JP2001357841A - Inspection method for electrode material - Google Patents
Inspection method for electrode materialInfo
- Publication number
- JP2001357841A JP2001357841A JP2000179340A JP2000179340A JP2001357841A JP 2001357841 A JP2001357841 A JP 2001357841A JP 2000179340 A JP2000179340 A JP 2000179340A JP 2000179340 A JP2000179340 A JP 2000179340A JP 2001357841 A JP2001357841 A JP 2001357841A
- Authority
- JP
- Japan
- Prior art keywords
- electrode material
- resistance value
- composition ratio
- inspection method
- electric resistance
- 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
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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
【０００１】[0001]
【発明の属する技術分野】本発明は、電池やコンデンサ
等の蓄電素子における電極材料成分の配合に係わる検査
方法に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for inspecting a storage element such as a battery or a capacitor in connection with the mixing of electrode material components.
【０００２】[0002]
【従来の技術】従来、蓄電素子の製造においては、電極
材料成分配合時（例えば、アルカリ電池の正極合剤で
は、二酸化マンガンと黒鉛の混合材料を使用）の品質確
認方法として、合剤の外観比重や水分の測定等の検査を
行っていた。ところが、このような検査方法だけでは合
剤の配合ミス（電極材料の種類や配合量の異常）を正確
に発見できないことが有り、そのまま工程が進んで電池
組立後の特性検査において初めて異常が発見されるケー
スもあった。例えば、前記合剤の配合量に異常が有る
と、電池の内部抵抗が所定値より大きくなり、組立後の
特性検査で所定の電流が流れないといった現象である。2. Description of the Related Art Conventionally, in the production of an electric storage device, the appearance of a mixture has been determined as a quality check method when compounding electrode material components (for example, a mixed material of manganese dioxide and graphite is used in a cathode mixture of an alkaline battery). Inspections such as measurement of specific gravity and moisture were performed. However, with such an inspection method alone, it may not be possible to accurately detect the compounding mistake of the mixture (an abnormality in the type and amount of the electrode material), and the process proceeds as it is, and an abnormality is found for the first time in the characteristic inspection after battery assembly. In some cases it was done. For example, when there is an abnormality in the amount of the mixture, the internal resistance of the battery becomes larger than a predetermined value, and a predetermined current does not flow in a characteristic test after assembly.
【０００３】[0003]
【発明が解決しようとする課題】上記のように、電極材
料の配合ミスが電池組立後の検査まで発見されない場
合、異常な電極材料が長時間に渡って継続して配合され
てしまうことになり、不良品が大量に発生してしまう。
これでは、極めて不経済である。As described above, if a mistake in the mixing of the electrode materials is not found until the inspection after the battery is assembled, an abnormal electrode material will be continuously mixed for a long time. In addition, a large number of defective products are generated.
This is extremely uneconomical.
【０００４】また、配合ミスを確実に発見するためには
配合組成比の定量分析が有効であるが、これには多くの
時間を要することから、現状では電極材料の製造工程中
で逐次実施する有効な手段はなかった。[0004] In addition, quantitative analysis of the composition ratio is effective for surely detecting a mixing error. However, since it takes a lot of time, the analysis is currently performed sequentially during the manufacturing process of the electrode material. There was no effective means.
【０００５】本発明は、上記従来の検査方法の問題点に
鑑みて成されたもので、加圧成形した電極材料の電気抵
抗値より配合組成比の良否を判断するようにした、簡単
で、且つ確実な電極材料の検査方法を提供することを目
的としている。The present invention has been made in view of the problems of the above-described conventional inspection methods, and is a simple and simple method for judging whether or not the composition ratio is good or bad based on the electric resistance value of a pressure-molded electrode material. It is another object of the present invention to provide a method for inspecting an electrode material reliably.
【０００６】[0006]
【課題を解決するための手段】すなわち、請求項１に記
載の電極材料の検査方法は、蓄電素子における電極材料
成分の配合が正規に成されたか判断するための検査方法
において、前記電極材料の電気抵抗値より配合組成比の
良否を判断することを特徴としている。According to a first aspect of the present invention, there is provided an electrode material inspection method for judging whether or not the mixture of electrode material components in a storage element is properly formed. It is characterized in that the quality of the composition ratio is judged from the electric resistance value.
【０００７】また、請求項２に記載の電極材料の検査方
法は、蓄電素子における電極材料成分の配合が正規に成
されたか判断するための検査方法において、所定の圧力
で加圧成形した前記電極材料の電気抵抗値より配合組成
比の良否を判断することを特徴としている。According to a second aspect of the present invention, there is provided an electrode material inspection method for judging whether or not the mixture of the electrode material components in the electric storage element is properly formed. It is characterized in that the quality of the composition ratio is judged from the electric resistance value of the material.
【０００８】所謂、蓄電素子の電極材料は、その原料と
なる各材料成分の配合比に応じて固有の電気抵抗値を示
す。従って、予め製造する電極材料の配合組成比とその
配合組成比における電気抵抗値の相関関係を求めておく
ことにより、製造工程において許容可能な配合組成比の
上限および下限に対応する電気抵抗値を明確に設定する
ことができる。そして、この電気抵抗値の範囲内を良品
として品質管理すれば、後工程に大量の不良品が流れる
といった不都合を回避することができる。また、抵抗測
定の際、電極材料を加圧成形することにより得られる電
気抵抗値は安定する。[0008] A so-called electrode material of a power storage element exhibits a unique electric resistance value in accordance with the mixing ratio of each material component as a raw material. Accordingly, by previously determining the correlation between the composition ratio of the electrode material to be manufactured and the electric resistance value at the composition ratio, the electric resistance values corresponding to the upper limit and the lower limit of the allowable composition ratio in the manufacturing process can be determined. Can be set clearly. If quality control is performed within the range of the electric resistance value as a non-defective product, it is possible to avoid an inconvenience that a large number of defective products flow in a subsequent process. Further, at the time of resistance measurement, the electric resistance value obtained by pressing the electrode material is stabilized.
【０００９】また、請求項３に記載の電極材料の検査方
法は、一定範囲の粒径を有する電極材料を使用すること
を特徴としている。The method for inspecting an electrode material according to the third aspect is characterized in that an electrode material having a certain range of particle size is used.
【００１０】サンプル電極材料（検査用電極材料）の粒
径を揃えることによって電気抵抗値のバラツキを抑え、
より信頼性の高い配合組成比の確認が行える。[0010] The uniformity of the particle size of the sample electrode material (electrode material for inspection) suppresses the variation of the electric resistance value,
A more reliable confirmation of the composition ratio can be performed.
【００１１】また、請求項４に記載の電極材料の検査方
法は、前記電極材料を絶縁性の筒状体に充填すると共
に、当該電極材料を前記筒状体の開口部より導電性の加
圧冶具にて所定圧で加圧・圧縮し、その際の前記加圧冶
具間の電気抵抗値を測定し、当該電気抵抗値が一定範囲
内にある場合に限り良品とすることを特徴としている。According to a fourth aspect of the present invention, there is provided a method for inspecting an electrode material, wherein the electrode material is filled in an insulating cylindrical body, and the electrode material is pressurized through an opening of the cylindrical body. The jig is pressurized and compressed at a predetermined pressure, and the electric resistance value between the pressing jigs at that time is measured, and a good product is obtained only when the electric resistance value is within a certain range.
【００１２】このように本検査方法では、専用冶具に電
極材料を充填して加圧するだけの簡単操作であるので、
電極材料の検査は製造工程の流れの中で実施でき、短時
間で配合組成比の良否判定を行うことができる。As described above, according to the present inspection method, it is a simple operation of filling the electrode material into the dedicated jig and pressurizing it.
The inspection of the electrode material can be performed in the flow of the manufacturing process, and the quality of the composition ratio can be determined in a short time.
【００１３】また、請求項５に記載の電極材料の検査方
法は、前記蓄電素子がアルカリ電池であることを特徴と
している。[0013] The method for inspecting an electrode material according to a fifth aspect is characterized in that the power storage element is an alkaline battery.
【００１４】[0014]
【発明の実施の形態】以下、図１および図２に基づい
て、本発明をアルカリ電池に適用した場合の実施形態を
説明する。DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS An embodiment in which the present invention is applied to an alkaline battery will be described below with reference to FIGS.
【００１５】一般に、筒型アルカリ電池に用いられてい
る正極合剤として、正極活物質である二酸化マンガン
（ＭｎＯ２）に炭素材料を混合したものが広く知られて
いる。ここで、前記炭素材料は、正極合剤中に分散して
いる二酸化マンガン粒子に有効に電子を運ぶ導電助剤と
して機能し、且つ、正極合剤を中空円筒状に加圧成形す
る時の潤滑材としても機能する。Generally, as a positive electrode mixture used in a cylindrical alkaline battery, a mixture of manganese dioxide (MnO 2 ), which is a positive electrode active material, and a carbon material is widely known. Here, the carbon material functions as a conductive aid that effectively carries electrons to the manganese dioxide particles dispersed in the positive electrode mixture, and lubrication when the positive electrode mixture is pressure-formed into a hollow cylindrical shape. Also functions as a material.
【００１６】この導電助剤として用いられる炭素材料の
条件は、導電性に優れていること、電解液の保液性
に優れていること、合剤の成形性（潤滑性向上）に優
れていること等であり、これらの条件を備えた材料とし
て専ら黒鉛（Ｇｒ）が使用されている。ところが、正極
合剤の導電性や成形性を重視して黒鉛の添加量を多くし
過ぎると、その分合剤中の正極活物質の量が減少して電
池組立後の電池放電容量が低下し、逆に黒鉛の含有量が
少な過ぎると加圧成形時に合剤の剥がれや割れが発生す
る等といった弊害を招くことになる。The condition of the carbon material used as the conductive additive is excellent in conductivity, excellent in retaining the electrolyte, and excellent in moldability (improving lubricity) of the mixture. Therefore, graphite (Gr) is exclusively used as a material satisfying these conditions. However, if the added amount of graphite is excessively increased with emphasis on the conductivity and moldability of the positive electrode mixture, the amount of the positive electrode active material in the mixture decreases, and the battery discharge capacity after battery assembly decreases. Conversely, if the content of graphite is too small, adverse effects such as peeling and cracking of the mixture during pressure molding are caused.
【００１７】このような事情から、高品質の正極合剤を
得るには二酸化マンガンと黒鉛の配合比（ＭｎＯ２／Ｇ
ｒ比）を常に好適な一定範囲に管理する必要があった。
図２は、上記配合組成比に対する電極材料の電気抵抗特
性を示しており、前記正極合剤において、Ｇｒの含有量
が多い（すなわち、ＭｎＯ２／Ｇｒ比が小さい）程電気
抵抗値は小さくなり、逆にＧｒの含有量が少ない（Ｍｎ
Ｏ２／Ｇｒ比が大きい）程電気抵抗値は大きくなる傾向
を示し、その変化量は指数関数的である。本実施形態で
は、ＭｎＯ２／Ｇｒ比の範囲Ａ〜Ｂを正常と見なせる配
合組成比の許容範囲としている。Under these circumstances, in order to obtain a high-quality positive electrode mixture, the mixing ratio of manganese dioxide and graphite (MnO 2 / G
r ratio) must always be maintained in a suitable constant range.
FIG. 2 shows the electrical resistance characteristics of the electrode material with respect to the above composition ratio. In the positive electrode mixture, the greater the content of Gr (that is, the smaller the MnO 2 / Gr ratio), the smaller the electrical resistance value. On the contrary, the Gr content is small (Mn
The electrical resistance value tends to increase as the O 2 / Gr ratio increases), and the change amount is exponential. In the present embodiment, the range A to B of the MnO 2 / Gr ratio is set as the allowable range of the composition ratio that can be regarded as normal.
【００１８】本発明は、正極合剤や負極合剤等、蓄電素
子における各電極材料の配合組成比の良否をそれらの電
気抵抗値より判断するようにしたもので、以下、その具
体的方法を説明する。According to the present invention, the quality of the composition ratio of each electrode material in a power storage element such as a positive electrode mixture and a negative electrode mixture is judged from their electrical resistance values. explain.
【００１９】図１は、電極材料の電気抵抗値を測定する
ための構成を示しており、図１中、符号１は絶縁材より
成る筒状体、符号２，３は導電性の良い金属製の加圧冶
具、符号５は電気抵抗値を測定するための測定器（例え
ば、ＬＣＲメータ等が好適である）であって、前記加圧
冶具２と３の間に接続されている。FIG. 1 shows a configuration for measuring the electric resistance of an electrode material. In FIG. 1, reference numeral 1 denotes a cylindrical body made of an insulating material, and reference numerals 2 and 3 denote a metal made of a metal having good conductivity. Reference numeral 5 designates a measuring instrument (for example, preferably an LCR meter or the like) for measuring an electric resistance value, and is connected between the pressing jigs 2 and 3.
【００２０】抵抗測定に際し、先ず、前記筒状体１の底
部開口部を加圧冶具３で塞いで合剤の容器を構成し、こ
の容器内に電極材料４、例えば、アルカリ電池の正極合
剤では、ＭｎＯ２粉末とＧｒ粉末を混合した粉体を筒状
体上面ですり切り、常に一定体積を充填する。次いで、
もう一方の加圧冶具２を用いて筒状体１の上部開口部よ
り内部の正極合剤を所定の圧力で加圧・圧縮し、ＬＣＲ
メータにてその時の電気抵抗値を測定する。この場合、
合剤の電気抵抗値は加圧力によって変化するので、常に
所定の圧力を掛ける必要がある。本実施形態では、加圧
力を１００ｋｇ／ｃｍ２に設定している。また、電気抵
抗値は同じ電極材料４を使用しても粉体の粒径によって
変化するので、安定した測定値を得るには予めサンプル
合剤の粒径を一定範囲内に限定しておくと良い。本実施
形態では、電極材料の種類によって３００μｍ、あるい
は６００μｍ以上のものを篩い分けして使用している。When measuring the resistance, first, the bottom opening of the cylindrical body 1 is closed with a pressing jig 3 to form a mixture container, and an electrode material 4 such as a positive electrode mixture of an alkaline battery is provided in the container. Then, the powder obtained by mixing the MnO 2 powder and the Gr powder is cut on the upper surface of the cylindrical body, and is always filled with a fixed volume. Then
The other positive pressure jig 2 is used to pressurize and compress the internal positive electrode mixture at a predetermined pressure from the upper opening of the cylindrical body 1 at a predetermined pressure, and perform LCR.
Measure the electrical resistance at that time with a meter. in this case,
Since the electric resistance value of the mixture changes with the applied pressure, it is necessary to always apply a predetermined pressure. In the present embodiment, the pressure is set to 100 kg / cm 2 . In addition, since the electrical resistance value varies depending on the particle size of the powder even when the same electrode material 4 is used, in order to obtain a stable measurement value, it is necessary to limit the particle size of the sample mixture in advance to a certain range. good. In the present embodiment, those having a size of 300 μm or 600 μm or more are sieved and used depending on the type of the electrode material.
【００２１】次に、ＬＲＣメータによる測定結果と、予
め用意しておいた前記測定条件における電極材料の電気
抵抗値と配合組成比との関係（図２参照）より、サンプ
ル合剤の配合組成比の良否を判断する。すなわち、測定
した電気抵抗値が図２に示す下限値ＣΩから上限値ＤΩ
までの範囲に入っている場合には良品と判断し、範囲外
の場合は不良品として処理する。尚、組成配合比と電気
抵抗値の関係はＭｎＯ ２、Ｇｒ以外の材料を含む電極材
料の構成内容により異なるので、電極材料成分の種類に
応じて組成配合比と電気抵抗値の関係をその都度求めて
おく必要がある。Next, the measurement result by the LRC meter and the preliminary
Of the electrode material under the measurement conditions prepared above
From the relationship between the resistance value and the composition ratio (see FIG. 2), the sump
The quality of the composition ratio of the mixture is judged. That is, measurement
From the lower limit CΩ shown in FIG. 2 to the upper limit DΩ
If it is within the range, it is judged as good and out of range
In the case of, it is processed as defective. The composition ratio and the electricity
The relationship between the resistance values is MnO 2Materials containing materials other than, Gr
It depends on the composition of the material.
The relationship between the composition ratio and the electrical resistance in each case
Need to be kept.
【００２２】以上のように、本発明の検査方法は、短時
間で行える極めて簡単なものであるから、電極材料の製
造工程の流れの中で逐次実施することができる。配合組
成比の異常を材料配合工程の直後に発見できれば、後工
程に大量の不良品が流れるといった不都合を回避するこ
とができる。As described above, since the inspection method of the present invention is very simple and can be performed in a short time, it can be sequentially performed in the flow of the manufacturing process of the electrode material. If an abnormality in the compounding composition ratio can be found immediately after the material compounding step, it is possible to avoid the inconvenience that a large number of defective products flow in the subsequent steps.
【００２３】尚、本実施形態では、アルカリ電池を例に
して説明したが、本発明の適応対象がこれのみに限定さ
れるものでないことは勿論であり、コンデンサ等の蓄電
素子にも広く適用可能である。Although the present embodiment has been described by taking an alkaline battery as an example, it is needless to say that the application of the present invention is not limited to this, and the present invention can be widely applied to power storage elements such as capacitors. It is.
【００２４】[0024]
【発明の効果】以上説明したように、本発明の電極材料
の検査方法では、当該電極材料の電気抵抗値より配合組
成比の良否を判断するようにしたので、検査に長時間を
要せず、配合ミスを材料配合工程の直後に素早く発見す
ることができ、これにより、従来のように後工程まで不
良品が流れてしまう不都合を無くすことができ、よっ
て、不良品の大量発生を未然に回避できる。As described above, according to the electrode material inspection method of the present invention, the quality of the composition ratio is determined based on the electric resistance value of the electrode material. In addition, it is possible to quickly find a compounding error immediately after the material compounding process, thereby eliminating the problem of defective products flowing to subsequent processes as in the past, and thus preventing the occurrence of large quantities of defective products. Can be avoided.
【００２５】また、抵抗測定の際、冶具を使用して電極
材料を所定の圧力で加圧成形したり、サンプル電極材料
を一定範囲の粒径に篩い分けすることにより、電気抵抗
値のバラツキを抑えることができ、より正確な配合組成
比の確認が行える。In addition, when measuring the resistance, the electrode material is press-formed at a predetermined pressure using a jig, or the sample electrode material is sieved to a certain range of particle size to reduce the variation in the electric resistance value. Thus, the composition ratio can be confirmed more accurately.
【図１】本発明に係る電極材料の検査方法を示す図であ
る。FIG. 1 is a diagram showing an electrode material inspection method according to the present invention.
【図２】電極材料の電気抵抗値と配合組成比の関係を示
す図である。FIG. 2 is a diagram showing a relationship between an electric resistance value of an electrode material and a composition ratio.
１ 筒状体 ２，３ 加圧冶具 ４ 電極材料 ５ ＬＣＲメータ DESCRIPTION OF SYMBOLS 1 Cylindrical body 2, 3 Pressing jig 4 Electrode material 5 LCR meter
───────────────────────────────────────────────────── フロントページの続き Ｆターム(参考） 2G060 AA09 AD03 AD04 AE40 AF07 AG03 EA07 EB07 GA01 HA02 KA15 5H050 AA19 BA04 BA11 CA05 DA02 DA10 EA08 GA03 GA28 GA30 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 2G060 AA09 AD03 AD04 AE40 AF07 AG03 EA07 EB07 GA01 HA02 KA15 5H050 AA19 BA04 BA11 CA05 DA02 DA10 EA08 GA03 GA28 GA30
Claims (5)
正規に成されたか判断するための検査方法において、 前記電極材料の電気抵抗値より配合組成比の良否を判断
することを特徴とする電極材料の検査方法。1. An inspection method for judging whether or not a mixture of electrode material components in a storage element is properly formed, wherein the quality of a composition ratio is judged from an electric resistance value of the electrode material. Inspection method.
正規に成されたか判断するための検査方法において、 所定の圧力で加圧成形した前記電極材料の電気抵抗値よ
り配合組成比の良否を判断することを特徴とする電極材
料の検査方法。2. An inspection method for judging whether or not the mixture of electrode material components in a power storage element is properly formed, wherein the quality of the composition ratio is judged based on the electric resistance value of the electrode material pressed under a predetermined pressure. A method for inspecting an electrode material.
することを特徴とする請求項２に記載の電極材料の検査
方法。3. The method for inspecting an electrode material according to claim 2, wherein an electrode material having a particle size in a certain range is used.
ると共に、当該電極材料を前記筒状体の開口部より導電
性の加圧冶具にて所定圧で加圧・圧縮し、 その際の前記加圧冶具間の電気抵抗値を測定し、当該電
気抵抗値が一定範囲内にある場合に限り良品とすること
を特徴とする請求項２または請求項３の何れかに記載の
電極材料の検査方法。4. An insulating cylindrical body is filled with the electrode material, and the electrode material is pressurized and compressed at a predetermined pressure from an opening of the cylindrical body by a conductive pressing jig. 4. The electrode according to claim 2, wherein an electrical resistance value between the pressing jigs is measured, and the product is determined to be non-defective only when the electrical resistance value is within a certain range. Material inspection method.
を特徴とする請求項１から請求項４までの何れかに記載
の電極材料の検査方法。5. The method for inspecting an electrode material according to claim 1, wherein the storage element is an alkaline battery.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8192864B2 (en) | 2007-02-01 | 2012-06-05 | Panasonic Corporation | Battery, examination method and manufacturing method for negative electrode thereof, and examination apparatus and manufacturing apparatus for negative electrode thereof |
| CN107421993A (en) * | 2017-05-27 | 2017-12-01 | 双登集团股份有限公司 | Powdered electrode material electric conductivity simulating test device |
| JP2020528643A (en) * | 2017-09-19 | 2020-09-24 | エルジー・ケム・リミテッド | Positive electrode material for lithium secondary battery, this manufacturing method, positive electrode for lithium secondary battery including this, and lithium secondary battery |
-
2000
- 2000-06-15 JP JP2000179340A patent/JP3719108B2/en not_active Expired - Lifetime
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8192864B2 (en) | 2007-02-01 | 2012-06-05 | Panasonic Corporation | Battery, examination method and manufacturing method for negative electrode thereof, and examination apparatus and manufacturing apparatus for negative electrode thereof |
| CN107421993A (en) * | 2017-05-27 | 2017-12-01 | 双登集团股份有限公司 | Powdered electrode material electric conductivity simulating test device |
| JP2020528643A (en) * | 2017-09-19 | 2020-09-24 | エルジー・ケム・リミテッド | Positive electrode material for lithium secondary battery, this manufacturing method, positive electrode for lithium secondary battery including this, and lithium secondary battery |
| US11637275B2 (en) | 2017-09-19 | 2023-04-25 | Lg Energy Solution, Ltd. | Positive electrode material for lithium secondary battery, method of preparing the same, and positive electrode for lithium secondary battery and lithium secondary battery which include the positive electrode material |
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| JP3719108B2 (en) | 2005-11-24 |
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