JP2015056282A - Polymer solid electrolyte battery - Google Patents

Polymer solid electrolyte battery Download PDF

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JP2015056282A
JP2015056282A JP2013188945A JP2013188945A JP2015056282A JP 2015056282 A JP2015056282 A JP 2015056282A JP 2013188945 A JP2013188945 A JP 2013188945A JP 2013188945 A JP2013188945 A JP 2013188945A JP 2015056282 A JP2015056282 A JP 2015056282A
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solid electrolyte
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恵介 本田
Keisuke Honda
恵介 本田
広和 大熊
Hirokazu Okuma
広和 大熊
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Yachiyo Industry Co Ltd
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Abstract

PROBLEM TO BE SOLVED: To provide a polymer solid electrolyte battery having stable discharge capacity by improving positive electrode active material utilization efficiency and also capable of minimizing temperature characteristics of a polymer solid electrolyte battery, specifically an increase in internal resistance of a battery in a low temperature environment.SOLUTION: In a polymer solid electrolyte battery 1 including a polymer electrolyte membrane 4 held between a positive electrode 2 and a negative electrode 3, the positive electrode 2 includes: an active material particle 22 comprising olivine type lithium phosphate (LiMPO(where M represents at least one selected from the group consisting of Co, Ni, Mn and Fe)); a solid electrolyte 25 comprising PEO-EM (polyethylene oxide in which ethyl methyl oxide is added to a side chain) having ion conductivity; and a conductive material 24 having electron conductivity.

Description

本発明は、正極と負極との間に高分子固体電解質を挟持させた高分子固体電解質電池に関する。   The present invention relates to a polymer solid electrolyte battery in which a polymer solid electrolyte is sandwiched between a positive electrode and a negative electrode.

近年、携帯電話等の情報端末や、ディジタルカメラ等の携帯用電子機器の電源として、小型の高分子固体電解質電池が二次電池として使用されている。高分子固体電解質をイオン移動媒体とする電池は、液体電解質の代わりに液体電解質をポリマー内に固着させたものを使用するため、液漏れが少なく、電池の信頼性、安全性を向上させることができる。更に、アルミラミネートフィルム等の簡易な電池容器を採用することで厚みを１ｍｍ以下とすることができ、電池形状の設計自由度も高く、パッケージの簡略化、軽量化が期待されている。高分子固体電解質電池は、今後、更に自動車等の輸送機器、電力貯蔵・負荷平準化（キャパシタ）等に本格的な使用が予想され、より一層の安定した電力供給性能が求められている。   In recent years, small polymer solid electrolyte batteries have been used as secondary batteries as power sources for information terminals such as mobile phones and portable electronic devices such as digital cameras. A battery using a solid polymer electrolyte as an ion transfer medium uses a liquid electrolyte fixed in a polymer instead of a liquid electrolyte, so there is little liquid leakage and the reliability and safety of the battery can be improved. it can. Furthermore, by adopting a simple battery container such as an aluminum laminate film, the thickness can be reduced to 1 mm or less, the design flexibility of the battery shape is high, and simplification and weight reduction of the package are expected. In the future, solid polymer electrolyte batteries are expected to be used in full-scale for transportation equipment such as automobiles, power storage and load leveling (capacitors), and further stable power supply performance is required.

このような、高分子固体電解質電池として、例えば、正極を構成する正極活物質粒子の表面を、正極活物質に比べて酸素を供給されても容易に酸化することのないイオン伝導性および電子伝導性を有する付着物で被覆し、活物質粒子表面の少なくとも一部を高分子固体電解質と直接接触しない状態とした高分子固体電解質電池が開示されている（特許文献１）。   As such a polymer solid electrolyte battery, for example, the surface of the positive electrode active material particles constituting the positive electrode is not easily oxidized even when oxygen is supplied compared to the positive electrode active material, and the ionic conductivity and the electronic conductivity. There has been disclosed a polymer solid electrolyte battery that is coated with an adherent having a property so that at least part of the surface of the active material particles is not in direct contact with the polymer solid electrolyte (Patent Document 1).

また、他の例として、アルミン酸エステルと、エチレン性不飽和結合を含む官能基を２つ以上有する多官能モノマーと、グライムと、リチウム塩とを含む電解質前駆体組成物を重合してなる高分子電解質、およびこれを用いたリチウムイオン二次電池が開示されている（特許文献２）。   As another example, a polymer electrolyte composition comprising an aluminate ester, a polyfunctional monomer having two or more functional groups containing an ethylenically unsaturated bond, glyme, and a lithium salt is polymerized. A molecular electrolyte and a lithium ion secondary battery using the same are disclosed (Patent Document 2).

また、他の例として、正極材料用の導電助剤（導電材）としてカーボンブラック（アセチレンブラック）と、平均繊維径５〜２５ｎｍ、平均繊維長１００〜１００００ｎｍ、平均比表面積１００〜５００ｍ２／ｇの範囲にあるカーボンナノファイバーとを含み、カーボンナノファイバーの質量と、カーボンブラック及びカーボンナノファイバーの合計質量との質量割合（（カーボンナノファイバー／（カーボンブラック＋カーボンナノファイバー））×１００）を０．０５〜５０％とする技術が開示され、更に、この導電助剤およびオリビン型リン酸鉄リチウム（正極活物質）、ポリフッ化ビニリデン（バインダー）を用いた正極の構成が開示されている（特許文献３）。 As another example, carbon black (acetylene black) as a conductive auxiliary agent (conductive material) for the positive electrode material, an average fiber diameter of 5 to 25 nm, an average fiber length of 100 to 10000 nm, and an average specific surface area of 100 to 500 m 2 / g The ratio of the mass of the carbon nanofiber and the total mass of carbon black and carbon nanofiber ((carbon nanofiber / (carbon black + carbon nanofiber)) × 100) A technique of 0.05 to 50% is disclosed, and further, a configuration of a positive electrode using this conductive additive, olivine type lithium iron phosphate (positive electrode active material), and polyvinylidene fluoride (binder) is disclosed ( Patent Document 3).

特許第４９９７４００号公報Japanese Patent No. 4997400 特開２０１０−０８０３０１号公報JP 2010-080301 A 特開２０１３−０７７４７５号公報JP 2013-077745 A

高分子固体電解質電池においては、正極材料として高分子固体電解質を使用した際、電池性能向上を実現するために、活物質の選定および活物質の特性に応じた導電材の選定が重要となり、活物質利用率の向上が必須である。更に、活物質、導電材およびバインダーの配合比率（重量比）による性能向上効果についても把握することが重要となる。   In polymer solid electrolyte batteries, when a polymer solid electrolyte is used as the positive electrode material, it is important to select an active material and a conductive material according to the characteristics of the active material in order to improve battery performance. Improvement of material utilization is essential. Furthermore, it is important to grasp the performance improvement effect by the blending ratio (weight ratio) of the active material, the conductive material and the binder.

しかしながら、特許文献１においては、正極シートにＬｉＣｏＯ２、導電材のアセチレンブラック、イオン伝導性バインダーのＰ（ＥＯ／ＭＥＥＧＥ）−ＬｉＢＥＴＩ（ＬｉＮ（ＳＯ２ＣＦ２ＣＦ３）２）を用い、重量比を正極活物質／導電材／バインダー＝８２／５／１３としたものが開示されているが、正極活物質としてオリビン型リン酸リチウムを用いた場合の正極活物質／導電材／バインダーの重量比、特にバインダーと導電材との重量比と正極活物質利用率との関係についてはなんら開示されていない。 However, in Patent Document 1, LiCoO 2 , acetylene black as a conductive material, and P (EO / MEEGE) -LiBETI (LiN (SO 2 CF 2 CF 3 ) 2 ) as an ion conductive binder are used for the positive electrode sheet, and the weight ratio. In which positive electrode active material / conductive material / binder = 82/5/13 is disclosed, but the weight ratio of positive electrode active material / conductive material / binder when olivine type lithium phosphate is used as the positive electrode active material In particular, there is no disclosure about the relationship between the weight ratio of the binder and the conductive material and the utilization ratio of the positive electrode active material.

また、特許文献２で開示された技術では、正極活物質であるオリビン型リン酸鉄リチウム（ＬｉＦｅＰＯ４）（平均粒子径：１μｍ）（８６質量％）、導電材であるアセチレンブラック（７質量％）、および結着材であるポリフッ化ビニリデン（ＰＶｄＦ）（７質量％）を用いた正極が開示されているが、バインダーとしてイオン伝導性が小さい高分子材料であるポリフッ化ビニリデン（ＰＶｄＦ）が使用されている。このようなイオン伝導性が小さい高分子材料を用いることで電極全体の電子伝導経路の形成が妨げられ、活物質添加量に対する電池性能向上効果に反映されにくいという課題がある。 In the technique disclosed in Patent Document 2, olivine-type lithium iron phosphate (LiFePO 4 ) (average particle size: 1 μm) (86% by mass) as a positive electrode active material, acetylene black (7% by mass) as a conductive material. ) And a binder using polyvinylidene fluoride (PVdF) (7% by mass), which is a binder, is disclosed, but polyvinylidene fluoride (PVdF), which is a polymer material having low ion conductivity, is used as a binder. Has been. By using such a polymer material having low ion conductivity, formation of the electron conduction path of the entire electrode is hindered, and there is a problem that it is difficult to be reflected in the effect of improving battery performance with respect to the amount of active material added.

また、特許文献３で開示された技術では、正極活物質としてカーボンコートされた平均粒径１．２μｍのＬｉＦｅＰＯ４粉末、結着剤としてポリフッ化ビニリデン（ＰＶｄＦ）、導電助剤として、比表面積７０ｍ２／ｇのアセチレンブラック（ＡＢ）を用いた正極が開示されている。しかしながら、特許文献３においても特許文献２と同様に、バインダーとしてイオン伝導性が小さい高分子材料であるポリフッ化ビニリデン（ＰＶｄＦ）が使用されており、イオン伝導性が小さい高分子材料を用いることで電極全体の電子伝導経路の形成が妨げられ、活物質添加量に対する電池性能向上効果に反映されにくいという課題がある。 In the technique disclosed in Patent Document 3, LiFePO 4 powder having an average particle diameter of 1.2 μm coated with carbon as a positive electrode active material, polyvinylidene fluoride (PVdF) as a binder, and a specific surface area of 70 m as a conductive auxiliary agent. A positive electrode using 2 / g acetylene black (AB) is disclosed. However, in Patent Document 3, as in Patent Document 2, polyvinylidene fluoride (PVdF), which is a polymer material having low ion conductivity, is used as a binder, and a polymer material having low ion conductivity is used. There is a problem in that the formation of the electron conduction path of the entire electrode is hindered and is not easily reflected in the effect of improving battery performance with respect to the amount of active material added.

本発明は、このような背景に鑑みなされたもので、正極に使用する活物質の利用率向上に着目して安定した放電容量を備える高分子固体電解質電池を提供することを目的とする。   This invention is made | formed in view of such a background, and it aims at providing the polymer solid electrolyte battery provided with the stable discharge capacity paying attention to the utilization factor improvement of the active material used for a positive electrode.

上記課題を解決するために、本発明は、正極（２）と負極（３）との間に高分子電解質膜（４）を挟持した固体高分子電解質電池（１）であって、前記正極の構成として、オリビン型リン酸リチウム（ＬｉＭＰＯ４（ただし、ＭはＣｏ、Ｎｉ、ＭｎおよびＦｅの群から選択される少なくとも一種である））からなる活物質粒子（２２）と、イオン伝導性を有するＰＥＯ−ＥＭ（エチルメチルオキシドが側鎖に付されたポリエチレンオキシド）からなる固体電解質（２５）と、電子伝導性を有する導電材（２４）と、を有するものである。 In order to solve the above problems, the present invention provides a solid polymer electrolyte battery (1) having a polymer electrolyte membrane (4) sandwiched between a positive electrode (2) and a negative electrode (3), The active material particles (22) made of olivine-type lithium phosphate (LiMPO 4 (wherein M is at least one selected from the group of Co, Ni, Mn, and Fe)) and ionic conductivity It has a solid electrolyte (25) made of PEO-EM (polyethylene oxide having ethylmethyl oxide attached to the side chain) and a conductive material (24) having electronic conductivity.

この構成によれば、活物質粒子と導電材とを結着するバインダーとして、それ自身がイオン伝導性を有する固体電解質であり、かつ低温時の電気伝導率が大きいＰＥＯ−ＥＭを使用することで、安定した充放電を行うことが可能となる。   According to this configuration, as a binder for binding the active material particles and the conductive material, a PEO-EM that is a solid electrolyte that has ionic conductivity and that has a high electric conductivity at low temperatures can be used. Stable charge / discharge can be performed.

また、本発明は、前記活物質粒子（２２）と前記固体電解質（２５）と前記導電材（２４）とを含む正極固体電解質部（２０）と、前記正極固体電解質部を外部と電気的に接続する正極集電体（２１）と、を備える正極構成を有し、前記正極固体電解質部において、前記正極固体電解質部の重量に対する前記活物質粒子の重量の比率を、重量比ｘとするとき、前記重量比ｘを、ｘ≧０．６５とし、かつ前記導電材の重量に対する前記固体電解質の重量の比率を、重量比ｙとするとき、前記重量比ｙを、２．０≦ｙ≦４．０の範囲としたものである。   The present invention also provides a positive electrode solid electrolyte part (20) including the active material particles (22), the solid electrolyte (25), and the conductive material (24), and the positive electrode solid electrolyte part electrically connected to the outside. A positive electrode current collector (21) to be connected, and in the positive electrode solid electrolyte part, the ratio of the weight of the active material particles to the weight of the positive electrode solid electrolyte part is a weight ratio x When the weight ratio x is x ≧ 0.65 and the ratio of the weight of the solid electrolyte to the weight of the conductive material is the weight ratio y, the weight ratio y is 2.0 ≦ y ≦ 4. .0 range.

これによって、電子伝導パス、イオン伝導パスの伝導経路の形成により相互作用が向上して、正極の活物質利用率の向上を図ることが可能となる。   Thereby, the interaction is improved by the formation of the conduction path of the electron conduction path and the ion conduction path, and the utilization rate of the active material of the positive electrode can be improved.

また、本発明は、前記活物質粒子（２２）と前記固体電解質（２５）と前記導電材（２４）とを含む正極固体電解質部（２０）と、前記正極固体電解質部を外部と電気的に接続する正極集電体（２１）と、を備える正極構成を有し、前記正極固体電解質部において、前記正極固体電解質部の重量に対する前記活物質粒子の重量の比率を、重量比ｘとするとき、前記重量比ｘを、ｘ≧０．６５とし、かつ前記導電材の重量に対する前記固体電解質の重量の比率を、重量比ｙとするとき、前記重量比ｙを、２．５≦ｙ≦４．０の範囲としたものである。   The present invention also provides a positive electrode solid electrolyte part (20) including the active material particles (22), the solid electrolyte (25), and the conductive material (24), and the positive electrode solid electrolyte part electrically connected to the outside. A positive electrode current collector (21) to be connected, and in the positive electrode solid electrolyte part, the ratio of the weight of the active material particles to the weight of the positive electrode solid electrolyte part is a weight ratio x When the weight ratio x is x ≧ 0.65 and the ratio of the weight of the solid electrolyte to the weight of the conductive material is the weight ratio y, the weight ratio y is 2.5 ≦ y ≦ 4. .0 range.

これによって、電子伝導パス、イオン伝導パスの相互作用が向上して、正極の活物質利用率を９０％以上とすることが可能となるとともに、高分子固体電解質電池全体としての電池容量を安定化することが可能になる。   As a result, the interaction between the electron conduction path and the ion conduction path is improved, the active material utilization rate of the positive electrode can be increased to 90% or more, and the battery capacity of the entire polymer solid electrolyte battery is stabilized. It becomes possible to do.

また、本発明は、前記導電材（２４）には炭素繊維の含有有無によらずアセチレンブラックを５０％以上含むことを特徴とするものである。   Moreover, this invention is characterized by including 50% or more of acetylene black in the said electrically conductive material (24) irrespective of the presence or absence of carbon fiber.

これによって、導電材として気相法炭素繊維のような高価な材料を用いることなく、正極の活物質利用率を向上させて、低コストの高分子固体電解質電池を製造することが可能となる。   This makes it possible to produce a low-cost polymer solid electrolyte battery by improving the active material utilization rate of the positive electrode without using an expensive material such as vapor grown carbon fiber as the conductive material.

また、本発明は、前記導電材（２４）が炭素繊維を更に含むようにしたものである。   In the present invention, the conductive material (24) further includes carbon fiber.

また、導電材として比較的安価なカーボンナノチューブを併用することで、正極の活物質利用率を向上させて、低コストの高分子固体電解質電池を製造することが可能となる。   In addition, by using a relatively inexpensive carbon nanotube as a conductive material, it is possible to improve the active material utilization rate of the positive electrode and manufacture a low-cost polymer solid electrolyte battery.

このように本発明を活用することにより、正極活物質利用率を向上させて、安定した充放電容量を備える高分子固体電解質電池を提供することが可能となる。   Thus, by utilizing the present invention, it is possible to improve the utilization rate of the positive electrode active material and provide a polymer solid electrolyte battery having a stable charge / discharge capacity.

本発明に係る高分子固体電解質電池の概略構成を示す構成図The block diagram which shows schematic structure of the polymer solid electrolyte battery which concerns on this invention イオン伝導性高分子であるＰＥＯ（ポリエチレンオキシド）およびＰＥＯ−ＥＭの温度に対する電気伝導率を示すグラフGraph showing electric conductivity with respect to temperature of ion conductive polymer PEO (polyethylene oxide) and PEO-EM （ａ）実施例１で作成した製作セルの充放電特性を示すグラフ(A) The graph which shows the charge / discharge characteristic of the production cell created in Example 1 （ｂ）比較例で作成した製作セルの充放電特性を示すグラフ(B) Graph showing the charge / discharge characteristics of the production cell created in the comparative example （ａ）実施例２で作成した製作セルの充放電特性を示すグラフ(A) Graph showing the charge / discharge characteristics of the production cell prepared in Example 2 （ｂ）比較例で作成した製作セルの充放電特性を示すグラフ(B) Graph showing the charge / discharge characteristics of the production cell created in the comparative example バインダーと導電材との重量比ｙを変化させた際の、正極活物質の単位重量あたりの電池容量の変化を示すグラフThe graph which shows the change of the battery capacity per unit weight of a positive electrode active material when changing the weight ratio y of a binder and a electrically conductive material.

以下、本発明の実施形態について、図面を参照しながら説明する。図１は、本発明に係る高分子固体電解質電池１の概略構成を示す構成図である。図１に示すように、高分子固体電解質電池１は、正極２と、負極３と、正極２および負極３に挟持された高分子電解質膜４とで構成される。   Hereinafter, embodiments of the present invention will be described with reference to the drawings. FIG. 1 is a configuration diagram showing a schematic configuration of a polymer solid electrolyte battery 1 according to the present invention. As shown in FIG. 1, the polymer solid electrolyte battery 1 includes a positive electrode 2, a negative electrode 3, and a polymer electrolyte membrane 4 sandwiched between the positive electrode 2 and the negative electrode 3.

正極２は、正極集電体２１と、コート層２３によって被覆された粒子状の正極活物質２２と、導電材２４と、固体電解質を兼ねるバインダー２５とを含んでいる（以降、正極活物質２２と導電材２４とバインダー２５とを含む部分を正極固体電解質部２０と呼称することがある）。バインダー２５は、正極活物質２２および導電材２４を分散された状態で保持するとともにイオン伝導性を備える。なお、正極固体電解質部２０においては、実際は、正極活物質２２が最密充填された構造となっており、正極活物質２２同士の隙間を埋めるように、バインダー２５（ポリマー）の中に微細な粒子状の導電材２４が均質に分散されている状態で充填されている。また正極固体電解質部２０は、後述するように塗布によって正極集電体２１の表面に形成するために、粘度調製用のアセトニトリル等が加えられており、微量ではあるが正極活物質２２、導電材２４、バインダー２５以外の成分を含む。   The positive electrode 2 includes a positive electrode current collector 21, a particulate positive electrode active material 22 covered with a coat layer 23, a conductive material 24, and a binder 25 that also serves as a solid electrolyte (hereinafter, positive electrode active material 22). The portion including the conductive material 24 and the binder 25 may be referred to as the positive electrode solid electrolyte portion 20). The binder 25 holds the positive electrode active material 22 and the conductive material 24 in a dispersed state and has ion conductivity. The positive electrode solid electrolyte part 20 actually has a structure in which the positive electrode active material 22 is closely packed, and a fine amount is contained in the binder 25 (polymer) so as to fill the gap between the positive electrode active materials 22. The particulate conductive material 24 is filled in a uniformly dispersed state. In addition, the positive electrode solid electrolyte portion 20 is added with acetonitrile for viscosity adjustment in order to be formed on the surface of the positive electrode current collector 21 by coating as will be described later. 24, components other than the binder 25 are included.

正極集電体２１は、正極固体電解質部２０と外部とを電気的に接合する部材であるとともに、電流を正極活物質２２に供給する。正極集電体２１の素材としては導電性を有する材料が好ましく、Ａｌ、Ｎｉ、Ｔｉ、ステンレス鋼等を用いることができる。本実施形態では、正極集電体２１としてＡｌ箔を用いている。   The positive electrode current collector 21 is a member that electrically joins the positive electrode solid electrolyte part 20 and the outside, and supplies current to the positive electrode active material 22. The material of the positive electrode current collector 21 is preferably a conductive material, and Al, Ni, Ti, stainless steel, or the like can be used. In the present embodiment, an Al foil is used as the positive electrode current collector 21.

負極３は、負極集電体３１と、粒子状の負極活物質３２と、導電材３３と、バインダー３４とで構成されている。負極集電体３１の素材としては、Ｃｕ、Ｎｉ、Ｔｉ、ステンレス等を単独で、あるいは２種以上を組み合わせて用いることができる。   The negative electrode 3 includes a negative electrode current collector 31, a particulate negative electrode active material 32, a conductive material 33, and a binder 34. As a material of the negative electrode current collector 31, Cu, Ni, Ti, stainless steel, or the like can be used alone or in combination of two or more.

正極活物質２２は、オリビン型リン酸リチウムを粒子状に加工したものである。正極活物質２２を構成するオリビン型リン酸リチウムは、一般式がＬｉＭＰＯ４（ＭはＣｏ、Ｎｉ、Ｍｎ、Ｆｅの群から選択される金属元素を１種類、または２種以上を混合したもの）で表されるリチウム複合化合物である。 The positive electrode active material 22 is obtained by processing olivine type lithium phosphate into particles. The olivine-type lithium phosphate constituting the positive electrode active material 22 has a general formula of LiMPO 4 (M is a metal element selected from the group of Co, Ni, Mn, and Fe, or a mixture of two or more) It is a lithium composite compound represented by these.

特にＭとして産出量が多く安価なＦｅを用いることで、高分子固体電解質電池１の生産コストを低減できる可能性があり、かつ毒性がないため安全性に優れることから、本実施形態では主に、正極活物質２２としてＬｉＦｅＰＯ４（オリビン型リン酸鉄リチウム）を用いている。 In particular, in the present embodiment, since the production cost of the polymer solid electrolyte battery 1 may be reduced by using Fe which is a large amount of output and is inexpensive as M, and is excellent in safety because it is not toxic. LiFePO 4 (olivine type lithium iron phosphate) is used as the positive electrode active material 22.

ＬｉＦｅＰＯ４粒子の製造方法としては、シュウ酸鉄や酢酸鉄を出発原料とした固相法、リン酸鉄を原料とした固相法や、より微細な粒子を得るためのゾルゲル法や、水熱法などがあるが、本実施例では固相法で得たものを用いた。 The production method of LiFePO 4 particles includes a solid phase method using iron oxalate and iron acetate as a starting material, a solid phase method using iron phosphate as a raw material, a sol-gel method for obtaining finer particles, hydrothermal method, In this example, the one obtained by the solid phase method was used.

オリビン型リン酸リチウムで構成される正極活物質２２は、それ自体では導電性がないが、コート層２３をカーボンコート層とすることで、正極活物質２２の表面に電子を供給することができる。   The positive electrode active material 22 composed of olivine-type lithium phosphate is not conductive by itself, but can supply electrons to the surface of the positive electrode active material 22 by using the coat layer 23 as a carbon coat layer. .

導電材２４は、正極材料用の導電助剤であって電子伝導性を有している。ここでは、アセチレンブラック、または、アセチレンブラックとカーボンナノチューブ（炭素繊維）の混合物を用いることができる。アセチレンブラックは、カーボンブラックの一種でアセチレンの熱分解によって製造される。   The conductive material 24 is a conductive aid for the positive electrode material and has electronic conductivity. Here, acetylene black or a mixture of acetylene black and carbon nanotube (carbon fiber) can be used. Acetylene black is a kind of carbon black and is produced by thermal decomposition of acetylene.

また、カーボンナノチューブとしては、市場で入手可能なもので構わない。例えば、分散溶媒ＮＭＰ系、濃度：１，３重量％の界面活性剤添加物を用いることができる。   Carbon nanotubes may be commercially available. For example, a surfactant additive having a dispersion solvent NMP system and a concentration of 1,3% by weight can be used.

導電材２４としてアセチレンブラックのみ、あるいは上述したカーボンナノチューブおよびアセチレンブラックの混合物を用いた場合、後述する製造工程によってバインダー２５中の分散性を向上させることができ、電子伝導経路が形成されやすくなる。   When only acetylene black or a mixture of the above-mentioned carbon nanotube and acetylene black is used as the conductive material 24, the dispersibility in the binder 25 can be improved by a manufacturing process described later, and an electron conduction path is easily formed.

バインダー２５は、イオン伝導性を有するＰＥＯ−ＥＭ（エチルメチルオキシドが側鎖に付されたポリエチレンオキシド）からなる固体電解質である。本実施形態では、イオン伝導性を有する高分子材料で形成された固体電解質をバインダー２５と兼用している。   The binder 25 is a solid electrolyte made of PEO-EM (polyethylene oxide having ethylmethyl oxide attached to the side chain) having ion conductivity. In the present embodiment, a solid electrolyte formed of a polymer material having ion conductivity is also used as the binder 25.

図２は、イオン伝導性高分子であるＰＥＯ（ポリエチレンオキシド）およびＰＥＯ−ＥＭの温度に対する電気伝導率を示すグラフである。図２に示すように、ＰＥＯおよびＰＥＯ−ＥＭは８０〜４０℃まではほぼ同等の電気伝導度を有するが、３０℃より低温になるとＰＥＯ−ＥＭの優位性が明らかとなり、０℃においては、ＰＥＯ−ＥＭはＰＥＯの１００倍程度の電気伝導度を示す。このように本実施形態では、バインダー兼固体電解質として、イオン伝導性高分子を用いることで、３０℃以下の高分子固体電解質電池の特性を大幅に向上させることができる。   FIG. 2 is a graph showing the electric conductivity with respect to temperature of PEO (polyethylene oxide) and PEO-EM which are ion conductive polymers. As shown in FIG. 2, PEO and PEO-EM have substantially the same electrical conductivity from 80 to 40 ° C., but the advantage of PEO-EM becomes clear when the temperature is lower than 30 ° C. At 0 ° C., PEO-EM exhibits an electric conductivity about 100 times that of PEO. Thus, in this embodiment, the characteristics of a polymer solid electrolyte battery at 30 ° C. or lower can be greatly improved by using an ion conductive polymer as the binder and solid electrolyte.

以降、図１に戻って説明を続ける。負極活物質３２として、炭素系活物質と、金属、金属塩、または酸化物等との混合物や、炭素系活物質の粒子表面を、金属、金属塩、または酸化物等で被覆したものを用いてもよい。無機系活物質としては、Ｓｉ、Ｓｎ、Ｚｎ、Ｍｎ、Ｆｅ、Ｎｉ等の酸化物や硫酸塩、リチウム金属、チタン酸リチウム等を使用することができる。   Hereinafter, returning to FIG. 1, the description will be continued. As the negative electrode active material 32, a mixture of a carbon-based active material and a metal, a metal salt, or an oxide, or a particle surface of a carbon-based active material coated with a metal, a metal salt, or an oxide is used. May be. As the inorganic active material, oxides such as Si, Sn, Zn, Mn, Fe, Ni, sulfates, lithium metal, lithium titanate, and the like can be used.

負極３は、負極活物質３２として難黒鉛化性炭素、導電材３３としてアセチレンブラック、バインダー３４としてポリフッ化ビニリデン（ＰＶｄＦ）、分散媒としてカーボンナノチューブ（炭素繊維）とで構成される。これらの負極材料を混合しスラリーを調製する。このスラリーを負極集電体３１に塗布し、乾燥させた後にプレス処理を行なうことで、負極３が得られる。   The negative electrode 3 is composed of non-graphitizable carbon as the negative electrode active material 32, acetylene black as the conductive material 33, polyvinylidene fluoride (PVdF) as the binder 34, and carbon nanotubes (carbon fibers) as the dispersion medium. These negative electrode materials are mixed to prepare a slurry. The slurry is applied to the negative electrode current collector 31, dried, and then subjected to a press treatment, whereby the negative electrode 3 is obtained.

高分子電解質膜４は、正極２と負極３とに挟持されている電解質シートである。高分子電解質膜４には電気伝導性を有する材料が求められ、本実施形態では、ポリ（エチレンオキサイド／末端をメトキシで置換したエチレンオキサイド／アリルグリシジルエーテル）共重合体（Ｐ（ＥＯ／ＥＭ／ＡＧＥ））等のポリエーテル共重合体を用いている。   The polymer electrolyte membrane 4 is an electrolyte sheet that is sandwiched between the positive electrode 2 and the negative electrode 3. The polymer electrolyte membrane 4 is required to have a material having electrical conductivity. In this embodiment, a poly (ethylene oxide / ethylene oxide / allyl glycidyl ether having a terminal substituted with methoxy) copolymer (P (EO / EM / EM) is used. A polyether copolymer such as AGE)) is used.

このように構成された高分子固体電解質電池１を充電すると、正極２の中のリチウムイオンが引き抜かれ、正極固体電解質部２０および高分子電解質膜４中を移動して負極３の中に吸収される。高分子固体電解質電池１を放電すると、逆に負極３からリチウムイオンが放出されて正極２に入る。この時に、外部に電気エネルギーが取り出される。   When the polymer solid electrolyte battery 1 configured in this way is charged, lithium ions in the positive electrode 2 are extracted, moved through the positive electrode solid electrolyte portion 20 and the polymer electrolyte membrane 4 and absorbed into the negative electrode 3. The When the polymer solid electrolyte battery 1 is discharged, lithium ions are released from the negative electrode 3 and enter the positive electrode 2. At this time, electric energy is extracted to the outside.

以降、本発明の作用効果について実施例に基づいて説明する。
［実施例１］
正極活物質２２としてＬｉＦｅＰＯ４、導電材２４としてアセチレンブラック、イオン伝導性のバインダー２５として、ＰＥＯ−ＥＭ−ＬｉＴＦＳＩを用いた。正極活物質２２／バインダー２５／導電材２４の重量比を６５／２５／１０とし、これらの正極材料をアセトニトリル中に導入、撹拌してスラリーを調製し、アルミニウム製の正極集電体２１上に塗布して正極シート（正極２。以下同じ）を得た。このようにして作成した正極シートは乾燥を行った後、アルゴン雰囲気下のグローブボックスに保存した。セル作製時は正極シート、高分子電解質膜４（電解質シート）、負極３を所定のサイズにカットし、貼り合わせた後、電極タブを設けたラミネート袋に封入し高分子固体電解質電池１を製作した。なお実施例１では、負極３として参照極の役割を果たすリチウム金属を使用し、電解質シートを正極シートと参照極で挟んだ構成を用いて正極２の評価を行っている（以降の各実施例、比較例についても同じ）。また、製作した電池の厚みは約３０μｍである（以降の各実施例、比較例についても同じ）。なお、以降、製作した電池を製作セルと呼称することがある。 Hereinafter, the function and effect of the present invention will be described based on examples.
[Example 1]
LiFePO 4 was used as the positive electrode active material 22, acetylene black was used as the conductive material 24, and PEO-EM-LiTFSI was used as the ion conductive binder 25. The weight ratio of the positive electrode active material 22 / binder 25 / conductive material 24 is 65/25/10, and these positive electrode materials are introduced into acetonitrile and stirred to prepare a slurry, which is then placed on the positive electrode current collector 21 made of aluminum. Application was performed to obtain a positive electrode sheet (positive electrode 2, the same applies hereinafter). The positive electrode sheet thus prepared was dried and then stored in a glove box under an argon atmosphere. At the time of cell preparation, the positive electrode sheet, the polymer electrolyte membrane 4 (electrolyte sheet), and the negative electrode 3 are cut into a predetermined size and bonded together, and then sealed in a laminate bag provided with electrode tabs to produce a solid polymer electrolyte battery 1 did. In Example 1, lithium metal that serves as a reference electrode is used as the negative electrode 3, and the positive electrode 2 is evaluated using a configuration in which an electrolyte sheet is sandwiched between the positive electrode sheet and the reference electrode (each of the following examples) The same applies to the comparative example). Moreover, the thickness of the manufactured battery is about 30 μm (the same applies to each of the following examples and comparative examples). Hereinafter, the manufactured battery may be referred to as a manufacturing cell.

［実施例２］
正極活物質２２としてＬｉＦｅＰＯ４、導電材２４としてアセチレンブラックとカーボンナノチューブの１：１混合物、イオン伝導性のバインダー２５として、ＰＥＯ−ＥＭ−ＬｉＴＦＳＩを用いた。 [Example 2]
LiFePO 4 was used as the positive electrode active material 22, a 1: 1 mixture of acetylene black and carbon nanotubes was used as the conductive material 24, and PEO-EM-LiTFSI was used as the ion conductive binder 25.

以降、実施例２〜１０の高分子固体電解質電池１に係る正極２の製造工程について説明する。まず、導電材２４としてカーボンナノチューブおよびアセチレンブラックを混合する。その後、混合された導電材２４とバインダー２５兼固体電解質であるＰＥＯ−ＥＭ−ＬｉＴＦＳＩと粘度調整用のアセトニトリルとを投入して混練する。これにさらに正極活物質２２としてＬｉＦｅＰＯ４粒子を加え、混練してスラリーを調製する。 Hereafter, the manufacturing process of the positive electrode 2 which concerns on the polymer solid electrolyte battery 1 of Examples 2-10 is demonstrated. First, carbon nanotubes and acetylene black are mixed as the conductive material 24. Thereafter, the mixed conductive material 24, PEO-EM-LiTFSI as the binder 25 and solid electrolyte, and acetonitrile for viscosity adjustment are added and kneaded. Further, LiFePO 4 particles are added as the positive electrode active material 22 and kneaded to prepare a slurry.

実施例２においてのスラリーを調製する際の重量比としては、正極活物質２２／バインダー２５／導電材２４を６５／２５／１０とした。（実施例３〜実施例１０について重量比は後述する）。調製したスラリーを、正極集電体２１上に塗布して正極シートを得た。このようにして作成した正極シートは、乾燥を行った後、アルゴン雰囲気下に保存した。セル作製時は正極シート、電解質シート、負極３を所定のサイズにカットし、貼り合わせた後、電極タブを設けたラミネート袋に封入し高分子固体電解質電池を製作した。   As a weight ratio at the time of preparing the slurry in Example 2, the positive electrode active material 22 / binder 25 / conductive material 24 was set to 65/25/10. (The weight ratio of Examples 3 to 10 will be described later). The prepared slurry was applied onto the positive electrode current collector 21 to obtain a positive electrode sheet. The positive electrode sheet thus prepared was dried and then stored in an argon atmosphere. At the time of cell preparation, the positive electrode sheet, the electrolyte sheet, and the negative electrode 3 were cut into a predetermined size and bonded together, and then sealed in a laminate bag provided with an electrode tab to produce a polymer solid electrolyte battery.

［比較例］
正極活物質２２としてＬｉＦｅＰＯ４、導電材２４として気相法炭素繊維、イオン伝導性のバインダー２５として、ＰＥＯ−ＥＭ−ＬｉＴＦＳＩを用いた。正極活物質２２／バインダー２５／導電材２４の重量比を６５／２５／１０とし、アセトニトリル中で撹拌してスラリーを調製し、正極集電体２１上に塗布して正極シートを得た。作成した正極シートは、乾燥を行った後、アルゴン雰囲気下に保存した。セル作製時は正極シート、電解質シート、負極３を所定のサイズにカットし、貼り合わせた後、電極タブを設けたラミネート袋に封入し高分子固体電解質電池を製作した。 [Comparative example]
LiFePO 4 was used as the positive electrode active material 22, vapor grown carbon fiber was used as the conductive material 24, and PEO-EM-LiTFSI was used as the ion conductive binder 25. A weight ratio of positive electrode active material 22 / binder 25 / conductive material 24 was set to 65/25/10, and the mixture was stirred in acetonitrile to prepare a slurry, which was applied onto the positive electrode current collector 21 to obtain a positive electrode sheet. The prepared positive electrode sheet was dried and then stored in an argon atmosphere. At the time of cell preparation, the positive electrode sheet, the electrolyte sheet, and the negative electrode 3 were cut into a predetermined size and bonded together, and then sealed in a laminate bag provided with an electrode tab to produce a polymer solid electrolyte battery.

実施例１、２および比較例で作成した製作セルについて、２．５−４．０［Ｖ］、６０℃の条件下で充放電試験を実施した。   About the production cell created in Example 1, 2 and the comparative example, the charge / discharge test was implemented on condition of 2.5-4.0 [V] and 60 degreeC.

図３（ａ）は、実施例１で作成した製作セルの充放電特性を示すグラフ、同（ｂ）は、比較例で作成した製作セルの充放電特性を示すグラフである。図３において、横軸は正極活物質２２の単位重量あたりの電池容量（充放電容量）であり、縦軸は充電ないし放電電圧である。図３（ａ）に示すように、実施例１に基づく製作セルは３回の充放電を経ても、放電容量は、１５５［ｍＡｈ／ｇ］を維持しているが、比較例では充放電を繰り返すほど放電容量が減少し、３回目の放電時においては１０２［ｍＡｈ／ｇ］にまで低下していることがわかる。   FIG. 3A is a graph showing the charge / discharge characteristics of the production cell created in Example 1, and FIG. 3B is a graph showing the charge / discharge characteristics of the production cell produced in the comparative example. In FIG. 3, the horizontal axis represents the battery capacity (charge / discharge capacity) per unit weight of the positive electrode active material 22, and the vertical axis represents the charge or discharge voltage. As shown in FIG. 3 (a), the manufactured cell based on Example 1 maintains the discharge capacity of 155 [mAh / g] even after being charged and discharged three times. It can be seen that the discharge capacity decreases with repetition and decreases to 102 [mAh / g] at the time of the third discharge.

図４（ａ）は、実施例２で作成した製作セルの充放電特性を示すグラフ、同（ｂ）は、比較例で作成した製作セルの充放電特性を示すグラフである。なお、図４（ｂ）は図３（ｂ）で示したグラフと同一のものである。図４（ａ）に示すように、実施例２に基づく製作セルにおいても、３回の充放電を経た後も、電池容量（放電容量）は、１５５［ｍＡｈ／ｇ］を維持していることがわかる。   FIG. 4A is a graph showing the charge / discharge characteristics of the production cell produced in Example 2, and FIG. 4B is a graph showing the charge / discharge characteristics of the production cell produced in the comparative example. FIG. 4B is the same as the graph shown in FIG. As shown in FIG. 4 (a), in the production cell based on Example 2, the battery capacity (discharge capacity) is maintained at 155 [mAh / g] even after being charged and discharged three times. I understand.

［実施例３〜１０］
正極活物質２２としてＬｉＦｅＰＯ４、導電材２４としてアセチレンブラックとカーボンナノチューブの１：１混合物、イオン伝導性のバインダー２５として、ＰＥＯ−ＥＭ−ＬｉＴＦＳＩを用いた。実施例３〜１０における正極活物質２２／バインダー２５／導電材２４の重量比を表１に示す。なお、表１には、参考として実施例１、実施例２における重量比も併記している。 [Examples 3 to 10]
LiFePO 4 was used as the positive electrode active material 22, a 1: 1 mixture of acetylene black and carbon nanotubes was used as the conductive material 24, and PEO-EM-LiTFSI was used as the ion conductive binder 25. The weight ratio of positive electrode active material 22 / binder 25 / conductive material 24 in Examples 3 to 10 is shown in Table 1. In Table 1, the weight ratios in Examples 1 and 2 are also shown for reference.

Figure 2015056282
Figure 2015056282

表１に示すように、固体電解質であるバインダー２５：導電材２４＝ｙ：１の重量比ｙ（即ち、重量比ｙ＝固体電解質の重量／導電材２４の重量）をｙ＝１．５〜５．０の範疇になるようにし、正極活物質２２とともにアセトニトリル中にて撹拌してスラリーを調製し、正極集電体２１上に塗布して正極シートを得た。このようにして作成した正極シートは乾燥を行った後、アルゴン雰囲気下に保存した。セル作製時は正極シート、電解質シート、負極３を所定のサイズにカットし、貼り合わせた後、電極タブを設けたラミネート袋に封入し高分子固体電解質電池１を製作した。   As shown in Table 1, a solid electrolyte binder 25: conductive material 24 = y: 1 weight ratio y (that is, weight ratio y = weight of solid electrolyte / weight of conductive material 24) is set to y = 1.5 to A slurry was prepared by stirring in acetonitrile together with the positive electrode active material 22 so as to be in the range of 5.0, and applied to the positive electrode current collector 21 to obtain a positive electrode sheet. The positive electrode sheet thus prepared was dried and then stored in an argon atmosphere. At the time of cell preparation, the positive electrode sheet, the electrolyte sheet, and the negative electrode 3 were cut to a predetermined size and bonded together, and then sealed in a laminate bag provided with electrode tabs to produce a polymer solid electrolyte battery 1.

なお、各実施例では、導電材２４とバインダー２５と正極活物質２２とを含む正極固体電解質部２０（図１参照）の全体重量（Ｗｈ）に対する正極活物質２２の重量（Ｗａ）の比率（重量比ｘ＝Ｗａ／Ｗｈ）が０．６５（６５％）以上となるようにしている。なお、比較例についても、正極活物質２２の重量比ｘは６５％としている。そして上述した重量比ｙは、導電材２４の重量（Ｗｂ）に対する固体電解質（バインダー２５）の重量（Ｗｃ）の比率（重量比ｙ＝Ｗｃ/Ｗｂ）である。   In each example, the ratio of the weight (Wa) of the positive electrode active material 22 to the total weight (Wh) of the positive electrode solid electrolyte portion 20 (see FIG. 1) including the conductive material 24, the binder 25, and the positive electrode active material 22 ( The weight ratio x = Wa / Wh) is set to 0.65 (65%) or more. In the comparative example, the weight ratio x of the positive electrode active material 22 is 65%. The weight ratio y described above is a ratio of the weight (Wc) of the solid electrolyte (binder 25) to the weight (Wb) of the conductive material 24 (weight ratio y = Wc / Wb).

実施例３〜１０で作成した製作セルについても、２．５−４．０［Ｖ］、６０℃の条件下で充放電試験を行って正極活物質２２の単位重量あたりの電池容量（充放電容量）を算出した。   The production cells prepared in Examples 3 to 10 were also subjected to a charge / discharge test under the conditions of 2.5 to 4.0 [V] and 60 ° C., and the battery capacity per unit weight (charge / discharge) Volume) was calculated.

図５は、横軸に重量比ｙをとり、縦軸に正極活物質２２の単位重量あたりの電池容量をプロットしたものである。   In FIG. 5, the horizontal axis represents the weight ratio y, and the vertical axis represents the battery capacity per unit weight of the positive electrode active material 22.

ここで改めて活物質利用率について説明を加える。活物質利用率とは充放電試験により評価した電池容量と、正極２に含まれる正極活物質２２の理論容量の比率をいう。なお、理論容量とは、構成材料種による純粋な電気化学反応において電極が蓄えることができる最大の電気量であり、ＬｉＦｅＰＯ４では１７０ｍＡｈ／ｇである。従って、正極活物質２２としてＬｉＦｅＰＯ４を採用した場合、電池容量が１５３［ｍＡｈ／ｇ］のときに活物質利用率は９０％となり、電池容量が１４５［ｍＡｈ／ｇ］のときに活物質利用率は８５％となる。 Here, the active material utilization rate will be explained again. The active material utilization rate refers to the ratio between the battery capacity evaluated by the charge / discharge test and the theoretical capacity of the positive electrode active material 22 included in the positive electrode 2. The theoretical capacity is the maximum amount of electricity that the electrode can store in a pure electrochemical reaction depending on the constituent material type, and is 170 mAh / g for LiFePO 4 . Therefore, when LiFePO 4 is employed as the positive electrode active material 22, the active material utilization rate is 90% when the battery capacity is 153 [mAh / g], and the active material utilization is performed when the battery capacity is 145 [mAh / g]. The rate is 85%.

図５に示すように、重量比ｙを変化させたとき、各製作セルの放電容量分布は上に凸の曲線を描き、重量比ｙ＝３．２５近傍で放電容量のピークが存在する。そして、重量比ｙを２．０≦ｙ≦４．６１の範囲としたときに活物質利用率は８５％以上となり、更に、重量比ｙを２．５≦ｙ≦４．０の範囲としたときに活物質利用率は９０％以上となる。   As shown in FIG. 5, when the weight ratio y is changed, the discharge capacity distribution of each manufactured cell draws a convex curve upward, and a discharge capacity peak exists in the vicinity of the weight ratio y = 3.25. When the weight ratio y is in the range of 2.0 ≦ y ≦ 4.61, the active material utilization is 85% or more, and the weight ratio y is in the range of 2.5 ≦ y ≦ 4.0. Sometimes the active material utilization is 90% or more.

このように本発明では、導電材２４（図１参照）として高価な気相法炭素繊維等を用いることなく、汎用材料で安価なアセチレンブラックを５０％以上含ませることで、正極２の活物質利用率を９０％以上とすることができる。   As described above, in the present invention, the active material of the positive electrode 2 is obtained by including 50% or more of acetylene black which is a general-purpose material without using an expensive vapor grown carbon fiber or the like as the conductive material 24 (see FIG. 1). The utilization rate can be 90% or more.

更に、重量比ｙを、２．５≦ｙ≦４．０の範囲とすることで、活物質利用率が９０％を越える、更に高効率の高分子固体電解質電池１を提供することができる。具体的活用例として、活物質利用率が大きいほど同一重量ではより多くの電気を蓄えることができ高分子固体電解質電池１の軽量化に貢献できることになる。   Furthermore, by setting the weight ratio y in the range of 2.5 ≦ y ≦ 4.0, it is possible to provide a more efficient polymer solid electrolyte battery 1 in which the active material utilization rate exceeds 90%. As a specific application example, the larger the active material utilization rate, the more the electricity can be stored with the same weight, which can contribute to the weight reduction of the polymer solid electrolyte battery 1.

以上で具体的実施形態についての説明を終えるが、本発明は上記実施形態に限定されるものではなく、発明の趣旨を逸脱しない範囲であれば適宜変更可能である。例えば、上述した高分子固体電解質電池１を複数段に積層して１つのセルとして構成してもよいし、図１に示す平板状の高分子固体電解質電池１を、絶縁シートを介在させたうえでロール状に巻回して円筒形状の電池を構成してもよい。また、実施形態に示した本発明に係る高分子固体電解質電池１の各構成要素は、必ずしも全てが必須ではなく、適宜取捨選択可能である。   Although the description of the specific embodiment is finished as described above, the present invention is not limited to the above-described embodiment, and can be changed as appropriate without departing from the spirit of the invention. For example, the polymer solid electrolyte battery 1 described above may be laminated in a plurality of stages to constitute one cell, or the flat polymer solid electrolyte battery 1 shown in FIG. A cylindrical battery may be formed by winding in a roll. In addition, all the constituent elements of the polymer solid electrolyte battery 1 according to the present invention shown in the embodiments are not necessarily essential, and can be appropriately selected.

１ 高分子固体電解質電池
２ 正極
３ 負極
４ 高分子電解質膜
２０ 正極固体電解質部
２１ 正極集電体
２２ 正極活物質（活物質粒子）
２３ コート層
２４ 導電材
２５ バインダー（固体電解質）
３１ 負極集電体
３２ 負極活物質
３３ 導電材
３４ バインダー DESCRIPTION OF SYMBOLS 1 Polymer solid electrolyte battery 2 Positive electrode 3 Negative electrode 4 Polymer electrolyte membrane 20 Positive electrode solid electrolyte part 21 Positive electrode collector 22 Positive electrode active material (active material particle)
23 Coat layer 24 Conductive material 25 Binder (solid electrolyte)
31 Negative electrode current collector 32 Negative electrode active material 33 Conductive material 34 Binder

Claims (5)

正極と負極との間に高分子電解質膜を挟持した固体高分子電解質電池であって、
前記正極の構成として、
オリビン型リン酸リチウム（ＬｉＭＰＯ４（ただし、ＭはＣｏ、Ｎｉ、ＭｎおよびＦｅの群から選択される少なくとも１種である））からなる活物質粒子と、
イオン伝導性を有するＰＥＯ−ＥＭ（エチルメチルオキシドが側鎖に付されたポリエチレンオキシド）からなる固体電解質と、
電子伝導性を有する導電材と、
を有することを特徴とする高分子固体電解質電池。 A solid polymer electrolyte battery having a polymer electrolyte membrane sandwiched between a positive electrode and a negative electrode,
As a configuration of the positive electrode,
Active material particles composed of olivine-type lithium phosphate (LiMPO 4 (where M is at least one selected from the group consisting of Co, Ni, Mn and Fe));
A solid electrolyte made of PEO-EM (polyethylene oxide having ethylmethyl oxide attached to the side chain) having ionic conductivity;
A conductive material having electron conductivity;
A polymer solid electrolyte battery comprising: 前記活物質粒子と前記固体電解質と前記導電材とを含む正極固体電解質部と、前記正極固体電解質部を外部と電気的に接続する正極集電体と、を備える正極構成を有し、
前記正極固体電解質部において、
前記正極固体電解質部の重量に対する前記活物質粒子の重量の比率を、重量比ｘとするとき、前記重量比ｘを、ｘ≧０．６５とし、かつ
前記導電材の重量に対する前記固体電解質の重量の比率を、重量比ｙとするとき、前記重量比ｙを、２．０≦ｙ≦４．０の範囲としたことを特徴とする請求項１に記載の高分子固体電解質電池。 A positive electrode configuration comprising: a positive electrode solid electrolyte portion including the active material particles, the solid electrolyte, and the conductive material; and a positive electrode current collector that electrically connects the positive electrode solid electrolyte portion to the outside.
In the positive electrode solid electrolyte part,
When the ratio of the weight of the active material particles to the weight of the positive electrode solid electrolyte part is a weight ratio x, the weight ratio x is x ≧ 0.65, and the weight of the solid electrolyte with respect to the weight of the conductive material 2. The polymer solid electrolyte battery according to claim 1, wherein the weight ratio y is in a range of 2.0 ≦ y ≦ 4.0, where the weight ratio y is a weight ratio y. 前記活物質粒子と前記固体電解質と前記導電材とを含む正極固体電解質部と、前記正極固体電解質部を外部と電気的に接続する正極集電体と、を備える正極構成を有し、
前記正極固体電解質部において、
前記正極固体電解質部の重量に対する前記活物質粒子の重量の比率を、重量比ｘとするとき、前記重量比ｘを、ｘ≧０．６５とし、かつ
前記導電材の重量に対する前記固体電解質の重量の比率を、重量比ｙとするとき、前記重量比ｙを、２．５≦ｙ≦４．０の範囲としたことを特徴とする請求項１に記載の高分子固体電解質電池。 A positive electrode configuration comprising: a positive electrode solid electrolyte portion including the active material particles, the solid electrolyte, and the conductive material; and a positive electrode current collector that electrically connects the positive electrode solid electrolyte portion to the outside.
In the positive electrode solid electrolyte part,
When the ratio of the weight of the active material particles to the weight of the positive electrode solid electrolyte part is a weight ratio x, the weight ratio x is x ≧ 0.65, and the weight of the solid electrolyte with respect to the weight of the conductive material 2. The polymer solid electrolyte battery according to claim 1, wherein the weight ratio y is in a range of 2.5 ≦ y ≦ 4.0, where the weight ratio y is a weight ratio y. 前記導電材には炭素繊維の含有有無によらずアセチレンブラックを５０％以上含むことを特徴とする請求項１ないし請求項３のいずれか１項に記載の高分子固体電解質電池。   The polymer solid electrolyte battery according to any one of claims 1 to 3, wherein the conductive material contains 50% or more of acetylene black regardless of the presence or absence of carbon fiber. 前記導電材が炭素繊維を更に含むことを特徴とする請求項４に記載の高分子固体電解質電池。   The polymer solid electrolyte battery according to claim 4, wherein the conductive material further contains carbon fiber.
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