JP2011216200A - Control method of lithium ion secondary battery - Google Patents
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本発明は、リチウムイオン二次電池の制御方法に関し、特に、正極を再活性化させるリチウムイオン電池の制御方法に関する。 The present invention relates to a method for controlling a lithium ion secondary battery, and more particularly to a method for controlling a lithium ion battery in which a positive electrode is reactivated.
リチウムイオン二次電池は、他の二次電池よりもエネルギー密度が高く、高電圧で作動させることができる。そのため、小型軽量化を図りやすい二次電池として携帯電話等の情報機器に使用されており、近年、ハイブリッド自動車用等、大型の動力用としての需要も高まっている。 A lithium ion secondary battery has a higher energy density than other secondary batteries and can be operated at a high voltage. For this reason, it is used as a secondary battery that can be easily reduced in size and weight in information equipment such as a mobile phone, and in recent years, there is an increasing demand for large-sized power such as for hybrid vehicles.
リチウムイオン二次電池には、正極及び負極と、これらの間に充填される電解質とが備えられ、電解質は、非水系の液体や固体等によって構成される。製造されたリチウムイオン二次電池は、充電した後に放電され、放電後に充電することにより、再生される。リチウムイオン二次電池の充電時には、正極に含有されている正極活物質からリチウムイオンが引き抜かれ、引き抜かれたリチウムイオンは、電解質を通って負極へと移動し、負極の中へ吸収される。一方、リチウムイオン二次電池の放電時には、負極に含有されている負極活物質からリチウムイオンが放出され、放出されたリチウムイオンが電解質を通って正極へと移動し、正極内に入り込む。このように、リチウムイオン二次電池の充放電時には、正極活物質と負極活物質との間をリチウムイオンが移動する。 A lithium ion secondary battery includes a positive electrode and a negative electrode, and an electrolyte filled therebetween, and the electrolyte is composed of a non-aqueous liquid, solid, or the like. The manufactured lithium ion secondary battery is discharged after being charged, and is regenerated by charging after discharging. At the time of charging the lithium ion secondary battery, lithium ions are extracted from the positive electrode active material contained in the positive electrode, and the extracted lithium ions move to the negative electrode through the electrolyte and are absorbed into the negative electrode. On the other hand, when the lithium ion secondary battery is discharged, lithium ions are released from the negative electrode active material contained in the negative electrode, and the released lithium ions move to the positive electrode through the electrolyte and enter the positive electrode. Thus, at the time of charge / discharge of the lithium ion secondary battery, lithium ions move between the positive electrode active material and the negative electrode active material.
このようなリチウムイオン二次電池に関する技術として、例えば非特許文献１には、金属リチウムからなる負極、金属銅からなる正極、負極と正極との間に配設された固体電解質、負極と固体電解質との間に充填された有機電解液、及び、固体電解質と正極との間に充填された水性電解液を有するリチウム−銅二次電池が開示されている。 As a technique related to such a lithium ion secondary battery, for example, Non-Patent Document 1 discloses a negative electrode made of metallic lithium, a positive electrode made of metallic copper, a solid electrolyte disposed between the negative electrode and the positive electrode, and a negative electrode and a solid electrolyte. And a lithium-copper secondary battery having an organic electrolyte filled between and an aqueous electrolyte filled between a solid electrolyte and a positive electrode.
非特許文献１に開示されている技術によれば、金属リチウムからなる負極及び金属銅からなる正極を用いているので、従来のリチウムイオン二次電池よりもリサイクルが容易になると考えられる。また、負極と正極との間に配設された固体電解質によって、有機電解液と水性電解液とを分離しているので、安定した電池反応を実現することも可能になると考えられる。しかしながら、金属銅の表面は、通常、酸化皮膜に覆われており、水性電解液中においても金属銅の表面は酸化皮膜に覆われていると考えられる。そのため、非特許文献１に開示されている技術では、電池の抵抗が増大しやすいという問題があり、かかる電池の性能を向上させるためには、金属銅の表面を覆っている酸化皮膜を除去して正極を活性化する技術の開発が求められていた。 According to the technique disclosed in Non-Patent Document 1, since a negative electrode made of metallic lithium and a positive electrode made of metallic copper are used, it is considered that recycling is easier than conventional lithium ion secondary batteries. Moreover, since the organic electrolyte and the aqueous electrolyte are separated by the solid electrolyte disposed between the negative electrode and the positive electrode, it is considered that a stable battery reaction can be realized. However, the surface of metallic copper is usually covered with an oxide film, and it is considered that the surface of metallic copper is covered with an oxide film even in an aqueous electrolyte solution. Therefore, the technique disclosed in Non-Patent Document 1 has a problem that the resistance of the battery is likely to increase. In order to improve the performance of the battery, the oxide film covering the surface of the metal copper is removed. Therefore, development of a technology for activating the positive electrode has been demanded.
そこで本発明は、正極を活性化させることが可能なリチウムイオン二次電池の制御方法を提供することを課題とする。 Then, this invention makes it a subject to provide the control method of the lithium ion secondary battery which can activate a positive electrode.
上記課題を解決するために、本発明は以下の手段をとる。すなわち、
本発明は、リチウムイオンを吸蔵放出可能な金属リチウムを含む負極、リチウム以外の金属を含む正極、負極と正極との間に配設された固体電解質、及び、正極と固体電解質との間に充填された正極電解液、を備えるリチウムイオン二次電池の充電時に、パルス状の、充電電圧よりも低い還元電圧を印加することを特徴とする、リチウムイオン二次電池の制御方法である。
In order to solve the above problems, the present invention takes the following means. That is,
The present invention relates to a negative electrode containing metallic lithium capable of occluding and releasing lithium ions, a positive electrode containing a metal other than lithium, a solid electrolyte disposed between the negative electrode and the positive electrode, and a filling between the positive electrode and the solid electrolyte. A control method for a lithium ion secondary battery, characterized in that a pulsed reduction voltage lower than the charging voltage is applied when a lithium ion secondary battery comprising the positive electrode electrolyte is charged.
ここに、「リチウム以外の金属」とは、例えば、銅やニッケル等、リチウムイオン二次電池の正極に用いられる金属をいう。また、「固体電解質」とは、リチウムイオン伝導性を有する固体電解質をいう。 Here, “metal other than lithium” refers to a metal used for a positive electrode of a lithium ion secondary battery, such as copper or nickel. The “solid electrolyte” refers to a solid electrolyte having lithium ion conductivity.
上記本発明において、リチウム以外の金属が銅である場合、充電電圧と還元電圧との差は０．６３Ｖ以上であることが好ましい。 In the present invention, when the metal other than lithium is copper, the difference between the charging voltage and the reduction voltage is preferably 0.63 V or more.
充電時にパルス状の還元電圧を印加すると、正極に用いられている金属の表面に形成されている酸化皮膜を電解により除去して正極を活性化させることが可能になる。したがって、本発明によれば、正極を活性化させることが可能な、リチウムイオン二次電池の制御方法を提供することができる。 When a pulsed reduction voltage is applied during charging, the oxide film formed on the surface of the metal used for the positive electrode can be removed by electrolysis to activate the positive electrode. Therefore, according to this invention, the control method of the lithium ion secondary battery which can activate a positive electrode can be provided.
本発明において、リチウム以外の金属が銅である場合、充電電圧と還元電圧との差を０．６３Ｖ以上とすることにより、銅表面に形成された酸化皮膜を除去することが容易になる。 In the present invention, when the metal other than lithium is copper, the oxide film formed on the copper surface can be easily removed by setting the difference between the charging voltage and the reduction voltage to 0.63 V or more.
負極に金属リチウムを、正極に金属銅を、負極と正極との間に配設した固体電解質にＬｉｘＡｌ２−ｘＴｉｘ（ＰＯ４）３（ＬＡＴＰ）を、負極と固体電解質との間に充填した有機電解液に１Ｍ ＬｉＴＦＳＩのＰＣ溶液を、固体電解質と正極との間に充填した水性電解液（正極電解液）に１ｍｏｌ／ＬのＣｕＳＯ４を溶解させたＣｕＳＯ４水溶液を、それぞれ用いた密閉型金属空気電池を作製した。そして、当該電池の作製直後、充電中、及び、放電中のそれぞれにおける、電池抵抗を測定した。結果を表１に示す。また、充電終了直後の電池の正極（金属銅）を観察した。結果を図３に示す。 Metal lithium for the negative electrode, metal copper for the positive electrode, Li x Al 2-x Ti x (PO 4 ) 3 (LATP) for the solid electrolyte disposed between the negative electrode and the positive electrode, and between the negative electrode and the solid electrolyte A 1M LiTFSI PC solution was used in the organic electrolyte filled in the sample, and a CuSO 4 aqueous solution in which 1 mol / L CuSO 4 was dissolved in the aqueous electrolyte (positive electrode electrolyte) filled between the solid electrolyte and the positive electrode was used for each. A sealed metal-air battery was produced. The battery resistance was measured immediately after the production of the battery, during charging, and during discharging. The results are shown in Table 1. Moreover, the positive electrode (metal copper) of the battery immediately after the end of charging was observed. The results are shown in FIG.
表１に示すように、作製直後の抵抗が２４５０Ωであった電池を充電すると、抵抗が１９５０Ωになり、放電すると、抵抗が１３００Ωになった。この結果は、充電時に正極で生じる反応（Ｃｕ → Ｃｕ２＋ ＋ ２ｅ−）や放電時に正極で生じる反応（Ｃｕ２＋ ＋ ２ｅ− → Ｃｕ）と関係しており、充電時よりも放電時の抵抗が小さくなるのは、正極表面に金属銅が析出するためである。一方、図３に示すように、電池作製時に清浄な金属銅を使用しても、充電終了直後の電池に含まれる正極（金属銅）は、表面が黒茶色、部分的に緑青色となっており、多くの酸化銅（ＣｕＯやＣｕ２Ｏ）が確認された。以上より、本発明者らは、正極の表面が酸化皮膜によって覆われていると正極が不活性化して抵抗が増大し、正極を活性化するには酸化皮膜を除去することが有効であることを知見した。 As shown in Table 1, when a battery having a resistance of 2450Ω immediately after fabrication was charged, the resistance was 1950Ω, and when discharged, the resistance was 1300Ω. This result is related to the reaction occurring at the positive electrode during charging (Cu → Cu 2+ + 2e − ) and the reaction occurring at the positive electrode during discharging (Cu 2+ + 2e − → Cu), and the resistance during discharging is higher than during charging. The reason for the decrease is that metallic copper is deposited on the surface of the positive electrode. On the other hand, as shown in FIG. 3, the surface of the positive electrode (metal copper) included in the battery immediately after the end of charging is black-brown and partially greenish-blue even when clean metal copper is used at the time of battery production. Many copper oxides (CuO and Cu 2 O) were confirmed. From the above, the present inventors show that when the surface of the positive electrode is covered with an oxide film, the positive electrode is inactivated and the resistance increases, and it is effective to remove the oxide film to activate the positive electrode. I found out.
このように、正極を構成する金属の表面に酸化皮膜が形成されていると、抵抗が増大する。特に充電時には、十分な過電圧がないと酸化皮膜を除去することができないため、正極を構成する金属の表面に酸化皮膜が形成されていることを考慮すると、充電過電圧を一定以上にすることが必要になると考えられる。しかしながら、単に充電過電圧を一定以上にしても、表面に形成された酸化皮膜の全てを除去することは困難である。また、一定以上の充電過電圧を維持することによって酸化皮膜を除去しても、表面に残された欠損等に起因するひずみが正極を構成する金属に残留する可能性があるほか、充放電を繰り返した水性電解液中には不純物が存在する。残留ひずみや不純物等によって正極が変形すると、正極の容量が低減するため、充電過電圧を過度に高めることは好ましくないと思われる。 Thus, when the oxide film is formed on the surface of the metal constituting the positive electrode, the resistance increases. Especially during charging, the oxide film cannot be removed without sufficient overvoltage. Therefore, considering that the oxide film is formed on the surface of the metal that constitutes the positive electrode, it is necessary to set the charge overvoltage to a certain level or more. It is thought that it becomes. However, it is difficult to remove all of the oxide film formed on the surface simply by setting the charging overvoltage to a certain level or higher. In addition, even if the oxide film is removed by maintaining a charge overvoltage of a certain level or more, strains due to defects left on the surface may remain on the metal constituting the positive electrode, and repeated charge and discharge Impurities are present in the aqueous electrolyte. If the positive electrode is deformed by residual strain, impurities, etc., the capacity of the positive electrode is reduced, so it seems undesirable to increase the charge overvoltage excessively.
他方、正極に接触する電解液を酸性にすれば、酸化皮膜の形成を抑制することが可能になるが、酸性の電解液に長期間耐性を有する金属イオン伝導性の固体電解質は、現在のところ発見されていない。したがって、酸化皮膜を除去するためには、充電過電圧制御や液性制御以外の方法を開発することが求められている。 On the other hand, if the electrolytic solution in contact with the positive electrode is acidified, it is possible to suppress the formation of an oxide film. However, metal ion conductive solid electrolytes that have long-term resistance to acidic electrolytic solutions are currently available. Not found. Therefore, in order to remove the oxide film, it is required to develop a method other than charge overvoltage control and liquidity control.
本発明者は、鋭意研究の結果、充電時に、充電電圧よりも低いパルス状の還元電圧（以下において、「還元パルス」ということがある。）を印加することにより、正極を構成する金属の表面に形成された酸化皮膜を除去することが可能になり、その結果、正極を活性化すること（正極表面における抵抗を低減すること）が可能になることを知見した。本発明は、かかる知見に基づいてなされたものである。本発明は、正極を活性化させることが可能な、リチウムイオン二次電池の制御方法を提供することを、主な要旨とする。 As a result of earnest research, the inventor has applied a pulsed reduction voltage lower than the charging voltage (hereinafter, also referred to as “reduction pulse”) at the time of charging, and thereby the surface of the metal constituting the positive electrode. It has been found that the oxide film formed on the surface can be removed, and as a result, it is possible to activate the positive electrode (reduce the resistance on the surface of the positive electrode). The present invention has been made based on such knowledge. The main gist of the present invention is to provide a method for controlling a lithium ion secondary battery capable of activating a positive electrode.
以下、図面を参照しつつ、本発明について説明する。なお、以下に示す形態は本発明の例示であり、本発明は以下に示す形態に限定されるものではない。 The present invention will be described below with reference to the drawings. In addition, the form shown below is an illustration of this invention and this invention is not limited to the form shown below.
図１は、本発明のリチウムイオン二次電池の制御方法（以下において、「本発明の制御方法」ということがある。）を説明する概念図である。図１（ａ）に示すリチウムイオン二次電池１０（以下において単に「電池１０」という。）は、金属リチウム箔によって構成した負極１、金属銅箔によって構成した正極２、負極１及び正極２の間に配設されたリチウムイオン伝導固体電解質３（以下において、単に「固体電解質３」という。）、負極１と固体電解質３との間に充填された有機電解液４、固体電解質３と正極２との間に充填された正極電解液５、負極１に接続された集電体６、並びに、正極２に接続された集電体７を備え、さらに、これらを収容する筐体８を有している。このような電池１０を充電すると、負極１においてＬｉ＋ ＋ ｅ− → Ｌｉという反応が生じるとともに、正極２においてＣｕ → Ｃｕ２＋ ＋ ２ｅ−という反応が生じる。そして、正極２を構成する金属銅は、正極電解液中で表面に酸化皮膜が形成されるので、充電を進めると、図１（ｂ）に示すように、正極電解液５に接触している正極２ａの表面に酸化皮膜９が形成される。こうして酸化皮膜９が形成されると、電池１０ａの抵抗が増大し、目的の充電電圧へ上昇する前に、充電が停止してしまう虞がある。そこで、本発明では、充電中に、充電電圧よりも低いパルス状の還元電圧を印加する。パルス状の還元電圧を印加すると、図１（ｃ）に示すように、正極２ａの表面を覆っていた酸化皮膜９を電解により除去することができ、活性化された正極２ｂを有する電池１０ｂとすることが可能になる。そのため、本発明の制御方法を実施することにより、正極２ｃを有する、目的の充電電圧まで充電された電池１０ｃを得ることが可能になる（図１（ｄ）参照）。 FIG. 1 is a conceptual diagram illustrating a method for controlling a lithium ion secondary battery according to the present invention (hereinafter sometimes referred to as “control method according to the present invention”). A lithium ion secondary battery 10 (hereinafter simply referred to as “battery 10”) shown in FIG. 1A includes a negative electrode 1 made of a metal lithium foil, a positive electrode 2 made of a metal copper foil, a negative electrode 1 and a positive electrode 2. A lithium ion conductive solid electrolyte 3 (hereinafter, simply referred to as “solid electrolyte 3”), an organic electrolyte solution 4 filled between the negative electrode 1 and the solid electrolyte 3, a solid electrolyte 3 and a positive electrode 2 And a current collector 6 connected to the negative electrode 1, and a current collector 7 connected to the positive electrode 2, and further includes a housing 8 for housing these. ing. When such a battery 10 is charged, a reaction of Li + + e − → Li occurs in the negative electrode 1 and a reaction of Cu → Cu 2+ + 2e − occurs in the positive electrode 2. And since the metal copper which comprises the positive electrode 2 forms an oxide film in the surface in a positive electrode electrolyte, when a charge is advanced, as shown in FIG.1 (b), it is contacting the positive electrode electrolyte 5. An oxide film 9 is formed on the surface of the positive electrode 2a. When the oxide film 9 is formed in this way, the resistance of the battery 10a increases, and there is a risk that the charging will stop before it rises to the target charging voltage. Therefore, in the present invention, a pulsed reduction voltage lower than the charging voltage is applied during charging. When a pulsed reduction voltage is applied, as shown in FIG. 1C, the oxide film 9 covering the surface of the positive electrode 2a can be removed by electrolysis, and a battery 10b having an activated positive electrode 2b It becomes possible to do. Therefore, by implementing the control method of the present invention, it is possible to obtain the battery 10c having the positive electrode 2c and charged to the target charging voltage (see FIG. 1 (d)).
図２は、電池１０の充電中に印加されるパルス状の還元電圧の形態を説明する図である。図２に示すように、本発明の制御方法では、充電中に、充電電圧よりも低い還元電圧を印加する。本発明の制御方法において、充電電圧と還元電圧との差は、正極に形成された酸化皮膜を除去可能な差であれば特に限定されるものではない。ただし、
Ｃｕ２＋ ＋ ２ｅ− → Ｃｕ 標準酸化還元電位＋０．３４Ｖ ｖｓ ＳＨＥ
ＣｕＯ＋Ｈ２Ｏ＋２ｅ−→Ｃｕ＋２ＯＨ− 標準酸化還元電位−０．２９Ｖ ｖｓ ＳＨＥ
という点を考慮すると、正極２を構成するリチウム以外の金属が銅である場合には、充電電圧と還元電圧との差を０．６３Ｖ以上とすることが好ましい。
FIG. 2 is a diagram for explaining the form of a pulsed reduction voltage applied during charging of the battery 10. As shown in FIG. 2, in the control method of the present invention, a reduction voltage lower than the charging voltage is applied during charging. In the control method of the present invention, the difference between the charging voltage and the reduction voltage is not particularly limited as long as it is a difference capable of removing the oxide film formed on the positive electrode. However,
Cu 2+ + 2e − → Cu standard oxidation-reduction potential + 0.34V vs SHE
CuO + H 2 O + 2e - → Cu + 2OH - standard oxidation-reduction potential -0.29V vs SHE
In view of the above, when the metal other than lithium constituting the positive electrode 2 is copper, the difference between the charging voltage and the reduction voltage is preferably 0.63 V or more.
また、本発明の制御方法において、還元パルス（パルス状の還元電圧）は放電電流を引き起こすため、充電で得られたエネルギーが損なわれる。この損失を抑えるためには、印加された還元パルスの三角波におけるピーク半値幅（あるいは矩形波におけるオン時間）の合計がパルス間隔（オフ時間）の５％未満であるようにすることが好ましい。本発明の制御方法において、パルス状の還元電圧は、一般的なパルスジェネレータ等による三角波や矩形波等を用いて印加することができる。 In the control method of the present invention, the reduction pulse (pulse-like reduction voltage) causes a discharge current, so that the energy obtained by charging is lost. In order to suppress this loss, it is preferable that the sum of the peak half-value widths in the triangular wave (or the on time in the rectangular wave) of the applied reduction pulse is less than 5% of the pulse interval (off time). In the control method of the present invention, the pulsed reduction voltage can be applied using a triangular wave, a rectangular wave or the like by a general pulse generator or the like.
また、本発明の制御方法において、正極を構成する金属の表面が、水性電解液中に含まれる不純物（例えば、放電時に水性電解液中に析出した塩等）と反応することによって正極の活性化が阻害される場合には、パルス状の還元電圧を複数回に亘って印加すること、すなわち、所定時間に亘るパルス状の還元電圧の印加が終了した後、再び、パルス状の還元電圧を所定時間に亘って印加することが好ましい。 In the control method of the present invention, the surface of the metal constituting the positive electrode reacts with impurities contained in the aqueous electrolytic solution (for example, salts deposited in the aqueous electrolytic solution during discharge) to activate the positive electrode. When the pulsed reduction voltage is applied multiple times, that is, after the application of the pulsed reduction voltage for a predetermined time is completed, the pulsed reduction voltage is again applied to the predetermined voltage. It is preferable to apply over time.
本発明の制御方法において、充電中に印加されるパルス状の還元電圧の周波数は、正極を構成する金属の表面に形成された酸化皮膜を除去可能であれば、特に限定されるものではないが、例えば、一般的な条件として１ＭＨｚ〜０．１Ｈｚをあげることができる。これより低い周波数では、電解液の濃度分極が起こるために効率よくパルス還元を行うことが難しい。また、本発明の制御方法において、充電中にパルス状の還元電圧を印加する時間は、正極を構成する金属の表面に形成された酸化皮膜を除去可能であれば、特に限定されるものではないが、例えば、１マイクロ秒〜１２０秒とすることができる。また、連続的にパルスを印加しながら充電することもできる。 In the control method of the present invention, the frequency of the pulsed reduction voltage applied during charging is not particularly limited as long as the oxide film formed on the surface of the metal constituting the positive electrode can be removed. For example, 1 MHz to 0.1 Hz can be given as a general condition. At frequencies lower than this, it is difficult to efficiently perform pulse reduction because concentration polarization of the electrolyte occurs. In the control method of the present invention, the time for applying the pulsed reduction voltage during charging is not particularly limited as long as the oxide film formed on the surface of the metal constituting the positive electrode can be removed. However, for example, it may be 1 microsecond to 120 seconds. Moreover, it can also charge, applying a pulse continuously.
本発明に関する上記説明では、正極２に金属銅が含まれる形態を例示したが、本発明の制御方法が適用されるリチウムイオン二次電池の正極を構成するリチウム以外の金属は、銅に限定されるものではない。正極は、ニッケル等、リチウムイオン二次電池の正極を構成可能な公知のリチウム以外の金属を適宜用いることができる。 In the above description related to the present invention, the form in which metallic copper is included in the positive electrode 2 is exemplified, but the metal other than lithium constituting the positive electrode of the lithium ion secondary battery to which the control method of the present invention is applied is limited to copper. It is not something. As the positive electrode, a known metal other than lithium that can form the positive electrode of a lithium ion secondary battery, such as nickel, can be used as appropriate.
また、本発明において、リチウムイオン伝導固体電解質は、リチウムイオン二次電池に用いられる公知の固体電解質を適宜用いることができる。リチウムイオン伝導固体電解質の具体例としては、（Ｌｉ、Ｌａ）ＴｉＯ３やＬｉ１．５Ａｌ０．５Ｔｉ１．５（ＰＯ４）３のほか、ガーネット型構造を有する固体電解質等を例示することができる。このような固体電解質を含む固体電解質３は、公知の方法によって作製することができる。 Moreover, in this invention, the well-known solid electrolyte used for a lithium ion secondary battery can be used suitably as a lithium ion conductive solid electrolyte. Specific examples of the lithium ion conductive solid electrolyte include (Li, La) TiO 3 and Li 1.5 Al 0.5 Ti 1.5 (PO 4 ) 3 as well as solid electrolytes having a garnet-type structure. be able to. The solid electrolyte 3 containing such a solid electrolyte can be produced by a known method.
また、本発明の制御方法を適用される電池に含まれる正極電解液は、リチウムイオン伝導性を有する水性電解液であり、例えば、多孔質のセパレータに保持された形態で筐体に収容されている。かかる正極電解液は、正極に銅が含まれている場合、例えば１ｍｏｌ／ＬのＣｕＳＯ４を溶解させたＣｕＳＯ４水溶液のほか、Ｃｕ（ＣｌＯ４）２、ＣｕＣｌ２、Ｃｕ（ＮＯ３）２、Ｃｕ２（ＣＨ３ＣＯＯ）４等を用いることができる。これに対し、正極にニッケルが含まれている場合には、例えば、Ｎｉ（ＣｌＯ４）２、ＮｉＣｌ２、Ｎｉ（ＮＯ３）２、ＮｉＳＯ４、Ｎｉ（ＮＨ２ＳＯ３）２、Ｎｉ（ＣＨ３ＣＯＯ）２等を用いることができる。また、正極電解液を保持するセパレータとしては、ポリエチレン、ポリプロピレン等の多孔膜のほか、樹脂不織布やガラス繊維不織布等の不織布等を例示することができる。 Moreover, the positive electrode electrolyte contained in the battery to which the control method of the present invention is applied is an aqueous electrolyte having lithium ion conductivity. For example, the cathode electrolyte is accommodated in a casing in a form held by a porous separator. Yes. When the positive electrode contains copper, the positive electrode electrolyte includes, for example, a CuSO 4 aqueous solution in which 1 mol / L CuSO 4 is dissolved, Cu (ClO 4 ) 2 , CuCl 2 , Cu (NO 3 ) 2 , Cu 2 (CH 3 COO) 4 or the like can be used. On the other hand, when the positive electrode contains nickel, for example, Ni (ClO 4 ) 2 , NiCl 2 , Ni (NO 3 ) 2 , NiSO 4 , Ni (NH 2 SO 3 ) 2 , Ni (CH 3 COO) 2 or the like can be used. Moreover, as a separator holding a positive electrode electrolyte, in addition to porous films such as polyethylene and polypropylene, nonwoven fabrics such as resin nonwoven fabrics and glass fiber nonwoven fabrics can be exemplified.
また、本発明の制御方法を適用される電池に含まれ得る有機電解液は、リチウムイオン二次電池に用いられる公知の有機電解液を適宜用いることができ、例えば、多孔質基材に保持された形態で備えられていても良い。かかる有機電解液は、リチウム塩および有機溶媒を含有している。有機電解液に含有されるリチウム塩としては、ＬｉＰＦ６、ＬｉＢＦ４、ＬｉＣｌＯ４、及び、ＬｉＡｓＦ６等の無機リチウム塩、並びに、ＬｉＣＦ３ＳＯ３、ＬｉＮ（ＣＦ３ＳＯ２）２、ＬｉＮ（Ｃ２Ｆ５ＳＯ２）２、及び、ＬｉＣ（ＣＦ３ＳＯ２）３等の有機リチウム塩等を例示することができる。また、有機電解液の有機溶媒としては、例えばエチレンカーボネート（ＥＣ）、プロピレンカーボネート（ＰＣ）、ジメチルカーボネート（ＤＭＣ）、ジエチルカーボネート（ＤＥＣ）、エチルメチルカーボネート（ＥＭＣ）、ブチレンカーボネート、γ−ブチロラクトン、スルホラン、アセトニトリル、１，２−ジメトキシメタン、１，３−ジメトキシプロパン、ジエチルエーテル、テトラヒドロフラン、２−メチルテトラヒドロフラン、及び、これらの混合物等を挙げることができる。また、有機電解液におけるリチウム塩の濃度は、例えば０．２ｍｏｌ／Ｌ〜３ｍｏｌ／Ｌの範囲内とすることができる。なお、本発明においては、有機電解液として、例えばイオン性液体等の低揮発性液体を用いても良い。また、有機電解液を保持するセパレータとしては、ポリエチレン、ポリプロピレン等の多孔膜のほか、樹脂不織布やガラス繊維不織布等の不織布等を例示することができる。 In addition, as the organic electrolyte that can be included in the battery to which the control method of the present invention is applied, a known organic electrolyte that is used for a lithium ion secondary battery can be used as appropriate, for example, held by a porous substrate. It may be provided in a different form. Such an organic electrolytic solution contains a lithium salt and an organic solvent. Examples of the lithium salt contained in the organic electrolyte include inorganic lithium salts such as LiPF 6 , LiBF 4 , LiClO 4 , and LiAsF 6 , LiCF 3 SO 3 , LiN (CF 3 SO 2 ) 2 , LiN (C Examples thereof include organic lithium salts such as 2 F 5 SO 2 ) 2 and LiC (CF 3 SO 2 ) 3 . Examples of the organic solvent for the organic electrolyte include ethylene carbonate (EC), propylene carbonate (PC), dimethyl carbonate (DMC), diethyl carbonate (DEC), ethyl methyl carbonate (EMC), butylene carbonate, γ-butyrolactone, Examples include sulfolane, acetonitrile, 1,2-dimethoxymethane, 1,3-dimethoxypropane, diethyl ether, tetrahydrofuran, 2-methyltetrahydrofuran, and mixtures thereof. Moreover, the density | concentration of the lithium salt in an organic electrolyte solution can be in the range of 0.2 mol / L-3 mol / L, for example. In the present invention, a low-volatile liquid such as an ionic liquid may be used as the organic electrolyte. Examples of the separator that holds the organic electrolyte include non-woven fabrics such as resin nonwoven fabrics and glass fiber nonwoven fabrics in addition to porous membranes such as polyethylene and polypropylene.
なお、本発明の制御方法に関する上記説明では、負極１と固体電解質３との間に有機電解液４が充填されている形態を例示したが、本発明の制御方法が適用されるリチウムイオン二次電池は当該形態に限定されるものではない。本発明の制御方法が適用されるリチウムイオン二次電池は、有機電解液が備えられない形態とすることも可能である。有機電解液が備えられない場合には、負極と正極との間に固体電解質を配設するとともに、正極と固体電解質との間に正極電解液を充填し、負極と固体電解質とを接触させれば良い。 In the above description regarding the control method of the present invention, an example in which the organic electrolyte solution 4 is filled between the negative electrode 1 and the solid electrolyte 3 is illustrated, but the lithium ion secondary to which the control method of the present invention is applied. The battery is not limited to this form. The lithium ion secondary battery to which the control method of the present invention is applied may be in a form in which no organic electrolyte is provided. If an organic electrolyte is not provided, a solid electrolyte is disposed between the negative electrode and the positive electrode, and the positive electrode electrolyte is filled between the positive electrode and the solid electrolyte so that the negative electrode and the solid electrolyte are brought into contact with each other. It ’s fine.
本発明のリチウムイオン二次電池の制御方法は、情報機器やハイブリッド自動車等に使用されるリチウムイオン二次電池の正極を活性化させる方法として利用することができる。 The method for controlling a lithium ion secondary battery of the present invention can be used as a method for activating the positive electrode of a lithium ion secondary battery used in information equipment, hybrid vehicles, and the like.
１…負極
２…正極
３…固体電解質
４…有機電解液
５…正極電解液
６、７…集電体
８…筐体
９…酸化皮膜
１０…電池（リチウムイオン二次電池）
DESCRIPTION OF SYMBOLS 1 ... Negative electrode 2 ... Positive electrode 3 ... Solid electrolyte 4 ... Organic electrolyte 5 ... Positive electrode electrolyte 6, 7 ... Current collector 8 ... Housing 9 ... Oxide film 10 ... Battery (lithium ion secondary battery)
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