JPH03280363A - Lithium battery - Google Patents
Lithium batteryInfo
- Publication number
- JPH03280363A JPH03280363A JP2118127A JP11812790A JPH03280363A JP H03280363 A JPH03280363 A JP H03280363A JP 2118127 A JP2118127 A JP 2118127A JP 11812790 A JP11812790 A JP 11812790A JP H03280363 A JPH03280363 A JP H03280363A
- Authority
- JP
- Japan
- Prior art keywords
- electrode
- lithium
- battery
- aluminum
- boron
- 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
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 40
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 20
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 11
- 239000000956 alloy Substances 0.000 claims abstract description 11
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052796 boron Inorganic materials 0.000 claims abstract description 9
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 8
- 239000010703 silicon Substances 0.000 claims abstract description 8
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 7
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims abstract description 7
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 5
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 7
- 229910052748 manganese Inorganic materials 0.000 claims description 7
- 239000011572 manganese Substances 0.000 claims description 7
- 229910052732 germanium Inorganic materials 0.000 claims description 5
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims description 5
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 4
- 229910052733 gallium Inorganic materials 0.000 claims description 4
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 9
- 238000007600 charging Methods 0.000 abstract description 5
- 229910001148 Al-Li alloy Inorganic materials 0.000 abstract description 2
- 238000007599 discharging Methods 0.000 abstract description 2
- 238000010298 pulverizing process Methods 0.000 abstract description 2
- 125000004122 cyclic group Chemical group 0.000 abstract 1
- 239000005486 organic electrolyte Substances 0.000 description 14
- 239000000843 powder Substances 0.000 description 13
- 230000000694 effects Effects 0.000 description 12
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 8
- 229910000838 Al alloy Inorganic materials 0.000 description 7
- 239000003792 electrolyte Substances 0.000 description 7
- 239000002994 raw material Substances 0.000 description 6
- 238000007792 addition Methods 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 4
- 238000003780 insertion Methods 0.000 description 4
- 230000037431 insertion Effects 0.000 description 4
- JFBZPFYRPYOZCQ-UHFFFAOYSA-N [Li].[Al] Chemical compound [Li].[Al] JFBZPFYRPYOZCQ-UHFFFAOYSA-N 0.000 description 3
- CKFRRHLHAJZIIN-UHFFFAOYSA-N cobalt lithium Chemical compound [Li].[Co] CKFRRHLHAJZIIN-UHFFFAOYSA-N 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- -1 polypropylene Polymers 0.000 description 3
- 229910000676 Si alloy Inorganic materials 0.000 description 2
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 229910000765 intermetallic Inorganic materials 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910000521 B alloy Inorganic materials 0.000 description 1
- 229910001152 Bi alloy Inorganic materials 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910000807 Ga alloy Inorganic materials 0.000 description 1
- 229910000927 Ge alloy Inorganic materials 0.000 description 1
- 229910032387 LiCoO2 Inorganic materials 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- KLARSDUHONHPRF-UHFFFAOYSA-N [Li].[Mn] Chemical compound [Li].[Mn] KLARSDUHONHPRF-UHFFFAOYSA-N 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- RNQKDQAVIXDKAG-UHFFFAOYSA-N aluminum gallium Chemical compound [Al].[Ga] RNQKDQAVIXDKAG-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000009689 gas atomisation Methods 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 230000004807 localization Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000012982 microporous membrane Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 238000003860 storage Methods 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
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/46—Alloys based on magnesium or aluminium
-
- 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)
- 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】 産業上の利用分野 本発明は、リチウム電池に関するものである。[Detailed description of the invention] Industrial applications The present invention relates to lithium batteries.
従来の技術
リチウム電池は、通常負極板に金属リチウム電極を用い
ている。金属リチウムは、きわめて卑な電位を有するの
で電解液や電解質を容易に還元分解する。リチウム−次
電池では、リチウム極の表面に安定な不動態皮膜を形成
して電解液の分解反応が停止するが、二次電池では、充
放電にともない不動態皮膜が生成分解を繰り返すので電
解ｔαの分解が常におこる。このような電解液の分解反
応がリチウム二次電池のサイクル寿命性能を低下させる
重大な原因になっている。Prior art lithium batteries typically use a metallic lithium electrode for the negative plate. Metallic lithium has an extremely base potential and therefore easily reductively decomposes electrolytes and electrolytes. In rechargeable lithium batteries, a stable passive film is formed on the surface of the lithium electrode to stop the decomposition reaction of the electrolyte, but in secondary batteries, the passive film repeatedly forms and decomposes as it charges and discharges, so the electrolytic tα decomposition always occurs. Such a decomposition reaction of the electrolyte is a major cause of deterioration of the cycle life performance of a lithium secondary battery.
現在のところ金属リチウムに対して完全に安定な電解液
または電解質は見いだされていない。このためリチウム
電池の負極板に金属リチウムの代わりにリチウムインサ
ージョン電極を用いることが検討されている。リチウム
インサージョン電極は、通常金属リチウムよりも責な電
位を有するので、電池の電圧が低下してエネルギー密度
も低下する。しかし、前記の電解液の分解が抑制される
ので、−次電池では高温下での貯蔵性能など電池特性が
安定し、また二次電池では開発にともなう技術的課題が
少なくなる。At present, no electrolyte or electrolyte has been found that is completely stable for metallic lithium. For this reason, consideration is being given to using a lithium insertion electrode instead of metallic lithium for the negative electrode plate of a lithium battery. Lithium insertion electrodes typically have a higher potential than metallic lithium, which lowers the voltage of the battery and lowers its energy density. However, since the decomposition of the electrolytic solution is suppressed, battery characteristics such as storage performance at high temperatures are stabilized in secondary batteries, and technical problems associated with development of secondary batteries are reduced.
アルミニウムは、リチウムイオンの優れた導伝体として
よく知られている。このためアルミニウムをリチウムイ
ンサージョン電極として負極板に用いたリチウム電池が
すでに多く検討されている。Aluminum is well known as an excellent conductor of lithium ions. For this reason, many lithium batteries using aluminum as a lithium insertion electrode for the negative electrode plate have already been studied.
しかし、アルミニウム電極は、リチウムの吸蔵放出を繰
り返すと電極が微粉化して崩壊する。このため電池容量
が低下したり、ショートが起きたりする問題があった。However, when aluminum electrodes repeatedly absorb and release lithium, they become pulverized and disintegrate. This has led to problems such as a decrease in battery capacity and short circuits.
これは、リチウムイオンのインサージョンにともないア
ルミニウムの金属結晶の格子定数が著しく増大すること
に起因している。This is due to the fact that the lattice constant of the aluminum metal crystal increases significantly with the insertion of lithium ions.
このようなアルミニウム電極の崩壊を抑制するために、
従来は、アルミニウムにマンガンを添加する方法が用い
られてきた。In order to suppress the collapse of such aluminum electrodes,
Conventionally, a method of adding manganese to aluminum has been used.
しかし、発明者は、マンガン添加の効果について詳しく
検討した結果、０．１ｍＡ／ｃｍ２以下の低電流密度の
充放電サイクル試験では、負極板の崩壊を抑制する優れ
た効果があるが、電流密度が増大するとその効果が著し
く低下することを見いだした。However, as a result of detailed study on the effect of manganese addition, the inventor found that in a charge/discharge cycle test at a low current density of 0.1 mA/cm2 or less, it has an excellent effect of suppressing the collapse of the negative electrode plate, but when the current density It was found that the effect decreases significantly as the amount increases.
そして、このような高電流密度での電極崩壊がアルミニ
ウム電極の表面近傍におけるリチウム濃度の増大に起因
することを見いだした。They also found that electrode collapse at such high current densities is due to an increase in lithium concentration near the surface of the aluminum electrode.
発明が解決しようとする課題
上記のように従来のアルミニウム電極は、充放電サイク
ルの進行にともなって、特にｌ ｍＡ／ ｃｍ２以上の
大電流密度の場合に負極板が崩壊するという課題があっ
た。Problems to be Solved by the Invention As mentioned above, the conventional aluminum electrode has a problem in that the negative electrode plate collapses as the charge/discharge cycle progresses, especially at a large current density of 1 mA/cm2 or more.
課題を解決すための手段
本発明は、アルミニウムにリチウム、ボロン、シリコン
、ビスマス、ガリウムもしくはゲルマニウムを単独でま
たは複合して添加した合金を用いた負極板を備えたこと
を特徴とするリチウム電池を用いて前記課題を解決する
ものである。また、前記合金にマンガンを添加した合金
を用いた負極板を備えたことを特徴とするリチウム電池
を用いて前記課題の解決をさらに容易にするものである
。Means for Solving the Problems The present invention provides a lithium battery characterized by having a negative electrode plate using an alloy in which lithium, boron, silicon, bismuth, gallium, or germanium is added alone or in combination to aluminum. The above-mentioned problem is solved by using the following method. Further, the above-mentioned problem can be more easily solved by using a lithium battery characterized by having a negative electrode plate using an alloy in which manganese is added to the above-mentioned alloy.
作用
アルミニウム電極は、リチウムイオンを吸蔵する場合、
吸蔵の初回に著しく格子定数が増加する。When the working aluminum electrode occludes lithium ions,
The lattice constant increases significantly during the first occlusion.
したがって、リチウムをアルミニウムにあらかじめ少量
添加して結晶格子を膨張させておくと、アルミニウム電
極の電池内での急激な格子膨張を抑ルノすることができ
る。この結果、電極の崩壊が抑制される。Therefore, if a small amount of lithium is added to aluminum in advance to expand the crystal lattice, rapid lattice expansion of the aluminum electrode within the battery can be suppressed. As a result, collapse of the electrode is suppressed.
ボロンは金属間化合物に靭性な付与する作用がある。し
たがって、ボロンの添加によってアルミニウムーリチウ
ム金属間化合物の微粉化を抑制することができる。Boron has the effect of imparting toughness to intermetallic compounds. Therefore, the addition of boron can suppress the pulverization of the aluminum-lithium intermetallic compound.
シリコンおよびビスマスは、リチウムイオンの拡散速度
を向上させる作用がある。したがって、これらの添加に
よってアルミニウム電極に吸蔵されたリチウムが電極表
面に局在することを抑制することができる。すなオつち
、リチウムの局在に起因する電極の崩壊を抑制すること
ができる。Silicon and bismuth have the effect of improving the diffusion rate of lithium ions. Therefore, these additions can prevent lithium occluded in the aluminum electrode from localizing on the electrode surface. In other words, collapse of the electrode due to localization of lithium can be suppressed.
ゲルマニウムおよびガリウムの作用は、充分明確でない
が、これらの添加によってアルミニウム表面の不動態皮
膜が不安定化して充放電の過電圧が低下することにより
電流密度が均一になって電極寿命が長期化するものと考
えられる。The effects of germanium and gallium are not fully clear, but their addition destabilizes the passive film on the aluminum surface, lowering the charging/discharging overvoltage, making the current density uniform, and extending the electrode life. it is conceivable that.
マンガンは、従来からよく知られているようにアルミニ
ウムの強度を向上させる作用がある。したがって、アル
ミニウムにリチウム、ボロン、シリコン、ビスマス、ゲ
ルマニウム、およびガリウムと共にマンガンを添加する
とアルミニウム電極の崩壊を抑制し、電極寿命を長期化
することができる。As is well known, manganese has the effect of improving the strength of aluminum. Therefore, adding manganese to aluminum together with lithium, boron, silicon, bismuth, germanium, and gallium can suppress the collapse of the aluminum electrode and extend the life of the electrode.
実施例 以下では、本発明をり１通な実施例を用いて説明する。Example In the following, the present invention will be explained using a single embodiment.
［実施例の１１
平均粒径８０ミクロンのα−リチウム・アルミニウム合
金（リチウム濃度が２ｗｔ％のもの）粉末を０．３５ｇ
採集して３２５メツシユのステンレス金網に包み込んで
、加圧成形し、径が１０ｍｍで、厚さが２．５ｍｍのポ
ケット式リチウム・アルミニウム粉末負極板（ａ）を試
作した。[Example 11 0.35 g of α-lithium aluminum alloy (with a lithium concentration of 2 wt%) powder with an average particle size of 80 microns
The samples were collected, wrapped in a 325-mesh stainless wire mesh, and pressure-molded to fabricate a pocket-type lithium-aluminum powder negative electrode plate (a) with a diameter of 10 mm and a thickness of 2.5 mm.
リチウム・コバルト複合酸化物（ＬｉＣｏ０２）に導電
材として電気化学工業製の易分散性アセチレンブラック
Ｈ５−１００を５ｗｔ％加え、さらに結着材としてＰＴ
ＦＥ粉末を２ ｗ ｔ％添加混合した後、３２５メツシ
ユのステンレス金網に０．８ｇ包み込んで加圧成形して
、径が１２ｍｍで厚さが２゜４ｍｍのポケット式リチウ
ム・コバルト複合酸化物正極板（１））を試作した。こ
の正極板の理論容量は、リチウム・コバルト複合酸化物
１モル当り０．５モルのリチウムイオンを吸蔵放出する
ものと考えると１０４ｍＡｈである。5 wt% of easily dispersible acetylene black H5-100 manufactured by Denki Kagaku Kogyo was added as a conductive material to lithium-cobalt composite oxide (LiCo02), and PT was added as a binder.
After adding and mixing 2 wt% of FE powder, 0.8 g of it was wrapped in a 325 mesh stainless wire mesh and pressure molded to form a pocket type lithium-cobalt composite oxide positive electrode plate with a diameter of 12 mm and a thickness of 2°4 mm. (1)) was prototyped. The theoretical capacity of this positive electrode plate is 104 mAh, assuming that 0.5 mole of lithium ions are intercalated and released per mole of lithium-cobalt composite oxide.
これらの極板を用いて第一図のボタン型有機電解ｔα電
池を試作した。この電池は、セパレーターとして、径が
１３ｍｍで厚さが０．２ｍｔｎのポリプロピレン製不織
布セパレーター（Ｃ）と、径が１４ＩＴＩ Ｉｎで厚さ
が０．０２ｍｔｎのポリエチレン製微孔膜セパレーター
（ｄ）を用いている。また、電解液には、団ＬｉＣ１０
，／ＰＣ−ＥＣを用いている。Using these electrode plates, a button-type organic electrolytic tα battery as shown in FIG. 1 was fabricated. This battery uses a polypropylene nonwoven fabric separator (C) with a diameter of 13 mm and a thickness of 0.2 mtn, and a polyethylene microporous membrane separator (d) with a diameter of 14 ITI In and a thickness of 0.02 mtn as separators. ing. In addition, the electrolyte contains group LiC10
,/PC-EC is used.
この電池は、正極にリチウムが吸蔵された状態で組み立
てられる。そして、第一回目の充電時に正極からリチウ
ムイオンが放出されて、負極のα−リチウム・アルミニ
ウム合金に吸蔵されるものである。This battery is assembled with lithium occluded in the positive electrode. During the first charging, lithium ions are released from the positive electrode and inserted into the α-lithium aluminum alloy of the negative electrode.
リチウム・アルミニウム合金のリチウム濃度を３ ｗ
ｔ％以以上すると、いわゆるα＋β−リチウム・アルミ
ニウム合金となる。このα＋β−リチウム・アルミニウ
ム合金は、空気中の水分と容易に反応するので、取り扱
いが難しい。したがって、空気中で安定なα−リチウム
・アルミニウム合金を用いることが望ましい。The lithium concentration of lithium-aluminum alloy is 3w
When the content is t% or more, a so-called α+β-lithium-aluminum alloy is formed. This α+β-lithium aluminum alloy is difficult to handle because it easily reacts with moisture in the air. Therefore, it is desirable to use an α-lithium aluminum alloy that is stable in air.
［実施例の２コ
アルミニウム・ボロン合金粉末を負極原料に用いた以外
は、実施例の１のボタン電池と同様の有機電解液電池を
実施例の２の電池とする。[The battery of Example 2 is an organic electrolyte battery similar to the button battery of Example 1 except that the 2-coaluminum-boron alloy powder of Example was used as the negative electrode raw material.
［実施例の３および４］
アルミニウム・シリコン合金粉末またはアルミニウム・
ビスマス合金粉末を負極原料に用いたＶ′外は、実施例
の１のボタン電池と同様の有機電解ｔα電池を実施例の
３または４の電池とする。[Example 3 and 4] Aluminum-silicon alloy powder or aluminum-silicon alloy powder
The battery of Example 3 or 4 is an organic electrolytic tα battery similar to the button battery of Example 1 except for V' in which bismuth alloy powder was used as the negative electrode raw material.
［実施例の５および６］
アルミニウム・ゲルマニウム合金粉末またはアルミニウ
ム・ガリウム合金粉末を負極原料に用いた以外は、実施
例の１のボタン電池と同様の有機電解液電池をそれぞれ
実施例の５および６の電池とする。[Example 5 and 6] Organic electrolyte batteries similar to the button battery of Example 1 were prepared in Examples 5 and 6, respectively, except that aluminum-germanium alloy powder or aluminum-gallium alloy powder was used as the negative electrode raw material. battery.
［実施例の７］
アルミニウム（８４ｗ ｔ％）・リチウム（２ｗｔ％）
・ボロン（ｌ ｗ ｔ％）・シリコン（５ｗ ｔ％）・
ビスマス（５ｗ ｔ％）・ゲルマニウム（１ｗｔ％）・
カリウム（ｌ Ｗ ｔ％）・マンガン（１ｗ ｔ％）合
金粉末を負極原料に用いた以外は、実施例の１のボタン
電池と同様の有機電解液電池を実施例の７の電池とする
。[Example 7] Aluminum (84wt%)/Lithium (2wt%)
・Boron (l w t%) ・Silicon (5 w t%) ・
Bismuth (5wt%), germanium (1wt%),
The battery of Example 7 is the same organic electrolyte battery as the button battery of Example 1, except that potassium (l W t%)/manganese (1 wt%) alloy powder is used as the negative electrode raw material.
この負極原料を用いた場合には、後述のように、リチウ
ムの吸蔵・放出にともなうアルミニウム電極の崩壊が少
なく、リチウムイオンの固体的拡散速度が速く、またリ
チウムイオンがアルミニウム合金に吸蔵・放出されると
きの過電圧が低いので、電池のサイクル寿命がもっとも
長いリチウム二次電池を得ることができた。When this negative electrode raw material is used, as will be described later, the collapse of the aluminum electrode due to intercalation and desorption of lithium is small, the solid-state diffusion rate of lithium ions is fast, and lithium ions are absorbed and desorbed into the aluminum alloy. Since the overvoltage during charging is low, we were able to obtain a lithium secondary battery with the longest battery cycle life.
以上の実施例では、負極板に粉末原料からなるポケット
式電極を用いている。これらの粉末は、ガスアトマイズ
法により製造するのが好適である。In the above embodiments, a pocket electrode made of powder raw material is used for the negative electrode plate. These powders are preferably manufactured by a gas atomization method.
また、粉末電極を用いずにそれぞれの合金薄板を打ち抜
いてなる円板状電極を用いてもよい。また、正極活物質
としてＬｉＣｏＯ２の代わりにＭｎＯ２やリチウムマン
ガン複合酸化物を用いてもよい。さらに、電池形式もボ
タン型電池に限らず角形電池または円筒型電池でもよい
。Alternatively, instead of using a powder electrode, a disk-shaped electrode formed by punching out each alloy thin plate may be used. Furthermore, MnO2 or lithium manganese composite oxide may be used instead of LiCoO2 as the positive electrode active material. Furthermore, the battery type is not limited to a button type battery, but may also be a prismatic battery or a cylindrical battery.
本発明の効果を検証するために、負極板にアルミニウム
粉末を用いた以外は、実施例の１の電池と同様なボタン
型電池を比較のための従来の電池８として試作した。In order to verify the effects of the present invention, a button-type battery similar to the battery of Example 1 was prototyped as a conventional battery 8 for comparison, except that aluminum powder was used for the negative electrode plate.
本発明の実施例の電池１〜７および比較のための電池８
を１ｍＡの電流で端子電圧が４．ＯＶになるまで充電し
た後、同じ＜１ｍＡの電流で端子電圧が２．ＩＶに降下
するまで放電するサイクル充放電試験をおこなった。こ
のときのサイクル寿命特性を第二図に示す。図から、本
発明の電池１〜７は、従来の電池８に比較して優れたサ
イクル寿命性能を有することがわかる。Batteries 1 to 7 of Examples of the present invention and Battery 8 for comparison
With a current of 1mA, the terminal voltage is 4. After charging until OV, the terminal voltage becomes 2.0 mA with the same current <1 mA. A cycle charge/discharge test was conducted in which the battery was discharged until it dropped to IV. The cycle life characteristics at this time are shown in Figure 2. From the figure, it can be seen that batteries 1 to 7 of the present invention have superior cycle life performance compared to conventional battery 8.
発明の効果
上記のように、本発明の電池は、長期のサイクル寿命性
能を可能にするというに優れた効果を有している。Effects of the Invention As described above, the battery of the present invention has an excellent effect of enabling long-term cycle life performance.
なお以上の効果とは別に、本発明のリチウム電池は、次
のような優れた特徴を持っている。すなわち、本発明の
リチウム電池は、金属リチウムを製造中に取り扱わずま
た電池内にも保有していないので、製造および使用時の
安全性がきわめて高い。安全性は、あらゆる電池性能の
中でもっとも重要な性能である。したがって、本発明の
リチウム電池は、二次電池のサイクル寿命を向上させる
だけでなく、−次電池に適用した場合にも安全性を向上
させる点で優れた効果を有している。In addition to the above effects, the lithium battery of the present invention has the following excellent features. That is, the lithium battery of the present invention has extremely high safety during manufacture and use because metallic lithium is not handled during manufacture and is not contained within the battery. Safety is the most important performance of all battery performance. Therefore, the lithium battery of the present invention not only improves the cycle life of a secondary battery, but also has excellent effects in improving safety when applied to a secondary battery.
第一図は、本発明の実施例の１のボタン型有機電解液電
池の概略図を示す。図中の記号（ｅ）、（ｆ）。
（ｇ）は、それぞれ、正極缶、負極缶、バッキングを示
す、また、第二図は、本発明の有機電解液電池と従来の
有機電解液電池とのサイクル寿命性能の比較を示す。第
二図中の記号は、それぞれ下記の内容を示す。
（１）・・・実施例１の有機電解液電池の特性（２）・
・・実施例２の有機電解液電池の特性（３）・・・実施
例３の有機電解液電池の特性（４）・・・実施例４の有
機電解液電池の特性（５）・・・実施例５の有機電解液
電池の特性（６）・・・実施例６の有機電解液電池の特
性（７）・・・実施例７の有機電解液電池の特性（８）
・・・比較のための有機電解液電池８の特性率
図
斉
図
Ｎｕｒｎｂｅｒ ｏｆ ｃｙｃｔｅｓ
（ｃｙｄｅ）FIG. 1 shows a schematic diagram of a button-type organic electrolyte battery according to Example 1 of the present invention. Symbols (e) and (f) in the figure. (g) shows a positive electrode can, a negative electrode can, and a backing, respectively, and FIG. 2 shows a comparison of cycle life performance between the organic electrolyte battery of the present invention and a conventional organic electrolyte battery. The symbols in Figure 2 indicate the following contents. (1) Characteristics of the organic electrolyte battery of Example 1 (2)
Characteristics of the organic electrolyte battery of Example 2 (3) Characteristics of the organic electrolyte battery of Example 3 (4) Characteristics of the organic electrolyte battery of Example 4 (5) Characteristics of the organic electrolyte battery of Example 5 (6) Characteristics of the organic electrolyte battery of Example 6 (7) Characteristics of the organic electrolyte battery of Example 7 (8)
...Characteristics diagram of organic electrolyte battery 8 for comparison Nurnber of cyctes (cyde)
Claims (1)
マス、ガリウムもしくはゲルマニウムを単独でまたは複
合して添加した合金を用いた負極板を備えたことを特徴
とするリチウム電池。 ２、請求項１記載の合金にマンガンを添加した合金を用
いた負極板を備えたことを特徴とするリチウム電池。[Claims] 1. A lithium battery comprising a negative electrode plate using an alloy in which lithium, boron, silicon, bismuth, gallium, or germanium is added singly or in combination to aluminum. 2. A lithium battery comprising a negative electrode plate made of an alloy obtained by adding manganese to the alloy according to claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11812790A JP3211086B2 (en) | 1990-03-02 | 1990-05-07 | Lithium battery |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2-52340 | 1990-03-02 | ||
| JP5234090 | 1990-03-02 | ||
| JP11812790A JP3211086B2 (en) | 1990-03-02 | 1990-05-07 | Lithium battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH03280363A true JPH03280363A (en) | 1991-12-11 |
| JP3211086B2 JP3211086B2 (en) | 2001-09-25 |
Family
ID=26392949
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP11812790A Expired - Fee Related JP3211086B2 (en) | 1990-03-02 | 1990-05-07 | Lithium battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3211086B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6835496B1 (en) | 1998-09-08 | 2004-12-28 | Sumitomo Metal Industries, Ltd. | Negative electrode material for a non-aqueous electrolyte secondary battery and processes for its manufacture |
-
1990
- 1990-05-07 JP JP11812790A patent/JP3211086B2/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6835496B1 (en) | 1998-09-08 | 2004-12-28 | Sumitomo Metal Industries, Ltd. | Negative electrode material for a non-aqueous electrolyte secondary battery and processes for its manufacture |
| US6881518B2 (en) | 1998-09-08 | 2005-04-19 | Sumitomo Metal Industries, Ltd. | Process for manufacture of negative electrode material for a non-aqueous electrolyte secondary battery |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3211086B2 (en) | 2001-09-25 |
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