , P 4 O 10 or the like, or phosphite can be used as a raw material. A compound such as LiH 2 PO 4 in which Li: P is contained at a ratio of 1: 1 can also be used as a compound that serves as both a lithium source and a phosphorus source. Furthermore, a compound that combines a phosphorus source, an iron source, and an oxidizing agent, such as FePO 4 .2H 2 O, can also be used .
また、本発明で用いる酸化剤としては、Fe3O4、Fe2O3、FePO4等の鉄化合物が挙げられる。特にFe3O4、Fe2O3、FePO4等の常温の空気中で安定な物質を用いると、組成と酸化の程度を容易に制御できる。反応雰囲気は炭素質の添加や雰囲気ガスの選択や原料化合物の選択の影響も受けるので、酸化剤の選択とそれらの混合比は、原料中の元素組成比と反応性と反応雰囲気の酸化状態に応じて決定、調節すればよい。特に金属鉄とFe3O4の混合物を不活性ガス雰囲気下で用いれば、Fe3O4が金属鉄の酸化剤として作用するため、製造したいポリアニオン型リチウム鉄複合酸化物中の鉄の価数を+2価に制御することができる。
As the oxidizing agent used in the present invention, Fe 3 O 4, Fe 2 O 3, FePO iron compounds such as 4. In particular, when a material stable in air at normal temperature such as Fe 3 O 4 , Fe 2 O 3 , FePO 4 is used, the composition and the degree of oxidation can be easily controlled. Since the reaction atmosphere is also affected by the addition of carbonaceous material, the selection of atmospheric gas, and the selection of raw material compounds, the selection of oxidants and their mixing ratio depend on the elemental composition ratio, reactivity, and oxidation state of the reaction atmosphere Decide and adjust accordingly. In particular, when a mixture of metallic iron and Fe 3 O 4 is used in an inert gas atmosphere, Fe 3 O 4 acts as an oxidizing agent for metallic iron, so the valence of iron in the polyanionic lithium iron composite oxide to be produced Can be controlled to +2.
次に、混合物の焼成条件は、300〜1000℃の温度範囲が好ましく、より好ましくは450〜700℃の範囲で行なう。300℃より低い温度ではポリアニオン型複合酸化物相が十分に成長せず、1000℃より高い温度では結晶粒が成長しすぎて表面積が少なくなり、正極活物質としての特性が低下するため好ましくない。 Next, the firing conditions of the mixture are preferably in the temperature range of 300 to 1000 ° C, more preferably in the range of 450 to 700 ° C. When the temperature is lower than 300 ° C., the polyanion type complex oxide phase does not grow sufficiently, and when the temperature is higher than 1000 ° C., the crystal grains grow too much to reduce the surface area and the characteristics as the positive electrode active material are deteriorated.
鉄含有物質の粒子径は0.1〜1000μmの範囲が好ましく、より好ましくは1〜150μmの範囲のものが用いやすい。1000μmより粒子径が大きい場合、接触面積が小さくなるために固相反応が進行しにくく、0.1μmより粒子径が小さい場合、特に金属鉄の粉末などの場合には発火しやすく、取り扱いが難しいので好ましくない。 The particle size of the iron-containing substance is preferably in the range of 0.1 to 1000 μm, more preferably in the range of 1 to 150 μm. When the particle diameter is larger than 1000 μm, the contact area is small, so that the solid phase reaction is difficult to proceed. When the particle diameter is smaller than 0.1 μm, especially in the case of metallic iron powder, it is easy to ignite and difficult to handle. Therefore, it is not preferable.
本発明の製造方法により、原子価の制御性があり、安価で簡単にリチウム鉄複合酸化物を製造することができる。 According to the production method of the present invention, the lithium iron composite oxide can be produced easily and inexpensively with controllability of valence.
以下、実施例により本発明を具体的に説明するが、本発明はかかる実施例により限定されるものではない。 EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited by this Example.
実施例1
金属鉄を0.72g(粒子径 45μm)、Fe3O4を2.99g(粒子径 5μm)、LiH2PO4を5.37g秤量し、適量のアセトンを添加してボールミルで混合した後、乾燥して原料混合物を得た。
Example 1
After weighing 0.72 g of metal iron (
この原料混合物をArガスの流通下、400℃で24時間焼成したところ、Fe(JCPDSカード6−696)、Fe3O4(JCPDSカード19−629)、LiPO3(JCPDSカード26−1177)の回折線が見られ、LiFePO4と思われる相の回折線は弱く不明瞭であった。 When this raw material mixture was calcined at 400 ° C. for 24 hours under the flow of Ar gas, Fe (JCPDS card 6-696), Fe 3 O 4 (JCPDS card 19-629), LiPO 3 (JCPDS card 26-1177) A diffraction line was observed, and a diffraction line of a phase considered to be LiFePO 4 was weak and unclear.
そこで、原料混合物2.42gをArガスの流通下、600℃で24時間焼成し、放冷後取り出して乳鉢で再混合し、さらに600℃で24時間焼成し、生成物2.15gを得た。図1にこの生成物のX線回折を示す。得られた生成物は、LiFePO4(JCPDSカード40−1499、Triphylite)と良く一致していた。 Therefore, 2.42 g of the raw material mixture was baked at 600 ° C. for 24 hours under the flow of Ar gas, left to cool, taken out and remixed in a mortar, and further baked at 600 ° C. for 24 hours to obtain 2.15 g of product. . FIG. 1 shows the X-ray diffraction of this product. The product obtained was in good agreement with LiFePO 4 (JCPDS card 40-1499, Triphylite).
この生成物を正極活物質に用いてリチウム二次電池を作成した。試験用セルは以下のように作製した。生成物粉末70重量部に導電材としてアセチレンブラックを25重量部混合し、さらにバインダーとして5重量部のポリテトラフルオロエチレン(PTFE)を添加、混合して試験用正極体とした。この正極体を一定の厚みに延ばし、直径10mmの円形に打抜き、120℃で12時間真空乾燥したところ、重量は37mgであった。負極には金属リチウムを用い、ポリエチレン製セパレーターに電解液として1M−LiPF6/EC+EMC(1:2)溶液を浸み込ませてセルを組み立てた。これを用いた充放電試験の結果、充放電試験の電流密度は、0.2mA/cm2、充電は4.2V、放電は2.5V(vs.Li/Li+ )まで行ったところ、放電容量は生成物粉末に対して80mAh/gであった。 Using this product as the positive electrode active material, a lithium secondary battery was prepared. The test cell was produced as follows. 25 parts by weight of acetylene black as a conductive material was mixed with 70 parts by weight of the product powder, and 5 parts by weight of polytetrafluoroethylene (PTFE) was further added and mixed as a binder to obtain a test positive electrode body. When this positive electrode body was extended to a certain thickness, punched out into a circle having a diameter of 10 mm, and vacuum dried at 120 ° C. for 12 hours, the weight was 37 mg. Metal lithium was used for the negative electrode, and a cell was assembled by immersing a 1M-LiPF 6 / EC + EMC (1: 2) solution as an electrolyte in a polyethylene separator. As a result of the charge / discharge test using this, the current density of the charge / discharge test was 0.2 mA / cm 2 , the charge was 4.2 V, and the discharge was 2.5 V (vs. Li / Li +). Was 80 mAh / g based on the product powder.
実施例2
実施例1の45μmの金属鉄の代わりに通常の金属鉄粉(150μm以下成分95%含有)を用いて同様の原料混合物を調製した。600℃で24時間焼成し、放冷後取り出して乳鉢で再混合し、さらに600℃で24時間焼成したところ、X線回折ではLiFePO4の他にFeとLi3Fe2(PO4)3(JCPDSカード43−526)が検出された。同じ原料混合物を700℃で24時間焼成し、放冷後取り出して乳鉢で再混合し、さらに700℃で24時間焼成したところ、X線回折ではLiFePO4が検出され、実施例1と同様の方法で作成した電池の放電容量は32mAh/gであった。
Example 2
A similar raw material mixture was prepared using ordinary metal iron powder (containing 95% of component of 150 μm or less) in place of the 45 μm metal iron of Example 1. It was baked at 600 ° C. for 24 hours, allowed to cool, taken out, remixed in a mortar, and further baked at 600 ° C. for 24 hours. In X-ray diffraction, in addition to LiFePO 4 , Fe and Li 3 Fe 2 (PO 4 ) 3 ( JCPDS card 43-526) has been detected. The same raw material mixture was baked at 700 ° C. for 24 hours, allowed to cool, taken out, remixed in a mortar, and further baked at 700 ° C. for 24 hours. LiFePO 4 was detected by X-ray diffraction, and the same method as in Example 1 The discharge capacity of the battery prepared in (3) was 32 mAh / g.
実施例3
実施例1の原料混合物0.81gにショ糖0.24gを含む水溶液を添加し、混合後に350℃で24時間焼成し、放冷後取り出して乳鉢で再混合し、さらに700℃で24時間焼成したところ、X線回折からはLiFePO4の他にFeが検出された。
Example 3
An aqueous solution containing 0.24 g of sucrose is added to 0.81 g of the raw material mixture of Example 1, and after mixing, baked at 350 ° C. for 24 hours, left to cool, taken out and remixed in a mortar, and further baked at 700 ° C. for 24 hours. As a result, Fe was detected in addition to LiFePO 4 from X-ray diffraction.
そこで、金属鉄を減らし、その分のFe量をFe3O4で補完した混合物、すなわち金属鉄を0.50g、Fe3O4を2.22g、LiH2PO4を3.92g秤量し、適量のアセトンを添加してボールミルで混合した後、乾燥して原料混合物を得た。この原料混合物0.80gにショ糖0.24gを含む水溶液を添加し、混合後に350℃で24時間焼成し、放冷後取り出して乳鉢で再混合し、さらに700℃で24時間焼成したところ、X線回折ではLiFePO4とFeが検出されたが、Feの回折線は上述のFeとFe3O4の当量混合物の場合よりも有意に弱くなっていた。 Therefore, reducing the metallic iron, the mixture was supplemented by that amount of Fe content in Fe 3 O 4, that is, the metallic iron 0.50 g, 2.22 g of Fe 3 O 4, the LiH 2 PO 4 and 3.92g weighed, An appropriate amount of acetone was added and mixed with a ball mill, and then dried to obtain a raw material mixture. An aqueous solution containing 0.24 g of sucrose was added to 0.80 g of this raw material mixture, baked at 350 ° C. for 24 hours after mixing, taken out after standing to cool, remixed in a mortar, and further baked at 700 ° C. for 24 hours. In X-ray diffraction, LiFePO 4 and Fe were detected, but the diffraction line of Fe was significantly weaker than that of the above-mentioned equivalent mixture of Fe and Fe 3 O 4 .
実施例4
金属鉄を0.85g(粒子径 45μm)、Fe2O3を2.43g、LiH2PO4を4.75g秤量し、適量のアセトンを添加してボールミルで混合した後、乾燥して原料混合物を得た。
Example 4
0.85 g of metallic iron (
この原料混合物をArガスの流通下、600℃で24時間焼成し、放冷後取り出して乳鉢で再混合し、さらに600℃で24時間焼成し、生成物を得た。X線回折からはLiFePO4のほかにFe、Fe2O3、LiPO3が検出された。 This raw material mixture was baked at 600 ° C. for 24 hours under the flow of Ar gas, allowed to cool, taken out, remixed in a mortar, and further baked at 600 ° C. for 24 hours to obtain a product. In addition to LiFePO 4 , Fe, Fe 2 O 3 and LiPO 3 were detected from X-ray diffraction.
実施例5
金属鉄を0.43g(粒子径 45μm)、FePO4・2H2Oを2.88g、Li3PO4を0.89g秤量し、適量のアセトンを添加してボールミルで混合した後、乾燥して原料混合物を得た。
Example 5
0.43 g of metallic iron (
この原料混合物をArガスの流通下、600℃で24時間焼成し、放冷後取り出して乳鉢で再混合し、さらに600℃で24時間焼成し、生成物を得た。X線回折からはLiFePO4のほかにFe、Li3Fe2(PO4)3が検出された。 This raw material mixture was baked at 600 ° C. for 24 hours under the flow of Ar gas, allowed to cool, taken out, remixed in a mortar, and further baked at 600 ° C. for 24 hours to obtain a product. In addition to LiFePO 4 , Fe and Li 3 Fe 2 (PO 4 ) 3 were detected from X-ray diffraction.
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CN101506094B (en) * | 2006-08-21 | 2011-12-28 | 株式会社Lg化学 | Method for preparing lithium metal phosphate |
JP5216960B2 (en) * | 2006-12-26 | 2013-06-19 | 日立マクセル株式会社 | Positive electrode active material for lithium ion secondary battery |
WO2008093551A1 (en) * | 2007-01-29 | 2008-08-07 | Kanto Denka Kogyo Co., Ltd. | Compound having olivine structure, method for producing the same, positive electrode active material using compound having olivine structure, and nonaqueous electrolyte battery |
JP5388822B2 (en) * | 2009-03-13 | 2014-01-15 | Jfeケミカル株式会社 | Method for producing lithium iron phosphate |
TW201038469A (en) * | 2009-03-17 | 2010-11-01 | Basf Se | Synthesis of lithium-iron-phosphates |
JP5581065B2 (en) * | 2010-01-14 | 2014-08-27 | Jfeケミカル株式会社 | Method for producing lithium iron phosphate |
CN103688392B (en) * | 2011-07-20 | 2017-04-26 | 英属盖曼群岛商立凯电能科技股份有限公司 | Method for preparing battery composite material and precursor thereof |
JP5424285B2 (en) * | 2012-11-30 | 2014-02-26 | 日立マクセル株式会社 | Method for producing positive electrode active material for lithium ion secondary battery |
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