JPH0343960A - Nonaqueous electrolyte battery - Google Patents
Nonaqueous electrolyte batteryInfo
- Publication number
- JPH0343960A JPH0343960A JP17940389A JP17940389A JPH0343960A JP H0343960 A JPH0343960 A JP H0343960A JP 17940389 A JP17940389 A JP 17940389A JP 17940389 A JP17940389 A JP 17940389A JP H0343960 A JPH0343960 A JP H0343960A
- Authority
- JP
- Japan
- Prior art keywords
- positive electrode
- electrolyte
- battery
- reaction
- electrolyte battery
- 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 description 15
- 239000003792 electrolyte Substances 0.000 claims abstract description 16
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims abstract description 12
- -1 lithium hexafluorophosphate Chemical compound 0.000 claims abstract description 12
- 239000011149 active material Substances 0.000 claims abstract description 3
- 239000002683 reaction inhibitor Substances 0.000 claims description 8
- 229910052744 lithium Inorganic materials 0.000 claims description 7
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 6
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 4
- 229910052698 phosphorus Inorganic materials 0.000 claims description 4
- 239000011574 phosphorus Substances 0.000 claims description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 3
- PONXTPCRRASWKW-UHFFFAOYSA-N 1,2-diphenylethane-1,2-diamine Chemical compound C=1C=CC=CC=1C(N)C(N)C1=CC=CC=C1 PONXTPCRRASWKW-UHFFFAOYSA-N 0.000 claims description 2
- 229910000733 Li alloy Inorganic materials 0.000 claims description 2
- DZHMRSPXDUUJER-UHFFFAOYSA-N [amino(hydroxy)methylidene]azanium;dihydrogen phosphate Chemical compound NC(N)=O.OP(O)(O)=O DZHMRSPXDUUJER-UHFFFAOYSA-N 0.000 claims description 2
- GJYJYFHBOBUTBY-UHFFFAOYSA-N alpha-camphorene Chemical compound CC(C)=CCCC(=C)C1CCC(CCC=C(C)C)=CC1 GJYJYFHBOBUTBY-UHFFFAOYSA-N 0.000 claims description 2
- LMBWSYZSUOEYSN-UHFFFAOYSA-N diethyldithiocarbamic acid Chemical compound CCN(CC)C(S)=S LMBWSYZSUOEYSN-UHFFFAOYSA-N 0.000 claims description 2
- 229950004394 ditiocarb Drugs 0.000 claims description 2
- 239000001989 lithium alloy Substances 0.000 claims description 2
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims 1
- XTTGYFREQJCEML-UHFFFAOYSA-N tributyl phosphite Chemical compound CCCCOP(OCCCC)OCCCC XTTGYFREQJCEML-UHFFFAOYSA-N 0.000 claims 1
- BDZBKCUKTQZUTL-UHFFFAOYSA-N triethyl phosphite Chemical compound CCOP(OCC)OCC BDZBKCUKTQZUTL-UHFFFAOYSA-N 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims 1
- 230000006866 deterioration Effects 0.000 abstract description 3
- 239000000463 material Substances 0.000 abstract description 3
- 229910001220 stainless steel Inorganic materials 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 8
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 6
- 230000007797 corrosion Effects 0.000 description 5
- 238000005260 corrosion Methods 0.000 description 5
- 239000008151 electrolyte solution Substances 0.000 description 5
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 3
- 239000007774 positive electrode material Substances 0.000 description 3
- 101150058243 Lipf gene Proteins 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000007769 metal material Substances 0.000 description 2
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- 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 description 1
- 229910013553 LiNO Inorganic materials 0.000 description 1
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- USHGRFXQYJEHII-UHFFFAOYSA-M [O-]P(O)(O)=O.[Li+].F.F.F.F.F.F Chemical compound [O-]P(O)(O)=O.[Li+].F.F.F.F.F.F USHGRFXQYJEHII-UHFFFAOYSA-M 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Inorganic materials [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- RBTVSNLYYIMMKS-UHFFFAOYSA-N tert-butyl 3-aminoazetidine-1-carboxylate;hydrochloride Chemical compound Cl.CC(C)(C)OC(=O)N1CC(N)C1 RBTVSNLYYIMMKS-UHFFFAOYSA-N 0.000 description 1
- CFJRPNFOLVDFMJ-UHFFFAOYSA-N titanium disulfide Chemical compound S=[Ti]=S CFJRPNFOLVDFMJ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- Y02E60/12—
Landscapes
- Primary Cells (AREA)
Abstract
Description
【発明の詳細な説明】 （イ）産業上の利用分野 本発明は非水電解液電池に関するものである。[Detailed description of the invention] (b) Industrial application fields The present invention relates to a non-aqueous electrolyte battery.
（ロ）従来の技術
ノチウム、ナトリウムあるいはこれらの合金からなる負
極を用いた非水電解液電池は、高エネルギー密度で且つ
自己放電率が低いという利点を有しているが、−球状に
電導度の低い非水電解液を用いているため、高率放電特
性に劣るという問題を有している。(b) Conventional technology Nonaqueous electrolyte batteries using negative electrodes made of notium, sodium, or their alloys have the advantages of high energy density and low self-discharge rate, but - spherical conductivity Since it uses a non-aqueous electrolyte with a low electrolyte, it has a problem of poor high rate discharge characteristics.
そこで、電解液の溶質として電導度の高い六フッ化リン
酸リチウム（ＬｉＰＦｓ）を用いて、ノチウム電池の高
率放電特性を改良するようなものが捉案さｔしている。Therefore, proposals are being made to improve the high rate discharge characteristics of Notium batteries by using lithium hexafluorophosphate (LiPFs), which has high conductivity, as a solute in the electrolytic solution.
しかし、上記Ｌ ｉ Ｐ Ｆ ６を溶質として用いた場
合、電池を長期間保存した場合には正極端子構成部材、
例えば正極缶或いは正極、集電体等の金属材料が腐食し
て電解液中に溶解する。更に、この金属材料が負極表面
に再析出する結果、保イ／−後の高率放電特性が劣化す
るという不都合がある。However, when the above L i P F 6 is used as a solute, when the battery is stored for a long period of time, the positive electrode terminal component,
For example, metal materials such as the positive electrode can, the positive electrode, and the current collector corrode and dissolve in the electrolyte. Furthermore, as a result of redepositing of this metal material on the surface of the negative electrode, there is a disadvantage that the high rate discharge characteristics after retention/- are deteriorated.
ここで、溶質にＬｉＰＦ、を用いた場合の正極端子構成
部材の腐食という問題は、正極にフッ化炭素（（ＣＦ）
ｎ）、二硫化チタン（Ｔ ｉ Ｓ２）、酸化銅（Ｃｕ
Ｏ）などを用いた場合にはほとんど見られなかったが、
正極に電位の高いマンガン酸化物を用いた場合には顕著
に見られる。Here, the problem of corrosion of the positive electrode terminal components when LiPF is used as the solute is that fluorocarbon ((CF)
n), titanium disulfide (T i S2), copper oxide (Cu
Although it was hardly seen when using O) etc.
This is noticeable when a high-potential manganese oxide is used as the positive electrode.
（ハ）発明が解決しようとする課題
本発明はマンガン酸化物を正極活物質とし、六フッ化リ
ン酸リチウムを溶質に用いる非水電解液電池において、
正極端子構成部材の腐食を抑制してこの種電池の保存後
の高率放電特性を改善することにある。(c) Problems to be Solved by the Invention The present invention provides a non-aqueous electrolyte battery using manganese oxide as a positive electrode active material and lithium hexafluorophosphate as a solute.
The purpose of this invention is to suppress corrosion of positive electrode terminal components and improve the high rate discharge characteristics of this type of battery after storage.
（ニ）課題を解決するための手段
マンガン酸化物を正極活物質とし、六フン化すン酸リチ
ウムを溶質に用いる非水電解液電池において、正極端子
構成部材と電解液との反応を抑制する反応抑制剤を電解
液中に添加したことを特徴とする。(d) Means for solving the problem In a non-aqueous electrolyte battery that uses manganese oxide as the positive electrode active material and lithium hexafluoride phosphate as the solute, a reaction that suppresses the reaction between the positive electrode terminal component and the electrolyte. It is characterized by adding an inhibitor to the electrolyte.
（ホ）作 川
本発明によれば、溶質として六フッ化リン酸リチウムを
用いた電解液と正極端子構成部材との反応を抑制する反
応抑制剤が電解液中に添加されているため、Ｌ記反応に
起因する保存後の高率放電特性の劣化を抑制しうる。(E) According to the present invention, since a reaction inhibitor is added to the electrolytic solution to suppress the reaction between the electrolytic solution using lithium hexafluorophosphate as a solute and the positive electrode terminal component, Deterioration of high rate discharge characteristics after storage due to reaction can be suppressed.
（へ）実施例
実施例１
本発明の実施例１を第１図に示す扇子型非水電解液電池
に基づいて以下に説明する。(F) Examples Example 1 Example 1 of the present invention will be described below based on a fan-shaped non-aqueous electrolyte battery shown in FIG.
）チウム金属から戊る負極２は負極集電体７の内面に圧
着されており、この負極集電体７は断面略コ字状の′ｆ
ｉ、極缶５極内５面に固着さ１１でいる。) The negative electrode 2 made of lithium metal is crimped to the inner surface of a negative electrode current collector 7, and this negative electrode current collector 7 has a substantially U-shaped cross section.
i, It is fixed at 11 on the 5 surfaces of the 5 electrodes of the electrode case.
上記負極毎５の周端はポリプロピレン製の絶縁パ・Ｉキ
ング８の内部に固定されておｊ＋、絶縁バッキング８の
外周には上記負極冶５とは反対方向に断面略コ字状を戊
す正極缶４が固定されている。The peripheral end of each of the negative electrodes 5 is fixed inside an insulating backing 8 made of polypropylene, and the outer periphery of the insulating backing 8 has a substantially U-shaped cross section in the opposite direction to the negative electrode 5. A positive electrode can 4 is fixed.
この正極缶４はフェライト系ステンレス鋼（Ｓじ５４３
０）からなり、その内底面には同様に５ＵＳ４３０から
なる正極集電体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が固定されている。この正極１と前記
負極２との間には電解液が含浸されたセパレータ３が介
装されている。This positive electrode can 4 is made of ferritic stainless steel (Sji543
0), and a positive electrode current collector 6 similarly made of 5US430 is fixed to the inner bottom surface of the positive electrode current collector 6.
A positive electrode 1 is fixed to the inner surface of the electrode. A separator 3 impregnated with an electrolyte is interposed between the positive electrode 1 and the negative electrode 2.
ところで、前記正極１は３５０〜４３０℃の温度範囲で
熱処理した二酸化マンガンを活物質として用い、この二
酸化マンガンと導電剤としてのカーボン粉末と結着剤と
してのフッ素樹脂粉末とを８５：１０：５の重量比で混
合し、次にこの混介物を加圧成形した後、２５０〜３５
０℃で熱処理して（１Ｅ製したものである。一方、前記
負極２はリチウム圧延板を所定寸法に打抜くことにより
作製したものである。また電解液としてはＰＣ（プロピ
レンカーボネート）とＤＭＥ （１，２−ジメトキシエ
タン）とを１＝１の割合で混合した混合溶媒に六フッ化
リン酸リチウム（ＬｉＰＦ６）を１モル／′Ｉ！溶解さ
せ、更に反応抑制剤として硝酸ノチウム（ＬｉＮＯ＋）
をＩｇ／ｊ！溶解させたものを用いた。尚、電池径は２
０ＩＩＩｍ、電池厚は２゜５ ｍｍ、電池容量は１３０
ｍＡＨである。Incidentally, the positive electrode 1 uses manganese dioxide heat-treated in a temperature range of 350 to 430°C as an active material, and the manganese dioxide, carbon powder as a conductive agent, and fluororesin powder as a binder are mixed in a ratio of 85:10:5. After mixing at a weight ratio of 250 to 35
The negative electrode 2 was manufactured by heat-treating at 0° C. (1E). On the other hand, the negative electrode 2 was manufactured by punching a rolled lithium plate into a predetermined size. The electrolyte was made of PC (propylene carbonate) and DME ( Lithium hexafluorophosphate (LiPF6) was dissolved at 1 mol/'I! in a mixed solvent of 1,2-dimethoxyethane) mixed at a ratio of 1=1, and notium nitrate (LiNO+) was added as a reaction inhibitor.
Ig/j! The dissolved one was used. In addition, the battery diameter is 2
0IIIm, battery thickness is 2゜5 mm, battery capacity is 130
mAH.
このようにして作製した電池を以下（Ａ１）と称する。The battery thus produced is hereinafter referred to as (A1).
実施例２
電解液に添加する反応抑制剤として亜すン酸トｊエチル
を用い、これを１ ｇ／ｌ溶解させた他は上記実施例１
と同様にして電池を作製した。このようにして作製した
電池を以下（Ａ２）と称する。Example 2 The same as Example 1 above except that toj-ethylsulfite was used as a reaction inhibitor added to the electrolytic solution and dissolved at 1 g/l.
A battery was prepared in the same manner as above. The battery thus produced is hereinafter referred to as (A2).
比較例
電解液に反応抑制剤を添加しない他は、上記実施例と同
様にして比較電池（Ｂ）を作製した。Comparative Example A comparative battery (B) was produced in the same manner as in the above example except that no reaction inhibitor was added to the electrolytic solution.
第２図及び第３図は本発明電池（ＡＩ）（Ａ２）と比較
電池（Ｂ）の初期の高率放電特性及び保存後の高率放電
特性とを示す。尚、第２図は電池組立後直ちに温度２５
℃、負荷３００Ωで放電したときの高率放電特性であり
、第３図は電池組立後６０℃で３力月保存したのち、温
度２５℃、負荷３にΩで放電したときの高率放電特性で
ある。FIGS. 2 and 3 show the initial high rate discharge characteristics and the high rate discharge characteristics after storage of the battery of the present invention (AI) (A2) and the comparative battery (B). In addition, Fig. 2 shows the temperature of 25% immediately after battery assembly.
℃ and a load of 300Ω. Figure 3 shows the high rate discharge characteristics when the battery was assembled and stored at 60℃ for 3 months and then discharged at a temperature of 25℃ and a load of 3Ω. It is.
第２図及び第３図から明らかなように、本発明電池（Ａ
１）（ｌ〜２）と比較電池（Ｂ）とは初期の高率放電特
性では同等の値を示しているが、保存後の高率放電特性
では本発明電池（ＡＩ）（Ａ２）の方が比較電池（Ｂ）
より優れていることが認められる。As is clear from FIGS. 2 and 3, the battery of the present invention (A
1) (l~2) and comparative battery (B) show similar values in initial high rate discharge characteristics, but the present invention battery (AI) (A2) has higher high rate discharge characteristics after storage. is the comparison battery (B)
It is recognized that it is better.
次に、高温保存後の電池の内部インピーダンスをＩ Ｋ
Ｉ−Ｉ ｚの周波数で測定したのでその結果を下記第
１表に示す。Next, the internal impedance of the battery after high temperature storage is I K
Measurements were made at a frequency of I-Iz, and the results are shown in Table 1 below.
第１表
上記第１表より、比較電池（Ｂ）は保存後に内部インピ
ーダンスが著しく増大しているのに比べて、本発明電池
（ＡＩ）（Ａ２）は保存後でも内部インピーダンスは若
干増大するのみである。Table 1 From Table 1 above, the internal impedance of the comparison battery (B) increases significantly after storage, while the internal impedance of the invention battery (AI) (A2) increases only slightly even after storage. It is.
また、保（’ｉ？＆の電池を分解してみたところ、比較
電池（Ｂ）では負極リチウム表面が黒く変色していたの
に対し本発明電池（ＡＩ）（Ａ２＞ではそのような現象
は見られなかった。Furthermore, when I disassembled the battery of Ho('i?&), I found that in the comparison battery (B), the surface of the negative electrode lithium had turned black, but in the battery of the present invention (AI) (A2>, such a phenomenon did not occur). I couldn't see it.
更に、保存後の正極缶を金属顕微鏡で観察したところ、
比較電池（Ｂ）ではがなり孔食がみられるのに対して、
本発明電池（ＡＩ）（Ａ２）の正極缶は腐食されていな
いことが認められた。Furthermore, when we observed the cathode can after storage using a metallurgical microscope, we found that
In contrast to the comparative battery (B), which suffered from peeling and pitting corrosion,
It was observed that the positive electrode can of the battery (AI) (A2) of the present invention was not corroded.
これらの結果より、比較電池（Ｂ）では、保存中に正極
缶が腐食し溶出金属が負極表面に再析出し、この結果、
保存後の低温放電特性が低下したものと考えられる。一
方、本発明電池（Ａｌ）（Ａ２）のように電解液中に硝
酸リチウム或いは亜リン酸トノエチルを加えると、正極
缶の腐食が抑制され、この結果保存後の高率放電特性の
低下を防止できるものと考えられる。From these results, in comparative battery (B), the positive electrode can corroded during storage and the eluted metal redeposited on the negative electrode surface, resulting in
It is thought that this is because the low-temperature discharge characteristics deteriorated after storage. On the other hand, when lithium nitrate or tonoethyl phosphite is added to the electrolyte as in the present invention battery (Al) (A2), corrosion of the positive electrode can is suppressed, and as a result, deterioration of high rate discharge characteristics after storage is prevented. It is considered possible.
正極端子溝床材と電解液との反応阻止剤として加えるＬ
ｉＮＯ２の量と放電容量との関係を、電池組立直後及び
６０℃で３力月保存した後のそれぞれについて調べたの
で、その結果を第４図に示す。尚、実験条件は温度２５
℃、負荷３００Ωで行った。実線は初期特性、破線は保
存後の特性である。L added as a reaction inhibitor between the positive terminal groove floor material and the electrolyte
The relationship between the amount of iNO2 and the discharge capacity was investigated immediately after battery assembly and after storage at 60° C. for 3 months, and the results are shown in FIG. The experimental conditions were a temperature of 25
The test was carried out at a temperature of 300Ω and a load of 300Ω. The solid line is the initial characteristic, and the broken line is the characteristic after storage.
第４図よりＬ ＋ Ｎ Ｏ＋添加量が０．０１〜Ｉｇ／
ｅであれば、保存後であっても放電容量が１００ｍ Ａ
Ｈ以上であることが認められる。従って、ＬｉＮｏｒ
添加量は０．０１〜Ｉｇ／ｌであることが望ましい。０
．０１ ｇ／ｆｆｉ未満であれば添加効果が余り認めら
れず、一方、１０ｇ／Ｎを越えればＬ ｉ Ｎ Ｏ、と
負極のＬ ｉが反応し負極容量が低下するため好ましく
ない。From Figure 4, the amount of L + N O + added is 0.01 to Ig/
e, the discharge capacity is 100mA even after storage.
It is recognized that it is H or higher. Therefore, LiNor
The amount added is preferably 0.01 to Ig/l. 0
．． If it is less than 0.01 g/ffi, no significant addition effect will be observed, while if it exceeds 10 g/N, Li in the negative electrode will react with Li N O and the negative electrode capacity will decrease, which is not preferable.
尚、反応抑制剤としてはチン素含有化合物或いはリン含
有化合物が好適し、チッ素含有化合物としては実施例１
で示した硫酸リチウム以外にＮＮＮ’Ｎ’−テトラメチ
ルエチレンジアミン、１．２−ジフェニルエチレンジア
ミン、ジエチルジチオカルバミン酸ナトリウムが挙げら
れ、リン含有化合物としては実施例２で示した亜リン酸
トリエチル以外に１リン酸トリ−ｎ−ブチル、リン酸ト
リエチル、次亜リン酸アンモニウム、オルトリン酸尿素
が挙げられる。In addition, as a reaction inhibitor, a tin-containing compound or a phosphorus-containing compound is suitable, and as a nitrogen-containing compound, Example 1
In addition to lithium sulfate shown in Example 2, examples of phosphorus-containing compounds include NNN'N'-tetramethylethylenediamine, 1,2-diphenylethylenediamine, and sodium diethyldithiocarbamate. Examples include tri-n-butyl acid, triethyl phosphate, ammonium hypophosphite, and urea orthophosphate.
又、正極活物質としては二酸化マンガンに限定されずリ
チウム含有のマンガン酸化物も適用でき、負極について
もリチウムに限定されずリチウム合金も適用できる。In addition, the positive electrode active material is not limited to manganese dioxide, but lithium-containing manganese oxide can also be used, and the negative electrode is not limited to lithium, but a lithium alloy can also be used.
（ト）発明の効果
本発明によれば、電池の保存中に正極端子構成部材が腐
食するのを抑制することができるので、初期の高率放電
特性のみならず、保存後の高率放電特性も優れた非水電
解液電池を提供す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 According to the present invention, since it is possible to suppress corrosion of the positive electrode terminal constituent members during battery storage, it is possible to suppress not only the initial high rate discharge characteristics but also the high rate discharge characteristics after storage. It is also possible to provide an excellent non-aqueous electrolyte battery, and its industrial value is extremely large.
第１図は本発明の非水電解液電池の断面図、第２図は本
発明電池（ＡＩ）（Ａ２）と比較電池（Ｂ）の初期の高
率放電特性、第３図は本発明電池（Ａｔ）（Ａ２）と比
較電池（Ｂ）の保存後の高率放電特性を示す図である。
また、第４図は硝酸リチウムの添加量と放電容量の関係
を示す図である。
１・正極、２・負極、３・・・セパレータ、４・・・正
極缶、５・・負補正、６・・・正極集電体、７・・・正
極集電体、８・・・絶縁バッキング。Figure 1 is a cross-sectional view of the non-aqueous electrolyte battery of the present invention, Figure 2 is the initial high rate discharge characteristics of the battery of the present invention (AI) (A2) and the comparative battery (B), and Figure 3 is the battery of the present invention. (At) It is a figure showing the high rate discharge characteristic after storage of (A2) and comparative battery (B). Moreover, FIG. 4 is a diagram showing the relationship between the amount of lithium nitrate added and the discharge capacity. 1. Positive electrode, 2. Negative electrode, 3... Separator, 4... Positive electrode can, 5... Negative correction, 6... Positive electrode current collector, 7... Positive electrode current collector, 8... Insulation backing.
Claims (4)
或いはリチウム合金よりなる負極と、少くとも一つの溶
媒と少くとも一つの溶質とからなる非水電解液とを備え
るものであって、前記溶質として六フッ化リン酸リチウ
ムを用いると共に、正極端子構成部材と電解液との反応
を抑制する反応抑制剤を電解液中に添加したことを特徴
とする非水電解液電池。(1) A positive electrode comprising a manganese oxide as an active material, a negative electrode comprising lithium or a lithium alloy, and a non-aqueous electrolyte comprising at least one solvent and at least one solute, A nonaqueous electrolyte battery characterized in that lithium hexafluorophosphate is used as a solute, and a reaction inhibitor is added to the electrolyte to suppress a reaction between a positive electrode terminal component and the electrolyte.
（１）記載の非水電解液電池。(2) The non-aqueous electrolyte battery according to claim 1, wherein the reaction inhibitor is a nitrogen-containing compound.
Ｎ’−テトラメチルエチレンジアミン、１，２ジフェニ
ルエチレンジアミン、ジエチルジチオカルバミン酸ナト
リウムの群から選ばれたものである請求項（２）記載の
非水電解液電池。(3) The nitrogen-containing compound is lithium nitrate, NNN'
The nonaqueous electrolyte battery according to claim 2, wherein the nonaqueous electrolyte battery is selected from the group of N'-tetramethylethylenediamine, 1,2 diphenylethylenediamine, and sodium diethyldithiocarbamate.
１）記載の非水電解液電池。 ５ 前記リン含有化合物は亜リン酸トリエチル、亜リン
酸トリ−ｎ−ブチル、リン酸トリエチル、次亜リン酸ア
ンモニウム、オルトリン酸尿素の群から選ばれたもので
ある請求項（４）記載の非水電解液電池。(4) Claim (
1) The non-aqueous electrolyte battery described above. 5. The non-phosphorus compound according to claim 4, wherein the phosphorus-containing compound is selected from the group of triethyl phosphite, tri-n-butyl phosphite, triethyl phosphate, ammonium hypophosphite, and urea orthophosphate. Water electrolyte battery.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1179403A JP2771612B2 (en) | 1989-07-11 | 1989-07-11 | Non-aqueous electrolyte battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1179403A JP2771612B2 (en) | 1989-07-11 | 1989-07-11 | Non-aqueous electrolyte battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0343960A true JPH0343960A (en) | 1991-02-25 |
| JP2771612B2 JP2771612B2 (en) | 1998-07-02 |
Family
ID=16065259
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1179403A Expired - Fee Related JP2771612B2 (en) | 1989-07-11 | 1989-07-11 | Non-aqueous electrolyte battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2771612B2 (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0662729A1 (en) * | 1993-12-20 | 1995-07-12 | Wilson Greatbatch Ltd. | Nonaqueous electrolyte for improved performance and stability |
| JP2002260735A (en) * | 2000-12-25 | 2002-09-13 | Mitsubishi Chemicals Corp | Non-aqueous electrolyte secondary battery |
| WO2003046653A1 (en) * | 2001-11-29 | 2003-06-05 | Nippon Oil Corporation | Electrolyte and electrochromic device |
| US8435674B2 (en) | 2009-12-22 | 2013-05-07 | Samsung Sdi Co., Ltd. | Lithium battery |
| JP2014011105A (en) * | 2012-07-02 | 2014-01-20 | Toyota Central R&D Labs Inc | Usage of nonaqueous electrolyte battery, and nonaqueous electrolyte battery |
| WO2014188503A1 (en) * | 2013-05-21 | 2014-11-27 | 株式会社日立製作所 | Electricity storage device and method for manufacturing same |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63198260A (en) * | 1987-02-12 | 1988-08-16 | Sanyo Electric Co Ltd | non-aqueous electrolyte battery |
-
1989
- 1989-07-11 JP JP1179403A patent/JP2771612B2/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63198260A (en) * | 1987-02-12 | 1988-08-16 | Sanyo Electric Co Ltd | non-aqueous electrolyte battery |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0662729A1 (en) * | 1993-12-20 | 1995-07-12 | Wilson Greatbatch Ltd. | Nonaqueous electrolyte for improved performance and stability |
| JP2002260735A (en) * | 2000-12-25 | 2002-09-13 | Mitsubishi Chemicals Corp | Non-aqueous electrolyte secondary battery |
| WO2003046653A1 (en) * | 2001-11-29 | 2003-06-05 | Nippon Oil Corporation | Electrolyte and electrochromic device |
| US8435674B2 (en) | 2009-12-22 | 2013-05-07 | Samsung Sdi Co., Ltd. | Lithium battery |
| JP2014011105A (en) * | 2012-07-02 | 2014-01-20 | Toyota Central R&D Labs Inc | Usage of nonaqueous electrolyte battery, and nonaqueous electrolyte battery |
| WO2014188503A1 (en) * | 2013-05-21 | 2014-11-27 | 株式会社日立製作所 | Electricity storage device and method for manufacturing same |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2771612B2 (en) | 1998-07-02 |
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