JPH02220358A - Nonaqueous secondary battery - Google Patents
Nonaqueous secondary batteryInfo
- Publication number
- JPH02220358A JPH02220358A JP1039923A JP3992389A JPH02220358A JP H02220358 A JPH02220358 A JP H02220358A JP 1039923 A JP1039923 A JP 1039923A JP 3992389 A JP3992389 A JP 3992389A JP H02220358 A JPH02220358 A JP H02220358A
- Authority
- JP
- Japan
- Prior art keywords
- lithium
- active material
- compound
- negative electrode
- 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.)
- Granted
Links
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims abstract description 20
- 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 7
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 6
- -1 aluminum compound Chemical class 0.000 claims abstract description 6
- 150000002642 lithium compounds Chemical class 0.000 claims abstract description 6
- 150000002697 manganese compounds Chemical class 0.000 claims abstract description 6
- 239000011149 active material Substances 0.000 claims abstract 6
- 239000002131 composite material Substances 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 5
- 229910000733 Li alloy Inorganic materials 0.000 claims description 4
- 239000001989 lithium alloy Substances 0.000 claims description 4
- 239000007774 positive electrode material Substances 0.000 abstract description 11
- 150000001875 compounds Chemical class 0.000 abstract description 4
- 229910045601 alloy Inorganic materials 0.000 abstract description 3
- 239000000956 alloy Substances 0.000 abstract description 3
- 239000003792 electrolyte Substances 0.000 abstract description 3
- 239000007773 negative electrode material Substances 0.000 abstract description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 2
- 239000013078 crystal Substances 0.000 abstract description 2
- 230000006866 deterioration Effects 0.000 abstract description 2
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 2
- 239000007790 solid phase Substances 0.000 abstract description 2
- 229910001148 Al-Li alloy Inorganic materials 0.000 abstract 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 abstract 1
- 239000006185 dispersion Substances 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 6
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 5
- 238000010586 diagram Methods 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- HSZCZNFXUDYRKD-UHFFFAOYSA-M lithium iodide Chemical compound [Li+].[I-] HSZCZNFXUDYRKD-UHFFFAOYSA-M 0.000 description 2
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 2
- 239000004570 mortar (masonry) Substances 0.000 description 2
- 239000011255 nonaqueous electrolyte Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 1
- 229910001020 Au alloy Inorganic materials 0.000 description 1
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- 241001268418 Lixa Species 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000003353 gold alloy Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 229910021450 lithium metal oxide 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
- 229910001386 lithium phosphate Inorganic materials 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 229940093474 manganese carbonate Drugs 0.000 description 1
- 235000006748 manganese carbonate Nutrition 0.000 description 1
- 239000011656 manganese carbonate Substances 0.000 description 1
- IPJKJLXEVHOKSE-UHFFFAOYSA-L manganese dihydroxide Chemical compound [OH-].[OH-].[Mn+2] IPJKJLXEVHOKSE-UHFFFAOYSA-L 0.000 description 1
- PPNAOCWZXJOHFK-UHFFFAOYSA-N manganese(2+);oxygen(2-) Chemical class [O-2].[Mn+2] PPNAOCWZXJOHFK-UHFFFAOYSA-N 0.000 description 1
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 description 1
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000007784 solid electrolyte 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
- 238000005979 thermal decomposition reaction Methods 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
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 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
- H01M4/485—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
Landscapes
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
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らの
である。DETAILED DESCRIPTION OF THE INVENTION A. Field of Industrial Application The present invention relates to a non-aqueous secondary battery using lithium or a lithium alloy as a negative electrode active material, and particularly relates to an improvement of a positive electrode.
口 従来の技術
この種二次電池の正価活物質としては三酸化モリブデン
、五酸１ヒバナジウム、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。Conventional technology The positive active materials for this type of secondary battery include molybdenum trioxide, monohyvanadium pentate, titanium or niobium sulfide,
Activated carbon and other materials have been proposed, and some have been put into practical use.
一方、非水系−次電池の正極活物質としては二酸化マン
ガン（Ｍｎ０２）、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 (Mn02) and carbon fluoride are known as typical positive electrode active materials for non-aqueous secondary batteries, and these have already been put into practical use.
ここで、特にＭｅＯ２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, MeO2 in particular has the advantage of being excellent in preservability, abundant as a resource, 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ＭｏＯ□を用いることが有益であると考えられるが
、ＭＯＯ□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 above background, it is considered to be beneficial to use MoO□ as a positive electrode active material for nonaqueous secondary batteries, but MOO□ has difficulty in reversibility and has problems in charge/discharge cycle characteristics.
ＭｅＯ２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Ｌｉ２Ｍｏ０．を含有
するＭｎＯ□を用いることを提案した（特開昭６３−１
１４０６４号公ｗｉ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 using MeO2, the applicant has developed Li2Mo0. proposed the use of MnO□ containing
(See No. 14064). Although improvements in cycle characteristics have been recognized through such proposals, further improvement in characteristics is desired for practical purposes.
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ＭＯｌＮｂ、Ｗ、Ｒ
ｕ、Ｃｏ、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６３−２１５
８７０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 discovered that manganese oxide, lithium salt, and metal oxide represented by MOX (where M is MOINb, W, R
At least one metal selected from the group consisting of Co, Ti, Bi, Cu, and Cr) was proposed to be used as a positive electrode active material.
(Refer to No. 870) However, even in this case, if the charging/discharging cycle is repeated many times, metal components will be eluted into the electrolyte.
There is a concern that it may precipitate on the negative electrode and deteriorate the cycle characteristics of the negative electrode.
ハ 発明が解決しようとする課題
改質されたマンガン酸化物を正極活物質に用いて、この
種電池のサイクル特性の向上を計ることを目的とする。C. Problems to be Solved by the Invention The object of the invention is to improve the cycle characteristics of this type of battery by using a modified manganese oxide as a positive electrode active material.
二 課題を解決するための手段
本発明の要旨とするところは、ＬｉｘＡｌｙＭａＯｘで
表される複合酸化物を正極活物質とすることにある。2. Means for Solving the Problems The gist of the present invention is to use a composite oxide represented by LixAlyMaOx as a positive electrode active material.
又、ＬｉｘＡｌｙＭａＯｘで表わされる複合酸化物を含
有するマンガン酸化物を正極活物質とすることにある。Another object of the present invention is to use a manganese oxide containing a complex oxide represented by LixAlyMaOx as a positive electrode active material.
尚、ＬｉｘＡ７７ＭｏＯｚで表わされる複合酸化物を含
有するマンガン酸化物は、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、熱処理して得ら
れたものであることが有益である。The manganese oxide containing the complex oxide represented by LixA77MoOz is advantageously obtained by mixing a manganese compound, a lithium compound, and an aluminum compound and heat-treating the mixture.
（ホ）作 用
ＬｉｘＡ７７ＭｏＯｘで表わされる複合酸化物は、結晶
構造が大きくひずんでいるためリチウムイオンの固相内
拡散が容易になると共に、Ａｇが電解液中に溶出し負極
上に析出してＬｉ−Ａ１合金が形成されるが、このＬｉ
−Ａ＃金合金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を生じることはない
。(E) Function The complex oxide represented by LixA77MoOx has a greatly distorted crystal structure, which facilitates the diffusion of lithium ions in the solid phase, and also causes Ag to dissolve into the electrolyte and precipitate on the negative electrode, causing Li -A1 alloy is formed, but this Li
-A# Gold alloy This is used as a negative electrode for non-aqueous secondary batteries, and does not cause deterioration of cycle characteristics.
又、ＬｉｘＡ？７ｊ！ｎＯｚで表される複合酸化物を含
有するマンガン酸化物は、各種のマンガン化合物、リチ
ウム化合物及びアルミニウム化合物を混合熱処理するこ
とによって容易に得ることができる。Also, LixA? 7j! A manganese oxide containing a composite oxide represented by nOz can be easily obtained by heat-treating a mixture of various manganese compounds, lithium compounds, and aluminum compounds.
尚、熱処理温度は複合酸化物中の水分の除去と、マンカ
ン酸化物の熱分解によるＭｎの価数低下の防止を目的と
するならば、酸素含有雰囲気中で３５０〜４３０℃の範
囲が特に望ましい。Note that the heat treatment temperature is particularly preferably in the range of 350 to 430°C in an oxygen-containing atmosphere if the purpose is to remove moisture in the composite oxide and prevent a decrease in the valence of Mn due to thermal decomposition of the mankan oxide. .
へ実施例 以下、本発明の実施例について詳述する。Examples Examples of the present invention will be described in detail below.
実施例１
平均粒径３０μｍ以下の化学二酸化マンガン５０ｇ、Ｌ
ｉ０Ｈ４ｇ及びＡ （１（Ｏｌｌ）３８ ｇ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 Chemical manganese dioxide 50g, L with an average particle size of 30μm or less
After mixing 4 g of i0H and 38 g of A (1(Oll)) in a mortar, the mixture is heat-treated at 375° C. for 20 hours in air.
この熱処理によって生成した物質は、Ｘ線回ス乍図にお
いてＭａＯ□とは異なる回折パターンを与え、元素分析
からＭｎ、Ｌｉ及びＡｌ１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Ｍ１１０２、（シｉ
、＾ｌ）Ｍｌｌｚ０４、Ｌｉ及びＡｇ複合酸化物（Ｌ＋
ＡＪＯｚ、Ｌｉ５ＡｆＯ４、ＬｉＡζ５０８）の回折ピ
ークもみられた。The substance produced by this heat treatment gave a diffraction pattern different from that of MaO□ in an X-ray diffraction diagram, and was confirmed by elemental analysis to be a composite oxide of Mn, Li, and Al1. Also, from the X-ray diffraction diagram, M1102, (Si
, ^l) Mllz04, Li and Ag composite oxide (L+
Diffraction peaks of AJOz, Li5AfO4, LiAζ508) were also observed.
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、この正極合剤を２トン／ ｃｍ ２で直径２０ｍｍ
に加圧成型したのち２５０℃で熱処理して正極とする。The positive electrode active material powder thus obtained is mixed with acetylene black as a conductive agent and fluororesin powder as a binder in a weight ratio of 90:6:4 to prepare a positive electrode mixture. 2 tons/cm2 of mixture with a diameter of 20 mm
After being pressure-molded, it is heat-treated at 250°C to form a positive electrode.
負極は所定厚みのリチウム板を直径２０Ｉ１ｗ１１に打
抜いたものである。The negative electrode was a lithium plate with a predetermined thickness punched out to a diameter of 20I1w11.
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
レス製の正負横笛であってこれらはボプロピレン製の絶
縁バッキング（３）により隔層されている。（４）は本
発明の要旨とする正極であって、正極缶（１１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、ｆＬ極横笛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／ｇ溶解したもの
を用いた。電池寸法は直径２４．０ｗｗａ、厚み３．０
ｍであった。この本発明電池を（＾、）とする。Figure 1 shows a half-sectional view of a flat non-aqueous electrolyte secondary battery assembled using the above-mentioned positive and negative electrodes. It is separated by an insulating backing (3). (4) is a positive electrode which is the gist of the present invention, and is pressed into contact with a positive electrode current collector (5) fixed to the inner bottom surface of a positive electrode can (11). (6)
is a negative electrode, and is crimped to a negative electrode current collector (7) fixed to the inner bottom surface of the fL polar transverse flute 2). (8) is a separator made of a microporous thin film made of polypropylene, and the electrolytic solution used was one in which 1 mol/g of lithium perchlorate was dissolved in a mixed solvent of propylene carbonate and dimethoxyethane. Battery dimensions are diameter 24.0 wwa, thickness 3.0
It was m. This invention battery is referred to as (^,).
実施例２
Ｍ ｎ （ＮＯ３１２１００ｇ 、 Ｌｉ２ＣＯ３２０
ｇ 、＾１２０，５ｇを乳鉢にて混合した後、空気中に
おいて３７５°Ｃで２０時間熱処理する。Example 2 M n (NO312100g, Li2CO320
After mixing 120.5 g of g and ^120.5 g in a mortar, heat treatment is performed at 375°C in air 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、Ｍ口２ＡＩ０４、Ｍ口＾Ｉ２０４の回折ピークもみ
られた。The substance produced by this heat treatment showed a diffraction pattern substantially similar to that obtained in Example 1 in the X-ray diffraction diagram, and diffraction peaks of M-2AI04 and M-2I204 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（＾２）を
作成した。A battery of the present invention (^2) was prepared in the same manner as in Example 1 except that the composite oxide thus obtained was used as the positive electrode active material.
比較例Ｉ
Ａρ（０１１１３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（Ｂｔ）を作成した。Comparative Example I A comparative battery (Bt) was prepared in the same manner as in Example 1 except that Aρ (01113) was not added.
比較例２
Ａ Ｑ （０）１）３８ ｇの代わりに賛。Ｏｉ１５ｇ
ｅ添加することを除いて池は実施ｒＩＡ１と同様の比較
電池（Ｂ２）を作成した。Comparative Example 2 A Q (0)1) 38 g instead of praise. Oi15g
A comparative cell (B2) was prepared which was similar to the IA1 experiment, except that E was added.
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、ＯＶとした。FIG. 2 shows the charge/discharge cycle characteristics of these batteries. In addition, the charging and discharging conditions are: discharging at a current of 3 mA for 4 hours;
The battery was charged at a charging end voltage of 4, OV.
第２図より本発明電池（Ａｌｌｆ＾２）は比較電池（Ｂ
、）（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 present invention battery (Allf^2) is different from the comparative battery (B
, ) (B2), it can be seen that the cycle characteristics are improved.
ＬｉｘＡｔ７ＭｎＯｘ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ｆヒリチウム等、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。The manganese compound, lithium compound, and aluminum compound used to obtain LixAt7MnOx are not limited to those shown in the examples, and other compounds can also be used. Examples of the manganese compound include manganese oxide, manganese hydroxide, manganese carbonate, etc. As the lithium compound, lithium nitrate, lithium phosphate, lithium iodide, etc., and as the aluminum compound, aluminum chloride, aluminum nitrate, etc. can be used.
ト 発明の効果
上述した如く、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おいて、正極活物質として、
ＬｉｘＡ７７ＭｏＯｘで表わされる複合酸化物、或いは
この複合酸化物を含有せるマンガン酸化物を用いること
により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。G. Effects of the invention As mentioned above, in a nonaqueous secondary battery using lithium or a lithium alloy as a negative electrode active material, as a positive electrode active material,
By using a composite oxide represented by LixA77MoOx or a manganese oxide containing this composite oxide, the cycle characteristics of this type of battery can be improved, and its industrial value is extremely large.
尚１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、固体電解買を用いる二次電池にも適用
できるものである。Note that the present invention is not limited to secondary batteries using non-aqueous electrolytes as shown in the examples, but can also be applied to secondary batteries using solid electrolytes.
イクル特性図を夫々示す。The cycle characteristic diagrams are shown respectively.
（１）・・・正極缶、（２）・・・負■缶、（３）・・
・絶縁パツキン・グ、（４）・・・正極、（６）・・・
負極、（８）・・・セパレータ、（ＡＩ）（＾２）・・
・本発明電池、＋Ｂｌｌ （８２１・・・比較電池。(1)... Positive electrode can, (2)... Negative ■ can, (3)...
・Insulation packing, (4)...Positive electrode, (6)...
Negative electrode, (8)... Separator, (AI) (^2)...
-Battery of the present invention, +Bll (821... comparative battery).
Claims (3)
と、Ｌｉ＿ｘＡｌ＿ｙＭｎＯ＿ｚで表わされる複合酸化
物を活物質とする正極とを備えた非水系二次電池。(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 represented by Li_xAl_yMnO_z as an active material.
と、Ｌｉ＿ｘＡｌ＿ｙＭｎＯ＿ｚで表わされる複合酸化
物を含有するマンガン酸化物を活物質とする正極とを備
えた非水系二次電池。(2) A nonaqueous secondary battery comprising a negative electrode using lithium or a lithium alloy as an active material, and a positive electrode using a manganese oxide containing a composite oxide represented by Li_xAl_yMnO_z as an active material.
合酸化物を含有するマンガン酸化物が、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、
熱処理して得られたものである請求項（２）記載の非水
系二次電池。(3) The manganese oxide containing the composite oxide represented by Li_xAl_yMnO_z is a mixture of a manganese compound, a lithium compound, and an aluminum compound,
The nonaqueous secondary battery according to claim 2, which is obtained by heat treatment.
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 true JPH02220358A (en) | 1990-09-03 |
| JP2957589B2 JP2957589B2 (en) | 1999-10-04 |
Family
ID=12566456
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1039923A Expired - Fee Related JP2957589B2 (en) | 1989-02-20 | 1989-02-20 | Non-aqueous secondary battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2957589B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02278661A (en) * | 1989-04-20 | 1990-11-14 | Fuji Elelctrochem Co Ltd | Nonaqueous electrolyte secondary battery |
| WO1999031745A1 (en) * | 1997-12-18 | 1999-06-24 | Research Corporation Technologies, Inc. | Mesostructural metal oxide materials useful as an intercalation cathode or anode |
| US7026071B2 (en) | 1996-10-11 | 2006-04-11 | Massachusetts Institute Of Technology | Non-crosslinked, amorphous, block copolymer electrolyte for batteries |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6290863A (en) * | 1985-05-10 | 1987-04-25 | Asahi Chem Ind Co Ltd | secondary battery |
| JPS63114064A (en) * | 1986-10-30 | 1988-05-18 | Sanyo Electric Co Ltd | Nonaqueous secondary battery |
-
1989
- 1989-02-20 JP JP1039923A patent/JP2957589B2/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6290863A (en) * | 1985-05-10 | 1987-04-25 | Asahi Chem Ind Co Ltd | secondary battery |
| JPS63114064A (en) * | 1986-10-30 | 1988-05-18 | Sanyo Electric Co Ltd | Nonaqueous secondary battery |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02278661A (en) * | 1989-04-20 | 1990-11-14 | Fuji Elelctrochem Co Ltd | Nonaqueous electrolyte secondary battery |
| US7026071B2 (en) | 1996-10-11 | 2006-04-11 | Massachusetts Institute Of Technology | Non-crosslinked, amorphous, block copolymer electrolyte for batteries |
| WO1999031745A1 (en) * | 1997-12-18 | 1999-06-24 | Research Corporation Technologies, Inc. | Mesostructural metal oxide materials useful as an intercalation cathode or anode |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2957589B2 (en) | 1999-10-04 |
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