Development of active materials of nonaqeous lithium secondary battery, based on its discharge and charge mechanisms.

基于其放电和充电机制的非水锂二次电池活性材料的开发。

• 批准号: 60470073
• 负责人: TAKEHARA Zen-ichiro
• 金额: $ 3.39万
• 依托单位: Kyoto University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for General Scientific Research (B)
• 财政年份: 1985
• 资助国家: 日本
• 起止时间: 1985 至 1986
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-60470073/
• 关键词: Lithium secondary battery; Titaninum dioxide; Molybdenum disulfide; ポリアセチレン; ポリアニリン

The discharge and charge mechanisms of metallic oxides, metallic sulfides, and conducting polymers in nonaqueous solvent were investigated in order to develop the positive active material of lithium secondary batteries. These reactions proceeds with the insertion and deinsertion of <Li^+> ion, <ClO(_4^-)> , <BF(_4^-)> , or <PF_6^-)> . In this study, the diffusion behavior of <Li^+> ion and <ClO(_4^-)> etc. in solid phase of active material were examined by using a potential step method.Rutile and anatase <TiO_2> thin films were prepared by rf-supptering method. Anatase <TiO_2> films was heated at 400゜C to increase its crystallinity. Diffusion coefficients of lithium in <TiO_2> films were estimated, assuming one-dimensional finite diffusion. Diffusion coefficient increased with decreasing of crystallinity of <TiO_2> film. Therefore, amorphous like <TiO_2> must be suitable for active material of lithium secondary battery. <MoS_2> were also investigated, which has a layer structure. In this case, solvated <Li^+> ion intercalated into <MoS_2> layer, resulting in large polarization caused by diffusion resistance of <Li^+> ion. Therefore, the solvent for the electrolyte must not strongly interact with <Li^+> ion.Diffusion behavior of anions in polyacetylene and polyaniline were studied and the diffusion coefficients of <ClO(_4^-)> , <BF(_4^-)> , and <PF(_6^-)> were obtained to be the order of 1x <10^(-14)> <cm^2> <s^(-1)> . This means that the discharge and charge reactions are limited by diffusion process of anions in polymer. Therefore, thin film of polyaniline was prepared by electrochemical polymerization and was examined its discharge and charge characteristics. Such film electrode indicates the good performance as active material of lithium secondary battery. This is because the diffusion path for anion in polymer becomes short.

为了开发锂二次电池正极活性材料，研究了金属氧化物、金属硫化物和导电聚合物在非水溶剂中的放电和充电机理。这些反应是随着~lt；Li^+&gt；离子、&lt；ClO(_4^-)&gt；、&lt；BF(_4^-)&gt；或&lt；PF_6^-)&gt；的插入和退出而进行的。本研究采用电势阶跃法研究了~lt；Li~(++)&gt；离子和~lt；ClO(_4^-)&gt；等在活性物质固相中的扩散行为，采用射频溅射法制备了金红石型和锐钛矿型薄膜。在400゜C下加热锐钛矿型TiO2GT；薄膜以提高其结晶度。在一维有限扩散的假设下，估算了锂在薄膜中的扩散系数。扩散系数随薄膜结晶度的降低而增大。因此，非晶态的类-lt；TiO2光催化剂必须适合作为锂二次电池的活性材料。研究了具有层状结构的&lt；MoS_2&gt；。在这种情况下，溶剂化的~lt；Li^+&gt；离子插入到~lt；MoS_2&gt；层中，由于~lt；Li^+&gt；离子的扩散阻力，导致了很大的极化。研究了阴离子在聚乙炔和聚苯胺中的扩散行为，得到了&lt；ClO(_4^-)&gt；，&lt；BF(_4^-)&gt；和&lt；PF(_6^-)&gt；的扩散系数为1x&lt；10^(-14)&gt；&lt；cm^2&gt；&lt；S^(-1)&gt；这意味着放电和充电反应受制于阴离子在聚合物中的扩散过程。为此，采用电化学聚合的方法制备了聚苯胺薄膜，并对其放电和充电特性进行了测试。这种薄膜电极作为锂二次电池的活性物质具有良好的性能。这是因为阴离子在聚合物中的扩散路径变短。

项目成果

K.Kanamura;Z.Takehara;K.Yuasa: J.Power Sources.

K.Kanamura；Z.Takehara；K.Yuasa：J.Power Sources。

Z.Takehara, K.Kanamura, T.hanawa: "Anion Behavior in a Polyacetylene Cathode for a Secondary Lithium Battery" J.Power Souces. in press.

Z.Takehara、K.Kanamura、T.hanawa：“二次锂电池聚乙炔阴极中的阴离子行为”J.Power Souces。

Z.Takehara;K.Kanamura;T.Hanawa: J.Power Sources.

Z.Takehara；K.Kanamura；T.Hanawa：J.Power Sources。

K.Kanamura, Z.Takehara, K.Yuasa: "The Diffusion of Lithium in the <TiO_2> Cathode of a Lithium Battery" J.Power Sources. in press.

K.Kanamura、Z.Takehara、K.Yuasa：“锂电池 <TiO_2> 阴极中锂的扩散”J.Power Sources。