JPH04129177A - Organic electrolyte cell - Google Patents
Organic electrolyte cellInfo
- Publication number
- JPH04129177A JPH04129177A JP2251379A JP25137990A JPH04129177A JP H04129177 A JPH04129177 A JP H04129177A JP 2251379 A JP2251379 A JP 2251379A JP 25137990 A JP25137990 A JP 25137990A JP H04129177 A JPH04129177 A JP H04129177A
- Authority
- JP
- Japan
- Prior art keywords
- powder
- lithium
- electrode
- cell
- negative electrode
- 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
- 239000005486 organic electrolyte Substances 0.000 title claims abstract description 13
- 239000000843 powder Substances 0.000 claims abstract description 31
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 16
- 229910052751 metal Inorganic materials 0.000 claims abstract description 16
- 239000002184 metal Substances 0.000 claims abstract description 16
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 11
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910001220 stainless steel Inorganic materials 0.000 claims abstract description 8
- 229910052802 copper Inorganic materials 0.000 claims abstract description 6
- 239000010949 copper Substances 0.000 claims abstract description 6
- 229910052742 iron Inorganic materials 0.000 claims abstract description 6
- 239000010935 stainless steel Substances 0.000 claims abstract description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000000203 mixture Substances 0.000 claims abstract description 5
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 5
- 239000010936 titanium Substances 0.000 claims abstract description 5
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 5
- 239000000835 fiber Substances 0.000 claims abstract description 4
- 150000002739 metals Chemical class 0.000 claims description 4
- 229910000733 Li alloy Inorganic materials 0.000 claims description 3
- 239000001989 lithium alloy Substances 0.000 claims description 3
- 239000003792 electrolyte Substances 0.000 abstract description 4
- 239000000654 additive Substances 0.000 abstract description 2
- 230000000996 additive effect Effects 0.000 abstract description 2
- 238000009792 diffusion process Methods 0.000 abstract description 2
- 239000002245 particle Substances 0.000 description 4
- -1 polytetrafluoroethylene Polymers 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- 229910000838 Al alloy Inorganic materials 0.000 description 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 238000009830 intercalation Methods 0.000 description 2
- 239000004745 nonwoven fabric Substances 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000004080 punching Methods 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- 229910018187 Li CoO2 Inorganic materials 0.000 description 1
- 229910000978 Pb alloy Inorganic materials 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- JFBZPFYRPYOZCQ-UHFFFAOYSA-N [Li].[Al] Chemical compound [Li].[Al] JFBZPFYRPYOZCQ-UHFFFAOYSA-N 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 238000000889 atomisation Methods 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- JWZCKIBZGMIRSW-UHFFFAOYSA-N lead lithium Chemical compound [Li].[Pb] JWZCKIBZGMIRSW-UHFFFAOYSA-N 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
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000012982 microporous membrane Substances 0.000 description 1
- 239000011812 mixed powder Substances 0.000 description 1
- 229920000573 polyethylene Polymers 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 本発明は、有機電解質電池に間する。[Detailed description of the invention] Industrial applications The present invention relates to organic electrolyte batteries.
従来の技術およびその課題
有機電解質電池は、金属リチウムまたはリチウムアルミ
ニウム合金もしくはリチウム鉛合金などの箔または板か
らなる負極を用いたものが多い。BACKGROUND ART Many organic electrolyte batteries use a negative electrode made of a foil or plate of metal lithium, lithium aluminum alloy, lithium lead alloy, or the like.
これに対して、アルミニウム、ビスマス、シリコン、ボ
ロンおよび鉛などのリチウムの吸蔵放出が可能な金属の
粉末またはこれらのリチウム合金の粉末を負極に用いた
ものもある。粉末負極板を用いた場合には、負極の作用
面積が増大するので電池性能の向上が期待できる。On the other hand, there are also negative electrodes using powders of metals capable of intercalating and extracting lithium, such as aluminum, bismuth, silicon, boron, and lead, or powders of lithium alloys of these metals. When a powder negative electrode plate is used, an improvement in battery performance can be expected because the active area of the negative electrode increases.
しかし、発明者は、粉末負極板を用いた有機電解質電池
について詳しく検討した結果、この電池が充電電気量に
比して放電電気量が少ないという問題点があることを見
いだした。However, as a result of detailed study of organic electrolyte batteries using powder negative electrode plates, the inventors found that this battery has a problem in that the amount of electricity discharged is smaller than the amount of electricity charged.
課題を解決するための手段
本発明は、リチウムの吸蔵放出が可能な金属を主体とす
る金属粉末またはそのリチウム合金粉末と、ニッケル、
チタン、ステンレス、銅、鉄などのリチウムを吸蔵しな
い金属の粉末または繊維との混合物を用いた負極板を備
えたことを特徴とする有機電解質電池を用いて前記課題
を解決するものである。Means for Solving the Problems The present invention provides a metal powder mainly consisting of a metal capable of intercalating and deintercalating lithium or a lithium alloy powder thereof, nickel,
The above problem is solved using an organic electrolyte battery characterized by having a negative electrode plate made of a mixture with powder or fiber of a metal that does not occlude lithium, such as titanium, stainless steel, copper, or iron.
作用
発明者は、粉末負極板の放電利用率が低い原因について
検討した結果つぎの現象を見いだした。The inventor investigated the cause of the low discharge utilization rate of the powder negative electrode plate and discovered the following phenomenon.
すなわち、粉末負極板は、充電によってリチウムを吸蔵
すると粉末粒子が著しく体積膨張して電極の孔をつぶす
結果、電極内部への電解液の拡散か困難になる。その後
、放電しても一旦膨張した粉末粒子の体積はほとんど収
縮しないので電解）夜の拡散は阻害されたままとなり電
極内部に吸蔵されたリチウムは放電が困難となる。この
ことが放電利用率か低い最大の原因と考えられる。した
かつて、粉末電極の放電利用率を向上させるには、電極
の多孔度を維持することが重要である。That is, when a powder negative electrode plate occludes lithium during charging, the powder particles significantly expand in volume and close the pores of the electrode, making it difficult for the electrolyte to diffuse into the electrode. After that, even if the powder particles are discharged, the volume of the once expanded powder particles will hardly shrink, so diffusion during the electrolysis period will remain inhibited, making it difficult to discharge the lithium occluded inside the electrode. This is considered to be the main reason for the low discharge utilization rate. Previously, in order to improve the discharge utilization rate of powder electrodes, it is important to maintain the porosity of the electrodes.
そこで、発明者は、粉末電極の多孔度を維持するために
リチウムを吸蔵しないニッケル、チタン。Therefore, the inventor developed nickel and titanium that do not absorb lithium in order to maintain the porosity of the powder electrode.
ステンレス、銅、鉄などの金属粉末を電極に添加した。Metal powders such as stainless steel, copper, and iron were added to the electrodes.
その結果、後の実施例に示すように電池の放電容量を著
しく向上させることができた。As a result, the discharge capacity of the battery could be significantly improved as shown in the examples below.
なお、電極の電子伝導性を損なわないためには金属粉末
なと電子伝導性に優れた添加物を用いた方がよい。In addition, in order not to impair the electronic conductivity of the electrode, it is better to use an additive with excellent electronic conductivity such as metal powder.
実施例 以下、本発明を好適な実施例を用いて説明する。Example The present invention will be explained below using preferred embodiments.
実施例では、アルミニウム合金についてだけ述へている
が、アルミニウムに代えてボロン、シリコンおよび鉛な
とのリチウムを吸蔵てきるその他の金属を用いてもよい
。In the embodiment, only an aluminum alloy is described, but other metals capable of occluding lithium such as boron, silicon, and lead may be used instead of aluminum.
第１図のようなホタン型有機電解液電池を下記の要領で
試作した。７０ｗｔ、ＸのＬ ｉ ＣｏＯ２，２０ｗｔ
％：のアセチレンブラックおよび１０ Ｎｄｔχのポリ
テトラフルオロエチレン（ＰＴＦＥ）を混合して正極合
剤とした。そして、この正極合剤を０．５０．ｇ採集し
て、３２５ｍｅｓｌ＋のステンレス製金網に包み込んで
、径か１２ｍｍで厚さが２．１丁の正極板ベレッ）（１
）を試作した。この正極板ベレットの放電容量は、０．
５モルのリチウムが吸蔵放出されるとした場合に約５０
ｍＡｈである。A hothane-type organic electrolyte battery as shown in FIG. 1 was prototyped in the following manner. 70wt, X Li CoO2, 20wt
%: of acetylene black and 10 Ndtχ of polytetrafluoroethylene (PTFE) were mixed to prepare a positive electrode mixture. Then, this positive electrode mixture was added to 0.50. g collected, wrapped it in a 325 mesl+ stainless steel wire mesh, and placed it in a positive electrode plate with a diameter of 12 mm and a thickness of 2.1 mm) (1
) was prototyped. The discharge capacity of this positive plate pellet is 0.
If 5 moles of lithium are intercalated and desorbed, approximately 50
It is mAh.
ＡＩ（９４ｖｔ％）−Ｂｉ（５ｗｔ％）−Ｍｎ（１ｗｔ
＊）合金をカスアトマイズ法によって平均粒径が８ミク
ロンの粉末に加工した。そして、このアルミニウム合金
粉末とＩＮｃＯ社製のＴＹＰＥ２５５ニッケル粉末とを
重量比２：１て混合し、０．２８３採集して３２５ｍｅ
ｓｈのステンレス金網に包み込んで径が１０闘で厚さか
１．９闘の負極板ペレット（２）を試作した。AI (94vt%) - Bi (5wt%) - Mn (1wt
*) The alloy was processed into powder with an average particle size of 8 microns by the cast atomization method. Then, this aluminum alloy powder and TYPE 255 nickel powder made by INcO were mixed at a weight ratio of 2:1, and 0.283 was collected and 325 me
A negative electrode plate pellet (2) with a diameter of 10 mm and a thickness of 1.9 mm was produced by wrapping it in a stainless steel wire mesh.
葉脈状の無孔部と、孔が３次元的に配列した有孔部とを
有する平均厚さが２３ミクロンのポリエチレン製微孔膜
を直径１４ｍｍに打ち抜いて微孔性セパレーター（３）
を試作した。また、ポリプロピレンの不織布を１２ｍｍ
に打ち抜いて平均厚さか０．２ｍｍの不織布セパレータ
ー（４）を試作した。これらに１．０Ｍ過塩素酸リすウ
ム／エチレンカーボネート＋アセトニトリル電解液を真
空含浸したのち、耐蝕性ステンレス鋼板製の正極缶（５
）、負極缶（６）、およびポリプロピレン製の絶縁力ス
ケット（７）からなる電池ケースに収納して径が１５．
４闘で厚さが ４．８ｍｍの本発明のボタン型有機電解
質電池（Ａ）を試作した。A microporous separator (3) made by punching a polyethylene microporous membrane with an average thickness of 23 microns into a diameter of 14 mm, which has a leaf-like non-porous part and a perforated part with three-dimensionally arranged pores.
We made a prototype. In addition, 12mm polypropylene nonwoven fabric
A non-woven fabric separator (4) having an average thickness of 0.2 mm was produced by punching out a sample. After vacuum impregnating these with 1.0M lithium perchlorate/ethylene carbonate + acetonitrile electrolyte, a positive electrode can made of corrosion-resistant stainless steel plate (5
), a negative electrode can (6), and a polypropylene insulation socket (7).
A button-type organic electrolyte battery (A) of the present invention having a thickness of 4.8 mm was manufactured using four tests.
また、前記Ｎ１粉末の代わりにＦｅ、 ＣｕおよびＴ１
の混合粉末を用いた以外は、前記（Ａ）電池と同様の構
成を有する本発明の有機電解質電池（Ｂ）を試作した。Also, instead of the N1 powder, Fe, Cu and T1
An organic electrolyte battery (B) of the present invention having the same configuration as the battery (A) above except that the mixed powder was used was fabricated.
また、前記Ｎ１粉末の代わりにＳＵＳ繊維（φ０．０５
ｍｍ、長さ０．３ｍｍ）を用いた以外は、前記（Ａ）電
池と同様の構成を有する本発明の有機電解質電池（Ｃ）
を試作した。Also, instead of the N1 powder, SUS fiber (φ0.05
An organic electrolyte battery (C) of the present invention having the same configuration as the battery (A) above, except that a battery (mm, length 0.3 mm) was used.
We made a prototype.
つぎに、ＡＩ（９４ｗｔ％）−Ｂｉ（５ｗｔ＄）−Ｍｎ
（１ｗｔ＄）合金粉末のみによって負極が構成されてい
る以外は、前記（Ａ）電池と同様の構成を有する比較の
ための有機電解質電池（Ｄ）を試作した。Next, AI (94wt%)-Bi (5wt$)-Mn
(1wt$) An organic electrolyte battery (D) for comparison having the same configuration as the battery (A) except that the negative electrode was composed of only the alloy powder was fabricated.
これらの電池を２ｍＡで端子電圧が４．ＯＶに至るまで
充電したのち２．５〜ｌまで放電した。このときの放電
容量を表１に示す。These batteries are connected at 2mA and the terminal voltage is 4. After charging to OV, the battery was discharged to 2.5 to 1 liters. Table 1 shows the discharge capacity at this time.
表１ 電池 放電容量（ｍＡｈ） （Ａ） （Ｂ） （Ｃ） （Ｄ） 表から明らかなように本発明の電池（Ａ）。Table 1 battery Discharge capacity (mAh) (A) (B) (C) (D) As is clear from the table, the battery (A) of the present invention.
（Ｂ）、（Ｃ）は、比較のための電池（Ｄ）よりも放電
容量が多い。これは、負極の放電利用率が高いことに起
因している。(B) and (C) have a higher discharge capacity than the comparative battery (D). This is due to the high discharge utilization rate of the negative electrode.
また、電池（Ａ）と（Ｄ）とを前記の充放電条件でサイ
クル寿命試験にかけた。その結果を第２図に示す。本発
明の電池（Ａ）か比較的良好な容量保持性能を示すのに
対して電池（Ｄ）は、急激に容量が低下している。これ
は、電池（Ｄ）は負極の放電利用率が低いために活物質
の一部が集中的に使われ、そのために急激に負極の劣化
が進むことに起因している。In addition, batteries (A) and (D) were subjected to a cycle life test under the above charging and discharging conditions. The results are shown in FIG. While the battery (A) of the present invention exhibits relatively good capacity retention performance, the battery (D) exhibits a rapid decrease in capacity. This is because in battery (D), a part of the active material is used intensively due to the low discharge utilization rate of the negative electrode, which causes rapid deterioration of the negative electrode.
発明の効果
本発明の電池は、従来の電池に比較して放電容量が大き
く、サイクル寿命も長い。Effects of the Invention The battery of the present invention has a larger discharge capacity and a longer cycle life than conventional batteries.
第１図は、本発明の有機電解質電池の一例であるボタン
電池の内部構造を示した図。第２図は、本発明の電池（
Ａ）と従来の電池（Ｄ）とのサイクル寿命性能の比較を
示した図。FIG. 1 is a diagram showing the internal structure of a button battery, which is an example of the organic electrolyte battery of the present invention. FIG. 2 shows the battery of the present invention (
A diagram showing a comparison of cycle life performance between A) and a conventional battery (D).
Claims (1)
末またはそのリチウム合金粉末と、ニッケル、チタン、
ステンレス、銅、鉄などのリチウムを吸蔵しない金属の
粉末または繊維との混合物を用いた負極板を備えたこと
を特徴とする有機電解質電池。Metal powder mainly composed of metals that can absorb and release lithium, or lithium alloy powder, and nickel, titanium,
An organic electrolyte battery characterized by having a negative electrode plate made of a mixture with powder or fiber of a metal that does not absorb lithium, such as stainless steel, copper, or iron.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2251379A JPH04129177A (en) | 1990-09-19 | 1990-09-19 | Organic electrolyte cell |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2251379A JPH04129177A (en) | 1990-09-19 | 1990-09-19 | Organic electrolyte cell |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH04129177A true JPH04129177A (en) | 1992-04-30 |
Family
ID=17221961
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2251379A Pending JPH04129177A (en) | 1990-09-19 | 1990-09-19 | Organic electrolyte cell |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH04129177A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009514181A (en) * | 2005-10-31 | 2009-04-02 | ティ／ジェイ テクノロジーズ インコーポレイテッド | High capacity electrodes and methods for their manufacture and use |
-
1990
- 1990-09-19 JP JP2251379A patent/JPH04129177A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009514181A (en) * | 2005-10-31 | 2009-04-02 | ティ／ジェイ テクノロジーズ インコーポレイテッド | High capacity electrodes and methods for their manufacture and use |
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