JPS62223969A - Manufacture of negative electrode for lithium battery - Google Patents
Manufacture of negative electrode for lithium batteryInfo
- Publication number
- JPS62223969A JPS62223969A JP6562886A JP6562886A JPS62223969A JP S62223969 A JPS62223969 A JP S62223969A JP 6562886 A JP6562886 A JP 6562886A JP 6562886 A JP6562886 A JP 6562886A JP S62223969 A JPS62223969 A JP S62223969A
- Authority
- JP
- Japan
- Prior art keywords
- lithium
- negative electrode
- solid
- alloy layer
- solid electrolyte
- 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
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 63
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 61
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 27
- 229910000733 Li alloy Inorganic materials 0.000 claims abstract description 24
- 239000001989 lithium alloy Substances 0.000 claims abstract description 24
- 239000007784 solid electrolyte Substances 0.000 claims abstract description 22
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 18
- 239000000956 alloy Substances 0.000 claims abstract description 18
- 229910052733 gallium Inorganic materials 0.000 claims abstract description 4
- 229910052738 indium Inorganic materials 0.000 claims abstract description 3
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims abstract 2
- 229910052782 aluminium Inorganic materials 0.000 claims abstract 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract 2
- 229910052787 antimony Inorganic materials 0.000 claims abstract 2
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims abstract 2
- 229910052797 bismuth Inorganic materials 0.000 claims abstract 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims abstract 2
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims abstract 2
- 239000007787 solid Substances 0.000 claims description 11
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 22
- 229910052751 metal Inorganic materials 0.000 abstract description 17
- 239000002184 metal Substances 0.000 abstract description 16
- 238000007740 vapor deposition Methods 0.000 abstract description 11
- 239000004615 ingredient Substances 0.000 abstract 1
- 239000010409 thin film Substances 0.000 description 13
- 239000010408 film Substances 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000007599 discharging Methods 0.000 description 4
- 238000005275 alloying Methods 0.000 description 3
- 238000000137 annealing Methods 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 230000009977 dual effect Effects 0.000 description 3
- 230000005611 electricity Effects 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 229910001152 Bi alloy Inorganic materials 0.000 description 1
- 229910007975 Li-Ga Inorganic materials 0.000 description 1
- 229910008029 Li-In Inorganic materials 0.000 description 1
- -1 Lithium metals Chemical class 0.000 description 1
- 229910006620 Li—Ga Inorganic materials 0.000 description 1
- 229910006670 Li—In Inorganic materials 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/06—Electrodes for primary cells
- H01M4/08—Processes of manufacture
- H01M4/12—Processes of manufacture of consumable metal or alloy electrodes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M6/00—Primary cells; Manufacture thereof
- H01M6/14—Cells with non-aqueous electrolyte
- H01M6/18—Cells with non-aqueous electrolyte with solid electrolyte
Landscapes
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Primary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は固体電解質／金属リチウム界面にリチウム合金
層を有する全固体リチウム電池用負極の製造方法に係り
、特にリチウム合金層のより簡便な形成方法を提供する
。[Detailed Description of the Invention] [Field of Industrial Application] The present invention relates to a method for producing a negative electrode for an all-solid lithium battery having a lithium alloy layer at the solid electrolyte/metallic lithium interface, and particularly relates to a method for manufacturing a negative electrode for an all-solid lithium battery, which facilitates the formation of a lithium alloy layer. provide a method.
全固体リチウム電池において、放電の進行に伴ない負極
／固体電解質界面の接触が劣下する現像は、広く知られ
ている。これは、負極／固体電解質界面で消費されるリ
チウム量が、負極中のリチウム原子の拡散によって補な
われる量を上回る結果、固体電解質と接するリチウム負
極中に空孔が形成され、そのために接触面積が減少する
ことによる。In all-solid-state lithium batteries, development in which the contact between the negative electrode/solid electrolyte interface deteriorates as discharge progresses is widely known. This is because the amount of lithium consumed at the negative electrode/solid electrolyte interface exceeds the amount compensated for by the diffusion of lithium atoms in the negative electrode, resulting in the formation of vacancies in the lithium negative electrode in contact with the solid electrolyte, resulting in the contact area This is due to a decrease in
これを解決する一例として、特願昭５９−２４８２４０
に記載されているように、固体電解質／金属リチウム界
面にリチウムの大きい拡散係数を有するリチウム合金薄
膜層を形成させる方法がある。しかしながら、二元同時
蒸着法に代表される化合物薄膜形成法は、厳密な蒸着条
件の制御を必要とし、ひいては電池の作製プロセスを複
雑化するという問題点がある。リチウム合金の作製法の
他の一例として、米国特許第３９８１７４３号に記載さ
れているように、Ａ Ｑ −Ｌ ｉ −ＡΩの各シート
をサンドイッチ状に圧着し、リチウムの融点下でアニー
ルする方法がある。As an example of solving this problem, patent application No. 59-248240
As described in , there is a method of forming a lithium alloy thin film layer having a large lithium diffusion coefficient at the solid electrolyte/metal lithium interface. However, the compound thin film forming method represented by the dual simultaneous vapor deposition method requires strict control of vapor deposition conditions, which has the problem of complicating the battery manufacturing process. Another example of a method for producing a lithium alloy is a method in which each sheet of AQ-L i -AΩ is pressed into a sandwich shape and annealed at a temperature below the melting point of lithium, as described in U.S. Pat. No. 3,981,743. be.
しかし、この方法はリチウムの融点下におけるアルミニ
ラ１１中のリチウムの拡散を利用して、シート状の原料
からシート状のバルク合金作製を目的としているため、
約１７５℃、約８時間、約３０ｐｓｉの圧力を加え続け
なければならないことや、高温、高圧処理を行うため表
面積／体積比率の大きい薄膜作製には適用し鴛いなどの
問題点があった。However, this method aims to produce a sheet-shaped bulk alloy from a sheet-shaped raw material by utilizing the diffusion of lithium in alumina 11 below the melting point of lithium.
There were problems such as the need to continue applying a pressure of about 30 psi at about 175° C. for about 8 hours, and the high temperature and high pressure treatment making it difficult to apply to the production of thin films with a large surface area/volume ratio.
本発明の目的は、固体解質／金属リチウム界面にリチウ
ム合金層を有する全国体リチウム電池用負極の製造にお
いて、上述した様な、厳密な蒸着制御が要求される化合
物薄膜形成技術や、高温。The purpose of the present invention is to use compound thin film formation technology that requires strict vapor deposition control and high temperature in the production of negative electrodes for nationwide lithium batteries that have a lithium alloy layer at the solid solute/metallic lithium interface.
高圧、長時間のアニールプロセスなどを必要としないよ
り簡単な、リチウム合金層を有する全固体リチウ１１電
池用負極の製造方法を提供することにある６
〔問題点を解決するための手段〕
固体電解質上に、リチウム、リチウムと合金化せしめる
金属、リチウムの順に蒸着する負極の製造方法をとれば
、二元同時蒸着法
プロセスや、長時間の高温・高圧のアニールプロセスな
どを用いなくとも、固体電解質／金属リチウム界面にリ
チウム合金層を有する負極を容易に形成し得る。The object of the present invention is to provide a simpler method for manufacturing an all-solid-state lithium-11 battery negative electrode having a lithium alloy layer that does not require high-pressure, long-time annealing processes, etc. 6 [Means for solving the problems] Solid electrolyte If we adopt a negative electrode manufacturing method in which lithium, a metal alloyed with lithium, and lithium are deposited in this order, a solid electrolyte can be produced without using a binary simultaneous deposition process or a long-term high-temperature, high-pressure annealing process. A negative electrode having a lithium alloy layer at the /metal lithium interface can be easily formed.
リチウム金属は、ＡＱ、Ｇａ、Ｉｎ、５ｉｔＳｂ、Ｂｉ
などの金属元素と室温でも合金化することが知られてい
る。この合金化反応は、リチウム原子が上記金属中へ拡
散することによって進行する。したがって、リチウム金
属と上記金属とを接触させた時のその接触面における合
金化の速度は接触させる各金属の表面状態、加える圧力
、周囲の温度によって異なる。５μｍ ｌ ｋの速度で
蒸着した金属リチウムの蒸着膜表面をＳＥＭ （走査型
電子顕鏡）で［察すると５蒸着膜が０．１〜０．５μｍ
程度の無数の粒状結晶によって形成されている。即ち、
その表面積はバルク表面と比較して極めて大きく、この
蒸着膜表面にリチウムと合金化させる上記金属を蒸着す
れば、バルク金属同志の接触よりも、さらに容易に合金
化固応が進行する。Lithium metals include AQ, Ga, In, 5itSb, Bi
It is known that it can be alloyed with metal elements such as at room temperature. This alloying reaction proceeds as lithium atoms diffuse into the metal. Therefore, when lithium metal and the above metals are brought into contact, the rate of alloying at the contact surface varies depending on the surface condition of each metal being contacted, the applied pressure, and the ambient temperature. The surface of the evaporated film of metallic lithium deposited at a rate of 5 μm lk was observed using an SEM (scanning electron microscope).
It is formed by countless granular crystals. That is,
Its surface area is extremely large compared to the bulk surface, and if the metal to be alloyed with lithium is deposited on the surface of the deposited film, the alloying solid reaction will proceed more easily than when the bulk metals come into contact with each other.
以下に実施例をあげ本発明をさらに詳細に説明する。 The present invention will be explained in more detail with reference to Examples below.
（実施例１）
第１図は本発明による、固体電解質上に、リチウム、リ
チウムと合金化させる金属、リチウムの順に各層を蒸着
して作製する負極の製造プロセスを模式的に示した電池
の概略断面図である。第２図は第１図に示した負極の製
造プロセスを用いて作製した、固体電解！ｆ￥／金舅リ
チウム界面にリチウム合金を有する全固体リチウム電池
、もしくは、リチウム合金層を二元同時蒸着法により作
製した全固体リチウム電池の栂成の一例を示す概略断面
図である。上記両図の正極１と正極６は、５００μｍの
厚さのＰｂＩｚとｐｂの圧粉成型体からなり、固体電解
質２と７は、１００μｍの厚さを持つＬｉ５Ｎ の圧粉
成型体である。３，５および９は、それぞれ０．５，４
０．４０μｍの厚さのリチウム蒸着膜、４は厚さ０．５
ｐｍ のＡＱ、Ｇａ。(Example 1) Fig. 1 is a schematic diagram of a battery according to the present invention, schematically showing the manufacturing process of a negative electrode produced by depositing layers of lithium, a metal to be alloyed with lithium, and lithium in this order on a solid electrolyte. FIG. Figure 2 shows a solid electrolyte produced using the negative electrode manufacturing process shown in Figure 1! FIG. 2 is a schematic cross-sectional view showing an example of the formation of an all-solid lithium battery having a lithium alloy at the f\/Kanaga lithium interface, or an all-solid lithium battery in which a lithium alloy layer is manufactured by a binary simultaneous vapor deposition method. The positive electrode 1 and the positive electrode 6 in the above figures are made of compacted powder of PbIz and pb with a thickness of 500 μm, and the solid electrolytes 2 and 7 are compacted compacted powder of Li5N with a thickness of 100 μm. 3, 5 and 9 are 0.5 and 4 respectively
Lithium vapor deposited film with a thickness of 0.40 μm, 4 is a thickness of 0.5
AQ of pm, Ga.
Ｉｎのいずれか一種の金属の蒸着膜、８は厚さ約０．５
μｍの上記金属のうちのいずれか一種を含むリチウム合
金層である。A vapor deposited film of any one of In, 8 has a thickness of about 0.5
It is a lithium alloy layer containing any one of the above metals of μm.
作製した電池は、合金層の形成方法で大別して２種類、
各々の形成方法について合金層の種類で分類して３種類
の計６種類と上記電池と全く同一方で作製したリチウム
合金層を有しない全固体電池の以上７個である。The produced batteries can be roughly divided into two types depending on the method of forming the alloy layer:
There are a total of 6 types, 3 types categorized by the type of alloy layer for each formation method, and 7 types of all-solid-state batteries without a lithium alloy layer, which were made in exactly the same way as the batteries described above.
まず、本発明の方法を用いて作製した電池について説明
する。第１図に示す正極１と固体電解質２の間に１５０
０ｋｇ／ａ＃の圧力を加え両者を圧着させた後、固体電
解ＩｆＩｔ２の表面に真空蒸着法により、リチウム上記
のＡｌ１ （Ａ）、 Ｇａ （Ｂ）、 Ｉ ｎ （Ｃ
）のいずれかの金属、リチウムを順に積層し、第２図に
示す構造を有する全固体リチウム電池（Ａ）。First, a battery manufactured using the method of the present invention will be described. 150 mm between the positive electrode 1 and the solid electrolyte 2 shown in FIG.
After applying a pressure of 0 kg/a# to bond them together, lithium (Al1 (A), Ga (B), I n (C
) An all-solid lithium battery (A) having the structure shown in FIG.
（Ｂ）、（Ｃ）の三種類を作製した。Three types (B) and (C) were produced.
次に合金層を二元同時蒸着法により形成させる従来の負
極の製造法を用いて作製した電池について説明する。第
２図に示す正極６と固体電解質７の間に１５００ｋｇ／
ｄの圧力を加え両者を圧着させた後、固体電解質７の表
面に、５０ａｔ％のＬｉを含有するＬｉ−ＡＱ金合金Ｄ
）、５０ａｔ％のＬｉを含有するＬｉ−Ｇａ合金（Ｅ）
、５０ａｔ％のＬｉを含有するＬｉ−Ｉｎ合金（Ｆ）
のいずれか１種から成るリチウム合金層８を二元同時蒸
着法により形成し、続いてリチウｔｓ ９を真空蒸着法
により積層し、第２図に示す構造を有する全固体リチウ
ム電池（Ｄ）、（Ｅ）、（Ｆ）の三種類を作製した。第
３．４．５図に、同種の合金層を有する（Ａ）と（Ｄ）
、（Ｂ）と（Ｅ）、（Ｃ）と（Ｆ）のそれぞれ、および
上記と同一条件で作製したＴ、ｉ合金層を有しない全固
体リチウム電池（Ｇ）について、常温、常圧、電流密度
１ｍＡ／ｄの条件で放電した時の端子電圧（Ｖ）と放ｆ
Ｉ！電気量（すべての電池の膜厚は同じであるので、単
位はｍＡｋ／−とした）との関係を示した。図から明ら
かなように、本発明による負極の製造法を用いて作製し
た電池（Ａ）、（Ｂ）、（Ｃ）が従来による負極の製造
法を用いて作製した電池（Ｄ）。Next, a battery manufactured using a conventional negative electrode manufacturing method in which an alloy layer is formed by dual simultaneous vapor deposition will be described. Between the positive electrode 6 and solid electrolyte 7 shown in Figure 2, 1500 kg/
After applying pressure of
), Li-Ga alloy containing 50 at% Li (E)
, Li-In alloy (F) containing 50 at% Li
A lithium alloy layer 8 made of any one of the following is formed by a binary simultaneous vapor deposition method, and then lithium TS 9 is laminated by a vacuum vapor deposition method to obtain an all-solid lithium battery (D) having the structure shown in FIG. Three types (E) and (F) were produced. Figure 3.4.5 shows (A) and (D) with the same type of alloy layer.
, (B) and (E), (C) and (F), and all solid-state lithium batteries (G) without T and i alloy layers produced under the same conditions as above, at room temperature, normal pressure, and current. Terminal voltage (V) and radiation f when discharging at a density of 1 mA/d
I! The relationship with the quantity of electricity (the unit is mAk/- since all the batteries have the same film thickness) is shown. As is clear from the figure, batteries (A), (B), and (C) were manufactured using the negative electrode manufacturing method according to the present invention, and battery (D) was manufactured using the conventional negative electrode manufacturing method.
＜Ｅ）、（Ｆ）とほぼ同じ放電特性を示すこと、および
合金層を有しない電池（Ｇ）との比較から、リチウム合
金層を設けたことによる固体電解質／金属リチウム界面
の接触改善という本来の目的を十分に達成していること
がわかる。From the fact that it shows almost the same discharge characteristics as <E) and (F), and from the comparison with the battery (G) that does not have an alloy layer, it is clear that the provision of a lithium alloy layer improves the contact between the solid electrolyte and the metal lithium interface. It can be seen that the objective has been fully achieved.
（実施例２）
次に、本発明よる負極の製造プロセスを、薄膜作製プロ
セスを用いて作製する全固体薄膜リチウム電池に適用し
た。第６図は、本発明による負極の製造プロセスを用い
て作製した、もしくは、二元同時蒸着法により作製した
、リチウム合金層を有する全固体薄膜リチウム電池の構
成の一例を示す概略断面図である。図に示すごとく、ス
テンレス基板１０上に化学気相成長法によって、厚さ１
００μｍのＴｉ５ｚ配向性薄膜である正極１１を成膜し
、その上にスパッタリング法を用いて厚さ１０ｐｍのＬ
ｉ Ｊ＋、８Ｓ ｉｏ、ｏＰｏ、ｔｏ＋非晶質薄膜で
ある固体電解質１２を積層する。そして、固体電解質１
２の上に、本発明による負極の製造プロセスを用いて、
（実施例１）と全く同様にしてＬｉ−８ｂ合金（Ｈ）ま
たはＬ ｉ −Ｂ ｉ合金（Ｉ）からなる厚さ０．８μ
ｍの合金層１３および厚さ４０μｍのリチウム層１４を
形成させ、（Ｈ）。(Example 2) Next, the negative electrode manufacturing process according to the present invention was applied to an all-solid-state thin film lithium battery manufactured using a thin film manufacturing process. FIG. 6 is a schematic cross-sectional view showing an example of the structure of an all-solid-state thin film lithium battery having a lithium alloy layer, manufactured using the negative electrode manufacturing process according to the present invention or manufactured by a binary simultaneous vapor deposition method. . As shown in the figure, a film with a thickness of 1 cm was deposited on a stainless steel substrate 10 by chemical vapor deposition.
A positive electrode 11, which is a 00 μm Ti5z oriented thin film, is formed, and a 10 pm thick L film is formed on it using a sputtering method.
i J+, 8S io, oPo, to+ Solid electrolyte 12, which is an amorphous thin film, is laminated. And solid electrolyte 1
2, using the negative electrode manufacturing process according to the present invention,
Made of Li-8b alloy (H) or Li-Bi alloy (I) in exactly the same manner as in (Example 1), with a thickness of 0.8μ
m alloy layer 13 and 40 μm thick lithium layer 14 are formed (H).
（Ｉ）二種類の全固体薄膜リチウム電池を作製した。次
に、合金層を二元同時蒸着法により形成させる従来の負
極の製造法を用いて、厚さ約０．８ｐｍの、８５ａ ｔ
％のＬｉを含有するＬｉ−８ｂ合金（Ｊ）または８５ａ
ｔ％のＬｉを含有するＬｉ−Ｂ１ （Ｋ）からなる
合金層１３およびリチウム層１４を形成させ、（Ｊ）、
（Ｋ）二種類の全固体′ｆｉ１１摸リチウム電池を作製
した。第７，８図に、同種の合金層を有する（Ｈ）と（
Ｊ）、（１）と（Ｋ）のそれぞれ、および上記と同一条
件で作製したＬｉ合金層を有しない全固体薄膜リチウム
電池（Ｌ）について、常温、常圧、電流密度４０μＡ／
ｃＩＡで放電した時の端子電圧（Ｖ）と放ｆ＄！’ｒｌ
気量（ｍＡｋ／ｃ１１）との関係を示した。図から明ら
かなように２本発明による負極の製造法を用いて作製し
た電池（Ｈ）、（Ｉ）が、従来法による負極の製造法を
用いて作製した電池（Ｊ）、（Ｋ）とほぼ同じ放電特性
を示すこと、および合金層を有しない電池（Ｌ）との比
較から、リチウム合金層を設けたことによる固体電解質
／金属リチウム界面の接触改善という本来の目的を十分
達成していることがわかる。(I) Two types of all-solid-state thin film lithium batteries were produced. Next, using a conventional negative electrode manufacturing method in which an alloy layer is formed by a dual simultaneous vapor deposition method, an 85a t film having a thickness of about 0.8 pm is formed.
Li-8b alloy (J) or 85a containing % Li
An alloy layer 13 and a lithium layer 14 made of Li-B1 (K) containing t% of Li are formed, (J),
(K) Two types of all-solid-state 'fi11 lithium batteries were fabricated. Figures 7 and 8 show (H) and (H) having the same type of alloy layer.
J), (1) and (K), and all-solid thin film lithium batteries (L) without a Li alloy layer produced under the same conditions as above, at room temperature, normal pressure, and current density 40 μA/
Terminal voltage (V) and discharge f$ when discharging with cIA! 'rl
The relationship with air volume (mAk/c11) is shown. As is clear from the figure, the two batteries (H) and (I) manufactured using the negative electrode manufacturing method according to the present invention are different from the batteries (J) and (K) manufactured using the conventional negative electrode manufacturing method. From the fact that it shows almost the same discharge characteristics and compared to the battery (L) that does not have an alloy layer, the original purpose of improving the contact between the solid electrolyte and metal lithium interface by providing the lithium alloy layer has been sufficiently achieved. I understand that.
以上詳細に説明したごとく、本発明による全固体リチウ
ム電池用負極の製造方法によれば、固体電解？ｊ／金属
リチウム界面にリチウム合金層を形成させる際に、二元
同時蒸着などの難かしいプロセスや、長時間の高温・高
圧のアニールプロセスなどを用いることなく、より簡便
に負極を製造し得るので、電池の製造プロセスを簡略化
することが可能であり、実用的価値は極めて大きい。As explained in detail above, according to the method for manufacturing a negative electrode for an all-solid-state lithium battery according to the present invention, solid electrolysis? When forming a lithium alloy layer at the j/metallic lithium interface, the negative electrode can be manufactured more easily without using difficult processes such as binary simultaneous vapor deposition or long-term high-temperature, high-pressure annealing processes. , it is possible to simplify the battery manufacturing process, and the practical value is extremely large.
第１図は実施例１における、本発明による負極の製造プ
ロセスを模式的に示した電池の概略断面図、第２図は実
施例１における全固体リチウ１１電他の構成を示す概Ｉ
ＩＩｇ断面図、第３．４．５図は実施例１における全固
体リチウム電池の放電時の端子電圧と放電電気量との関
係を示すグラフ、第６図は実施例２における全固体薄膜
リチウム電池の構成を示す概略断面図、第７，８図は実
施例２における全固体薄膜リチウム電池の放電時の端子
電圧と放電電気量との関係を示すグラフである。
１・・・正極、２・・・固体電解質、３・・・リチウム
、４・・・リチウ１１と合金化させる金属、５・・・リ
チウム、６・・・正極、７・・・固体電解質、８・・・
リチウム合金層。
９・・・リチウム、１０・・・ステンレス基板、１１・
・・正極、１２・・・固体電解質、１３・・・リチウム
合金層、早 ／ｆｆｉ
早 ７ 図
第 δ 図FIG. 1 is a schematic cross-sectional view of a battery schematically showing the manufacturing process of the negative electrode according to the present invention in Example 1, and FIG.
IIg sectional view, Figure 3.4.5 is a graph showing the relationship between terminal voltage and amount of discharged electricity during discharging of the all-solid-state lithium battery in Example 1, and Figure 6 is the all-solid-state thin-film lithium battery in Example 2. FIGS. 7 and 8 are graphs showing the relationship between the terminal voltage and the amount of discharged electricity during discharging of the all-solid-state thin film lithium battery in Example 2. FIGS. DESCRIPTION OF SYMBOLS 1... Positive electrode, 2... Solid electrolyte, 3... Lithium, 4... Metal alloyed with lithium 11, 5... Lithium, 6... Positive electrode, 7... Solid electrolyte, 8...
Lithium alloy layer. 9... Lithium, 10... Stainless steel substrate, 11.
...Positive electrode, 12...Solid electrolyte, 13...Lithium alloy layer, Figure 7 Figure δ
Claims (1)
有する全固体リチウム電池において、上記リチウム合金
層がその合金成分単体を交互に積層することによつて形
成されることを特徴とする全固体リチウム電池用負極の
製造方法。 ２、上記リチウム合金層を形成するリチウム合金がリチ
ウム元素の他にアルミニウム、ガリウム、インジウム、
アンチモン、ビスマスのいずれか一種の元素を含むこと
を特徴とする特許請求の範囲第１項記載の全固体リチウ
ム電池用負極の製造方法。[Claims] 1. An all-solid lithium battery having a lithium alloy layer at the solid electrolyte/metallic lithium interface, characterized in that the lithium alloy layer is formed by alternately stacking single alloy components. A method for producing a negative electrode for an all-solid-state lithium battery. 2. The lithium alloy forming the lithium alloy layer contains aluminum, gallium, indium, in addition to lithium element.
The method for producing a negative electrode for an all-solid-state lithium battery according to claim 1, characterized in that the negative electrode contains one of antimony and bismuth.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6562886A JPS62223969A (en) | 1986-03-26 | 1986-03-26 | Manufacture of negative electrode for lithium battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6562886A JPS62223969A (en) | 1986-03-26 | 1986-03-26 | Manufacture of negative electrode for lithium battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS62223969A true JPS62223969A (en) | 1987-10-01 |
Family
ID=13292472
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP6562886A Pending JPS62223969A (en) | 1986-03-26 | 1986-03-26 | Manufacture of negative electrode for lithium battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62223969A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6613477B2 (en) | 2000-02-22 | 2003-09-02 | Sanyo Electric Co., Ltd. | Lithium secondary battery |
-
1986
- 1986-03-26 JP JP6562886A patent/JPS62223969A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6613477B2 (en) | 2000-02-22 | 2003-09-02 | Sanyo Electric Co., Ltd. | Lithium secondary battery |
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