JP3622676B2 - Thermal material and thermal element - Google Patents
Thermal material and thermal element Download PDFInfo
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- JP3622676B2 JP3622676B2 JP2001008558A JP2001008558A JP3622676B2 JP 3622676 B2 JP3622676 B2 JP 3622676B2 JP 2001008558 A JP2001008558 A JP 2001008558A JP 2001008558 A JP2001008558 A JP 2001008558A JP 3622676 B2 JP3622676 B2 JP 3622676B2
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- 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
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- Protection Of Static Devices (AREA)
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Description
【０００１】
【発明の属する技術分野】
本発明は、温度の上昇に伴って低抵抗化するＮＴＣ(Negative Temperature Coefficient)素子に関する。
【０００２】
【従来の技術】
リチウムイオン二次電池の過充電保護素子として、温度の上昇に伴って高抵抗化するＰＴＣ素子、バイメタル素子、温度ヒューズが一般に用いられている。
【０００３】
しかし、これらの過充電保護素子は、いずれも充電回路に対し直列に配置されるために、電力を消費して二次電池の可使用時間を短縮してしまうという問題がある。また、過充電が実際に生じた場合であっても、リチウムイオン二次電池にも過充電保護素子にも外見上の変化がすぐには現れないという問題がある。
【０００４】
そこで、図１に示すように、リチウムイオン二次電池と並列に抵抗Ｒ（例えば豆電球）とＮＴＣ素子とを接続することにより、過充電が生じた場合にはリチウムイオン二次電池が発熱し、その熱によりＮＴＣ素子がトリップして低抵抗化し、電流がＮＴＣ素子と抵抗Ｒ側に流れるようにし、二次電池への充電電流を遮断することが考えられる。
【０００５】
【発明が解決しようとする課題】
しかしながら、従来のＮＴＣ素子はセラミックス系であり、低抵抗化したときの抵抗値（例えば、約１０Ω程度）が十分に小さいとは言えず、過充電電流を遮断するには不十分であった。また、低抵抗化後に保護素子の温度が低下すると可逆的に抵抗値が増大し、充電電流が再びリチウムイオン二次電池に流れるようになり、本来使用すべきでない電池を再度使用する結果を招き、安全面で問題があり、過充電保護素子としては使用できないものであった。
【０００６】
本発明は、以上の従来の技術の問題を解決しようとするものであり、特に、リチウムイオン二次電池の過充電保護素子用材料として、平常時には非常に高い抵抗値を示すが、所定の温度以上に加熱された後には過充電電流を十分に遮断できる程度に不可逆的に低抵抗化する性質（ＮＴＣ特性）を有し、二次電池に対し並列に接続可能な新規な感熱材料を提供することを目的とする。
【０００７】
【課題を解決するための手段】
本発明者は、図２（ａ）に示すように熱収縮性材料１中に導電粒子２を分散させることにより得られた材料を加熱することにより収縮させると、図２（ｂ）に示すように導電粒子２同士が接触するようになり、収縮前に比べ収縮後の抵抗値を大きく減少させることができることを見出し、本発明を完成するに至った。
【０００９】
即ち、本発明は、熱収縮性樹脂中に導電粒子を分散させてなる感熱材料に一対の電極端子が設けられている不可逆性ＮＴＣ素子を提供する。この不可逆性ＮＴＣ素子は、リチウムイオン二次電池用の過充電保護素子として有用である。
【００１０】
また、本発明は、上述の不可逆性ＮＴＣ素子の製造方法として、熱収縮性樹脂中に導電粒子を分散させて筒状に成形してなる感熱材料の両端のそれぞれの開口部に電極端子を差込み、両端を熱収縮させて電極端子を当該感熱材料に一体化する不可逆性ＮＴＣ素子の製造方法を提供する。
【００１１】
【発明の実施の形態】
本発明の不可逆性ＮＴＣ素子は、熱収縮性樹脂中に導電粒子を分散させた感熱材料に一対の電極端子が設けられているものであり、熱収縮性樹脂の熱収縮開始温度以上に加熱されることにより不可逆的に低抵抗化する。
【００１２】
本発明で使用する熱収縮性樹脂としては、絶縁材料であって所定の温度以上に加熱されると熱収縮し、加工成形が容易なものを好ましく使用することができる。このような熱収縮性樹脂としては、シラン共重合低密度ポリエチレン（特開平６−３３５９６７号公報）、エチレン−（メタ）アクリル酸共重合体アイオノマー（特開平１１−１７０３６５号公報、特開平８−２５９７０４号公報）、フッ素系共重合体（特開平９−３１２８５号公報、特開平８−２４５８５０号公報、特開平８−２１６２５２号公報、特開平７−２０５２８５号公報）、スチレン系共重合体（特開平１０−９５８６３号公報）、芳香族ポリエステル−ポリエステルエラストマーブレンド物（特開平１０−４６０１４号公報）等を挙げることができる。これらの材料は必要に応じて架橋剤を含有し、あるいは導電粒子を分散させた後に電子線照射により架橋処理されていることが好ましい。
【００１３】
本発明において、導電粒子としては公知の導電粒子を使用することができ、カーボンブラック、金属粉、金属ケイ化物粉、金属窒化物粉、樹脂コア金属メッキ被覆粒子等を挙げることできる。
【００１４】
導電粒子の粒径は、熱収縮性材料の収縮率や低抵抗化した際の抵抗値等を考慮して選択する。熱収縮性材料に対する導電粒子の配合量も熱収縮性材料の収縮率や低抵抗化した際の抵抗値等を考慮して選択する。
【００１５】
本発明で使用する感熱材料の形態は、特に制限はないが、通常、シート状又は筒状に成形しておくこと好ましい。シート状の感熱材料は、熱収縮性樹脂に導電粒子をニーダーにて均一に分散し、圧延ロール間を通過させ、必要に応じて電子線を照射し、更に高温で延伸しながら所定の厚さに固定することにより製造できる。また、筒状の感熱材料は、熱収縮性樹脂に導電粒子を均一に分散したコンパウンドを押出し成形機で筒状に押出し、必要に応じて電子線を照射し、更に高温で延伸しながら所定の径に固定することにより製造できる。
【００１６】
本発明で使用する感熱材料には、収縮率や抵抗値の調整のために、架橋剤、非導電粒子等を適宜添加することができる。
【００１７】
以上説明した感熱材料に一対の電極端子を設けることにより電子素子として使用可能な本発明の不可逆性ＮＴＣ素子となる。
【００１８】
電極端子のサイズや感熱材料への電極端子の取り付け方法には特に制限はなく、不可逆性ＮＴＣ素子の使用目的に応じて適宜選択することができる。取り付け方法の好ましい例としては、筒状に成形されている感熱材料の両端のそれぞれの開口部に電極端子を差込み、両端を熱収縮させて電極端子を不可逆性ＮＴＣ素子に一体化する方法を挙げることができる。
【００１９】
本発明の感熱素子は、図１におけるＮＴＣ素子、即ちリチウムイオン二次電池用過充電保護素子として有用である。また、空冷ファンの熱スイッチや火災センサーとしても有用である。
【００２０】
【実施例】
以下、本発明を実施例により、具体的に説明する。
【００２１】
実施例１
シラン共重合低密度ポリエチレン（リンクロンＸＦ８００Ｔ、三菱化学社製）１００重量部にカーボン粒子（ＰＣ−１０２０、日本カーボン社製）１５０重量部をニーダーにて均一に混合した。
【００２２】
得られた混合物を、押出し成形機（ＫＥＸ−２５、栗本鉄工所製）を使用して筒状に成形し、更に電子線を５Ｍｒａｄ照射することにより架橋させ、その後に１５０℃の温度雰囲気下で延伸しながら所期の径の筒状感熱材料を作製した。
【００２３】
得られた筒状感熱材料の両端の開口部に、それぞれ電極端子を差し込み、両端部を加熱することにより電極端子を感熱材料に固定し、不可逆性ＮＴＣ素子とした。
【００２４】
この感熱素子の抵抗値は１００ｋΩであった。また、１００℃の湯に３０秒間浸漬させた後の抵抗値は０．５Ωであった。
【００２５】
得られた感熱素子を図１に示すリチウムイオン二次電池用充電回路のＮＴＣ素子として二次電池に密着させるように組み込んだところ、過充電が生じた場合には、二次電池への電流が遮断された。二次電池の温度が低下しても遮断した電流は回復しなかった。従って、この感熱素子は、不可逆的に過充電電流を遮断したことがわかった。
【００２６】
【発明の効果】
本発明の不可逆性ＮＴＣ素子は、特に、リチウムイオン二次電池の過充電保護素子として、平常時には非常に高い抵抗値を示すが、所定の温度以上に加熱された後には過充電電流を十分に遮断できる程度に不可逆的に低抵抗化する性質（ＮＴＣ特性）を有し、二次電池に対し並列に接続可能である。
【図面の簡単な説明】
【図１】ＮＴＣ素子を二次電池用過充電保護素子として使用した充電回路図である。
【図２】本発明の感熱材料の動作説明図である。
【符号の説明】
１ 熱収縮性材料、２ 導電粒子[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a NTC (Negative Temperature Coefficient) device to reduce the resistance of with increasing temperature.
[0002]
[Prior art]
As an overcharge protection element for a lithium ion secondary battery, a PTC element, a bimetal element, and a thermal fuse that increase in resistance with an increase in temperature are generally used.
[0003]
However, since these overcharge protection elements are all arranged in series with respect to the charging circuit, there is a problem that power consumption is consumed and the usable time of the secondary battery is shortened. In addition, even when overcharging actually occurs, there is a problem that an apparent change does not immediately appear in the lithium ion secondary battery or the overcharge protection element.
[0004]
Therefore, as shown in FIG. 1, when a resistor R (for example, a miniature bulb) and an NTC element are connected in parallel with the lithium ion secondary battery, the lithium ion secondary battery generates heat when overcharge occurs. It is conceivable that the NTC element is tripped by the heat to reduce the resistance so that current flows to the NTC element and the resistance R side, and the charging current to the secondary battery is cut off.
[0005]
[Problems to be solved by the invention]
However, conventional NTC elements are ceramic-based, and cannot be said to have a sufficiently small resistance value (for example, about 10Ω) when the resistance is lowered, and are insufficient to cut off the overcharge current. Also, when the temperature of the protective element decreases after the resistance is lowered, the resistance value increases reversibly, and the charging current flows again to the lithium ion secondary battery, resulting in the reuse of a battery that should not be used originally. There was a problem in safety, and it could not be used as an overcharge protection element.
[0006]
The present invention is intended to solve the above-described problems of the prior art, and in particular, as a material for an overcharge protection element of a lithium ion secondary battery, it exhibits a very high resistance value under normal conditions, but has a predetermined temperature. Provided is a novel heat-sensitive material that has a property (NTC characteristic) of irreversibly reducing the resistance so that overcharge current can be sufficiently cut off after being heated as described above and can be connected in parallel to a secondary battery. For the purpose.
[0007]
[Means for Solving the Problems]
When the present inventor contracts the material obtained by dispersing the
[0009]
That is, the present invention provides an irreversible NTC element in which a pair of electrode terminals are provided on a heat-sensitive material obtained by dispersing conductive particles in a heat-shrinkable resin . This irreversible NTC element is useful as an overcharge protection element for a lithium ion secondary battery.
[0010]
Further, in the present invention, as a method of manufacturing the above-described irreversible NTC element, electrode terminals are inserted into respective openings at both ends of a heat-sensitive material formed by dispersing conductive particles in a heat-shrinkable resin and forming a cylindrical shape. The manufacturing method of the irreversible NTC element which heat-shrinks both ends and integrates an electrode terminal with the said heat-sensitive material is provided.
[0011]
DETAILED DESCRIPTION OF THE INVENTION
Irreversible NTC element of the present invention has a pair of electrode terminals are disposed on the heat-sensitive material obtained by dispersing conductive particles in a heat-shrinkable resin is heated above the heat shrinkage starting temperature of the heat-shrinkable resin that it turns into irreversibly low resistance by Rukoto.
[0012]
As a heat-shrinkable resin to be used in the present invention can when heated above a predetermined temperature an insulating material heat shrunk, processing molding is preferably used easy. Examples of such heat-shrinkable resins include silane copolymerized low-density polyethylene (JP-A-6-335967), ethylene- (meth) acrylic acid copolymer ionomer (JP-A-11-170365, JP-A-8- 259704), fluorine-based copolymers (JP-A-9-31285, JP-A-8-245850, JP-A-8-216252, JP-A-7-205285), styrene-based copolymers ( JP-A-10-95863), aromatic polyester-polyester elastomer blends (JP-A-10-46014), and the like. These materials preferably contain a crosslinking agent as necessary, or are subjected to crosslinking treatment by electron beam irradiation after dispersing conductive particles.
[0013]
In the present invention, known conductive particles can be used as the conductive particles, and examples thereof include carbon black, metal powder, metal silicide powder, metal nitride powder, and resin core metal plating coated particles.
[0014]
The particle size of the conductive particles is selected in consideration of the shrinkage rate of the heat-shrinkable material, the resistance value when the resistance is lowered, and the like. The blending amount of the conductive particles with respect to the heat-shrinkable material is also selected in consideration of the shrinkage rate of the heat-shrinkable material, the resistance value when the resistance is lowered, and the like.
[0015]
The form of the heat-sensitive material used in the present invention is not particularly limited, but it is usually preferable to form it into a sheet or cylinder . Sheet over preparative shaped heat sensitive material, the conductive particles in the heat-shrinkable resin uniformly dispersed in a kneader, and passed through a rolling roll, irradiated with an electron beam as necessary, given while further stretched at a high temperature It can be manufactured by fixing to a thickness. In addition, the cylindrical heat-sensitive material is formed by extruding a compound in which conductive particles are uniformly dispersed in a heat-shrinkable resin into a cylindrical shape by an extrusion molding machine, irradiating with an electron beam as necessary, and further stretching at a high temperature to obtain a predetermined temperature. It can be manufactured by fixing to a diameter.
[0016]
In the heat-sensitive material used in the present invention , a crosslinking agent, non-conductive particles and the like can be appropriately added in order to adjust the shrinkage rate and the resistance value.
[0017]
The irreversible NTC element of the present invention can be used as an electronic device by providing a pair of electrode terminals on the heat-sensitive materials described above.
[0018]
There is no restriction | limiting in particular in the attachment method of the size of an electrode terminal, or the electrode terminal to a heat sensitive material, According to the intended purpose of using an irreversible NTC element, it can select suitably. A preferable example of the attachment method is a method in which electrode terminals are inserted into respective openings at both ends of the heat-sensitive material formed into a cylindrical shape, and both ends are thermally contracted to integrate the electrode terminals into the irreversible NTC element. be able to.
[0019]
The thermosensitive element of the present invention is useful as the NTC element in FIG. 1, that is, the overcharge protection element for a lithium ion secondary battery. It is also useful as an air cooling fan heat switch and fire sensor.
[0020]
【Example】
Hereinafter, the present invention will be specifically described by way of examples.
[0021]
Example 1
150 parts by weight of carbon particles (PC-1020, manufactured by Nippon Carbon Co., Ltd.) and 100 parts by weight of silane copolymerized low density polyethylene (Linklon XF800T, manufactured by Mitsubishi Chemical Corporation) were uniformly mixed with a kneader.
[0022]
The obtained mixture was formed into a cylindrical shape using an extrusion molding machine (KEX-25, manufactured by Kurimoto Iron Works), and further crosslinked by irradiating with 5 Mrad of an electron beam, and then at a temperature atmosphere of 150 ° C. A cylindrical heat-sensitive material having an intended diameter was produced while stretching.
[0023]
Electrode terminals were inserted into the openings at both ends of the obtained cylindrical heat-sensitive material, and the electrode terminals were fixed to the heat-sensitive material by heating both ends to obtain an irreversible NTC element.
[0024]
The resistance value of this thermosensitive element was 100 kΩ. The resistance value after being immersed in hot water at 100 ° C. for 30 seconds was 0.5Ω.
[0025]
When the obtained thermosensitive element is assembled so as to be in close contact with the secondary battery as the NTC element of the lithium ion secondary battery charging circuit shown in FIG. 1, when overcharge occurs, the current to the secondary battery is Blocked. The interrupted current did not recover even when the temperature of the secondary battery decreased. Therefore, it was found that this thermosensitive element irreversibly cuts off the overcharge current.
[0026]
【The invention's effect】
Irreversible NTC element of the present invention, in particular, as an overcharge protection element of the lithium ion secondary battery shows a normal state very high resistance value, is after being heated above a predetermined temperature overcharge current Therefore, it can be connected in parallel to the secondary battery.
[Brief description of the drawings]
FIG. 1 is a charging circuit diagram using an NTC element as an overcharge protection element for a secondary battery.
FIG. 2 is an operation explanatory view of the heat-sensitive material of the present invention.
[Explanation of symbols]
1 heat shrinkable material, 2 conductive particles
Claims (4)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001008558A JP3622676B2 (en) | 2000-05-18 | 2001-01-17 | Thermal material and thermal element |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000147061 | 2000-05-18 | ||
| JP2000-147061 | 2000-05-18 | ||
| JP2001008558A JP3622676B2 (en) | 2000-05-18 | 2001-01-17 | Thermal material and thermal element |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2002043104A JP2002043104A (en) | 2002-02-08 |
| JP3622676B2 true JP3622676B2 (en) | 2005-02-23 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2001008558A Expired - Fee Related JP3622676B2 (en) | 2000-05-18 | 2001-01-17 | Thermal material and thermal element |
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| Country | Link |
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| JP (1) | JP3622676B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8835031B2 (en) | 2012-09-04 | 2014-09-16 | Samsung Sdi Co., Ltd. | Rechargeable battery |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100959982B1 (en) * | 2004-05-19 | 2010-05-27 | 주식회사 엘지화학 | Safety element for battery and battery with the same |
| KR100745354B1 (en) * | 2004-08-24 | 2007-08-02 | 주식회사 엘지화학 | A safty device for preventing overcharge of secondary batteries and a secondary device therewith |
| WO2021240660A1 (en) * | 2020-05-26 | 2021-12-02 | 日本電気株式会社 | Bolometer material, infrared sensor, and production method therefor |
| CN116830218A (en) * | 2021-02-01 | 2023-09-29 | 艾利电力能源有限公司 | Thermistor layer, electrode for battery, and thermistor |
-
2001
- 2001-01-17 JP JP2001008558A patent/JP3622676B2/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8835031B2 (en) | 2012-09-04 | 2014-09-16 | Samsung Sdi Co., Ltd. | Rechargeable battery |
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| Publication number | Publication date |
|---|---|
| JP2002043104A (en) | 2002-02-08 |
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