JPH03182049A - Negative electrode for secondary battery - Google Patents
Negative electrode for secondary batteryInfo
- Publication number
- JPH03182049A JPH03182049A JP1320605A JP32060589A JPH03182049A JP H03182049 A JPH03182049 A JP H03182049A JP 1320605 A JP1320605 A JP 1320605A JP 32060589 A JP32060589 A JP 32060589A JP H03182049 A JPH03182049 A JP H03182049A
- Authority
- JP
- Japan
- Prior art keywords
- aluminum
- lithium
- negative electrode
- alloy
- layer
- 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
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 51
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 50
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 49
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 46
- 239000000758 substrate Substances 0.000 claims abstract description 13
- JFBZPFYRPYOZCQ-UHFFFAOYSA-N [Li].[Al] Chemical compound [Li].[Al] JFBZPFYRPYOZCQ-UHFFFAOYSA-N 0.000 claims description 4
- 238000010030 laminating Methods 0.000 claims description 4
- 229910002056 binary alloy Inorganic materials 0.000 claims 1
- 229910045601 alloy Inorganic materials 0.000 abstract description 23
- 239000000956 alloy Substances 0.000 abstract description 23
- 238000005275 alloying Methods 0.000 abstract description 17
- 229910000838 Al alloy Inorganic materials 0.000 abstract description 11
- 238000007599 discharging Methods 0.000 abstract description 4
- 239000013078 crystal Substances 0.000 abstract description 2
- 230000001815 facial effect Effects 0.000 abstract 1
- 239000000463 material Substances 0.000 description 19
- 238000000034 method Methods 0.000 description 17
- 239000003792 electrolyte Substances 0.000 description 11
- 229910000733 Li alloy Inorganic materials 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 7
- 239000008151 electrolyte solution Substances 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- -1 Na5C N Inorganic materials 0.000 description 4
- 239000011888 foil Substances 0.000 description 4
- 239000011255 nonaqueous electrolyte Substances 0.000 description 4
- 238000007740 vapor deposition Methods 0.000 description 4
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 3
- 229920000767 polyaniline Polymers 0.000 description 3
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 3
- QENGPZGAWFQWCZ-UHFFFAOYSA-N 3-Methylthiophene Chemical compound CC=1C=CSC=1 QENGPZGAWFQWCZ-UHFFFAOYSA-N 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- 229910013075 LiBF Inorganic materials 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 239000003125 aqueous solvent Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 229920001940 conductive polymer Polymers 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 239000011133 lead Substances 0.000 description 2
- 150000002641 lithium Chemical class 0.000 description 2
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 description 2
- 229910001486 lithium perchlorate Inorganic materials 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- LZDKZFUFMNSQCJ-UHFFFAOYSA-N 1,2-diethoxyethane Chemical compound CCOCCOCC LZDKZFUFMNSQCJ-UHFFFAOYSA-N 0.000 description 1
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 description 1
- KZVBBTZJMSWGTK-UHFFFAOYSA-N 1-[2-(2-butoxyethoxy)ethoxy]butane Chemical compound CCCCOCCOCCOCCCC KZVBBTZJMSWGTK-UHFFFAOYSA-N 0.000 description 1
- JRRDISHSXWGFRF-UHFFFAOYSA-N 1-[2-(2-ethoxyethoxy)ethoxy]-2-methoxyethane Chemical compound CCOCCOCCOCCOC JRRDISHSXWGFRF-UHFFFAOYSA-N 0.000 description 1
- YZWVMKLQNYGKLJ-UHFFFAOYSA-N 1-[2-[2-(2-ethoxyethoxy)ethoxy]ethoxy]-2-methoxyethane Chemical compound CCOCCOCCOCCOCCOC YZWVMKLQNYGKLJ-UHFFFAOYSA-N 0.000 description 1
- RRQYJINTUHWNHW-UHFFFAOYSA-N 1-ethoxy-2-(2-ethoxyethoxy)ethane Chemical compound CCOCCOCCOCC RRQYJINTUHWNHW-UHFFFAOYSA-N 0.000 description 1
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 description 1
- 229910001558 CF3SO3Li Inorganic materials 0.000 description 1
- 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
- 229910000713 I alloy Inorganic materials 0.000 description 1
- 229910000846 In alloy Inorganic materials 0.000 description 1
- 229910020261 KBF4 Inorganic materials 0.000 description 1
- 229910007909 Li-Al-Mg Inorganic materials 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 229910008472 Li—Al—Mg Inorganic materials 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910003092 TiS2 Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- 239000001989 lithium alloy Substances 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 229910052960 marcasite Inorganic materials 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920000128 polypyrrole Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- NIFIFKQPDTWWGU-UHFFFAOYSA-N pyrite Chemical compound [Fe+2].[S-][S-] NIFIFKQPDTWWGU-UHFFFAOYSA-N 0.000 description 1
- 229910052683 pyrite Inorganic materials 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- BAZAXWOYCMUHIX-UHFFFAOYSA-M sodium perchlorate Chemical compound [Na+].[O-]Cl(=O)(=O)=O BAZAXWOYCMUHIX-UHFFFAOYSA-M 0.000 description 1
- 229910001488 sodium perchlorate Inorganic materials 0.000 description 1
- 229910001495 sodium tetrafluoroborate Inorganic materials 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 238000004804 winding Methods 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］ 本発明は二次電池用負極に関する。[Detailed description of the invention] [Industrial application field] The present invention relates to a negative electrode for secondary batteries.
［従来の技術］
近年充放電可能な高エネルギー密度電池としてリチウム
二次電池が注目されている。このリチウム二次電池の負
極活物質として金属リチウムを使用した場合、充放電に
よって電池負極にはデンドライトが発生したり活性を失
ったモス状リチウムが析出するなどの問題点があり、電
解液組成物あるいは負極リチウムの合金化が検討されて
いる。後者は負極リチウムの問題点を確実に解決する方
法として注目される。リチウム合金を形成する元素とし
てはアルミニウム、シリコン、スズ、マグネシウム、亜
鉛、鉛などが挙げられるがリチウムとアルミニウムの合
金化は反応も容易に進行し、又リチウムの吸蔵量、電極
の軽量性にも優れている。しかしリチウム／アルミニウ
ムを主体とする合金はリチウムとアルミニウムの合金化
比率により各種の性状のものができる。冶金学的方法で
作製された合金ではリチウム比率がｌＯａｔｏｇｆｃ％
以下では高い強度をもつ安定な構造材料として用いられ
る。[Prior Art] In recent years, lithium secondary batteries have attracted attention as high energy density batteries that can be charged and discharged. When metallic lithium is used as the negative electrode active material of this lithium secondary battery, there are problems such as the formation of dendrites on the battery negative electrode and the precipitation of moss-like lithium that has lost its activity during charging and discharging. Alternatively, alloying the negative electrode lithium is being considered. The latter is attracting attention as a way to reliably solve the problems of negative electrode lithium. Elements that form lithium alloys include aluminum, silicon, tin, magnesium, zinc, lead, etc. The reaction of alloying lithium and aluminum progresses easily, and the amount of lithium absorbed and the weight of the electrode are also affected. Are better. However, alloys mainly composed of lithium/aluminum can have various properties depending on the alloying ratio of lithium and aluminum. In alloys made by metallurgical methods, the lithium proportion is lOatogfc%.
Below, it is used as a stable structural material with high strength.
リチウム比率が８０ａｔｏｍｉｃ％以上ではＬｉ中にリ
チウム／アルミ合金が分散された状態のものが得られ、
この範囲ではリチウムの延展性が保持されているがいず
れもリチウムイオンを吸蔵する電極としては適していな
い。When the lithium ratio is 80 atomic% or more, a state in which lithium/aluminum alloy is dispersed in Li is obtained,
Within this range, the malleability of lithium is maintained, but neither is suitable as an electrode for storing lithium ions.
しかし、この２つの領域にはさまれた１０〜８０％ノ領
域ではα、β、γ層を有するリチウム／アルミニウム合
金が塊状粉末状態として得られ、電池電極としては本組
成の合金を利用することになる。However, in the 10-80% region between these two regions, a lithium/aluminum alloy having α, β, and γ layers is obtained as a lumpy powder, and it is difficult to use an alloy with this composition as a battery electrode. become.
上述したように冶金学的方法では自己保持性を持った合
金が得られないために電極としては次のような方法で作
製された合金が使用されている。As mentioned above, alloys with self-retention properties cannot be obtained by metallurgical methods, so alloys produced by the following method are used as electrodes.
（１）リチウム塩を含む非水電解液中で合金化対象金属
にリチウムを電着して合金化する電気化学的製造方法、
（２）充分な厚みをもったアルミニウム基板上になリチ
ウムを貼り合わせた後加熱処理を行いアルミニウム基板
表面を合金化する方法、（３） （２）の貼り合わせ
を電解液中で電気化学的処理により合金化する方法、
（４）リチウムとアルミニウムを電解液を介在させて接
触させることによりアルミニウム表面を合金化せしめる
方法
しかしながら、こうして得られた従来のリチウム／アル
ミニウム合金では二次電池用負極として用いた場合に、
広い放電電流範囲において正極のエネルギーを十分に取
り出すことができず、合金層の厚みを厚くしないと充放
電サイクル特性においても未だ不十分である。(1) An electrochemical production method in which lithium is electrodeposited on the metal to be alloyed in a non-aqueous electrolyte containing lithium salt to form an alloy. (2) Lithium is pasted on an aluminum substrate with sufficient thickness. (3) A method of alloying the aluminum substrate surface by heat treatment after bonding, (3) A method of alloying the bonded material of (2) by electrochemical treatment in an electrolytic solution, (4) A method of alloying the bonded layer of (2) with an electrolytic solution. However, when the conventional lithium/aluminum alloy obtained in this way is used as a negative electrode for a secondary battery,
It is not possible to sufficiently extract the energy of the positive electrode in a wide discharge current range, and the charge/discharge cycle characteristics are still insufficient unless the thickness of the alloy layer is increased.
又、上述のリチウム／アルミニウム合金とアルミニウム
の積層体は合金層がもろいためにアルミニウム基材の表
面から脱落してしまうなどの問題もあり、リチウムの充
分な拡散層を有し、かつシート状として十分な性能を有
するものは現在のところ得られていない。In addition, the above-mentioned laminate of lithium/aluminum alloy and aluminum has problems such as the alloy layer falling off the surface of the aluminum base material due to its brittleness. At present, no one with sufficient performance has been obtained.
［発明が解決しようとする課題］
本発明は、こうした実情に鑑み、高エネルギー密度をも
ち、充放電特性にも優れた二次電池用の負極を提供する
ことを目的とするものである。[Problems to be Solved by the Invention] In view of these circumstances, an object of the present invention is to provide a negative electrode for a secondary battery that has high energy density and excellent charge/discharge characteristics.
［課題を解決するための手段］
本発明者らは、前記した課題を解決するため鋭意検討し
てきた結果、リチウムと合金化するアルミニウム基板と
して、面の垂直方向に（１００）面を有するアルミニウ
ムを用いることにより、自己保存性、電池の充放電サイ
クル性能に優れた負極が得られることを見い出し本発明
に至った。ＬｉとＡＩの比率がほぼ１：１のβ層の特性
を有するリチウム／アルミニウム合金層が形成され、結
晶が面方向にそろっているため合金化が均一に進みかつ
合金化による厚みの変化が少なく、合金層の脱落が防止
された積層体が得られる。[Means for Solving the Problems] As a result of intensive studies to solve the problems described above, the present inventors have developed an aluminum substrate having a (100) plane in the direction perpendicular to the surface as an aluminum substrate to be alloyed with lithium. The present inventors have discovered that by using this material, a negative electrode with excellent self-preservability and battery charge/discharge cycle performance can be obtained, leading to the present invention. A lithium/aluminum alloy layer with the characteristics of a β layer with a ratio of Li to AI of approximately 1:1 is formed, and because the crystals are aligned in the plane direction, alloying progresses uniformly and there is little change in thickness due to alloying. , a laminate in which the alloy layer is prevented from falling off is obtained.
すなわち、本発明は、少なくともリチウム層をアルミニ
ウム基板上にＶＩＸ着積層積層ことにより得られるリチ
ウム−アルミニウムの少なくとも２元合金（以下リチウ
ム／アルミニウム合金と呼ぶ）と、アルミニウムの積層
体からなる二次電池用負極に関するものであり、当該ア
ルミニウム基板が面に対して垂直方向に（１００）面を
有する二次電池用負極である。That is, the present invention provides a secondary battery comprising a laminate of at least a binary lithium-aluminum alloy (hereinafter referred to as lithium/aluminum alloy) obtained by laminating at least a lithium layer on an aluminum substrate by VIX deposition, and aluminum. This is a negative electrode for a secondary battery in which the aluminum substrate has a (100) plane in a direction perpendicular to the plane.
更に本電極を単３スパイラル型電池ベーパー電池に用い
る場合には屈曲によるＬ ｉ ／ Ａ Ｉ合金層の脱落
には更にきびしい要求があり、本電極の合金層を３５〜
６０μ−の範囲にすることにより充放電性能を確保する
のみならずフレキシビリティ−が確保されることが要求
される。Furthermore, when this electrode is used in an AA spiral type vapor battery, there are even more stringent requirements to prevent the Li/A I alloy layer from falling off due to bending, and the alloy layer of this electrode is
It is required to ensure not only charging and discharging performance but also flexibility by setting the range to 60μ.
本発明の負極は、（１００）面を有するアルミニウム基
材の上に、リチウムを主体とする金属を積層した後、合
金化処理をすることによりアルミニウム基材を残したま
まリチウム／アルミニウムの少なくとも２元合金層を形
成することとにより得られる。The negative electrode of the present invention is produced by laminating a metal mainly composed of lithium on an aluminum base material having a (100) plane, and then performing an alloying treatment to form at least two layers of lithium/aluminum while leaving the aluminum base material. It is obtained by forming a base alloy layer.
本発明に使用するアルミニウム基材は主に（１００）面
を５０％以上有する高純度アルミニウムで厚みは５０μ
ｍ以上が好ましい。５０μｍ以下では（１００）面の結
晶化を５０％以上にすることは難しく、特に高表面積多
孔体を作製する場合には基材の強度を保つ上で好ましく
ない。The aluminum base material used in the present invention is mainly high-purity aluminum having 50% or more (100) planes and has a thickness of 50 μm.
m or more is preferable. If the diameter is less than 50 μm, it is difficult to increase the crystallization of the (100) plane to 50% or more, which is not preferable in order to maintain the strength of the base material, especially when producing a high surface area porous body.
本発明におけるリチウム／アルミニウムの少なくとも２
元合金を得るためにはリチウムを主体とする金属、すな
わちリチウムの他、リチウムを８０ａｔｏｍｉｃ％以上
含有する合金又は混合金属例えばＬｉ−Ａ１％ Ｌｉ−
３ｉＳＬｉ−３ｎ。At least two of lithium/aluminum in the present invention
In order to obtain the original alloy, in addition to a metal mainly containing lithium, that is, an alloy or mixed metal containing 80 atomic% or more of lithium, such as Li-A1% Li-
3iSLi-3n.
Ｌｉ−Ａｌ−Ｍｇ、Ｌｉ−Ｎａ−Ｐｂ等を積層すること
により得られる。又蒸着法により形成する場合には蒸着
が可能な低融点、リチウム含有金属を直接蒸着すること
が好ましい。又Ｍｇ、Ｚｎなどをおいおい蒸着した後リ
チウムを蒸着することも可能である。このようなリチウ
ム／金属／アルミニウム積層体の合金化の方法としては
、上述した （１）〜（４）の方法により行われる他、
蒸着法により形成されたリチウムを主体とする金属層を
（２）又は（３）の方法に準じて合金化する方法がとら
れる。It can be obtained by laminating Li-Al-Mg, Li-Na-Pb, etc. In addition, when forming by a vapor deposition method, it is preferable to directly vapor deposit a low melting point, lithium-containing metal that can be vapor deposited. It is also possible to deposit lithium after depositing a large amount of Mg, Zn, etc. As a method for alloying such a lithium/metal/aluminum laminate, in addition to methods (1) to (4) described above,
A method is used in which a metal layer mainly composed of lithium formed by vapor deposition is alloyed according to method (2) or (3).
（２）又は（４）の貼り合わせの場合にはリチウムを主
体とする金属層と（１００）而を有するアルミニウムと
を貼り合わせた後、非水電解液中で直流又は交流を印加
することにより合金化する１Ｇ気化学的方広、あるいは
リチウムの融点以下の温度で加熱することにより合金化
する加熱法が有効である。又シート状負極とする場合に
は貼り合わせでは合金層が厚くなり可撓性がなくなるた
め（１００）面を有するアルミニウムシート基村上にリ
チウムを蒸着し、その後加熱あるいは電解液中で直流あ
るいは交流を印加することにより合金化する方法、リチ
ウムとアルミニウムを電解液を介して接触により得られ
る（４〉の方法により得られる。In the case of bonding (2) or (4), after bonding a metal layer mainly composed of lithium and aluminum having (100), by applying direct current or alternating current in a non-aqueous electrolyte. A 1G vapor chemical square for alloying or a heating method for alloying by heating at a temperature below the melting point of lithium is effective. In addition, in the case of forming a sheet negative electrode, since the alloy layer becomes thick and loses flexibility when laminated, lithium is vapor-deposited on an aluminum sheet base layer having a (100) plane, and then heated or subjected to direct current or alternating current in an electrolytic solution. It can be obtained by the method of alloying by applying an electric current, and the method of contacting lithium and aluminum through an electrolytic solution (method 4).
（１００）面をもたない一般のアルミニウムではアルミ
ニウム表面の酸化被膜層を除去しないと合金化が起らな
いのに対して（１００）面を有するアルミニウムではそ
のままの状態でリチウムと接触させるだけで迅速に合金
化せしめることが可能である。In general aluminum, which does not have a (100) plane, alloying does not occur unless the oxide film layer on the aluminum surface is removed, but with aluminum, which has a (100) plane, it can be simply brought into contact with lithium in its original state. It is possible to alloy quickly.
特に本アルミニウム基材をエツチングした多孔質基材は
０００）面にそってエツチングピットが面に対して垂直
にエツチングされるため基材強度が保たれる。この多孔
体を表面を均一に合金化するためには蒸着法が好ましく
本方法によればシート状多孔質基材表面にβ層のリチウ
ムアルミ合金を形成させることができ、かつ強度も保た
れる。最も好ましくはエツチングした箔の表面を１μｍ
以下の範囲で化成処理したものはリチウムを蒸着した後
の合金化の条件がマイルドであるため均質合金層を得る
上で適している。１μｍを越えると電極抵抗が大となる
ため好ましくない。又電池用電極と使用した場合面に垂
直にビットが存在しているため高比表面積化がなされ、
これにより電極表面の電流密度による負担が軽威される
。In particular, in the porous base material obtained by etching the present aluminum base material, the strength of the base material is maintained because the etching pits are etched along the 000) plane perpendicularly to the plane. In order to uniformly alloy the surface of this porous body, the vapor deposition method is preferable. According to this method, a β-layer lithium-aluminum alloy can be formed on the surface of the sheet-like porous base material, and the strength can also be maintained. . Most preferably, the surface of the etched foil is 1 μm thick.
Those subjected to chemical conversion treatment within the following range are suitable for obtaining a homogeneous alloy layer because the conditions for alloying after lithium vapor deposition are mild. If it exceeds 1 μm, the electrode resistance becomes large, which is not preferable. In addition, when used with battery electrodes, the bits are perpendicular to the surface, resulting in a high specific surface area.
This reduces the burden of current density on the electrode surface.
かくして得られたリチウム／アルミニウム合金の層厚は
基材のアルミニウムに対して、８０％以下であることが
望まれる。８０％以上であれば基材そのものの役割が失
われる。従ってアルミニウム基材の両面を含金化したと
しても、アルミニウム基材は総厚の２０％以上残在させ
る必要がある。この場合、基材が（１００）面を５０％
以上有することのない場合にはほとんど自己保持性はな
く、大面積のシート型電池、スパイラル実装の筒型電池
として、実装することは不可能である。The layer thickness of the lithium/aluminum alloy thus obtained is desirably 80% or less of the aluminum of the base material. If it exceeds 80%, the role of the base material itself is lost. Therefore, even if both sides of the aluminum base material are metallized, the aluminum base material must remain at least 20% of the total thickness. In this case, the base material has a (100) plane of 50%
If the battery does not have the above characteristics, it has almost no self-retention properties, and it is impossible to mount it as a large-area sheet-type battery or a spiral-mounted cylindrical battery.
又本基材を使用した場合には本基材との組み合わせによ
り得られた合金層の電位はリチウムに対して０．３５０
〜０．３９０ Ｖの範囲を示しリチウムとアルミニウム
の合金化がほぼ１：１で進行しβ層を形成していること
を示している。In addition, when this base material is used, the potential of the alloy layer obtained in combination with this base material is 0.350 with respect to lithium.
~0.390 V, indicating that alloying of lithium and aluminum progresses at a ratio of approximately 1:1 to form a β layer.
本発明の負極を使用してリチウム二次電池とすることが
できるが、このリチウム二次電池の基本構成は、前記負
極と正極及び電解液からなり必要に応じてセパレータ、
固体電解質を用いることができる。A lithium secondary battery can be made using the negative electrode of the present invention, and the basic structure of this lithium secondary battery consists of the negative electrode, the positive electrode, and an electrolyte, and if necessary, a separator,
Solid electrolytes can be used.
非水電解液としては電解質塩を非水溶媒に溶解させたも
のが用いられ、電解質塩としては通常の非水電解液電池
に用いるものであれば特に制限はないが、例えばＬｉＣ
ＩＯ４、ＬｉＢＦ＋、ＬｉＡｓＦａ、ＬｉＰＦｂ、Ｌｉ
ＳｂＦ６ ＬｉＣＦ：＋５Ｏ３
ＣＦ３００Ｌｉ、ＮａＣｌＯ４、ＮａＢＦ４、Ｎａ５Ｃ
Ｎ、ＫＢＦ４、（ＢＵ）４ＮＢＦ４ （Ｅｔ）４−Ｎ
Ｂ Ｆ４ （ＢＬＩ） ４ ＮＣｌＯ４（Ｂｕ） ４
ＮＣｌＯ４等の一種あるいは二種以上の塩を用いること
ができる。As the non-aqueous electrolyte, an electrolyte salt dissolved in a non-aqueous solvent is used, and the electrolyte salt is not particularly limited as long as it is used in normal non-aqueous electrolyte batteries, but for example, LiC
IO4, LiBF+, LiAsFa, LiPFb, Li
SbF6 LiCF: +5O3 CF300Li, NaClO4, NaBF4, Na5C
N, KBF4, (BU)4NBF4 (Et)4-N
B F4 (BLI) 4 NClO4 (Bu) 4
One or more salts such as NClO4 can be used.
本負極との組合せにおいてはＬｉＣｌＯ４、ＣＦｚＳＯ
３Ｌｉが特に好ましく充放電効率を飛躍的に上昇せしめ
ることが可能である。In combination with this negative electrode, LiClO4, CFzSO
3Li is particularly preferable and can dramatically increase charge/discharge efficiency.
非水溶媒としては、プロピレンカーボネート、γ−ブチ
ルラクトン、エチレンカーボネート、スルホラン、ジオ
キソラン、テトラヒドロフラン、２メチルテトラヒドロ
フラン、ジメチルスルホキシド、及び１．２−ジメトキ
シエタン、１゜２−エトキシメトキシエタン、メチルジ
グライム、メチルトリグライム、メチルテトラグライム
、エチルグライム、エチルジグライム、ブチルジグライ
ムを例示することができるが、プロピレンカーボネート
、γ−ブチルラクトン及び又はグライム類の組み合わせ
が電気伝導度、無機塩の溶解性の点で最も好ましく、本
負極との組合せにおいてはγ−ＢＬを主体とした溶媒組
成が充放電効率を高める上で特に好ましい。電解質垣の
濃度はＣ１，５Ｍ〜７Ｍ、好ましくは１Ｍ〜５Ｍである
。Examples of non-aqueous solvents include propylene carbonate, γ-butyl lactone, ethylene carbonate, sulfolane, dioxolane, tetrahydrofuran, 2methyltetrahydrofuran, dimethylsulfoxide, and 1,2-dimethoxyethane, 1°2-ethoxymethoxyethane, methyl diglyme, Examples include methyl triglyme, methyl tetraglyme, ethyl glyme, ethyl diglyme, and butyl diglyme, but combinations of propylene carbonate, γ-butyl lactone, and/or glymes improve electrical conductivity and solubility of inorganic salts. In this respect, it is most preferable, and in combination with the present negative electrode, a solvent composition mainly composed of γ-BL is particularly preferable in terms of increasing charge/discharge efficiency. The concentration of the electrolyte wall is C1.5M to 7M, preferably 1M to 5M.
本発明における電池用正極活物質としては、ＴｉＳ２、
Ｎｂ５Ｓ４、ＭｏｚＳ４、Ｃ０８２、ＦｅＳ２、Ｖ２Ｏ
５、Ｃｒ２０Ｃｒ２０ｓＳ等のカルフゲナイト化合物、
及び無機酸化物、ポリアニリン、ポリピロール、ポリ
３メチルチオフエン、ポリジフェニルベンジン等の導電
性高分子を挙げることができる。As the positive electrode active material for batteries in the present invention, TiS2,
Nb5S4, MozS4, C082, FeS2, V2O
5, calfgenite compounds such as Cr20Cr20sS,
and inorganic oxides, polyaniline, polypyrrole, poly
Examples include conductive polymers such as 3-methylthiophene and polydiphenylbenzine.
高分子の活物質においては電解液中の電解質はドーピン
グ量に相当する以上溶解せしめる必要があり、高濃度で
かつ液の含有量も高いことが望まれる。In the case of a polymer active material, it is necessary to dissolve the electrolyte in the electrolytic solution in an amount equivalent to the amount of doping, and it is desirable that the electrolyte be highly concentrated and have a high content.
これらの正極、電解液の各要素は特に限定されるもので
はないが、正極に導電性高分子材料、電解質塩がＣＦ３
Ｓ０３ Ｌｉ、ＬｉＣｌＯ４、溶媒にγ−ＢＬを使用
した電池系の場合、本負極はサイクル特性が飛躍的に向
上する。The elements of the positive electrode and electrolyte are not particularly limited, but the positive electrode may include a conductive polymer material and an electrolyte salt of CF3.
In the case of a battery system using S03 Li, LiClO4, and γ-BL as a solvent, the cycle characteristics of this negative electrode are dramatically improved.
［実施例］
負極製造例１
（１００）面を９３％を有する厚さ３００μ膠のアルミ
ニウムと １００μ四のリチウムホイルを圧着してホッ
トプレートによりアルミニウム面から １５０℃で１５
秒加熱した。その結果アルミニウムとリチウムアルミニ
ウム合金の積層体が得られた。[Example] Negative electrode production example 1 A 300μ thick aluminum having 93% (100) surface and a 100μ4 lithium foil were pressed together and heated from the aluminum surface using a hot plate at 150°C for 15 minutes.
Heated for seconds. As a result, a laminate of aluminum and lithium aluminum alloy was obtained.
合金層の厚みは約１２０μｍ、電極の総厚は４０５μ−
であった（負極Ａ−１）。The thickness of the alloy layer is approximately 120 μm, and the total thickness of the electrode is 405 μm.
(Negative electrode A-1).
負極製造例２
（１００）面を５５％有する厚さ７０μｌのアルミニウ
ム表面に１モルのＬｉＢＦ＋を溶解せしめたプロピレン
カーボネート／ジメトキシエタン７対３溶液を均一に滴
下し５０μ■のリチウム箔と約１５分間接触してアルミ
ニウム表面の両面を合金化した。Negative electrode production example 2 A 7:3 solution of propylene carbonate/dimethoxyethane in which 1 mol of LiBF+ was dissolved was evenly dropped onto a 70 μl thick aluminum surface with 55% (100) surface and lithium foil of 50 μl for about 15 minutes. The contact alloyed both sides of the aluminum surface.
合金層の厚みは片面で１５μｍ、電極の総厚は８５μ厘
であった（負極Ａ−２）。The thickness of the alloy layer was 15 μm on one side, and the total thickness of the electrode was 85 μm (negative electrode A-2).
負極製造例３
（１００）面を５５％有する厚さ７０μ厘のアルミニウ
ム表面に片面で２０μ−厚になるようにリチウムを両面
に蒸着した。その後赤外線により表面温度を１６０℃に
加熱してアルミニウム表面を合金化した。合金層の厚み
は片面で２２μｍ電極の総厚は９８μ−であった（負極
Ａ−３）。Negative Electrode Production Example 3 Lithium was deposited on both sides of an aluminum surface having a thickness of 70 μm and having 55% (100) planes so that one side had a thickness of 20 μm. Thereafter, the aluminum surface was alloyed by heating the surface temperature to 160° C. using infrared rays. The thickness of the alloy layer was 22 μm on one side, and the total thickness of the electrode was 98 μ− (negative electrode A-3).
負極製造例４
（１００）面を６８％有する厚さ７５μ■のアルミニウ
ム箔を電気化学的にエツチングして面に垂直方向に無数
のピットを形成した。これに片面で２０μ■厚になるよ
うにリチウムを両面に蒸着した。Negative Electrode Production Example 4 A 75 μm thick aluminum foil having 68% (100) planes was electrochemically etched to form numerous pits in the direction perpendicular to the plane. Lithium was deposited on both sides of this to a thickness of 20 μm on one side.
そして加熱炉内で１４０℃で加熱してピット内までも合
金化した。合金層の厚みは片面で２５μ■電極の総厚み
は１０２μ■であった（負極へ−４）。Then, it was heated at 140° C. in a heating furnace to form an alloy even in the pits. The thickness of the alloy layer was 25 μι on one side, and the total thickness of the electrode was 102 μι (−4 to the negative electrode).
比較としての負極製造例
Ｘ線回折により（１００）面をほとんど検出できないア
ルミニウムシート［（１１０）面を有する］を用いた他
は負極製造例１〜４と同様にして製造した負極をそれぞ
れ順番にＢ−１、Ｂ−２、Ｂ−３、Ｂ−４とした。Negative electrode manufacturing example as a comparison Negative electrodes were manufactured in the same manner as negative electrode manufacturing examples 1 to 4, except that an aluminum sheet [having a (110) plane] in which the (100) plane could hardly be detected by X-ray diffraction was used. They were designated as B-1, B-2, B-3, and B-4.
［各負極のリチウムに対する自然電位］ＶｖｓＬＩ／Ｌ
ｌ”
実施例１
電解二酸化マンガン焼結体（０，１ｇ）に２５％のアセ
チレンブラック ５％のＰＴＦＥを添加し、ペースト状
にしたものから真空加圧により厚さ０．６ａ＋ １．［
ｉｎｍφの正極合剤ベレットを作製した、セパレータ（
ジュラガード２５００） 、電解液として１ＭＬｉＰＦ
６を溶解させたＰＣ／ＥＭＥ（７／３） 、負極にはＡ
−１を用いて２０１６タイプのコイン型電池を作製した
。[Natural potential of each negative electrode with respect to lithium] VvsLI/L
Example 1 25% acetylene black and 5% PTFE were added to electrolytic manganese dioxide sintered body (0.1g), and the paste was made into a paste with a thickness of 0.6a+1.[
Separator (
Duraguard 2500), 1MLiPF as electrolyte
PC/EME (7/3) in which 6 was dissolved, A for the negative electrode
A 2016 type coin-type battery was produced using -1.
実施例２
ポリアニリン０．２１ｇを４０Ｘ ２１０ａｖのステン
レスシート（厚さ２０μ編〉上に電解重合法により析出
せしめたポリアニリンシート電極を正極にセパレータ（
ジュラガード２５００）負極にはＡ−２を用いて捲回し
単３型の実装を行った電解液として３Ｍ ＬｉＣＩＯ
４を溶解させたγ−ブチルラクトン溶液を用いた。Example 2 A polyaniline sheet electrode in which 0.21 g of polyaniline was deposited on a 40×210 av stainless steel sheet (thickness 20 μm) by electrolytic polymerization was used as a positive electrode and a separator (
Duraguard 2500) For the negative electrode, 3M LiCIO was used as the electrolyte for winding and AA type mounting using A-2.
A γ-butyllactone solution in which 4 was dissolved was used.
実施例３
負極にＡ−４を用い電解質として
ＣＦ３ＳＯ３Ｌｉを用いた他は実施例２と同様にして単
３型電池を製作した。Example 3 An AA battery was produced in the same manner as in Example 2, except that A-4 was used as the negative electrode and CF3SO3Li was used as the electrolyte.
比較例１〜３
実施例１〜３の負極をそれぞれ順番にＢ−１、Ｂ−２、
Ｂ−４を用いたものを比較例１．２．３とした。Comparative Examples 1 to 3 The negative electrodes of Examples 1 to 3 were sequentially B-1, B-2,
Comparative Example 1.2.3 used B-4.
［発明の効果〕
以上説明したように、本発明の負極を用いることにより
、エネルギー密度、容量が大きく、しかも充放電特性に
優れたリチウム二次電池を得ることができる。[Effects of the Invention] As explained above, by using the negative electrode of the present invention, a lithium secondary battery with high energy density and capacity and excellent charge/discharge characteristics can be obtained.
Claims (2)
層することにより得られるリチウム−アルミニウムの少
なくとも２元合金と、アルミニウムの積層体からなる二
次電池用負極において、当該アルミニウム基板が主に（
１００）面を有することを特徴とするシート状二次電池
用負極。(1) In a negative electrode for a secondary battery consisting of a laminate of aluminum and at least a binary alloy of lithium-aluminum obtained by closely laminating at least lithium on an aluminum substrate, the aluminum substrate mainly consists of (
100) A negative electrode for a sheet-like secondary battery, characterized by having a surface.
により高表面積化された多孔体であることを特徴とする
請求項（１）記載の二次電池用負極。(2) The negative electrode for a secondary battery according to claim (1), wherein the aluminum substrate is a porous body having a high surface area with a large number of pits in a direction perpendicular to the surface.
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1320605A JPH03182049A (en) | 1989-12-12 | 1989-12-12 | Negative electrode for secondary battery |
| DE4030205A DE4030205C3 (en) | 1989-09-25 | 1990-09-24 | Negative electrode for secondary battery and a method of manufacturing this electrode |
| US07/587,864 US5077152A (en) | 1989-09-25 | 1990-09-25 | Negative electrode for secondary battery |
| US07/745,281 US5100437A (en) | 1989-09-25 | 1991-08-14 | Method of producing a negative electrode for a secondary battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1320605A JPH03182049A (en) | 1989-12-12 | 1989-12-12 | Negative electrode for secondary battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH03182049A true JPH03182049A (en) | 1991-08-08 |
Family
ID=18123274
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1320605A Pending JPH03182049A (en) | 1989-09-25 | 1989-12-12 | Negative electrode for secondary battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH03182049A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010170901A (en) * | 2009-01-23 | 2010-08-05 | Kobelco Kaken:Kk | Negative-electrode active material, secondary battery and capacitor using the same |
-
1989
- 1989-12-12 JP JP1320605A patent/JPH03182049A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010170901A (en) * | 2009-01-23 | 2010-08-05 | Kobelco Kaken:Kk | Negative-electrode active material, secondary battery and capacitor using the same |
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