JPH04169076A - Nonaqueous electrolyte secondary battery and its manufacture - Google Patents
Nonaqueous electrolyte secondary battery and its manufactureInfo
- Publication number
- JPH04169076A JPH04169076A JP2295802A JP29580290A JPH04169076A JP H04169076 A JPH04169076 A JP H04169076A JP 2295802 A JP2295802 A JP 2295802A JP 29580290 A JP29580290 A JP 29580290A JP H04169076 A JPH04169076 A JP H04169076A
- Authority
- JP
- Japan
- Prior art keywords
- positive electrode
- lithium
- battery
- active material
- aqueous electrolyte
- 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
- 239000011255 nonaqueous electrolyte Substances 0.000 title claims abstract description 24
- 238000004519 manufacturing process Methods 0.000 title claims description 8
- 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 8
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 8
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000002131 composite material Substances 0.000 claims abstract description 6
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 6
- 239000011572 manganese Substances 0.000 claims abstract description 6
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 6
- 229910052715 tantalum Inorganic materials 0.000 claims abstract description 6
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 6
- 150000002642 lithium compounds Chemical class 0.000 claims abstract description 5
- 229910000733 Li alloy Inorganic materials 0.000 claims abstract 3
- 239000001989 lithium alloy Substances 0.000 claims abstract 3
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 13
- 239000007774 positive electrode material Substances 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 6
- 229910052804 chromium Inorganic materials 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 abstract description 33
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 abstract description 31
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 abstract description 26
- 238000006243 chemical reaction Methods 0.000 abstract description 2
- 239000005486 organic electrolyte Substances 0.000 abstract description 2
- 238000007789 sealing Methods 0.000 abstract description 2
- 229910000000 metal hydroxide Inorganic materials 0.000 abstract 3
- 150000004692 metal hydroxides Chemical class 0.000 abstract 3
- 229910052802 copper Inorganic materials 0.000 abstract 1
- -1 aOH is added.Also Chemical class 0.000 description 8
- 239000000203 mixture Substances 0.000 description 5
- 238000000354 decomposition reaction Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 4
- 229910015645 LiMn Inorganic materials 0.000 description 3
- 239000004743 Polypropylene Substances 0.000 description 3
- 239000006182 cathode active material Substances 0.000 description 3
- 230000005611 electricity Effects 0.000 description 3
- 229920001155 polypropylene Polymers 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 239000006230 acetylene black Substances 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 description 2
- 229910001486 lithium perchlorate Inorganic materials 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 1
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-M triflate Chemical compound [O-]S(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-M 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】
産業上の利用分野
本発明（友 非水電解液二次電池に関し 特に正極活物
質を改良した非水電解液二次電池およびその製造法に関
すａ
従来の技術
リチウな リチウム、リチウム化合物を負極とする非水
電解液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も
特へ これら電池の正極活物質としてＭｎＯ＊やＴｉＳ
＊がよく検討されていも 最近 タックレイらによりＬ
ｉＭｎａＱ４が正極活物質となることが報告されｔも（
マテリアル リサーチ ブレチン１９８３年１８巻４６
１−４７２ページ） ＬｉＭｎａＯ４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、電池の放電電圧が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もＬｉ
ｘＭｎ２Ｑ４正極活物質中のＸ値と開路電位の関係を第
４図に示す。４ボルト付近と２．８ボルト付近の２段の
電位曲線となム
これまで、電位曲線の２．８ボルト付近の２段目に着目
し 充電電圧を４ボルト程度とし 放電を２ボルト程度
まで行なう充放電サイクルを行なわせることにより、サ
イクル特性の良好な電池を得る工夫がなされていも
しかじ より高エネルギー密度を得るに（Ｌ４゜５ボル
トまで充電し３ボルトまで放電する電位曲線のうち１段
目を利用する充放電サイクル、つまりＸ値が１以下、好
ましくは龜 ７以下になるまで充電ＬＡ Ｘ値が１にな
るまでまたζｉ１．８５になるまで放電する方が有利で
あａ しかＬＸ値が０．７以下になるまで充電する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 この劣化の度合ｃヨ２段
目の電位曲線を用いるサイクルに較べ極めて太きＬ〜
またＸ値が０．７を越える程度に充電した場合に（よ
十分な放電容量を得ることができなｌ、％そこで、式
Ｌ ｉ ｘＭｖＭ ｎ （＊−ｖ＋ ０４で表わされＭ
はＣ０１ＣｒＸ Ｎｉ、Ｔａ、Ｚｎの中の少な（とも一
種であり、かつ ０．８５≦Ｘ≦１．１５であり、 ０
．０２≦Ｙ≦０．３である正極活物質を用いる改良がな
され サイクル特性の向上が図られていも
発明が解決しようとする課題
上記の正極活物質を用いることによりサイクル特性の大
幅な向上が実現できる力（充電電圧が４Ｖを越えるた数
充電後の電池の自己放電特性が不充分であるという問
題があっｔも 非水電解液二次電池の自己放電につい
ては電池内部の微量水分や電解液溶媒の分解が原因とな
り、電池内部抵抗の増大や充放電容量の低下という問題
を引き起こす。特に電池電圧が高くなるほどこれらの現
象は顕著になり、また 高温保存時においてより著しい
ものとなも
本発明はこのような課題を解決するもので、自己放電特
性を向上した非水電解液二次電池およびその製造法を提
供することを目的とす４課題を解決するための手段
この課題を解決するため本発明の非水電解液二次電池お
よびその製造法（友 リチウム リチウム、リチウム化
合物を負楓Ｌ ＩＭ ｎ ２−ＸＭｅｘｏａ（Ｍｅ：
Ｃｏ、 Ｃｒ、 Ｎｉ、 Ｔａ、 Ｚｎからな
る少なくとも一種）で表わされるマンガン主体の複合酸
化物を活物質とする正極 および非水電解液を有する非
水電解液二次電池において、前記正極に水酸化リチウム
Ｌｉ０Ｈ１水酸化カリウムＫＯＨ１水酸化ナトリウムＮ
ａＯＨなどのアルカリ金属水酸化物の少なくとも１種を
添加するものであム
また アルカリ金属水酸化物の添加量が前記正極活物質
１００ｇあたり０．０５〜０． １モルであることが望
ましく〜
作用
この構成により本発明の非水電解液二次電池およびその
製造法（友 二次電池内部におけるアルカリ金属水酸化
物の働きは明確ではない戟 その作用として（よ 有機
電解液の分解の抑制や分解生成物との反応などを挙げる
ことができも この結果溶媒分解生成物が原因と考えら
れる電池性能の低下を軽減できるものと思われも
実施例
以下本発明の一実施例の非水電解液二次電池およびその
製造法について図面を基にして説明すも（実施例１）
電池の製造は次のようにして行なった すなわち正極活
物質として、Ｌ ｉＭｎ＋、５ｃｏｉ、２０４１００ｇ
に導電剤としてアセチレンブラック３．０ｇを混合し
さら番！ アルカリ金属水酸化物として水酸化リチウ
ムＬｉ０８１． ５ｇを水溶液として添加し混合した
この混合物を８０℃で１０時間乾燥し その後結着剤と
してのポリ４弗化エチレン樹脂４６０ｇを混合して正極
合剤とした 正極合剤０．１グラムを直径１７．５ｍｍ
に１トン／Ｃｍ’でプレス成型して正極とじ九 製造し
た電池の断面図を第３図に示も 成型した正極ｌ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九 負極４として直径１
７．５ｍｍ厚さ０．３ｍｍのリチウム板を、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 非水
電解液として、 １モル／ｌの過塩素酸リチウムを溶解
したプロピレンカーボネート溶液を用１．Ｘ、これをセ
パレータ３上および負極４上に加え九 その後電池を封
口した上記のようにして得られた電池をＡとすム同様の
方法により水酸化カリウムＫＯＨを添加した正極を用い
た電池をＫ 水酸化ナトリウムＮａＯＨを添加した正極
を用いた電池をα 水酸化カリウムＫＯＨと水酸化ナト
リウムＮａＯＨをそれぞれ０．７５ｇ添加した正極を用
いた電池を■水酸化リチウムＬｉ０Ｈ１水酸化カリウム
ＫＯＨ１水酸化ナトリウムＮａＯＨをそれぞれ０．５０
ｇ添加した正極を用いた電池をＥとする。[Detailed Description of the Invention] Industrial Application Field of the Invention The present invention relates to a non-aqueous electrolyte secondary battery, and in particular relates to a non-aqueous electrolyte secondary battery with an improved positive electrode active material and a method for manufacturing the same. Non-aqueous electrolyte secondary batteries that use lithium or lithium compounds as negative electrodes are expected to have high voltage and high energy density, and although much research has been conducted on them, MnO* and TiS are particularly important as positive electrode active materials for these batteries.
Although * has been well studied, recently L
It has been reported that iMnaQ4 can be used as a positive electrode active material (
Material Research Bulletin 1983 Volume 18 46
(Page 1-472) LiMnaO4 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 about 4 volts, and it is considered to be a promising cathode active material. Teimo Li
FIG. 4 shows the relationship between the X value and the open circuit potential in the xMn2Q4 positive electrode active material. A two-stage potential curve near 4 volts and near 2.8 volts.So far, we have focused on the second stage of the potential curve near 2.8 volts, setting the charging voltage to about 4 volts and discharging to about 2 volts. Efforts have been made to obtain batteries with good cycle characteristics by performing charge-discharge cycles. It is more advantageous to charge and discharge the battery until the X value becomes 1 or less, preferably 7 or less, and then discharge until the X value reaches 1 and ζi1.85. The cycle characteristics of the first stage of charging and discharging, in which the battery is charged to 0.7 or less, were poor, and the discharge capacity decreased by half after about 50 cycles. Extremely thick L ~ Also, when charging to the extent that the X value exceeds 0.7 (
If sufficient discharge capacity cannot be obtained, the formula
L i xMvM n (*−v+ 04 and M
is C01CrX Ni, Ta, and Zn (both are one type, and 0.85≦X≦1.15, 0
．． Improvements have been made using positive electrode active materials with 02≦Y≦0.3, and even though the cycle characteristics have been improved, the problem to be solved by the invention: By using the above-mentioned positive electrode active materials, a significant improvement in cycle characteristics has been realized. There is a problem that the self-discharge characteristics of the battery after charging are insufficient (when the charging voltage exceeds 4 V).The self-discharge of non-aqueous electrolyte secondary batteries is caused by trace amounts of moisture and electrolyte inside the battery. The decomposition of the solvent causes problems such as an increase in battery internal resistance and a decrease in charge/discharge capacity.In particular, these phenomena become more pronounced as the battery voltage increases, and they become more pronounced during high-temperature storage. To solve these problems, the purpose is to provide a non-aqueous electrolyte secondary battery with improved self-discharge characteristics and a method for manufacturing the same. Nonaqueous electrolyte secondary battery of the present invention and its manufacturing method (Me:
In a non-aqueous electrolyte secondary battery having a positive electrode having a manganese-based composite oxide represented by at least one of Co, Cr, Ni, Ta, and Zn as an active material and a non-aqueous electrolyte, the positive electrode is hydrated. Lithium Li0H1 Potassium hydroxide KOH1 Sodium hydroxide N
At least one kind of alkali metal hydroxide such as aOH is added.Also, the amount of the alkali metal hydroxide added is 0.05 to 0.0% per 100 g of the positive electrode active material. The amount of alkali metal hydroxide is preferably 1 mole. Examples of this method include suppression of decomposition of the organic electrolyte and reaction with decomposition products.As a result, it is thought that the deterioration in battery performance that is thought to be caused by solvent decomposition products can be alleviated. An example of a non-aqueous electrolyte secondary battery and its manufacturing method will be explained based on the drawings (Example 1). The battery was manufactured as follows. Namely, as the positive electrode active material, LiMn+, 5coi , 204100g
3.0g of acetylene black was mixed as a conductive agent into
Sara's turn! Lithium hydroxide Li081. as alkali metal hydroxide. 5g was added as an aqueous solution and mixed.
This mixture was dried at 80°C for 10 hours, and then 460 g of polytetrafluoroethylene resin as a binder was mixed to prepare a positive electrode mixture. 0.1 g of the positive electrode mixture was made into a 17.5 mm diameter
A cross-sectional view of the manufactured battery is shown in Figure 3.The molded positive electrode is placed in case 2. A porous polypropylene film as a separator 3 is placed on top of the positive electrode 1. A porous polypropylene film with a diameter of 1 as the negative electrode 4 is placed on top of the positive electrode 1.
A 7.5 mm x 0.3 mm thick lithium plate was pressed onto a sealing plate 5 with a polypropylene gasket 6. As a non-aqueous electrolyte, a propylene carbonate solution in which 1 mol/l of lithium perchlorate was dissolved was used. ．． X, add this to the separator 3 and the negative electrode 4, and then seal the battery. The battery obtained as described above is labeled A. A battery using a positive electrode to which potassium hydroxide KOH has been added is prepared by the same method. K A battery using a positive electrode to which sodium hydroxide NaOH has been added α A battery using a positive electrode to which 0.75 g of potassium hydroxide KOH and sodium hydroxide NaOH have been added ■ Lithium hydroxide Li0H1 Potassium hydroxide KOH1 Sodium hydroxide NaOH 0.50 each
A battery using a positive electrode containing g is designated as E.
比較例として、アルカリ金属水酸化物を添加しない電池
として、Ｌ ｉＭｎ＋、＊ｃｏ＠、２０４１００、アセ
チレンブラック３．０ｇ、ポリ４弗化エチレン樹脂４．
０ｇを混合して正極合剤として使用し以下、同様に電池
を構成し九 この電池をＦとする。As a comparative example, as a battery to which no alkali metal hydroxide was added, LiMn+, *co@, 204100, acetylene black 3.0g, polytetrafluoroethylene resin 4.
0g was mixed and used as a positive electrode mixture to construct a battery in the same manner. This battery will be referred to as F.
前記電池Ａ−Ｆの自己放電試験を次のようにして行なっ
九 すなわち上記の方法で得られた電池について、２ｍ
Ａの定電流で４．５ボルトまで充電Ｌ ３ボルトまで放
電し この充電 放電を１０サイクル行なったａｌｌサ
イクル目の充電が終わった徽 ６０℃で４週間貯蔵した
貯蔵後同じ条件で放電した ここて 自己放電率は次
のように定復すも
自己放電率＝（１０サイクル目の放電電気量−１１サイ
クル目の放電電気量）／１０サイクル目の放電電気量
上記各電池の６０℃保存にともなう電池内部抵抗の変化
を第２図に示す。A self-discharge test was conducted on the batteries A-F as follows.
Charged to 4.5 volts with a constant current of A, discharged to 3 volts, performed this charge for 10 cycles. Stored at 60°C for 4 weeks. Discharged under the same conditions after storage. Here. The self-discharge rate stabilizes as follows: Self-discharge rate = (Amount of electricity discharged at the 10th cycle - Amount of electricity discharged at the 11th cycle) / Amount of electricity discharged at the 10th cycle As each of the above batteries is stored at 60℃ Figure 2 shows the change in battery internal resistance.
従来構成の電池Ｆでは保存直後から急激な電池内部抵抗
の増加が認められ ４週間後には４０Ω以上になム一方
本実施例の電池Ａ−Ｅにおいては 電池内部抵抗の
増加は小さいものであり、電池Ｆの１１５程度であａ
また 第１表に審ヨ 各電池の４週間後の自己放電率
を示す。In battery F with the conventional configuration, a rapid increase in battery internal resistance was observed immediately after storage, and after 4 weeks, it rose to 40Ω or more.On the other hand, in batteries A to E of this example, the increase in battery internal resistance was small. Table 1 shows the self-discharge rate of each battery after 4 weeks.
電池Ｆは非常に大きな自己放電率であるカミ 本実施例
の電池Ａ−Ｅでは１０％以内に抑えられていも このよ
うに正極へアルカリ金属水酸化物を添加することは高温
保存にともなう自己放電を抑制する効果があり、水酸化
カリウムＫＯＨ１水酸化ナトリウ入 水酸化リチウムの
いずれを添加した場合にも効果があム
さらに これらのアルカリ金属水酸化物を混合して添加
した場合にも同様の効果が認められる。Battery F has a very high self-discharge rate.Although it was suppressed to within 10% in Batteries A-E of this example, adding an alkali metal hydroxide to the positive electrode in this way increases the self-discharge rate due to high-temperature storage. It has the effect of suppressing hydroxide, and it is effective when adding either potassium hydroxide, KOH, sodium hydroxide, or lithium hydroxide.Furthermore, the same effect is obtained when a mixture of these alkali metal hydroxides is added. is recognized.
表
（実施例２）
さらに 正極への水酸化リチウムの添加量について検討
した
第１図に水酸化リチウムの添加量（活物質１００ｇに対
するモル数）とこれらの正極を用いた電池の６０ｔ、４
週間保存後の電池内部抵抗との関係を示す。結果から正
極への水酸化リチウムの添加量が０．０５モル〜０．１
モルの範囲で電池内部抵抗の増加を抑える効果がみられ
も したがって、正極への水酸化リチウムの添加量は活
物質１００ｇに対して、 ０．０５モル〜０．１モルの
範囲が望ましし−
また 水酸化カリウムＫ ＯＨ，水酸化ナトリウムの場
合にＬ 同様の結果が得られ 正極活物質としてＬ ｉ
Ｍｒｚ、ｓＮ ｉｓ、２０４、Ｌ ｉ Ｍｒｚ、ｓＣｒ
＠、２０４、 Ｌ ｉ Ｍ ｎ ＋、＊Ｔ
ａ １．２ ０４、 ＬｉＭｎ １、−Ｚ
ｎ・、２０４Ｃｏを用いた場合にも同じ効果が認められ
九
以上のようｉ：ｘ Ｌ ｉ Ｍ ｎ １．ａＣＯ＠、
２０４を正極活物質とする非水電解質電池において、正
極中にアルカリ金属水酸化物を添加することにより、自
己放電特性の優れた非水電解質二次電池を得ることがで
きも
以上の実施例では 電解液として１モル／ｌの過塩素酸
リチウムを溶解したプロピレンカーボネート溶液を用い
た場合の結果である力ｔ 電解液としてこれ以外番！
溶質として過塩素酸９チウム６フツ化燐酸リチウムやト
リフロロメタンスルフォン酸すチウへ ホウフッ化リチ
ウ八 溶媒としてプロピレンカーボネート、エチレンカ
ーボネートなどのカーボネート類 ガンマ−ブチロラク
トン、酢酸メチルなどのエステル類を用いた電解液が良
好であった しかしなか収 ジメトキシエタンやテトラ
ヒドロフランなどのエーテル類を使用した場合に（よ
自己放電特性は悪く、正極中にアルカリ金属水酸化物を
添加することによる自己放電特性の向上は認められず、
本実施例で示したプロピレンカーボネートを用いた場合
の約２倍であっ九 本実施例では正極は４Ｖ以上の電圧
となるたべ エーテル類は酸化されるためと考えていも
発明の効果
以上の実施例の説明で明らかなように本発明の非水電解
液二次電池およびその製造法によれはリチウム リチウ
ム、リチウム化合物を負楓 Ｌ ｉＭｎｔ−ｘＭｅ＊ｏ
ｎ （Ｍｅ： Ｃｏ、Ｃｒ、Ｎｉ、Ｔａ、Ｚｎの中の
少なくとも一種）で表わされるマンガン主体の複合酸化
物を活物質とする正極 および非水電解液を有し 前記
正極にアルカリ金属水酸化物を正極活物質１００ｇあた
り０゜０５〜０．１モル添加したことにより、自己放電
特性が良好な非水電解液二次電池を得ることができ、産
業上の意義は太き（〜Table (Example 2) Figure 1 further examines the amount of lithium hydroxide added to the positive electrode.
The relationship between the internal resistance of the battery and the battery after storage for a week is shown. From the results, the amount of lithium hydroxide added to the positive electrode is 0.05 mol to 0.1 mol.
Although the effect of suppressing the increase in battery internal resistance is observed in the molar range, the amount of lithium hydroxide added to the positive electrode is preferably in the range of 0.05 mol to 0.1 mol per 100 g of active material. - Similar results were obtained with potassium hydroxide (KOH) and sodium hydroxide (Li as the positive electrode active material).
Mrz, sN is, 204, L i Mrz, sCr
@, 204, L i M n +, *T
a 1.2 04, LiMn 1, -Z
The same effect was observed when using n., 204Co, and the result was 9 or more i:x L i M n 1. aCO@,
In a non-aqueous electrolyte battery using 204 as the positive electrode active material, by adding an alkali metal hydroxide to the positive electrode, a non-aqueous electrolyte secondary battery with excellent self-discharge characteristics can be obtained. The force t is the result when a propylene carbonate solution containing 1 mol/l of lithium perchlorate is used as the electrolyte.
Electrolysis using nine tium perchlorate, lithium hexafluorophosphate, and trifluoromethanesulfonate as a solute, lithium fluoroborate, carbonates such as propylene carbonate and ethylene carbonate, and esters such as gamma-butyrolactone and methyl acetate as a solvent. The liquid was good, but the yield was poor.When using ethers such as dimethoxyethane and tetrahydrofuran (
The self-discharge characteristics were poor, and no improvement in self-discharge characteristics was observed by adding alkali metal hydroxide to the positive electrode.
This is about twice as high as when using propylene carbonate as shown in this example.9 In this example, the positive electrode has a voltage of 4 V or more. As is clear from the explanation, the non-aqueous electrolyte secondary battery of the present invention and the method for manufacturing the same require that lithium, lithium, and lithium compounds be used in a negative manner.
a positive electrode having a manganese-based composite oxide represented by n (Me: at least one of Co, Cr, Ni, Ta, and Zn) as an active material; and a non-aqueous electrolyte, the positive electrode containing an alkali metal hydroxide. By adding 0.05 to 0.1 mol of per 100 g of positive electrode active material, a non-aqueous electrolyte secondary battery with good self-discharge characteristics can be obtained, which has great industrial significance (~
第１図は本発明の一実施例および従来の非水電解液二次
電池およびその製造法の水酸化リチウムの添加量（正極
活物質１００ｇあたりのモル数）と、これらの正極を用
いた電池の６０＼ ４週間保存後の電池内部抵抗との関
係を示すグラフ、第２図は同電池の６０℃保存にともな
う電池内部抵抗の変化を示すグラフ、第３図は同試験に
用いた電池の縦断置皿 第４図は同ＬｉｘＭｎａＯｎ正
極活物質の活物質中のＸ値と開路電位の関係を示すグラ
フであム
第１図
ｔ； ｏｔ−ｔ ４ ｆｉｎ ｔ
（（７１／／ １００／ −ＬＩｌ’ｌｎ、１，１ＣＯ
ａ、Ａ冨２図
初期 ／ Ｚ Ｊ ４鐸
８ｎ間（還）
篇３図Figure 1 shows the amount of lithium hydroxide added (number of moles per 100 g of positive electrode active material) of an embodiment of the present invention and a conventional non-aqueous electrolyte secondary battery and its manufacturing method, and batteries using these positive electrodes. Figure 2 is a graph showing the change in battery internal resistance as the battery was stored at 60°C, Figure 3 is a graph showing the relationship between the battery internal resistance after storage for 4 weeks, and Figure 3 is the graph showing the relationship between the battery internal resistance and the battery used in the test. Figure 4 is a graph showing the relationship between the X value in the active material and the open circuit potential of the same LixMnaOn cathode active material. 'ln,1,1CO
a, A-tou 2 figure early / Z J 4-taku 8n (return) version 3 figure
Claims (3)
負極、ＬｉＭｎ＿２＿−＿ｘＭｅ＿ｘＯ＿４（Ｍｅ：Ｃ
ｏ、Ｃｒ、Ｎｉ、Ｔａ、Ｚｎの中の少なくとも一種）で
表わされるマンガン主体の複合酸化物を活物質とする正
極、および非水電解液を有し、前記正極にアルカリ金属
水酸化物を添加した非水電解液二次電池。(1) Lithium, lithium alloy or lithium compound is used as a negative electrode, LiMn_2_-_xMe_xO_4(Me:C
a positive electrode whose active material is a manganese-based composite oxide represented by at least one of O, Cr, Ni, Ta, and Zn), and a non-aqueous electrolyte, and an alkali metal hydroxide is added to the positive electrode. Non-aqueous electrolyte secondary battery.
０ｇあたり０．０５〜０．１モルである請求項１記載の
非水電解液二次電池。(2) The amount of alkali metal hydroxide added to the positive electrode active material is 10
The non-aqueous electrolyte secondary battery according to claim 1, wherein the amount is 0.05 to 0.1 mol per 0 g.
負極、ＬｉＭｎ＿２＿−＿ｘＭｅ＿ｘＯ＿４（Ｍｅ：Ｃ
ｏ、Ｃｒ、Ｎｉ、Ｔａ、Ｚｎの中の少なくとも一種）で
表わされるマンガン主体の複合酸化物を活物質とする正
極、および非水電解液を有し、前記正極にアルカリ金属
水酸化物を添加した非水電解液二次電池の製造法。(3) LiMn_2_-_xMe_xO_4 (Me:C
a positive electrode whose active material is a manganese-based composite oxide represented by at least one of O, Cr, Ni, Ta, and Zn), and a non-aqueous electrolyte, and an alkali metal hydroxide is added to the positive electrode. A method for manufacturing a non-aqueous electrolyte secondary battery.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2295802A JPH0770329B2 (en) | 1990-10-31 | 1990-10-31 | Non-aqueous electrolyte secondary battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2295802A JPH0770329B2 (en) | 1990-10-31 | 1990-10-31 | Non-aqueous electrolyte secondary battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04169076A true JPH04169076A (en) | 1992-06-17 |
| JPH0770329B2 JPH0770329B2 (en) | 1995-07-31 |
Family
ID=17825357
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2295802A Expired - Fee Related JPH0770329B2 (en) | 1990-10-31 | 1990-10-31 | Non-aqueous electrolyte secondary battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0770329B2 (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0778629A1 (en) * | 1995-12-06 | 1997-06-11 | Kerr-Mcgee Chemical Corporation | Lithium manganese oxide compound and method of preparation |
| JP2002298845A (en) * | 2001-03-30 | 2002-10-11 | Sony Corp | Positive electrode active material and method for synthesizing the same, and battery and method of manufacturing the same |
| KR100378012B1 (en) * | 2000-11-09 | 2003-03-29 | 삼성에스디아이 주식회사 | Positive active material composition for lithium secondary battery and lithium secondary battery using same |
| JP2013534031A (en) * | 2010-06-30 | 2013-08-29 | ベリー スモール パーティクル カンパニー リミテッド | Improved adhesion of active electrode materials to metal electrode substrates |
| US8609283B2 (en) | 2009-09-09 | 2013-12-17 | Sony Corporation | Positive electrode active material, positive electrode, nonaqueous electrolyte cell, and method of preparing positive electrode active material |
| US9105926B2 (en) | 2009-07-24 | 2015-08-11 | Sony Corporation | Positive electrode active material, positive electrode, and nonaqueous electrolyte cell |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60116330U (en) * | 1984-01-10 | 1985-08-06 | 原ヘルス工業株式会社 | health bath equipment |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0254865A (en) * | 1988-08-20 | 1990-02-23 | Japan Storage Battery Co Ltd | Manufacture of nonaqueous electrolytic secondary battery and positive electrode active material used therefor |
| JPH02199770A (en) * | 1989-01-27 | 1990-08-08 | Fuji Elelctrochem Co Ltd | Nonaqueous electrolyte secondary battery |
-
1990
- 1990-10-31 JP JP2295802A patent/JPH0770329B2/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0254865A (en) * | 1988-08-20 | 1990-02-23 | Japan Storage Battery Co Ltd | Manufacture of nonaqueous electrolytic secondary battery and positive electrode active material used therefor |
| JPH02199770A (en) * | 1989-01-27 | 1990-08-08 | Fuji Elelctrochem Co Ltd | Nonaqueous electrolyte secondary battery |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0778629A1 (en) * | 1995-12-06 | 1997-06-11 | Kerr-Mcgee Chemical Corporation | Lithium manganese oxide compound and method of preparation |
| KR100378012B1 (en) * | 2000-11-09 | 2003-03-29 | 삼성에스디아이 주식회사 | Positive active material composition for lithium secondary battery and lithium secondary battery using same |
| JP2002298845A (en) * | 2001-03-30 | 2002-10-11 | Sony Corp | Positive electrode active material and method for synthesizing the same, and battery and method of manufacturing the same |
| US9105926B2 (en) | 2009-07-24 | 2015-08-11 | Sony Corporation | Positive electrode active material, positive electrode, and nonaqueous electrolyte cell |
| US8609283B2 (en) | 2009-09-09 | 2013-12-17 | Sony Corporation | Positive electrode active material, positive electrode, nonaqueous electrolyte cell, and method of preparing positive electrode active material |
| US8808920B2 (en) | 2009-09-09 | 2014-08-19 | Sony Corporation | Positive electrode active material, positive electrode, nonaqueous electrolyte cell, and method of preparing positive electrode active material |
| JP2013534031A (en) * | 2010-06-30 | 2013-08-29 | ベリー スモール パーティクル カンパニー リミテッド | Improved adhesion of active electrode materials to metal electrode substrates |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0770329B2 (en) | 1995-07-31 |
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