JPH11273665A - Nonaqueous electrolyte battery and its manufacture - Google Patents
Nonaqueous electrolyte battery and its manufactureInfo
- Publication number
- JPH11273665A JPH11273665A JP10079596A JP7959698A JPH11273665A JP H11273665 A JPH11273665 A JP H11273665A JP 10079596 A JP10079596 A JP 10079596A JP 7959698 A JP7959698 A JP 7959698A JP H11273665 A JPH11273665 A JP H11273665A
- Authority
- JP
- Japan
- Prior art keywords
- binder
- positive electrode
- electrolyte battery
- temperature
- electrode
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
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】DETAILED DESCRIPTION OF THE INVENTION
【０００１】[0001]
【発明の属する技術分野】本発明は、リチウム一次電
池、リチウム二次電池、リチウムイオン蓄電池などのリ
チウム、リチウム合金、リチウムを吸蔵・放出可能な物
質を負極活物質とし、電解液の溶媒として非水溶媒を用
いる非水電解液電池に係り、特に、少なくとも一方の電
極の活物質に結着剤を添加する非水電解液電池およびそ
の製造方法に関するものである。The present invention relates to a lithium active material such as a lithium primary battery, a lithium secondary battery, or a lithium ion storage battery, which is a material capable of occluding and releasing lithium. The present invention relates to a non-aqueous electrolyte battery using an aqueous solvent, and more particularly to a non-aqueous electrolyte battery in which a binder is added to an active material of at least one electrode, and a method for manufacturing the same.
【０００２】[0002]
【従来の技術】従来のリチウム一次電池、リチウム二次
電池、リチウムイオン蓄電池などのリチウム、リチウム
合金、リチウムを吸蔵・放出可能な物質を負極活物質と
して用い、電解液の溶媒として非水溶媒を用いる非水電
解液電池では、その正極あるいは負極は、活物質粉体と
導電剤などの添加剤を樹脂結着剤を用いて成形するよう
にしている。この場合、電池の組立前に電極内の水分を
除去するための熱処理を行う必要がある。これは電極内
に水分が残留していると、電池内のリチウムが水分と反
応して、電池の内部抵抗が上昇したり、ガスが発生する
などの不具合を生ずるためである。2. Description of the Related Art Conventional lithium primary batteries, lithium secondary batteries, lithium ion storage batteries and other lithium, lithium alloys, and substances capable of absorbing and releasing lithium are used as negative electrode active materials, and nonaqueous solvents are used as electrolyte solvents. In the nonaqueous electrolyte battery used, the positive electrode or the negative electrode is formed by molding an active material powder and an additive such as a conductive agent using a resin binder. In this case, it is necessary to perform a heat treatment for removing water in the electrodes before assembling the battery. This is because if moisture remains in the electrode, lithium in the battery reacts with the moisture, causing problems such as an increase in internal resistance of the battery and generation of gas.
【０００３】したがって、このような非水電解液電池の
電極を成形するために用いられる結着剤は、水分除去の
ための熱処理に対する耐熱性と、化学的な安定性との観
点から、フッ素系樹脂が用いられることが一般的であ
る。その中でも、ポリテトラフルオロエチレン（ＰＴＦ
Ｅ）あるいはテトラフルオロエチレン・ヘキサフルオロ
プロピレン共重合体（ＦＥＰ）が特によく用いられてい
る。[0003] Accordingly, the binder used for forming the electrode of such a non-aqueous electrolyte battery is a fluorine-based binder from the viewpoint of heat resistance to heat treatment for removing moisture and chemical stability. Generally, a resin is used. Among them, polytetrafluoroethylene (PTF)
E) or tetrafluoroethylene / hexafluoropropylene copolymer (FEP) is particularly often used.
【０００４】[0004]
【発明が解決しようとする課題】ところで、このような
電極において、電極活物質などを成形して実用上十分な
強度を得るためには、通常は電極重量の数％の重量の結
着剤を配合する必要がある。しかしながら、電極の機械
的強度を上げるために結着剤を多く配合すると、その
分、活物質量が相対的に減少し、あるいは、活物質表面
が結着剤で覆われて活物質の利用率が低下するため、電
極の放電容量が減少するという問題点があった。In order to obtain a practically sufficient strength by molding an electrode active material or the like in such an electrode, usually, a binder having a weight of several% of the weight of the electrode is used. It needs to be blended. However, when a large amount of binder is added to increase the mechanical strength of the electrode, the amount of the active material is relatively reduced, or the surface of the active material is covered with the binder and the utilization rate of the active material is reduced. , There is a problem that the discharge capacity of the electrode is reduced.
【０００５】[0005]
【課題を解決するための手段およびその作用・効果】そ
こで、本発明では、少量の結着剤を用いて、強度が大き
く、かつ放電容量が増大した電極を得ることを目的とし
てなされたものである。このため、本発明の非水電解液
電池は、結着剤として、せん断応力により繊維化する第
１の結着剤と、せん断応力により繊維化しない第２の結
着剤とを用い、第１の結着剤の融点以下で、かつ第２の
結着剤の軟化温度以上で熱処理した電極を備えるように
している。第１の結着剤はせん断応力により繊維化して
結着力を発揮し、第２の結着剤は軟化温度以上の熱処理
で結着力を発揮する。このため、２種類の結着剤の相乗
効果により、少量の結着剤で十分な機械的強度を有する
電極が得られるため、電池容量が増大した非水電解液電
池が得られる。Means for Solving the Problems and Actions / Effects Therefor, the present invention has been made to obtain an electrode having a large strength and an increased discharge capacity by using a small amount of a binder. is there. For this reason, the non-aqueous electrolyte battery of the present invention uses a first binder that is fiberized by shearing stress and a second binder that is not fiberized by shearing stress as the first binder. The electrode is heat-treated at a temperature equal to or lower than the melting point of the binder and equal to or higher than the softening temperature of the second binder. The first binder is converted into a fiber by shear stress to exhibit a binding force, and the second binder exhibits a binding force by a heat treatment at a softening temperature or higher. For this reason, an electrode having sufficient mechanical strength can be obtained with a small amount of the binder due to a synergistic effect of the two types of binders, so that a nonaqueous electrolyte battery having an increased battery capacity can be obtained.
【０００６】一方、本発明の非水電解液電池の製造方法
においては、せん断応力により繊維化する第１の結着剤
と、せん断応力により繊維化しない第２の結着剤とを正
・負極の少なくとも一方の活物質に添加する結着剤添加
工程と、この結着剤添加工程により第１と第２の結着剤
が添加された活物質にせん断応力を付与するようにして
混合する活物質混合工程と、第１の結着剤の融点以下
で、かつ第２の結着剤の軟化温度以上で熱処理する熱処
理工程とを備えるようにしている。On the other hand, in the method for manufacturing a non-aqueous electrolyte battery according to the present invention, the first binder which forms fibers by shearing stress and the second binder which does not form fibers by shearing stress include a positive electrode and a negative electrode. A step of adding a binder to at least one of the active materials, and an activity of mixing the active materials to which the first and second binders have been added by the binder adding step so as to impart shear stress. The method includes a substance mixing step and a heat treatment step of performing a heat treatment at a temperature equal to or lower than the melting point of the first binder and equal to or higher than the softening temperature of the second binder.
【０００７】第１の結着剤はせん断応力により繊維化す
るため、活物質混合工程における混合により、せん断応
力が付与されるようになって結着力を発揮するようにな
るとともに、熱処理工程においてはこの第１の結着剤の
融点以下の温度で加熱されるため、この熱処理により何
ら悪影響が及ぼされない。一方、第２の結着剤はせん断
応力により繊維化しないため、活物質混合工程でせん断
応力を付与されても結着力を発揮するようなことはない
が、熱処理工程においてはこの第２の結着剤の軟化温度
以上で加熱されるため、結着力を発揮するようになる。[0007] Since the first binder is fiberized by shearing stress, the shearing stress is applied by mixing in the active material mixing step, so that the first binder exerts a binding force. Since the heating is performed at a temperature equal to or lower than the melting point of the first binder, the heat treatment has no adverse effect. On the other hand, since the second binder does not fibrillate due to shear stress, it does not exert a binding force even when shear stress is applied in the active material mixing step. Since the adhesive is heated at a temperature equal to or higher than the softening temperature of the adhesive, the adhesive exerts a binding force.
【０００８】このように、本発明においては、第１と第
２の２種類の結着剤を用い、第１の結着剤は物理的摩擦
力によって繊維化して結着力を発揮した後、第２の結着
剤は熱処理により溶融結合することによって、さらに大
きな結着力を発揮するようになる。この結果、少量の結
着剤を用いても十分な機械的強度を有する電極が得られ
るようになるため、電池容量が増大した非水電解液電池
が得られるようになる。As described above, in the present invention, the first and second types of binders are used, and the first binder is formed into fibers by physical frictional force to exhibit the binding force. The binder of No. 2 exhibits a larger binding force by being melt-bonded by heat treatment. As a result, an electrode having a sufficient mechanical strength can be obtained even if a small amount of the binder is used, so that a nonaqueous electrolyte battery having an increased battery capacity can be obtained.
【０００９】そして、第１の結着剤としてポリテトラフ
ルオロエチレン（ＰＴＦＥ）あるいはテトラフルオロエ
チレン・ヘキサフルオロプロピレン共重合体（ＦＥＰ）
などのフッ素樹脂を用い、第２の結着剤としてポリエチ
レンテレフタレート樹脂（ＰＥＴ）を用いるようにする
と、第１の結着剤として用いたＰＴＦＥあるいはＦＥＰ
の融点以下、第２の結着剤のＰＥＴ樹脂の軟化温度以上
で熱処理することにより、電極中でＰＥＴ樹脂の粒子が
互いに溶融結合し、少ない配合量でも大きな結着強度が
得られる。これにより、結着剤の配合比を減少させるこ
とが可能となるので、活物質粒子の表面を覆う結着剤の
量も低下することとなって、単純な結着剤の添加量減少
効果以上の放電容量の増加が期待できるようになる。Then, polytetrafluoroethylene (PTFE) or tetrafluoroethylene-hexafluoropropylene copolymer (FEP) is used as the first binder.
When a fluororesin such as is used and a polyethylene terephthalate resin (PET) is used as the second binder, PTFE or FEP used as the first binder is used.
By performing the heat treatment at a temperature equal to or lower than the melting point of the second binder and equal to or higher than the softening temperature of the PET resin as the second binder, the particles of the PET resin are melt-bonded to each other in the electrode, and a large binding strength can be obtained even with a small amount. This makes it possible to reduce the compounding ratio of the binder, so that the amount of the binder covering the surface of the active material particles also decreases, which is more than the effect of simply adding the binder. Can be expected to increase.
【００１０】ただし、ＰＥＴ樹脂のみを結着剤として用
いて電極を成形した場合、十分な電極強度を得ることが
できない。これは、フッ素樹脂とＰＥＴ樹脂の結着機構
の違いによるものと思われる。すなわち、ＰＴＦＥ、Ｆ
ＥＰなどのフッ素樹脂は、せん断応力によって容易に繊
維化するため、成形時に活物質粒子にこの繊維化したフ
ッ素樹脂が絡み合って結着力が得られるようになる。し
かしながら、ＰＥＴ樹脂は繊維化しないため、ＰＥＴ樹
脂粒子のみを活物質と混合してもほとんど結着力を発生
しないため、全く電極の形状に成形することができな
い。このため、これを熱処理して結着力を上げるという
熱処理工程に移行させることが不可能になる。However, when an electrode is formed using only a PET resin as a binder, sufficient electrode strength cannot be obtained. This seems to be due to the difference in the binding mechanism between the fluororesin and the PET resin. That is, PTFE, F
Since a fluororesin such as EP is easily fiberized by shear stress, the fibrous fluororesin is entangled with the active material particles at the time of molding so that a binding force can be obtained. However, since the PET resin does not fibrillate, even if only the PET resin particles are mixed with the active material, almost no binding force is generated, so that it cannot be formed into an electrode shape at all. For this reason, it becomes impossible to shift to a heat treatment step of increasing the binding force by heat treatment.
【００１１】そして、第１の結着剤としてポリテトラフ
ルオロエチレンを用いた場合の熱処理温度は１７０〜３
２７℃の範囲とすることが好ましく、第１の結着剤とし
てテトラフルオロエチレン・ヘキサフルオロプロピレン
共重合体を用いた場合の熱処理温度は１７０〜２７０℃
の範囲とすることが好ましい。The heat treatment temperature when polytetrafluoroethylene is used as the first binder is 170 to 3
The temperature is preferably in the range of 27 ° C., and the heat treatment temperature when the tetrafluoroethylene / hexafluoropropylene copolymer is used as the first binder is 170 to 270 ° C.
It is preferable to be within the range.
【００１２】[0012]
１．正極の作製 （ａ）実施例１ 正極活物質としての二酸化マンガン９３ｇに、導電剤と
してのアセチレンブラック５ｇと、第１の結着剤として
のポリテトラフルオロエチレン（ＰＴＦＥ）の水性ディ
スパージョンをＰＴＦＥ固形分で１ｇ相当量を添加する
とともに、第２の結着剤としてのポリエチレンテレフタ
レート樹脂（ＰＥＴ）の水性ディスパージョンをＰＥＴ
固形分で１ｇ相当量を添加し、これらに適量の水を加え
て混合・混練して、粘土状の正極合剤の塊を作製する。
この正極合剤を空気中で１２０℃の温度で乾燥した後、
粉砕し、金型に入れて圧縮成形して実施例１の正極ペレ
ットａを作製する。正極ペレットａの寸法は直径１６ｍ
ｍで、厚み０．５ｍｍとした。1. Preparation of Positive Electrode (a) Example 1 An aqueous dispersion of 93 g of manganese dioxide as a positive electrode active material, 5 g of acetylene black as a conductive agent, and polytetrafluoroethylene (PTFE) as a first binder was used as PTFE solid. And an aqueous dispersion of polyethylene terephthalate resin (PET) as a second binder.
An equivalent amount of 1 g in terms of solid content is added, and an appropriate amount of water is added thereto, followed by mixing and kneading to prepare a clay-like mass of the positive electrode mixture.
After drying this positive electrode mixture at a temperature of 120 ° C. in air,
The mixture is pulverized, placed in a mold, and compression-molded to produce a positive electrode pellet a of Example 1. The dimensions of the positive electrode pellet a are 16 m in diameter.
m and the thickness was 0.5 mm.
【００１３】（ｂ）実施例２ 実施例１の第１の結着剤としてのＰＴＦＥの水性ディス
パージョンの代わりに、テトラフルオロエチレン・ヘキ
サフルオロプロピレン共重合体（ＦＥＰ）の水性ディス
パージョンをＦＥＰ樹脂固形分で１ｇ相当量を用いたこ
とを除いては、実施例１と同様にして正極ペレットを作
製して、実施例２の正極ペレットｂとする。(B) Example 2 Instead of the aqueous dispersion of PTFE as the first binder in Example 1, an aqueous dispersion of a tetrafluoroethylene / hexafluoropropylene copolymer (FEP) was replaced with an FEP resin. A positive electrode pellet was prepared in the same manner as in Example 1 except that an equivalent amount of 1 g in terms of solid content was used, and used as a positive electrode pellet b in Example 2.
【００１４】（ｃ）比較例１ 実施例１の第２の結着剤としてのＰＥＴの水性ディスパ
ージョンを用いないことを除いては、実施例１と同様に
して正極ペレットを作製して、比較例１の正極ペレット
ｃとする。(C) Comparative Example 1 A positive electrode pellet was prepared in the same manner as in Example 1 except that the aqueous dispersion of PET as the second binder in Example 1 was not used. The positive electrode pellet c of Example 1 is used.
【００１５】（ｄ）比較例２ 実施例１の第１の結着剤としてのＰＴＦＥの水性ディス
パージョンを、ＰＴＦＥ樹脂固形分で２ｇ相当量を添加
し、第２の結着剤としてのＰＥＴの水性ディスパージョ
ンを用いないことを除いては、実施例１と同様にして正
極ペレットを作製して、比較例２の正極ペレットｄとす
る。(D) Comparative Example 2 An aqueous dispersion of PTFE as the first binder in Example 1 was added in an amount equivalent to 2 g in terms of PTFE resin solid content, and PET as the second binder was added. A positive electrode pellet was prepared in the same manner as in Example 1 except that the aqueous dispersion was not used, and used as a positive electrode pellet d of Comparative Example 2.
【００１６】（ｅ）比較例３ 実施例１の第１の結着剤としてのＰＴＦＥの水性ディス
パージョンを、ＰＴＦＥ樹脂固形分で５ｇ相当量を添加
し、第２の結着剤としてＰＥＴの水性ディスパージョン
を用いないことを除いては、実施例１と同様にして正極
ペレットを作製して、比較例３の正極ペレットｅとす
る。(E) Comparative Example 3 An aqueous dispersion of PTFE as the first binder in Example 1 was added in an amount of 5 g in terms of PTFE resin solid content, and an aqueous dispersion of PET was used as the second binder. A positive electrode pellet was prepared in the same manner as in Example 1 except that no dispersion was used, and used as a positive electrode pellet e of Comparative Example 3.
【００１７】（ｆ）比較例４ 実施例１の第１の結着剤としてのＰＴＦＥの水性ディス
パージョンの代わりにＦＥＰの水性ディスパージョン
を、ＦＥＰ樹脂固形分で２ｇ相当量を添加し、第２の結
着剤としてのＰＥＴの水性ディスパージョンを用いない
ことを除いては、実施例１と同様にして正極ペレットを
作製して、比較例４の正極ペレットｆとする。(F) Comparative Example 4 In place of the aqueous dispersion of PTFE as the first binder of Example 1, an aqueous dispersion of FEP was added in an amount of 2 g in terms of FEP resin solid content. A positive electrode pellet was prepared in the same manner as in Example 1 except that the aqueous dispersion of PET was not used as the binder of Example 4, and a positive electrode pellet f of Comparative Example 4 was obtained.
【００１８】（ｇ）比較例５ 実施例１の第１の結着剤としてのＰＴＦＥの水性ディス
パージョンの代わりにＦＥＰの水性ディスパージョン
を、ＦＥＰ樹脂固形分で５ｇ相当量を添加し、第２の結
着剤としてのＰＥＴの水性ディスパージョンを用いない
ことを除いては、実施例１と同様にして正極ペレットを
作製して、比較例５の正極ペレットｇとする。(G) Comparative Example 5 Instead of the aqueous dispersion of PTFE as the first binder in Example 1, an aqueous dispersion of FEP was added in an amount equivalent to 5 g of the solid content of the FEP resin. A positive electrode pellet was prepared in the same manner as in Example 1 except that the aqueous dispersion of PET was not used as the binder of Comparative Example 5 to obtain a positive electrode pellet g of Comparative Example 5.
【００１９】（ｈ）比較例６ 実施例１の第１の結着剤としてのＰＴＦＥの水性ディス
パージョンを用いず、第２の結着剤としてのＰＥＴの水
性ディスパージョンのみをＰＥＴ樹脂固形分で５ｇ相当
量を添加したことを除いては実施例１と同様にしたが、
正極ペレットを成形することができなった。従って、こ
の正極合剤を比較例６の正極ｈとする。(H) Comparative Example 6 Only the aqueous dispersion of PET as the second binder was used in the form of PET resin solids without using the aqueous dispersion of PTFE as the first binder of Example 1. Same as Example 1 except that 5 g equivalent was added,
Positive electrode pellets could not be formed. Therefore, this positive electrode mixture is referred to as a positive electrode h of Comparative Example 6.
【００２０】２．強度測定 上述のようにして作製したａ〜ｈの各正極ペレット１０
を、図１に示すような、治具２０の上に載置し、治具２
０の上に載置された各正極ペレット１０に押し棒３０を
押し当て、押し棒３０で押す力を徐々に強くしていっ
て、各正極ペレット１０が割れるときの押圧力を各正極
ペレット１０の強度として測定した。なお、強度測定に
際しては、各正極ペレット１０を熱処理を行わないで測
定した場合と、各正極ペレット１０を真空中で２００℃
の温度で２時間の熱処理を行った後に測定した場合の２
種類の測定を行った。2. Strength Measurement Each positive electrode pellet 10 of a to h produced as described above
Is placed on a jig 20 as shown in FIG.
The pressing rod 30 is pressed against each of the positive electrode pellets 10 placed on the positive electrode 0, and the pressing force of the pressing rod 30 is gradually increased. Was measured. In the strength measurement, each positive electrode pellet 10 was measured without heat treatment, and each positive electrode pellet 10 was heated at 200 ° C. in vacuum.
2 after the heat treatment for 2 hours at the temperature of
Kinds of measurements were made.
【００２１】３．放電容量試験 ついで、上述のようにして作製したａ〜ｈの各正極ペレ
ット１０を用い、真空中で２００℃の温度で２時間の熱
処理を行った各正極ペレット１０を用いて試作電池を作
製する。この試作電池は、図２に示すように、正極缶１
１内に正極ペレット１０を載置し、この正極ペレット１
０上に電解液を含浸させたプロピレン製不織布からなる
セパレータ１２を配置する。なお、電解液としては、非
水溶媒としてのプロピレンカーボネイト（ＰＣ）とジメ
トキシエタン（ＤＭＥ）の１：１混合溶媒に、電解質と
してのトリフルオロメタンスルホン酸リチウム（ＬｉＣ
Ｆ3ＳＯ3）を１モル／リットルの濃度で溶解させたもの
を用いる。3. Discharge capacity test Next, a prototype battery is manufactured using each of the positive electrode pellets 10 of a to h prepared as described above and using each of the positive electrode pellets 10 that has been subjected to a heat treatment at 200 ° C. for 2 hours in a vacuum. . This prototype battery has a positive electrode can 1 as shown in FIG.
1, a positive electrode pellet 10 is placed, and the positive electrode pellet 1
A separator 12 made of a propylene nonwoven fabric impregnated with an electrolytic solution is disposed on the separator 0. As an electrolyte, a 1: 1 mixed solvent of propylene carbonate (PC) and dimethoxyethane (DME) as a non-aqueous solvent was mixed with lithium trifluoromethanesulfonate (LiC) as an electrolyte.
F 3 SO 3 ) at a concentration of 1 mol / liter.
【００２２】一方、所定の厚みのリチウム金属を直径１
６ｍｍの円板状に打ち抜いたリチウム負極板１３をその
内面に圧着した負極キャップ１４を用意し、負極キャッ
プ１４をポリプロピレン製ガスケット１５を介して正極
缶１１内に圧入し、正極缶１１開口部を負極キャップ１
４側にかしめ付けて、コイン型リチウム電池を作製す
る。作製した電池の直径は２０ｍｍであり、厚みは１．
６ｍｍである。このようにして作製した電池を２ｍＡの
定電流で放電し、放電終止電圧２．０Ｖまでの時間から
放電容量を算出した。On the other hand, lithium metal having a predetermined thickness
A negative electrode cap 14 is prepared by pressing a lithium negative electrode plate 13 punched into a 6 mm disk shape on the inner surface thereof, and the negative electrode cap 14 is press-fitted into the positive electrode can 11 via a polypropylene gasket 15 so that the opening of the positive electrode can 11 is closed. Negative electrode cap 1
By caulking on the four sides, a coin-type lithium battery is produced. The diameter of the manufactured battery was 20 mm, and the thickness was 1.
6 mm. The battery thus produced was discharged at a constant current of 2 mA, and the discharge capacity was calculated from the time until the discharge end voltage was 2.0 V.
【００２３】上述のように測定した正極ペレットの強度
および上述のように算出した放電容量を示すと、下記の
表１に示すような結果となった。When the strength of the positive electrode pellet measured as described above and the discharge capacity calculated as described above are shown, the results shown in Table 1 below are obtained.
【００２４】[0024]
【表１】 [Table 1]
【００２５】なお、上記表１において、第１の結着剤お
よび第２の結着剤は正極合剤の全重量に対する添加量
（重量％）を表している。In Table 1, the first binder and the second binder represent the amounts (% by weight) based on the total weight of the positive electrode mixture.
【００２６】上記表１において特徴的なことは、ＰＥＴ
樹脂を第２の結着剤に用いた正極ペレットａ（実施例
１）および正極ペレットｂ（実施例２）は熱処理後に正
極ペレット１０の強度が大きく増加していることであ
る。これはＰＥＴ樹脂の軟化温度が１７０℃であるた
め、２００℃の温度での熱処理により、正極ペレット１
０内のＰＥＴ樹脂粒子が互いに溶融結合し、正極ペレッ
ト１０の強度が増すためであると考えられる。The characteristic of Table 1 is that PET is
In the positive electrode pellet a (Example 1) and the positive electrode pellet b (Example 2) using the resin as the second binder, the strength of the positive electrode pellet 10 is greatly increased after the heat treatment. Since the softening temperature of the PET resin is 170 ° C., the heat treatment at a temperature of 200 ° C. causes the positive electrode pellet 1
It is considered that the reason is that the PET resin particles within 0 melt-bond with each other, and the strength of the positive electrode pellet 10 increases.
【００２７】この結果、実施例１および実施例２の正極
ペレット１０は、正極合剤の全重量に対して両結着剤の
合計で２重量％を添加することにより、１４０〜１５０
ｇという大きな強度を得ることができる。また、その放
電容量も９０ｍＡｈと大きい放電容量の電池が得られ
る。As a result, the positive electrode pellets 10 of Example 1 and Example 2 were added in an amount of 140 to 150 by adding a total of 2% by weight of both binders to the total weight of the positive electrode mixture.
g can be obtained. Further, a battery having a discharge capacity as large as 90 mAh can be obtained.
【００２８】他方、第２の結着剤としてのＰＥＴ樹脂を
用いない正極ペレットｃ（比較例１）、正極ペレットｄ
（比較例２）、正極ペレットｅ（比較例３）、正極ペレ
ットｆ（比較例４）、正極ペレットｇ（比較例５）にあ
っては、熱処理を行った後であっても正極ペレット１０
の強度に変化は見られない。これは、ＰＴＦＥの融点が
３２７℃、ＦＥＰの融点が２７０℃であるため、２００
℃の熱処理では結着剤に変化が起こらないためである。On the other hand, a positive electrode pellet c without using a PET resin as the second binder (Comparative Example 1), a positive electrode pellet d
In Comparative Example 2, the positive electrode pellet e (Comparative Example 3), the positive electrode pellet f (Comparative Example 4), and the positive electrode pellet g (Comparative Example 5), the positive electrode pellet 10 was obtained even after the heat treatment.
No change is seen in the intensity of This is because the melting point of PTFE is 327 ° C. and the melting point of FEP is 270 ° C.
This is because the binder does not change in the heat treatment at ℃.
【００２９】この結果、第２の結着剤としてのＰＥＴ樹
脂を用いず、第１の結着剤としてのＰＴＦＥあるいはＦ
ＥＰのみを用いた比較例１〜比較例５では、正極合剤の
全重量に対して１重量％〜２重量％という少量の結着剤
を用いた正極ペレットｃ（比較例１）、正極ペレットｄ
（比較例２）および正極ペレットｆ（比較例４）におい
ては、正極の強度が３０ｇ〜６０ｇと小さくなる。一
方、正極合剤の全重量に対して５重量％という多量の結
着剤を添加した正極ペレットｅ（比較例３）および正極
ペレットｇ（比較例５）においては、正極強度は１４０
ｇ〜１５０ｇと実施例１，２と同等になるが、その放電
容量は８０ｍＡｈと実施例１，２より１割以上低下して
いる。As a result, PTFE or F was used as the first binder without using the PET resin as the second binder.
In Comparative Examples 1 to 5 using only EP, positive electrode pellets c (Comparative Example 1) using a small amount of binder of 1 to 2% by weight based on the total weight of the positive electrode mixture, and positive electrode pellets d
In Comparative Example 2 and the positive electrode pellet f (Comparative Example 4), the strength of the positive electrode was reduced to 30 g to 60 g. On the other hand, in the positive electrode pellet e (Comparative Example 3) and the positive electrode pellet g (Comparative Example 5) to which the binder was added in a large amount of 5% by weight based on the total weight of the positive electrode mixture, the positive electrode strength was 140%.
g to 150 g, which is equivalent to Examples 1 and 2, but the discharge capacity is 80 mAh, which is 10% or more lower than Examples 1 and 2.
【００３０】ここで、結着剤の添加量を正極合剤の全重
量に対して５％重量と多くした場合の放電容量の低下
が、この量の結着剤の添加により正極活物質量が相対的
に少なくなる量よりもさらに小さくなっている。この理
由は定かではないが、結着剤の添加量が多くなると、そ
の表面が結着剤で覆われる活物質量が多くなり、活物質
の有効表面積が低下することに起因して、添加量以上に
放電容量が低下するものと考えられる。Here, when the amount of the binder added was increased to 5% by weight with respect to the total weight of the positive electrode mixture, the discharge capacity was reduced. It is even smaller than the relatively small amount. The reason for this is not clear, but as the amount of binder added increases, the amount of active material whose surface is covered with the binder increases, resulting in a decrease in the effective surface area of the active material. It is considered that the discharge capacity is reduced as described above.
【００３１】さらに、比較例６ではＰＥＴ樹脂のみを用
いて正極ペレット１０を作製しようと試みたが、ＰＥＴ
樹脂のみではペレットの成形ができなかった。これは、
ＰＥＴ樹脂粒子はフッ素樹脂粒子のような混合・混練時
のせん断応力による繊維化がおこりにくいため、粒子の
状態のままで存在することとなって、ＰＴＦＥあるいは
ＦＥＰなどのフッ素樹脂のように、繊維化した微粒子の
絡み合いによる結着がおこらないためであると考えられ
る。Further, in Comparative Example 6, an attempt was made to produce the positive electrode pellet 10 using only the PET resin.
Pellets could not be formed only with the resin. this is,
Since PET resin particles are unlikely to be fiberized due to shear stress during mixing and kneading as in fluororesin particles, they are present in the state of particles, and fibers such as fluororesin such as PTFE or FEP are used. It is considered that binding due to entanglement of the formed fine particles does not occur.
【００３２】このように、本発明においては、実施例
１，２で示したように、第１の結着剤としてのＰＴＦＥ
あるいはＦＥＰと、第２の結着剤としてのＰＥＴとを組
み合わせて用いることにより、少ない結着剤の添加量で
大きな正極強度を得ることができるので、相対的に活物
質量を多くできるようになる。また、結着剤の添加量が
少ないため、正極活物質の表面が結着剤で覆われる比率
も小さくなるので、大きな電池容量を得ることができ
る。Thus, in the present invention, as shown in Examples 1 and 2, PTFE as the first binder was used.
Alternatively, by using FEP in combination with PET as the second binder, a large positive electrode strength can be obtained with a small amount of the added binder, so that the amount of the active material can be relatively increased. Become. In addition, since the amount of the binder added is small, the ratio of the surface of the positive electrode active material covered with the binder is reduced, so that a large battery capacity can be obtained.
【００３３】なお、上述した実施形態においては、本発
明の第１と第２の結着剤を添加するに際して、正極のみ
に適用する例について説明したが、負極として活物質粉
体を結着して成形する場合には、本発明を負極に適用し
てもほぼ同等の効果が得られるようになる。In the above-described embodiment, an example has been described in which the first and second binders of the present invention are applied only to the positive electrode, but the active material powder is bound as the negative electrode. In the case of forming by molding, substantially the same effect can be obtained even if the present invention is applied to a negative electrode.
【００３４】また、本発明での電極の熱処理温度は第１
の結着剤の融点以下でかつ、第２の結着剤の軟化点以上
であればよく、第２の結着剤としてＰＥＴ樹脂を用いる
場合は、第１の結着剤としてＰＴＦＥを用いれば１７０
℃〜３２７℃の温度範囲が好ましく、第１の結着剤とし
てＦＥＰを用いれば１７０℃〜２７０℃の温度範囲が好
ましい。The heat treatment temperature of the electrode according to the present invention is the first temperature.
It is sufficient that the melting point of the binder is not more than the softening point of the second binder, and if a PET resin is used as the second binder, if PTFE is used as the first binder, 170
C. to 327.degree. C. are preferable, and if FEP is used as the first binder, a temperature range of 170.degree. C. to 270.degree. C. is preferable.
【００３５】さらに、上述した実施形態においては、本
発明の非水電解液電池としてコイン型の１次電池に適用
する例について説明したが、本発明は、電池の形状につ
いてはコイン型に限らず、円筒型、角形電池にも適用可
能であり、電池の種類については、１次電池、２次電池
ともに適用可能である。Further, in the above-described embodiment, an example has been described in which the nonaqueous electrolyte battery of the present invention is applied to a coin-type primary battery. However, the present invention is not limited to a coin-shaped battery. , Cylindrical and prismatic batteries, and the types of batteries are applicable to both primary batteries and secondary batteries.
【図１】 本発明により作製した正極ペレットの強度を
測定する状態を模式的に示す図である。FIG. 1 is a view schematically showing a state in which the strength of a positive electrode pellet produced according to the present invention is measured.
【図２】 本発明により作製した正極ペレットを用いて
構成したコイン型電池を示す断面図である。FIG. 2 is a cross-sectional view showing a coin-type battery constituted by using a positive electrode pellet produced according to the present invention.
１０…正極ペレット、１１…正極缶、１２…セパレー
タ、１３…リチウム負極板、１４…負極キャップ、１５
…ガスケット、２０…治具、３０…押し棒DESCRIPTION OF SYMBOLS 10 ... Positive electrode pellet, 11 ... Positive electrode can, 12 ... Separator, 13 ... Lithium negative electrode plate, 14 ... Negative electrode cap, 15
... gasket, 20 ... jig, 30 ... push rod
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 ＦＩ Ｈ０１Ｍ 10/40 Ｈ０１Ｍ 10/40 Ｚ (72)発明者 近藤 正雄 大阪府守口市京阪本通２丁目５番５号 三 洋エナジー鳥取株式会社内──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. 6 Identification symbol FI H01M 10/40 H01M 10/40 Z (72) Inventor Masao Kondo 2-5-5 Keihanhondori, Moriguchi-shi, Osaka Sanyo Energy Tottori Co., Ltd.
Claims (8)
加した電極を備えた非水電解液電池であって、 前記結着剤として、せん断応力により繊維化する第１の
結着剤と、せん断応力により繊維化しない第２の結着剤
とを用い、 前記第１の結着剤の融点以下で、かつ前記第２の結着剤
の軟化温度以上で熱処理した電極を備えたことを特徴と
する非水電解液電池。1. A non-aqueous electrolyte battery provided with an electrode in which a binder is added to at least one of a positive electrode and a negative electrode, wherein a first binder that is fiberized by shear stress is used as the binder. Using a second binder that does not fibrillate due to shear stress, and having an electrode that has been heat-treated at a temperature equal to or lower than the melting point of the first binder and equal to or higher than the softening temperature of the second binder. Characteristic non-aqueous electrolyte battery.
オロエチレンあるいはテトラフルオロエチレン・ヘキサ
フルオロプロピレン共重合体を用い、前記第２の結着剤
としてポリエチレンテレフタレート樹脂を用いたことを
特徴とする請求項１に記載の非水電解液電池。2. The method according to claim 1, wherein polytetrafluoroethylene or a tetrafluoroethylene-hexafluoropropylene copolymer is used as the first binder, and polyethylene terephthalate resin is used as the second binder. The non-aqueous electrolyte battery according to claim 1.
オロエチレンを用い、かつ１７０〜３２７℃の温度で熱
処理した電極を備えたことを特徴とする請求項１に記載
の非水電解液電池。3. The non-aqueous electrolyte battery according to claim 1, further comprising an electrode using polytetrafluoroethylene as the first binder and heat-treated at a temperature of 170 to 327 ° C. .
エチレン・ヘキサフルオロプロピレン共重合体を用い、
かつ１７０〜２７０℃の温度で熱処理した電極を備えた
ことを特徴とする請求項１に記載の非水電解液電池。4. Use of a tetrafluoroethylene / hexafluoropropylene copolymer as the first binder,
The non-aqueous electrolyte battery according to claim 1, further comprising an electrode heat-treated at a temperature of 170 to 270C.
加して製造した電極を備えた非水電解液電池の製造方法
であって、 せん断応力により繊維化する第１の結着剤と、せん断応
力により繊維化しない第２の結着剤とを正・負極の少な
くとも一方の活物質に添加する結着剤添加工程と、 前記第１と第２の結着剤が添加された前記活物質にせん
断応力を付与するようにして混合する活物質混合工程
と、 前記第１の結着剤の融点以下で、かつ前記第２の結着剤
の軟化温度以上で熱処理する熱処理工程とを備えたこと
を特徴とする非水電解液電池の製造方法。5. A method for producing a non-aqueous electrolyte battery provided with an electrode produced by adding a binder to at least one of a positive electrode and a negative electrode, comprising: a first binder that is fiberized by shear stress; A binder adding step of adding a second binder that does not fibrillate due to shear stress to at least one of the positive and negative active materials; and the active agent to which the first and second binders are added. An active material mixing step of mixing so as to apply a shear stress to the substance; and a heat treatment step of performing a heat treatment at a temperature equal to or lower than the melting point of the first binder and equal to or higher than a softening temperature of the second binder. A method for manufacturing a non-aqueous electrolyte battery.
オロエチレンあるいはテトラフルオロエチレン・ヘキサ
フルオロプロピレン共重合体を用い、前記第２の結着剤
としてポリエチレンテレフタレート樹脂を用いたことを
特徴とする請求項５に記載の非水電解液電池の製造方
法。6. The method according to claim 1, wherein polytetrafluoroethylene or a tetrafluoroethylene-hexafluoropropylene copolymer is used as the first binder, and polyethylene terephthalate resin is used as the second binder. A method for manufacturing the nonaqueous electrolyte battery according to claim 5.
オロエチレンを用いた場合、前記熱処理工程において１
７０〜３２７℃の温度で熱処理するようにしたことを特
徴とする請求項５に記載の非水電解液電池の製造方法。7. When polytetrafluoroethylene is used as the first binder, in the heat treatment step,
The method according to claim 5, wherein the heat treatment is performed at a temperature of 70 to 327C.
エチレン・ヘキサフルオロプロピレン共重合体を用いた
場合、前記熱処理工程において１７０〜２７０℃の温度
で熱処理するようにしたことを特徴とする請求項５に記
載の非水電解液電池の製造方法。8. The method according to claim 1, wherein when a tetrafluoroethylene / hexafluoropropylene copolymer is used as the first binder, the heat treatment is performed at a temperature of 170 to 270 ° C. Item 6. The method for producing a nonaqueous electrolyte battery according to Item 5.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP07959698A JP4059556B2 (en) | 1998-03-26 | 1998-03-26 | Non-aqueous electrolyte battery and manufacturing method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP07959698A JP4059556B2 (en) | 1998-03-26 | 1998-03-26 | Non-aqueous electrolyte battery and manufacturing method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH11273665A true JPH11273665A (en) | 1999-10-08 |
| JP4059556B2 JP4059556B2 (en) | 2008-03-12 |
Family
ID=13694391
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP07959698A Expired - Lifetime JP4059556B2 (en) | 1998-03-26 | 1998-03-26 | Non-aqueous electrolyte battery and manufacturing method thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP4059556B2 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100396492B1 (en) * | 2001-10-17 | 2003-09-02 | 삼성에스디아이 주식회사 | Positive active material for lithium-sulfur battery and method of preparing positive active material composition comprising same |
| WO2009112920A1 (en) * | 2008-03-10 | 2009-09-17 | Nissan Motor Co., Ltd. | Battery with battery electrode and method of manufacturing same |
| WO2021192541A1 (en) * | 2020-03-24 | 2021-09-30 | パナソニックＩｐマネジメント株式会社 | Electrode for secondary batteries and method for producing same |
| CN114243104A (en) * | 2021-12-20 | 2022-03-25 | 惠州亿纬锂能股份有限公司 | Flexible electrolyte membrane, battery and preparation method |
| WO2023043245A1 (en) * | 2021-09-16 | 2023-03-23 | 주식회사 엘지에너지솔루션 | Electrode for lithium secondary battery, method for manufacturing same, and lithium secondary battery comprising same |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR102261501B1 (en) | 2017-09-29 | 2021-06-07 | 주식회사 엘지에너지솔루션 | Method for Electrode Mixture and Electrode Mixture |
| KR20230149760A (en) * | 2022-04-20 | 2023-10-27 | 주식회사 엘지에너지솔루션 | Film for electrode, electrode, secondary battery comprising the same, and method for manufacturing the same |
-
1998
- 1998-03-26 JP JP07959698A patent/JP4059556B2/en not_active Expired - Lifetime
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100396492B1 (en) * | 2001-10-17 | 2003-09-02 | 삼성에스디아이 주식회사 | Positive active material for lithium-sulfur battery and method of preparing positive active material composition comprising same |
| WO2009112920A1 (en) * | 2008-03-10 | 2009-09-17 | Nissan Motor Co., Ltd. | Battery with battery electrode and method of manufacturing same |
| JP2009245925A (en) * | 2008-03-10 | 2009-10-22 | Nissan Motor Co Ltd | Electrode for battery, battery using it, and its method for manufacturing |
| CN101960652A (en) * | 2008-03-10 | 2011-01-26 | 日产自动车株式会社 | Battery with battery electrode and method of manufacturing same |
| US9105939B2 (en) | 2008-03-10 | 2015-08-11 | Nissan Motor Co., Ltd. | Battery with battery electrode and method of manufacturing same |
| WO2021192541A1 (en) * | 2020-03-24 | 2021-09-30 | パナソニックＩｐマネジメント株式会社 | Electrode for secondary batteries and method for producing same |
| WO2023043245A1 (en) * | 2021-09-16 | 2023-03-23 | 주식회사 엘지에너지솔루션 | Electrode for lithium secondary battery, method for manufacturing same, and lithium secondary battery comprising same |
| CN114243104A (en) * | 2021-12-20 | 2022-03-25 | 惠州亿纬锂能股份有限公司 | Flexible electrolyte membrane, battery and preparation method |
Also Published As
| Publication number | Publication date |
|---|---|
| JP4059556B2 (en) | 2008-03-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP2000040504A (en) | Manufacture of positive mix for organic electrolyte battery | |
| CA1125849A (en) | Method of preparing a battery paste containing fibrous polyfluoroethylene for use in the plates of a lead-acid storage battery | |
| KR101661050B1 (en) | Composite graphite material, method for producing same, negative electrode material for lithium ion secondary batteries, negative electrode for lithium ion secondary batteries, and lithium ion secondary battery | |
| EP2296207A1 (en) | Electrode for non-aqueous electrolyte secondary battery, manufacturing method therefor, and non-aqueous electrolyte secondary battery | |
| JP4659367B2 (en) | Battery electrode and manufacturing method thereof | |
| US11258069B2 (en) | Current collector, battery and methods for producing the same | |
| WO2022050252A1 (en) | All-solid-state secondary cell mixture, all-solid-state secondary cell mixture sheet, method for manufacturing same, and all-solid-state secondary cell | |
| JP4059556B2 (en) | Non-aqueous electrolyte battery and manufacturing method thereof | |
| JP3503688B2 (en) | Lithium secondary battery | |
| JP6162482B2 (en) | Negative electrode material for lithium ion secondary battery and production method thereof, negative electrode for lithium ion secondary battery and lithium ion secondary battery using the same | |
| JP2000149954A (en) | Nonaqueous electrolyte battery, and its manufacture | |
| JPH10162811A (en) | Electrode material for battery and secondary battery | |
| JP3022758B2 (en) | Alkaline manganese battery | |
| JP2006269110A (en) | Metal-graphite composite particle, cathode material for lithium ion secondary battery, cathode, and the lithium ion secondary battery | |
| JP6518975B2 (en) | Method for producing non-graphitizable carbon material | |
| JP5358938B2 (en) | Flat nonaqueous electrolyte battery | |
| JP2005071712A (en) | Manufacturing method of positive electrode | |
| JPH0850894A (en) | Nonaqueous solvent secondary battery | |
| JPH10106546A (en) | Manufacture of electrode for battery | |
| JPS5990364A (en) | Manufacture of positive electrode for battery | |
| JPH10106528A (en) | Manufacture of separator | |
| TWI767490B (en) | Carbonaceous material, method of producing carbonaceous material, negative electrode for lithium ion secondary battery and lithium ion secondary battery | |
| JP6911221B1 (en) | Carbonaceous material, manufacturing method of carbonaceous material, negative electrode for lithium ion secondary battery and lithium ion secondary battery | |
| EP4310933A1 (en) | Method for manufacturing positive electrode mixture for flat lithium primary battery and flat lithium primary battery | |
| JPH01151158A (en) | Manufacture of positive electrode for nonaqueous solvent cell |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20070220 |
|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20070406 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20071120 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20071218 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20101228 Year of fee payment: 3 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20101228 Year of fee payment: 3 |
|
| S531 | Written request for registration of change of domicile |
Free format text: JAPANESE INTERMEDIATE CODE: R313531 |
|
| S533 | Written request for registration of change of name |
Free format text: JAPANESE INTERMEDIATE CODE: R313533 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20101228 Year of fee payment: 3 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20101228 Year of fee payment: 3 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20111228 Year of fee payment: 4 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20111228 Year of fee payment: 4 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20121228 Year of fee payment: 5 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20121228 Year of fee payment: 5 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20131228 Year of fee payment: 6 |
|
| S111 | Request for change of ownership or part of ownership |
Free format text: JAPANESE INTERMEDIATE CODE: R313117 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| S531 | Written request for registration of change of domicile |
Free format text: JAPANESE INTERMEDIATE CODE: R313531 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| S111 | Request for change of ownership or part of ownership |
Free format text: JAPANESE INTERMEDIATE CODE: R313115 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| EXPY | Cancellation because of completion of term |