JP2003081639A - Manganese-containing layer lithium-transition metal compound oxide, and production method therefor - Google Patents
Manganese-containing layer lithium-transition metal compound oxide, and production method thereforInfo
- Publication number
- JP2003081639A JP2003081639A JP2002057053A JP2002057053A JP2003081639A JP 2003081639 A JP2003081639 A JP 2003081639A JP 2002057053 A JP2002057053 A JP 2002057053A JP 2002057053 A JP2002057053 A JP 2002057053A JP 2003081639 A JP2003081639 A JP 2003081639A
- Authority
- JP
- Japan
- Prior art keywords
- manganese
- transition metal
- metal composite
- composite oxide
- lithium
- 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.)
- Pending
Links
Classifications
-
- 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
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明はマンガン含有層状リチウ
ム−遷移金属複合酸化物及びその製造方法に関し、詳し
くは、非水電解質二次電池用正極材料にした時に、安全
性に優れ、充填性が高く、サイクル後も高い放電容量を
維持し、レート特性に優れたマンガン含有層状リチウム
−遷移金属複合酸化物及びその製造方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a layered lithium-transition metal composite oxide containing manganese, and a method for producing the same. TECHNICAL FIELD The present invention relates to a manganese-containing layered lithium-transition metal composite oxide which is high, maintains a high discharge capacity even after cycling, and is excellent in rate characteristics, and a method for producing the same.
【０００２】[0002]
【従来技術】近年のパソコンや電話等のポータブル化、
コードレス化の急速な進歩によりそれらの駆動用電源と
しての二次電池の需要が高まっている。その中でも非水
電解質二次電池は最も小型かつ高エネルギー密度を持つ
ため特に期待されている。上記の要望を満たす非水電解
質二次電池の正極活物質としてはコバルト酸リチウム
（ＬｉＣｏＯ２）、ニッケル酸リチウム（ＬｉＮｉ
Ｏ２）、マンガン酸リチウム（ＬｉＭｎ２Ｏ４）等があ
る。これらの複合酸化物はリチウムに対し４V以上の電
圧を有していることから、高エネルギー密度を有する電
池となり得る。2. Description of the Related Art In recent years, portable computers and telephones,
Due to the rapid progress of making cordless, the demand for secondary batteries as a power source for driving them is increasing. Among them, the non-aqueous electrolyte secondary battery is particularly expected because it is the smallest and has the highest energy density. Lithium cobalt oxide (LiCoO 2 ), lithium nickel oxide (LiNi) is used as a positive electrode active material of a non-aqueous electrolyte secondary battery satisfying the above demands.
O 2 ), lithium manganate (LiMn 2 O 4 ) and the like. Since these composite oxides have a voltage of 4 V or more with respect to lithium, they can be a battery having a high energy density.
【０００３】上記の複合酸化物のうちコバルト酸リチウ
ム（ＬｉＣｏＯ２）、ニッケル酸リチウム（ＬｉＮｉＯ
２）では初期放電容量が高いものの安全性が悪い。マン
ガン酸リチウム（ＬｉＭｎ２Ｏ４）は安全性が高いもの
の初期容量が低いという問題があった。そこで現在、ニ
ッケルやコバルトなどにマンガンを固溶させて安全性に
優れかつサイクル後も高い放電容量を維持した非水電解
質二次電池用正極活物質が検討されている。しかし、現
在のところ粒子が細かいため充填性が低くなるやレート
特性は悪いという課題である。Among the above composite oxides, lithium cobalt oxide (LiCoO 2 ) and lithium nickel oxide (LiNiO)
In 2 ), the initial discharge capacity is high but the safety is poor. Lithium manganate (LiMn 2 O 4 ) has high safety but has a problem of low initial capacity. Therefore, at present, a positive electrode active material for a non-aqueous electrolyte secondary battery, which is excellent in safety by dissolving manganese in nickel, cobalt or the like and maintains a high discharge capacity after cycling, is being studied. However, at present, since the particles are fine, the rate characteristic is poor as the filling property becomes low.
【０００４】[0004]
【発明が解決しようとする課題】従って本発明の目的
は、非水電解質二次電池用正極活物質としたときに、安
全性に優れ、充填性が高く、サイクル後も高い放電容量
を維持し、レート特性に優れたマンガン含有リチウム−
遷移金属複合酸化物を提供することにある。Therefore, an object of the present invention is to provide a positive electrode active material for a non-aqueous electrolyte secondary battery, which is excellent in safety, has a high filling property, and maintains a high discharge capacity even after cycling. , Manganese-containing lithium with excellent rate characteristics
It is to provide a transition metal composite oxide.
【０００５】[0005]
【課題を解決するための手段】本発明者は鋭意研究の結
果、粉体特性および含有させるマンガン量を特定したマ
ンガン含有層状リチウム−遷移金属複合酸化物およびそ
の原料となる遷移金属複合水酸化物の製造方法を規定す
ることにより上記目的を達し得ることを知見した。Means for Solving the Problems As a result of earnest research by the present inventors, the manganese-containing layered lithium-transition metal composite oxide and the transition metal composite hydroxide which is a raw material thereof are specified in powder characteristics and manganese content to be contained. It was found that the above object can be achieved by defining the manufacturing method of.
【０００６】よって、本発明は、比表面積１ｍ２／ｇ以
下、タップ密度１.６ｇ／ｃｍ３以上、平均粒径５〜５
０μｍであり、マンガン含有量が全遷移元素に対して１
０〜６０モル％であることを特徴とするマンガン含有層
状リチウム−遷移金属複合酸化物である。Therefore, the present invention has a specific surface area of 1 m 2 / g or less, a tap density of 1.6 g / cm 3 or more, and an average particle diameter of 5 to 5.
0 μm, manganese content is 1 relative to all transition elements
It is a manganese-containing layered lithium-transition metal composite oxide characterized by being 0 to 60 mol%.
【０００７】また、リチウムと全遷移金属のモル比が
１．０５〜１．４５であることを特徴とする前記記載の
マンガン含有層状リチウム−遷移金属複合酸化物であ
る。The above manganese-containing layered lithium-transition metal composite oxide is characterized in that the molar ratio of lithium to all transition metals is 1.05 to 1.45.
【０００８】また、前記記載のマンガン含有層状リチウ
ム−遷移金属複合酸化物がリチウム原料とマンガン含有
遷移金属複合水酸化物とをリチウム／全遷移金属のモル
比が１．０５〜１．４５となるように混合し、最終温度
として７５０℃以上で焼成されることを特徴とするマン
ガン含有層状リチウム−遷移金属複合酸化物の製造方法
である。Further, the manganese-containing layered lithium-transition metal composite oxide described above has a lithium raw material and a manganese-containing transition metal composite hydroxide having a lithium / total transition metal molar ratio of 1.05 to 1.45. Is mixed and baked at a final temperature of 750 ° C. or higher.
【０００９】また、マンガン含有層状リチウム−遷移金
属複合酸化物の原料であるマンガン含有遷移金属複合水
酸化物の合成工程が不活性ガス雰囲気下においてこのマ
ンガン含有層状リチウム−遷移金属複合酸化物中に含ま
れる遷移金属元素塩の水溶液とアルカリ水溶液及びアン
モニウムイオンを含む水溶液を密閉された反応槽内に連
続的に供給し、成長した複合水酸化物を連続的に取り出
されることを特徴とする前記記載のマンガン含有層状リ
チウム−遷移金属複合酸化物の製造方法である。Further, the manganese-containing layered lithium-transition metal composite oxide, which is a raw material for the manganese-containing layered lithium-transition metal composite oxide, is synthesized in the inert gas atmosphere in the manganese-containing layered lithium-transition metal composite oxide. An aqueous solution of a transition metal element salt contained therein, an aqueous alkali solution and an aqueous solution containing ammonium ions are continuously supplied into a closed reaction tank, and the grown composite hydroxide is continuously taken out. Is a method for producing the layered lithium-transition metal composite oxide containing manganese.
【００１０】また、密閉された槽内溶液中の溶存酸素量
が０．５ｍｇ／Ｌ以下で合成されることを特徴とする前
記記載のマンガン含有層状リチウム−遷移金属複合酸化
物の製造方法である。The method for producing a manganese-containing layered lithium-transition metal composite oxide as described above, characterized in that the dissolved oxygen content in the sealed solution in the tank is 0.5 mg / L or less. .
【００１１】また、槽内の平均滞留時間が３時間以上１
８時間以下であり、槽内の反応温度が２５℃以上５５℃
以下で反応させることを特徴とする前記記載のマンガン
含有層状リチウム−遷移金属複合酸化物の製造方法であ
る。The average residence time in the tank is 3 hours or more 1
8 hours or less, the reaction temperature in the tank is 25 ° C or more and 55 ° C
The method for producing a layered lithium-transition metal composite oxide containing manganese as described above, characterized in that the reaction is carried out below.
【００１２】また、前記記載のマンガン含有層状リチウ
ム−遷移金属複合酸化物または、前記記載のいずれか一
項に記載の製造方法によって得られたマンガン含有層状
リチウム−遷移金属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材料である。Further, it is composed of the above-mentioned manganese-containing layered lithium-transition metal composite oxide or the manganese-containing layered lithium-transition metal composite oxide obtained by the manufacturing method according to any one of the above-mentioned. It is a featured positive electrode material for a non-aqueous electrolyte secondary battery.
【００１３】また、前記記載の非水電解質二次電池用正
極材料を用いた正極とリチウムを吸蔵、脱蔵できる負極
と非水電解質とから構成されることを特徴とする非水電
解質二次電池である。A non-aqueous electrolyte secondary battery comprising a positive electrode using the above-mentioned positive electrode material for a non-aqueous electrolyte secondary battery, a negative electrode capable of inserting and extracting lithium, and a non-aqueous electrolyte. Is.
【００１４】[0014]
【発明の実施の形態】以下、本発明の実施の形態である
マンガン含有層状リチウム−遷移金属複合酸化物の詳細
について説明する。マンガン含有層状リチウム−遷移金
属複合酸化物の安全性を高めるために、比表面積が１ｍ
２／ｇ以下であり、マンガン含有量が全遷移金属元素に
対して１０モル％以上であることが好ましい。また、マ
ンガン含有量は６０モル％を超えると初期放電容量が低
下するので好ましくない。充填性はタップ密度で１．６
ｇ／ｃｃ以上であることが好ましい。平均粒径は５〜５
０μｍが好ましく、５μｍ未満だとタップ密度が１．６
ｇ／ｃｃ以上であっても電極に塗着した場合充填性があ
がらず、５０μｍを超えると正極材料として形成される
膜にひび割れ等発生し、均一な膜厚が形成しにくくなる
からである。BEST MODE FOR CARRYING OUT THE INVENTION The details of the manganese-containing layered lithium-transition metal composite oxide, which is an embodiment of the present invention, will be described below. In order to enhance the safety of the manganese-containing layered lithium-transition metal composite oxide, the specific surface area is 1 m.
It is preferably 2 / g or less and the manganese content is 10 mol% or more based on all transition metal elements. Further, if the manganese content exceeds 60 mol%, the initial discharge capacity decreases, which is not preferable. Fillability is tap density of 1.6
It is preferably at least g / cc. Average particle size is 5-5
0 μm is preferable, and if it is less than 5 μm, the tap density is 1.6.
This is because even if it is g / cc or more, the filling property does not decrease when it is applied to the electrode, and if it exceeds 50 μm, cracks or the like occur in the film formed as the positive electrode material, and it becomes difficult to form a uniform film thickness.
【００１５】マンガン含有層状リチウム−遷移金属複合
酸化物はリチウム原料とマンガン含有遷移金属複合水酸
化物とを混合し、焼成して得られる。リチウム原料とし
ては、炭酸リチウム（Ｌｉ２ＣＯ３）、硝酸リチウム
（ＬｉＮＯ３）、水酸化リチウム（ＬｉＯＨ）等が挙げ
られる。マンガン含有層状リチウム−遷移金属複合酸化
物の合成はリチウムと全遷移金属元素のモル比が１．０
５〜１．４５が好ましい。このモル比が１．０５未満で
は、レート特性が悪く、１．４５を超えては初期放電容
量が低下するので好ましくない。マンガン含有遷移金属
複合水酸化物とリチウム原料は、より大きな反応面積を
得るために、原料混合前あるいは後に粉砕することも好
ましい。秤量、混合された原料はそのままでもあるいは
造粒して使用してもよい。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、あるいはロール等を
用いたフレーク造粒でもよい。The manganese-containing layered lithium-transition metal composite oxide is obtained by mixing a lithium raw material and a manganese-containing transition metal composite hydroxide and firing the mixture. Examples of the lithium raw material include lithium carbonate (Li 2 CO 3 ), lithium nitrate (LiNO 3 ), and lithium hydroxide (LiOH). The manganese-containing layered lithium-transition metal composite oxide was synthesized with a molar ratio of lithium to all transition metal elements of 1.0.
5 to 1.45 is preferable. When the molar ratio is less than 1.05, the rate characteristics are poor, and when it exceeds 1.45, the initial discharge capacity is reduced, which is not preferable. It is also preferable that the manganese-containing transition metal composite hydroxide and the lithium raw material are pulverized before or after mixing the raw materials in order to obtain a larger reaction area. The weighed and mixed raw materials may be used as they are or after granulation. The granulation method may be wet or dry, and may be extrusion granulation, tumbling granulation, fluidized granulation, mixed granulation, spray drying granulation, pressure molding granulation, or flake granulation using a roll or the like. .
【００１６】このようにして得られた原料は焼成炉内に
投入され、６００〜１０００℃で焼成することによっ
て、マンガン含有層状リチウム−遷移金属複合酸化物が
得られる。単一相のマンガン含有層状リチウム−遷移金
属複合酸化物を得るには６００℃程度でも十分である
が、焼成温度が低いと粒成長が進まないので７５０℃以
上の焼成温度、好ましくは８５０℃以上の焼成温度が必
要となる。ここで用いられる焼成炉としては、ロータリ
ーキルンあるいは静置炉等が例示される。焼成時間は１
時間以上、好ましくは５〜２０時間である。The raw material thus obtained is put into a firing furnace and fired at 600 to 1000 ° C. to obtain a manganese-containing layered lithium-transition metal composite oxide. About 600 ° C. is sufficient to obtain a single-phase manganese-containing layered lithium-transition metal composite oxide, but grain growth does not proceed if the firing temperature is low, so a firing temperature of 750 ° C. or higher, preferably 850 ° C. or higher Firing temperature is required. Examples of the firing furnace used here include a rotary kiln and a stationary furnace. Firing time is 1
It is time or more, preferably 5 to 20 hours.
【００１７】マンガン含有層状リチウム−遷移金属複合
酸化物の原料であるマンガン含有遷移金属複合水酸化物
の合成工程は不活性ガス雰囲気下においてこのマンガン
含有層状リチウム−遷移金属複合酸化物中に含まれる遷
移金属元素塩の水溶液とアルカリ水溶液及びアンモニウ
ムイオンを含む水溶液を密閉された反応槽内に連続的に
供給し、成長した複合水酸化物を連続的に取り出される
ことを特徴とする製造方法である。この密閉された槽内
溶液中の溶存酸素量が０．５ｍｇ／Ｌ以下で合成され
る。溶存酸素量が０．５ｍｇ／Ｌを超えると合成された
マンガン含有遷移金属複合水酸化物がマンガンとその他
の元素に分離してしまうため、焼成して得られたマンガ
ン含有層状リチウム−遷移金属複合酸化物は単一相にな
らない。The manganese-containing layered lithium-transition metal composite oxide, which is a raw material of the manganese-containing layered lithium-transition metal composite oxide, is synthesized in the manganese-containing layered lithium-transition metal composite oxide under an inert gas atmosphere. A production method characterized in that an aqueous solution of a transition metal element salt, an aqueous alkali solution and an aqueous solution containing ammonium ions are continuously supplied into a closed reaction tank, and the grown composite hydroxide is continuously taken out. . The amount of dissolved oxygen in the sealed in-tank solution is 0.5 mg / L or less. When the dissolved oxygen amount exceeds 0.5 mg / L, the synthesized manganese-containing transition metal composite hydroxide separates into manganese and other elements. Therefore, the manganese-containing layered lithium-transition metal composite obtained by firing was obtained. The oxide does not become a single phase.
【００１８】合成工程の平均滞留時間は３時間以上１８
時間以下であることが好ましく、槽内の反応温度が２５
℃以上５５℃以下で反応させることが好ましい。平均滞
留時間が３時間以下であると平均粒径が小さくなりす
ぎ、１８時間を超えると平均粒径が大きくなりすぎるた
め好ましくない。このような製造法によって得られたマ
ンガン含有層状リチウム−遷移金属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であ
る。本発明の非水電解質二次電池では、上記正極材料と
カーボンブラック等の導電材とテトラフルオロエチレン
・バインダー等の結着剤とを混合して正極合剤とし、ま
た、負極にはリチウムまたはカーボン等のリチウムを吸
蔵、脱蔵できる材料が用いられ、非水系電解質として
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が用いられるが、特に限定さ
れるものではない。The average residence time in the synthesis process is 3 hours or more 18
The reaction temperature in the tank is preferably 25 hours or less.
It is preferable to carry out the reaction at a temperature of not less than 0 ° C and not more than 55 ° C. If the average residence time is 3 hours or less, the average particle size becomes too small, and if it exceeds 18 hours, the average particle size becomes too large, which is not preferable. A positive electrode active material for a non-aqueous electrolyte secondary battery, comprising a manganese-containing layered lithium-transition metal composite oxide obtained by such a production method. In the non-aqueous electrolyte secondary battery of the present invention, the positive electrode material, a conductive material such as carbon black, and a binder such as tetrafluoroethylene binder are mixed to form a positive electrode mixture, and lithium or carbon is used for the negative electrode. A material capable of inserting and extracting lithium such as lithium is used as the non-aqueous electrolyte, and a lithium salt such as lithium hexafluorophosphate (LiPF 6 ) dissolved in a mixed solvent such as ethylene carbonate-dimethyl carbonate is used. However, it is not particularly limited.
【００１９】[0019]
【実施例】実施例１
１．７５ｍｏｌ／Ｌに調整したニッケル／マンガン＝
５：５の硫酸塩水溶液、１３ｍｏｌ／Ｌのアンモニア水
溶液、６ｍｏｌ／Ｌの水酸化ナトリウム水溶液を準備し
た。槽内には窒素ガスを毎分１リットルバブリングさせ
た。そのときの溶存酸素量は０．２ｍｇ／Ｌであった。
上記ニッケル−マンガン塩水溶液を毎分１０ｍｌ及びア
ンモニアを毎分１ｍｌの速度で、３０℃に保ちながら速
やかに均一になるよう混合撹拌した。槽内温度を３０℃
に保ったまま６ｍｏｌ／Ｌの水酸化ナトリウム水溶液を
平均毎分６．２ｍｌの速度で反応槽内のｐＨが１２．０
±０．２の範囲で保持するように供給しつつ撹拌した。
ニッケル、マンガン塩の総量１に対して水酸化ナトリ
ウムは２．０、アンモニアは１．３５になるようにし
た。EXAMPLES Example 1 Nickel / manganese adjusted to 1.75 mol / L =
A 5: 5 sulfate aqueous solution, a 13 mol / L aqueous ammonia solution, and a 6 mol / L aqueous sodium hydroxide solution were prepared. Nitrogen gas was bubbled through the tank at 1 liter per minute. The amount of dissolved oxygen at that time was 0.2 mg / L.
The above nickel-manganese salt aqueous solution was mixed and stirred at a rate of 10 ml / min and ammonia at a rate of 1 ml / min so as to be rapidly uniform while maintaining the temperature at 30 ° C. The temperature in the tank is 30 ℃
The pH in the reaction tank was kept at 12.0 at an average rate of 6.2 ml per minute with a 6 mol / L sodium hydroxide aqueous solution.
The mixture was stirred while being supplied so as to maintain the range of ± 0.2.
Sodium hydroxide was 2.0 and ammonia was 1.35 with respect to the total amount of nickel and manganese salts.
【００２０】生成したマンガン含有複合水酸化物を反応
槽上部よりオーバーフローさせ連続的に取り出した。こ
のときの滞留時間は７時間であり、７時間連続作動させ
たのちサンプルを採取し、水洗濾過後、８０℃で１２時
間乾燥してマンガン含有複合水酸化物を得た。 得られ
たマンガン含有複合水酸化物とリチウム原料として水酸
化リチウムをリチウム／（ニッケル＋マンガン）のモル
比が１．２５となるように混合し、箱型炉中、８００℃
で２０時間焼成してマンガン含有層状リチウム−遷移金
属複合酸化物を得た。このときの比表面積、タップ密度
および平均粒径を表１に示す。The produced manganese-containing composite hydroxide was overflowed from the upper part of the reaction tank and continuously taken out. The residence time at this time was 7 hours, and after operating continuously for 7 hours, a sample was collected, washed with water and filtered, and then dried at 80 ° C. for 12 hours to obtain a manganese-containing composite hydroxide. The obtained manganese-containing composite hydroxide was mixed with lithium hydroxide as a lithium raw material so that the molar ratio of lithium / (nickel + manganese) was 1.25, and the mixture was heated in a box furnace at 800 ° C.
And was baked for 20 hours to obtain a manganese-containing layered lithium-transition metal composite oxide. Table 1 shows the specific surface area, tap density and average particle size at this time.
【００２１】[0021]
【表１】 [Table 1]
【００２２】このようにして得られたスピネル型マンガ
ン酸リチウムを８０重量部、導電剤としてカーボンプラ
ック１５重量部および結着剤としてポリ四フッ化エチレ
ン５重量部を混合して正極合剤を作製した。この正極合
剤を用いて図１に示すコイン型非水電解質二次電池を作
製した。すなわち、耐有機電解液性のステンレス鋼製の
正極ケース１の内側には同じくステンレス鋼製の集電体
３がスポット熔接されている。集電体３の上面には上記
正極合剤からなる正極５が圧着されている。正極５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６が配置されている。正極ケース１の開
口部には、下方に金属リチウムからなる負極４を接合し
た封口板２が、ポリプロピレン製のガスケット７を挟ん
で配置されており、これにより電池は密封されている。
封口板２は、負極端子を兼ね、正極ケース１と同様のス
テンレス鋼製である。電池の直径は２０ｍｍ、電池総高
１．６ｍｍである。電解液には、エチレンカーボネート
と１，３−ジメトキシエタンを等体積混合したものを溶
媒とし、これに溶質として六フッ化リン酸リチウムを１
ｍｏｌ／リットル溶解させたものを用いた。80 parts by weight of the spinel-type lithium manganate thus obtained, 15 parts by weight of carbon plaque as a conductive agent, and 5 parts by weight of polytetrafluoroethylene as a binder were mixed to prepare a positive electrode mixture. did. A coin type non-aqueous electrolyte secondary battery shown in FIG. 1 was produced using this positive electrode mixture. That is, the stainless steel collector 3 is also spot-welded inside the organic electrolytic solution-resistant stainless steel positive electrode case 1. A positive electrode 5 made of the positive electrode mixture is pressure-bonded to the upper surface of the current collector 3. A separator 6 made of microporous polypropylene resin impregnated with an electrolytic solution is arranged on the upper surface of the positive electrode 5. At the opening of the positive electrode case 1, a sealing plate 2 to which a negative electrode 4 made of metallic lithium is joined is arranged with a gasket 7 made of polypropylene sandwiched therebetween, whereby the battery is sealed.
The sealing plate 2 also serves as a negative electrode terminal and is made of the same stainless steel as the positive electrode case 1. The diameter of the battery is 20 mm, and the total height of the battery is 1.6 mm. For the electrolyte, a mixture of ethylene carbonate and 1,3-dimethoxyethane in equal volumes was used as a solvent, and lithium hexafluorophosphate was added as a solute to the solvent.
Mol / liter was used after being dissolved.
【００２３】このようにして得られた電池について充放
電試験を行った。充放電試験は２０℃において行われ、
電流密度を０．５ｍＡ／ｃｍ２とし、電圧４．３Ｖから
３．０Ｖの範囲で行った。その初期放電容量および２５
サイクル時の放電容量の測定結果を表１に示す。また、
電流密度を５ｍＡ／ｃｍ２として放電したときの放電容
量と０．５ｍＡ／ｃｍ２としたときの放電容量の比
（（５ｍＡ／ｃｍ２の放電容量）／０．５ｍＡ／ｃｍ２
時の放電容量））をレート特性として表1に示す。The battery thus obtained was subjected to a charge / discharge test. The charge / discharge test is performed at 20 ° C,
The current density was 0.5 mA / cm 2 and the voltage was in the range of 4.3V to 3.0V. Its initial discharge capacity and 25
Table 1 shows the measurement results of the discharge capacity during the cycle. Also,
The ratio of the discharge capacity when the discharge capacity and 0.5 mA / cm 2 when discharged at a current density of 5mA / cm 2 ((discharge capacity 5mA / cm 2) /0.5mA/cm 2
Table 1 shows the discharge capacity))) as rate characteristics.
【００２４】実施例２
１．７５ｍｏｌ／Ｌに調整したニッケル／マンガンの比
が９：１とした以外は、実施例１と同様にマンガン含有
層状リチウム−遷移金属複合酸化物の合成を行った。こ
のときの比表面積、タップ密度および平均粒径を表１に
示す。また、このマンガン含有層状リチウム−遷移金属
複合酸化物を正極材料として実施例１と同様にしてコイ
ン型非水電解質二次電池を作製し、初期放電容量、２５
サイクル時の放電容量およびレート特性の測定結果を表
１に示す。Example 2 A manganese-containing layered lithium-transition metal composite oxide was synthesized in the same manner as in Example 1 except that the nickel / manganese ratio adjusted to 1.75 mol / L was 9: 1. Table 1 shows the specific surface area, tap density and average particle size at this time. A coin-type non-aqueous electrolyte secondary battery was prepared in the same manner as in Example 1 using the manganese-containing layered lithium-transition metal composite oxide as a positive electrode material.
Table 1 shows the measurement results of the discharge capacity and rate characteristics during the cycle.
【００２５】実施例３
７５ｍｏｌ／Ｌに調整したニッケル／マンガンの比が
４：６とした以外は、実施例１と同様にマンガン含有層
状リチウム−遷移金属複合酸化物の合成を行った。この
ときの比表面積、タップ密度および平均粒径を表１に示
す。また、このマンガン含有層状リチウム−遷移金属複
合酸化物を正極材料として実施例１と同様にしてコイン
型非水電解質二次電池を作製し、初期放電容量、２５サ
イクル時の放電容量およびレート特性の測定結果を表１
に示す。Example 3 A manganese-containing layered lithium-transition metal composite oxide was synthesized in the same manner as in Example 1 except that the nickel / manganese ratio adjusted to 75 mol / L was 4: 6. Table 1 shows the specific surface area, tap density and average particle size at this time. Further, a coin-type non-aqueous electrolyte secondary battery was prepared in the same manner as in Example 1 using the manganese-containing layered lithium-transition metal composite oxide as a positive electrode material, and the initial discharge capacity, discharge capacity at 25 cycles and rate characteristics were evaluated. Table 1 shows the measurement results
Shown in.
【００２６】実施例４
ニッケルの替わりにコバルトとした以外は、実施例１と
同様にマンガン含有層状リチウム−遷移金属複合酸化物
の合成を行った。このときの比表面積、タップ密度およ
び平均粒径を表１に示す。また、このマンガン含有層状
リチウム−遷移金属複合酸化物を正極材料として実施例
１と同様にしてコイン型非水電解質二次電池を作製し、
初期放電容量、２５サイクル時の放電容量およびレート
特性の測定結果を表１に示す。Example 4 A manganese-containing layered lithium-transition metal composite oxide was synthesized in the same manner as in Example 1 except that cobalt was used instead of nickel. Table 1 shows the specific surface area, tap density and average particle size at this time. A coin-type non-aqueous electrolyte secondary battery was prepared in the same manner as in Example 1 using the manganese-containing layered lithium-transition metal composite oxide as a positive electrode material.
Table 1 shows the measurement results of the initial discharge capacity, the discharge capacity after 25 cycles, and the rate characteristics.
【００２７】実施例５
１．７５ｍｏｌ／Ｌに調整したコバルト／マンガンの比
が９：１とした以外は、実施例４と同様にマンガン含有
層状リチウム−遷移金属複合酸化物の合成を行った。こ
のときの比表面積、タップ密度および平均粒径を表１に
示す。また、このマンガン含有層状リチウム−遷移金属
複合酸化物を正極材料として実施例１と同様にしてコイ
ン型非水電解質二次電池を作製し、初期放電容量、２５
サイクル時の放電容量およびレート特性の測定結果を表
１に示す。Example 5 A manganese-containing layered lithium-transition metal composite oxide was synthesized in the same manner as in Example 4 except that the cobalt / manganese ratio adjusted to 1.75 mol / L was 9: 1. Table 1 shows the specific surface area, tap density and average particle size at this time. A coin-type non-aqueous electrolyte secondary battery was prepared in the same manner as in Example 1 using the manganese-containing layered lithium-transition metal composite oxide as a positive electrode material.
Table 1 shows the measurement results of the discharge capacity and rate characteristics during the cycle.
【００２８】実施例６
１．７５ｍｏｌ／Ｌに調整したコバルト／マンガンの比
が４：６とした以外は、実施例４と同様にマンガン含有
層状リチウム−遷移金属複合酸化物の合成を行った。こ
のときの比表面積、タップ密度および平均粒径を表１に
示す。また、このマンガン含有層状リチウム−遷移金属
複合酸化物を正極材料として実施例１と同様にしてコイ
ン型非水電解質二次電池を作製し、初期放電容量、２５
サイクル時の放電容量およびレート特性の測定結果を表
１に示す。Example 6 A manganese-containing layered lithium-transition metal composite oxide was synthesized in the same manner as in Example 4 except that the cobalt / manganese ratio adjusted to 1.75 mol / L was 4: 6. Table 1 shows the specific surface area, tap density and average particle size at this time. A coin-type non-aqueous electrolyte secondary battery was prepared in the same manner as in Example 1 using the manganese-containing layered lithium-transition metal composite oxide as a positive electrode material.
Table 1 shows the measurement results of the discharge capacity and rate characteristics during the cycle.
【００２９】実施例７
遷移金属元素をニッケル、マンガン、コバルトとし、そ
のモル比を１：１：１とした以外は、実施例１と同様に
マンガン含有層状リチウム−遷移金属複合酸化物の合成
を行った。このときの比表面積、タップ密度および平均
粒径を表１に示す。また、このマンガン含有層状リチウ
ム−遷移金属複合酸化物を正極材料として実施例１と同
様にしてコイン型非水電解質二次電池を作製し、初期放
電容量、２５サイクル時の放電容量およびレート特性の
測定結果を表１に示す。Example 7 A manganese-containing layered lithium-transition metal composite oxide was synthesized in the same manner as in Example 1 except that the transition metal elements were nickel, manganese, and cobalt, and the molar ratio was 1: 1: 1. went. Table 1 shows the specific surface area, tap density and average particle size at this time. Further, a coin-type non-aqueous electrolyte secondary battery was prepared in the same manner as in Example 1 using the manganese-containing layered lithium-transition metal composite oxide as a positive electrode material, and the initial discharge capacity, discharge capacity at 25 cycles and rate characteristics were evaluated. The measurement results are shown in Table 1.
【００３０】実施例８
遷移金属元素をニッケル、マンガン、コバルトとし、そ
のモル比を６：３：１とした以外は、実施例１と同様に
マンガン含有層状リチウム−遷移金属複合酸化物の合成
を行った。このときの比表面積、タップ密度および平均
粒径を表１に示す。また、このマンガン含有層状リチウ
ム−遷移金属複合酸化物を正極材料として実施例１と同
様にしてコイン型非水電解質二次電池を作製し、初期放
電容量、２５サイクル時の放電容量およびレート特性の
測定結果を表１に示す。Example 8 A manganese-containing layered lithium-transition metal composite oxide was synthesized in the same manner as in Example 1 except that the transition metal elements were nickel, manganese, and cobalt, and the molar ratio was 6: 3: 1. went. Table 1 shows the specific surface area, tap density and average particle size at this time. Further, a coin-type non-aqueous electrolyte secondary battery was prepared in the same manner as in Example 1 using the manganese-containing layered lithium-transition metal composite oxide as a positive electrode material, and the initial discharge capacity, discharge capacity at 25 cycles and rate characteristics were evaluated. The measurement results are shown in Table 1.
【００３１】実施例９
遷移金属元素をニッケル、マンガン、コバルトとし、そ
のモル比を１：３：６とした以外は、実施例１と同様に
マンガン含有層状リチウム−遷移金属複合酸化物の合成
を行った。このときの比表面積、タップ密度および平均
粒径を表１に示す。また、このマンガン含有層状リチウ
ム−遷移金属複合酸化物を正極材料として実施例１と同
様にしてコイン型非水電解質二次電池を作製し、初期放
電容量、２５サイクル時の放電容量およびレート特性の
測定結果を表１に示す。Example 9 A manganese-containing layered lithium-transition metal composite oxide was synthesized in the same manner as in Example 1 except that the transition metal elements were nickel, manganese, and cobalt, and the molar ratio thereof was 1: 3: 6. went. Table 1 shows the specific surface area, tap density and average particle size at this time. Further, a coin-type non-aqueous electrolyte secondary battery was prepared in the same manner as in Example 1 using the manganese-containing layered lithium-transition metal composite oxide as a positive electrode material, and the initial discharge capacity, discharge capacity at 25 cycles and rate characteristics were evaluated. The measurement results are shown in Table 1.
【００３２】実施例１０
リチウム原料として水酸化リチウムをリチウム／（ニッ
ケル＋マンガン）のモル比が１．０５となるように混合
した以外は、実施例１と同様にマンガン含有層状リチウ
ム−遷移金属複合酸化物の合成を行った。このときの比
表面積、タップ密度および平均粒径を表１に示す。ま
た、このマンガン含有層状リチウム−遷移金属複合酸化
物を正極材料として実施例１と同様にしてコイン型非水
電解質二次電池を作製し、初期放電容量、２５サイクル
時の放電容量およびレート特性の測定結果を表１に示
す。Example 10 A manganese-containing layered lithium-transition metal composite was prepared in the same manner as in Example 1 except that lithium hydroxide was mixed as a lithium raw material so that the molar ratio of lithium / (nickel + manganese) was 1.05. The oxide was synthesized. Table 1 shows the specific surface area, tap density and average particle size at this time. Further, a coin-type non-aqueous electrolyte secondary battery was prepared in the same manner as in Example 1 using the manganese-containing layered lithium-transition metal composite oxide as a positive electrode material, and the initial discharge capacity, discharge capacity at 25 cycles and rate characteristics were evaluated. The measurement results are shown in Table 1.
【００３３】実施例１１
リチウム原料として水酸化リチウムをリチウム／（ニッ
ケル＋マンガン）のモル比が１．４５となるように混合
した以外は、実施例１と同様にマンガン含有層状リチウ
ム−遷移金属複合酸化物の合成を行った。このときの比
表面積、タップ密度および平均粒径を表１に示す。ま
た、このマンガン含有層状リチウム−遷移金属複合酸化
物を正極材料として実施例１と同様にしてコイン型非水
電解質二次電池を作製し、初期放電容量、２５サイクル
時の放電容量およびレート特性の測定結果を表１に示
す。Example 11 A manganese-containing layered lithium-transition metal composite was prepared in the same manner as in Example 1 except that lithium hydroxide was mixed as a lithium raw material so that the molar ratio of lithium / (nickel + manganese) was 1.45. The oxide was synthesized. Table 1 shows the specific surface area, tap density and average particle size at this time. Further, a coin-type non-aqueous electrolyte secondary battery was prepared in the same manner as in Example 1 using the manganese-containing layered lithium-transition metal composite oxide as a positive electrode material, and the initial discharge capacity, discharge capacity at 25 cycles and rate characteristics were evaluated. The measurement results are shown in Table 1.
【００３４】実施例１２
焼成温度を７５０℃とした以外は、実施例１と同様にマ
ンガン含有層状リチウム−遷移金属複合酸化物の合成を
行った。このときの比表面積、タップ密度および平均粒
径を表１に示す。また、このマンガン含有層状リチウム
−遷移金属複合酸化物を正極材料として実施例１と同様
にしてコイン型非水電解質二次電池を作製し、初期放電
容量、２５サイクル時の放電容量およびレート特性の測
定結果を表１に示す。Example 12 A manganese-containing layered lithium-transition metal composite oxide was synthesized in the same manner as in Example 1 except that the firing temperature was 750 ° C. Table 1 shows the specific surface area, tap density and average particle size at this time. Further, a coin-type non-aqueous electrolyte secondary battery was prepared in the same manner as in Example 1 using the manganese-containing layered lithium-transition metal composite oxide as a positive electrode material, and the initial discharge capacity, discharge capacity at 25 cycles and rate characteristics were evaluated. The measurement results are shown in Table 1.
【００３５】実施例１３
焼成温度を９００℃とした以外は、実施例１と同様にマ
ンガン含有層状リチウム−遷移金属複合酸化物の合成を
行った。このときの比表面積、タップ密度および平均粒
径を表１に示す。また、このマンガン含有層状リチウム
−遷移金属複合酸化物を正極材料として実施例１と同様
にしてコイン型非水電解質二次電池を作製し、初期放電
容量、２５サイクル時の放電容量およびレート特性の測
定結果を表１に示す。Example 13 A manganese-containing layered lithium-transition metal composite oxide was synthesized in the same manner as in Example 1 except that the firing temperature was 900 ° C. Table 1 shows the specific surface area, tap density and average particle size at this time. Further, a coin-type non-aqueous electrolyte secondary battery was prepared in the same manner as in Example 1 using the manganese-containing layered lithium-transition metal composite oxide as a positive electrode material, and the initial discharge capacity, discharge capacity at 25 cycles and rate characteristics were evaluated. The measurement results are shown in Table 1.
【００３６】実施例１４
上記ニッケル−マンガン塩水溶液を毎分２０ｍｌ及びア
ンモニアを毎分２ｍｌの速度で、３０℃に保ちながら速
やかに均一になるよう混合撹拌した。槽内温度を３０℃
に保ったまま６ｍｏｌ／Ｌの水酸化ナトリウム水溶液を
平均毎分１２．４ｍｌの速度で反応槽内のｐＨが１２．
０±０．２の範囲で保持するように供給しつつ撹拌した
以外は、実施例１と同様にマンガン含有層状リチウム−
遷移金属複合酸化物の合成を行った。このときの比表面
積、タップ密度および平均粒径を表１に示す。また、こ
のマンガン含有層状リチウム−遷移金属複合酸化物を正
極材料として実施例１と同様にしてコイン型非水電解質
二次電池を作製し、初期放電容量、２５サイクル時の放
電容量およびレート特性の測定結果を表１に示す。Example 14 The above nickel-manganese salt aqueous solution was mixed and stirred at a rate of 20 ml / min and ammonia at a rate of 2 ml / min so as to be rapidly uniform while maintaining the temperature at 30 ° C. The temperature in the tank is 30 ℃
The pH in the reaction vessel was kept at 12.4 ml / min of a 6 mol / L sodium hydroxide aqueous solution at an average rate of 12.4 ml / min.
Manganese-containing layered lithium-as in Example 1 except that stirring was carried out while supplying so as to maintain the range of 0 ± 0.2.
A transition metal composite oxide was synthesized. Table 1 shows the specific surface area, tap density and average particle size at this time. Further, a coin-type non-aqueous electrolyte secondary battery was prepared in the same manner as in Example 1 using the manganese-containing layered lithium-transition metal composite oxide as a positive electrode material, and the initial discharge capacity, discharge capacity at 25 cycles and rate characteristics were evaluated. The measurement results are shown in Table 1.
【００３７】実施例１５
上記ニッケル−マンガン塩水溶液を毎分５ｍｌ及びアン
モニアを毎分０．５ｍｌの速度で、３０℃に保ちながら
速やかに均一になるよう混合撹拌した。槽内温度を３０
℃に保ったまま６ｍｏｌ／Ｌの水酸化ナトリウム水溶液
を平均毎分３．１ｍｌの速度で反応槽内のｐＨが１２．
０±０．２の範囲で保持するように供給しつつ撹拌した
以外は、実施例１と同様にマンガン含有層状リチウム−
遷移金属複合酸化物の合成を行った。このときの比表面
積、タップ密度および平均粒径を表１に示す。また、こ
のマンガン含有層状リチウム−遷移金属複合酸化物を正
極材料として実施例１と同様にしてコイン型非水電解質
二次電池を作製し、初期放電容量、２５サイクル時の放
電容量およびレート特性の測定結果を表１に示す。Example 15 The above nickel-manganese salt aqueous solution was mixed and stirred at a rate of 5 ml / min and ammonia at a rate of 0.5 ml / min so as to be rapidly uniform while maintaining the temperature at 30 ° C. The tank temperature is 30
While keeping the temperature at 0 ° C, 6 mol / L sodium hydroxide aqueous solution had an average pH of 3.1 ml / min and a pH of 12.
Manganese-containing layered lithium-as in Example 1 except that stirring was carried out while supplying so as to maintain the range of 0 ± 0.2.
A transition metal composite oxide was synthesized. Table 1 shows the specific surface area, tap density and average particle size at this time. Further, a coin-type non-aqueous electrolyte secondary battery was prepared in the same manner as in Example 1 using the manganese-containing layered lithium-transition metal composite oxide as a positive electrode material, and the initial discharge capacity, discharge capacity at 25 cycles and rate characteristics were evaluated. The measurement results are shown in Table 1.
【００３８】実施例１６
槽内温度を２５℃にした以外は、実施例１と同様にマン
ガン含有層状リチウム−遷移金属複合酸化物の合成を行
った。このときの比表面積、タップ密度および平均粒径
を表１に示す。また、このマンガン含有層状リチウム−
遷移金属複合酸化物を正極材料として実施例１と同様に
してコイン型非水電解質二次電池を作製し、初期放電容
量、２５サイクル時の放電容量およびレート特性の測定
結果を表１に示す。Example 16 A manganese-containing layered lithium-transition metal composite oxide was synthesized in the same manner as in Example 1 except that the temperature in the bath was set to 25 ° C. Table 1 shows the specific surface area, tap density and average particle size at this time. In addition, this manganese-containing layered lithium-
A coin-type non-aqueous electrolyte secondary battery was prepared in the same manner as in Example 1 using the transition metal composite oxide as a positive electrode material, and Table 1 shows the measurement results of the initial discharge capacity, the discharge capacity at 25 cycles, and the rate characteristics.
【００３９】実施例１７
槽内温度を５５℃にした以外は、実施例１と同様にマン
ガン含有層状リチウム−遷移金属複合酸化物の合成を行
った。このときの比表面積、タップ密度および平均粒径
を表１に示す。また、このマンガン含有層状リチウム−
遷移金属複合酸化物を正極材料として実施例１と同様に
してコイン型非水電解質二次電池を作製し、初期放電容
量、２５サイクル時の放電容量およびレート特性の測定
結果を表１に示す。Example 17 A manganese-containing layered lithium-transition metal composite oxide was synthesized in the same manner as in Example 1 except that the temperature in the bath was set to 55 ° C. Table 1 shows the specific surface area, tap density and average particle size at this time. In addition, this manganese-containing layered lithium-
A coin-type non-aqueous electrolyte secondary battery was prepared in the same manner as in Example 1 using the transition metal composite oxide as a positive electrode material, and Table 1 shows the measurement results of the initial discharge capacity, the discharge capacity at 25 cycles, and the rate characteristics.
【００４０】比較例１
７５ｍｏｌ／Ｌに調整したニッケル／マンガンの比が９
５：５とした以外は、実施例１と同様にマンガン含有層
状リチウム−遷移金属複合酸化物の合成を行った。この
ときの比表面積、タップ密度および平均粒径を表２に示
す。また、このマンガン含有層状リチウム−遷移金属複
合酸化物を正極材料として実施例１と同様にしてコイン
型非水電解質二次電池を作製し、初期放電容量、２５サ
イクル時の放電容量およびレート特性の測定結果を表２
に示す。Comparative Example 1 The nickel / manganese ratio adjusted to 75 mol / L was 9
A manganese-containing layered lithium-transition metal composite oxide was synthesized in the same manner as in Example 1 except that the ratio was set to 5: 5. Table 2 shows the specific surface area, tap density and average particle size at this time. Further, a coin-type non-aqueous electrolyte secondary battery was prepared in the same manner as in Example 1 using the manganese-containing layered lithium-transition metal composite oxide as a positive electrode material, and the initial discharge capacity, discharge capacity at 25 cycles and rate characteristics were evaluated. Table 2 shows the measurement results
Shown in.
【００４１】[0041]
【表２】 [Table 2]
【００４２】比較例２
１．７５ｍｏｌ／Ｌに調整したニッケル／マンガンの比
が３：７とした以外は、実施例１と同様にマンガン含有
層状リチウム−遷移金属複合酸化物の合成を行った。こ
のときの比表面積、タップ密度および平均粒径を表２に
示す。また、このマンガン含有層状リチウム−遷移金属
複合酸化物を正極材料として実施例１と同様にしてコイ
ン型非水電解質二次電池を作製し、初期放電容量、２５
サイクル時の放電容量およびレート特性の測定結果を表
１に示す。Comparative Example 2 A manganese-containing layered lithium-transition metal composite oxide was synthesized in the same manner as in Example 1 except that the nickel / manganese ratio adjusted to 1.75 mol / L was 3: 7. Table 2 shows the specific surface area, tap density and average particle size at this time. A coin-type non-aqueous electrolyte secondary battery was prepared in the same manner as in Example 1 using the manganese-containing layered lithium-transition metal composite oxide as a positive electrode material.
Table 1 shows the measurement results of the discharge capacity and rate characteristics during the cycle.
【００４３】比較例３
ニッケルの替わりにコバルトとした以外は、比較例１と
同様にマンガン含有層状リチウム−遷移金属複合酸化物
の合成を行った。このときの比表面積、タップ密度およ
び平均粒径を表２に示す。また、このマンガン含有層状
リチウム−遷移金属複合酸化物を正極材料として実施例
１と同様にしてコイン型非水電解質二次電池を作製し、
初期放電容量、２５サイクル時の放電容量およびレート
特性の測定結果を表１に示す。Comparative Example 3 A manganese-containing layered lithium-transition metal composite oxide was synthesized in the same manner as in Comparative Example 1 except that cobalt was used instead of nickel. Table 2 shows the specific surface area, tap density and average particle size at this time. A coin-type non-aqueous electrolyte secondary battery was prepared in the same manner as in Example 1 using the manganese-containing layered lithium-transition metal composite oxide as a positive electrode material.
Table 1 shows the measurement results of the initial discharge capacity, the discharge capacity after 25 cycles, and the rate characteristics.
【００４４】比較例４
１．７５ｍｏｌ／Ｌに調整したコバルト／マンガンの比
が３：７とした以外は、比較例３と同様にマンガン含有
層状リチウム−遷移金属複合酸化物の合成を行った。こ
のときの比表面積、タップ密度および平均粒径を表２に
示す。また、このマンガン含有層状リチウム−遷移金属
複合酸化物を正極材料として実施例１と同様にしてコイ
ン型非水電解質二次電池を作製し、初期放電容量、２５
サイクル時の放電容量およびレート特性の測定結果を表
１に示す。Comparative Example 4 A manganese-containing layered lithium-transition metal composite oxide was synthesized in the same manner as in Comparative Example 3 except that the cobalt / manganese ratio adjusted to 1.75 mol / L was 3: 7. Table 2 shows the specific surface area, tap density and average particle size at this time. A coin-type non-aqueous electrolyte secondary battery was prepared in the same manner as in Example 1 using the manganese-containing layered lithium-transition metal composite oxide as a positive electrode material.
Table 1 shows the measurement results of the discharge capacity and rate characteristics during the cycle.
【００４５】比較例５
遷移金属元素をニッケル、マンガン、コバルトとし、そ
のモル比を９０：５：５とした以外は、実施例１と同様
にマンガン含有層状リチウム−遷移金属複合酸化物の合
成を行った。このときの比表面積、タップ密度および平
均粒径を表２に示す。また、このマンガン含有層状リチ
ウム−遷移金属複合酸化物を正極材料として実施例１と
同様にしてコイン型非水電解質二次電池を作製し、初期
放電容量、２５サイクル時の放電容量およびレート特性
の測定結果を表１に示す。Comparative Example 5 A manganese-containing layered lithium-transition metal composite oxide was synthesized in the same manner as in Example 1 except that the transition metal elements were nickel, manganese, and cobalt, and the molar ratio was 90: 5: 5. went. Table 2 shows the specific surface area, tap density and average particle size at this time. Further, a coin-type non-aqueous electrolyte secondary battery was prepared in the same manner as in Example 1 using the manganese-containing layered lithium-transition metal composite oxide as a positive electrode material, and the initial discharge capacity, discharge capacity at 25 cycles and rate characteristics were evaluated. The measurement results are shown in Table 1.
【００４６】比較例６
遷移金属元素をニッケル、マンガン、コバルトとし、そ
のモル比を５：５：９０とした以外は、実施例１と同様
にマンガン含有層状リチウム−遷移金属複合酸化物の合
成を行った。このときの比表面積、タップ密度および平
均粒径を表２に示す。また、このマンガン含有層状リチ
ウム−遷移金属複合酸化物を正極材料として実施例１と
同様にしてコイン型非水電解質二次電池を作製し、初期
放電容量、２５サイクル時の放電容量およびレート特性
の測定結果を表１に示す。Comparative Example 6 A manganese-containing layered lithium-transition metal composite oxide was synthesized in the same manner as in Example 1 except that the transition metal elements were nickel, manganese, and cobalt and the molar ratio was 5: 5: 90. went. Table 2 shows the specific surface area, tap density and average particle size at this time. Further, a coin-type non-aqueous electrolyte secondary battery was prepared in the same manner as in Example 1 using the manganese-containing layered lithium-transition metal composite oxide as a positive electrode material, and the initial discharge capacity, discharge capacity at 25 cycles and rate characteristics were evaluated. The measurement results are shown in Table 1.
【００４７】比較例７
遷移金属元素をニッケル、マンガン、コバルトとし、そ
のモル比を１：７：２とした以外は、実施例１と同様に
マンガン含有層状リチウム−遷移金属複合酸化物の合成
を行った。このときの比表面積、タップ密度および平均
粒径を表２に示す。また、このマンガン含有層状リチウ
ム−遷移金属複合酸化物を正極材料として実施例１と同
様にしてコイン型非水電解質二次電池を作製し、初期放
電容量、２５サイクル時の放電容量およびレート特性の
測定結果を表１に示す。Comparative Example 7 A manganese-containing layered lithium-transition metal composite oxide was synthesized in the same manner as in Example 1 except that the transition metal elements were nickel, manganese, and cobalt and the molar ratio was 1: 7: 2. went. Table 2 shows the specific surface area, tap density and average particle size at this time. Further, a coin-type non-aqueous electrolyte secondary battery was prepared in the same manner as in Example 1 using the manganese-containing layered lithium-transition metal composite oxide as a positive electrode material, and the initial discharge capacity, discharge capacity at 25 cycles and rate characteristics were evaluated. The measurement results are shown in Table 1.
【００４８】比較例８
遷移金属元素をニッケル、マンガン、コバルトとし、そ
のモル比を２：７：１とした以外は、実施例１と同様に
マンガン含有層状リチウム−遷移金属複合酸化物の合成
を行った。このときの比表面積、タップ密度および平均
粒径を表２に示す。また、このマンガン含有層状リチウ
ム−遷移金属複合酸化物を正極材料として実施例１と同
様にしてコイン型非水電解質二次電池を作製し、初期放
電容量、２５サイクル時の放電容量およびレート特性の
測定結果を表１に示す。Comparative Example 8 A manganese-containing layered lithium-transition metal composite oxide was synthesized in the same manner as in Example 1 except that the transition metal elements were nickel, manganese, and cobalt, and the molar ratio was 2: 7: 1. went. Table 2 shows the specific surface area, tap density and average particle size at this time. Further, a coin-type non-aqueous electrolyte secondary battery was prepared in the same manner as in Example 1 using the manganese-containing layered lithium-transition metal composite oxide as a positive electrode material, and the initial discharge capacity, discharge capacity at 25 cycles and rate characteristics were evaluated. The measurement results are shown in Table 1.
【００４９】比較例９
リチウム原料として水酸化リチウムをリチウム／（ニッ
ケル＋マンガン）のモル比が１．０３となるように混合
した以外は、実施例１と同様にマンガン含有層状リチウ
ム−遷移金属複合酸化物の合成を行った。このときの比
表面積、タップ密度および平均粒径を表２に示す。ま
た、このマンガン含有層状リチウム−遷移金属複合酸化
物を正極材料として実施例１と同様にしてコイン型非水
電解質二次電池を作製し、初期放電容量、２５サイクル
時の放電容量およびレート特性の測定結果を表１に示
す。Comparative Example 9 A manganese-containing layered lithium-transition metal composite was prepared in the same manner as in Example 1 except that lithium hydroxide was mixed as the lithium raw material so that the molar ratio of lithium / (nickel + manganese) was 1.03. The oxide was synthesized. Table 2 shows the specific surface area, tap density and average particle size at this time. Further, a coin-type non-aqueous electrolyte secondary battery was prepared in the same manner as in Example 1 using the manganese-containing layered lithium-transition metal composite oxide as a positive electrode material, and the initial discharge capacity, discharge capacity at 25 cycles and rate characteristics were evaluated. The measurement results are shown in Table 1.
【００５０】比較例１０
リチウム原料として水酸化リチウムをリチウム／（ニッ
ケル＋マンガン）のモル比１．４８となるように混合し
た以外は、実施例１と同様にマンガン含有層状リチウム
−遷移金属複合酸化物の合成を行った。このときの比表
面積、タップ密度および平均粒径を表２に示す。また、
このマンガン含有層状リチウム−遷移金属複合酸化物を
正極材料として実施例１と同様にしてコイン型非水電解
質二次電池を作製し、初期放電容量、２５サイクル時の
放電容量およびレート特性の測定結果を表１に示す。Comparative Example 10 A manganese-containing layered lithium-transition metal composite oxide was prepared in the same manner as in Example 1 except that lithium hydroxide was mixed as a lithium raw material so that the lithium / (nickel + manganese) molar ratio was 1.48. The product was synthesized. Table 2 shows the specific surface area, tap density and average particle size at this time. Also,
Using this manganese-containing layered lithium-transition metal composite oxide as a positive electrode material, a coin-type non-aqueous electrolyte secondary battery was prepared in the same manner as in Example 1, and the initial discharge capacity, the discharge capacity at 25 cycles, and the measurement results of rate characteristics. Is shown in Table 1.
【００５１】比較例１１
焼成温度を７００℃とした以外は、実施例１と同様にマ
ンガン含有層状リチウム−遷移金属複合酸化物の合成を
行った。このときの比表面積、タップ密度および平均粒
径を表２に示す。また、このマンガン含有層状リチウム
−遷移金属複合酸化物を正極材料として実施例１と同様
にしてコイン型非水電解質二次電池を作製し、初期放電
容量、２５サイクル時の放電容量およびレート特性の測
定結果を表１に示す。Comparative Example 11 A manganese-containing layered lithium-transition metal composite oxide was synthesized in the same manner as in Example 1 except that the firing temperature was 700 ° C. Table 2 shows the specific surface area, tap density and average particle size at this time. Further, a coin-type non-aqueous electrolyte secondary battery was prepared in the same manner as in Example 1 using the manganese-containing layered lithium-transition metal composite oxide as a positive electrode material, and the initial discharge capacity, discharge capacity at 25 cycles and rate characteristics were evaluated. The measurement results are shown in Table 1.
【００５２】比較例１２
上記ニッケル−マンガン塩水溶液を毎分４０ｍｌ及びア
ンモニアを毎分４ｍｌの速度で、３０℃に保ちながら速
やかに均一になるよう混合撹拌した。槽内温度を３０℃
に保ったまま６ｍｏｌ／Ｌの水酸化ナトリウム水溶液を
平均毎分２４．８ｍｌの速度で反応槽内のｐＨが１２．
０±０．２の範囲で保持するように供給しつつ撹拌した
以外は、実施例１と同様にマンガン含有層状リチウム−
遷移金属複合酸化物の合成を行った。このときの比表面
積、タップ密度および平均粒径を表２に示す。また、こ
のマンガン含有層状リチウム−遷移金属複合酸化物を正
極材料として実施例１と同様にしてコイン型非水電解質
二次電池を作製し、初期放電容量、２５サイクル時の放
電容量およびレート特性の測定結果を表１に示す。Comparative Example 12 The above nickel-manganese salt aqueous solution was mixed and stirred at a rate of 40 ml / min and ammonia at a rate of 4 ml / min so as to be rapidly uniform while maintaining the temperature at 30 ° C. The temperature in the tank is 30 ℃
The pH in the reaction tank was 12.2 ml / min with an average of 6 mol / L sodium hydroxide aqueous solution kept at 12.
Manganese-containing layered lithium-as in Example 1 except that stirring was carried out while supplying so as to maintain the range of 0 ± 0.2.
A transition metal composite oxide was synthesized. Table 2 shows the specific surface area, tap density and average particle size at this time. Further, a coin-type non-aqueous electrolyte secondary battery was prepared in the same manner as in Example 1 using the manganese-containing layered lithium-transition metal composite oxide as a positive electrode material, and the initial discharge capacity, discharge capacity at 25 cycles and rate characteristics were evaluated. The measurement results are shown in Table 1.
【００５３】比較例１３
上記ニッケル−マンガン塩水溶液を毎分２．５ｍｌ及び
アンモニアを毎分０．２５ｍｌの速度で、３０℃に保ち
ながら速やかに均一になるよう混合撹拌した。槽内温度
を３０℃に保ったまま６ｍｏｌ／Ｌの水酸化ナトリウム
水溶液を平均毎分１．５５ｍｌの速度で反応槽内のｐＨ
が１２．０±０．２の範囲で保持するように供給しつつ
撹拌した以外は、実施例１と同様にマンガン含有層状リ
チウム−遷移金属複合酸化物の合成を行った。このとき
の比表面積、タップ密度および平均粒径を表２に示す。
また、このマンガン含有層状リチウム−遷移金属複合酸
化物を正極材料として実施例１と同様にしてコイン型非
水電解質二次電池を作製し、初期放電容量、２５サイク
ル時の放電容量およびレート特性の測定結果を表１に示
す。Comparative Example 13 The above nickel-manganese salt aqueous solution was mixed and stirred at a rate of 2.5 ml / min and ammonia at a rate of 0.25 ml / min so as to be rapidly uniform while maintaining the temperature at 30 ° C. With the temperature inside the tank kept at 30 ° C., the pH in the reaction tank was 6 mol / L aqueous sodium hydroxide solution at an average rate of 1.55 ml / min.
Of the manganese-containing layered lithium-transition metal composite oxide was synthesized in the same manner as in Example 1 except that the stirring was performed while supplying so as to maintain the ratio of 12.0 ± 0.2. Table 2 shows the specific surface area, tap density and average particle size at this time.
Further, a coin-type non-aqueous electrolyte secondary battery was prepared in the same manner as in Example 1 using the manganese-containing layered lithium-transition metal composite oxide as a positive electrode material, and the initial discharge capacity, discharge capacity at 25 cycles and rate characteristics were evaluated. The measurement results are shown in Table 1.
【００５４】比較例１４
槽内温度を２０℃にした以外は、実施例１と同様にマン
ガン含有層状リチウム−遷移金属複合酸化物の合成を行
った。このときの比表面積、タップ密度および平均粒径
を表２に示す。また、このマンガン含有層状リチウム−
遷移金属複合酸化物を正極材料として実施例１と同様に
してコイン型非水電解質二次電池を作製し、初期放電容
量、２５サイクル時の放電容量およびレート特性の測定
結果を表１に示す。Comparative Example 14 A manganese-containing layered lithium-transition metal composite oxide was synthesized in the same manner as in Example 1 except that the temperature in the bath was 20 ° C. Table 2 shows the specific surface area, tap density and average particle size at this time. In addition, this manganese-containing layered lithium-
A coin-type non-aqueous electrolyte secondary battery was prepared in the same manner as in Example 1 using the transition metal composite oxide as a positive electrode material, and Table 1 shows the measurement results of the initial discharge capacity, the discharge capacity at 25 cycles, and the rate characteristics.
【００５５】比較例１５
槽内温度を６０℃にした以外は、実施例１と同様にマン
ガン含有層状リチウム−遷移金属複合酸化物の合成を行
った。このときの比表面積、タップ密度および平均粒径
を表２に示す。また、このマンガン含有層状リチウム−
遷移金属複合酸化物を正極材料として実施例１と同様に
してコイン型非水電解質二次電池を作製し、初期放電容
量、２５サイクル時の放電容量およびレート特性の測定
結果を表１に示す。Comparative Example 15 A manganese-containing layered lithium-transition metal composite oxide was synthesized in the same manner as in Example 1 except that the temperature inside the bath was set to 60 ° C. Table 2 shows the specific surface area, tap density and average particle size at this time. In addition, this manganese-containing layered lithium-
A coin-type non-aqueous electrolyte secondary battery was prepared in the same manner as in Example 1 using the transition metal composite oxide as a positive electrode material, and Table 1 shows the measurement results of the initial discharge capacity, the discharge capacity at 25 cycles, and the rate characteristics.
【００５６】比較例１６
槽内に窒素ガスを吹き込まなかった以外は、実施例１と
同様にマンガン含有層状リチウム−遷移金属複合酸化物
の合成を行った。このときの比表面積、タップ密度およ
び平均粒径を表２に示す。また、このマンガン含有層状
リチウム−遷移金属複合酸化物を正極材料として実施例
１と同様にしてコイン型非水電解質二次電池を作製し、
初期放電容量、２５サイクル時の放電容量およびレート
特性の測定結果を表１に示す。Comparative Example 16 A manganese-containing layered lithium-transition metal composite oxide was synthesized in the same manner as in Example 1 except that nitrogen gas was not blown into the tank. Table 2 shows the specific surface area, tap density and average particle size at this time. A coin-type non-aqueous electrolyte secondary battery was prepared in the same manner as in Example 1 using the manganese-containing layered lithium-transition metal composite oxide as a positive electrode material.
Table 1 shows the measurement results of the initial discharge capacity, the discharge capacity after 25 cycles, and the rate characteristics.
【００５７】[0057]
【発明の効果】以上説明したように、本発明の製造方法
で得られたマンガン含有層状リチウム−遷移金属複合酸
化物を非水電解質二次電池用正極材料として用いること
によって、安全性に優れ、充填性が高く、サイクル後も
高い放電容量を維持したリチウムイオン二次電池とする
ことができる。As described above, by using the manganese-containing layered lithium-transition metal composite oxide obtained by the production method of the present invention as a positive electrode material for a non-aqueous electrolyte secondary battery, excellent safety can be obtained. It is possible to obtain a lithium-ion secondary battery having a high filling property and maintaining a high discharge capacity even after cycling.
【図１】本発明で用いた非水電解質二次電池を例示する
断面図FIG. 1 is a cross-sectional view illustrating a non-aqueous electrolyte secondary battery used in the present invention.
１ 正極ケース ２ 封口板 ３ 集電体 ４ 金属リチウム負極 ５ 正極 ６ セパレータ ７ ガスケット 1 Positive case 2 Seal plate 3 Current collector 4 Metal lithium negative electrode 5 Positive electrode 6 separator 7 gasket
フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ テーマコート゛(参考） Ｈ０１Ｍ 10/40 Ｈ０１Ｍ 10/40 Ｚ Ｆターム(参考） 4G048 AA04 AB01 AB06 AC06 AD06 AE05 5H029 AJ03 AJ05 AJ12 AK03 AL12 AM03 AM04 AM05 AM07 BJ03 CJ02 CJ28 EJ04 EJ12 HJ02 HJ05 HJ07 HJ08 HJ14 5H050 AA07 AA08 AA15 BA15 BA16 CA09 CB12 GA02 GA27 HA02 HA05 HA07 HA08 HA14 HA20Front page continued (51) Int.Cl. 7 Identification code FI theme code (reference) H01M 10/40 H01M 10/40 ZF term (reference) 4G048 AA04 AB01 AB06 AC06 AD06 AE05 5H029 AJ03 AJ05 AJ12 AK03 AL12 AM03 AM04 AM05 AM07 BJ03 CJ02 CJ28 EJ04 EJ12 HJ02 HJ05 HJ07 HJ08 HJ14 5H050 AA07 AA08 AA15 BA15 BA16 CA09 CB12 GA02 GA27 HA02 HA05 HA07 HA08 HA14 HA20
Claims (8)
６ｇ／ｃｍ３以上、平均粒径５〜５０μｍであり、マン
ガン含有量が全遷移元素に対して１０〜６０モル％であ
ることを特徴とするマンガン含有層状リチウム−遷移金
属複合酸化物。1. A specific surface area of 1 m 2 / g or less and a tap density of 1.
A manganese-containing layered lithium-transition metal composite oxide, which has a mean particle size of 6 g / cm 3 or more, an average particle size of 5 to 50 μm, and a manganese content of 10 to 60 mol% with respect to all transition elements.
〜１．４５であることを特徴とする請求項１記載のマン
ガン含有層状リチウム−遷移金属複合酸化物。2. The molar ratio of lithium to all transition metals is 1.05.
It is -1.45, The manganese-containing layered lithium-transition metal composite oxide according to claim 1.
ウム−遷移金属複合酸化物がリチウム原料とマンガン含
有遷移金属複合水酸化物とをリチウム／全遷移金属のモ
ル比が１．０５〜１．４５となるように混合し、最終温
度として７５０℃以上で焼成されることを特徴とするマ
ンガン含有層状リチウム−遷移金属複合酸化物の製造方
法。3. The manganese-containing layered lithium-transition metal composite oxide according to claim 1, wherein the lithium raw material and the manganese-containing transition metal composite hydroxide have a lithium / total transition metal molar ratio of 1.05 to 1. A method for producing a manganese-containing layered lithium-transition metal composite oxide, which comprises mixing so as to be 45 and calcining at a final temperature of 750 ° C. or higher.
合酸化物の原料であるマンガン含有遷移金属複合水酸化
物の合成工程が不活性ガス雰囲気下においてこのマンガ
ン含有層状リチウム−遷移金属複合酸化物中に含まれる
遷移金属元素塩の水溶液とアルカリ水溶液及びアンモニ
ウムイオンを含む水溶液を密閉された反応槽内に連続的
に供給し、成長した複合水酸化物を連続的に取り出され
ることを特徴とする請求項３に記載のマンガン含有層状
リチウム−遷移金属複合酸化物の製造方法4. The manganese-containing layered lithium-transition metal composite oxide, which is a raw material of the manganese-containing layered lithium-transition metal composite oxide, is synthesized in the step of synthesizing the manganese-containing layered lithium-transition metal composite oxide under an inert gas atmosphere. An aqueous solution of a transition metal element salt, an aqueous alkali solution, and an aqueous solution containing ammonium ions contained therein are continuously supplied into a closed reaction tank, and the grown composite hydroxide is continuously taken out. The method for producing a layered lithium-transition metal composite oxide containing manganese according to Item 3.
０．５ｍｇ／Ｌ以下で合成されることを特徴とする請求
項４に記載のマンガン含有層状リチウム−遷移金属複合
酸化物の製造方法。5. The method for producing a manganese-containing layered lithium-transition metal composite oxide according to claim 4, wherein the dissolved oxygen content in the closed bath solution is 0.5 mg / L or less. Method.
間以下であり、槽内の反応温度が２５℃以上５５℃以下
で反応させることを特徴とする請求項４，５に記載のマ
ンガン含有層状リチウム−遷移金属複合酸化物の製造方
法。6. The manganese according to claim 4, wherein the average residence time in the tank is 3 hours or more and 18 hours or less, and the reaction is performed at a reaction temperature in the tank of 25 ° C. or more and 55 ° C. or less. Method for producing contained layered lithium-transition metal composite oxide.
リチウム−遷移金属複合酸化物または、請求項３から６
のいずれかに記載の製造方法によって得られたマンガン
含有層状リチウム−遷移金属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材料。7. The manganese-containing layered lithium-transition metal composite oxide according to claim 1, or claim 3 to 6.
5. A positive electrode material for a non-aqueous electrolyte secondary battery, comprising a manganese-containing layered lithium-transition metal composite oxide obtained by the method according to any one of 1.
正極材料を用いた正極とリチウムを吸蔵、脱蔵できる負
極と非水電解質とから構成されることを特徴とする非水
電解質二次電池。8. A non-aqueous electrolyte comprising a positive electrode using the positive electrode material for a non-aqueous electrolyte secondary battery according to claim 7, a negative electrode capable of inserting and extracting lithium, and a non-aqueous electrolyte. Secondary battery.
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