JP2957589B2 - Non-aqueous secondary battery - Google Patents

Non-aqueous secondary battery

Info

Publication number
JP2957589B2
JP2957589B2 JP1039923A JP3992389A JP2957589B2 JP 2957589 B2 JP2957589 B2 JP 2957589B2 JP 1039923 A JP1039923 A JP 1039923A JP 3992389 A JP3992389 A JP 3992389A JP 2957589 B2 JP2957589 B2 JP 2957589B2
Authority
JP
Japan
Prior art keywords
lithium
secondary battery
positive electrode
aqueous secondary
manganese
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Fee Related
Application number
JP1039923A
Other languages
Japanese (ja)
Other versions
JPH02220358A (en
Inventor
修弘 古川
俊之 能間
祐司 山本
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sanyo Denki Co Ltd
Original Assignee
Sanyo Denki Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Sanyo Denki Co Ltd filed Critical Sanyo Denki Co Ltd
Priority to JP1039923A priority Critical patent/JP2957589B2/en
Publication of JPH02220358A publication Critical patent/JPH02220358A/en
Application granted granted Critical
Publication of JP2957589B2 publication Critical patent/JP2957589B2/en
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

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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
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • 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

Description

【発明の詳細な説明】 イ 産業上の利用分野 本発明はリチウム或いはリチウム合金を負極活物質と
する非水系二次電池に係り、特に正極の改良に関するも
のである。The present invention relates to a non-aqueous secondary battery using lithium or a lithium alloy as a negative electrode active material, and more particularly to an improvement in a positive electrode.

ロ 従来の技術 この種二次電池の正極活物質としては三酸化モリブデ
ン、五酸化バナジウム、チタン或いはニオブの硫化物、
活性炭などが提案されており一部実用化されているもの
もある。B Conventional technology The positive electrode active material of this type of secondary battery includes molybdenum trioxide, vanadium pentoxide, sulfide of titanium or niobium,
Activated carbon and the like have been proposed and some have been put to practical use.

一方、非水系一次電池の正極活物質としては二酸化マ
ンガン（MnO2）、フッ化炭素が代表的なものとして知ら
れており、且これらは既に実用化されている。On the other hand, manganese dioxide (MnO 2 ) and fluorocarbon are known as typical examples of a positive electrode active material of a nonaqueous primary battery, and these have already been put to practical use.

ここで、特にMnO2は保存性に優れ、資源的に豊富であ
り且安価であるという利点を有するものである。Here, in particular, MnO 2 has an advantage of being excellent in preservability, abundant in resources, and inexpensive.

上記せる背景に鑑みて、非水系二次電池の正極活物質
としてMnO2を用いることが有益であると考えられるが、
MnO2は可逆性に難があり充放電サイクル特性に問題があ
った。In view of the background described above, it is thought that it is beneficial to use MnO 2 as a positive electrode active material of a non-aqueous secondary battery,
MnO 2 has difficulty in reversibility and has a problem in charge / discharge cycle characteristics.

MnO2を用いる場合の前述せる問題点を改善するため
に、本出願人は正極活物質としてLi2MnO3を含有するMnO
2を用いることを提案した（特開昭63−114064号公報参
照）。かかる提案によりサイクル特性の向上が認められ
たが、実用上更に特性の向上が望まれる。In order to improve the above-mentioned problems when MnO 2 is used, the present applicant has proposed a MnO containing Li 2 MnO 3 as a positive electrode active material.
No. 2 was proposed (see Japanese Patent Application Laid-Open No. 63-114064). Although improvement in cycle characteristics was recognized by such a proposal, further improvement in characteristics is desired in practical use.

又、本出願人はマンガン酸化物とリチウム塩とMOxで
表わされる金属酸化物（ここでＭはMo、Nb、Ｗ、Ru、C
o、Ti、Bi、Cu或いはCrから選ばれる少なくとも一種の
金属）とを混合熱処理して得た化合物を正極活物質とす
ることを提案した（特願昭63−215870号参照）。しかし
ながら、この場合にも充放電サイクルを多数回繰返すと
金属成分が電解液中に溶出し、負極上に析出して負極の
サイクル特性が劣化する懸念がある。In addition, the present applicant has proposed a manganese oxide, a lithium salt and a metal oxide represented by MOx (where M is Mo, Nb, W, Ru, C
and at least one metal selected from the group consisting of o, Ti, Bi, Cu and Cr), and proposed to use a compound obtained by heat-treating the mixture as a positive electrode active material (see Japanese Patent Application No. 63-215870). However, also in this case, if the charge / discharge cycle is repeated many times, there is a concern that the metal component elutes into the electrolytic solution, deposits on the negative electrode, and deteriorates the cycle characteristics of the negative electrode.

ハ 発明が解決しようとする課題 本発明では、リチウム、アルミニウム及びマンガンと
を含む複合酸化物を活物質とする正極を使用することに
より、この種電池のサイクル特性の向上を図るものであ
る。(C) Problems to be Solved by the Invention In the present invention, the use of a positive electrode having a composite oxide containing lithium, aluminum and manganese as an active material is used to improve the cycle characteristics of this type of battery.

ニ 課題を解決するための手段 本発明は、リチウム或いはリチウム合金を活物質とす
る負極と、リチウム、アルミニウム及びマンガンとを含
む複合酸化物を活物質とする正極とを備えた非水系二次
電池であって、前記複合酸化物が、Ｘ線回折によるMn2A
lO4、MnAl2O4の少なくとも１種の回折ピークを有するこ
とを特徴とする。The present invention provides a non-aqueous secondary battery including a negative electrode using lithium or a lithium alloy as an active material, and a positive electrode using a composite oxide containing lithium, aluminum, and manganese as an active material. Wherein the composite oxide is Mn 2 A by X-ray diffraction.
It has at least one kind of diffraction peak of lO 4 and MnAl 2 O 4 .

そして、前記複合酸化物が、マンガン化合物、リチウ
ム化合物及びアルミニウム化合物を混合し、350℃〜430
℃の範囲で熱処理して得られたものであることを特徴と
する。Then, the composite oxide is a mixture of a manganese compound, a lithium compound and an aluminum compound,
It is characterized by being obtained by heat treatment in the range of ° C.

ホ 作用 本発明で使用する、リチウム、アルミニウム及びマン
ガンとを含む複合酸化物からなる正極活物質は、Ｘ線回
折分析を行うと、Mn2AlO4、MnAl2O4の少なくとも１種の
特定回折ピークが観察される。この回折ピークが観察さ
れる複合酸化物は、結晶構造が大きく歪んでいるため
に、リチウムイオンの固相内拡散が容易となると共に、
マンガンに代わって一部アルミニウムが電解液中に溶出
し、負極上に析出する。この結果、負極上にLi−Al合金
が形成されるが、このLi−Al合金は非水系二次電池の負
極として用いられているものであり、サイクル特性の劣
化は生じない。E Action The positive electrode active material comprising a composite oxide containing lithium, aluminum and manganese used in the present invention can be analyzed by X-ray diffraction analysis to obtain at least one specific diffraction of Mn 2 AlO 4 , MnAl 2 O 4. A peak is observed. In the composite oxide where this diffraction peak is observed, the crystal structure is greatly distorted, so that diffusion of lithium ions in the solid phase becomes easy, and
Part of aluminum is eluted in the electrolyte instead of manganese, and is deposited on the negative electrode. As a result, a Li-Al alloy is formed on the negative electrode, but this Li-Al alloy is used as the negative electrode of the non-aqueous secondary battery, and the cycle characteristics do not deteriorate.

また、リチウム、アルミニウム及びマンガンとを含む
複合酸化物は、マンガン化合物、リチウム化合物及びア
ルミニウム化合物を混合し、350℃〜430℃の範囲で熱処
理することによって、得ることができる。Further, the composite oxide containing lithium, aluminum and manganese can be obtained by mixing a manganese compound, a lithium compound and an aluminum compound and subjecting the mixture to a heat treatment at 350 to 430 ° C.

ヘ 実施例 以下、本発明の実施例について詳述する。F Examples Hereinafter, examples of the present invention will be described in detail.

実施例１ 平均粒径30μｍ以下の化学二酸化マンガン50g、LiOH4
g及びAl（OH）38gを乳鉢で混合した後、空気中において
375℃で20時間熱処理する。Example 1 50 g of chemical manganese dioxide having an average particle diameter of 30 μm or less, LiOH 4
g and Al (OH) 3 8g in a mortar and then in the air
Heat treatment at 375 ° C for 20 hours.

この熱処理によって生成した物質は、Ｘ線回折図にお
いてMnO2とは異なる回折パターンを与え、元素分析から
Mn、Li及びAlの複合酸化物であることが認められた。
又、Ｘ線回折図から他にMnO2、（Li、Al）Mn2O4、Li及
びAl複合酸化物（LiAlO2、Li5AlO4、LiAl5O8）の回折ピ
ークもみられた。The substance produced by this heat treatment gives a diffraction pattern different from MnO 2 in the X-ray diffraction diagram,
It was confirmed that it was a composite oxide of Mn, Li and Al.
In addition, other diffraction peaks of MnO 2 , (Li, Al) Mn 2 O 4 , Li and Al composite oxides (LiAlO 2 , Li 5 AlO 4 , LiAl 5 O 8 ) were also observed from the X-ray diffraction diagram.

このようにして得た正極活物質粉末と、導電剤として
のアセチレンブラック及び結着剤としてのフッ素樹脂粉
末とを重量比で90:6:4の比率で混合して正極合剤とし、
正極合剤を２トン/cm2で直径20mmに加圧成型したのち25
0℃で熱処理して正極とする。The positive electrode active material powder thus obtained and acetylene black as a conductive agent and a fluororesin powder as a binder were mixed at a weight ratio of 90: 6: 4 to form a positive electrode mixture,
After the positive electrode mixture is press-molded to a diameter of 20 mm at 2 ton / cm 2 , 25
Heat treated at 0 ° C. to form a positive electrode.

負極は所定厚みのリチウム板を直径20mmに打抜いたも
のである。The negative electrode is obtained by punching a lithium plate having a predetermined thickness to a diameter of 20 mm.

第１図は上記せる正負極を用いて組立てた扁平型非水
電解液二次電池の半断面図を示し、（１）（２）はステ
ンレス製の正負極缶であってこれらはポプロピレン製の
絶縁パッキング（３）により隔離されている。（４）は
本発明の要旨とする正極であって、正極缶（１）の内底
面に固着せる正極集電体（５）に圧接されている。
（６）は負極であって、負極缶（２）の内底面に固着せ
る負極集電体（７）に圧着されている。（８）はポリプ
ロピレン製微孔性薄膜よりなるセパレータであり、又電
解液としてプロピレンカーボネートとジメトキシエタン
との混合溶媒に過塩素酸リチウムを１モル／溶解した
ものを用いた。電池寸法は直径24.0mm、厚み3.0mmであ
った。この本発明電池を（A1）とする。FIG. 1 shows a half cross-sectional view of a flat type nonaqueous electrolyte secondary battery assembled using the above positive and negative electrodes. Are separated by an insulating packing (3). Reference numeral (4) denotes a positive electrode according to the present invention, which is pressed against a positive electrode current collector (5) fixed to the inner bottom surface of the positive electrode can (1).
Reference numeral (6) denotes a negative electrode, which is crimped to a negative electrode current collector (7) fixed to the inner bottom surface of the negative electrode can (2). (8) is a separator made of a polypropylene microporous thin film, and used as an electrolytic solution was 1 mol / dissolved lithium perchlorate in a mixed solvent of propylene carbonate and dimethoxyethane. The battery dimensions were 24.0 mm in diameter and 3.0 mm in thickness. This battery of the present invention is referred to as (A 1 ).

実施例２ Mn（NO3）2100g、Li2CO320g、Al2O35gを乳鉢にて混合
した後、空気中において375℃で20時間熱処理する。After mixing Example 2 Mn (NO 3) 2 100g , Li 2 CO 3 20g, the Al 2 O 3 5 g in a mortar, to a heat treatment at 375 ° C. 20 hours in air.

この熱処理によって生成した物質は、Ｘ線回折図にお
いて実施例１で得られたものと略同様の回折パターンを
示し、Mn2AlO4、MnAl2O4の回折ピークもみられた。The substance produced by this heat treatment showed, in an X-ray diffraction diagram, a diffraction pattern substantially similar to that obtained in Example 1, and diffraction peaks of Mn 2 AlO 4 and MnAl 2 O 4 were also observed.

このようにして得た複合酸化物を正極活物質に用いる
ことを除いて他は実施例１と同様の本発明電池（A2）を
作成した。A battery of the present invention (A 2 ) was produced in the same manner as in Example 1, except that the composite oxide thus obtained was used as a positive electrode active material.

比較例１ Al（OH）３を添加しないことを除いて他は実施例１と
同様の比較電池（B1）を作成した。Comparative Example 1 A comparative battery (B 1 ) was prepared in the same manner as in Example 1 except that Al (OH) 3 was not added.

比較例２ Al（OH）38gの代わりにM0O315gを添加することを除い
て他は実施例１と同様の比較電池（B2）を作成した。Other in place of Comparative Example 2 Al (OH) 3 8g, except that the addition of M 0 O 3 15 g was prepared in the same manner as in Comparative Battery Example 1 (B 2).

第２図はこれら電池の充放電サイクル特性図を示す。
尚、充放電条件は電流3mAで４時間放電し、電流3mAで充
電し、充電終止電圧4.0Vとした。FIG. 2 shows a charge / discharge cycle characteristic diagram of these batteries.
The charge and discharge conditions were as follows: discharge at a current of 3 mA for 4 hours; charge at a current of 3 mA;

第２図より本発明電池（A1）（A2）は比較電池（B1）
（B2）に比してサイクル特性が改善されているのがわか
る。From FIG. 2, the batteries of the present invention (A 1 ) and (A 2 ) are comparative batteries (B 1 )
It can be seen that the cycle characteristics are improved as compared with (B 2 ).

リチウム、マンガン及びアルミニウムとからなる複合
酸化物を得るために用いるマンガン化合物、リチウム化
合物及びアルミニウム化合物としては実施例で示したも
のに限定されず他のものも使用可能であり、マンガン化
合物としてはマンガン酸化物、水酸化マンガン、炭酸マ
ンガン等、リチウム化合物としては硝酸リチウム、リン
酸リチウム、ヨウ化リチウム等、又アルミニウム化合物
としては塩化アルミニウム、硝酸アルミニウム等も適用
できる。Lithium, a manganese compound used to obtain a composite oxide composed of manganese and aluminum, the lithium compound and the aluminum compound are not limited to those shown in the examples, and other compounds can be used. Oxides, manganese hydroxide, manganese carbonate and the like, lithium compounds such as lithium nitrate, lithium phosphate and lithium iodide, and aluminum compounds such as aluminum chloride and aluminum nitrate can also be used.

ト 発明の効果 上述した如く、本発明はリチウム或いはリチウム合金
を活物質とする負極と、リチウム、アルミニウム及びマ
ンガンとを含む複合酸化物を活物質とする正極とを備え
た非水系二次電池であって、前記複合酸化物が、Ｘ線回
折によるMn2AlO4、MnAl2O4の少なくとも１種の回折ピー
クを有するものであるので、この種電池のサイクル特性
を向上させることができるものであり、その工業的価値
は極めて大である。As described above, the present invention relates to a nonaqueous secondary battery including a negative electrode using lithium or a lithium alloy as an active material, and a positive electrode using a composite oxide containing lithium, aluminum, and manganese as an active material. Since the composite oxide has at least one kind of diffraction peaks of Mn 2 AlO 4 and MnAl 2 O 4 by X-ray diffraction, the cycle characteristics of this kind of battery can be improved. And its industrial value is extremely large.

尚、本発明は実施例で示した非水電解液を用いる二次
電池に限定されず、固体電解質を用いる二次電池にも適
用できるものである。The present invention is not limited to the secondary battery using the non-aqueous electrolyte shown in the examples, but can be applied to a secondary battery using a solid electrolyte.

【図面の簡単な説明】[Brief description of the drawings]

第１図は本発明電池の半断面図、第２図は電池のサイク
ル特性図を夫々示す。 （１）……正極缶、（２）……負極缶、（３）……絶縁
パッキング、（４）……正極、（６）……負極、（８）
……セパレータ、（A1）（A2）……本発明電池、（B1）
（B2）……比較電池。FIG. 1 is a half sectional view of the battery of the present invention, and FIG. 2 is a cycle characteristic diagram of the battery. (1) Positive electrode can, (2) Negative electrode can, (3) Insulating packing, (4) Positive electrode, (6) Negative electrode, (8)
… Separator, (A 1 ) (A 2 )… Battery of the present invention, (B 1 )
(B 2 ): Comparative battery.

───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 昭63−114064（ＪＰ，Ａ) 特開 昭62−90863（ＪＰ，Ａ) (58)調査した分野(Int.Cl.6，ＤＢ名) H01M 4/58 H01M 4/02 H01M 10/40 ────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-63-114064 (JP, A) JP-A-62-190863 (JP, A) (58) Fields investigated (Int. Cl. 6 , DB name) H01M 4/58 H01M 4/02 H01M 10/40

Claims (2)

(57)【特許請求の範囲】(57) [Claims] 【請求項１】リチウム或いはリチウム合金を活物質とす
る負極と、リチウム、アルミニウム及びマンガンとを含
む複合酸化物を活物質とする正極とを備えた非水系二次
電池であって、 前記複合酸化物が、Ｘ線回折によるMn2AlO4、MnAl2O4の
少なくとも１種の回折ピークを有することを特徴とする
非水系二次電池。1. A non-aqueous secondary battery comprising: a negative electrode using lithium or a lithium alloy as an active material; and a positive electrode using a composite oxide containing lithium, aluminum and manganese as an active material, A non-aqueous secondary battery, wherein the object has at least one kind of diffraction peak of Mn 2 AlO 4 or MnAl 2 O 4 by X-ray diffraction. 【請求項２】前記複合酸化物が、マンガン化合物、リチ
ウム化合物及びアルミニウム化合物を混合し、350℃〜4
30℃の範囲で熱処理して得られたものであることを特徴
とする請求項（１）記載の非水系二次電池。2. A mixed oxide comprising a manganese compound, a lithium compound and an aluminum compound mixed at 350 ° C. to 4 ° C.
2. The non-aqueous secondary battery according to claim 1, wherein the non-aqueous secondary battery is obtained by heat treatment at a temperature in the range of 30.degree.
JP1039923A 1989-02-20 1989-02-20 Non-aqueous secondary battery Expired - Fee Related JP2957589B2 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP1039923A JP2957589B2 (en) 1989-02-20 1989-02-20 Non-aqueous secondary battery

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP1039923A JP2957589B2 (en) 1989-02-20 1989-02-20 Non-aqueous secondary battery

Publications (2)

Publication Number Publication Date
JPH02220358A JPH02220358A (en) 1990-09-03
JP2957589B2 true JP2957589B2 (en) 1999-10-04

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Country Link
JP (1) JP2957589B2 (en)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2528183B2 (en) * 1989-04-20 1996-08-28 富士電気化学株式会社 Positive electrode active material for non-aqueous electrolyte secondary battery and method for producing the same
KR20000049093A (en) 1996-10-11 2000-07-25 자르밀라 제트. 흐르벡 Polymer electrolyte, intercalation compounds and electrodes for batteries
US5958624A (en) * 1997-12-18 1999-09-28 Research Corporation Technologies, Inc. Mesostructural metal oxide materials useful as an intercalation cathode or anode

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6290863A (en) * 1985-05-10 1987-04-25 Asahi Chem Ind Co Ltd Secondary cell
JPH0746608B2 (en) * 1986-10-30 1995-05-17 三洋電機株式会社 Non-aqueous secondary battery

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JPH02220358A (en) 1990-09-03

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