JP2008251497A - Lithium ion secondary battery before initial charging, lithium ion secondary battery, vehicle, and battery-mounting apparatus - Google Patents

Lithium ion secondary battery before initial charging, lithium ion secondary battery, vehicle, and battery-mounting apparatus Download PDF

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JP2008251497A
JP2008251497A JP2007095029A JP2007095029A JP2008251497A JP 2008251497 A JP2008251497 A JP 2008251497A JP 2007095029 A JP2007095029 A JP 2007095029A JP 2007095029 A JP2007095029 A JP 2007095029A JP 2008251497 A JP2008251497 A JP 2008251497A
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Tomoyoshi Ueki
智善 上木
Hiroyuki Yagi
洋行 八木
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Toyota Motor Corp
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Abstract

<P>PROBLEM TO BE SOLVED: To provide a lithium ion secondary battery before initial charging capable of reducing the usage of a positive electrode active material by supplying a part of lithium (lithium ions) from a substance different from the positive electrode active material in initial charging, and increasing the utilization factor of the positive electrode active material after that, and improved in the conductivity of a positive electrode active material layer; a lithium ion secondary battery manufacturable by using it, and capable of suppressing degradation of battery capacity when charge and discharge are repeated; a vehicle with the lithium ion secondary battery mounted thereto; and a battery-mounting apparatus. <P>SOLUTION: This lithium ion secondary battery 1 before initial charging is provided with a positive electrode member 21 having a positive electrode active material layer 24 containing a positive electrode active material 24a, and a negative electrode member 25 having a negative electrode active material layer 28 containing a negative electrode active material 28a. In the lithium ion secondary battery 1 before initial charging, the negative electrode active material 28a is a negative electrode active material 28a before initial charging without having lithium doped. At least one of LiCrTiO<SB>4</SB>: L1, LiFeTiO<SB>4</SB>: L2 and LiFeVO<SB>4</SB>: L3 is included in the positive electrode active material layer 24. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

本発明は、初充電前リチウムイオン二次電池、初充電前リチウムイオン二次電池を充電したリチウムイオン二次電池、リチウムイオン二次電池を用いる車両、およびリチウムイオン二次電池を用いる電池搭載機器に関する。   The present invention relates to a lithium ion secondary battery before initial charge, a lithium ion secondary battery charged with a lithium ion secondary battery before initial charge, a vehicle using the lithium ion secondary battery, and a battery-equipped device using the lithium ion secondary battery. About.

一般的にリチウムイオン二次電池は、正極活物質と負極活物質の間でリチウムイオンを授受させることにより電気エネルギーを蓄積、放出を行う。このリチウムイオン（リチウム）は、充電時には正極活物質から負極活物質に電解質体を通じて移動しドープされる。放電時にはその逆に、負極活物質から正極活物質に電解質体を通じて移動する。   Generally, a lithium ion secondary battery stores and discharges electric energy by transferring lithium ions between a positive electrode active material and a negative electrode active material. This lithium ion (lithium) is transferred and doped from the positive electrode active material to the negative electrode active material through the electrolyte during charging. Conversely, when discharging, the negative electrode active material moves from the positive electrode active material through the electrolyte body.

リチウムが予めドープされていない負極活物質を用いてリチウムイオン二次電池を製造した場合（以下、初充電を行う前のリチウムイオン二次電池を、初充電前リチウムイオン二次電池という）、当初は負極活物質中にリチウムが存在しないため、十分な放電ができずに電池の機能を果たすことができない。そこでこの初充電前リチウムイオン二次電池に初充電を行い、正極活物質からリチウムイオンを放出させ、負極活物質にリチウムをドープする必要がある。しかし、この初充電の際、負極活物質の表面にリチウムイオンの授受を阻害する固体電解質界面（ＳＥＩ）が形成されたり、リチウムイオンの一部が偶発的に、負極活物質のうちの、充放電反応に寄与できない領域にドープされる場合がある。これらは不可逆な反応であるため、高価な正極活物質を用いたにも拘わらず、その一部がその後の充放電に寄与できなくなることになる。これを防止するためには、負極活物質にドープされたリチウムのうちの、放電時に放出できない分に相当するリチウム（リチウムイオン）を、予め電池内に過剰に確保しておけば良い。そこで、その過剰分のリチウム（リチウムイオン）を正極に確保する技術が知られている。例えば、正極活物質層にＬｉ2ＴｉＯ3を混合する技術が挙げられる（特許文献１参照）。 When a lithium ion secondary battery is manufactured using a negative electrode active material not previously doped with lithium (hereinafter, the lithium ion secondary battery before the first charge is referred to as a lithium ion secondary battery before the first charge) Since lithium does not exist in the negative electrode active material, sufficient discharge cannot be performed and the function of the battery cannot be achieved. Therefore, it is necessary to first charge the lithium ion secondary battery before the first charge, release lithium ions from the positive electrode active material, and dope lithium into the negative electrode active material. However, during this initial charge, a solid electrolyte interface (SEI) that inhibits the exchange of lithium ions is formed on the surface of the negative electrode active material, or some of the lithium ions are accidentally charged. In some cases, a region that cannot contribute to the discharge reaction is doped. Since these are irreversible reactions, some of them cannot contribute to the subsequent charge / discharge despite the use of an expensive positive electrode active material. In order to prevent this, an excess of lithium (lithium ions) corresponding to the amount of lithium doped in the negative electrode active material that cannot be released during discharge may be secured in advance in the battery. Therefore, a technique for securing an excess amount of lithium (lithium ions) in the positive electrode is known. For example, there is a technique of mixing Li 2 TiO 3 into the positive electrode active material layer (see Patent Document 1).

特開平７−２８８１２４公報JP-A-7-288124

しかしながら、特許文献１に示されたＬｉ2ＴｉＯ3は正極活物質よりも導電性が低く、これを正極活物質層に添加すると、電池の内部抵抗値を増大させて電池出力を低下させる。なお、正極の作製時、Ｌｉ2ＴｉＯ3は正極活物質と混練し難く、工数およびコストアップとなる不具合もある。 However, Li 2 TiO 3 disclosed in Patent Document 1 has lower conductivity than the positive electrode active material, and when this is added to the positive electrode active material layer, the internal resistance value of the battery is increased and the battery output is decreased. It should be noted that Li 2 TiO 3 is difficult to knead with the positive electrode active material during the production of the positive electrode, and there is a problem that man-hours and costs are increased.

本発明は、かかる現状に鑑みてなされたものであって、初充電時、リチウム（リチウムイオン）の一部を正極活物質とは異なる物質から供給させ、その後の正極活物質の利用率を上げ、正極活物質の使用量を減らすと共に、正極活物質層の導電性を向上させた初充電前リチウムイオン二次電池を提供することを目的とする。さらに、この初充電前リチウムイオン二次電池を用いてできる、充放電を繰り返したときの電池容量の低下を抑制したリチウムイオン二次電池、さらに上述のリチウムイオン二次電池を搭載した車両および電池搭載機器を提供することを目的とする。   The present invention has been made in view of the present situation, and at the time of initial charge, a part of lithium (lithium ion) is supplied from a material different from the positive electrode active material, and the utilization rate of the positive electrode active material thereafter is increased. An object of the present invention is to provide a pre-initial charge lithium ion secondary battery in which the amount of positive electrode active material used is reduced and the conductivity of the positive electrode active material layer is improved. Furthermore, a lithium ion secondary battery that suppresses a decrease in battery capacity when repeated charging and discharging can be performed using the lithium ion secondary battery before the initial charge, and a vehicle and a battery equipped with the lithium ion secondary battery described above The purpose is to provide on-board equipment.

そして、その解決手段は、正極活物質を含む正極活物質層を有する正極部材と、負極活物質を含む負極活物質層を有する負極部材と、を備え、上記負極活物質は、リチウムがドープされていない初充電前負極活物質である初充電前リチウムイオン二次電池であって、上記正極活物質層には、ＬｉＣｒＴｉＯ4、ＬｉＦｅＴｉＯ4、およびＬｉＦｅＶＯ4、の少なくともいずれかを含む初充電前リチウムイオン二次電池である。 The solving means includes a positive electrode member having a positive electrode active material layer containing a positive electrode active material, and a negative electrode member having a negative electrode active material layer containing a negative electrode active material, wherein the negative electrode active material is doped with lithium. A lithium ion secondary battery before initial charge, which is a negative electrode active material before initial charge, wherein the positive electrode active material layer includes at least one of LiCrTiO 4 , LiFeTiO 4 , and LiFeVO 4 . It is an ion secondary battery.

本発明の初充電前リチウムイオン二次電池では、正極活物質層にＬｉＣｒＴｉＯ4、ＬｉＦｅＴｉＯ4、およびＬｉＦｅＶＯ4の少なくともいずれかを含む。これらのリチウム酸化物は、初充電を行うと正極活物質に先立ってリチウムイオンを放出する。このため、これらのリチウム酸化物を用いることで、初充電の際に不可逆的に負極活物質にドープされるリチウムの少なくとも一部を、これらから放出させたリチウムイオンでまかなうことができるから、正極活物質の利用効率を上げ、より少量の正極活物質で足りるようにできる。しかも、これらのリチウム酸化物はＬｉＣｏＯ2などの正極活物質と混合して用いると、前述したＬｉ2ＴｉＯ3とは逆に、正極部材（正極活物質層）の導電性が高くなり、この電池の内部抵抗値が小さくなる。従って、この電池出力を向上させることができる。
さらに、上述のリチウム酸化物を正極活物質層に含む本発明の初充電前リチウムイオン二次電池を充電したリチウムイオン二次電池においては、繰り返し充放電させた場合でも電池容量の低下を、上述のリチウム酸化物を正極活物質層に含有しない場合よりも抑制することができる。即ち、リチウムイオン二次電池の電池容量劣化を抑制することができる。 In the lithium ion secondary battery before initial charge of the present invention, the positive electrode active material layer includes at least one of LiCrTiO 4 , LiFeTiO 4 , and LiFeVO 4 . These lithium oxides release lithium ions prior to the positive electrode active material when initially charged. For this reason, by using these lithium oxides, at least a part of the lithium irreversibly doped into the negative electrode active material at the time of initial charge can be covered by lithium ions released from them. The utilization efficiency of the active material can be increased, and a smaller amount of the positive electrode active material can be sufficient. In addition, when these lithium oxides are mixed with a positive electrode active material such as LiCoO 2 , the conductivity of the positive electrode member (positive electrode active material layer) is increased, contrary to the above-described Li 2 TiO 3. The internal resistance value of becomes smaller. Therefore, this battery output can be improved.
Further, in the lithium ion secondary battery charged with the lithium ion secondary battery before the initial charge of the present invention containing the above lithium oxide in the positive electrode active material layer, the battery capacity is reduced even when repeatedly charged and discharged. This lithium oxide can be suppressed as compared with the case where it is not contained in the positive electrode active material layer. That is, the battery capacity deterioration of the lithium ion secondary battery can be suppressed.

なお、正極活物質としては、電気化学的に自由にリチウムイオンの授受が可能な固体リチウム化合物であれば良く、例えばＬｉＣｏＯ2、ＬｉＮｉＯ2、ＬｉＭｎ2Ｏ4、ＬｉＦｅＯ2、Ｌｉ5ＦｅＯ4、Ｌｉ2ＭｎＯ3、ＬｉＦｅＰＯ4、ＬｉＶ2Ｏ4、これらの混合物等が挙げられる。また、正極活物質層は、正極活物質および上述のリチウム酸化物を含んでなるものであれば良いが、それらに加えて結着剤や導電化剤を含んでいても良い。 The positive electrode active material may be a solid lithium compound that can electrochemically freely exchange lithium ions. For example, LiCoO 2 , LiNiO 2 , LiMn 2 O 4 , LiFeO 2 , Li 5 FeO 4 , Li 2 MnO 3 , LiFePO 4 , LiV 2 O 4 , mixtures thereof and the like. In addition, the positive electrode active material layer may be any layer that includes the positive electrode active material and the above-described lithium oxide, but may include a binder or a conductive agent in addition to them.

さらに、初充電前負極活物質としては、電気化学的に自由にリチウムイオンの授受が可能な導電性物質であれば良いが、例えば、リチウムイオンを内部にドープ可能な黒鉛、炭素化材料、および低温焼成炭素が挙げられる。   Furthermore, the negative electrode active material before the initial charge may be any conductive material that can electrochemically freely exchange lithium ions. For example, graphite capable of doping lithium ions therein, a carbonized material, and A low-temperature calcination carbon is mentioned.

さらに、上述の初充電前リチウムイオン二次電池であって、前記初充電前負極活物質は、黒鉛からなり、前記正極活物質層には、前記正極活物質の１０〜１５ｗｔ％の前記ＬｉＣｒＴｉＯ4、上記正極活物質の１５〜２０ｗｔ％の前記ＬｉＦｅＴｉＯ4、上記正極活物質の１５〜２０ｗｔ％の前記ＬｉＦｅＶＯ4、のいずれかを含む初充電前リチウムイオン二次電池とすると良い。 Further, in the above-described lithium ion secondary battery before initial charge, the negative electrode active material before initial charge is made of graphite, and the positive electrode active material layer includes 10-15 wt% of the LiCrTiO 4 of the positive electrode active material. A lithium ion secondary battery before initial charge including any one of 15 to 20 wt% of the LiFeTiO 4 of the positive electrode active material and 15 to 20 wt% of the LiFeVO 4 of the positive electrode active material is preferable.

本発明の初充電前リチウムイオン二次電池では、初充電前負極活物質に黒鉛を用いている。一方、正極活物質層には、適切な量のＬｉＣｒＴｉＯ4、ＬｉＦｅＴｉＯ4、およびＬｉＦｅＶＯ4のいずれかを含んでいる。これにより、この初充電前リチウムイオン二次電池を初充電し、さらに充放電させたリチウムイオン二次電池において、電池容量の低下を抑制することができる。 In the lithium ion secondary battery before initial charge of the present invention, graphite is used as the negative electrode active material before initial charge. On the other hand, the positive electrode active material layer contains an appropriate amount of any one of LiCrTiO 4 , LiFeTiO 4 , and LiFeVO 4 . Thereby, in the lithium ion secondary battery which carried out the initial charge of this lithium ion secondary battery before initial charge, and was further charged / discharged, the fall of battery capacity can be suppressed.

さらに、上述のリチウムイオン二次電池であって、前記初充電前負極活物質は、炭素化材料からなり、前記正極活物質層には、前記正極活物質の１２〜２０ｗｔ％の前記ＬｉＣｒＴｉＯ4、上記正極活物質の１７〜２５ｗｔ％の前記ＬｉＦｅＴｉＯ4、上記正極活物質の１７〜２５ｗｔ％の前記ＬｉＦｅＶＯ4、のいずれかを含む初充電前リチウムイオン二次電池とすると良い。 Furthermore, in the above lithium ion secondary battery, the negative active material before initial charging is made of a carbonized material, and the positive active material layer includes 12 to 20 wt% of the LiCrTiO 4 of the positive active material, A lithium ion secondary battery before initial charge including any of 17 to 25 wt% of the LiFeTiO 4 of the positive electrode active material and 17 to 25 wt% of the LiFeVO 4 of the positive electrode active material may be used.

本発明の初充電前リチウムイオン二次電池では、初充電前負極活物質に炭素化材料を用いている。一方、正極活物質層には、適切な量のＬｉＣｒＴｉＯ4、ＬｉＦｅＴｉＯ4、およびＬｉＦｅＶＯ4のいずれかを含んでいる。これにより、この初充電前リチウムイオン二次電池を初充電し、さらに充放電させたリチウムイオン二次電池において、電池容量の低下を抑制することができる。 In the lithium ion secondary battery before initial charge of the present invention, a carbonized material is used as the negative electrode active material before initial charge. On the other hand, the positive electrode active material layer contains an appropriate amount of any one of LiCrTiO 4 , LiFeTiO 4 , and LiFeVO 4 . Thereby, in the lithium ion secondary battery which carried out the initial charge of this lithium ion secondary battery before initial charge, and was further charged / discharged, the fall of battery capacity can be suppressed.

なお、炭素化材料としては、例えば、熱分解性炭素や有機前駆体を１０００〜２０００℃で熱処理・焼成を行った炭素体が挙げられる。これらは、原料に含まれていた酸素、水素、窒素などのヘテロ原子の脱離がほぼ終了し、黒鉛結晶類似の層状結晶子からなる炭素体をなす。但し、グラフェン層の層間距離は黒鉛結晶のそれ（０．３３５４ｎｍ）よりも大きく、層の積層状態は乱層となっているという特徴を有する。   In addition, as a carbonization material, the carbon body which heat-processed and baked the pyrolyzable carbon and the organic precursor at 1000-2000 degreeC is mentioned, for example. These substantially complete elimination of hetero atoms such as oxygen, hydrogen and nitrogen contained in the raw material, and form a carbon body composed of layered crystallites similar to graphite crystals. However, the interlayer distance of the graphene layer is larger than that of the graphite crystal (0.3354 nm), and the laminated state of the layers is a disordered layer.

さらに、上述のリチウムイオン二次電池であって、前記初充電前負極活物質は、低温焼成炭素からなり、前記正極活物質層には、前記正極活物質の１３〜２０ｗｔ％の前記ＬｉＣｒＴｉＯ4、上記正極活物質の２０〜２５ｗｔ％の前記ＬｉＦｅＴｉＯ4、上記正極活物質の２０〜２５ｗｔ％の前記ＬｉＦｅＶＯ4、のいずれかを含む初充電前リチウムイオン二次電池とすると良い。 Furthermore, in the above lithium ion secondary battery, the negative electrode active material before initial charge is made of low-temperature fired carbon, and the positive electrode active material layer includes 13 to 20 wt% of the LiCrTiO 4 of the positive electrode active material, A lithium ion secondary battery before initial charge including any one of 20 to 25 wt% of the LiFeTiO 4 in the positive electrode active material and 20 to 25 wt% of the LiFeVO 4 in the positive electrode active material may be used.

本発明の初充電前リチウムイオン二次電池では、初充電前負極活物質に低温焼成炭素を用いている。一方、正極活物質層には、適切な量のＬｉＣｒＴｉＯ4、ＬｉＦｅＴｉＯ4、およびＬｉＦｅＶＯ4のいずれかを含んでいる。これにより、この初充電前リチウムイオン二次電池を初充電し、さらに充放電させたリチウムイオン二次電池において、電池容量の低下を抑制することができる。 In the lithium ion secondary battery before initial charge of the present invention, low-temperature calcined carbon is used as the negative electrode active material before initial charge. On the other hand, the positive electrode active material layer contains an appropriate amount of any one of LiCrTiO 4 , LiFeTiO 4 , and LiFeVO 4 . Thereby, in the lithium ion secondary battery which carried out the initial charge of this lithium ion secondary battery before initial charge, and was further charged / discharged, the fall of battery capacity can be suppressed.

なお、低温焼成炭素としては、例えば、熱分解性炭素や有機前駆体を１０００℃以下、特に７００〜８００℃で熱処理・焼成を行った炭素体が挙げられる。原料に含まれていた酸素、水素、窒素などのヘテロ原子を未だ多く含み、Ｘ線回折では黒鉛や炭素化材料と比べて、ブロードなピークを示す特徴を有する。   Examples of the low-temperature calcined carbon include carbon bodies obtained by heat-treating and calcining a thermally decomposable carbon or an organic precursor at 1000 ° C. or lower, particularly 700 to 800 ° C. It still contains many heteroatoms such as oxygen, hydrogen, and nitrogen contained in the raw material, and X-ray diffraction is characterized by a broad peak compared to graphite and carbonized materials.

さらに、他の解決手段は、上述の初充電前リチウムイオン二次電池を、充電してなるリチウムイオン二次電池である。   Furthermore, another solution is a lithium ion secondary battery obtained by charging the above-mentioned pre-initial charge lithium ion secondary battery.

本発明のリチウムイオン二次電池では、充電により正極活物質層の正極活物質のみならずリチウム酸化物からリチウムイオンが放出され、リチウムが負極活物質中にドープされる。このため、リチウム酸化物からリチウムをドープした分、不可逆的に負極活物質にドープされるリチウムをまかなうことができ、その後の正極活物質の利用効率を高めることができる。しかも、正極活物質層には、リチウム酸化物あるいはこれからリチウムイオンが欠損したリチウム欠損酸化物を含んでいるので、正極部材（正極活物質層）の導電性を、これらを含まない場合に比べて高くできる。従って、電池の内部抵抗値を小さくでき、また電池出力を大きくできる。
また、この電池では、繰り返し充放電させた後の電池容量の低下を、正極活物質層に前述のリチウム酸化物を含有させない場合よりも抑制できる利点もある。 In the lithium ion secondary battery of the present invention, lithium ions are released from lithium oxide as well as the positive electrode active material of the positive electrode active material layer by charging, and lithium is doped into the negative electrode active material. For this reason, the amount of lithium doped from the lithium oxide can irreversibly cover the lithium doped into the negative electrode active material, and the subsequent utilization efficiency of the positive electrode active material can be increased. In addition, since the positive electrode active material layer includes lithium oxide or a lithium deficient oxide from which lithium ions are lost, the conductivity of the positive electrode member (positive electrode active material layer) is higher than that in the case where these are not included. Can be high. Therefore, the internal resistance value of the battery can be reduced and the battery output can be increased.
In addition, this battery has an advantage that a decrease in battery capacity after repeated charge and discharge can be suppressed as compared with the case where the above-described lithium oxide is not contained in the positive electrode active material layer.

さらに、他の解決手段は、正極活物質を含む正極活物質層を有する正極部材と、負極活物質を含む負極活物質層を有する負極部材と、を備えるリチウムイオン二次電池であって、上記負極活物質には、リチウムがドープされてなり、上記正極活物質層は、ＬｉＣｒＴｉＯ4、ＬｉＦｅＴｉＯ4、およびＬｉＦｅＶＯ4、の少なくともいずれかのリチウム酸化物から、上記リチウム酸化物に含まれるリチウムイオンの少なくとも一部を欠損させた組成のリチウム欠損酸化物を含むリチウムイオン二次電池である。 Furthermore, another solution is a lithium ion secondary battery comprising: a positive electrode member having a positive electrode active material layer containing a positive electrode active material; and a negative electrode member having a negative electrode active material layer containing a negative electrode active material, The negative electrode active material is doped with lithium, and the positive electrode active material layer is formed of at least one of LiCrTiO 4 , LiFeTiO 4 , and LiFeVO 4 , lithium ions contained in the lithium oxide. It is a lithium ion secondary battery including a lithium deficient oxide having a composition in which at least a part is deficient.

本発明のリチウムイオン二次電池では、正極活物質層は、前述のリチウム欠損酸化物を含む。このリチウム欠損酸化物は、初充電時にリチウム酸化物からリチウムイオンを放出させたものである。初充電時に放出された分のリチウムイオンは、負極活物質中にリチウムとしてドープされるので、不可逆的に負極活物質にドープされるリチウムの少なくとも一部をまかなうことができる。従って、その後の充放電の際、正極活物質の利用効率を上げ、より少量の正極活物質で足りるようにできる。しかも、リチウム欠損酸化物を用いると、正極部材（正極活物質層）の導電性が高くなり、このリチウムイオン二次電池の内部抵抗値は小さくできる。従って、この電池出力を向上させることができる。
さらに、本発明のリチウムイオン二次電池においては、繰り返し充放電させた場合でも電池容量の低下を、上述のリチウム欠損酸化物を正極活物質層に含有しない場合よりも抑制することができる。即ち、リチウムイオン二次電池の電池容量劣化を抑制することができる。 In the lithium ion secondary battery of the present invention, the positive electrode active material layer includes the above-described lithium deficient oxide. This lithium deficient oxide is one in which lithium ions are released from the lithium oxide during the initial charge. Since the lithium ions released during the initial charge are doped as lithium in the negative electrode active material, it is possible to cover at least a portion of the lithium irreversibly doped in the negative electrode active material. Therefore, in the subsequent charge / discharge, the utilization efficiency of the positive electrode active material can be increased, and a smaller amount of the positive electrode active material can be sufficient. In addition, when a lithium deficient oxide is used, the conductivity of the positive electrode member (positive electrode active material layer) is increased, and the internal resistance value of the lithium ion secondary battery can be reduced. Therefore, this battery output can be improved.
Furthermore, in the lithium ion secondary battery of the present invention, even when the battery is repeatedly charged and discharged, a decrease in battery capacity can be suppressed as compared with the case where the above-described lithium deficient oxide is not included in the positive electrode active material layer. That is, the battery capacity deterioration of the lithium ion secondary battery can be suppressed.

さらに、他の解決手段は、上述のリチウムイオン二次電池システムを用いた車両である。   Furthermore, another solution is a vehicle using the above-described lithium ion secondary battery system.

本発明の車両では、上述のリチウムイオン二次電池を用いているので、電池出力は向上し、通常使用に伴う電池容量劣化を抑制できる車両とすることが可能である。   Since the above-described lithium ion secondary battery is used in the vehicle of the present invention, the battery output can be improved and the vehicle can be prevented from being deteriorated in battery capacity due to normal use.

なお、リチウムイオン二次電池システムを用いた車両としては、その動力源の全部あるいは一部に電池による電気エネルギーを使用している車両であれば良く、電気自動車、ハイブリッド電気自動車、フォークリフト、電気車いす、電動アシスト自転車、電動スクータ、鉄道車両が挙げられる。   The vehicle using the lithium ion secondary battery system may be a vehicle that uses electric energy from the battery for all or a part of its power source, such as an electric vehicle, a hybrid electric vehicle, a forklift, an electric wheelchair. , Electric assist bicycles, electric scooters, railway vehicles.

さらに、他の解決手段は、上述のリチウムイオン二次電池システムを用いた電池搭載機器である。   Still another solution is a battery-equipped device using the above-described lithium ion secondary battery system.

本発明の電池搭載機器では、上述のリチウムイオン二次電池を用いているので、電池出力は向上し、通常使用に伴うこの電池容量劣化を抑制できる電池搭載機器とすることが可能である。   In the battery-equipped device of the present invention, since the above-described lithium ion secondary battery is used, the battery output can be improved, and the battery-equipped device that can suppress the battery capacity deterioration due to normal use can be obtained.

なお、リチウムイオン二次電池システムを用いた電池搭載機器としては、電池を搭載しこれをエネルギー源の少なくとも１つとして利用する機器であれば良く、例えば、パーソナルコンピュータ、携帯電話、電池駆動の電動工具、パワーショベルなどの、各種の家電製品、オフィス機器、産業機器が挙げられる。   Note that the battery-equipped device using the lithium ion secondary battery system may be any device equipped with a battery and using it as at least one energy source. For example, a personal computer, a cellular phone, a battery-driven electric motor Various home appliances such as tools and power shovels, office equipment, and industrial equipment.

（実施形態１）
次に、本発明の実施形態１について、図面を参照しつつ説明する。まず、初充電前リチウムイオン二次電池１について説明する。図１に初充電前リチウムイオン二次電池１の斜視図を、図２に初充電前リチウムイオン二次電池１の断面図（図１のＡ−Ａ断面）を、図３に初充電前リチウムイオン二次電池１の断面図（図２のＢ−Ｂ断面）を示す。
本実施形態にかかる初充電前リチウムイオン二次電池１は、電池ケース本体１１および封口蓋１２を備える電池ケース１０、発電要素２０、および図示しない電解液を備える、捲回形の初充電前リチウムイオン二次電池である。 (Embodiment 1)
Next, Embodiment 1 of the present invention will be described with reference to the drawings. First, the pre-initial charge lithium ion secondary battery 1 will be described. FIG. 1 is a perspective view of a lithium ion secondary battery 1 before initial charge, FIG. 2 is a sectional view of the lithium ion secondary battery 1 before initial charge (cross section AA in FIG. 1), and FIG. 3 is lithium before initial charge. Sectional drawing (BB cross section of FIG. 2) of the ion secondary battery 1 is shown.
A lithium ion secondary battery 1 before initial charge according to the present embodiment includes a battery case 10 including a battery case body 11 and a sealing lid 12, a power generation element 20, and an electrolyte solution (not shown). It is an ion secondary battery.

電池ケース本体１１および封口蓋１２は共にステンレス鋼製であり、封口蓋１２は電池ケース本体１１の開口部を閉塞して配置されている。そして、正極端子部材１３および負極端子部材１４はそれぞれ封口蓋１２の上面に貫通突出しており、封口蓋１２との間には絶縁部材１６がそれぞれ介在している。また、封口蓋１２の上面には安全弁１５も配置されている。   The battery case main body 11 and the sealing lid 12 are both made of stainless steel, and the sealing lid 12 is arranged with the opening of the battery case main body 11 closed. The positive electrode terminal member 13 and the negative electrode terminal member 14 project through the upper surface of the sealing lid 12, and insulating members 16 are interposed between the sealing lid 12 and the positive electrode terminal member 13 and the negative electrode terminal member 14, respectively. A safety valve 15 is also arranged on the upper surface of the sealing lid 12.

また、発電要素２０は、正極部材２１および初充電前負極部材２５が、ポリエチレンからなるセパレータ２８を介して扁平形状に捲回されてなる（図３参照）。
なお、図３に示すように、初充電前負極部材２５の銅箔２７は、そのうちセパレータ２８からはみ出た部位で互いに重ねられ、捲回体の長円形状のおおよそ半分をつぶすように、負極集電部材１８にかしめられ溶接されている。正極部材２１のアルミニウム箔２３も同様に、そのうち負極集電部材１８とは反対側のセパレータ２８からはみ出た部位で互いに重ねられ、金属製の正極集電部材１７にかしめられ溶接されている。
また、電解液は、ＥＣ（エチレンカーボネート）、ＥＭＣ（エチルメチルカーボネート）、およびＤＭＣ（ジメチルカーボネート）を調整した混合有機溶媒に、溶質としてＬｉＰＦ6を添加した有機電解液である。 The power generation element 20 is formed by winding a positive electrode member 21 and a negative electrode member 25 before initial charging into a flat shape via a separator 28 made of polyethylene (see FIG. 3).
In addition, as shown in FIG. 3, the copper foils 27 of the negative electrode member 25 before the initial charge are overlapped with each other at a part protruding from the separator 28, and the negative electrode current collector is crushed so as to crush approximately half of the oval shape of the wound body. The electric member 18 is caulked and welded. Similarly, the aluminum foil 23 of the positive electrode member 21 is overlapped with each other at a portion protruding from the separator 28 on the side opposite to the negative electrode current collector member 18, and is caulked and welded to the metal positive electrode current collector member 17.
The electrolytic solution is an organic electrolytic solution obtained by adding LiPF 6 as a solute to a mixed organic solvent prepared by adjusting EC (ethylene carbonate), EMC (ethyl methyl carbonate), and DMC (dimethyl carbonate).

次いで、本実施形態１にかかる正極部材２１を図４に示す。正極部材２１は、アルミニウム箔２３の表裏面に、正極活物質層２４をそれぞれ担持する（図４（ａ）参照）。正極活物質層２４は、ＬｉＣｏＯ2からなる正極活物質２４ａ、ＬｉＣｒＴｉＯ4からなる第１リチウム酸化物Ｌ１、結着剤２４ｂ、および導電化剤２４ｃを混練し塗工したものである（図４（ｂ）参照）。このうち、第１リチウム酸化物Ｌ１は、正極活物質２４ａの１０ｗｔ％の量としてある。
一方、本実施形態１にかかる初充電前負極部材２５を図５に示すが、初充電前負極部材２５は、銅箔２７の表裏面に、黒鉛からなる初充電前負極活物質２８ａと結着剤２８ｂを混練したものを塗工してなる初充電前負極活物質層２８を有するものである（図５（ｂ）参照）。 Next, the positive electrode member 21 according to the first embodiment is shown in FIG. The positive electrode member 21 supports the positive electrode active material layer 24 on the front and back surfaces of the aluminum foil 23 (see FIG. 4A). The positive electrode active material layer 24 is obtained by kneading and coating a positive electrode active material 24a made of LiCoO 2 , a first lithium oxide L1 made of LiCrTiO 4 , a binder 24b, and a conductive agent 24c (FIG. 4 ( b)). Of these, the first lithium oxide L1 is in an amount of 10 wt% of the positive electrode active material 24a.
On the other hand, FIG. 5 shows the negative electrode member 25 before initial charge according to the first embodiment. The negative electrode member 25 before initial charge is bound to the negative electrode active material 28a before charge made of graphite on the front and back surfaces of the copper foil 27. It has the negative electrode active material layer 28 before the initial charge formed by coating a kneaded agent 28b (see FIG. 5B).

初充電前リチウムイオン二次電池１に、公知の手法で充電（初充電）する。つまり、充電装置を用いて、正極部材２１に正電圧を、初充電前負極部材２５に負電圧をそれぞれ印加する。すると、正極部材２１を通じて正極活物質２４ａのみならず、第１リチウム酸化物Ｌ１にも正電圧が印加されるので、正極活物質２４ａおよび第１リチウム酸化物Ｌ１からリチウムイオンが放出されて、初充電前負極活物質２８ａにドープされる。かくして、リチウムがドープされた負極活物質２８ａＤを有するリチウムイオン二次電池２ができる（図６参照）。なお、充電によって、第１リチウム酸化物Ｌ１は第１リチウム欠損酸化物Ｌ１Ｒとなり、正極活物質層２４は、この第１リチウム欠損酸化物Ｌ１Ｒを有する正極活物質層２４Ｒになる（図７（ａ）参照）。また初充電前負極活物質２８ａは充電によりリチウムがドープされた負極活物質２８ａＤとなり、初充電前負極活物質層２８は、負極活物質２８ａＤを有する負極活物質層２８Ｄとなる。   The lithium ion secondary battery 1 before the initial charge is charged (initial charge) by a known method. That is, using the charging device, a positive voltage is applied to the positive electrode member 21 and a negative voltage is applied to the negative electrode member 25 before initial charging. Then, since a positive voltage is applied not only to the positive electrode active material 24a but also to the first lithium oxide L1 through the positive electrode member 21, lithium ions are released from the positive electrode active material 24a and the first lithium oxide L1, The negative electrode active material 28a before charging is doped. Thus, the lithium ion secondary battery 2 having the negative electrode active material 28aD doped with lithium can be obtained (see FIG. 6). By charging, the first lithium oxide L1 becomes the first lithium deficient oxide L1R, and the positive electrode active material layer 24 becomes the positive electrode active material layer 24R having the first lithium deficient oxide L1R (FIG. 7A )reference). In addition, the negative electrode active material 28a before initial charge becomes a negative electrode active material 28aD doped with lithium by charging, and the negative electrode active material layer 28 before initial charge becomes a negative electrode active material layer 28D having the negative electrode active material 28aD.

本実施形態１にかかるリチウムイオン二次電池２は、正極部材２１（正極活物質層２４）の導電性の良好な初充電前リチウムイオン二次電池１を充電（初充電）したものである。また、このリチウムイオン二次電池２の正極活物質層２４Ｒには、正極活物質２４ａおよび第１リチウム欠損酸化物Ｌ１Ｒを含む。この第１リチウム欠損酸化物Ｌ１Ｒは、第１リチウム酸化物Ｌ１が、正極活物質２４ａに先立ってリチウムイオンを放出してできたものである。充電（初充電）時に、この第１リチウム酸化物Ｌ１から放出されたリチウムイオンは、初充電前負極活物質２８ａ（負極活物質２８ａＤ）にドープされる。従って、不可逆的に負極活物質にドープされるリチウムの少なくとも一部をまかなうことができる。従って、このリチウムイオン二次電池２において、正極活物質２４ａの利用効率を上げ、より少量の正極活物質２４ａで、電池容量を満足させることができる。   The lithium ion secondary battery 2 according to the first embodiment is obtained by charging (initial charging) the pre-initial charging lithium ion secondary battery 1 with good conductivity of the positive electrode member 21 (positive electrode active material layer 24). The positive electrode active material layer 24R of the lithium ion secondary battery 2 includes a positive electrode active material 24a and a first lithium deficient oxide L1R. The first lithium deficient oxide L1R is formed by releasing lithium ions from the first lithium oxide L1 prior to the positive electrode active material 24a. At the time of charging (initial charging), lithium ions released from the first lithium oxide L1 are doped into the negative electrode active material 28a (negative electrode active material 28aD) before initial charging. Therefore, at least a part of lithium irreversibly doped into the negative electrode active material can be provided. Therefore, in this lithium ion secondary battery 2, the utilization efficiency of the positive electrode active material 24a can be increased, and the battery capacity can be satisfied with a smaller amount of the positive electrode active material 24a.

しかも、第１リチウム欠損酸化物Ｌ１Ｒは、正極活物質２４ａと混合して用いると、従来のＬｉ2ＴｉＯ3を用いた場合とは逆に、正極部材２１Ｒ（正極活物質層２４Ｒ）の導電性が高くなり、このリチウムイオン二次電池２の内部抵抗値は小さくできる。このことは、リチウムイオン二次電池に用いる正極活物質をＬｉＣｏＯ2のみとしたもの、およびＬｉＣｒＴｉＯ4のみとしたものについて、交流インピーダンス測定により直流抵抗成分を算出したところ、ＬｉＣｒＴｉＯ4のみを正極活物質に使用した電池は、ＬｉＣｏＯ2のみを用いた電池に比べて直流抵抗が約８％低くなることからも確かめられる。なお比較として、Ｌｉ2ＴｉＯ3のみを正極活物質に用いた電池について、同様にして直流抵抗成分を算出したところ、ＬｉＣｏＯ2に比べて約４％高いことが確かめられた。つまり、正極活物質２４ａのＬｉＣｏＯ2に、導電性のより高いＬｉＣｒＴｉＯ4を混ぜるので、正極部材２１Ｒ全体として導電性が高くでき、リチウムイオン二次電池２の直流抵抗を低下させることができる。従って、この電池出力を向上させることができる。 Moreover, when the first lithium-deficient oxide L1R is used in combination with the positive electrode active material 24a, the conductivity of the positive electrode member 21R (positive electrode active material layer 24R) is opposite to the case where the conventional Li 2 TiO 3 is used. The internal resistance value of the lithium ion secondary battery 2 can be reduced. This means that when the positive electrode active material used in the lithium ion secondary battery is only LiCoO 2 and only LiCrTiO 4 is calculated, the direct current resistance component is calculated by measuring the AC impedance, and only LiCrTiO 4 is used as the positive electrode active material. It can be confirmed that the battery used in this example has a DC resistance of about 8% lower than that of the battery using only LiCoO 2 . As a comparison, when the direct current resistance component was calculated in the same manner for a battery using only Li 2 TiO 3 as the positive electrode active material, it was confirmed that it was about 4% higher than LiCoO 2 . That is, since LiCrTiO 4 having higher conductivity is mixed with LiCoO 2 of the positive electrode active material 24a, the conductivity of the positive electrode member 21R as a whole can be increased, and the DC resistance of the lithium ion secondary battery 2 can be reduced. Therefore, this battery output can be improved.

次いで、上述のリチウムイオン二次電池２において充放電サイクル試験を行った。
具体的には、雰囲気温度６０℃に温度制御された恒温槽内にリチウムイオン二次電池２を静置し、この電池ＳＯＣが０〜１００％の幅で充放電を繰り返した。その際、充放電レートは２Ｃとした。 Subsequently, the above-described lithium ion secondary battery 2 was subjected to a charge / discharge cycle test.
Specifically, the lithium ion secondary battery 2 was allowed to stand in a thermostat controlled at an ambient temperature of 60 ° C., and this battery SOC was repeatedly charged and discharged with a width of 0 to 100%. At that time, the charge / discharge rate was set to 2C.

また、上述の初充電前リチウムイオン二次電池１と同様であるが、ＬｉＣｒＴｉＯ4からなる第１リチウム酸化物Ｌ１の含有量を、正極活物質２４ａの５，１５，２０ｗｔ％の量とした初充電前リチウムイオン二次電池１を作製した。なお併せて、第１リチウム酸化物Ｌ１を含まない（含有率０ｗｔ％）電池も作製した。その後、上述の充放電サイクル試験を同様に行った。 Moreover, although it is the same as that of the above-mentioned lithium ion secondary battery 1 before the initial charge, the content of the first lithium oxide L1 made of LiCrTiO 4 is set to an amount of 5, 15, 20 wt% of the positive electrode active material 24a. A lithium ion secondary battery 1 before charging was produced. In addition, a battery not containing the first lithium oxide L1 (content ratio 0 wt%) was also produced. Thereafter, the above-described charge / discharge cycle test was similarly performed.

図８は、第１リチウム酸化物Ｌ１の含有量と、試験前の電池容量を基準とした、上述の充放電サイクル試験（５００サイクル）後の、電池容量維持率との関係を示すグラフである。このグラフによれば、第１リチウム酸化物Ｌ１の含有量を正極活物質２４ａの５ｗｔ％以上の量とすると容量維持率が向上し、第１リチウム酸化物Ｌ１添加の効果が得られることが判る。また、含有量を１０ｗｔ％以上の量とすることで、電池容量維持率を最大（９６％）とすることができることが判る。
但し、第１リチウム酸化物Ｌ１の含有量を増やすと、正極活物質層２４Ｒの体積や重量、ひいてはリチウムイオン二次電池２の体積、重量が増加することから、正極活物質層２４Ｒにおける第１リチウム酸化物Ｌ１の含有量は小さい方が良いと考えられる。従って、正極活物質２４ａの５〜１５ｗｔ％の、さらには１０〜１５ｗｔ％の量の第１リチウム酸化物Ｌ１を含有するリチウムイオン二次電池２が、電池容量の低下を確実に抑制できると共に、電池構成上好ましい。 FIG. 8 is a graph showing the relationship between the content of the first lithium oxide L1 and the battery capacity retention rate after the above-described charge / discharge cycle test (500 cycles) based on the battery capacity before the test. . According to this graph, it is understood that when the content of the first lithium oxide L1 is 5 wt% or more of the positive electrode active material 24a, the capacity retention rate is improved and the effect of adding the first lithium oxide L1 is obtained. . It can also be seen that the battery capacity retention rate can be maximized (96%) by setting the content to 10 wt% or more.
However, when the content of the first lithium oxide L1 is increased, the volume and weight of the positive electrode active material layer 24R, and thus the volume and weight of the lithium ion secondary battery 2, are increased. It is thought that the smaller the content of the lithium oxide L1, the better. Therefore, the lithium ion secondary battery 2 containing the first lithium oxide L1 in an amount of 5 to 15 wt%, further 10 to 15 wt% of the positive electrode active material 24a can reliably suppress a decrease in battery capacity, It is preferable in terms of battery configuration.

（変形形態１）
次に、変形形態１について、図１〜５を参照しつつ説明する。
本変形形態１の初充電前リチウムイオン二次電池１０１、および、リチウムイオン二次電池１０２は、実施形態１の初充電前リチウムイオン二次電池１、および、リチウムイオン二次電池２と、炭素化材料からなる初充電前負極活物質１２５、および、負極活物質１２５Ｄを用いている点で異なり、それ以外は同様である。
そこで、異なる点を中心として説明すると共に、同様の部分の説明は省略または簡略化するが、同様の部分については同様の作用効果を生じる。また、同内容のものには同番号を付して説明する。 (Modification 1)
Next, the modification 1 is demonstrated, referring FIGS.
The first pre-charge lithium ion secondary battery 101 and the lithium ion secondary battery 102 according to the first modification are the same as the first pre-charge lithium ion secondary battery 1 and the lithium ion secondary battery 2 according to the first embodiment, and carbon. The difference is that the negative electrode active material 125 and the negative electrode active material 125 </ b> D before the initial charge made of the activating material are used, and the rest is the same.
Therefore, different points will be mainly described, and description of similar parts will be omitted or simplified, but similar functions and effects will occur for similar parts. In addition, the same contents are described with the same numbers.

初充電前負極部材１２５は、銅箔２７の表裏面に、炭素化材料からなる初充電前負極活物質１２８ａと結着剤２８ｂを混練してなる初充電前負極活物質層１２８を塗工したものである（図５参照）。   The pre-initial charge negative electrode member 125 was coated on the front and back surfaces of the copper foil 27 with a pre-initial charge negative electrode active material layer 128 made by kneading a pre-initial charge negative electrode active material 128a made of a carbonized material and a binder 28b. (See FIG. 5).

次いで、実施形態１と同様の構造であるが、上述の初充電前負極活物質１２５を用い、また正極部材２１に含むＬｉＣｒＴｉＯ4からなる第１リチウム酸化物Ｌ１の含有量を、正極活物質２４ａの５，１０，１２，１５，２０ｗｔ％の量とした初充電前リチウムイオン二次電池１０１を作製した。なお、併せて第１リチウム酸化物Ｌ１を含有させない（含有率０ｗｔ％）初充電前リチウムイオン二次電池も作製した。
その後、これらについて実施形態１と同様な充放電サイクル試験を行った。 Next, the structure is the same as that of the first embodiment, but the content of the first lithium oxide L1 made of LiCrTiO 4 contained in the positive electrode member 21 using the pre-initial negative electrode active material 125 described above is changed to the positive electrode active material 24a. Thus, a lithium ion secondary battery 101 before the initial charge in an amount of 5, 10, 12, 15, 20 wt% was manufactured. In addition, a lithium ion secondary battery before initial charge that does not contain the first lithium oxide L1 (content ratio 0 wt%) was also manufactured.
Thereafter, a charge / discharge cycle test similar to that of the first embodiment was performed.

この試験により、第１リチウム酸化物Ｌ１の含有量を正極活物質２４ａの５ｗｔ％以上の量とすると容量維持率が向上し、第１リチウム酸化物Ｌ１添加の効果が得られる。また、含有量を１２ｗｔ％以上の量とすることで、電池容量維持率を最大（９５％）とすることができることが判った。但し、第１リチウム酸化物Ｌ１の含有量の増加に伴う、リチウムイオン二次電池の体積、重量の増加を考慮すると、正極活物質２４ａの５〜２０ｗｔ％の、さらには１２〜２０ｗｔ％の量の第１リチウム酸化物Ｌ１を含有するリチウムイオン二次電池１０２が、電池容量の低下を確実に抑制できると共に、電池構成上好ましい。   According to this test, when the content of the first lithium oxide L1 is set to 5 wt% or more of the positive electrode active material 24a, the capacity retention rate is improved, and the effect of adding the first lithium oxide L1 is obtained. It was also found that the battery capacity retention rate can be maximized (95%) by setting the content to 12 wt% or more. However, in consideration of an increase in volume and weight of the lithium ion secondary battery accompanying an increase in the content of the first lithium oxide L1, an amount of 5 to 20 wt%, further 12 to 20 wt% of the positive electrode active material 24a. The lithium ion secondary battery 102 containing the first lithium oxide L1 is preferable in terms of battery configuration, while being able to reliably suppress a decrease in battery capacity.

（変形形態２）
次に、変形形態２について、図１〜５を参照しつつ説明する。
本変形形態２の初充電前リチウムイオン二次電池２０１、および、リチウムイオン二次電池２０２は、実施形態１の初充電前リチウムイオン二次電池１、および、リチウムイオン二次電池２と、低温焼成炭素からなる初充電前負極活物質２２５、および、負極活物質２２５Ｄを用いている点で異なり、それ以外は同様である。
そこで、異なる点を中心として説明すると共に、同様の部分の説明は省略または簡略化するが、同様の部分については同様の作用効果を生じる。また、同内容のものには同番号を付して説明する。 (Modification 2)
Next, the modification 2 is demonstrated, referring FIGS.
The pre-initial charge lithium ion secondary battery 201 and the lithium ion secondary battery 202 of the second modification are the same as the pre-initial charge lithium ion secondary battery 1 and the lithium ion secondary battery 2 of the first embodiment, and the low temperature. The difference is that the negative electrode active material 225 and the negative electrode active material 225D before the initial charge made of baked carbon are used, and the other points are the same.
Therefore, different points will be mainly described, and description of similar parts will be omitted or simplified, but similar functions and effects will occur for similar parts. In addition, the same contents are described with the same numbers.

本変形形態２にかかる初充電前負極部材２２５は、銅箔２７の表裏面に、低温焼成炭素からなる初充電前負極活物質２２８ａと結着剤２８ｂを混練してなる初充電前負極活物質層２２８を塗工したものである（図５参照）。   The pre-initial charge negative electrode member 225 according to the second modification is formed by kneading the pre-initial charge negative electrode active material 228a and the binder 28b made of low-temperature calcined carbon on the front and back surfaces of the copper foil 27. Layer 228 is applied (see FIG. 5).

次いで、実施形態１と同様の構造であるが、上述の初充電前負極活物質２２５を用い、また正極部材２１に含むＬｉＣｒＴｉＯ4からなる第１リチウム酸化物Ｌ１の含有量を、正極活物質２４ａの５，１０，１３，１５，２０ｗｔ％の量とした初充電前リチウムイオン二次電池２０１を作製した。なお、併せて第１リチウム酸化物Ｌ１を含有させない（含有率０ｗｔ％）初充電前リチウムイオン二次電池も作製した。
その後、これらについて実施形態１と同様な充放電サイクル試験を行った。 Next, the structure is the same as that of the first embodiment, but the content of the first lithium oxide L1 made of LiCrTiO 4 contained in the positive electrode member 21 using the negative electrode active material 225 before initial charge is changed to the positive electrode active material 24a. Thus, a lithium ion secondary battery 201 before the initial charge in an amount of 5, 10, 13, 15, 20 wt% was produced. In addition, a lithium ion secondary battery before initial charge that does not contain the first lithium oxide L1 (content ratio 0 wt%) was also manufactured.
Thereafter, a charge / discharge cycle test similar to that of the first embodiment was performed.

この試験により、第１リチウム酸化物Ｌ１の含有量を正極活物質２４ａの５ｗｔ％以上の量とすると容量維持率が向上し、第１リチウム酸化物Ｌ１添加の効果が得られる。また、含有量を１３ｗｔ％以上の量とすることで、電池容量維持率を最大（９５％）とすることができることが判った。但し、第１リチウム酸化物Ｌ１の含有量の増加に伴う、リチウムイオン二次電池の体積、重量の増加を考慮すると、正極活物質２４ａの５〜２０ｗｔ％の、さらには１３〜２０ｗｔ％の量の第１リチウム酸化物Ｌ１を含有するリチウムイオン二次電池２０２が、電池容量の低下を確実に抑制できると共に、電池構成上好ましい。   According to this test, when the content of the first lithium oxide L1 is set to 5 wt% or more of the positive electrode active material 24a, the capacity retention rate is improved, and the effect of adding the first lithium oxide L1 is obtained. It was also found that the battery capacity retention rate could be maximized (95%) by setting the content to 13 wt% or more. However, in consideration of an increase in volume and weight of the lithium ion secondary battery accompanying an increase in the content of the first lithium oxide L1, an amount of 5 to 20 wt%, further 13 to 20 wt% of the positive electrode active material 24a. The lithium ion secondary battery 202 containing the first lithium oxide L1 is preferable in terms of the battery configuration while being able to reliably suppress a decrease in battery capacity.

（実施形態２）
次に、実施形態２について、図１〜５を参照しつつ説明する。
本実施形態２の初充電前リチウムイオン二次電池３０１、および、リチウムイオン二次電池３０２は、実施形態１の初充電前リチウムイオン二次電池１、および、リチウムイオン二次電池２と、第１リチウム酸化物Ｌ１に代えて、ＬｉＦｅＴｉＯ4からなる第２リチウム酸化物Ｌ２を用いている点で異なり、それ以外は同様である。
そこで、異なる点を中心として説明すると共に、同様の部分の説明は省略または簡略化するが、同様の部分については同様の作用効果を生じる。また、同内容のものには同番号を付して説明する。 (Embodiment 2)
Next, Embodiment 2 will be described with reference to FIGS.
The pre-initial charge lithium ion secondary battery 301 and the lithium ion secondary battery 302 of Embodiment 2 are the same as the pre-initial charge lithium ion secondary battery 1 and the lithium ion secondary battery 2 of Embodiment 1, The difference is that a second lithium oxide L2 made of LiFeTiO 4 is used in place of the one lithium oxide L1, and the rest is the same.
Therefore, different points will be mainly described, and description of similar parts will be omitted or simplified, but similar functions and effects will occur for similar parts. In addition, the same contents are described with the same numbers.

本実施形態２にかかる正極部材１２１は、アルミニウム箔２３の表裏面に、ＬｉＣｏＯ2からなる正極活物質２４ａ、ＬｉＦｅＴｉＯ4からなる第２リチウム酸化物Ｌ２、結着剤２４ｂ、および導電化剤２４ｃを混練してなる正極活物質層１２４を塗工したものである（図４参照）。 The positive electrode member 121 according to the second embodiment includes a positive electrode active material 24a made of LiCoO 2 , a second lithium oxide L2 made of LiFeTiO 4 , a binder 24b, and a conductive agent 24c on the front and back surfaces of the aluminum foil 23. The positive electrode active material layer 124 formed by kneading is applied (see FIG. 4).

この正極部材１２１を用いてなる初充電前リチウムイオン二次電池３０１を、充電してできるリチウムイオン二次電池３０２でも、充電（初充電）時に、第２リチウム酸化物Ｌ２から放出されたリチウムイオンは、初充電前負極活物質２８ａ（負極活物質２８ａＤ）にドープされる。従って、不可逆的に負極活物質にドープされるリチウムの少なくとも一部をまかなうことができる。従って、このリチウムイオン二次電池３０２において、正極活物質２４ａの利用効率を上げ、より少量の正極活物質２４ａで、電池容量を満足させることができる。
さらに、この正極部材１２１Ｒ（正極活物質層１２４Ｒ）の導電性が高くでき、このリチウムイオン二次電池３０２の内部抵抗値を小さくできる。これは、このリチウムイオン二次電池に用いる正極活物質をＬｉＦｅＴｉＯ4のみとしたものについて、交流インピーダンス測定により直流抵抗成分を算出したところ、ＬｉＦｅＴｉＯ4のみを用いた電池は、ＬｉＣｏＯ2のみを用いた電池に比べて直流抵抗成分が約３％低くなることからも確かめられる。つまり、正極活物質２４ａのＬｉＣｏＯ2に、導電性のより高いＬｉＦｅＴｉＯ4を添加すると、正極部材１２１Ｒ全体として導電性が高くでき、リチウムイオン二次電池３０２の直流抵抗を低下させることができる。従って、この電池出力を向上させることができる。 Even in the lithium ion secondary battery 302 that can be obtained by charging the pre-initial charge lithium ion secondary battery 301 using the positive electrode member 121, the lithium ions released from the second lithium oxide L2 during the charge (initial charge). Is doped into the negative electrode active material 28a (negative electrode active material 28aD) before initial charge. Therefore, at least a part of lithium irreversibly doped into the negative electrode active material can be provided. Therefore, in this lithium ion secondary battery 302, the utilization efficiency of the positive electrode active material 24a can be increased, and the battery capacity can be satisfied with a smaller amount of the positive electrode active material 24a.
Further, the conductivity of the positive electrode member 121R (positive electrode active material layer 124R) can be increased, and the internal resistance value of the lithium ion secondary battery 302 can be decreased. As for this, when the positive electrode active material used for this lithium ion secondary battery was only LiFeTiO 4 , the DC resistance component was calculated by AC impedance measurement, and the battery using only LiFeTiO 4 used only LiCoO 2 . This is also confirmed by the fact that the DC resistance component is about 3% lower than that of the battery. That is, when LiFeTiO 4 having higher conductivity is added to LiCoO 2 of the positive electrode active material 24a, the conductivity of the positive electrode member 121R as a whole can be increased, and the DC resistance of the lithium ion secondary battery 302 can be reduced. Therefore, this battery output can be improved.

次いで、実施形態１と同様の構造であるが、前述の初充電前負極活物質２５を用い、また正極部材１２１に含むＬｉＦｅＴｉＯ4からなる第２リチウム酸化物Ｌ２の含有量を、正極活物質２４ａの５，１０，１２，１５，２０ｗｔ％の量とした初充電前リチウムイオン二次電池３０１を作製した。なお、併せて第２リチウム酸化物Ｌ２を含有させない（含有率０ｗｔ％）初充電前リチウムイオン二次電池も作製した。
その後、これらについて実施形態１と同様な充放電サイクル試験を行った。 Next, the structure is the same as that of the first embodiment. However, the content of the second lithium oxide L2 made of LiFeTiO 4 contained in the positive electrode member 121 is changed to the positive electrode active material 24a. Thus, a lithium ion secondary battery 301 before the initial charge was manufactured in amounts of 5, 10, 12, 15, and 20 wt%. In addition, a lithium ion secondary battery before initial charge that does not contain the second lithium oxide L2 (content ratio 0 wt%) was also manufactured.
Thereafter, a charge / discharge cycle test similar to that of the first embodiment was performed.

この試験により、第２リチウム酸化物Ｌ２の含有量を正極活物質２４ａの５ｗｔ％以上の量とすると容量維持率が向上し、第２リチウム酸化物Ｌ２添加の効果が得られる。また、含有量を１２ｗｔ％以上の量とすることで、電池容量維持率を最大（９６％）とすることができることが判った。但し、第２リチウム酸化物Ｌ２の含有量の増加に伴う、リチウムイオン二次電池の体積、重量の増加を考慮すると、正極活物質２４ａの５〜２０ｗｔ％の、さらには１２〜２０ｗｔ％の量の第２リチウム酸化物Ｌ２を含有するリチウムイオン二次電池３０２が、電池容量の低下を確実に抑制できると共に、電池構成上好ましい。   According to this test, when the content of the second lithium oxide L2 is set to 5 wt% or more of the positive electrode active material 24a, the capacity retention rate is improved, and the effect of adding the second lithium oxide L2 is obtained. It was also found that the battery capacity retention rate can be maximized (96%) by setting the content to 12 wt% or more. However, in consideration of the increase in volume and weight of the lithium ion secondary battery accompanying the increase in the content of the second lithium oxide L2, the amount of 5 to 20 wt%, further 12 to 20 wt% of the positive electrode active material 24a. The lithium ion secondary battery 302 containing the second lithium oxide L2 is preferable in terms of the battery configuration while being able to reliably suppress a decrease in battery capacity.

（変形形態３）
次に、変形形態３について、図１〜５を参照しつつ説明する。
本変形形態３の初充電前リチウムイオン二次電池４０１、および、リチウムイオン二次電池４０２は、実施形態２の初充電前リチウムイオン二次電池３０１、および、リチウムイオン二次電池３０２と、炭素化材料からなる初充電前負極活物質１２５、および、負極活物質１２５Ｄを用いている点で異なり、それ以外は同様である。
そこで、異なる点を中心として説明すると共に、同様の部分の説明は省略または簡略化するが、同様の部分については同様の作用効果を生じる。また、同内容のものには同番号を付して説明する。 (Modification 3)
Next, the modification 3 is demonstrated, referring FIGS.
The pre-initial charge lithium ion secondary battery 401 and the lithium ion secondary battery 402 of Modification 3 are the same as the pre-initial charge lithium ion secondary battery 301 and the lithium ion secondary battery 302 of Embodiment 2 and carbon. The difference is that the negative electrode active material 125 and the negative electrode active material 125 </ b> D before the initial charge made of the activating material are used, and the rest is the same.
Therefore, different points will be mainly described, and description of similar parts will be omitted or simplified, but similar functions and effects will occur for similar parts. In addition, the same contents are described with the same numbers.

本変形形態３にかかる初充電前負極部材１２５は、銅箔２７の表裏面に、炭素化材料からなる初充電前負極活物質１２８ａと結着剤２８ｂを混練してなる初充電前負極活物質層１２８を塗工したものである（図５参照）。   The pre-initial charge negative electrode member 125 according to the third modification is obtained by kneading the pre-initial charge negative electrode active material 128 a made of a carbonized material and the binder 28 b on the front and back surfaces of the copper foil 27. The layer 128 is applied (see FIG. 5).

次いで、実施形態２と同様の構造であるが、上述の初充電前負極活物質１２５を用い、また正極部材１２１に含むＬｉＦｅＴｉＯ4からなる第２リチウム酸化物Ｌ２の含有量を、正極活物質２４ａの５，１０，１５，１７，２０，２５ｗｔ％の量とした初充電前リチウムイオン二次電池４０１を作製した。なお、併せて第２リチウム酸化物Ｌ２を含有させない（含有率０ｗｔ％）初充電前リチウムイオン二次電池も作製した。
その後、これらについて実施形態１と同様な充放電サイクル試験を行った。 Next, the structure is the same as that of the second embodiment, but the content of the second lithium oxide L2 made of LiFeTiO 4 contained in the positive electrode member 121 is changed to the positive electrode active material 24a. Thus, a lithium ion secondary battery 401 before the initial charge having an amount of 5, 10, 15, 17, 20, 25 wt% was manufactured. In addition, a lithium ion secondary battery before initial charge that does not contain the second lithium oxide L2 (content ratio 0 wt%) was also manufactured.
Thereafter, a charge / discharge cycle test similar to that of the first embodiment was performed.

この試験により、第２リチウム酸化物Ｌ２の含有量を正極活物質２４ａの５ｗｔ％以上の量とすると容量維持率が向上し、第２リチウム酸化物Ｌ２添加の効果が得られる。また、含有量を１７ｗｔ％以上の量とすることで、電池容量維持率を最大（９５％）とすることができることが判った。但し、第２リチウム酸化物Ｌ２の含有量の増加に伴う、リチウムイオン二次電池の体積、重量の増加を考慮すると、正極活物質２４ａの５〜２５ｗｔ％の、さらには１７〜２５ｗｔ％の量の第２リチウム酸化物Ｌ２を含有するリチウムイオン二次電池４０２が、電池容量の低下を確実に抑制できると共に、電池構成上好ましい。   According to this test, when the content of the second lithium oxide L2 is set to 5 wt% or more of the positive electrode active material 24a, the capacity retention rate is improved, and the effect of adding the second lithium oxide L2 is obtained. Further, it was found that the battery capacity retention rate can be maximized (95%) by setting the content to 17 wt% or more. However, in consideration of the increase in volume and weight of the lithium ion secondary battery accompanying the increase in the content of the second lithium oxide L2, the amount of 5 to 25 wt%, further 17 to 25 wt% of the positive electrode active material 24a. The lithium ion secondary battery 402 containing the second lithium oxide L2 is preferable in terms of the battery configuration while being able to reliably suppress a decrease in battery capacity.

（変形形態４）
次に、変形形態４について、図１〜５を参照しつつ説明する。
本変形形態４の初充電前リチウムイオン二次電池５０１、および、リチウムイオン二次電池５０２は、実施形態２の初充電前リチウムイオン二次電池３０１、および、リチウムイオン二次電池３０２と、低温焼成炭素からなる初充電前負極活物質２２５、および、負極活物質２２５Ｄを用いている点で異なり、それ以外は同様である。
そこで、異なる点を中心として説明すると共に、同様の部分の説明は省略または簡略化するが、同様の部分については同様の作用効果を生じる。また、同内容のものには同番号を付して説明する。 (Modification 4)
Next, the modification 4 is demonstrated, referring FIGS.
The pre-initial charge lithium ion secondary battery 501 and the lithium ion secondary battery 502 of Modification 4 are the same as the pre-initial charge lithium ion secondary battery 301 and the lithium ion secondary battery 302 of Embodiment 2 and at a low temperature. The difference is that the negative electrode active material 225 and the negative electrode active material 225D before the initial charge made of baked carbon are used, and the other points are the same.
Therefore, different points will be mainly described, and description of similar parts will be omitted or simplified, but similar functions and effects will occur for similar parts. In addition, the same contents are described with the same numbers.

本変形形態４にかかる初充電前負極部材２２５は、銅箔２７の表裏面に、低温焼成炭素からなる初充電前負極活物質２２８ａと結着剤２８ｂを混練してなる初充電前負極活物質層２２８を塗工したものである（図５参照）。   The pre-initial charge negative electrode member 225 according to the fourth modification is obtained by kneading the pre-initial charge negative electrode active material 228a and the binder 28b made of low-temperature calcined carbon on the front and back surfaces of the copper foil 27. Layer 228 is applied (see FIG. 5).

次いで、実施形態２と同様の構造であるが、上述の初充電前負極活物質２２５を用い、また正極部材１２１に含むＬｉＦｅＴｉＯ4からなる第２リチウム酸化物Ｌ２の含有量を、正極活物質２４ａの５，１０，１５，２０，２５ｗｔ％の量とした初充電前リチウムイオン二次電池５０１を作製した。なお、併せて第２リチウム酸化物Ｌ２を含有させない（含有率０ｗｔ％）初充電前リチウムイオン二次電池も作製した。
その後、これらについて実施形態１と同様な充放電サイクル試験を行った。 Next, the structure is the same as that of the second embodiment, but the content of the second lithium oxide L2 made of LiFeTiO 4 contained in the positive electrode member 121 using the negative electrode active material 225 before initial charge is changed to the positive electrode active material 24a. Thus, a lithium ion secondary battery 501 before the initial charge having an amount of 5, 10, 15, 20, 25 wt% was manufactured. In addition, a lithium ion secondary battery before initial charge that does not contain the second lithium oxide L2 (content ratio 0 wt%) was also manufactured.
Thereafter, a charge / discharge cycle test similar to that of the first embodiment was performed.

この試験により、第２リチウム酸化物Ｌ２の含有量を正極活物質２４ａの５ｗｔ％以上の量とすると容量維持率が向上し、第２リチウム酸化物Ｌ２添加の効果が得られる。また、含有量を２０ｗｔ％以上の量とすることで、電池容量維持率を最大（９５％）とすることができることが判った。但し、第２リチウム酸化物Ｌ２の含有量の増加に伴う、リチウムイオン二次電池の体積、重量の増加を考慮すると、正極活物質２４ａの５〜２５ｗｔ％の、さらには２０〜２５ｗｔ％の量の第２リチウム酸化物Ｌ２を含有するリチウムイオン二次電池５０２が、電池容量の低下を確実に抑制できると共に、電池構成上好ましい。   According to this test, when the content of the second lithium oxide L2 is set to 5 wt% or more of the positive electrode active material 24a, the capacity retention rate is improved, and the effect of adding the second lithium oxide L2 is obtained. It was also found that the battery capacity retention rate could be maximized (95%) by setting the content to 20 wt% or more. However, in consideration of the increase in volume and weight of the lithium ion secondary battery accompanying the increase in the content of the second lithium oxide L2, the amount of 5 to 25 wt% of the positive electrode active material 24a, and further 20 to 25 wt% The lithium ion secondary battery 502 containing the second lithium oxide L2 is preferable in terms of battery configuration, while being able to reliably suppress a decrease in battery capacity.

（実施形態３）
次に、実施形態３について、図１〜５を参照しつつ説明する。
本実施形態３の初充電前リチウムイオン二次電池６０１、および、リチウムイオン二次電池６０２は、実施形態１の初充電前リチウムイオン二次電池１、および、リチウムイオン二次電池２と、第１リチウム酸化物Ｌ１に代えて、ＬｉＦｅＶＯ4からなる第３リチウム酸化物Ｌ３を用いている点で異なり、それ以外は同様である。
そこで、異なる点を中心として説明すると共に、同様の部分の説明は省略または簡略化するが、同様の部分については同様の作用効果を生じる。また、同内容のものには同番号を付して説明する。 (Embodiment 3)
Next, Embodiment 3 will be described with reference to FIGS.
The pre-initial charge lithium ion secondary battery 601 and the lithium ion secondary battery 602 of Embodiment 3 are the same as the pre-initial charge lithium ion secondary battery 1 and the lithium ion secondary battery 2 of Embodiment 1, The difference is that a third lithium oxide L3 made of LiFeVO 4 is used instead of the one lithium oxide L1, and the rest is the same.
Therefore, different points will be mainly described, and description of similar parts will be omitted or simplified, but similar functions and effects will occur for similar parts. In addition, the same contents are described with the same numbers.

本実施形態３にかかる正極部材２２１は、アルミニウム箔２３の表裏面に、ＬｉＣｏＯ2からなる正極活物質２４ａ、ＬｉＦｅＶＯ4からなる第３リチウム酸化物Ｌ３、結着剤２４ｂ、および導電化剤２４ｃを混練してなる正極活物質層２２４を塗工したものである（図４参照）。 The positive electrode member 221 according to the third embodiment includes a positive electrode active material 24a made of LiCoO 2 , a third lithium oxide L3 made of LiFeVO 4 , a binder 24b, and a conductive agent 24c on the front and back surfaces of the aluminum foil 23. A positive electrode active material layer 224 formed by kneading is applied (see FIG. 4).

この正極部材２２１を用いてなる初充電前リチウムイオン二次電池６０１を、充電してできるリチウムイオン二次電池６０２でも、充電（初充電）時に、第３リチウム酸化物Ｌ３から放出されたリチウムイオンは、初充電前負極活物質２８ａ（負極活物質２８ａＤ）にドープされる。従って、不可逆的に負極活物質にドープされるリチウムの少なくとも一部をまかなうことができる。従って、このリチウムイオン二次電池６０２において、正極活物質２４ａの利用効率を上げ、より少量の正極活物質２４ａで、電池容量を満足させることができる。
さらに、この正極部材２２１Ｒ（正極活物質層２２４Ｒ）の導電性が高くでき、このリチウムイオン二次電池６０２の内部抵抗値を小さくできる。これは、このリチウムイオン二次電池に用いる正極活物質をＬｉＦｅＶＯ4のみとしたものについて、交流インピーダンス測定により直流抵抗成分を算出したところ、ＬｉＦｅＶＯ4の導電率は、ＬｉＣｏＯ2のみを用いた電池に比べて直流抵抗成分が約５％低くなることからも確かめられる。つまり、正極活物質２４ａのＬｉＣｏＯ2に、導電性のより高いＬｉＦｅＶＯ4を添加すると、正極部材２２１Ｒ全体として導電性が高くでき、リチウムイオン二次電池６０２の直流抵抗を低下させることができる。従って、この電池出力を向上させることができる。 Even in the lithium ion secondary battery 602 that is obtained by charging the pre-initial charge lithium ion secondary battery 601 using the positive electrode member 221, lithium ions released from the third lithium oxide L3 during charging (initial charge) Is doped into the negative electrode active material 28a (negative electrode active material 28aD) before initial charge. Therefore, at least a part of lithium irreversibly doped into the negative electrode active material can be provided. Therefore, in this lithium ion secondary battery 602, the utilization efficiency of the positive electrode active material 24a can be increased, and the battery capacity can be satisfied with a smaller amount of the positive electrode active material 24a.
Further, the conductivity of the positive electrode member 221R (positive electrode active material layer 224R) can be increased, and the internal resistance value of the lithium ion secondary battery 602 can be decreased. This is because when the positive electrode active material used in this lithium ion secondary battery was only LiFeVO 4 , the DC resistance component was calculated by measuring the AC impedance, and the LiFeVO 4 conductivity was that of a battery using only LiCoO 2. This is also confirmed by the fact that the DC resistance component is reduced by about 5%. That is, when LiFeVO 4 having higher conductivity is added to LiCoO 2 of the positive electrode active material 24a, the overall conductivity of the positive electrode member 221R can be increased, and the DC resistance of the lithium ion secondary battery 602 can be reduced. Therefore, this battery output can be improved.

次いで、実施形態１と同様の構造であるが、前述の初充電前負極活物質２５を用い、また正極部材２２１に含むＬｉＦｅＶＯ4からなる第３リチウム酸化物Ｌ３の含有量を、正極活物質２４ａの５，１０，１５，２０ｗｔ％の量とした初充電前リチウムイオン二次電池６０１を作製した。なお、併せて第３リチウム酸化物Ｌ３を含有させない（含有率０ｗｔ％）初充電前リチウムイオン二次電池も作製した。
その後、これらについて実施形態１と同様な充放電サイクル試験を行った。 Next, the structure is the same as that of Embodiment 1, but the content of the third lithium oxide L3 made of LiFeVO 4 contained in the positive electrode member 221 is changed to the positive electrode active material 24a. Thus, a lithium ion secondary battery 601 before the initial charge having an amount of 5, 10, 15, 20 wt% was manufactured. In addition, a lithium ion secondary battery before initial charge that does not contain the third lithium oxide L3 (content ratio 0 wt%) was also manufactured.
Thereafter, a charge / discharge cycle test similar to that of the first embodiment was performed.

この試験により、第３リチウム酸化物Ｌ３の含有量を正極活物質２４ａの５ｗｔ％以上の量とすると容量維持率が向上し、第３リチウム酸化物Ｌ３添加の効果が得られる。また、含有量を１５ｗｔ％以上の量とすることで、電池容量維持率を最大（９６％）とすることができることが判った。但し、第３リチウム酸化物Ｌ３の含有量の増加に伴う、リチウムイオン二次電池の体積、重量の増加を考慮すると、正極活物質２４ａの５〜２０ｗｔ％の、さらには１５〜２０ｗｔ％の量の第３リチウム酸化物Ｌ３を含有するリチウムイオン二次電池６０２が、電池容量の低下を確実に抑制できると共に、電池構成上好ましい。   According to this test, when the content of the third lithium oxide L3 is set to 5 wt% or more of the positive electrode active material 24a, the capacity retention rate is improved, and the effect of adding the third lithium oxide L3 is obtained. It was also found that the battery capacity retention rate can be maximized (96%) by setting the content to 15 wt% or more. However, in consideration of an increase in volume and weight of the lithium ion secondary battery accompanying an increase in the content of the third lithium oxide L3, an amount of 5 to 20 wt%, further 15 to 20 wt% of the positive electrode active material 24a. The lithium ion secondary battery 602 containing the third lithium oxide L3 is preferable in terms of the battery configuration while being able to reliably suppress a decrease in battery capacity.

（変形形態５）
次に、変形形態５について、図１〜５を参照しつつ説明する。
本変形形態５の初充電前リチウムイオン二次電池７０１、および、リチウムイオン二次電池７０２は、実施形態３の初充電前リチウムイオン二次電池６０１、および、リチウムイオン二次電池６０２と、炭素化材料からなる初充電前負極活物質１２５、および、負極活物質１２５Ｄを用いている点で異なり、それ以外は同様である。
そこで、異なる点を中心として説明すると共に、同様の部分の説明は省略または簡略化するが、同様の部分については同様の作用効果を生じる。また、同内容のものには同番号を付して説明する。 (Modification 5)
Next, the modification 5 is demonstrated, referring FIGS.
The pre-initial charge lithium ion secondary battery 701 and the lithium ion secondary battery 702 of the fifth modified embodiment are the same as the pre-initial charge lithium ion secondary battery 601 and the lithium ion secondary battery 602 of the third embodiment, and carbon. The difference is that the negative electrode active material 125 and the negative electrode active material 125 </ b> D before the initial charge made of the activating material are used, and the rest is the same.
Therefore, different points will be mainly described, and description of similar parts will be omitted or simplified, but similar functions and effects will occur for similar parts. In addition, the same contents are described with the same numbers.

本変形形態５にかかる初充電前負極部材１２５は、銅箔２７の表裏面に、炭素化材料からなる初充電前負極活物質１２８ａと結着剤２８ｂを混練してなる初充電前負極活物質層１２８を塗工したものである（図５参照）。   The pre-initial charge negative electrode member 125 according to the modified embodiment 5 is obtained by kneading the pre-initial charge negative electrode active material 128 a made of a carbonized material and the binder 28 b on the front and back surfaces of the copper foil 27. The layer 128 is applied (see FIG. 5).

次いで、実施形態３と同様の構造であるが、上述の初充電前負極活物質１２５を用い、また正極部材２２１に含むＬｉＦｅＶＯ4からなる第３リチウム酸化物Ｌ３の含有量を、正極活物質２４ａの５，１０，１５，１７，２０，２５ｗｔ％の量とした初充電前リチウムイオン二次電池７０１を作製した。なお、併せて第３リチウム酸化物Ｌ３を含有させない（含有率０ｗｔ％）初充電前リチウムイオン二次電池も作製した。
その後、これらについて実施形態１と同様な充放電サイクル試験を行った。 Next, the structure is the same as that of the third embodiment, but the content of the third lithium oxide L3 made of LiFeVO 4 contained in the positive electrode member 221 is changed to the positive electrode active material 24a. Thus, a lithium ion secondary battery 701 before the initial charge having an amount of 5, 10, 15, 17, 20, 25 wt% was manufactured. In addition, a lithium ion secondary battery before initial charge that does not contain the third lithium oxide L3 (content ratio 0 wt%) was also manufactured.
Thereafter, a charge / discharge cycle test similar to that of the first embodiment was performed.

この試験により、第３リチウム酸化物Ｌ３の含有量を正極活物質２４ａの５ｗｔ％以上の量とすると容量維持率が向上し、第３リチウム酸化物Ｌ３添加の効果が得られる。また、含有量を１７ｗｔ％以上の量とすることで、電池容量維持率を最大（９５％）とすることができることが判った。但し、第３リチウム酸化物Ｌ３の含有量の増加に伴う、リチウムイオン二次電池の体積、重量の増加を考慮すると、正極活物質２４ａの５〜２５ｗｔ％の、さらには１７〜２５ｗｔ％の量の第３リチウム酸化物Ｌ３を含有するリチウムイオン二次電池７０２が、電池容量の低下を確実に抑制できると共に、電池構成上好ましい。   According to this test, when the content of the third lithium oxide L3 is set to 5 wt% or more of the positive electrode active material 24a, the capacity retention rate is improved, and the effect of adding the third lithium oxide L3 is obtained. Further, it was found that the battery capacity retention rate can be maximized (95%) by setting the content to 17 wt% or more. However, in consideration of an increase in volume and weight of the lithium ion secondary battery accompanying an increase in the content of the third lithium oxide L3, an amount of 5 to 25 wt%, further 17 to 25 wt% of the positive electrode active material 24a. The lithium ion secondary battery 702 containing the third lithium oxide L3 is preferable in terms of the battery configuration while being able to reliably suppress a decrease in battery capacity.

（変形形態６）
次に、変形形態６について、図１〜５を参照しつつ説明する。
本変形形態６の初充電前リチウムイオン二次電池８０１、および、リチウムイオン二次電池８０２は、実施形態３の初充電前リチウムイオン二次電池６０１、および、リチウムイオン二次電池６０２と、低温焼成炭素からなる初充電前負極活物質２２５、および、負極活物質２２５Ｄを用いている点で異なり、それ以外は同様である。
そこで、異なる点を中心として説明すると共に、同様の部分の説明は省略または簡略化するが、同様の部分については同様の作用効果を生じる。また、同内容のものには同番号を付して説明する。 (Modification 6)
Next, the modified embodiment 6 will be described with reference to FIGS.
The pre-initial charge lithium ion secondary battery 801 and the lithium ion secondary battery 802 of Modification 6 are the same as the pre-initial charge lithium ion secondary battery 601 and the lithium ion secondary battery 602 of Embodiment 3 and at a low temperature. The difference is that the negative electrode active material 225 and the negative electrode active material 225D before the initial charge made of baked carbon are used, and the other points are the same.
Therefore, different points will be mainly described, and description of similar parts will be omitted or simplified, but similar functions and effects will occur for similar parts. In addition, the same contents are described with the same numbers.

本変形形態６にかかる初充電前負極部材２２５は、銅箔２７の表裏面に、低温焼成炭素からなる初充電前負極活物質２２８ａと結着剤２８ｂを混練してなる初充電前負極活物質層２２８を塗工したものである（図５参照）。   The pre-initial charge negative electrode member 225 according to the modified embodiment 6 is obtained by kneading the pre-initial charge negative electrode active material 228a and the binder 28b made of low-temperature calcined carbon on the front and back surfaces of the copper foil 27. Layer 228 is applied (see FIG. 5).

次いで、実施形態３と同様の構造であるが、上述の初充電前負極活物質２２５を用い、また正極部材２２１に含むＬｉＦｅＶＯ4からなる第３リチウム酸化物Ｌ３の含有量を、正極活物質２４ａの５，１０，１５，２０，２５ｗｔ％の量とした初充電前リチウムイオン二次電池８０１を作製した。なお、併せて第３リチウム酸化物Ｌ３を含有させない（含有率０ｗｔ％）初充電前リチウムイオン二次電池も作製した。
その後、これらについて実施形態１と同様な充放電サイクル試験を行った。 Next, the structure is the same as that of the third embodiment, but the content of the third lithium oxide L3 made of LiFeVO 4 contained in the positive electrode member 221 is changed to the positive electrode active material 24a. Thus, a lithium ion secondary battery 801 before the initial charge having an amount of 5, 10, 15, 20, 25 wt% was manufactured. In addition, a lithium ion secondary battery before initial charge that does not contain the third lithium oxide L3 (content ratio 0 wt%) was also manufactured.
Thereafter, a charge / discharge cycle test similar to that of the first embodiment was performed.

この試験により、第３リチウム酸化物Ｌ３の含有量を正極活物質２４ａの５ｗｔ％以上の量とすると容量維持率が向上し、第３リチウム酸化物Ｌ３添加の効果が得られる。また、含有量を２０ｗｔ％以上の量とすることで、電池容量維持率を最大（９５％）とすることができることが判った。但し、第３リチウム酸化物Ｌ３の含有量の増加に伴う、リチウムイオン二次電池の体積、重量の増加を考慮すると、正極活物質２４ａの５〜２５ｗｔ％の、さらには２０〜２５ｗｔ％の量の第３リチウム酸化物Ｌ３を含有するリチウムイオン二次電池８０２が、電池容量の低下を確実に抑制できると共に、電池構成上好ましい。   According to this test, when the content of the third lithium oxide L3 is set to 5 wt% or more of the positive electrode active material 24a, the capacity retention rate is improved, and the effect of adding the third lithium oxide L3 is obtained. It was also found that the battery capacity retention rate could be maximized (95%) by setting the content to 20 wt% or more. However, in consideration of the increase in volume and weight of the lithium ion secondary battery accompanying the increase in the content of the third lithium oxide L3, the amount of 5 to 25 wt%, further 20 to 25 wt% of the positive electrode active material 24a. The lithium ion secondary battery 802 containing the third lithium oxide L3 is preferable in terms of the battery configuration while being able to reliably suppress a decrease in battery capacity.

（実施形態４）
本実施形態４の車両９００は、前述した実施形態１〜３、変形形態１〜６のいずれかで示したリチウムイオン二次電池２，１０２，２０２，３０２，４０２，５０２，６０２，７０２，８０２を、公知の手法で搭載したものである。具体的には、図９に示すように、本実施形態４の車両９００は、エンジン９０４、フロントモータ９０２およびリアモータ９０３を併用して駆動するハイブリッド電気自動車である。この車両９００は、車体９０９、エンジン９０４、これに取り付けられたフロントモータ９０２、リアモータ９０３、ケーブル９０５、インバータ９０６およびバッテリパック９０１を有している。バッテリパック９０１は、車両９００の車体９０９に取り付けられている。そして、このバッテリパック９０１の内部には、図示しないが複数のリチウムイオン二次電池２，１０２，２０２，３０２，４０２，５０２，６０２，７０２，８０２が電気的に直列に連結されて配置されている。そして、この複数のリチウムイオン二次電池２，１０２，２０２，３０２，４０２，５０２，６０２，７０２，８０２は、電池出力が向上し、充放電使用による電池容量の低下を抑制できる。従って、このリチウムイオン二次電池２，１０２，２０２，３０２，４０２，５０２，６０２，７０２，８０２を用いる車両９００は、電池出力が向上し、電池容量劣化を抑制した車両とすることができる。 (Embodiment 4)
The vehicle 900 according to the fourth embodiment includes the lithium ion secondary batteries 2, 102, 202, 302, 402, 502, 602, 702, and 802 described in any one of the first to third embodiments and the first to sixth modifications. Is mounted by a known method. Specifically, as shown in FIG. 9, a vehicle 900 according to the fourth embodiment is a hybrid electric vehicle that is driven by using an engine 904, a front motor 902, and a rear motor 903 in combination. The vehicle 900 includes a vehicle body 909, an engine 904, a front motor 902, a rear motor 903, a cable 905, an inverter 906, and a battery pack 901 attached thereto. The battery pack 901 is attached to the vehicle body 909 of the vehicle 900. In the battery pack 901, a plurality of lithium ion secondary batteries 2, 102, 202, 302, 402, 502, 602, 702, and 802 (not shown) are electrically connected in series. Yes. The plurality of lithium ion secondary batteries 2, 102, 202, 302, 402, 502, 602, 702, 802 can improve battery output and suppress a decrease in battery capacity due to charge / discharge use. Therefore, the vehicle 900 using the lithium ion secondary batteries 2, 102, 202, 302, 402, 502, 602, 702, 802 can be a vehicle with improved battery output and suppressed battery capacity deterioration.

（実施形態５）
また、本実施形態５のノート型パーソナルコンピュータ９１０は、前述した実施形態１〜３、変形形態１〜６のいずれかで示したリチウムイオン二次電池２，１０２，２０２，３０２，４０２，５０２，６０２，７０２，８０２を、公知の手法で搭載したものであり、図１０に示すように、バッテリパック９１１、本体９１２を有する電池搭載機器である。バッテリパック９１１はノート型パーソナルコンピュータ９１０の本体９１２に収容されており、バッテリパック９１１の内部には、図示しないが複数のリチウムイオン二次電池２，１０２，２０２，３０２，４０２，５０２，６０２，７０２，８０２が電気的に直列に連結されて配置されている。そして、この複数のリチウムイオン二次電池２，１０２，２０２，３０２，４０２，５０２，６０２，７０２，８０２は、電池出力が向上し、充放電使用による電池容量の低下を抑制できる。従って、このリチウムイオン二次電池２，１０２，２０２，３０２，４０２，５０２，６０２，７０２，８０２を用いるノート型パーソナルコンピュータ９１０は、電池出力が向上し、電池容量劣化を抑制した電池搭載機器とすることができる。 (Embodiment 5)
Further, the notebook personal computer 910 of the fifth embodiment includes the lithium ion secondary batteries 2, 102, 202, 302, 402, 502, shown in any of the first to third embodiments and the first to sixth modifications. 602, 702, and 802 are mounted by a known method, and as shown in FIG. 10, a battery-mounted device having a battery pack 911 and a main body 912. The battery pack 911 is accommodated in the main body 912 of the notebook personal computer 910, and a plurality of lithium ion secondary batteries 2, 102, 202, 302, 402, 502, 602, not shown, are included in the battery pack 911. 702 and 802 are electrically connected in series. The plurality of lithium ion secondary batteries 2, 102, 202, 302, 402, 502, 602, 702, 802 can improve battery output and suppress a decrease in battery capacity due to charge / discharge use. Therefore, the notebook personal computer 910 using the lithium ion secondary batteries 2, 102, 202, 302, 402, 502, 602, 702, and 802 is improved in battery output and has a battery-equipped device that suppresses battery capacity deterioration. can do.

以上において、本発明を実施形態１〜５、および変形形態１〜６に即して説明したが、本発明は上述の実施形態等に限定されるものではなく、その要旨を逸脱しない範囲で、適宜変更して適用できることは言うまでもない。
例えば、上述の実施形態等では、捲回形の発電要素を持つリチウムイオン二次電池に適用した例を示した。しかし、複数の正電極板および負電極板を積層した、積層形のリチウムイオン二次電池においても適用できる。
また、上述の実施形態等では、正極活物質層にＬｉＣｒＴｉＯ4、ＬｉＦｅＴｉＯ4、ＬｉＦｅＶＯ4のいずれかのリチウム酸化物を含有している初充電前リチウムイオン二次電池としたが、これらのリチウム酸化物を適宜混合して用いることもできる。 In the above, the present invention has been described with reference to the first to fifth embodiments and the first to sixth modified embodiments. Needless to say, the present invention can be applied with appropriate changes.
For example, in the above-described embodiment, an example in which the present invention is applied to a lithium ion secondary battery having a wound-type power generation element has been shown. However, the present invention can also be applied to a stacked lithium ion secondary battery in which a plurality of positive electrode plates and negative electrode plates are stacked.
Further, in the above-described embodiment, etc., the positive electrode active material layer is a lithium ion secondary battery before initial charge containing any one of LiCrTiO 4 , LiFeTiO 4 , and LiFeVO 4 lithium oxides. Goods can also be used by appropriately mixing them.

実施形態１〜３、および変形形態１〜６にかかる初充電前リチウムイオン二次電池の斜視図である。It is a perspective view of the lithium ion secondary battery before the first charge concerning Embodiments 1-3 and modification 1-6. 実施形態１〜３、および変形形態１〜６にかかる初充電前リチウムイオン二次電池の断面図（図１のＡ−Ａ断面）である。It is sectional drawing (AA cross section of FIG. 1) of the lithium ion secondary battery before the first charge concerning Embodiments 1-3 and modification 1-6. 実施形態１〜３、および変形形態１〜６にかかる初充電前リチウムイオン二次電池の断面図（図２のＢ−Ｂ断面）である。It is sectional drawing (BB cross section of FIG. 2) of the lithium ion secondary battery before first charge concerning Embodiments 1-3 and the modifications 1-6. 実施形態１〜３、および変形形態１〜６にかかる正極部材を示す図であり、（ａ）は斜視図、（ｂ）は部分拡大断面図（図４（ａ）のＣ部）である。It is a figure which shows the positive electrode member concerning Embodiments 1-3 and the modifications 1-6, (a) is a perspective view, (b) is a partial expanded sectional view (C section of Fig.4 (a)). 実施形態１〜３、および変形形態１〜６にかかる初充電前負極部材を示す図であり、（ａ）は斜視図、（ｂ）は部分拡大断面図（図５（ａ）のＤ部）である。It is a figure which shows the negative electrode member before first charge concerning Embodiments 1-3 and the deformation | transformation forms 1-6, (a) is a perspective view, (b) is a partial expanded sectional view (D section of Fig.5 (a)). It is. 実施形態１〜３、および変形形態１〜６にかかるリチウムイオン二次電池の断面図である。It is sectional drawing of the lithium ion secondary battery concerning Embodiments 1-3 and modification 1-6. 実施形態１〜３、および変形形態１〜６にかかるリチウムイオン二次電池の図であり、（a）は正極部材の部分拡大断面図、（ｂ）は負極部材の部分拡大断面図である。It is a figure of the lithium ion secondary battery concerning Embodiments 1-3 and the modifications 1-6, (a) is the elements on larger scale of a positive electrode member, (b) is the elements on larger scale of a negative electrode member. 実施形態１にかかり、リチウムイオン二次電池について、ＬｉＣｒＴｉＯ4含有量と電池容量維持率との関係を示すグラフである。Relates to Embodiment 1, the lithium ion secondary battery is a graph showing the relationship between LiCrTiO 4 content and the battery capacity retention ratio. 実施形態４にかかる車両９００（ハイブリッド電気自動車）を示す説明図である。It is explanatory drawing which shows the vehicle 900 (hybrid electric vehicle) concerning Embodiment 4. FIG. 実施形態５にかかるノート型パーソナルコンピュータ９１０を示す説明図である。FIG. 10 is an explanatory diagram illustrating a notebook personal computer 910 according to a fifth embodiment.

符号の説明Explanation of symbols

１，１０１，２０１，３０１，４０１，５０１，６０１，７０１，８０１ 初充電前リチウムイオン二次電池
２，１０２，２０２，３０２，４０２，５０２，６０２，７０２，８０２ リチウムイオン二次電池
２１，１２１，２２１ 正極部材
２１Ｒ，１２１Ｒ，２２１Ｒ （初充電後の）正極部材
２４，１２４，２２４ 正極活物質層
２４ａ 正極活物質
２４Ｒ，１２４Ｒ，２２４Ｒ （初充電後の）正極活物質層
２５，１２５，２２５ 負極部材
２５Ｄ，１２５Ｄ，２２５Ｄ 負極部材
２８，１２８，２２８ 負極活物質層
２８ａ，１２８ａ，２２８ａ 初充電前負極活物質（負極活物質）
２８ａＤ，１２８ａＤ，２２８ａＤ （初充電後の）負極活物質
２８Ｄ，１２８Ｄ，２２８Ｄ （初充電後の）負極活物質層
Ｌ１ 第１リチウム酸化物
Ｌ１Ｒ 第１リチウム欠損酸化物
Ｌ２ 第２リチウム酸化物
Ｌ２Ｒ 第２リチウム欠損酸化物
Ｌ３ 第３リチウム酸化物
Ｌ３Ｒ 第３リチウム欠損酸化物
９００ 車両
９０１ バッテリパック（リチウムイオン二次電池）
９１０ ノート型パーソナルコンピュータ（電池搭載機器）
９１１ バッテリパック（リチウムイオン二次電池） 1, 101, 201, 301, 401, 501, 601, 701, 801 Before initial charge lithium ion secondary battery 2, 102, 202, 302, 402, 502, 602, 702, 802 Lithium ion secondary battery 21, 121 , 221 Cathode members 21R, 121R, 221R Cathode members 24, 124, 224 (after initial charge) Cathode active material layer 24a Cathode active materials 24R, 124R, 224R Cathode active material layers 25, 125, 225 (after initial charge) Negative electrode member 25D, 125D, 225D Negative electrode member 28, 128, 228 Negative electrode active material layer 28a, 128a, 228a Negative electrode active material (negative electrode active material) before initial charge
28aD, 128aD, 228aD Negative electrode active material 28D, 128D, 228D (after initial charge) Negative electrode active material layer L1 First lithium oxide L1R First lithium deficient oxide L2 Second lithium oxide L2R 2 lithium deficient oxide L3 3rd lithium oxide L3R 3rd lithium deficient oxide 900 vehicle 901 battery pack (lithium ion secondary battery)
910 Notebook personal computer (equipment with battery)
911 Battery pack (Lithium ion secondary battery)

Claims (8)

正極活物質を含む正極活物質層を有する正極部材と、
負極活物質を含む負極活物質層を有する負極部材と、を備え、
上記負極活物質は、リチウムがドープされていない初充電前負極活物質である
初充電前リチウムイオン二次電池であって、
上記正極活物質層には、ＬｉＣｒＴｉＯ4、ＬｉＦｅＴｉＯ4、およびＬｉＦｅＶＯ4、の少なくともいずれかを含む
初充電前リチウムイオン二次電池。 A positive electrode member having a positive electrode active material layer containing a positive electrode active material;
A negative electrode member having a negative electrode active material layer containing a negative electrode active material,
The negative electrode active material is a lithium ion secondary battery before initial charge which is a negative electrode active material before initial charge which is not doped with lithium,
The lithium ion secondary battery before initial charge including at least one of LiCrTiO 4 , LiFeTiO 4 , and LiFeVO 4 in the positive electrode active material layer. 請求項１に記載の初充電前リチウムイオン二次電池であって、
前記初充電前負極活物質は、黒鉛からなり、
前記正極活物質層には、
前記正極活物質の１０〜１５ｗｔ％の前記ＬｉＣｒＴｉＯ4、
上記正極活物質の１５〜２０ｗｔ％の前記ＬｉＦｅＴｉＯ4、
上記正極活物質の１５〜２０ｗｔ％の前記ＬｉＦｅＶＯ4、のいずれかを含む
初充電前リチウムイオン二次電池。 The lithium ion secondary battery before initial charge according to claim 1,
The negative active material before the initial charge is made of graphite,
In the positive electrode active material layer,
10-15 wt% of the positive electrode active material, the LiCrTiO 4 ,
15-20 wt% of the positive electrode active material, the LiFeTiO 4 ,
15～20Wt% of the LiFeVO 4, initial charge prior to the lithium ion secondary battery comprising any of the above positive electrode active material. 請求項１に記載の初充電前リチウムイオン二次電池であって、
前記初充電前負極活物質は、炭素化材料からなり、
前記正極活物質層には、
前記正極活物質の１２〜２０ｗｔ％の前記ＬｉＣｒＴｉＯ4、
上記正極活物質の１７〜２５ｗｔ％の前記ＬｉＦｅＴｉＯ4、
上記正極活物質の１７〜２５ｗｔ％の前記ＬｉＦｅＶＯ4、のいずれかを含む
初充電前リチウムイオン二次電池。 The lithium ion secondary battery before initial charge according to claim 1,
The negative active material before the first charge is made of a carbonized material,
In the positive electrode active material layer,
12-20 wt% of the LiCrTiO 4 of the positive electrode active material,
17-25 wt% of the positive electrode active material, the LiFeTiO 4 ,
17～25Wt% of the LiFeVO 4, initial charge prior to the lithium ion secondary battery comprising any of the above positive electrode active material. 請求項１に記載の初充電前リチウムイオン二次電池であって、
前記初充電前負極活物質は、低温焼成炭素からなり、
前記正極活物質層には、
前記正極活物質の１３〜２０ｗｔ％の前記ＬｉＣｒＴｉＯ4、
上記正極活物質の２０〜２５ｗｔ％の前記ＬｉＦｅＴｉＯ4、
上記正極活物質の２０〜２５ｗｔ％の前記ＬｉＦｅＶＯ4、のいずれかを含む
初充電前リチウムイオン二次電池。 The lithium ion secondary battery before initial charge according to claim 1,
The negative active material before the first charge is made of low-temperature calcined carbon,
In the positive electrode active material layer,
13-20 wt% of the LiCrTiO 4 of the positive electrode active material,
20-25 wt% of said positive electrode active material, said LiFeTiO 4 ,
20～25Wt% of the LiFeVO 4, initial charge prior to the lithium ion secondary battery comprising any of the above positive electrode active material. 請求項１〜４のいずれか一項に記載の初充電前リチウムイオン二次電池を、充電してなる
リチウムイオン二次電池。 The lithium ion secondary battery formed by charging the lithium ion secondary battery before initial charge as described in any one of Claims 1-4. 正極活物質を含む正極活物質層を有する正極部材と、
負極活物質を含む負極活物質層を有する負極部材と、を備える
リチウムイオン二次電池であって、
上記負極活物質には、リチウムがドープされてなり、
上記正極活物質層は、ＬｉＣｒＴｉＯ4、ＬｉＦｅＴｉＯ4、およびＬｉＦｅＶＯ4、の少なくともいずれかのリチウム酸化物から、上記リチウム酸化物に含まれるリチウムイオンの少なくとも一部を欠損させた組成のリチウム欠損酸化物を含む
リチウムイオン二次電池。 A positive electrode member having a positive electrode active material layer containing a positive electrode active material;
A negative electrode member having a negative electrode active material layer containing a negative electrode active material, and a lithium ion secondary battery comprising:
The negative electrode active material is doped with lithium,
The positive electrode active material layer is a lithium deficient oxide having a composition in which at least a part of lithium ions contained in the lithium oxide is deficient from at least one of LiCrTiO 4 , LiFeTiO 4 , and LiFeVO 4 . Lithium ion secondary battery containing. 請求項５および請求項６のいずれかに記載のリチウムイオン二次電池を用いた車両。   A vehicle using the lithium ion secondary battery according to claim 5. 請求項５および請求項６のいずれかに記載のリチウムイオン二次電池を用いた電池搭載機器。   The battery mounting apparatus using the lithium ion secondary battery in any one of Claim 5 and Claim 6.
JP2007095029A 2007-03-30 2007-03-30 Lithium ion secondary battery before initial charging, lithium ion secondary battery, vehicle, and battery-mounting apparatus Withdrawn JP2008251497A (en)

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WO2011039890A1 (en) * 2009-10-02 2011-04-07 トヨタ自動車株式会社 Lithium secondary battery and positive electrode for said battery
JP2011108394A (en) * 2009-11-13 2011-06-02 Fujitsu Component Ltd Connector device, female connector, and male connector
WO2014073701A1 (en) * 2012-11-12 2014-05-15 国立大学法人九州大学 Positive electrode active material, lithium battery, and manufacturing method for positive electrode active material
US9559359B2 (en) 2009-10-02 2017-01-31 Toyota Jidosha Kabushiki Kaisha Lithium secondary battery and positive electrode for the battery

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WO2011039890A1 (en) * 2009-10-02 2011-04-07 トヨタ自動車株式会社 Lithium secondary battery and positive electrode for said battery
US9362554B2 (en) 2009-10-02 2016-06-07 Toyota Jidosha Kabushiki Kaisha Method of manufacturing a positive electrode with a condensation reaction initiated by heating and reduced pressure
US9559359B2 (en) 2009-10-02 2017-01-31 Toyota Jidosha Kabushiki Kaisha Lithium secondary battery and positive electrode for the battery
JP2011108394A (en) * 2009-11-13 2011-06-02 Fujitsu Component Ltd Connector device, female connector, and male connector
WO2014073701A1 (en) * 2012-11-12 2014-05-15 国立大学法人九州大学 Positive electrode active material, lithium battery, and manufacturing method for positive electrode active material
JP2014096330A (en) * 2012-11-12 2014-05-22 Kyushu Univ Positive electrode active material, lithium battery, and process of manufacturing positive electrode active material
CN104823310A (en) * 2012-11-12 2015-08-05 国立大学法人九州大学 Positive electrode active material, lithium battery, and manufacturing method for positive electrode active material

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