JPH02270268A - Nonaqueous electrolyte secondary battery - Google Patents
Nonaqueous electrolyte secondary batteryInfo
- Publication number
- JPH02270268A JPH02270268A JP1091345A JP9134589A JPH02270268A JP H02270268 A JPH02270268 A JP H02270268A JP 1091345 A JP1091345 A JP 1091345A JP 9134589 A JP9134589 A JP 9134589A JP H02270268 A JPH02270268 A JP H02270268A
- Authority
- JP
- Japan
- Prior art keywords
- lithium
- nonaqueous electrolyte
- active material
- positive electrode
- electrolyte secondary
- 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
- 239000011255 nonaqueous electrolyte Substances 0.000 title claims abstract description 12
- 239000007774 positive electrode material Substances 0.000 claims abstract description 16
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 8
- 150000002642 lithium compounds Chemical class 0.000 claims abstract description 5
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 4
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 7
- 229910052760 oxygen Inorganic materials 0.000 abstract description 7
- 239000001301 oxygen Substances 0.000 abstract description 7
- 229910052596 spinel Inorganic materials 0.000 abstract description 6
- 239000011029 spinel Substances 0.000 abstract description 6
- 239000013078 crystal Substances 0.000 abstract description 4
- 229910052751 metal Inorganic materials 0.000 abstract description 4
- 239000002184 metal Substances 0.000 abstract description 4
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 abstract description 2
- 229910015329 LixMn2O4 Inorganic materials 0.000 abstract 2
- 150000001875 compounds Chemical class 0.000 abstract 1
- 208000028659 discharge Diseases 0.000 description 17
- 239000000203 mixture Substances 0.000 description 6
- 229910014549 LiMn204 Inorganic materials 0.000 description 5
- 230000006866 deterioration Effects 0.000 description 5
- 238000007599 discharging Methods 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000011149 active material Substances 0.000 description 2
- 239000006182 cathode active material Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- -1 polytetrafluoroethylene Polymers 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- 229910017326 LixMn Inorganic materials 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 description 1
- 229910001486 lithium perchlorate Inorganic materials 0.000 description 1
- AMWRITDGCCNYAT-UHFFFAOYSA-L manganese oxide Inorganic materials [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
-
- 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
【発明の詳細な説明】
産業上の利用分野
本発明は、非水電解質二次電池の改良、特に正極活物質
の改良に関わり、電池のサイクル特性の向上を目指すも
のである。DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to the improvement of non-aqueous electrolyte secondary batteries, particularly to the improvement of positive electrode active materials, and aims at improving the cycle characteristics of the batteries.
従来の技術
リチウムまたはリチウム化合物を負極とする非水電解質
二次電池は高電圧で高エネルギー密度となることが期待
され、多くの研究が行なわれている。BACKGROUND OF THE INVENTION Non-aqueous electrolyte secondary batteries using lithium or lithium compounds as negative electrodes are expected to have high voltage and high energy density, and many studies are being conducted on them.
特に、これら電池の正極活物質としてＭｎＯ２やＴｉＳ
＊がよ（検討されている。最近、タックレイ等によりＬ
ｉＭｎ２０ａが正極活物質となることが報告された（マ
テリアル リサーチ ブレチン１９８３年１８巻４６１
−４７２ページ）。ＬｉＭ ｎ ｅ Ｏｓはスピネル構
造をした立方晶の結晶構造であり、電池の正極活物質と
して用いた場合、電池の放電電圧は４ボルト程度の高い
電圧となり、正極活物質として有望と考えられている。In particular, MnO2 and TiS are used as positive electrode active materials for these batteries.
*Gayo (being considered.Recently, L
It was reported that iMn20a can be used as a positive electrode active material (Material Research Bulletin 1983, Vol. 18, 461).
-472 pages). LiMneOs has a cubic crystal structure with a spinel structure, and when used as a cathode active material in a battery, the battery discharge voltage is as high as 4 volts, and it is considered to be a promising cathode active material. .
発明が解決しようとする課題
しかし、これら正極活物質はサイクル特性に問題があっ
た。つまり充電放電を繰り返すと放電容量の低下が顕著
であった。ＬｉＭｎ２０ａの正極活物質では、４．５ボ
ルトまで充電し２ボルトまで放電すると４ボルト付近と
２．８ボルト付近の２段の放電曲線となる。これまで、
２．８ボルト付近の２段目の放電に対して充′ＩＩＮ圧
を３．８ボルトに制限することによりサイクル特性を向
上させる試みがある。しかしこれでは、高エネルギー密
度を達成できない。高エネルギー密度を達成するには、
４．５ボルトまで充電し３ボルトまで放電する１段目の
放電を利用する方が育利である。しかし、１段目の充放
電のサイクル特性は悪く約５０サイクル程度で放電容量
は半分に低下した。Problems to be Solved by the Invention However, these positive electrode active materials had problems in cycle characteristics. In other words, when charging and discharging were repeated, the discharge capacity decreased significantly. In the positive electrode active material of LiMn20a, when it is charged to 4.5 volts and discharged to 2 volts, a two-step discharge curve is formed near 4 volts and near 2.8 volts. Until now,
There has been an attempt to improve the cycle characteristics by limiting the charging IIN pressure to 3.8 volts for the second stage discharge at around 2.8 volts. However, this method cannot achieve high energy density. To achieve high energy density,
It is more advantageous to use the first stage of discharge, which charges to 4.5 volts and discharges to 3 volts. However, the cycle characteristics of the first stage charging and discharging were poor and the discharge capacity was reduced to half after about 50 cycles.
本発明は、非水電解質二次電池のサイクル特性を向上を
目的とし、正極活物質の改良を行なうものである。The present invention aims to improve the cycle characteristics of non-aqueous electrolyte secondary batteries by improving positive electrode active materials.
課題を解決するための手段
本発明はリチウムまたはリチウム化合物を負極とし、リ
チウム塩を含む排水電解質と、式、ＬｉＭｎ２０４
で表わされ、１．０２５≦Ｘ≦１．１８５である物質を
正極活物質とすることにより、サイクル特性を向上させ
たものである。Means for Solving the Problems The present invention uses lithium or a lithium compound as a negative electrode, a wastewater electrolyte containing a lithium salt, and the formula: LiMn204.
The cycle characteristics are improved by using, as the positive electrode active material, a material expressed by 1.025≦X≦1.185.
作 用
一般にスピネルは、ＬｉＭｎ２０４のようにＡＢａ Ｏ
ａの組成を持つ。ここでＡは、酸素の４面体に囲まれた
金属元素、Ｂは、酸素の８面体に囲まれた金属元素であ
る。Function Generally, spinel is made of ABaO like LiMn204.
It has a composition of a. Here, A is a metal element surrounded by oxygen tetrahedra, and B is a metal element surrounded by oxygen octahedrons.
本発明のＬｉｘＭｎ２０４では、１より大きい分のＬｉ
は、スピネル中の空いている酸素４面体のなかに入ると
考えられる。これにより、充放電における結晶の安定性
が増したと思われる。In the LixMn204 of the present invention, the LixMn204 is larger than 1.
is thought to fit into the vacant oxygen tetrahedra in spinel. This seems to have increased the stability of the crystal during charging and discharging.
以下に実施例を述べる。Examples will be described below.
実施例
（ＬｉＭｎ２０４の製法）
Ｌｉ２ＣＯａが３モルに対しＭ ｎ ３０４を４モルの
割合でよく混合したのち、混合物を大気中で９００℃で
１０時間加熱し、ＬｉＭｎ２０４を作った。Example (Production method of LiMn204) After thoroughly mixing 3 moles of Li2COa and 4 moles of Mn304, the mixture was heated in the air at 900° C. for 10 hours to produce LiMn204.
（ＬｉＭｎ２０４の製法）
ＬｉｅＣＯｓとＭ ｎ ａ Ｏａを用いて、Ｌｉ原原子
炉Ｘモル、Ｍｎｎ原子炉２モルの割合になるようによく
混合したのち、混合物を大気中で９００°Ｃで１０時間
加熱して作った。ここでは、Ｘ＝１． ０１．１． ０
２５．１． ０５．１． １０．１． １５．１．２０
とした。(Manufacturing method of LiMn204) Using LieCOs and Mna Oa, the mixture was thoroughly mixed in a ratio of X moles for Li nuclear reactor and 2 moles for Mnn reactor, and then the mixture was heated at 900°C in the air for 10 hours. I made it. Here, X=1. 01.1. 0
25.1. 05.1. 10.1. 15.1.20
And so.
（電池の製造）
正極活物質としてのＬｉｘＭｎ２０４７重量部に対し、
導電剤としてのアセチレンブラック２重量部、結着剤と
してのポリ４弗化工チレン樹脂１重量部を混合して正極
合剤とした。正極合剤０． １ダラムを直径１７．５ｍ
ｍに１トン／ｃｍ”でプレス成型して、正極とした。製
造した電池の断面図を第２図に示す。成型した正極１を
ケース２に置く。正極１の上にセパレータ３としての多
孔性ポリプロピレンフィルムを置いた。負極として直径
１７．５ｍｍ厚さ０．３ｍｍのリチウム板４を、ポリプ
ロピレン製ガスケット６を付けた封口板５に圧着した。(Manufacture of battery) For 2047 parts by weight of LixMn as a positive electrode active material,
A positive electrode mixture was prepared by mixing 2 parts by weight of acetylene black as a conductive agent and 1 part by weight of polytetrafluoroethylene resin as a binder. Positive electrode mixture 0. 1 duram has a diameter of 17.5m
A positive electrode was formed by press molding at a rate of 1 ton/cm" at a rate of 1 ton/cm. A cross-sectional view of the manufactured battery is shown in FIG. 2. The molded positive electrode 1 is placed in a case 2. A lithium plate 4 having a diameter of 17.5 mm and a thickness of 0.3 mm was press-bonded to a sealing plate 5 equipped with a polypropylene gasket 6 as a negative electrode.
非水電解質として、１モル／１の過塩素酸リチウムを溶
解し、体積比で１対１のプロピレンカーボネートとジメ
トキシエタンの混合溶液を用い、これをセパレータ上お
よび負極上に加えた。その後電池を封口した。Ｘ＝１．
１０の活物質を用いた電池をＡとする。As a non-aqueous electrolyte, a mixed solution of propylene carbonate and dimethoxyethane in a volume ratio of 1:1 in which 1 mol/1 lithium perchlorate was dissolved was added onto the separator and the negative electrode. After that, the battery was sealed. X=1.
Let A be a battery using 10 active materials.
同様に、従来例としてのＬｉＭｎ２Ｏ４を正極活物質と
して用いた電池をＢとする。これら電池を、２ｍＡの定
電流で４．５ボルトまで充電し、３ボルトまで放電し、
この充電放電を繰り返した。第１図は、これら電池の各
サイクルでの放電容量をプロットしたものである。Similarly, a battery B uses LiMn2O4 as a positive electrode active material as a conventional example. These batteries were charged to 4.5 volts with a constant current of 2 mA, discharged to 3 volts,
This charging and discharging process was repeated. FIG. 1 is a plot of the discharge capacity of these batteries at each cycle.
これより本実施例の正極活物質では充放電サイクルを繰
り返しても劣化は小さいことがわかる。This shows that the positive electrode active material of this example shows little deterioration even after repeated charge/discharge cycles.
また第３図には、代表的な放電特性としてまだ劣化の少
ない第１０サイクル目での各電池の放電曲線を示す。こ
れより本発明の 正極活物質は、ＬｉＭｎ２０Ｊと同じ
電位で放電していることがわかる。Further, FIG. 3 shows the discharge curve of each battery at the 10th cycle, where there is still little deterioration, as a typical discharge characteristic. This shows that the positive electrode active material of the present invention discharges at the same potential as LiMn20J.
１より大きい分のＬｉは、スピネル中の空いている酸素
４面体のなかに入り、充放電における結晶の安定性が増
したと思われる。It is thought that the Li in an amount larger than 1 enters the vacant oxygen tetrahedra in the spinel, increasing the stability of the crystal during charging and discharging.
正極活物質のサイクル特性を表わす指数として、第１０
サイクル目の放電容量から第５０サイクル目の放電容量
を引き、それを第１０サイクル目の放電容量で除した値
を用いることにした。すなわち、サイクルによる劣化率
でありこの値が小さいほど良いことになる。第４図は、
ＬｒにＭ ｎ ｅ ０４中のＸに対して、その活物質の
サイクル特性としての劣化率をプロットしたものである
。Ｘが増えるにしたがってサイクル特性が向上した。し
かし、Ｘが１．１０を越えるとサイクル特性は低下し始
める。The 10th index represents the cycle characteristics of the positive electrode active material.
It was decided to use a value obtained by subtracting the discharge capacity of the 50th cycle from the discharge capacity of the cycle and dividing it by the discharge capacity of the 10th cycle. That is, it is the deterioration rate due to cycles, and the smaller this value is, the better. Figure 4 shows
The deterioration rate as a cycle characteristic of the active material is plotted against X in M n e 04 on Lr. The cycle characteristics improved as X increased. However, when X exceeds 1.10, the cycle characteristics begin to deteriorate.
これより、Ｘは１．０２５以上、１．１８５以下が良い
と思われる。From this, it seems that X is preferably 1.025 or more and 1.185 or less.
発明の効果
以上述べたように本発明の式、Ｌｉｉ＋Ｍｎ２０ｚで表
わされ、１．０２５≦Ｘ≦１．１８５である物質を正極
活物質とすることにより、非水電解質二次電池のサイク
ル特性を向上させることができ、産業上の意義は大きい
。Effects of the Invention As described above, the cycle characteristics of a non-aqueous electrolyte secondary battery can be improved by using the material of the present invention as a positive electrode active material, which is expressed by the formula Lii+Mn20z and satisfies 1.025≦X≦1.185. This is of great industrial significance.
第１図は本発明の一実施例における非水電解質二次電池
と従来例の電池サイクル特性を比較して示す特性図、第
２図は試験に用いた電池の縦断面図、第３図は電池の放
電特性を示す特性図、第４図はサイクル特性としての劣
化率をり、ｉｘＭｎ２０４中のＸに対してプロットした
グラフである。
１３０．正極、２１９．ケース、 ３０９．セパレータ
、 ４００．リチウム板、５．、、封口板、ｅ、、、ガ
スケット。
代理人の氏名 弁理士 粟野重孝 ほか１名第１図
Ｏｕ） ４１） ｕ
８０ １ｔ）ａブイ グ ル老（
第２図
１ど
第 ３ 図
０ ／ Ｚ
３ ４放電時間（時間）
第４図
ＬＯＯ１，１０ｒ、ｚ。
Ｌｉｘ Ｍ？Ｌｚ ０４の×Figure 1 is a characteristic diagram that compares the battery cycle characteristics of a non-aqueous electrolyte secondary battery according to an embodiment of the present invention and a conventional example, Figure 2 is a vertical cross-sectional view of the battery used in the test, and Figure 3 is a FIG. 4, a characteristic diagram showing the discharge characteristics of the battery, is a graph in which the deterioration rate as a cycle characteristic is plotted against X in ixMn204. 130. Positive electrode, 219. Case, 309. Separator, 400. Lithium plate, 5. ,, sealing plate, e,, gasket. Name of agent: Patent attorney Shigetaka Awano and one other person (Figure 1) 41) u
80 1t) a Buiguruo (Fig. 2 1 d 3 Fig. 0 / Z
3 4 Discharge time (hours) Figure 4 LOO1, 10r, z. Lix M? Lz 04×
Claims (1)
を含む非水電解質と、式 Ｌｉ＿ｘＭｎ＿２Ｏ＿４ で表わされ、１．０２５≦Ｘ≦１．１８５ である正極活物質を用いたたことを特徴とする非水電解
質二次電池。[Claims] Lithium or a lithium compound is used as a negative electrode, a non-aqueous electrolyte containing a lithium salt, and a positive electrode active material represented by the formula Li_xMn_2O_4 and satisfying 1.025≦X≦1.185. Characteristics of non-aqueous electrolyte secondary batteries.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1091345A JPH02270268A (en) | 1989-04-11 | 1989-04-11 | Nonaqueous electrolyte secondary battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1091345A JPH02270268A (en) | 1989-04-11 | 1989-04-11 | Nonaqueous electrolyte secondary battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH02270268A true JPH02270268A (en) | 1990-11-05 |
Family
ID=14023832
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1091345A Pending JPH02270268A (en) | 1989-04-11 | 1989-04-11 | Nonaqueous electrolyte secondary battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH02270268A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5478672A (en) * | 1993-12-24 | 1995-12-26 | Sharp Kabushiki Kaisha | Nonaqueous secondary battery, positive-electrode active material |
| WO1997037934A1 (en) * | 1996-04-08 | 1997-10-16 | Duracell, Inc. | Method of preparation of lithium manganese oxide spinel |
| US5716737A (en) * | 1995-03-20 | 1998-02-10 | Matsushita Electric Industrial Co. | Nonaqueous electrolyte secondary battery, cathode active material and method for producing the same |
| US5807646A (en) * | 1995-02-23 | 1998-09-15 | Tosoh Corporation | Spinel type lithium-mangenese oxide material, process for preparing the same and use thereof |
| JP2009541938A (en) * | 2006-06-23 | 2009-11-26 | ボストン−パワー，インコーポレイテッド | Lithium ion secondary battery |
-
1989
- 1989-04-11 JP JP1091345A patent/JPH02270268A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5478672A (en) * | 1993-12-24 | 1995-12-26 | Sharp Kabushiki Kaisha | Nonaqueous secondary battery, positive-electrode active material |
| US5807646A (en) * | 1995-02-23 | 1998-09-15 | Tosoh Corporation | Spinel type lithium-mangenese oxide material, process for preparing the same and use thereof |
| US5716737A (en) * | 1995-03-20 | 1998-02-10 | Matsushita Electric Industrial Co. | Nonaqueous electrolyte secondary battery, cathode active material and method for producing the same |
| WO1997037934A1 (en) * | 1996-04-08 | 1997-10-16 | Duracell, Inc. | Method of preparation of lithium manganese oxide spinel |
| JP2009541938A (en) * | 2006-06-23 | 2009-11-26 | ボストン−パワー，インコーポレイテッド | Lithium ion secondary battery |
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