JPS63274058A - Negative electrode for nonaqueous electrolyte secondary battery - Google Patents
Negative electrode for nonaqueous electrolyte secondary batteryInfo
- Publication number
- JPS63274058A JPS63274058A JP62108518A JP10851887A JPS63274058A JP S63274058 A JPS63274058 A JP S63274058A JP 62108518 A JP62108518 A JP 62108518A JP 10851887 A JP10851887 A JP 10851887A JP S63274058 A JPS63274058 A JP S63274058A
- Authority
- JP
- Japan
- Prior art keywords
- negative electrode
- melting point
- alloy
- alkali metal
- charge
- 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
- 239000011255 nonaqueous electrolyte Substances 0.000 title claims description 9
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 29
- 239000000956 alloy Substances 0.000 claims abstract description 29
- 238000002844 melting Methods 0.000 claims abstract description 16
- 230000008018 melting Effects 0.000 claims abstract description 13
- 229910052751 metal Inorganic materials 0.000 claims abstract description 11
- 239000002184 metal Substances 0.000 claims abstract description 11
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 9
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 9
- 229910001413 alkali metal ion Inorganic materials 0.000 claims abstract description 6
- 229910052738 indium Inorganic materials 0.000 claims abstract description 3
- 229910052797 bismuth Inorganic materials 0.000 claims abstract 2
- 229910052793 cadmium Inorganic materials 0.000 claims abstract 2
- 229910052745 lead Inorganic materials 0.000 claims abstract 2
- 229910052753 mercury Inorganic materials 0.000 claims abstract 2
- 239000000758 substrate Substances 0.000 claims description 19
- 229910052782 aluminium Inorganic materials 0.000 claims description 13
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 13
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 10
- 229910052744 lithium Inorganic materials 0.000 claims description 10
- 239000002585 base Substances 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 5
- 229910052718 tin Inorganic materials 0.000 abstract description 4
- 239000010419 fine particle Substances 0.000 abstract 2
- 101100396994 Drosophila melanogaster Inos gene Proteins 0.000 abstract 1
- 238000003795 desorption Methods 0.000 abstract 1
- 230000007774 longterm Effects 0.000 abstract 1
- 230000000717 retained effect Effects 0.000 abstract 1
- 238000001179 sorption measurement Methods 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 8
- 210000004027 cell Anatomy 0.000 description 6
- 238000007599 discharging Methods 0.000 description 6
- JFBZPFYRPYOZCQ-UHFFFAOYSA-N [Li].[Al] Chemical compound [Li].[Al] JFBZPFYRPYOZCQ-UHFFFAOYSA-N 0.000 description 4
- 210000001787 dendrite Anatomy 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000010935 stainless steel Substances 0.000 description 4
- 229910001220 stainless steel Inorganic materials 0.000 description 4
- 229910000838 Al alloy Inorganic materials 0.000 description 3
- 239000011133 lead Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000010298 pulverizing process Methods 0.000 description 3
- 239000011135 tin Substances 0.000 description 3
- 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 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- 229910001128 Sn alloy Inorganic materials 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 239000002390 adhesive tape Substances 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- LQBJWKCYZGMFEV-UHFFFAOYSA-N lead tin Chemical compound [Sn].[Pb] LQBJWKCYZGMFEV-UHFFFAOYSA-N 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- SBUOHGKIOVRDKY-UHFFFAOYSA-N 4-methyl-1,3-dioxolane Chemical compound CC1COCO1 SBUOHGKIOVRDKY-UHFFFAOYSA-N 0.000 description 1
- 229910001148 Al-Li alloy Inorganic materials 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 229910001651 emery Inorganic materials 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000001989 lithium alloy Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 239000002904 solvent Substances 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
-
- 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
- H01M4/04—Processes of manufacture in general
- H01M4/0438—Processes of manufacture in general by electrochemical processing
- H01M4/0459—Electrochemical doping, intercalation, occlusion or alloying
- H01M4/0461—Electrochemical alloying
-
- 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
- H01M4/40—Alloys based on alkali metals
-
- 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
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/661—Metal or alloys, e.g. alloy coatings
-
- 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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
-
- 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
- H01M4/40—Alloys based on alkali metals
- H01M4/405—Alloys based on lithium
-
- 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)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (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〉
この発明は非水電解液二次電池用負極に関するものであ
る。DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to a negative electrode for a non-aqueous electrolyte secondary battery.
〈従来の技術〉
非水電解液二次電池は、リチウムやナトリウムなどのア
ルカリ金属を負極活物質とし、また非水系の電解液を用
いた購成が採られるが、未だ実用化さ・れるには至って
いないのが現状である。これは、放電時に電解液中にイ
オンとなって溶出した負極中のアルカリ金属が充電■４
には負極表面に元通りに電析せずにデンドライト（樹枝
状結晶）となり、充放電サイクルの進行によりこのデン
ドライトが生長しセパレータを貫通して正極に達し電池
内部短絡を起こすなどすることが要因であり、このため
に長期に亘って高い充放電効率を保つことが困難で、υ
イクル寿命が短いことに起因している。<Conventional technology> Non-aqueous electrolyte secondary batteries use an alkali metal such as lithium or sodium as the negative electrode active material and use a non-aqueous electrolyte, but these batteries have yet to be put into practical use. The current situation is that this has not been achieved. This is because the alkali metal in the negative electrode, which is ionized and eluted into the electrolyte during discharge, charges ■4.
This is because dendrites (dendritic crystals) are formed without being deposited on the negative electrode surface as before, and as the charge/discharge cycle progresses, these dendrites grow, penetrate the separator, and reach the positive electrode, causing an internal short circuit in the battery. Therefore, it is difficult to maintain high charge/discharge efficiency over a long period of time, and υ
This is due to the short cycle life.
このため、充放電サイクルにおいてアルカリ金属イオン
を可逆的に吸蔵、放出する能力を持った構成体を負極基
体として用い、充電時にはこの負極基体表面に電析した
アルカリ金属を負極基体中に拡散しつつ吸蔵ざＵるよう
にし、もってデンドライトの発生並びにデンドライト生
長を抑制して電池の特性向上を図ることが提案されてい
る。For this reason, a structure that has the ability to reversibly absorb and release alkali metal ions during charge and discharge cycles is used as the negative electrode substrate, and during charging, the alkali metal deposited on the surface of the negative electrode substrate is diffused into the negative electrode substrate. It has been proposed to improve battery characteristics by preventing occlusion and thereby suppressing dendrite generation and dendrite growth.
このような負極基体としてはアルミニウム。Aluminum is used as such a negative electrode substrate.
亜鉛、マグネシウム、スズ、鉛、鉛−スズ合金４工どの
ようなリチウムと合金化し易い金属ないし合金が広く用
いられ、例えばアルミニウムを用いてなる負極基体では
、充電時にはリチウム−アルミニウム合金が形成される
ように上記吸蔵がなされることから、上記プントライ１
〜の発生を有効に防止することができるようになる。Zinc, magnesium, tin, lead, lead-tin alloy 4 Metals or alloys that are easily alloyed with lithium are widely used. For example, in a negative electrode substrate made of aluminum, a lithium-aluminum alloy is formed during charging. Since the above-mentioned occlusion is performed as follows, the above-mentioned Puntorai 1
It becomes possible to effectively prevent the occurrence of ~.
なかでもこのアルミニウムよりなる負ＪＩ ｕ体はリチ
ウムの拡散が速く、且つ重最当りの電気容尼が大でおる
ことから、最も有力なものとして注目されている。Among these, the negative JI u body made of aluminum is attracting attention as the most promising material because lithium diffuses quickly and the electric capacity at the maximum weight is large.
〈発明が解決しようと１６問題点〉
しかしながら、上記のようなリチウムと合金化し易い金
属ないし合金を負極基体に用いた負極では、充放電の繰
返しにより膨張、収縮などによって微粉化し易く、この
ため負極の電子伝導性が損われたり、また微粉化した負
極構成材が脱落するなどして次第に特性が低下してしま
うという問題がある。<16 Problems to be Solved by the Invention> However, in a negative electrode that uses a metal or alloy that easily alloys with lithium as the negative electrode substrate, it is easy to become pulverized due to expansion and contraction due to repeated charging and discharging, and for this reason, the negative electrode There is a problem that the electronic conductivity of the negative electrode is impaired, and the finely powdered negative electrode constituent material falls off, resulting in a gradual deterioration of the characteristics.
〈問題点を解決するための手段〉
この発明の非水電解液二茨電池用負極は、アルカリ金属
゛イオンを可逆的に吸蔵、放出する金属ないし合金より
なる負極基体の表面を、１ＢｉとＰｂにＳｎ、Ｉｎ、Ｃ
ｄ、Ｈｑより選ばれる少なくとも１種の金属を加えてな
る低融点合金にて被覆したことを要旨とするものである
。<Means for Solving the Problems> The negative electrode for a non-aqueous electrolyte dual-thorn battery of the present invention has a surface of a negative electrode substrate made of a metal or an alloy that reversibly occludes and releases alkali metal ions, and is made of 1Bi and Pb. Sn, In, C
The gist of the present invention is to coat with a low melting point alloy made by adding at least one metal selected from d and Hq.
く作 用〉
上記の低融点合金は負極の充放電口４にはアルカリ金属
の吸蔵（合金化）、放出（非合金化）を繰返すが、アル
ミニウムなどの前記金属ないし合金に較べて充放電サイ
クルに伴う微粉化が発生しにくい。このため、この低融
点合金により上記負極基体表面を被覆することで、基体
表面の低融点合金層が基体の微粉化による負極の電子伝
導性低下や負極構成材の脱落を防止する保護層となり、
長期サイクルにわたり高い充放電効率を維持できる。尚
、負極充電ないし放電時、負極基体には低融点合金層を
介してアルカリ金属イオンが拡散ないし放出されること
は言うまでもない。Function> The above-mentioned low melting point alloy repeatedly stores (alloyed) and releases (non-alloyed) alkali metal in the charging/discharging port 4 of the negative electrode, but the charging/discharging cycle is shorter than that of the metal or alloy such as aluminum. pulverization is less likely to occur. Therefore, by coating the surface of the negative electrode substrate with this low melting point alloy, the low melting point alloy layer on the surface of the substrate becomes a protective layer that prevents the electronic conductivity of the negative electrode from decreasing and the negative electrode constituent materials from falling off due to pulverization of the substrate.
High charge/discharge efficiency can be maintained over long cycles. It goes without saying that during negative electrode charging or discharging, alkali metal ions are diffused or released into the negative electrode substrate through the low melting point alloy layer.
〈実施例〉
第１表に示した組成で各種金属を採り、これらを夫々ル
ツボに入れ、アルゴン雰囲気下で加熱溶融しつつ混合し
て低融点合金Ａ〜Ｇを作った。これら低融点合金Ａ−Ｇ
の溶融混合物中にそれぞれ、両表面をエメリー紙で研磨
しまた片面はテフロン粘着テープを貼イ４して被覆した
０、 ３ｍｍ厚のアルミニウム板を浸漬することで、ア
ルミニウム板の上記粘着テープを貼付しない面に低融点
合金Ａ−Ｇからなる合金層をそれぞれ形成したアルミニ
ウム板Ａ−Ｇを作製した。<Example> Various metals having the compositions shown in Table 1 were taken, placed in a crucible, and mixed while being heated and melted in an argon atmosphere to produce low melting point alloys A to G. These low melting point alloys A-G
The above adhesive tape was applied to the aluminum plate by dipping a 0.3 mm thick aluminum plate, both surfaces of which had been polished with emery paper and one side covered with Teflon adhesive tape, into the molten mixture. Aluminum plates A to G were prepared in which alloy layers made of low melting point alloys A to G were formed on the non-contact surfaces, respectively.
尚、これら合金層の厚さは３０μｍとなるように調整し
た。The thickness of these alloy layers was adjusted to 30 μm.
第１表
こうして得たアルミニウム板Ａ−Ｇを夫々直径１０．８
ｍｍの円板状に打ら汰いた。そしてこれらをそれぞれ、
開口径１１．０ｍｍでステンレス製で皿状の容器の内底
面にスポット溶接したステンレスネットの上に上記合金
層を上面にして載置し、次いで加圧してステンレスネッ
ト並びに容器内底面に圧着し、本発明に係る試験極Ａ−
Ｇを作った。第１図はこの試験極の構造を示し、図中１
は容器、２はステンレスネット、３は上記アルミニウム
円板からなる負極基体、４は低融点合金からなる合金層
である。Table 1 Aluminum plates A-G thus obtained each have a diameter of 10.8 mm.
It was punched into a disk shape of mm. And each of these
Place the alloy layer on top of a stainless steel net with an opening diameter of 11.0 mm spot-welded to the inner bottom surface of a dish-shaped container made of stainless steel, and then pressurize the stainless steel net and the inner bottom surface of the container, Test electrode A- according to the present invention
I made G. Figure 1 shows the structure of this test electrode.
2 is a container, 2 is a stainless steel net, 3 is a negative electrode substrate made of the above-mentioned aluminum disk, and 4 is an alloy layer made of a low melting point alloy.
次いで、これらの試験極Ａ−Ｇを人容足のりチウム−ア
ルミニウム合金を対極６とし更に金属リチウムを照合電
極７として、第２図に示したようなハーフセルＡ〜Ｇを
組立てた。尚、電解液８としては、プロピレンカーボネ
ートと４メチル−１，３ジオキソランとを体積比１：１
で混ぜた溶媒にＬ！ＰＦ６を１ ｍｏｌ／Ｊ２．溶解シ
タものを使用した。また、上記のリチウム−アルミニウ
ム合金は複連する充放電サイクル中に劣化した場合には
適宜取替えた。Next, these test electrodes A to G were used to assemble half cells A to G as shown in FIG. 2 by using a lithium-aluminum alloy as a counter electrode 6 and metal lithium as a reference electrode 7. The electrolytic solution 8 is made of propylene carbonate and 4-methyl-1,3 dioxolane in a volume ratio of 1:1.
Add L to the solvent mixed with ! PF6 at 1 mol/J2. I used the dissolved one. In addition, the above lithium-aluminum alloy was replaced as appropriate when it deteriorated during multiple charge/discharge cycles.
一方、上記の如き低融点合金からなる合金層を形成しな
いアルミニウム板を用いて作った負極基体を使用した他
は試験極Δ〜Ｇと同様にして比較用の試験極Ｈを作り、
この試験極Ｈを用いてハーフセルΔ〜Ｇと同様な構造の
ハーフセルＨを作製した。On the other hand, test electrodes H for comparison were made in the same manner as test electrodes Δ~G, except that a negative electrode substrate made of an aluminum plate without forming an alloy layer made of a low melting point alloy as described above was used.
Using this test electrode H, a half cell H having a structure similar to half cells Δ to G was manufactured.
そして、最初１ｍＡの定電流で２５時間（２５ｍＡＨ）
試験極Ａ−Ｈを充電してこれら試験極にリチウムを電着
してアルミニウムーリチウム合金化した。次いで、ハー
フセルＡ〜１−１について、１ｍＡの電流で１０時間放
電した俊に電流１ｍ八で１０時間放電するという充放電
サイクルを繰返した。第２・表に、放電時における電位
（ＶＳＬｉ／Ｌ＋ ）が１．０■に達したサイクルを
、試験極Ａ−Ｈの夫々について、それぞれ３個測定し、
その結果を示した。Then, for 25 hours (25mAH) at a constant current of 1mA at first.
Test electrodes A to H were charged and lithium was electrodeposited onto these test electrodes to form an aluminum-lithium alloy. Next, for the half cells A to 1-1, a charge/discharge cycle was repeated in which the cells were discharged at a current of 1 mA for 10 hours, and then discharged at a current of 1 mA for 10 hours. Table 2 shows three cycles in which the potential during discharge (VSLi/L+) reached 1.0■ for each of test electrodes A to H.
The results were shown.
第２表
第２表に示したように、従来品ト１に較べ本発明品Ａ−
Ｇはいずれもサイクル数が向上しており、特に試験極△
〜Ｃのような組成とするのが電極の保形効果が高く好ま
しい。Table 2 As shown in Table 2, the invention product A-
For G, the number of cycles has improved, especially for the test electrode △
It is preferable to have a composition such as -C because the shape retention effect of the electrode is high.
尚、以上はアルカリ金属としてリチウムを、またこのア
ルカリ金属イオンを可逆的に吸蔵。In the above, lithium is used as the alkali metal, and this alkali metal ion is reversibly occluded.
放出する負極基体としてアルミニウムよりなるものを用
いた例であるが、亜鉛、マグネシウム。This is an example in which a material made of aluminum is used as the emitting negative electrode substrate, but zinc and magnesium are used.
スズ、鉛、鉛−スズ合金などよ７りなる負極基体にナト
リウムやカリウムなどのアルカリ金属のイオンを可逆的
に吸蔵、放出させる負極にも同様に適用でき、同様の効
果を上げられる。The present invention can be similarly applied to negative electrodes in which ions of alkali metals such as sodium and potassium are reversibly occluded and released from a negative electrode substrate made of tin, lead, lead-tin alloy, etc., and similar effects can be achieved.
〈発明の効果〉
以上のように、この発明の非水電解液二次電池用負極は
、充放電（ノイクルに伴う負極基体の微粉化や電子伝導
性低下が抑制できて充放電り”イクル特性の向上を図れ
るという効果を奏する。<Effects of the Invention> As described above, the negative electrode for nonaqueous electrolyte secondary batteries of the present invention can suppress the pulverization of the negative electrode substrate and the decrease in electronic conductivity associated with charging and discharging (noicles), and has excellent cycle characteristics during charging and discharging. This has the effect of improving the
このため、この発明を例えばアルミニウムよりなる負極
基体にリチウムを可逆的に吸蔵、放出させる構成の負極
に適用すれば、＠扇当りの電気客足が大であること、並
びにリチウムの拡散速度が大きいといったこの負極基体
の特長を損うことなく、そのリイクル寿命を向上させる
ことができ、その工業上の利用価値は大きい。Therefore, if this invention is applied to a negative electrode having a structure in which lithium is reversibly inserted into and released from a negative electrode base made of aluminum, for example, the electric customer per fan will be large and the diffusion rate of lithium will be high. The recycle life of this negative electrode substrate can be improved without impairing its features, and its industrial utility value is great.
第１図は本発明の実施例に係る試験極の断面図、第２図
はこの試験極を用いて作製したハーフセルの説明図であ
る。
１・・・容器、３・・・負極基体、４・・・低融点合金
層。FIG. 1 is a sectional view of a test electrode according to an example of the present invention, and FIG. 2 is an explanatory diagram of a half cell manufactured using this test electrode. DESCRIPTION OF SYMBOLS 1... Container, 3... Negative electrode substrate, 4... Low melting point alloy layer.
Claims (1)
ないし合金よりなる負極基体の表面を、ＢｉとＰｂにＳ
ｎ、Ｉｎ、Ｃｄ、Ｈｇより選ばれる少なくとも１種の金
属を加えてなる低融点合金にて被覆したことを特徴とす
る非水電解液二次電池用負極。 ２、前記アルカリ金属がリチウムであることを特徴とす
る特許請求の範囲第１項記載の非水電解液二次電池用負
極。 ３、前記負極基体がアルミニウムよりなることを特徴と
する特許請求の範囲第１項記載の非水電解液二次電池用
負極。[Claims] 1. The surface of the negative electrode substrate made of a metal or alloy that reversibly occludes and releases alkali metal ions is coated with Bi and Pb.
1. A negative electrode for a non-aqueous electrolyte secondary battery, characterized in that the negative electrode is coated with a low melting point alloy formed by adding at least one metal selected from n, In, Cd, and Hg. 2. The negative electrode for a nonaqueous electrolyte secondary battery according to claim 1, wherein the alkali metal is lithium. 3. The negative electrode for a non-aqueous electrolyte secondary battery according to claim 1, wherein the negative electrode base is made of aluminum.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62108518A JPS63274058A (en) | 1987-05-01 | 1987-05-01 | Negative electrode for nonaqueous electrolyte secondary battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62108518A JPS63274058A (en) | 1987-05-01 | 1987-05-01 | Negative electrode for nonaqueous electrolyte secondary battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS63274058A true JPS63274058A (en) | 1988-11-11 |
Family
ID=14486825
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62108518A Pending JPS63274058A (en) | 1987-05-01 | 1987-05-01 | Negative electrode for nonaqueous electrolyte secondary battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63274058A (en) |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000024070A1 (en) * | 1998-10-22 | 2000-04-27 | Matsushita Electric Industrial Co., Ltd. | Secondary cell having non-aqueous electrolyte |
| WO2000033400A1 (en) * | 1998-12-02 | 2000-06-08 | Matsushita Electric Industrial Co., Ltd. | Non-aqueous electrolyte secondary cell |
| JP2001102052A (en) * | 1999-10-01 | 2001-04-13 | Matsushita Electric Ind Co Ltd | Secondary cell of non-aqueous electrolyte |
| US6506520B1 (en) | 1998-12-02 | 2003-01-14 | Matsushita Electric Industrial Co., Ltd. | Non-aqueous electrolyte secondary battery |
| US6605386B1 (en) | 1998-12-02 | 2003-08-12 | Matsushita Electric Industrial Co., Ltd. | Non-aqueous electrolyte secondary battery comprising composite particles |
| US6653019B1 (en) | 1998-06-03 | 2003-11-25 | Matsushita Electric Industrial Co., Ltd. | Non-aqueous electrolyte secondary cell |
| US6821675B1 (en) | 1998-06-03 | 2004-11-23 | Matsushita Electric Industrial Co., Ltd. | Non-Aqueous electrolyte secondary battery comprising composite particles |
| EP1100134A4 (en) * | 1999-03-31 | 2005-03-23 | Matsushita Electric Ind Co Ltd | Nonaqueous electrolyte secondary cell and its negative plate |
| JP2005129254A (en) * | 2003-10-21 | 2005-05-19 | Daiwa Fine Chemicals Co Ltd (Laboratory) | Negative electrode for lithium secondary battery |
| EP1302994A4 (en) * | 2000-07-19 | 2006-01-25 | Matsushita Electric Ind Co Ltd | Non-aqueous electrolyte secondary cell |
| JP2012142297A (en) * | 1995-06-28 | 2012-07-26 | Ube Ind Ltd | Nonaqueous secondary battery |
-
1987
- 1987-05-01 JP JP62108518A patent/JPS63274058A/en active Pending
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012142297A (en) * | 1995-06-28 | 2012-07-26 | Ube Ind Ltd | Nonaqueous secondary battery |
| US6653019B1 (en) | 1998-06-03 | 2003-11-25 | Matsushita Electric Industrial Co., Ltd. | Non-aqueous electrolyte secondary cell |
| US6821675B1 (en) | 1998-06-03 | 2004-11-23 | Matsushita Electric Industrial Co., Ltd. | Non-Aqueous electrolyte secondary battery comprising composite particles |
| US6265111B1 (en) | 1998-10-22 | 2001-07-24 | Matsushita Electric Industrial Co., Ltd. | Non-aqueous electrolyte secondary battery |
| WO2000024070A1 (en) * | 1998-10-22 | 2000-04-27 | Matsushita Electric Industrial Co., Ltd. | Secondary cell having non-aqueous electrolyte |
| US6506520B1 (en) | 1998-12-02 | 2003-01-14 | Matsushita Electric Industrial Co., Ltd. | Non-aqueous electrolyte secondary battery |
| US6605386B1 (en) | 1998-12-02 | 2003-08-12 | Matsushita Electric Industrial Co., Ltd. | Non-aqueous electrolyte secondary battery comprising composite particles |
| WO2000033400A1 (en) * | 1998-12-02 | 2000-06-08 | Matsushita Electric Industrial Co., Ltd. | Non-aqueous electrolyte secondary cell |
| EP1100134A4 (en) * | 1999-03-31 | 2005-03-23 | Matsushita Electric Ind Co Ltd | Nonaqueous electrolyte secondary cell and its negative plate |
| JP2001102052A (en) * | 1999-10-01 | 2001-04-13 | Matsushita Electric Ind Co Ltd | Secondary cell of non-aqueous electrolyte |
| JP4635283B2 (en) * | 1999-10-01 | 2011-02-23 | パナソニック株式会社 | Nonaqueous electrolyte secondary battery |
| EP1302994A4 (en) * | 2000-07-19 | 2006-01-25 | Matsushita Electric Ind Co Ltd | Non-aqueous electrolyte secondary cell |
| JP2005129254A (en) * | 2003-10-21 | 2005-05-19 | Daiwa Fine Chemicals Co Ltd (Laboratory) | Negative electrode for lithium secondary battery |
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