JP4867161B2 - Nonaqueous electrolyte secondary battery - Google Patents
Nonaqueous electrolyte secondary battery Download PDFInfo
- Publication number
- JP4867161B2 JP4867161B2 JP2004342240A JP2004342240A JP4867161B2 JP 4867161 B2 JP4867161 B2 JP 4867161B2 JP 2004342240 A JP2004342240 A JP 2004342240A JP 2004342240 A JP2004342240 A JP 2004342240A JP 4867161 B2 JP4867161 B2 JP 4867161B2
- Authority
- JP
- Japan
- Prior art keywords
- positive electrode
- active material
- electrode active
- electrolyte secondary
- secondary battery
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Images
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Description
本発明は、正極活物質粒子表面と粒子界面の少なくとも一部に化合物を形成した、安全性に優れた非水電解質二次電池に関する。 The present invention relates to a non-aqueous electrolyte secondary battery excellent in safety, in which a compound is formed on at least a part of a positive electrode active material particle surface and a particle interface.
近年、携帯用無線電話、携帯用パソコン、携帯用ビデオカメラ等の電子機器が開発され、各種電子機器が携帯可能な程度に小型化されている。それに伴って、内蔵される電池としても、高エネルギー密度を有し、且つ軽量なものが採用されている。 In recent years, electronic devices such as portable radio telephones, portable personal computers, and portable video cameras have been developed, and various electronic devices have been miniaturized to the extent that they can be carried. Accordingly, a battery having a high energy density and a light weight has been adopted as a built-in battery.
そのような要求を満たす典型的な電池は、金属リチウム、リチウム合金またはリチウムを可逆的に吸蔵および放出可能な炭素を負極活物質とし、リチウムを可逆的に吸蔵および放出可能な正極活物質を用い、ＬｉＣｌＯ４、ＬｉＰＦ６等のリチウム塩を溶解した非プロトン性の有機溶媒を電解液とする非水電解質二次電池である。 A typical battery that satisfies such a requirement uses metallic lithium, a lithium alloy, or carbon capable of reversibly occluding and releasing lithium as a negative electrode active material and using a positive electrode active material capable of reversibly occluding and releasing lithium. , A non-aqueous electrolyte secondary battery using an aprotic organic solvent in which a lithium salt such as LiClO 4 or LiPF 6 is dissolved as an electrolytic solution.
非水電解質二次電池の中では、特に、負極活物質としてリチウムを可逆的に吸蔵および放出可能な炭素を用い、正極活物質としてＬｉＣｏＯ２、ＬｉＮｉＯ２またはＬｉＭｎ２Ｏ４などのリチウム遷移金属複合酸化物を用いたリチウムイオン電池は、エネルギー密度が高く、充放電サイクル特性に優れることから実用に適している。
Among non-aqueous electrolyte secondary batteries, in particular, carbon capable of reversibly occluding and releasing lithium is used as the negative electrode active material, and lithium transition metal composites such as LiCoO 2 , LiNiO 2 or LiMn 2 O 4 are used as the positive electrode active material. A lithium ion battery using an oxide is suitable for practical use because of its high energy density and excellent charge / discharge cycle characteristics.
リチウムイオン電池などの非水電解質二次電池は、正極の電位が非常に貴であり、負極の電位が非常に卑であるために、高電圧となり、エネルギー密度の高い二次電池をえることができる。 Non-aqueous electrolyte secondary batteries, such as lithium ion batteries, have a very positive potential on the positive electrode and a very low potential on the negative electrode. it can.
しかし、非水電解質二次電池の電解質には通常液体の有機電解液が用いられ、電解液溶媒が高電位の正極で酸化分解されやすい。電解液溶媒の分解によって、電池内ではガスが発生し、同時に発熱が起こる。 However, a liquid organic electrolyte is usually used for the electrolyte of the nonaqueous electrolyte secondary battery, and the electrolyte solvent is easily oxidatively decomposed by the positive electrode having a high potential. Due to the decomposition of the electrolyte solvent, gas is generated in the battery and heat is generated at the same time.
電池内で発生したガスが、電極表面とセパレータの間にたまると、活物質と電解液の接触が妨げられ、電池特性が劣化する。また、発生したガスと熱の影響で、電池が膨れ、漏液が起こり、場合によっては発火などの危険な状態になる恐れも考えられる。これらの問題は、高温で電池を放置した場合や、高温で過充電した場合に、特に顕著であった。 If the gas generated in the battery accumulates between the electrode surface and the separator, the contact between the active material and the electrolytic solution is hindered, and the battery characteristics deteriorate. In addition, due to the generated gas and heat, the battery may swell, liquid leakage may occur, and in some cases, a dangerous state such as ignition may occur. These problems were particularly remarkable when the battery was left at a high temperature or overcharged at a high temperature.
電解液溶媒の分解を防止するための方法として、特許文献１に、正極活物質粒子表面をＬｉＦ、ＴｉＦ４、ＶＦ５などの金属フッ化物からなる被膜で覆う技術が開示されている。また、特許文献２に、一般式ＬｉＭＯ２（Ｍは、ＮｉまたはＮｉおよびその他１種以上の遷移金属元素）で表される複合酸化物からなる正極活物質粒子表面を、Ｌｉ３ＶＯ４などのバナジウム化合物で被覆する技術が開示されている。さらに、特許文献３に、活物質粒子表面の少なくとも一部をリチウムイオン伝導性ガラスで被覆する技術が開示されている。
As a method for preventing the decomposition of the electrolyte solvent,
しかし、これらの従来の技術では、溶媒の分解抑制効果は不十分であり、高温過充電時に電池が不安全に陥るという問題があった。 However, these conventional techniques have a problem that the effect of suppressing the decomposition of the solvent is insufficient, and the battery falls unsafe during high-temperature overcharge.
さらに、非水電解質二次電池を電気自動車用などに使用する場合には、電池の容量が５Ａｈ以上の大型となり、特に、高温での過充電の安全性が重視されるようになってきた。 Furthermore, when the non-aqueous electrolyte secondary battery is used for an electric vehicle or the like, the capacity of the battery becomes a large size of 5 Ah or more, and in particular, safety of overcharge at a high temperature has been emphasized.
そこで本発明は、このような課題を解決するためになされたものであり、正極活物質粒子表面での電解液溶媒の酸化分解を抑制することにより、安全性に優れた、特に高温過充電時の安全性に優れた非水電解質二次電池を提供することを目的とするものである。 Therefore, the present invention has been made to solve such problems, and by suppressing the oxidative decomposition of the electrolyte solvent on the surface of the positive electrode active material particles, it has excellent safety, particularly at high temperature overcharge. An object of the present invention is to provide a non-aqueous electrolyte secondary battery excellent in safety.
請求項１の発明は、正極と負極と非水電解質とを備えた非水電解質二次電池において、正極活物質粒子表面と粒子界面の少なくとも一部に、Ｌｉ ２ ＰＦＯ ３ 、ＮａＨＦ ２ およびＫＨＦ ２ から選ばれた少なくとも１種の化合物を形成したことを特徴とする。
The invention of
請求項２の発明は、上記非水電解質二次電池において、正極活物質粒子表面と粒子界面の少なくとも一部に形成した化合物の正極活物質に対する割合が０．０５〜５重量％であることを特徴とする。
According to a second aspect of the present invention, in the nonaqueous electrolyte secondary battery, the ratio of the compound formed on at least a part of the positive electrode active material particle surface and the particle interface to the positive electrode active material is 0.05 to 5% by weight. Features.
本発明によれば、正極活物質粒子表面と粒子界面の少なくとも一部に、アルカリ金属とフッ素を含み、さらにリン、酸素、水素から選ばれた少なくとも１種の元素を含む化合物を形成することにより、正極活物質と電解液との接触面積を小さくすることで、電解液溶媒の酸化分解を抑制し、安全性に優れた非水電解質二次電池を得ることができる。 According to the present invention, by forming at least a part of the positive electrode active material particle surface and the particle interface a compound containing an alkali metal and fluorine and further containing at least one element selected from phosphorus, oxygen, and hydrogen. By reducing the contact area between the positive electrode active material and the electrolytic solution, it is possible to suppress the oxidative decomposition of the electrolytic solution solvent and obtain a non-aqueous electrolyte secondary battery excellent in safety.
本発明は、正極と負極と非水電解質とを備えた非水電解質二次電池において、正極活物質粒子表面と粒子界面の少なくとも一部に、アルカリ金属とフッ素を含み、さらにリン、酸素、水素から選ばれた少なくとも１種の元素を含む化合物を形成したことを特徴とするもので、本発明により、正極活物質と電解液との接触面積を小さくすることで、電解液溶媒の酸化分解を抑制し、安全性に優れた非水電解質二次電池を得ることができる。 The present invention relates to a non-aqueous electrolyte secondary battery comprising a positive electrode, a negative electrode, and a non-aqueous electrolyte, wherein at least part of the positive electrode active material particle surface and the particle interface contains an alkali metal and fluorine, and further contains phosphorus, oxygen, hydrogen According to the present invention, the contact area between the positive electrode active material and the electrolytic solution is reduced to reduce the oxidative decomposition of the electrolytic solution solvent. It is possible to obtain a nonaqueous electrolyte secondary battery that is suppressed and excellent in safety.
本発明において、アルカリ金属とフッ素を含み、さらにリン、酸素、水素から選ばれた少なくとも１種の元素を含む化合物としては、具体的には、ＬｉｘＰＦｙＯｚ（０＜ｘ＜４、０＜ｙ＜６、０＜ｚ＜４）、ＮａＨＦ２またはＫＨＦ２などの化合物、あるいはこれら化合物の混合物を用いることができる。これらの化合物の中では、電解液との反応性が低いことから、ＬｉｘＰＦｙＯｚ（０＜ｘ＜４、０＜ｙ＜６、０＜ｚ＜４）が好ましい。 In the present invention, the compound containing an alkali metal and fluorine and further containing at least one element selected from phosphorus, oxygen, and hydrogen is specifically Li x PF y O z (0 <x <4, A compound such as 0 <y <6, 0 <z <4), NaHF 2 or KHF 2 or a mixture of these compounds can be used. Among these compounds, Li x PF y O z (0 <x <4, 0 <y <6, 0 <z <4) is preferable because of low reactivity with the electrolytic solution.
化合物ＬｉｘＰＦｙＯｚにおいて、ｘ、ｙおよびｚがこの範囲以外のものは、現在のところ、合成することができない。 In the compound Li x PF y O z , x, y and z outside this range cannot be synthesized at present.
正極活物質粒子表面と粒子界面の少なくとも一部に化合物を形成する方法としては、例えば湿式法やメカニカルミーリング法を用いることができ、化合物は正極活物質粒子表面と粒子界面に、粒子状や被膜状に形成される。これらの方法以外にも、正極活物質粒子表面にリチウム化合物を形成した後、フッ素雰囲気に保つ方法などを用いることができる。 As a method for forming a compound on at least a part of the positive electrode active material particle surface and the particle interface, for example, a wet method or a mechanical milling method can be used. It is formed into a shape. In addition to these methods, a method of maintaining a fluorine atmosphere after forming a lithium compound on the surface of the positive electrode active material particles can be used.
湿式法の例としては、水酸化リチウム（ＬｉＯＨ）の飽和溶液中に正極活物質を一定時間浸漬させ（リップコーティング法）、ブフナーロートで吸引ろ過した後、１００℃を越える温度で数時間乾燥させ、その後、フッ化ホスホリルガス（ＰＯＦ３）中に一定時間曝して被膜する方法がある。 As an example of the wet method, a positive electrode active material is immersed in a saturated solution of lithium hydroxide (LiOH) for a certain period of time (lip coating method), suction filtered with a Buchner funnel, and then dried at a temperature exceeding 100 ° C. for several hours. Then, there is a method of coating by exposing to phosphoryl fluoride gas (POF 3 ) for a certain time.
メカニカルミーリング法の例としては、正極活物質と水酸化リチウム（ＬｉＯＨ）粉末とを、目的の重量比となるように秤量・混合した後に、フッ化ホスホニルガス（ＰＯＦ３）中で一定時間メカニカルミーリングする方法がある。 As an example of the mechanical milling method, a positive electrode active material and lithium hydroxide (LiOH) powder are weighed and mixed so as to have a target weight ratio, and then mechanically milled in phosphonyl fluoride gas (POF 3 ) for a certain period of time. There is a way.
本発明において、正極活物質粒子表面と粒子界面の少なくとも一部に形成した化合物の正極活物質に対する好適な割合は０．０５〜５重量％とすることが好ましい。０．０５重量％未満の場合には、正極活物質粒子表面の化合物量が少ないため、正極活物質と電解液との接触を妨げることが不十分で、正極での電解液溶媒の酸化分解を有効に抑制することができない。また、５重量％を越える場合には、化合物の抵抗が大きく、電池の内部抵抗が上昇し、充放電時の電圧低下が大きくなり、電池内の正極活物質量が少なくなって、電池のエネルギー密度が小さくなってしまう。 In this invention, it is preferable that the suitable ratio with respect to the positive electrode active material of the compound formed in at least one part of the positive electrode active material particle surface and particle | grain interface shall be 0.05-5 weight%. When the amount is less than 0.05% by weight, the amount of the compound on the surface of the positive electrode active material particles is small, so that the contact between the positive electrode active material and the electrolytic solution is insufficient to prevent oxidative decomposition of the electrolytic solution solvent at the positive electrode. It cannot be effectively suppressed. If it exceeds 5% by weight, the resistance of the compound is large, the internal resistance of the battery is increased, the voltage drop during charging and discharging is increased, the amount of the positive electrode active material in the battery is reduced, and the energy of the battery Density will decrease.
なお、上記好適な化合物の重量割合に対応して、化合物の厚さは、正極活物質粒子の大きさにもよるが、０．０１〜１μｍの範囲とすることが好ましい。化合物の厚みは、光電子分光法（ＸＰＳ）の深さ方向の測定の際に用いるアルゴンエッチングに要する時間と各元素のエッチング率によって確認することができる。 The thickness of the compound is preferably in the range of 0.01 to 1 μm, although it depends on the size of the positive electrode active material particles, corresponding to the weight ratio of the preferable compound. The thickness of the compound can be confirmed by the time required for argon etching used for measurement in the depth direction of photoelectron spectroscopy (XPS) and the etching rate of each element.
正極活物質粒子表面と粒子界面の少なくとも一部に形成した化合物と正極活物質との割合は、湿式法やメカニカルミーリング法における、化合物原料と正極活物質との重量比によって調製することができる。また、正極活物質粒子表面と粒子界面の少なくとも一部に形成された化合物の組成は、飛行時間型二次イオン質量分析（ＴＯＦ−ＳＩＭＳ）の負二次イオンスペクトルとＩＣＰの併用によって確認することができる。さらに、化合物と正極活物質との重量比はＩＣＰ分析によって確認することができる。 The ratio of the compound formed on at least part of the positive electrode active material particle surface and the particle interface to the positive electrode active material can be adjusted by the weight ratio of the compound raw material and the positive electrode active material in a wet method or a mechanical milling method. The composition of the compound formed on at least a part of the positive electrode active material particle surface and the particle interface should be confirmed by the combined use of negative secondary ion spectrum of time-of-flight secondary ion mass spectrometry (TOF-SIMS) and ICP. Can do. Furthermore, the weight ratio between the compound and the positive electrode active material can be confirmed by ICP analysis.
正極活物質粒子表面の少なくとも一部に化合物が形成された状態の模式図を図１〜図５に示す。図１〜図５において、１は正極活物質粒子、２はアルカリ金属とフッ素を含み、さらにリン、酸素、水素から選ばれた少なくとも１種の元素を含む化合物、３はカーボン、４は粒子界面の少なくとも一部に形成された化合物である。 1 to 5 are schematic views showing a state in which a compound is formed on at least a part of the surface of the positive electrode active material particles. 1 to 5, 1 is a positive electrode active material particle, 2 is a compound containing alkali metal and fluorine, and further containing at least one element selected from phosphorus, oxygen, and hydrogen, 3 is carbon, and 4 is a particle interface. A compound formed on at least a part of
図１は、正極活物質粒子表面の一部に化合物を形成した場合を示し、この場合には活物質粒子間の電子伝導は、化合物が形成されていない表面同士の接触によって行われる。しかし、図２に示したように、正極活物質粒子表面全体に化合物が形成された場合には、活物質粒子間の電子伝導を保つことが困難になるので、図３に示すように、化合物中にアセチレンブラックなどの導電性物質を含ませるか、あるいは図４に示したように、個々の正極活物質粒子間の接触が保持された状態で化合物を形成することにより、正極活物質粒子間の電子伝導性を保つことができる。なお、図１の正極活物質粒子表面の一部に化合物を形成した場合においても、化合物中に導電性物質を含ませてもよい。また、正極活物質粒子が凝集して二次粒子を形成する場合には、図５に示すように、粒子界面の少なくとも一部に化合物４を形成してもよい。
FIG. 1 shows a case where a compound is formed on a part of the surface of the positive electrode active material particles. In this case, electronic conduction between the active material particles is performed by contact between surfaces on which no compound is formed. However, as shown in FIG. 2, when a compound is formed on the entire surface of the positive electrode active material particles, it becomes difficult to maintain electronic conduction between the active material particles. By containing a conductive material such as acetylene black in the inside, or as shown in FIG. 4, by forming a compound in a state in which the contact between the individual positive electrode active material particles is maintained, Can maintain the electron conductivity. Even when the compound is formed on a part of the surface of the positive electrode active material particle in FIG. 1, a conductive material may be included in the compound. When the positive electrode active material particles are aggregated to form secondary particles, the
本発明の非水電解質二次電池の容量は、特に限定されず、小型電池にも大型電池にも適用可能であるが、大型電池の場合には、発火などが起きた場合には大事故につながる可能性があり、安全性が特に重視されるため、容量が５Ａｈ以上の大型の非水電解質二次電池の場合に、特に有効である。 The capacity of the non-aqueous electrolyte secondary battery of the present invention is not particularly limited, and can be applied to both small batteries and large batteries. However, in the case of large batteries, a large accident may occur if ignition occurs. This is particularly effective in the case of a large-sized non-aqueous electrolyte secondary battery having a capacity of 5 Ah or more.
本発明の非水電解質二次電池に用いる正極活物質としては、従来から非水電解質二次電池に用いられてきた活物質を用いることができる。例えば、一般式ＬｉｘＭｙＡｚＯ２（ただし、ＭはＮｉ、Ｃｏ、Ｍｎから選ばれた少なくとも１種の元素、または、２種もしくは３種の元素の混合物、ＡはＮｉ、Ｃｏ、Ｍｎを除く遷移金属元素、０＜ｘ≦１、０≦ｚ≦０．５、０．９≦ｙ＋ｚ≦１．１）で表されるリチウム複合酸化物や一般式ＬｉａＭｎ２−ｂＢｂＯ４（ただし、ＢはＭｎを除く遷移金属元素、０＜ａ≦１、０≦ｂ≦１）で表されるスピネル型リチウムマンガン複合酸化物、オリビン材料などを単独で、または２種以上混合して用いることができる。具体的には、ＬｉＣｏＯ２、ＬｉＮｉＯ２、ＭｎＯ2、ＬｉＭｎ2Ｏ4、ＬｉＣｏＰＯ４、ＬｉＶＯＰＯ４などを用いることができる。
As the positive electrode active material used in the non-aqueous electrolyte secondary battery of the present invention, an active material conventionally used in non-aqueous electrolyte secondary batteries can be used. For example, the general formula Li x M y A z O 2 (where M is at least one element selected from Ni, Co, and Mn, or a mixture of two or three elements, A is Ni, Co, Transition metal elements excluding Mn, 0 <x ≦ 1, 0 ≦ z ≦ 0.5, 0.9 ≦ y + z ≦ 1.1), and lithium composite oxides or general formula Li a Mn 2-b B b Spinel type lithium manganese composite oxide represented by O 4 (where B is a transition metal element excluding Mn, 0 <a ≦ 1, 0 ≦ b ≦ 1), olivine material, or a mixture of two or more thereof Can be used. Specifically, the like can be used LiCoO 2, LiNiO 2, MnO 2 , LiMn 2
本発明の非水電解質二次電池に用いる負極活物質としては、リチウムを吸蔵・放出することができる炭素（例えば、天然黒鉛、人造黒鉛、鱗片状黒鉛、低結晶性炭素、ソフトカーボン、ハードカーボン、活性炭）、リチウムと合金化反応するケイ素、スズなどの化合物を、混合またはメッキした混合材料などを用いることができる。 As the negative electrode active material used in the nonaqueous electrolyte secondary battery of the present invention, carbon capable of occluding and releasing lithium (for example, natural graphite, artificial graphite, flake graphite, low crystalline carbon, soft carbon, hard carbon) , Activated carbon), mixed materials obtained by mixing or plating compounds such as silicon and tin that are alloyed with lithium can be used.
本発明の非水電解質二次電池の電解液溶媒としては、エチレンカーボネート、プロピレンカーボネート、ジメチルカーボネート、ジエチルカーボネート、メチルエチルカーボネート、γ−ブチロラクトン、エチルアセテート、メチルプロピオネート等の溶媒およびこれらの混合溶媒を使用することができる。 As the electrolyte solution solvent of the non-aqueous electrolyte secondary battery of the present invention, solvents such as ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, γ-butyrolactone, ethyl acetate, methyl propionate, and mixtures thereof A solvent can be used.
本発明の非水電解質二次電池の電解質塩としては、ＬｉＰＦ６、ＬｉＰＦ３（Ｃ２Ｆ５）３、ＬｉＢＦ４、ＬｉＡｓＦ６、ＬｉＣｌＯ４、ＬｉＳＣＮ、ＬｉＣＦ３ＣＯ２、ＬｉＣＦ３ＳＯ３、ＬｉＮ（ＳＯ２ＣＦ３）２、ＬｉＮ（ＳＯ２ＣＦ２ＣＦ３）２、ＬｉＮ（ＣＯＣＦ３）２およびＬｉＮ（ＣＯＣＦ２ＣＦ３）２、ＬｉＢ（Ｃ２Ｏ４）２などの塩もしくはこれらの混合物を使用することができる。
As the electrolyte salt of the non-aqueous electrolyte secondary battery of the present invention, LiPF 6, LiPF 3 (C 2 F 5) 3,
本発明の非水電解質二次電池においては、電解質中に添加剤を添加することが望ましい。例えば、ビニレンカボーネートおよびその誘導体、ビフェニルやシクロヘキシルベンゼンなどのベンゼン類、プロパンスルトンなどの硫黄類、エチレンサルファイド、トリアゾール系環状化合物、フッ素含有エステル類、テトラエチルアンモニウムフルオライドのフッ化水素錯体またはこれらの誘導体、ホスファゼンおよびその誘導体、アミド基含有化合物、イミノ基含有化合物、または窒素含有化合物からなる群から選択される少なくとも１種を含有しても使用できる。 In the nonaqueous electrolyte secondary battery of the present invention, it is desirable to add an additive to the electrolyte. For example, vinylene carbonate and derivatives thereof, benzenes such as biphenyl and cyclohexylbenzene, sulfurs such as propane sultone, ethylene sulfide, triazole-based cyclic compounds, fluorine-containing esters, hydrogen fluoride complexes of tetraethylammonium fluoride, or these Or at least one selected from the group consisting of amide group-containing compounds, imino group-containing compounds, and nitrogen-containing compounds.
本発明の非水電解質二次電池の発電要素の形状としては、正極板および負極板とも帯状電極を用いた円筒型や長円筒型の巻回型が最適であるが、平板電極を積層した形状とすることも可能である。 As the shape of the power generation element of the nonaqueous electrolyte secondary battery of the present invention, the positive electrode plate and the negative electrode plate are optimally a cylindrical type or a long cylindrical type using a strip electrode, but a shape in which flat plate electrodes are laminated. It is also possible.
本発明の非水電解質二次電池の形状としては、円筒型、長円筒型、角型などの従来から用いられているあらゆる形状を用いることができる。また、電池ケースとしては、アルミニウム合金などの金属ケースや、アルミニウムなどの金属と樹脂を積層したラミネート型ケースを用いることができる。 As the shape of the non-aqueous electrolyte secondary battery of the present invention, any conventionally used shape such as a cylindrical shape, a long cylindrical shape, and a rectangular shape can be used. As the battery case, a metal case such as an aluminum alloy or a laminate type case in which a metal such as aluminum and a resin are laminated can be used.
以下では、本発明を実施例に基づきさらに詳細に説明するが、本発明はこれらの実施例に何ら限定されるものではなく、その趣旨を変更しない範囲において適宜変更して実施することが可能なものである。 In the following, the present invention will be described in more detail based on examples. However, the present invention is not limited to these examples, and can be implemented with appropriate modifications without departing from the scope of the present invention. Is.
［実施例１〜７および比較例１、２］
［実施例１］
正極活物質として平均粒子径１５μｍのＬｉＣｏＯ２を用いた。このＬｉＣｏＯ２粒子表面に、リップコーティング法（湿式法）によってＬｉＯＨを形成させ、その後、１００ｍｌのＰＦＯ３ガス中に１０分間曝してＬｉ２ＰＦＯ３の組成に調節した化合物を形成した。
[Examples 1 to 7 and Comparative Examples 1 and 2]
[Example 1]
LiCoO 2 having an average particle size of 15 μm was used as the positive electrode active material. LiOH was formed on the surface of the LiCoO 2 particles by a lip coating method (wet method), and then exposed to 100 ml of PFO 3 gas for 10 minutes to form a compound adjusted to the composition of Li 2 PFO 3 .
ＩＣＰ分析によれば、正極活物質粒子表面に形成した化合物Ｌｉ２ＰＦＯ３の正極活物質に対する割合は２重量％であり、ＥＰＭＡによれば、化合物は図１に示したように正極活物質粒子表面の一部に形成されていた。 According to the ICP analysis, the ratio of the compound Li 2 PFO 3 formed on the surface of the positive electrode active material particles to the positive electrode active material is 2% by weight. According to EPMA, the compound is positive electrode active material particles as shown in FIG. It was formed on a part of the surface.
このようにして得られた粒子表面の一部に化合物Ｌｉ２ＰＦＯ３を形成したＬｉＣｏＯ２に対して、カーボンブラックとポリフッ化ビニリデンを溶解させたＮ−メチルピロリドン溶液を加え、正極活物質８８ｗｔ％に対して、カーボンブラックが７ｗｔ％、ポリフッ化ビニリデンが５ｗｔ％の割合になるようにし、これらを混練してスラリーを作成した。そして、このスラリーをアルミニウム箔にドクターブレード法により塗布し、これを１５０℃で真空乾燥させて正極板を作製した。 An N-methylpyrrolidone solution in which carbon black and polyvinylidene fluoride are dissolved is added to LiCoO 2 in which the compound Li 2 PFO 3 is formed on a part of the particle surface thus obtained, and the positive electrode active material is 88 wt%. On the other hand, the carbon black content was 7 wt% and the polyvinylidene fluoride content was 5 wt%, and these were kneaded to prepare a slurry. And this slurry was apply | coated to the aluminum foil by the doctor blade method, this was vacuum-dried at 150 degreeC, and the positive electrode plate was produced.
一方、負極板は、厚さ１５μｍの銅箔集電体の両面に、グラファイト（黒鉛）９２ｗｔ％とＰＶＤＦ８ｗｔ％とを混合し、適宜Ｎ−メチルピロリドンを加えてペースト状に調製したものを塗布・乾燥することによって作製した。 On the other hand, the negative electrode plate was prepared by mixing 92% by weight of graphite (graphite) and 8% by weight of PVDF on both sides of a 15 μm thick copper foil current collector, and appropriately adding N-methylpyrrolidone to form a paste. It was prepared by drying.
上記のようにして作製した正極板、負極板と、厚さ２５μｍのポリエチレン製セパレータを用いて巻回型電極群とし、この電極群をアルミニウム合金製電池ケースに入れて、電解液を注液し、大きさ幅８０ｍｍ、厚さ２０ｍｍ、高さ１００ｍｍで、２５℃、電流５Ａで放電した場合の、１００サイクル目の放電容量が約１０Ａｈの、実施例１の長円筒型非水電解質二次電池を作製した。 A positive electrode plate and a negative electrode plate prepared as described above and a polyethylene separator having a thickness of 25 μm are used as a wound electrode group. The electrode group is placed in an aluminum alloy battery case, and an electrolyte is injected. A long cylindrical non-aqueous electrolyte secondary battery of Example 1 having a discharge capacity of about 10 Ah when discharged at 25 ° C. and a current of 5 A, with a size width of 80 mm, a thickness of 20 mm, and a height of 100 mm. Was made.
作製した長円筒型非水電解質二次電池の外観を図６に示す。図６において、１１は電池ケース、１２は電池蓋、１３は正極端子、１４は負極端子、１５はハーメチックシール、１６は安全弁、１７は注液口である。電池ケース１１には巻回長円筒型発電要素（図示せず）が収納され、電池ケース１１と電池蓋はレーザー溶接されている。 The external appearance of the produced long cylindrical nonaqueous electrolyte secondary battery is shown in FIG. In FIG. 6, 11 is a battery case, 12 is a battery lid, 13 is a positive terminal, 14 is a negative terminal, 15 is a hermetic seal, 16 is a safety valve, and 17 is a liquid injection port. The battery case 11 houses a wound long cylindrical power generation element (not shown), and the battery case 11 and the battery lid are laser welded.
［実施例２］
正極活物質として平均粒子径１２μｍのＬｉＮｉＯ２を用いたこと以外は実施例１と同様にして、実施例２の非水電解質二次電池を作製した。
[Example 2]
A nonaqueous electrolyte secondary battery of Example 2 was produced in the same manner as Example 1 except that LiNiO 2 having an average particle diameter of 12 μm was used as the positive electrode active material.
［実施例３］
正極活物質として平均粒子径１１μｍのＬｉＣｏ０．２Ｎｉ０．８Ｏ２を用いたこと以外は実施例１と同様にして、実施例３の非水電解質二次電池を作製した。
[Example 3]
A nonaqueous electrolyte secondary battery of Example 3 was produced in the same manner as Example 1 except that LiCo 0.2 Ni 0.8 O 2 having an average particle diameter of 11 μm was used as the positive electrode active material.
［実施例４］
正極活物質として平均粒子径１２μｍのＬｉＣｏ０．３３Ｎｉ０．３３Ｍｎ０．３３Ｏ２を用いたこと以外は実施例１と同様にして、実施例４の非水電解質二次電池を作製した。
[Example 4]
A nonaqueous electrolyte secondary battery of Example 4 was produced in the same manner as Example 1 except that LiCo 0.33 Ni 0.33 Mn 0.33 O 2 having an average particle diameter of 12 μm was used as the positive electrode active material. .
［実施例５］
正極活物質として平均粒子径１５μｍのスピネル型ＬｉＭｎ２Ｏ４を用いたこと以外は実施例１と同様にして、実施例５の非水電解質二次電池を作製した。
[Example 5]
A nonaqueous electrolyte secondary battery of Example 5 was produced in the same manner as Example 1 except that spinel type LiMn 2 O 4 having an average particle diameter of 15 μm was used as the positive electrode active material.
［実施例６］
正極活物質として平均粒子径１５μｍのスピネル型ＬｉＭｎ１．５Ｎｉ０．５Ｏ４を用いたこと以外は実施例１と同様にして、実施例６の非水電解質二次電池を作製した。
[Example 6]
A nonaqueous electrolyte secondary battery of Example 6 was produced in the same manner as Example 1 except that spinel type LiMn 1.5 Ni 0.5 O 4 having an average particle diameter of 15 μm was used as the positive electrode active material.
［実施例７］
メカニカルミーリング法によって化合物Ｌｉ２ＰＦＯ３を形成したこと以外は実施例１と同様にして、実施例７の非水電解質二次電池を作製した。
[Example 7]
A nonaqueous electrolyte secondary battery of Example 7 was produced in the same manner as in Example 1 except that the compound Li 2 PFO 3 was formed by the mechanical milling method.
［比較例１］
正極活物質粒子表面に化合物を形成しなかったこと以外は実施例１と同様にして、比較例１の非水電解質二次電池を作製した。
[Comparative Example 1]
A nonaqueous electrolyte secondary battery of Comparative Example 1 was produced in the same manner as in Example 1 except that no compound was formed on the surface of the positive electrode active material particles.
［比較例２］
固相法によって、正極活物質粒子表面にフッ化リチウム（ＬｉＦ）を形成したこと以外は実施例１と同様にして、比較例２の非水電解質二次電池を作製した。
[Comparative Example 2]
A nonaqueous electrolyte secondary battery of Comparative Example 2 was produced in the same manner as in Example 1 except that lithium fluoride (LiF) was formed on the surface of the positive electrode active material particles by the solid phase method.
実施例１〜７および比較例１、２の非水電解質二次電池を、４０℃において電流１０Ａで過充電試験を行い、電池の状態を観察した。電池の内容を表１に、また試験結果を表２にまとめた。なお、電池膨れは、過充電試験前後の、長円筒型電池の側面の平坦部（図６の×印の部分）の厚さの差から求めた。 The nonaqueous electrolyte secondary batteries of Examples 1 to 7 and Comparative Examples 1 and 2 were subjected to an overcharge test at a current of 10 A at 40 ° C., and the state of the batteries was observed. The contents of the battery are summarized in Table 1, and the test results are summarized in Table 2. In addition, the battery swelling was calculated | required from the thickness difference of the flat part (part of x mark of FIG. 6) of the side surface of a long cylindrical battery before and after an overcharge test.
表１および表２の結果から、本発明の実施例１〜７の電池はきわめて安全性が高く、電池の膨れも小さいことが示された。一方、正極活物質粒子表面に化合物を形成しなかった比較例１の電池は発火し、正極活物質粒子表面にフッ化リチウム（ＬｉＦ）の被膜を形成した比較例２の電池では漏液が見られた。 From the results of Table 1 and Table 2, it was shown that the batteries of Examples 1 to 7 of the present invention were extremely safe and the swelling of the batteries was small. On the other hand, the battery of Comparative Example 1 in which no compound was formed on the surface of the positive electrode active material particles ignited, and the battery of Comparative Example 2 in which a lithium fluoride (LiF) film was formed on the surface of the positive electrode active material particles showed liquid leakage. It was.
また、本発明の実施例１〜７の電池のように、正極活物質の種類や化合物の取り付け方法が異なる場合でも、電池の安全性を確保できることがわかった。 Moreover, even if the kind of positive electrode active material and the attachment method of a compound differ like the batteries of Examples 1-7 of this invention, it turned out that the safety | security of a battery can be ensured.
［実施例８〜１１］
［実施例８］
湿式法によって、平均粒子径１５μｍのＬｉＣｏＯ２粒子の表面にＬｉ２ＰＦ３Ｏ2を形成したこと以外は実施例１と同様にして、実施例８の非水電解質二次電池を作製した。
[Examples 8 to 11]
[Example 8]
A nonaqueous electrolyte secondary battery of Example 8 was produced in the same manner as Example 1 except that Li 2 PF 3 O 2 was formed on the surface of LiCoO 2 particles having an average particle diameter of 15 μm by a wet method.
［実施例９］
湿式法によって、平均粒子径１５μｍのＬｉＣｏＯ２粒子の表面にＬｉＰＦ2Ｏ2を形成したこと以外は実施例１と同様にして、実施例９の非水電解質二次電池を作製した。
[Example 9]
A nonaqueous electrolyte secondary battery of Example 9 was produced in the same manner as in Example 1 except that LiPF 2 O 2 was formed on the surface of LiCoO 2 particles having an average particle diameter of 15 μm by a wet method.
［実施例１０］
湿式法によって、平均粒子径１５μｍのＬｉＣｏＯ２粒子の表面にＮａＨＦ２を形成したこと以外は実施例１と同様にして、実施例１０の非水電解質二次電池を作製した。
[Example 10]
A nonaqueous electrolyte secondary battery of Example 10 was produced in the same manner as in Example 1 except that NaHF 2 was formed on the surface of LiCoO 2 particles having an average particle diameter of 15 μm by a wet method.
［実施例１１］
湿式法によって、平均粒子径１５μｍのＬｉＣｏＯ２粒子の表面にＫＨＦ２を形成したこと以外は実施例１と同様にして、実施例１１の非水電解質二次電池を作製した。
[Example 11]
A nonaqueous electrolyte secondary battery of Example 11 was produced in the same manner as in Example 1 except that KHF 2 was formed on the surface of LiCoO 2 particles having an average particle diameter of 15 μm by a wet method.
実施例８〜１１の非水電解質二次電池を、実施例１と同様、４０℃において電流１０Ａで過充電試験を行い、電池の状態を観察し、電池膨れを測定した。その結果、いずれの電池も、１時間後にも異常なく、電池の膨れは、実施例８の電池では１．２ｍｍ、実施例９の電池では１．２ｍｍ、実施例１０の電池では１．２ｍｍ、実施例１１の電池では１．１ｍｍと、いずれも実施例１の電池と同程度であった。 The non-aqueous electrolyte secondary batteries of Examples 8 to 11 were subjected to an overcharge test at a current of 10 A at 40 ° C. in the same manner as in Example 1, the state of the battery was observed, and the battery swelling was measured. As a result, none of the batteries were abnormal after 1 hour, and the swelling of the batteries was 1.2 mm for the battery of Example 8, 1.2 mm for the battery of Example 9, 1.2 mm for the battery of Example 10, The battery of Example 11 was 1.1 mm, which was almost the same as the battery of Example 1.
この結果から、正極活物質粒子表面に形成する化合物の種類が異なる場合でも、電池の安全性は高く、電池の膨れは小さいことがわかった。 From these results, it was found that even when the types of compounds formed on the surfaces of the positive electrode active material particles are different, the safety of the battery is high and the swelling of the battery is small.
［実施例１２〜１５および比較例３〜６］
［実施例１２］
電池の大きさを、幅４０ｍｍ、厚さ１０ｍｍ、高さ２０ｍｍとし、２５℃、電流５Ａで放電した場合の、１００サイクル目の放電容量が約０．５Ａhとしたこと以外は実施例１と同様にして、実施例１２の長円筒型非水電解質二次電池を作製した。
[Examples 12 to 15 and Comparative Examples 3 to 6]
[Example 12]
Similar to Example 1, except that the battery size was 40 mm wide, 10 mm thick, 20 mm high, and the discharge capacity at the 100th cycle was about 0.5 Ah when discharged at 25 ° C. and a current of 5 A. Thus, a long cylindrical nonaqueous electrolyte secondary battery of Example 12 was produced.
［実施例１３］
電池の大きさを、幅８０ｍｍ、厚さ１０ｍｍ、高さ２０ｍｍとし、２５℃、電流５Ａで放電した場合の、１００サイクル目の放電容量が約１．０Ａhとしたこと以外は実施例１と同様にして、実施例１３の長円筒型非水電解質二次電池を作製した。
[Example 13]
Example 1 except that the battery was 80 mm wide, 10 mm thick, 20 mm high, discharged at 25 ° C. and a current of 5 A, and the discharge capacity at the 100th cycle was about 1.0 Ah. Thus, a long cylindrical nonaqueous electrolyte secondary battery of Example 13 was produced.
［実施例１４］
電池の大きさを、幅４０ｍｍ、厚さ２０ｍｍ、高さ１００ｍｍとし、２５℃、電流５Ａで放電した場合の、１００サイクル目の放電容量が約５Ａhとしたこと以外は実施例１と同様にして、実施例１４の長円筒型非水電解質二次電池を作製した。
[Example 14]
The battery size is 40 mm in width, 20 mm in thickness, and 100 mm in height, and when discharged at 25 ° C. and a current of 5 A, the discharge capacity at the 100th cycle is about 5 Ah. A long cylindrical nonaqueous electrolyte secondary battery of Example 14 was produced.
［実施例１５］
電池の大きさを、幅８０ｍｍ、厚さ２０ｍｍ、高さ２００ｍｍとし、２５℃、電流５Ａで放電した場合の、１００サイクル目の放電容量が約２０Ａhとしたこと以外は実施例１と同様にして、実施例１５の長円筒型非水電解質二次電池を作製した。
[Example 15]
The battery size was 80 mm wide, 20 mm thick, 200 mm high, and when discharged at 25 ° C. and a current of 5 A, the discharge capacity at the 100th cycle was about 20 Ah. A long cylindrical nonaqueous electrolyte secondary battery of Example 15 was produced.
［比較例３］
正極活物質粒子表面に化合物を形成しなかったこと以外は実施例１２と同様にして、比較例３の非水電解質二次電池を作製した。
[Comparative Example 3]
A nonaqueous electrolyte secondary battery of Comparative Example 3 was produced in the same manner as in Example 12 except that no compound was formed on the surface of the positive electrode active material particles.
［比較例４］
正極活物質粒子表面に化合物を形成しなかったこと以外は実施例１３と同様にして、比較例４の非水電解質二次電池を作製した。
[Comparative Example 4]
A nonaqueous electrolyte secondary battery of Comparative Example 4 was produced in the same manner as in Example 13 except that no compound was formed on the surface of the positive electrode active material particles.
［比較例５］
正極活物質粒子表面に化合物を形成しなかったこと以外は実施例１４と同様にして、比較例５の非水電解質二次電池を作製した。
[Comparative Example 5]
A nonaqueous electrolyte secondary battery of Comparative Example 5 was produced in the same manner as in Example 14 except that no compound was formed on the surface of the positive electrode active material particles.
［比較例６］
正極活物質粒子表面に化合物を形成しなかったこと以外は実施例１５と同様にして、比較例６の非水電解質二次電池を作製した。
[Comparative Example 6]
A nonaqueous electrolyte secondary battery of Comparative Example 6 was produced in the same manner as in Example 15 except that no compound was formed on the surface of the positive electrode active material particles.
実施例１２〜１５および比較例３〜６の非水電解質二次電池を、実施例１と同様、４０℃において電流１ＣＡで過充電試験を行い、電池の状態を観察し、電池膨れを測定した。試験結果を表３にまとめた。なお、表３には比較のため、実施例１の電池の結果も示した。 The nonaqueous electrolyte secondary batteries of Examples 12 to 15 and Comparative Examples 3 to 6 were subjected to an overcharge test at a current of 1 CA at 40 ° C., as in Example 1, to observe the state of the battery and to measure the battery swelling. . The test results are summarized in Table 3. Table 3 also shows the results of the battery of Example 1 for comparison.
表３の結果から、本発明の実施例１２〜１５の電池は安全性が高く、電池の膨れも小さいことが示された。一方、正極活物質粒子表面に化合物を形成しなかった比較例３〜６の電池では、容量の小さい比較例３および４の電池では漏液が見られ、容量の大きい比較例５および６の電池では発火が見られた。このように、本発明は、実施例１４、１およびの１５のように、容量が５Ａｈ以上の電池の場合に、特に有効であることがわかった。 From the results in Table 3, it was shown that the batteries of Examples 12 to 15 of the present invention were high in safety and small in battery swelling. On the other hand, in the batteries of Comparative Examples 3 to 6 in which no compound was formed on the surface of the positive electrode active material particles, leakage was observed in the batteries of Comparative Examples 3 and 4 having a small capacity, and the batteries of Comparative Examples 5 and 6 having a large capacity. Then there was a fire. Thus, the present invention was found to be particularly effective in the case of a battery having a capacity of 5 Ah or more, as in Examples 14, 1 and 15.
［実施例１６〜２５］
［実施例１６］
正極活物質粒子表面の一部にＬｉ２ＰＦＯ３を形成し、Ｌｉ２ＰＦＯ３の正極活物質に対する割合を０．０３重量％としたこと以外は実施例１と同様にして、実施例１６の非水電解質二次電池を作製した。
[Examples 16 to 25]
[Example 16]
In the same manner as in Example 1, except that Li 2 PFO 3 was formed on a part of the surface of the positive electrode active material particles, and the ratio of Li 2 PFO 3 to the positive electrode active material was 0.03% by weight. A non-aqueous electrolyte secondary battery was produced.
［実施例１７］
Ｌｉ２ＰＦＯ３の正極活物質に対する割合を０．０５重量％としたこと以外は実施例１６と同様にして、実施例１７の非水電解質二次電池を作製した。
[Example 17]
A nonaqueous electrolyte secondary battery of Example 17 was made in the same manner as Example 16 except that the ratio of Li 2 PFO 3 to the positive electrode active material was 0.05% by weight.
［実施例１８］
Ｌｉ２ＰＦＯ３の正極活物質に対する割合を１．０重量％としたこと以外は実施例１６と同様にして、実施例１８の非水電解質二次電池を作製した。
[Example 18]
A nonaqueous electrolyte secondary battery of Example 18 was made in the same manner as Example 16 except that the ratio of Li 2 PFO 3 to the positive electrode active material was 1.0 wt%.
［実施例１９］
Ｌｉ２ＰＦＯ３の正極活物質に対する割合を５重量％としたこと以外は実施例１６と同様にして、実施例１９の非水電解質二次電池を作製した。
[Example 19]
A nonaqueous electrolyte secondary battery of Example 19 was made in the same manner as Example 16 except that the ratio of Li 2 PFO 3 to the positive electrode active material was 5 wt%.
［実施例２０］
Ｌｉ２ＰＦＯ３の正極活物質に対する割合を１０重量％としたこと以外は実施例１６と同様にして、実施例２０の非水電解質二次電池を作製した。
[Example 20]
A nonaqueous electrolyte secondary battery of Example 20 was produced in the same manner as Example 16 except that the ratio of Li 2 PFO 3 to the positive electrode active material was 10% by weight.
［実施例２１］
図４に示したように、正極活物質粒子表面の全面にＬｉ２ＰＦＯ３を形成し、Ｌｉ２ＰＦＯ３の正極活物質に対する割合を０．０３重量％、被膜の厚みを０．０２μｍとしたこと以外は実施例１と同様にして、実施例２１の非水電解質二次電池を作製した。
[Example 21]
As shown in FIG. 4, Li 2 PFO 3 was formed on the entire surface of the positive electrode active material particles, the ratio of Li 2 PFO 3 to the positive electrode active material was 0.03% by weight, and the thickness of the coating was 0.02 μm. A nonaqueous electrolyte secondary battery of Example 21 was made in the same manner as Example 1 except for the above.
［実施例２２］
Ｌｉ２ＰＦＯ３の正極活物質に対する割合を０．０５重量％、被膜の厚みを０．０４μｍとしたこと以外は実施例２１と同様にして、実施例２２の非水電解質二次電池を作製した。
[Example 22]
A nonaqueous electrolyte secondary battery of Example 22 was produced in the same manner as in Example 21, except that the ratio of Li 2 PFO 3 to the positive electrode active material was 0.05% by weight and the thickness of the film was 0.04 μm. .
［実施例２３］
Ｌｉ２ＰＦＯ３の正極活物質に対する割合を１．０重量％、被膜の厚みを０．１１μｍとしたこと以外は実施例２１と同様にして、実施例２３の非水電解質二次電池を作製した
。
[Example 23]
A nonaqueous electrolyte secondary battery of Example 23 was produced in the same manner as in Example 21 except that the ratio of Li 2 PFO 3 to the positive electrode active material was 1.0 wt% and the thickness of the coating film was 0.11 μm. .
［実施例２４］
Ｌｉ２ＰＦＯ３の正極活物質に対する割合を５重量％、被膜の厚みを０．４μｍとしたこと以外は実施例２１と同様にして、実施例２４の非水電解質二次電池を作製した。
[Example 24]
A nonaqueous electrolyte secondary battery of Example 24 was produced in the same manner as in Example 21, except that the ratio of Li 2 PFO 3 to the positive electrode active material was 5% by weight and the thickness of the film was 0.4 μm.
［実施例２５］
Ｌｉ２ＰＦＯ３の正極活物質に対する割合を１０重量％、被膜の厚みを０．１２μｍとしたこと以外は実施例２１と同様にして、実施例２５の非水電解質二次電池を作製した。
[Example 25]
A nonaqueous electrolyte secondary battery of Example 25 was made in the same manner as Example 21 except that the ratio of Li 2 PFO 3 to the positive electrode active material was 10 wt% and the thickness of the coating film was 0.12 μm.
実施例１６〜２５の非水電解質二次電池を、実施例１と同様、４０℃において電流１０Ａで過充電試験を行い、電池の状態を観察し、電池膨れを測定した。試験結果を表４にまとめた。なお、表４において「重量割合、％」は、Ｌｉ２ＰＦＯ３の正極活物質に対する重量割合（％）を示し、「異常なし」は「１時間後、異常なし」を示す。 The non-aqueous electrolyte secondary batteries of Examples 16 to 25 were subjected to an overcharge test at a current of 10 A at 40 ° C. in the same manner as in Example 1, the state of the battery was observed, and the battery swelling was measured. The test results are summarized in Table 4. In Table 4, “weight ratio,%” indicates the weight ratio (%) of Li 2 PFO 3 to the positive electrode active material, and “no abnormality” indicates “no abnormality after 1 hour”.
表４から、正極活物質粒子の表面にＬｉ２ＰＦＯ３を形成した場合には、Ｌｉ２ＰＦＯ３が粒子表面一部または全面の場合とも、過充電試験において１時間後に異常はないことがわかった。 Table 4 shows that when Li 2 PFO 3 is formed on the surface of the positive electrode active material particles, there is no abnormality after 1 hour in the overcharge test, even when Li 2 PFO 3 is partly or entirely on the particle surface. It was.
しかしながら、実施例１６と実施例２１のように、Ｌｉ２ＰＦＯ３が正極活物質に対し０．０５重量％未満の場合には、電池の膨れがやや大きく、正極での電解液溶媒が少し分解しているものと推定される。また、実施例２０と実施例２５のように、Ｌｉ２ＰＦＯ３が正極活物質に対し５重量％を越える場合には、実施例１９や実施例２４に比べて放電容量がやや小さくなった。 However, as in Example 16 and Example 21, when Li 2 PFO 3 is less than 0.05% by weight with respect to the positive electrode active material, the swelling of the battery is somewhat large, and the electrolyte solvent at the positive electrode is slightly decomposed. It is estimated that Further, as in Example 20 and Example 25, when Li 2 PFO 3 exceeded 5% by weight with respect to the positive electrode active material, the discharge capacity was slightly smaller than in Example 19 and Example 24.
したがって、正極活物質粒子表面に形成したＬｉ２ＰＦＯ３の正極活物質に対する割合は、０．０５〜５重量％であることが好ましいことがわかった。 Therefore, it was found that the ratio of Li 2 PFO 3 formed on the surface of the positive electrode active material particles to the positive electrode active material is preferably 0.05 to 5% by weight.
［実施例２６］
実施例２の電極における、化合物形成後のフッ素原子の最内核電子（Ｆ−１ｓ）の結合エネルギー分布を図７に示した。図７から、正極活物質表面にＬｉ２ＰＦＯ３を形成した場合には、Ｆ−１ｓの結合エネルギーが６８２〜６８９ｅＶに強度分布をもつ化合物が生成していることがわかった。
[Example 26]
FIG. 7 shows the bond energy distribution of the innermost core electron (F-1s) of the fluorine atom after the formation of the compound in the electrode of Example 2. From FIG. 7, it was found that when Li 2 PFO 3 was formed on the surface of the positive electrode active material, a compound having an intensity distribution with an F-1s binding energy of 682 to 689 eV was generated.
１ 正極活物質粒子
２ 正極活物質粒子表面に形成された化合物
３ カーボン
４ 正極活物質粒子界面に形成された化合物
１１ 電池ケース
１２ 電池蓋
１３ 正極端子
１４ 負極端子
DESCRIPTION OF
Claims (2)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2004342240A JP4867161B2 (en) | 2004-11-26 | 2004-11-26 | Nonaqueous electrolyte secondary battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2004342240A JP4867161B2 (en) | 2004-11-26 | 2004-11-26 | Nonaqueous electrolyte secondary battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2006156008A JP2006156008A (en) | 2006-06-15 |
| JP4867161B2 true JP4867161B2 (en) | 2012-02-01 |
Family
ID=36634051
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2004342240A Expired - Fee Related JP4867161B2 (en) | 2004-11-26 | 2004-11-26 | Nonaqueous electrolyte secondary battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP4867161B2 (en) |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5070754B2 (en) * | 2006-07-21 | 2012-11-14 | パナソニック株式会社 | Manufacturing method of non-aqueous electrolyte secondary battery |
| JP2009123576A (en) * | 2007-11-16 | 2009-06-04 | Sony Corp | Nonaqueous electrolyte secondary battery and nonaqueous electrolyte composition |
| JP5445103B2 (en) * | 2009-12-18 | 2014-03-19 | ソニー株式会社 | Secondary battery, electrolyte for secondary battery, electric tool, electric vehicle and power storage system |
| EP2511976A4 (en) | 2009-12-07 | 2013-07-17 | Sony Corp | Secondary cell, electrolyte, cell pack, electronic device, electric vehicle |
| CN104781954B (en) | 2012-11-07 | 2017-08-08 | 株式会社半导体能源研究所 | The manufacture method of electrode for power storage device, electrical storage device and electrode for power storage device |
| JP2016154061A (en) * | 2013-06-19 | 2016-08-25 | 日産自動車株式会社 | Nonaqueous electrolyte secondary battery |
| JP6600449B2 (en) * | 2013-10-04 | 2019-10-30 | 旭化成株式会社 | Lithium ion secondary battery |
| CN106104862B (en) | 2014-03-13 | 2020-04-28 | 株式会社半导体能源研究所 | Electrode, power storage device, electronic apparatus, and method for manufacturing electrode |
| JP6268049B2 (en) * | 2014-06-23 | 2018-01-24 | 信越化学工業株式会社 | Non-aqueous electrolyte secondary battery negative electrode material, non-aqueous electrolyte secondary battery, and method for producing negative electrode active material particles |
| JP6623083B2 (en) * | 2016-02-29 | 2019-12-18 | 富士フイルム株式会社 | Solid electrolyte composition, sheet for all-solid secondary battery and all-solid-state secondary battery using the same, and method for producing them |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3736045B2 (en) * | 1997-06-19 | 2006-01-18 | 松下電器産業株式会社 | All solid lithium battery |
-
2004
- 2004-11-26 JP JP2004342240A patent/JP4867161B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JP2006156008A (en) | 2006-06-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP3844733B2 (en) | Nonaqueous electrolyte secondary battery | |
| JP5232631B2 (en) | Non-aqueous electrolyte battery | |
| JP2009164082A (en) | Nonaqueous electrolyte secondary battery, and manufacturing method thereof | |
| JP2010135329A (en) | Cathode and lithium battery adopting this | |
| KR20100087679A (en) | Nonaqueous electrolyte secondary battery | |
| JP2002358999A (en) | Non-aqueous electrolyte secondary battery | |
| JP4288402B2 (en) | Secondary battery electrolyte, secondary battery, and method of using secondary battery | |
| US11289688B2 (en) | Positive electrode active material for nonaqueous electrolyte secondary batteries, production method thereof, and nonaqueous electrolyte secondary battery | |
| JP2013041844A (en) | Active material for battery, nonaqueous electrolyte battery and battery pack | |
| JP2015170542A (en) | Nonaqueous electrolyte secondary battery | |
| WO2008048006A1 (en) | Electrolyte of high temperature property and overcharge-prevention property and secondary battery employed with the same | |
| JP2004022523A (en) | Nonaqueous electrolyte secondary battery | |
| JP5109349B2 (en) | Secondary battery | |
| JP4867161B2 (en) | Nonaqueous electrolyte secondary battery | |
| JP2009164053A (en) | Battery | |
| JP3969072B2 (en) | Nonaqueous electrolyte secondary battery | |
| CN111052486B (en) | Nonaqueous electrolyte secondary battery | |
| JP5326923B2 (en) | Non-aqueous electrolyte secondary battery | |
| WO2013018607A1 (en) | Nonaqueous electrolyte secondary battery | |
| US20210013489A1 (en) | Non-aqueous electrolyte secondary battery | |
| US20210376384A1 (en) | Electrolyte composition for a lithium-ion electrochemical cell | |
| JP5646661B2 (en) | Positive electrode, non-aqueous electrolyte battery and battery pack | |
| JP2008016316A (en) | Nonaqueous electrolyte secondary battery | |
| JP6258180B2 (en) | ELECTROLYTE SOLUTION FOR LITHIUM SECONDARY BATTERY, ELECTROLYTE SOLUTION FOR LITHIUM SECONDARY BATTERY USING THE SAME, LITHIUM SECONDARY BATTERY | |
| JP6042195B2 (en) | Nonaqueous electrolyte secondary battery |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20071115 |
|
| A711 | Notification of change in applicant |
Free format text: JAPANESE INTERMEDIATE CODE: A712 Effective date: 20100507 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20101115 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20101207 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20110125 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20111018 |
|
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20111031 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 4867161 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20141125 Year of fee payment: 3 |
|
| LAPS | Cancellation because of no payment of annual fees |