JP2012209150A - Secondary battery and method of manufacturing the same - Google Patents

Secondary battery and method of manufacturing the same Download PDF

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JP2012209150A
JP2012209150A JP2011074424A JP2011074424A JP2012209150A JP 2012209150 A JP2012209150 A JP 2012209150A JP 2011074424 A JP2011074424 A JP 2011074424A JP 2011074424 A JP2011074424 A JP 2011074424A JP 2012209150 A JP2012209150 A JP 2012209150A
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secondary battery
vapor deposition
negative electrode
positive electrode
deposition material
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Yoshihiro Ono
芳裕 小野
Yuji Otome
佑次 乙▲め▼
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    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1393—Processes of manufacture of electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2220/00—Batteries for particular applications
    • H01M2220/20—Batteries in motive systems, e.g. vehicle, ship, plane
    • 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

PROBLEM TO BE SOLVED: To provide a secondary battery of high safety in which no explosion occurs, and which can be manufactured stably at a low cost.SOLUTION: Relating to a secondary battery containing a positive electrode, a negative electrode, a separator, and an electrolyte, the secondary battery 1 includes a positive electrode 2 which is formed by plasma vapor deposition with a vapor deposition material on a copper plate, and a negative electrode 3 which is formed by plasma vapor deposition with the vapor deposition material on an aluminum plate. The vapor deposition material contains carbon by 90.00-100.00% at mass ratio.

Description

本発明は、二次電池及びその製造方法に関するものである。   The present invention relates to a secondary battery and a method for manufacturing the same.

電気自動車、携帯電話、ノート型パソコン等に、リチウムイオン二次電池が使用されている。このリチウム二次電池は、得られる電圧が高い点、メモリー効果がほとんどない点、自己放電特性が良い点などメリットがある。（例えば特許文献１参照）。   Lithium ion secondary batteries are used in electric vehicles, mobile phones, notebook computers, and the like. This lithium secondary battery has advantages such as a high voltage obtained, almost no memory effect, and good self-discharge characteristics. (For example, refer to Patent Document 1).

しかしながら、リチウムイオン二次電池は、以下の問題点を有している。第１に、過熱、発火、爆発等が発生するという問題を有している。   However, the lithium ion secondary battery has the following problems. First, there is a problem that overheating, ignition, explosion, and the like occur.

第２に、レアメタルであるリチウムの取得が困難となる可能性がある。これは、リチウム産地の偏在性のため、供給が不安定となる危険性がある。   Second, it may be difficult to obtain lithium, which is a rare metal. This is a risk of unstable supply due to the uneven distribution of lithium production areas.

特開２００９−２６６７３７号公報JP 2009-266737 A

本発明は、上記の問題を鑑みてなされたものであり、その目的は、爆発等が発生しない安全性の高い二次電池を提供することにある。また、低コストで且つ安定して製造することのできる二次電池を提供することにある。   The present invention has been made in view of the above problems, and an object of the present invention is to provide a highly safe secondary battery that does not cause an explosion or the like. Moreover, it is providing the secondary battery which can be manufactured stably at low cost.

上記の目的を達成するための本発明に係る二次電池は、正極と、負極と、セパレータと、電解液を有する二次電池において、前記二次電池が、銅平板に蒸着材料をプラズマ蒸着して形成した正極と、アルミニウム平板に前記蒸着材料をプラズマ蒸着して形成した負極を有しており、前記蒸着材料が、質量比で９０．００〜１００．００％のカーボンを含有していることを特徴とする。この構成により、爆発等が発生しない安全性の高い二次電池を提供することができる。また、低コストで且つ安定して製造することのできる二次電池を提供することができる。   In order to achieve the above object, a secondary battery according to the present invention is a secondary battery having a positive electrode, a negative electrode, a separator, and an electrolyte, wherein the secondary battery plasma-deposits a deposition material on a copper plate. A negative electrode formed by plasma-depositing the vapor deposition material on an aluminum flat plate, and the vapor deposition material contains 90.00 to 100.00% carbon by mass ratio. It is characterized by. With this configuration, it is possible to provide a highly safe secondary battery that does not cause an explosion or the like. In addition, a secondary battery that can be stably manufactured at low cost can be provided.

上記の二次電池において、前記蒸着材料が、質量比で０．０１〜１０．００％の継ぎ剤を含有しており、前記継ぎ剤が、ウラン、又はラジウム、又はリチウムの少なくとも１つであることを特徴とする。この構成により、上記と同様の作用効果を得ることができる。   Said secondary battery WHEREIN: The said vapor deposition material contains 0.01-10.00% splicing agent by mass ratio, and the said splicing agent is at least 1 of uranium, radium, or lithium. It is characterized by that. With this configuration, the same effects as described above can be obtained.

上記の二次電池において、前記電解液が、質量比で０．０１〜１０．００％の添加物を含有しており、前記添加物が、ウラン、又はラジウム、又はモナサイトの少なくとも１つであることを特徴とする。この構成により、上記と同様の作用効果を得ることができる。   In the above secondary battery, the electrolytic solution contains an additive of 0.01 to 10.00% by mass ratio, and the additive is at least one of uranium, radium, or monasite. It is characterized by being. With this configuration, the same effects as described above can be obtained.

上記の目的を達成するための本発明に係る二次電池は、正極と、負極と、セパレータと、電解液を有する二次電池の製造方法において、銅平板及びアルミニウム平板に蒸着材料をプラズマ蒸着して正極及び負極を作成ステップと、前記セパレータに前記電解液を供給しながら、前記セパレータを前記正極及び負極で挟み、ケースに封入するステップを有し、前記蒸着材料が、質量比で９０．００〜１００．００％のカーボンを含有していることを特徴とする。この構成により、前述と同様の作用効果を得ることができる。   In order to achieve the above object, a secondary battery according to the present invention includes a positive electrode, a negative electrode, a separator, and a method for manufacturing a secondary battery having an electrolyte solution. A positive electrode and a negative electrode, and a step of sandwiching the separator between the positive electrode and the negative electrode while supplying the electrolytic solution to the separator and enclosing it in a case, and the vapor deposition material is 90.00 by mass ratio. It is characterized by containing -100.00% carbon. With this configuration, the same effects as described above can be obtained.

本発明に係る二次電池によれば、爆発等が発生しない安全性の高い二次電池を提供することができる。また、低コストで且つ安定して製造することのできる二次電池を提供することができる。   According to the secondary battery of the present invention, it is possible to provide a highly safe secondary battery that does not cause an explosion or the like. In addition, a secondary battery that can be stably manufactured at low cost can be provided.

本発明に係る実施の形態の二次電池の概略を示した透視図である。It is the perspective view which showed the outline of the secondary battery of embodiment which concerns on this invention. 本発明に係る実施の形態の二次電池の概略を示した図である。It is the figure which showed the outline of the secondary battery of embodiment which concerns on this invention. 本発明に係る実施の形態の二次電池の出力特性を示したグラフである。It is the graph which showed the output characteristic of the secondary battery of embodiment which concerns on this invention.

以下、本発明に係る実施の形態の二次電池について、図面を参照しながら説明する。図１に、本発明に係る実施の形態の二次電池１の概略を示した透視図を示す。また、図２に、二次電池１を分解した際の概略を示す。この二次電池１は、正極２と負極３と、セパレータ６と、これらを包むケース７と、ケース７内に充填した電解液８を有している。   Hereinafter, a secondary battery according to an embodiment of the present invention will be described with reference to the drawings. FIG. 1 is a perspective view schematically showing a secondary battery 1 according to an embodiment of the present invention. FIG. 2 shows an outline when the secondary battery 1 is disassembled. The secondary battery 1 includes a positive electrode 2, a negative electrode 3, a separator 6, a case 7 that wraps them, and an electrolyte 8 filled in the case 7.

正極２は、厚みが例えば０．１〜０．５ｍｍ程度の銅平板と、正極端子４で構成している。この銅平板の両面には、ナノカーボン（カーボン）を主原料とする蒸着剤をプラズマ蒸着している。この蒸着剤は、厚さが１０〜５０μｍ、望ましくは２５〜３５μｍとなるように蒸着させる。また、蒸着剤には、極微量の継ぎ剤（リチウム、又はウラン、又はラジウム）を混入している。この継ぎ剤は、蒸着剤の全重量に対して、重量比で０．０１〜１０％、望ましくは０．１〜５％、更に望ましくは０．１〜０．２％混入する。   The positive electrode 2 includes a copper flat plate having a thickness of, for example, about 0.1 to 0.5 mm and a positive electrode terminal 4. On both surfaces of this copper flat plate, a vapor deposition agent made mainly of nanocarbon (carbon) is plasma-deposited. This vapor deposition agent is vapor-deposited so that thickness may be 10-50 micrometers, desirably 25-35 micrometers. In addition, a very small amount of a splicing agent (lithium, uranium, or radium) is mixed in the vapor deposition agent. The splicing agent is mixed in a weight ratio of 0.01 to 10%, desirably 0.1 to 5%, and more desirably 0.1 to 0.2% with respect to the total weight of the vapor deposition agent.

負極３は、厚みが例えば０．１〜０．５ｍｍ程度のアルミニウム平板と、負極端子５で構成している。このアルミニウム平板の両面には、上記の銅平板と同様に、蒸着剤をプラズマ蒸着している。   The negative electrode 3 includes an aluminum flat plate having a thickness of, for example, about 0.1 to 0.5 mm and a negative electrode terminal 5. The vapor deposition agent is plasma-deposited on both surfaces of the aluminum flat plate in the same manner as the copper flat plate.

セパレータ６は、正極２と負極３を絶縁し、且つイオン伝導性を有していればよい。例えば、プラスチック製の微多孔膜や、シルク（絹）シートを使用することができる。   The separator 6 only needs to insulate the positive electrode 2 and the negative electrode 3 and have ion conductivity. For example, a plastic microporous film or a silk sheet can be used.

電解液８は、電気伝導性を有する液体であればよい。この電解液８には、極微量の添加物（ウラン、又はラジウム、又はモナサイト）を混入することが望ましい。この添加物は、電解液８の全重量に対して、重量比で０．０１〜１０％、望ましくは０．１〜５％、更に望ましくは０．１〜０．２％混入する。   The electrolyte solution 8 may be any liquid having electrical conductivity. It is desirable that a very small amount of additive (uranium, radium, or monasite) is mixed in the electrolytic solution 8. This additive is mixed in a weight ratio of 0.01 to 10%, desirably 0.1 to 5%, and more desirably 0.1 to 0.2% with respect to the total weight of the electrolytic solution 8.

ケース７は、従来のリチウムイオン二次電池と同様、プラスチックケース等で構成することができる。ここで、図１では簡単のため、電解液８を封入している領域を大きく図示しているが、実際の二次電池１においては、ケース７が正極２及び負極３に接触した状態となる。従って、電解液８は、セパレータ６を濡らす程度の量としている。   The case 7 can be formed of a plastic case or the like, like a conventional lithium ion secondary battery. Here, for the sake of simplicity, FIG. 1 shows a large region in which the electrolytic solution 8 is sealed. However, in the actual secondary battery 1, the case 7 is in contact with the positive electrode 2 and the negative electrode 3. . Therefore, the amount of the electrolyte 8 is set so as to wet the separator 6.

次に、二次電池の製造方法について説明する。まず、銅平板及びアルミニウム平板に、蒸着剤をプラズマ蒸着し、正極２及び負極３を作成する。セパレータ６に電解液８を供給しながら、セパレータ６を正極２及び負極３で挟み、ケース７に封入する。   Next, a method for manufacturing a secondary battery will be described. First, a vapor deposition agent is plasma-deposited on a copper flat plate and an aluminum flat plate to form the positive electrode 2 and the negative electrode 3. While supplying the electrolytic solution 8 to the separator 6, the separator 6 is sandwiched between the positive electrode 2 and the negative electrode 3 and sealed in the case 7.

上記の構成により、以下の作用効果を得ることができる。なお、リチウムイオン二次電池を、従来の二次電池として比較する。第１に、爆発等が発生しない安全性の高い二次電池を提供することができる。この二次電池は、使用時に温度が上昇しない。また、衝撃破壊した場合であっても、発火する危険性がない。具体的には、二次電池に釘を打ち込んでも、発火しない。更に、二次電池を燃焼させても爆発することがない。   With the above configuration, the following operational effects can be obtained. In addition, a lithium ion secondary battery is compared as a conventional secondary battery. First, it is possible to provide a highly safe secondary battery that does not cause an explosion or the like. This secondary battery does not rise in temperature during use. In addition, there is no risk of ignition even in the event of impact destruction. Specifically, even if a nail is driven into the secondary battery, it does not ignite. Furthermore, even if the secondary battery is burned, it does not explode.

第２に、低コスト（イニシャルコストは従来の３分の１程度）で、二次電池１を製造することができる。これは、二次電池１を、入手の容易な材料で構成しているためである。また、ランニングコストも抑制することができる。これは、二次電池の繰り返し使用回数（サイクル寿命）が、１０万回から２０万回であるためである。従来のリチウムイオン二次電池は、２０００から７０００回程度となる。   Secondly, the secondary battery 1 can be manufactured at a low cost (the initial cost is about one third of the conventional cost). This is because the secondary battery 1 is made of an easily available material. Also, the running cost can be suppressed. This is because the number of repeated use (cycle life) of the secondary battery is 100,000 to 200,000 times. A conventional lithium ion secondary battery is about 2000 to 7000 times.

第３に、リチウム等のレアメタルを使用しない、又は使用しても微量であるため、二次電池の安定的な供給を実現することができる。   Thirdly, since a rare metal such as lithium is not used or is used in a very small amount, stable supply of the secondary battery can be realized.

また、この二次電池は、従来に比べ、急速充電及び放電が可能である、長期間放置しても自己放電がほとんどない、−４０〜７０℃の環境下で使用することが可能等のメリットがある。更に、電極（正極２及び負極３）の面積に変更により、電池容量を容易に変更することができる。加えて、二次電池に使用した材料のリサイクルが容易である等、多種のメリットがある。   In addition, this secondary battery can be quickly charged and discharged compared to conventional batteries, has little self-discharge even when left for a long time, and can be used in an environment of -40 to 70 ° C. There is. Furthermore, the battery capacity can be easily changed by changing the area of the electrodes (the positive electrode 2 and the negative electrode 3). In addition, there are various merits such as easy recycling of materials used for the secondary battery.

なお、本発明の二次電池１は、電極を積層して、１つのケース７内に封入して製造してもよい。この構成により、高電圧の二次電池を提供することができる。また、二次電池１の形状は、円形、角形、球形等、任意の形状に形成することができる。   The secondary battery 1 of the present invention may be manufactured by stacking electrodes and enclosing them in one case 7. With this configuration, a high voltage secondary battery can be provided. Moreover, the shape of the secondary battery 1 can be formed in an arbitrary shape such as a circle, a square, or a sphere.

更に、二次電池１を大型パネル状に形成し、建築物の壁面等に埋め込むことができる。この構成により、二次電池１を夜間電力で充電し、日中使用する電力の全てを、この二次電池から供給するように構成することができる。   Furthermore, the secondary battery 1 can be formed in a large panel shape and embedded in a wall surface of a building. With this configuration, the secondary battery 1 can be charged with nighttime power, and all the power used during the day can be supplied from the secondary battery.

加えて、二次電池１を、電気自動車の屋根、又はドア等の内部に設置することもできる。つまり、二次電池を設置する自由度が高いため、従来のように、トランクルームが狭くなることがない。特に、電気自動車が、交通事故等を起した場合であっても、本発明の二次電池１は、爆発等の事故を起すことがない。   In addition, the secondary battery 1 can be installed inside the roof or door of an electric vehicle. That is, since the degree of freedom for installing the secondary battery is high, the trunk room is not narrowed as in the conventional case. In particular, even when an electric vehicle causes a traffic accident or the like, the secondary battery 1 of the present invention does not cause an accident such as an explosion.

図３に、本発明の二次電池と、リチウムイオンポリマー（Ｌｉ−Ｐｏ）二次電池に、同一の負荷をかけ、電圧の降下量と経過時間の関係を比較した結果を示す。グラフは、縦軸を電圧（Ｖ）、横軸を経過時間（ｍｉｎ）としている。また、実線は本発明の二次電池の結果を、破線はＬｉ−Ｐｏ二次電池の結果を示している。   FIG. 3 shows the results of comparing the relationship between the voltage drop and the elapsed time by applying the same load to the secondary battery of the present invention and the lithium ion polymer (Li-Po) secondary battery. In the graph, the vertical axis represents voltage (V) and the horizontal axis represents elapsed time (min). The solid line shows the result of the secondary battery of the present invention, and the broken line shows the result of the Li-Po secondary battery.

ここで、本発明の二次電池は、蒸着材料に対して０．１％のウランを継ぎ剤として混入した。電解液は、リチウムを含有しないものを使用した。具体的には、三菱化学製の商品名「エチレンカーボネイト」を使用した。また、電解液に対して、０．１％のウランを添加物として混入した。以上より、電圧が３．７Ｖ、バッテリー容量（電池容量）が１Ａｈである二次電池を作成し、実験に使用した。   Here, in the secondary battery of the present invention, 0.1% uranium was mixed as a joining agent with respect to the vapor deposition material. The electrolytic solution used did not contain lithium. Specifically, the product name “ethylene carbonate” manufactured by Mitsubishi Chemical was used. Further, 0.1% of uranium was added as an additive to the electrolytic solution. From the above, a secondary battery having a voltage of 3.7 V and a battery capacity (battery capacity) of 1 Ah was prepared and used for the experiment.

また、比較対象であるＬｉ−Ｐｏ二次電池は、一般的に販売されているものを使用した。このＬｉ−Ｐｏ二次電池は、電圧が３．７Ｖ、バッテリー容量が４．５Ａｈである。   Moreover, what was generally marketed was used for the Li-Po secondary battery which is a comparison object. This Li-Po secondary battery has a voltage of 3.7 V and a battery capacity of 4.5 Ah.

実験結果を示すグラフより、本発明の二次電池は、従来のＬｉ−Ｐｏ二次電池と同様の出力特性を得られることがわかった。なお、バッテリー容量が異なるため、本発明の二次電池（実線）の方が、若干早い段階で、電圧降下が見られる。   From the graph showing the experimental results, it was found that the secondary battery of the present invention can obtain output characteristics similar to those of the conventional Li-Po secondary battery. Note that since the battery capacities are different, the secondary battery (solid line) of the present invention shows a voltage drop at a slightly earlier stage.

また、別途行った実験により、本発明の二次電池のエネルギー密度は以下の通りであった。本発明の二次電池は、体積エネルギー密度が６９２．１Ｗｈ／Ｌ、重量エネルギー密度が２５０．５Ｗｈ／Ｋｇである。ちなみに、従来のＬｉ−Ｐｏ二次電池は、体積エネル
ギー密度が２５０〜３６０Ｗｈ／Ｌ、重量エネルギー密度が１００〜２５０Ｗｈ／Ｋｇである。 Moreover, the energy density of the secondary battery of this invention was as follows by the experiment conducted separately. The secondary battery of the present invention has a volume energy density of 692.1 Wh / L and a weight energy density of 250.5 Wh / Kg. Incidentally, the conventional Li-Po secondary battery has a volume energy density of 250 to 360 Wh / L and a weight energy density of 100 to 250 Wh / Kg.

１ 二次電池
２ 正極
３ 負極
６ セパレータ
７ ケース
８ 電解液 DESCRIPTION OF SYMBOLS 1 Secondary battery 2 Positive electrode 3 Negative electrode 6 Separator 7 Case 8 Electrolyte

Claims (4)

正極と、負極と、セパレータと、電解液を有する二次電池において、
前記二次電池が、銅平板に蒸着材料をプラズマ蒸着して形成した正極と、アルミニウム平板に前記蒸着材料をプラズマ蒸着して形成した負極を有しており、
前記蒸着材料が、質量比で９０．００〜１００．００％のカーボンを含有していることを特徴とする二次電池。 In a secondary battery having a positive electrode, a negative electrode, a separator, and an electrolyte,
The secondary battery has a positive electrode formed by plasma deposition of a vapor deposition material on a copper flat plate, and a negative electrode formed by plasma vapor deposition of the vapor deposition material on an aluminum flat plate,
The secondary battery, wherein the vapor deposition material contains 90.00 to 100.00% of carbon by mass ratio. 前記蒸着材料が、質量比で０．０１〜１０．００％の継ぎ剤を含有しており、
前記継ぎ剤が、ウラン、又はラジウム、又はリチウムの少なくとも１つであることを特徴とする請求項１に記載の二次電池。 The vapor deposition material contains 0.01 to 10.00% splicing agent by mass ratio,
The secondary battery according to claim 1, wherein the splicing agent is at least one of uranium, radium, or lithium. 前記電解液が、質量比で０．０１〜１０．００％の添加物を含有しており、
前記添加物が、ウラン、又はラジウム、又はモナサイトの少なくとも１つであることを特徴とする請求項１又は２に記載の二次電池。 The electrolytic solution contains 0.01 to 10.00% additive in mass ratio,
The secondary battery according to claim 1, wherein the additive is at least one of uranium, radium, or monasite. 正極と、負極と、セパレータと、電解液を有する二次電池の製造方法において、
銅平板及びアルミニウム平板に蒸着材料をプラズマ蒸着して正極及び負極を作成ステップと、
前記セパレータに前記電解液を供給しながら、前記セパレータを前記正極及び負極で挟み、ケースに封入するステップを有し、
前記蒸着材料が、質量比で９０．００〜１００．００％のカーボンを含有していることを特徴とする二次電池の製造方法。 In a method for producing a secondary battery having a positive electrode, a negative electrode, a separator, and an electrolytic solution,
Creating a positive electrode and a negative electrode by plasma-depositing a vapor deposition material on a copper flat plate and an aluminum flat plate;
While supplying the electrolyte solution to the separator, the separator is sandwiched between the positive electrode and the negative electrode and sealed in a case,
The method for producing a secondary battery, wherein the vapor deposition material contains 90.00 to 100.00% of carbon by mass ratio.
JP2011074424A 2011-03-30 2011-03-30 Secondary battery and method of manufacturing the same Withdrawn JP2012209150A (en)

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