JPH0421986B2 - - Google Patents
Info
- Publication number
- JPH0421986B2 JPH0421986B2 JP3688083A JP3688083A JPH0421986B2 JP H0421986 B2 JPH0421986 B2 JP H0421986B2 JP 3688083 A JP3688083 A JP 3688083A JP 3688083 A JP3688083 A JP 3688083A JP H0421986 B2 JPH0421986 B2 JP H0421986B2
- Authority
- JP
- Japan
- Prior art keywords
- lithium
- alloy
- negative electrode
- cadmium
- charging
- 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.)
- Expired
Links
- 229910045601 alloy Inorganic materials 0.000 claims description 35
- 239000000956 alloy Substances 0.000 claims description 35
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims description 21
- 229910052793 cadmium Inorganic materials 0.000 claims description 19
- 238000007599 discharging Methods 0.000 claims description 19
- 239000007773 negative electrode material Substances 0.000 claims description 19
- 229910052751 metal Inorganic materials 0.000 claims description 12
- 239000002184 metal Substances 0.000 claims description 12
- 239000011255 nonaqueous electrolyte Substances 0.000 claims description 12
- 239000003792 electrolyte Substances 0.000 claims description 9
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 4
- 229910052797 bismuth Inorganic materials 0.000 claims description 4
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 4
- 239000000654 additive Substances 0.000 claims description 3
- 229910001413 alkali metal ion Inorganic materials 0.000 claims description 3
- 229910052718 tin Inorganic materials 0.000 claims description 3
- 230000000996 additive effect Effects 0.000 claims description 2
- 229910052738 indium Inorganic materials 0.000 claims description 2
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 2
- 229910021645 metal ion Inorganic materials 0.000 claims 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 32
- 229910052744 lithium Inorganic materials 0.000 description 32
- 230000005611 electricity Effects 0.000 description 9
- 229910052783 alkali metal Inorganic materials 0.000 description 8
- 150000001340 alkali metals Chemical class 0.000 description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- 229910000925 Cd alloy Inorganic materials 0.000 description 5
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 4
- HSZCZNFXUDYRKD-UHFFFAOYSA-M lithium iodide Chemical compound [Li+].[I-] HSZCZNFXUDYRKD-UHFFFAOYSA-M 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 4
- 229910052753 mercury Inorganic materials 0.000 description 4
- 150000002739 metals Chemical class 0.000 description 4
- 229910052709 silver Inorganic materials 0.000 description 4
- 239000004332 silver Substances 0.000 description 4
- 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 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 229910000978 Pb alloy Inorganic materials 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 229910000645 Hg alloy Inorganic materials 0.000 description 2
- 229910013684 LiClO 4 Inorganic materials 0.000 description 2
- 210000004027 cell Anatomy 0.000 description 2
- JWZCKIBZGMIRSW-UHFFFAOYSA-N lead lithium Chemical compound [Li].[Pb] JWZCKIBZGMIRSW-UHFFFAOYSA-N 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000006104 solid solution Substances 0.000 description 2
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- 229910000733 Li alloy Inorganic materials 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229910001128 Sn alloy Inorganic materials 0.000 description 1
- 229910003092 TiS2 Inorganic materials 0.000 description 1
- JFBZPFYRPYOZCQ-UHFFFAOYSA-N [Li].[Al] Chemical compound [Li].[Al] JFBZPFYRPYOZCQ-UHFFFAOYSA-N 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- ZIXVIWRPMFITIT-UHFFFAOYSA-N cadmium lead Chemical compound [Cd].[Pb] ZIXVIWRPMFITIT-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 239000001989 lithium alloy Substances 0.000 description 1
- BOEOGTSNJBLPHD-UHFFFAOYSA-N lithium mercury Chemical compound [Li].[Hg] BOEOGTSNJBLPHD-UHFFFAOYSA-N 0.000 description 1
- IDBFBDSKYCUNPW-UHFFFAOYSA-N lithium nitride Chemical compound [Li]N([Li])[Li] IDBFBDSKYCUNPW-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
- 150000002730 mercury Chemical class 0.000 description 1
- MJGFBOZCAJSGQW-UHFFFAOYSA-N mercury sodium Chemical compound [Na].[Hg] MJGFBOZCAJSGQW-UHFFFAOYSA-N 0.000 description 1
- 239000005486 organic electrolyte Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000011148 porous material Substances 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
- 238000001556 precipitation Methods 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 229910001023 sodium amalgam Inorganic materials 0.000 description 1
- -1 sodium and potassium Chemical class 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- CFJRPNFOLVDFMJ-UHFFFAOYSA-N titanium disulfide Chemical compound S=[Ti]=S CFJRPNFOLVDFMJ-UHFFFAOYSA-N 0.000 description 1
- 238000012795 verification 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Battery Electrode And Active Subsutance (AREA)
Description
産業上の利用分野
本発明は非水電解質二次電池用の負極の改良に
係るもので、この改良の結果高エネルギー密度で
充放電寿命が長く、安全性、信頼性に優れた充電
可能な電池を提供するものである。
従来例の構成とその問題点
現在まで、リチウム、ナトリウムなどのアルカ
リ金属を負極とする非水電解質二次電池として
は、たとえば、二硫化チタン（TiS2）をはじめ
各種の層間化合物などを正極活物質として用い、
電解質としては、炭酸プロピレン（以後PCと略
す）などの有機溶媒に過塩素酸リチウム
（LiClO4）などを溶解した有機電解質を用いる電
池の開発が活発に進められてきた。この二次電池
の特徴は、負極にリチウムを用いることにより、
電池電圧が高くなり、高エネルギー密度の二次電
池となることである。
しかし、この種の二次電池は、現在、まだ実用
化されていない。その主な理由は、充放電回数
（サイクル）の寿命が短かく、また充放電に際し
ての充放電効率が低いためである。この原因は、
リチウム負極の劣化によるところが非常に大き
い。すなわち、現在のリチウム負極はニツケルな
どのスクリーン状集電体に板状の金属リチウムを
圧着したものが主に用いられているが、放電時に
金属リチウムは、電解質中にリチウムイオンとし
て溶解する。しかしこれを充電して、放電前のよ
うな板状のリチウムに析出させることは難しく、
デンドライト状（樹枝状）のリチウムが発生して
これが根元より折れて脱落したり、あるいは、小
球状（苔状）に析出したリチウムが集電体より脱
離するなどの現象が起こる。このため充放電が不
能の電池となつてしまう。また、発生したデンド
ライト状の金属リチウムが、正極、負極間を隔離
しているセパレータを貫通して正極に接し短絡を
起こし、電池の機能を失なわせるようなことも
度々生じる。
このような負極の欠点を改良するための方法は
従来から各種試みられている。一般的には、負極
集電体の材料を替えて析出するリチウムとの密着
性を良くしたり、あるいは、電解質中にデンドラ
イト発生防止の添加剤を加えたりする方法が報告
されている。しかしこれらの方法は必ずしも効果
的ではない。すなわち、集電体材料に関しては、
集電体材料に直接析出するリチウムに有効である
が、更に充電（析出）を続けると析出リチウム上
へリチウムを析出することになり、集電体材料の
効果は消失する。また添加剤に関しても、充放電
サイクルの初期では有効であるが、サイクルが進
むと電池内での酸化還元反応などにより分解し、
その効果がなくなるものが殆んどである。さらに
最近は、負極として、リチウムとの合金を用いる
ことが提案されている。この例としては、リチウ
ム−アルミニウム合金がよく知られている。この
場合は、一応均一の合金が形成されるが、充放電
をくり返すとその均一性を消失し、特にリチウム
量を多くすると電極が微粒化し崩壊するなどの欠
点があつた。また、銀とアルカリ金属との固溶体
を用いることも提案されている。（特開昭56−
7386）この場合は、アルミニウムとの合金のよう
な崩壊はないとされているが、十分に速く合金化
するリチウムの量は少なく、金属状のリチウムが
合金化しないまゝ析出する場合があり、これを防
ぐために多孔体の使用などを推奨している。した
がつて、大電流の充電効率は悪く、たリチウム量
の多い合金は、充放電による微細化が徐々に加速
され、サイクル寿命が急激に減少する。
この他にはリチウム−水銀合金を用いる考案
（特開昭57−98978）、リチウム−鉛合金を用いる
考案（特開昭57−141869）がある。しかし、リチ
ウム．水銀合金の場合は、放電により、負極は液
状粒子の水銀となり電極形状を保持しなくなる。
また、リチウム−鉛合金の場合は、電極の充放電
による微細粉化は、銀固溶体以上であり、このた
め合金中の鉛量を80％位にすることが望ましいと
されているが、これでは高エネルギー密度電池を
実現できない。以上のように非水電解質二次電池
用負極としては、実用上満足できるものは、まだ
見い出されていないといえる。
したがつて、優れた負極としては、アルカリ金
属の吸蔵量が大きく、しかも放出や吸蔵速度の大
なる負極材料の開発が望まれている。
発明の目的
本発明は負極材料を特定することにより、単位
体積当りの充放電量の多い、また充放電寿命の長
い、良好な特性を示す非水電解質二次電池を提供
するものである。
発明の構成
本発明の二次電池は、カドミウムまたはカドミ
ウムを主成分とする合金を負極材料に用いること
を特徴とし、充電により負極材料に用いた金属や
合金中に、リチウムを吸蔵せしめ、放電により電
解質中にリチウムイオン放出させるものである。
実施例の説明
前記のように本発明の二次電池においては、負
極材料合金に充電によりリチウムを吸蔵させ、放
電により電解質中にリチウムイオンを放出させる
ものであるので、充電により、カドミウムとリチ
ウムの合金、またはカドミウム合金とリチウムの
合金が出来ることになる。本発明で述べる負極材
料とは、リチウムとの合金を作る以前の金属カド
ミウムやカドミウム合金のことである。
例えば重量パーセントで70％のカドミウムと30
％のスズよりなる合金を用いた時の充放電反応は
(1)式のようになる。
Cd（70）−Sn（30）＋xLi+＋xe-
充電
―――→
←―――
放電〔Cd（70）−Sn（30）〕Lix ………(1)
式中、〔Cd（70）−Sn（30）〕Lixは充電により生
成した、カドミウム、スズ、リチウム合金を示し
ており、本発明で定義した負極材料とは(1)式中で
はCd（70）−Sn（30）のことである。
また、充放電の範囲としては、(1)式のように完
全に負極中よりリチウムがなくなるまで放電する
必要はなく、(2)式のように負極中に吸蔵されたリ
チウム
〔Cd（70）−Sn（30）〕Lix
＋yLi+＋ye-充電
―――→
←―――
放電〔Cd（70）
−Sn（30）〕Lix+y ………(2)
量を変えるようにして、充放電ができることは当
然である。また(2)式においても負極材料がCd
（70）−Sn（30）であることは自明である。
また、カドミウムを主成分とする合金とは、合
金中最も重量が多い金属がカドミウムである合金
とする。
発明者らは、カドミウムやカドミウムを主成分
とする合金を負極材料として、アルカリ金属イオ
ンを含む非水電解質中で充電を行うことにより、
高率充電を行つてもアルカリ金属の析出が起らず
に負極材料中にアルカリ金属が吸蔵され、さらに
放電を行うと高電流効率で吸蔵されたアルカリ金
属がアルカリ金属イオンとして電解質中に放出さ
れることを見い出した。また充放電をくり返し行
つても負極材料の微細粉化が起らず、良好な非水
電解質二次電池の負極特性を示すことがわかつ
た。
負極材料として、金属カドミウムとカドミウム
を主成分とする合金を比較すると合金の方が良好
な負極特性を示した。カドミウムを主成分とする
合金の他の成分として、鉛、ビスマス、スズ、イ
ンジウムなどを加えて作つた合金の多くは、微視
的に見ると、各金属成分や、金属間化合物などの
多くの相からなつており、均一なものではない。
充電により吸蔵されたリチウムなどのアルカリ金
属は合金中の相と相の間の界面に沿つて、早い速
度で拡散してゆくと考えられ、高率充放電を行う
とカドミウムを主成分とする合金を用いる方が良
好であつた。
第１図に示したセルを構成して、各種金属や合
金の非水電解質二次電池の負極の特性を調べた。
第１図中、Ａは検討した金属、合金よりなる試験
極、ＢはTiS2よりなる正極、Ｃは照合電極とし
てのリチウム板である。各々の電極のリードEA，
EB，ECにはニツケル線を用いた。試験極Ａは第
２図に示すように、１cm×１cm厚さ１mmの金属あ
るいは合金Ｄに、リードとしてニツケルリボン
EAをとりつけた。電解質には、１モル／の
LiClO4を溶したPCを用いた。試験極Ａの液槽Ｈ
と照合極Ｃの液槽Ｇとは連通管Ｉで接続されてい
る。金属や合金の非水電解質二次電池の負極とし
ての特性を測定するために、試験極Ａの電位が、
リチウム照合電極Ｃに対して０ｍＶになるまで５
ｍＡの定電流でカソード方向に充電した。この条
件では、試験極上にリチウムは析出せず、合金中
に入る。試験極Ａの電位が0mVに達した後、照
合電極Ｃに対して10Vになるまで、５ｍＡの定電
流でアノード方向に放電し、その後充電、放電を
同じ条件で繰り返した。表には、試験室Ａに用い
た合金、金属の第１サイクルと第10サイクルにお
ける充電電気量、放電電気量、および効率として
放電電気量を充電電気量で除したもの、サイクル
特性として、第10サイクルの放電電気量を第１サ
イクルの放電電気量で除したものを示す。充電電
気量、放電電気量、効率、サイクル特性の数値が
大である程よい負極と言える。また表中に記号で
示した試験極Ａの第10サイクルでの充電曲線を第
３図に、放電曲線を第４図に示す。
INDUSTRIAL APPLICATION FIELD The present invention relates to the improvement of negative electrodes for non-aqueous electrolyte secondary batteries, and as a result of this improvement, rechargeable batteries with high energy density, long charging/discharging life, and excellent safety and reliability. It provides: Conventional configurations and their problems Until now, non-aqueous electrolyte secondary batteries that use alkali metals such as lithium or sodium as negative electrodes have used various intercalation compounds such as titanium disulfide (TiS 2 ) as positive electrode active materials. used as a substance,
Batteries that use organic electrolytes such as lithium perchlorate (LiClO 4 ) dissolved in organic solvents such as propylene carbonate (hereinafter abbreviated as PC) have been actively developed. The feature of this secondary battery is that by using lithium for the negative electrode,
The battery voltage increases, resulting in a secondary battery with high energy density. However, this type of secondary battery has not yet been put into practical use. The main reason for this is that the life of the number of charging and discharging times (cycles) is short and the charging and discharging efficiency during charging and discharging is low. The cause of this is
This is largely due to the deterioration of the lithium negative electrode. That is, current lithium negative electrodes are mainly made by pressing a plate-shaped metallic lithium onto a screen-shaped current collector such as nickel, but the metallic lithium dissolves in the electrolyte as lithium ions during discharge. However, it is difficult to charge this and deposit it into a plate-shaped lithium as before discharging.
Phenomena occur such as dendrite-like (dendritic) lithium is generated and breaks off from the base and falls off, or small spherical (moss-like) lithium deposits are detached from the current collector. This results in a battery that cannot be charged or discharged. Furthermore, the generated dendrite-like metallic lithium often penetrates the separator that separates the positive and negative electrodes and comes into contact with the positive electrode, causing a short circuit and causing the battery to lose its functionality. Various methods have been tried in the past to improve these drawbacks of negative electrodes. Generally, methods have been reported in which the material of the negative electrode current collector is changed to improve its adhesion to the precipitated lithium, or an additive to prevent the formation of dendrites is added to the electrolyte. However, these methods are not always effective. That is, regarding the current collector material,
It is effective for lithium deposited directly on the current collector material, but if charging (deposition) continues further, lithium will be deposited on the precipitated lithium, and the effect of the current collector material will disappear. Additionally, additives are effective at the beginning of the charge/discharge cycle, but as the cycle progresses, they decompose due to oxidation-reduction reactions within the battery.
In most cases, the effect disappears. Furthermore, recently, it has been proposed to use an alloy with lithium as a negative electrode. A well-known example of this is lithium-aluminum alloy. In this case, a somewhat uniform alloy is formed, but this uniformity disappears when charging and discharging are repeated, and especially when the amount of lithium is increased, the electrode becomes atomized and collapses. It has also been proposed to use a solid solution of silver and an alkali metal. (Unexamined Japanese Patent Publication 1983-
7386) In this case, it is said that there is no collapse like in alloying with aluminum, but the amount of lithium that alloys quickly enough is small, and metallic lithium may precipitate without being alloyed. To prevent this, the use of porous materials is recommended. Therefore, the charging efficiency at large currents is poor, and alloys with a large amount of lithium gradually accelerate the refinement due to charging and discharging, resulting in a sharp decrease in cycle life. In addition, there are ideas using a lithium-mercury alloy (Japanese Patent Laid-Open No. 57-98978) and a idea using a lithium-lead alloy (Japanese Patent Laid-Open No. 57-141869). However, lithium. In the case of a mercury alloy, the negative electrode becomes liquid particle mercury due to discharge and no longer maintains its electrode shape.
In addition, in the case of lithium-lead alloys, the fineness due to charging and discharging of the electrode is greater than that of silver solid solution, and therefore it is said that it is desirable to keep the amount of lead in the alloy at around 80%. High energy density batteries cannot be realized. As described above, it can be said that a practically satisfactory negative electrode for non-aqueous electrolyte secondary batteries has not yet been found. Therefore, as an excellent negative electrode, it is desired to develop a negative electrode material that has a large amount of alkali metal occlusion and a high desorption and occlusion rate. OBJECTS OF THE INVENTION The present invention provides a non-aqueous electrolyte secondary battery that exhibits good characteristics such as a large charge/discharge amount per unit volume and a long charge/discharge life by specifying a negative electrode material. Structure of the Invention The secondary battery of the present invention is characterized in that cadmium or an alloy containing cadmium as a main component is used as a negative electrode material, and lithium is occluded in the metal or alloy used as the negative electrode material by charging, and by discharging. It releases lithium ions into the electrolyte. Description of Examples As mentioned above, in the secondary battery of the present invention, lithium is occluded in the negative electrode material alloy by charging, and lithium ions are released into the electrolyte by discharging. This results in the creation of an alloy, or an alloy of cadmium alloy and lithium. The negative electrode material described in the present invention refers to metal cadmium or cadmium alloy before forming an alloy with lithium. For example, 70% cadmium and 30% by weight
The charge-discharge reaction when using an alloy consisting of % tin is
It becomes as shown in equation (1). Cd(70)−Sn(30)+xLi + +xe -Charge―― → ←――― Discharge [Cd(70)−Sn(30)]Li x ……(1) In the formula, [Cd(70) −Sn(30)]Li x indicates a cadmium, tin, and lithium alloy produced by charging, and the negative electrode material defined in the present invention is Cd(70)−Sn(30) in formula (1). That's true. In addition, regarding the range of charging and discharging, it is not necessary to discharge until lithium completely disappears from the negative electrode as shown in equation (1), and it is not necessary to discharge until lithium is completely removed from the negative electrode as shown in equation (2). −Sn(30)〕Li x +yLi + +ye -Charging―― → ←――― Discharging [Cd(70) −Sn(30)]Li x+y ……(2) By changing the amount, It goes without saying that it can be charged and discharged. Also, in equation (2), the negative electrode material is Cd.
It is obvious that it is (70)−Sn(30). Furthermore, an alloy whose main component is cadmium is an alloy in which the heaviest metal in the alloy is cadmium. The inventors used cadmium or an alloy mainly composed of cadmium as a negative electrode material, and by charging it in a non-aqueous electrolyte containing alkali metal ions,
Even when high-rate charging is performed, alkali metals are occluded in the negative electrode material without precipitation of alkali metals, and when further discharge is performed, the occluded alkali metals are released into the electrolyte as alkali metal ions with high current efficiency. I discovered that. It was also found that the negative electrode material did not become finely powdered even after repeated charging and discharging, and exhibited good negative electrode characteristics of a non-aqueous electrolyte secondary battery. When comparing cadmium metal and an alloy mainly composed of cadmium as negative electrode materials, the alloy showed better negative electrode characteristics. Many alloys made by adding other ingredients such as lead, bismuth, tin, and indium to alloys containing cadmium as the main component can be seen microscopically to contain various metal components and intermetallic compounds. It consists of phases and is not uniform.
Alkali metals such as lithium absorbed by charging are thought to diffuse at a high rate along the interface between phases in the alloy, and when high-rate charging and discharging is performed, alloys mainly composed of cadmium It was better to use The cell shown in FIG. 1 was constructed and the characteristics of the negative electrode of a non-aqueous electrolyte secondary battery made of various metals and alloys were investigated.
In FIG. 1, A is a test electrode made of the studied metal or alloy, B is a positive electrode made of TiS2 , and C is a lithium plate as a reference electrode. Lead E A of each electrode,
Nickel wires were used for E B and E C. As shown in Figure 2, the test electrode A is a metal or alloy D with a size of 1 cm x 1 cm and a thickness of 1 mm, with a nickel ribbon as a lead.
I installed E A. The electrolyte contains 1 mol/
PC in which LiClO 4 was dissolved was used. Test electrode A liquid tank H
and the liquid tank G of the reference electrode C are connected through a communication pipe I. In order to measure the characteristics of a metal or alloy non-aqueous electrolyte secondary battery as a negative electrode, the potential of test electrode A is
5 until it reaches 0 mV with respect to lithium reference electrode C.
It was charged in the cathode direction with a constant current of mA. Under these conditions, lithium does not precipitate on the test electrode but enters the alloy. After the potential of test electrode A reached 0 mV, it was discharged toward the anode at a constant current of 5 mA until it reached 10 V with respect to reference electrode C, and then charging and discharging were repeated under the same conditions. The table shows the amount of electricity charged and the amount of electricity discharged in the first and tenth cycles of the alloys and metals used in test chamber A, the efficiency calculated by dividing the amount of electricity discharged by the amount of electricity charged, and the cycle characteristics of the It shows the amount of electricity discharged in 10 cycles divided by the amount of electricity discharged in the first cycle. It can be said that the larger the numerical values of the amount of charging electricity, the amount of discharging electricity, the efficiency, and the cycle characteristics are, the better the negative electrode is. Further, the charging curve and the discharging curve at the 10th cycle of test electrode A, which are indicated by symbols in the table, are shown in FIG. 3 and FIG. 4, respectively.
【表】【table】
【表】
以上の結果より、非水電解質二次電池用負極材
料として、従来より用いられて来たアルミニウ
ム、鉛、銀、水銀に比べ、本発明のカドミウムあ
るいはカドミウムを主成分とする合金が良好であ
ることがわかつた。
またカドミウムとカドミウム合金を比較すると
合金の方が良好な特性を示している。表中には、
カドミウム合金を作るのに使用した他の成分であ
る金属単体の負極特性をも示した。これより、各
成分の金属単体より合金を用いた方が性能が向上
していた。また表に示したようにカドミウム−鉛
合金で示すように、他の成分量が増加する程、性
能は向上する傾向が見られた。
なお、負極材料として水銀を用いた場合、充放
電電気量が小さいのは、水銀の食塩電解における
ナトリウムアマルガム中のナトリウムが0.2％程
度しかないことと関連しているかもしれない。
上記実施例では、負極電極材料にリチウムを吸
蔵、放出させる例を示した。リチウム以外にもナ
トリウムやカリウムなどのアルカリ金属の吸蔵、
放出を行わせる負極を構成することも可能であ
る。
また電解質として、実施例に示したLiClO4を
溶解したPCだけでなく、Li3N（窒化リチウム）
やLiI（ヨウ化リチウム）のような固体電解質を用
いた場合でも、従来のアルミニウム、鉛、銀、水
銀に比べビスマスまたはビスマスを主成分とする
合金を負極材料とする方が優れた負極が得られ
た。
発明の効果
以上のようにカドミウムまたは主成分をカドミ
ウムとする合金を負極材料とすることにより、充
放電電気量の多い、サイクル特性の良い、すなわ
ち充放電寿命の長い信頼性に優れた非水電解質電
池を得ることができる。[Table] From the above results, the cadmium or cadmium-based alloy of the present invention is better as a negative electrode material for nonaqueous electrolyte secondary batteries than the conventionally used aluminum, lead, silver, and mercury. It turns out that it is. Furthermore, when comparing cadmium and cadmium alloy, the alloy shows better properties. In the table,
They also demonstrated the negative electrode properties of other metals used to make the cadmium alloy. This shows that the performance was better when using an alloy than when using individual metals of each component. Furthermore, as shown in the table, as shown in the case of the cadmium-lead alloy, there was a tendency for the performance to improve as the amount of other components increased. Note that when mercury is used as the negative electrode material, the small amount of charge and discharge electricity may be related to the fact that the sodium content of the sodium amalgam in mercury salt electrolysis is only about 0.2%. In the above embodiment, an example was shown in which lithium was inserted into and released from the negative electrode material. In addition to lithium, occlusion of alkali metals such as sodium and potassium,
It is also possible to construct a negative electrode that allows emission to take place. Furthermore, as an electrolyte, not only PC in which LiClO 4 is dissolved as shown in the example, but also Li 3 N (lithium nitride) can be used.
Even when a solid electrolyte such as LiI (lithium iodide) is used, a better negative electrode can be obtained by using bismuth or an alloy mainly composed of bismuth as the negative electrode material compared to conventional aluminum, lead, silver, or mercury. It was done. Effects of the Invention As described above, by using cadmium or an alloy containing cadmium as a main component as a negative electrode material, a highly reliable non-aqueous electrolyte with a large amount of charge and discharge, good cycle characteristics, and a long charge and discharge life can be achieved. You can get batteries.
第１図は負極特性の検討に用いたセルの構成
図、第２図は試験極の側面図、第３図および第４
図は充電曲線図と放電曲線図である。
Ａ……試験極、Ｂ……正極、Ｃ……照合電極。
Figure 1 is a block diagram of the cell used for examining the negative electrode characteristics, Figure 2 is a side view of the test electrode, Figures 3 and 4.
The figure shows a charging curve diagram and a discharging curve diagram. A...test electrode, B...positive electrode, C...verification electrode.
Claims (1)
蔵し、放電時に上記金属イオンを電解質中に放出
する機能を有し、負電極材料として、金属カドミ
ウム、または、カドミウムを主成分とする合金を
用いることを特徴とする非水電解質二次電池。 ２ 負極材料は、主成分をカドミウムとする合金
とし、添加成分としてビスマス、鉛、スズ、イン
ジウムのうち少くとも一つを用いることを特徴と
する特許請求の範囲第１項記載の非水電解質二次
電池。[Scope of Claims] 1. It has the function of occluding alkali metal ions in the electrolyte during charging and releasing the metal ions into the electrolyte during discharging, and has a negative electrode material containing metal cadmium or cadmium as a main component. A non-aqueous electrolyte secondary battery characterized by using an alloy that 2. The nonaqueous electrolyte 2 according to claim 1, wherein the negative electrode material is an alloy containing cadmium as a main component, and at least one of bismuth, lead, tin, and indium is used as an additive component. Next battery.
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3688083A JPS59163761A (en) | 1983-03-07 | 1983-03-07 | Nonaqueous electrolyte secondary battery |
| PCT/JP1984/000086 WO1984003590A1 (en) | 1983-03-07 | 1984-03-06 | Rechargeable electrochemical apparatus and negative pole therefor |
| US06/873,093 US4683182A (en) | 1983-03-07 | 1984-03-06 | Rechargeable electrochemical apparatus |
| EP84901015A EP0144429B1 (en) | 1983-03-07 | 1984-03-06 | Rechargeable electrochemical apparatus and negative pole therefor |
| DE8484901015T DE3483244D1 (en) | 1983-03-07 | 1984-03-06 | RECHARGEABLE ELECTROCHEMICAL DEVICE AND NEGATIVE POLE THEREOF. |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3688083A JPS59163761A (en) | 1983-03-07 | 1983-03-07 | Nonaqueous electrolyte secondary battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS59163761A JPS59163761A (en) | 1984-09-14 |
| JPH0421986B2 true JPH0421986B2 (en) | 1992-04-14 |
Family
ID=12482088
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3688083A Granted JPS59163761A (en) | 1983-03-07 | 1983-03-07 | Nonaqueous electrolyte secondary battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS59163761A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0648625B2 (en) * | 1984-04-19 | 1994-06-22 | 松下電器産業株式会社 | Non-aqueous electrolyte secondary battery |
-
1983
- 1983-03-07 JP JP3688083A patent/JPS59163761A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS59163761A (en) | 1984-09-14 |
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