JPH0393163A - Nonaqueous system secondary battery - Google Patents
Nonaqueous system secondary batteryInfo
- Publication number
- JPH0393163A JPH0393163A JP1227990A JP22799089A JPH0393163A JP H0393163 A JPH0393163 A JP H0393163A JP 1227990 A JP1227990 A JP 1227990A JP 22799089 A JP22799089 A JP 22799089A JP H0393163 A JPH0393163 A JP H0393163A
- Authority
- JP
- Japan
- Prior art keywords
- battery
- manganese dioxide
- active material
- positive electrode
- sodium
- 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
- 239000002131 composite material Substances 0.000 claims abstract description 12
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 9
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000011149 active material Substances 0.000 claims abstract description 7
- 229910000733 Li alloy Inorganic materials 0.000 claims description 2
- 239000001989 lithium alloy Substances 0.000 claims description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 abstract description 90
- 239000011734 sodium Substances 0.000 abstract description 25
- 239000007774 positive electrode material Substances 0.000 abstract description 11
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 abstract description 6
- 229910052708 sodium Inorganic materials 0.000 abstract description 6
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 239000002994 raw material Substances 0.000 abstract description 5
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 abstract description 3
- 239000003513 alkali Substances 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 3
- 229910052748 manganese Inorganic materials 0.000 abstract description 3
- 239000011572 manganese Substances 0.000 abstract description 3
- 229910015685 LixMnOy Inorganic materials 0.000 abstract description 2
- 230000002411 adverse Effects 0.000 abstract description 2
- 230000002194 synthesizing effect Effects 0.000 abstract description 2
- 230000003247 decreasing effect Effects 0.000 abstract 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 239000007864 aqueous solution Substances 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 238000006386 neutralization reaction Methods 0.000 description 5
- AMWRITDGCCNYAT-UHFFFAOYSA-L manganese oxide Inorganic materials [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- RPACBEVZENYWOL-XFULWGLBSA-M sodium;(2r)-2-[6-(4-chlorophenoxy)hexyl]oxirane-2-carboxylate Chemical compound [Na+].C=1C=C(Cl)C=CC=1OCCCCCC[C@]1(C(=O)[O-])CO1 RPACBEVZENYWOL-XFULWGLBSA-M 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000008151 electrolyte solution Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 239000004743 Polypropylene Substances 0.000 description 2
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- PPNAOCWZXJOHFK-UHFFFAOYSA-N manganese(2+);oxygen(2-) Chemical class [O-2].[Mn+2] PPNAOCWZXJOHFK-UHFFFAOYSA-N 0.000 description 2
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 2
- -1 polypropylene Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 238000003756 stirring 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
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910001416 lithium ion Inorganic materials 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
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 239000011255 nonaqueous electrolyte Substances 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- NYPFJVOIAWPAAV-UHFFFAOYSA-N sulfanylideneniobium Chemical compound [Nb]=S NYPFJVOIAWPAAV-UHFFFAOYSA-N 0.000 description 1
- TXEYQDLBPFQVAA-UHFFFAOYSA-N tetrafluoromethane Chemical compound FC(F)(F)F TXEYQDLBPFQVAA-UHFFFAOYSA-N 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
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
【発明の詳細な説明】
童呈上曵租且公立
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関し、特に正極の改良に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a non-aqueous secondary battery using lithium or a lithium alloy as a negative electrode active material, and particularly to improvements in the positive electrode.
従来生技歪
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など
が提案されており、一部実用化されているものがある。Conventional production techniques have been proposed as positive electrode active materials for this type of secondary battery, such as molybdenum trioxide, vanadium pentoxide, titanium or niobium sulfide, and some of them have been put into 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、フン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 and carbon fluoride are known as typical positive electrode active materials for non-aqueous primary batteries.
Moreover, these have already been put into practical use.
特に、二酸化マンガンは保存性に優れ、資源的に豊富で
あり且つ安価であるという利点を有している。In particular, manganese dioxide has the advantages of excellent preservability, abundant resources, and low cost.
このような背景に鑑みて、非水系二次電池の正極活物質
として二酸化マンガンを用いることが有益であると考え
られるが、二酸化マンガンは可逆性に難があり充放電サ
イクル特性に問題がある。In view of this background, it is considered to be beneficial to use manganese dioxide as a positive electrode active material for non-aqueous secondary batteries, but manganese dioxide has difficulty in reversibility and has problems in charge-discharge cycle characteristics.
そこで本願出願人は、二酸化マンガンを用いる場合の上
記欠点を抑制すべく、特開昭６３−１１４０６４号公報
に示すようにｌｉｚＭｎｏ，１を含有するＭｎＯ，、或
いはリチウムを含有しており、ＣｕＫαにおけるＸ＆ｌ
１回折図において２θ＝２２３１．５” ３７’．４
２”，５５’にピークを有するマンガン酸化物、更にス
ピネル型，λ型，或いはその両者の中間的な構造を持つ
マンガン酸化物を正極活物質として用いることを先に提
案している。Therefore, in order to suppress the above-mentioned drawbacks when using manganese dioxide, the applicant of the present application has developed a method that contains MnO containing lizMno,1 or lithium, as shown in Japanese Patent Application Laid-Open No. 63-114064, and that X&l
2θ=2231.5” 37’.4 in 1 diffractogram
It has previously been proposed to use manganese oxides having peaks at 2'' and 55', as well as manganese oxides having a spinel type, λ type, or an intermediate structure between the two, as positive electrode active materials.
”しよ゜と る
これらは、いずれも［，ｉｘＭｎｏ＞’で表わされるリ
チウムを含有するマンガン複合酸化物であり、結晶構造
がリチウムイオンの侵入・脱離に対して可逆性を有する
ので、サイクル特性の向上が認められる。但し、実用上
は更に他の特性をも改良することが望まれる。All of these are manganese composite oxides containing lithium expressed as [,ixMno>', and their crystal structures are reversible against the entry and exit of lithium ions, so they can be easily cycled. Improvements in properties are observed. However, in practical terms, it is desirable to further improve other properties.
本発明はかかる現状に鑑みてなされたものであり、サイ
クル特性を一層向上させることができる非水系二次電池
を提供することを目的とする。The present invention has been made in view of the current situation, and an object of the present invention is to provide a non-aqueous secondary battery that can further improve cycle characteristics.
ｉ． ″゛ るための
本発明は上記目的を達或するために、リチウムる正極と
を有する非水系二次電池において、前記複合酸化物中の
Ｎａ量が低減されていることを特徴とする。i. In order to achieve the above object, the present invention provides a non-aqueous secondary battery having a lithium positive electrode, characterized in that the amount of Na in the composite oxide is reduced.
葺一一一一服
本願出願人は、正極活物質としてＬ ｉ ｘＭｎｏｙ複
合酸化物を用いた場合の電池特性を一層向上させるため
に、種々の検討を行った。その結果、Ｌ ｉ ｘＭｎｏ
ｙ複合酸化物を合或する際の原料となる二酸化マンガン
にＮａがほとんど含まれなければ、正極活物質の放電容
量が増大することを解明した。The applicant of the present application has conducted various studies in order to further improve battery characteristics when Li x Mnoy composite oxide is used as a positive electrode active material. As a result, L i xMno
It has been found that the discharge capacity of the positive electrode active material increases if the manganese dioxide, which is the raw material for combining the y-composite oxide, contains almost no Na.
即ち、一般的に、電池活物質として用いられる二酸化マ
ンガンはその製造過程において、アルカリによる中和処
理が行われるが、この際アルカリとしてＮａ塩が多く用
いられる。Ｎａ塩による中和処理を処した二酸化マンガ
ンは、通常１０００〜５０００ｐｐｍ程度のＮａを含有
していることが判明した。このようなＮａを含有した二
酸化マンガンとＬｉ塩との熱処理により合威されるＬｉ
ｘ Ｍ ｎ Ｏ ｙ複合酸化物では、理由は定かではな
いが、焼或反応時に二酸化マンガン中のＮａがＭｎＯ２
とＬｉ塩との焼成反応に悪影響を及ぼして放電容量が小
さくなる。また、充放電をくり返した場合には、充放電
サイクルの進行に伴って正極中のＮａが溶出しこれが負
極上に析出することによって、負極表面でのＬｉの充放
電反応が阻害されてサイクル寿命の低下を引きおこす。That is, manganese dioxide used as a battery active material is generally neutralized with an alkali during its manufacturing process, and in this case, Na salt is often used as the alkali. It has been found that manganese dioxide that has been neutralized with Na salt usually contains about 1000 to 5000 ppm of Na. Li is synthesized by heat treatment of such Na-containing manganese dioxide and Li salt.
x M n O y In the composite oxide, Na in manganese dioxide changes to MnO2 during the sintering reaction, although the reason is not clear.
This adversely affects the firing reaction between Li salt and Li salt, resulting in a decrease in discharge capacity. In addition, when charging and discharging are repeated, as the charge and discharge cycles progress, Na in the positive electrode is eluted and deposited on the negative electrode, which inhibits the charge and discharge reaction of Li on the surface of the negative electrode, resulting in a cycle lifespan. causes a decrease in
上記実験結果より、正極活物質であるＬｉｘＭｎｏｙを
合成する際に原料としてＮａ量が低減さた二酸化マンガ
ンを用いれば、即ちＬｉｘＭｎＯｙ中にＮａが殆ど含ま
れていなければ、上記のＮａによる悪影響を排除するこ
とができる。From the above experimental results, if manganese dioxide with a reduced amount of Na is used as a raw material when synthesizing LixMnoy, which is the positive electrode active material, that is, if LixMnOy contains almost no Na, the negative effects of Na mentioned above can be eliminated. can do.
去一施一斑
本発明の実施例を第ｌ図〜第３図に基づいて、以下に説
明する。Embodiments of the present invention will be described below with reference to FIGS. 1 to 3.
第１図は本発明の非水系二次電池の半断面図であり、リ
チウム金属から戒る負極２は負極集電体７の内面に圧着
されている。この負極集電体７は断面略コ字状のステン
レスから或る負極缶５の内底面に固着されている。上記
負極缶５の周端はポリプロピレン製の絶縁バンキング８
の内部に固定されており、絶縁パッキング８の外周には
上記負極缶５とは反対方向に断面略コ字状を威すステン
レス製の正極缶４が固定されている。この正極缶４の内
底面には正極集電体６が固定されており、この正極集電
体６の内面には正極１が固定さている。この正極ｌと前
記負極２この間にはポリプロピレン製微孔性薄膜より成
るセバレータ３が介装されている。尚、電池寸法は直径
２４．０ｍｍ、厚み３．０ｍである。また、電解液とし
ては、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／１溶解したもの
を用いている。FIG. 1 is a half-sectional view of a non-aqueous secondary battery of the present invention, in which a negative electrode 2 made of lithium metal is crimped onto the inner surface of a negative electrode current collector 7. This negative electrode current collector 7 is made of stainless steel and has a substantially U-shaped cross section and is fixed to the inner bottom surface of a certain negative electrode can 5 . The peripheral edge of the negative electrode can 5 is an insulating banking 8 made of polypropylene.
A positive electrode can 4 made of stainless steel and having a substantially U-shaped cross section is fixed to the outer periphery of the insulating packing 8 in the opposite direction to the negative electrode can 5. A positive electrode current collector 6 is fixed to the inner bottom surface of the positive electrode can 4, and a positive electrode 1 is fixed to the inner surface of this positive electrode current collector 6. A separator 3 made of a microporous thin film made of polypropylene is interposed between the positive electrode 1 and the negative electrode 2. Note that the battery dimensions are 24.0 mm in diameter and 3.0 m in thickness. The electrolytic solution used is one in which lithium perchlorate is dissolved at 1 mol/1 in a mixed solvent of propylene carbonate and dimethoxyethane.
ここで、本発明の要旨である正極ｌは、以下のようにし
て作製した。Here, the positive electrode I, which is the gist of the present invention, was produced as follows.
先ず、正極活物質となるｌ，ｉｘＭｎｏｙ複合酸化物の
原料となる二酸化マンガンを、以下に示す手順にて作威
した。ＭｎＳＯｎ溶液（２ｍｏｌ／ｊ！）とＨｚ ＳＯ
ａ （２ｍｏｌ／ｆ）溶液を等量混合シテ電解液を作
威し、この電解液（液温：９５℃）と黒鉛電極とを用い
て電解二酸化マンガンを合威した。First, manganese dioxide, which is a raw material for a l,ixMnoy composite oxide, which is a positive electrode active material, was prepared according to the procedure shown below. MnSOn solution (2 mol/j!) and Hz SO
An electrolytic solution was prepared by mixing equal amounts of a (2 mol/f) solution, and electrolytic manganese dioxide was synthesized using this electrolytic solution (solution temperature: 95° C.) and a graphite electrode.
尚、この場合の電流密度は１０ｍＡ／ｃｄである。Note that the current density in this case is 10 mA/cd.
次に、上記電解二酸化マンガンを温水中で十分に洗浄し
た後、電解二酸化マンガン１００ｇに、ＮＨ．ＯＨ溶液
（０． ８ｍｏｌ／ｆ） １／を加えた後、６０″
に保ちながらビーカー中で１時間攪拌し、電解二酸化マ
ンガンの中和処理を行った。次いで、電解二酸化マンガ
ンを冷水で洗浄した後、濾過、乾燥した。Next, after thoroughly washing the electrolytic manganese dioxide in warm water, 100 g of electrolytic manganese dioxide was added with NH. After adding 1/2 OH solution (0.8 mol/f), 60″
The mixture was stirred in a beaker for 1 hour while maintaining the temperature to neutralize the electrolytic manganese dioxide. Next, the electrolytic manganese dioxide was washed with cold water, filtered, and dried.
このようにして得られた電解二酸化マンガン８０ｇと水
酸化リチウム２０ｇとを乳鉢にて混合した後、空気中に
おいて３７５℃で２０時間熱処理し、ｌ，ｉｚＭｎｏｚ
を含有するマンガン酸化物を作威した。このようにして
得られた活物質粉末と、導電剤としてのアセチレンブラ
ンクと、結着剤としてのフッ素樹脂粉末とを重量比で９
０：６：４の比率で混合して正極合剤とし、この正極合
剤を２トン／ｃｄで直径２０１１に加圧威型した後２５
０℃で熱処理することにより正極を作製した。また、負
極は所定厚みのリチウム板を直径２０ｍに打抜いたもの
を用いた。After mixing 80 g of electrolytic manganese dioxide and 20 g of lithium hydroxide thus obtained in a mortar, heat treatment was performed at 375°C in air for 20 hours, and l,izMnoz
Manganese oxide containing manganese was produced. The active material powder thus obtained, the acetylene blank as a conductive agent, and the fluororesin powder as a binder were mixed in a weight ratio of 9.
After mixing at a ratio of 0:6:4 to form a positive electrode mixture, this positive electrode mixture was pressurized to a diameter of 2011 at 2 tons/cd.
A positive electrode was produced by heat treatment at 0°C. The negative electrode used was a lithium plate with a predetermined thickness punched out to a diameter of 20 m.
このようにして作製した電池を、以下（ＡＩ ）電池と
称する．
〔実施例■〕
上記実施例■の電解二酸化マンガンの作威工程おにいて
、ＮＨ．ＯＨ水溶液（ ０ ． ８ ｍｏｌ／ １
）の代わりにＬｉＯＨ水溶液（ ０ ． ８ ｎ＋ｏ
ｌ／ １ ）を用いて中和処理を行う他は、上記実施例
１と同様にして電池を作製した。The battery thus produced is hereinafter referred to as an (AI) battery. [Example ■] In the production process of electrolytic manganese dioxide in Example ■ above, NH. OH aqueous solution (0.8 mol/1
) instead of LiOH aqueous solution (0.8 n+o
A battery was produced in the same manner as in Example 1 above, except that the neutralization treatment was performed using 1/1).
このようにして作製した電池を、以下（Ａ２）電池と称
する。The battery thus produced is hereinafter referred to as (A2) battery.
前記実施例Ｉの電解二酸化マンガンの作成工程において
、ＮＨ．ＯＨ水溶液による中和処理を行わない他は、前
記実施例Ｉと同様にして電池を作製した。In the process of producing electrolytic manganese dioxide in Example I, NH. A battery was produced in the same manner as in Example I above, except that the neutralization treatment with an OH aqueous solution was not performed.
このようにして作製した電池を、以下（Ａ，〉電池と称
する。The battery thus produced is hereinafter referred to as (A,> battery).
前記実施例Ｉの電解二酸化マンガンの作或工程において
、ＮＨ４０Ｈ水溶液の代わりにＮａＯＨ水溶液（０．
８ｓｏｌ／１）を用いて二酸化マンガンの中和処理を
行ない、更にこの二酸化マンガンをＨｚＳＯｍ水溶液（
０．５ｍｏｌ＃！）１ １中で８時間攪拌して脱Ｎａ処
理を行なう。次いで、二酸化マンガンを冷水で洗浄した
後、ＮＨ．ＯＨ水溶液（０． ８ｎ＋ｏｌ／ｊ！）
Ｉ Ｉｔ中で１時間中和処理する。In a step of producing electrolytic manganese dioxide in Example I, a NaOH aqueous solution (0.
The manganese dioxide was neutralized using a HzSOm aqueous solution (8sol/1).
0.5mol#! ) 1 Stir in 1 for 8 hours to remove sodium. Next, after washing the manganese dioxide with cold water, NH. OH aqueous solution (0.8n+ol/j!)
Neutralize in I It for 1 hour.
次に、再度冷水で洗浄した後、濾過、乾燥することによ
り電解二酸化マンガンを作威した。このようにして電解
二酸化マンガンを作戒する他は前記実施例■と同様にし
て電池を作製した。Next, after washing with cold water again, electrolytic manganese dioxide was produced by filtering and drying. A battery was produced in the same manner as in Example 2 above, except that the electrolytic manganese dioxide was prepared in this manner.
このようにして作製した電池を、以下（Ａ４）電池と称
する。The battery thus produced is hereinafter referred to as (A4) battery.
前記実施例Ｉの電解二酸化マンガンの作或工程において
、ＮＨ４ ０Ｈ水溶液の代わりにＮａＯＨ水溶液（ ０
． ８ ｓ＋ｏｌ／ １ ）を用いて中和処理を行
なう．次に、得られた二酸化マンガンを６０℃の温水（
１ ｆ）中で１時間攪拌して濾過した後、再度６０℃温
水（Ｉｎ）中で１時間攪拌する。このような温水での脱
Ｎａ処理を計８回繰り返して電解二酸化マンガンを作成
する。このようにして電解二酸化マンガンを作成する他
は前記実施例■と同様にして電池を作製した。In a step of producing electrolytic manganese dioxide in Example I, a NaOH aqueous solution ( 0
．． Neutralization treatment is performed using 8 s+ol/1). Next, the obtained manganese dioxide was added to 60°C hot water (
After stirring for 1 hour in 1f) and filtering, the mixture was stirred again for 1 hour in 60°C warm water (In). Electrolytic manganese dioxide is produced by repeating this Na removal treatment using hot water a total of 8 times. A battery was produced in the same manner as in Example 2 above, except that electrolytic manganese dioxide was produced in this manner.
このようにして作製した電池を、以下（Ａ，〉電池と称
する。The battery thus produced is hereinafter referred to as (A,> battery).
前記実施例Ｉの電解二酸化マンガンの作戒工程において
、ＮＨ４０Ｈ水溶液の代わりにＮａＯＨ水溶液（ ０
． ８ ｍｏｌ／ ｌ ）を用いて中和処理を行なう
他は、前記実施例Ｉと同様にして電池を作製した。In the process of preparing electrolytic manganese dioxide in Example I, a NaOH aqueous solution (0
．． A battery was produced in the same manner as in Example I above, except that the neutralization treatment was performed using (8 mol/l).
このようにして作製した電池を、以下（Ｘ）電池と称す
る。The battery thus produced is hereinafter referred to as the (X) battery.
上記本発明の（Ａ１）電池〜（Ａ５〉電池及び比較例の
＜Ｘ＞電池において、正極活物質を作製する際に用いる
電解二酸化マンガン中のＮａ含有量と、初期放電容量と
を調べたので、その結果を下記第１表に示す。尚、初期
放電容量の実験条件は、３ｍＡで２．Ｏｖまで放電する
という条件で行った．
〔以下余白〕
第ｌ表
上記第１表に示すように、本発明の（Ａ，〉電池〜（Ａ
，）電池に用いる電解二酸化マンガンではＮａ含有量が
５０〜８００ｐｐｍであって低い値を示しているのに対
して、比較例の（Ｘ）電池に用いる電解二酸化マンガン
では、Ｎａ含有量が５０００ｐｐｍであるって高い値を
示していることが認められる。特に、電解二酸化マンガ
ンの作製工程で中和処理にＮａ塩を用いていないものの
Ｎａ含有量は５０〜２００ｐｐｍであって、著しく低い
値を示していることが認められる。In the above-mentioned batteries (A1) to (A5) of the present invention and the <X> battery of the comparative example, the Na content in the electrolytic manganese dioxide used in preparing the positive electrode active material and the initial discharge capacity were investigated. The results are shown in Table 1 below.The experimental conditions for the initial discharge capacity were to discharge to 2.0V at 3mA. , (A,> battery of the present invention ~ (A
,) The electrolytic manganese dioxide used in the battery has a Na content of 50 to 800 ppm, which is a low value, whereas the electrolytic manganese dioxide used in the comparative example (X) battery has a Na content of 5000 ppm. It can be seen that the value is quite high. In particular, it is recognized that the Na content is 50 to 200 ppm, which is a significantly low value even though Na salt is not used in the neutralization treatment in the production process of electrolytic manganese dioxide.
尚、Ｎａ塩による中和処理を行なっていない二酸化マン
ガン中のＮａ含有量は一般にｉｏ００ｐｐｍ以下であっ
てこの範囲のＮａ含有量の二酸化マンガンを用いること
が望ましいが、上記（ＡＩ）電池〜（Ａ，）電池に用い
る電解二酸化マンガンでは全て１０００ｐｐｍ以下であ
り、上記範囲内に入っていることがわかる。The Na content in manganese dioxide that has not been neutralized with Na salt is generally io00 ppm or less, and it is desirable to use manganese dioxide with a Na content in this range. ,) It can be seen that the electrolytic manganese dioxide used in batteries all have a concentration of 1000 ppm or less, which is within the above range.
次に、初期放電容量は、（Ａ１）電池〜（Ａｓ）電池で
は３３〜４８ｍＡＨであるのに対して、（Ｘ）電池では
２９ｍＡＨＬかないことが認められる。特にＮａ含有量
が２００ｐｐｍ以下の（Ａ１）電池〜（Ａ３）電池では
全て４０ｍＡＨ以上であることが認められる。したがっ
て、Ｎａ含有量の低い二酸化マンガンを用いて正極を作
或するのが望ましい。Next, it is recognized that the initial discharge capacity of the (A1) battery to (As) battery is 33 to 48 mAH, while that of the (X) battery is only 29 mAHL. In particular, it is recognized that all of the batteries (A1) to (A3) with Na content of 200 ppm or less have a power of 40 mAH or more. Therefore, it is desirable to fabricate the positive electrode using manganese dioxide with a low Na content.
本発明の（ＡＩ ）電池〜（Ａ，）及び比較例の（Ｘ）
電池の充放電サイクル特性を調べたので、その結果を第
２図に示す。尚、実験条件は、３ｍＡで４時間放電した
後、３ｍＡで充電終止電圧４Ｖまで充電するという条件
である。(AI) battery of the present invention ~ (A,) and comparative example (X)
The charge/discharge cycle characteristics of the battery were investigated and the results are shown in FIG. The experimental conditions were to discharge at 3 mA for 4 hours and then charge at 3 mA to a charge end voltage of 4V.
第２図に示すように、（Ａ，）電池〜（Ａ，）電池では
１００サイクル以上にならないと放電終止電圧が大きく
低下し始めないのに対して、（Ｘ）電池では１００サイ
クル以下で放電終止電圧が低下し始めることが認められ
る。特に、Ｎａ含有量の少ない二酸化マンガンを用いた
（Ａ，）電池〜（Ａ，）電池では特に良好な特性を示し
ていることが認められる。As shown in Figure 2, for the (A,) battery to (A,) battery, the end-of-discharge voltage does not begin to decrease significantly until 100 cycles or more, whereas for the (X) battery, the discharge end voltage does not start to decrease significantly after 100 cycles or less. It is observed that the final voltage begins to decrease. In particular, it is recognized that the (A,) to (A,) batteries using manganese dioxide with a low Na content exhibit particularly good characteristics.
尚、上記実施例では正極活物質であるＬｉｘＭｎｏｙの
原料として電解二酸化マンガンを用いたが、これに限定
するものではなく、本発明は化学二酸化マンガンや天然
二酸化マンガンも適用できることは勿論である。In the above example, electrolytic manganese dioxide was used as the raw material for LixMnoy, which is the positive electrode active material, but the present invention is not limited to this, and it goes without saying that chemical manganese dioxide and natural manganese dioxide can also be applied.
また、本発明は上記非水電解液を用いた非水系二次電池
に限定されるものではなく、固定電解質を用いた非水系
二次電池にも適用することが可能である。Furthermore, the present invention is not limited to non-aqueous secondary batteries using the above-mentioned non-aqueous electrolyte, but can also be applied to non-aqueous secondary batteries using a fixed electrolyte.
発里夏盟来
以上説明したように、複合酸化物中のＮａｉを低減すれ
ば、初期放電容量が増大すると共に、サ４．
イクル特性を飛躍的に向上させることができる。As explained above, if Nai in the composite oxide is reduced, the initial discharge capacity will increase, and 4. The cycle characteristics can be dramatically improved.
したがって、電池の性能を飛躍的に向上させることがで
きるという効果を奏する。Therefore, there is an effect that the performance of the battery can be dramatically improved.
第１図は本発明電池の半断面図、第２図は本発明の（Ａ
，）電池〜（Ａ，）電池及び比較例の（Ｘ）電池のサイ
クル特性を示すグラフである。
１・・・正極、２・・・負極、３・・・セバレータ。FIG. 1 is a half-sectional view of the battery of the present invention, and FIG. 2 is a half-sectional view of the battery of the present invention (A
, ) battery - (A,) battery and a comparative example (X) battery are graphs showing the cycle characteristics of the battery. 1...Positive electrode, 2...Negative electrode, 3...Separator.
Claims (1)
と、Ｌｉ＿ｘＭｎＯ＿ｙで表される複合酸化物を活物質
とする正極とを有する非水系二次電池において、 前記複合酸化物中のＮａ量が低減されていることを特徴
とする非水系二次電池。(1) In a non-aqueous secondary battery having a negative electrode using lithium or a lithium alloy as an active material and a positive electrode using a composite oxide represented by Li_xMnO_y as an active material, the amount of Na in the composite oxide is reduced. A non-aqueous secondary battery characterized by:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1227990A JPH0393163A (en) | 1989-09-01 | 1989-09-01 | Nonaqueous system secondary battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1227990A JPH0393163A (en) | 1989-09-01 | 1989-09-01 | Nonaqueous system secondary battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0393163A true JPH0393163A (en) | 1991-04-18 |
Family
ID=16869442
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1227990A Pending JPH0393163A (en) | 1989-09-01 | 1989-09-01 | Nonaqueous system secondary battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0393163A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1128452A1 (en) * | 2000-02-25 | 2001-08-29 | Mitsui Mining & Smelting Co., Ltd | Manganese dioxide for lithium primary battery and process for producing the same |
| JP2005285572A (en) * | 2004-03-30 | 2005-10-13 | Nikko Materials Co Ltd | Precursor for lithium-ion secondary battery anode material, its manufacturing method, and manufacturing method of anode material using it |
| JP2007182032A (en) * | 2006-01-10 | 2007-07-19 | Tohoku Ricoh Co Ltd | Printing equipment and stencil printing equipment |
| US7524581B2 (en) | 2004-07-23 | 2009-04-28 | The Gillette Company | Non-aqueous electrochemical cells |
| JP2011198772A (en) * | 2011-06-27 | 2011-10-06 | Jx Nippon Mining & Metals Corp | Precursor for positive electrode material of lithium ion secondary battery |
-
1989
- 1989-09-01 JP JP1227990A patent/JPH0393163A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1128452A1 (en) * | 2000-02-25 | 2001-08-29 | Mitsui Mining & Smelting Co., Ltd | Manganese dioxide for lithium primary battery and process for producing the same |
| US6821678B2 (en) | 2000-02-25 | 2004-11-23 | Mitsui Mining & Smelting Company, Ltd. | Process of producing manganese dioxide for a lithium primary battery |
| JP2005285572A (en) * | 2004-03-30 | 2005-10-13 | Nikko Materials Co Ltd | Precursor for lithium-ion secondary battery anode material, its manufacturing method, and manufacturing method of anode material using it |
| US7524581B2 (en) | 2004-07-23 | 2009-04-28 | The Gillette Company | Non-aqueous electrochemical cells |
| JP2007182032A (en) * | 2006-01-10 | 2007-07-19 | Tohoku Ricoh Co Ltd | Printing equipment and stencil printing equipment |
| JP2011198772A (en) * | 2011-06-27 | 2011-10-06 | Jx Nippon Mining & Metals Corp | Precursor for positive electrode material of lithium ion secondary battery |
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