JPH0935705A - Polymer electrolyte-lithium battery and manufacture of its electrode - Google Patents
Polymer electrolyte-lithium battery and manufacture of its electrodeInfo
- Publication number
- JPH0935705A JPH0935705A JP7179835A JP17983595A JPH0935705A JP H0935705 A JPH0935705 A JP H0935705A JP 7179835 A JP7179835 A JP 7179835A JP 17983595 A JP17983595 A JP 17983595A JP H0935705 A JPH0935705 A JP H0935705A
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- particles
- active material
- electrode
- battery
- polymer electrolyte
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Classifications
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- 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
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- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明はポリマー電解質を用いた
リチウム電池の、とくにその電極の構成に関するもので
ある。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a lithium battery using a polymer electrolyte, and more particularly to the structure of its electrode.
【０００２】[0002]
【従来の技術】ポリマー電解質を用いたリチウム電池
は、活物質の連続塗着法により長尺の薄膜電極の作製が
容易でしかも大電流での充放電が可能である。2. Description of the Related Art In a lithium battery using a polymer electrolyte, a long thin film electrode can be easily manufactured by a continuous coating method of an active material and can be charged and discharged with a large current.
【０００３】この電解質は固体としての特長を有し、特
に負極に金属リチウムを用いた二次電池の場合、電解液
として有機電解液を用いた時に問題となるリチウムデン
ドライト析出が抑制される。このため、内部短絡による
発熱・発火が非常に起こりにくく十分な安全性の確保が
可能となる。ポリマー電解質にはポリエチレンオキサイ
ド（ＰＥＯ）やポリプロピレンオキサイド（ＰＰＯ）に
リチウム塩を添加した型のものやリチウム塩を溶解した
非水電解液にポリアクリロニトリル（ＰＡＮ）やポリフ
ッ化ビニリデン（ＰＶｄＦ）などを溶解させたものある
いは多官能性のモノマーを電磁波などにより三次元的に
重合させてゲル状にしたものがある。一方、正、負極に
はイオン伝導性を確保するために正、負極構成材料に前
記ポリマー電解質を混合したものを用いている。This electrolyte has a characteristic of being solid, and particularly in the case of a secondary battery using metallic lithium for the negative electrode, lithium dendrite deposition, which is a problem when an organic electrolyte is used as the electrolyte, is suppressed. For this reason, it is possible to secure sufficient safety because heat generation and ignition due to an internal short circuit hardly occur. As the polymer electrolyte, polyethylene oxide (PEO) or polypropylene oxide (PPO) with a lithium salt added, or a non-aqueous electrolyte in which the lithium salt is dissolved, such as polyacrylonitrile (PAN) or polyvinylidene fluoride (PVdF) is dissolved. There is a gelled product obtained by three-dimensionally polymerizing a cured product or a polyfunctional monomer by electromagnetic waves. On the other hand, positive and negative electrodes are prepared by mixing the polymer electrolyte with the positive and negative electrode constituent materials in order to ensure ionic conductivity.
【０００４】[0004]
【発明が解決しようとする課題】有機電解液を使用した
リチウム電池の場合、活物質、導電剤および結着剤等か
らなる正、負極構成材料の混合物を塗着または加圧成型
した正、負極に電解液を浸透させており、各構成成分と
電解液は密接に接触して電子伝導のパスを保持している
とともに、十分な反応界面を形成して良好なイオン伝導
性をも確保している。In the case of a lithium battery using an organic electrolytic solution, a positive or negative electrode obtained by applying or pressure molding a mixture of positive and negative electrode constituent materials consisting of an active material, a conductive agent, a binder and the like. The electrolyte is permeated into the electrolyte, and each component and the electrolyte are in intimate contact with each other to maintain a path for electron conduction, and a sufficient reaction interface is formed to ensure good ionic conductivity. There is.
【０００５】一方、ポリマー電解質を用いた電池では通
常、活物質粒子等にポリマー電解質を混合させているの
みであるので、活物質粒子等とポリマー電解質との接触
性が充分でなく、電池のインピーダンスは有機電解液を
用いた電池に比べて大きくなり電池作動時の電圧低下の
要因となっていた。このインピーダンスを低減させるた
めには正極中の導電剤の量を多くすることにより解決で
きるが正極中の導電剤量の増加は活物質量の減少をもた
らし正極の単位面積あるいは体積当たりの容量は減少す
ることになる。On the other hand, in a battery using a polymer electrolyte, the polymer electrolyte is usually only mixed with the active material particles and the like, so that the contact between the active material particles and the polymer electrolyte is not sufficient and the impedance of the battery is impaired. Is larger than that of a battery using an organic electrolyte, which causes a voltage drop during battery operation. In order to reduce this impedance, it can be solved by increasing the amount of conductive agent in the positive electrode, but an increase in the amount of conductive agent in the positive electrode reduces the amount of active material, and the capacity per unit area or volume of the positive electrode decreases. Will be done.
【０００６】また、添加された導電剤がゲル状電解質中
の電解液を吸収するのでインピーダンスも予想したほど
には改善されない。Further, since the added conductive agent absorbs the electrolytic solution in the gel electrolyte, the impedance is not improved as expected.
【０００７】一方、負極に炭素材料等の粉末を用いた場
合にも負極の構成材料の粒子間にポリマー粒子が混合さ
れるため、正極と同様の現象が見られ、電池のインピー
ダンスが増大する。On the other hand, when a powder of a carbon material or the like is used for the negative electrode, polymer particles are mixed between the particles of the constituent material of the negative electrode, so that a phenomenon similar to that of the positive electrode is observed and the impedance of the battery increases.
【０００８】本発明はこのような課題を解決するもので
あり、ポリマー電解質を用いた電池の電極の電子伝導性
とイオン伝導性を、電極中の導電剤粒子の量を増やすこ
となく向上させ、インピーダンスが小さく容量密度に優
れたリチウム電池を提供するものである。The present invention is intended to solve such a problem by improving the electronic conductivity and ionic conductivity of an electrode of a battery using a polymer electrolyte without increasing the amount of conductive agent particles in the electrode, A lithium battery having a low impedance and an excellent capacity density is provided.
【０００９】[0009]
【課題を解決するための手段】上記の課題を解決するた
めに、本発明のポリマー電解質・リチウム電池は活物質
粒子と導電剤粒子とゲル状ポリマー電解質を備え、前記
活物質粒子の表面に少なくとも導電剤粒子を機械的エネ
ルギーによって埋め込んだ材料を用いて電極としたもの
である。In order to solve the above-mentioned problems, the polymer electrolyte / lithium battery of the present invention comprises active material particles, conductive agent particles and gel polymer electrolyte, and at least the surface of the active material particles. An electrode is formed by using a material in which conductive agent particles are embedded by mechanical energy.
【００１０】[0010]
【作用】従来のポリマー電解質・リチウム電池に用いる
電極は、活物質粒子にポリマー電解質を単に混合させて
いるものであり、有機電解液を用いた場合に比べて電極
内の電子伝導性やイオン伝導性が低下し、結果として電
池の容量密度が低下していた。[Function] The electrode used in the conventional polymer electrolyte / lithium battery is one in which the polymer electrolyte is simply mixed with the active material particles. Compared to the case where the organic electrolyte is used, the electron conductivity and ionic conductivity in the electrode are increased. Property was lowered, and as a result, the capacity density of the battery was lowered.
【００１１】しかしながら、本発明では活物質粒子の表
面に導電剤粒子を機械的エネルギーによって埋め込み固
定しているので、活物質粒子相互間の電子伝導性を導電
剤粒子を過剰に添加することなく最少必要量で確保する
ことができる。However, in the present invention, since the conductive material particles are embedded and fixed on the surface of the active material particles by mechanical energy, the electronic conductivity between the active material particles is minimized without adding the conductive material particles excessively. It can be secured in the required amount.
【００１２】さらに、導電剤粒子は活物質粒子の表面に
最小必要量に近い量で存在するため、従来のように電極
中に過剰に存在する導電剤がゲル状電解質中の電解液を
吸収して電解液中のリチウムイオンが活物質粒子に到達
することを妨害することもない。そして、これらの作用
により電極の電子伝導性とイオン伝導性を向上させて電
池のインピーダンスを低下させることができる。また、
導電剤粒子の量を最小必要量にすることによって、電極
内の活物質の充填量を大きくすることができ、電池の容
量密度やサイクル寿命を向上させることができる。Further, since the conductive agent particles are present on the surface of the active material particles in an amount close to the minimum required amount, the conductive agent excessively present in the electrode absorbs the electrolytic solution in the gel electrolyte as in the conventional case. Therefore, it does not prevent lithium ions in the electrolytic solution from reaching the active material particles. These actions can improve the electron conductivity and ionic conductivity of the electrode and reduce the impedance of the battery. Also,
By setting the amount of conductive agent particles to the minimum required amount, the filling amount of the active material in the electrode can be increased, and the capacity density and cycle life of the battery can be improved.
【００１３】[0013]
【実施例】以下、本発明の実施例を図面を参照にしなが
ら説明する。Embodiments of the present invention will be described below with reference to the drawings.
【００１４】［実施例１］図１に本発明の電池の断面図
を示す。図において１は高クロム含有量の耐食性ステン
レス製ケース、２はステンレス製封口板である。３はＶ
2Ｏ5を活物質に用いた正極である。この正極は以下のよ
うにして作製した。[Embodiment 1] FIG. 1 shows a sectional view of a battery of the present invention. In the figure, 1 is a corrosion-resistant stainless steel case having a high chromium content, and 2 is a stainless steel sealing plate. 3 is V
It is a positive electrode using 2 O 5 as an active material. This positive electrode was manufactured as follows.
【００１５】まず、活物質となるＶ2Ｏ5微粒子１００重
量部とアセチレンブラック導電剤微粒子４重量部を準備
し、高速気流衝撃法、具体的にはハイブリダイゼーショ
ンシステムを用いて、Ｖ2Ｏ5微粒子の表面にアセチレン
ブラック導電剤微粒子を機械的エネルギーにより打ち込
み、固定化した。この表面処理を施したＶ2Ｏ5微粒子１
０４重量部に対し水溶液分散型フッ素樹脂結着剤７重量
部を混合してスラリー状にした後、このスラリーをマル
チコーターにより集電体であるアルミニウム箔４上に８
０μｍの厚みで塗布して乾燥させた。そして、炭酸プロ
ピレンと炭酸エチレンの等体積混合溶媒にＬｉＰＦ6を
１モル／ｌの濃度で溶解させてなる電解液８０重量部に
架橋剤であるポリエチレングリコールジアクリレート１
８重量部とトリメチロールプロパントリアクリレート２
重量部および熱重合開始剤アゾビスイソブチロニトリル
（ＡＩＢＮ）０．５重量部からなる混合溶液を所定量、
減圧含浸した。最後にこれを８０℃密封下にて熱硬化法
により正極をゲル化させ、円盤状に打ち抜いた後、ケー
ス１の内面に載置した。First, 100 parts by weight of V 2 O 5 fine particles as an active material and 4 parts by weight of acetylene black conductive agent fine particles were prepared, and V 2 O 5 was prepared by using a high-speed air flow impact method, specifically, a hybridization system. Fine particles of acetylene black conductive agent were implanted on the surface of the fine particles by mechanical energy to be fixed. V 2 O 5 fine particles 1 subjected to this surface treatment
7 parts by weight of an aqueous solution-dispersible fluororesin binder was mixed with 04 parts by weight to form a slurry, and the slurry was placed on the aluminum foil 4 serving as a current collector by a multi-coater.
It was applied to a thickness of 0 μm and dried. Then, 80 parts by weight of an electrolytic solution prepared by dissolving LiPF 6 in an equal volume mixed solvent of propylene carbonate and ethylene carbonate at a concentration of 1 mol / l is used as a cross-linking agent, polyethylene glycol diacrylate 1.
8 parts by weight and trimethylolpropane triacrylate 2
A predetermined amount of a mixed solution containing 0.5 part by weight of a thermal polymerization initiator azobisisobutyronitrile (AIBN),
It was impregnated under reduced pressure. Finally, the positive electrode was gelled by a thermosetting method while hermetically sealed at 80 ° C., punched into a disk shape, and then placed on the inner surface of the case 1.
【００１６】５は厚さ４０μｍのポリマー電解質であ
り、炭酸プロピレンと炭酸エチレンの等体積混合溶媒に
ＬｉＰＦ6を１モル／ｌの濃度で溶解させてなる電解液
８０重量部にポリエチレングリコールジアクリレート１
８重量部、トリメチロールプロパントリアクリレート２
重量部および光重合開始剤ベンジルジメチルケタール
０．１重量部を添加混合し、この溶液を波長３６５ｎｍ
の紫外線照射により硬化させゲル状にしたものである。Numeral 5 is a polymer electrolyte having a thickness of 40 μm, and polyethylene glycol diacrylate 1 is added to 80 parts by weight of an electrolytic solution prepared by dissolving LiPF 6 at a concentration of 1 mol / l in a mixed solvent of propylene carbonate and ethylene carbonate in an equal volume.
8 parts by weight, trimethylolpropane triacrylate 2
Parts by weight and 0.1 part by weight of the photopolymerization initiator benzyl dimethyl ketal are added and mixed, and this solution is irradiated at a wavelength of 365 nm.
It is a gel-like product that is cured by UV irradiation.
【００１７】６は厚さ８０μｍの金属リチウム負極であ
り、７はポリプロピレン製のガスケットである。これを
本発明の電池Ａとした。電池の評価は２０℃にてインピ
ーダンス測定と充放電試験により行い、放電は電流密度
１．０ｍＡ／ｃｍ2で放電下限電圧２．０ＶもしくはＶ2
Ｏ5１モル当たり１ファラデー（１Ｆ）まで、充電は電
流密度０．２８ｍＡ／ｃｍ2で充電上限電圧３．８Ｖの
範囲でサイクルさせて行った。Reference numeral 6 is a metal lithium negative electrode having a thickness of 80 μm, and reference numeral 7 is a polypropylene gasket. This was designated as Battery A of the present invention. The battery was evaluated by impedance measurement and charge / discharge test at 20 ° C., and the discharge was carried out at a current density of 1.0 mA / cm 2 and a discharge lower limit voltage of 2.0 V or V 2.
Charging was performed at a current density of 0.28 mA / cm 2 and a charging upper limit voltage of 3.8 V in a cycle up to 1 Faraday (1 F) per mol of O 5 .
【００１８】［実施例２］Ｖ2Ｏ5微粒子１００重量部と
アセチレンブラック導電剤微粒子４重量部を準備し、高
速乾式粉砕機、具体的には圧縮力とせん断力を利用した
メカノフュージョンシステムを用い、この機械的エネル
ギーによってＶ2Ｏ5微粒子の表面にアセチレンブラック
微粒子を打ち込み固定化した。この表面処理を施したＶ
2Ｏ5微粒子を用いた以外は、（実施例１）と同様にして
電池を作製し、これを本発明の電池Ｂとした。また、電
池の充放電試験は（実施例１）と同様に行った。Example 2 100 parts by weight of V 2 O 5 fine particles and 4 parts by weight of acetylene black conductive agent fine particles were prepared, and a high speed dry pulverizer, specifically, a mechanofusion system utilizing compression force and shearing force was used. By using this mechanical energy, acetylene black fine particles were implanted and fixed on the surface of the V 2 O 5 fine particles. V with this surface treatment
A battery was produced in the same manner as in (Example 1) except that 2 O 5 fine particles were used, and this was designated as battery B of the present invention. The battery charge / discharge test was performed in the same manner as in (Example 1).
【００１９】［実施例３］以下のようにして正極を作製
した。[Example 3] A positive electrode was prepared as follows.
【００２０】まず、Ｖ2Ｏ5微粒子１００重量部とアセチ
レンブラック導電剤微粒子２重量部を準備し、高速気流
衝撃法、具体的にはハイブリダイゼーションシステムを
用い、この機械的エネルギーによってＶ2Ｏ5微粒子の表
面にアセチレンブラック微粒子を打ち込み、固定化し
た。ついで、この表面処理を施したＶ2Ｏ5微粒子１０２
重量部と、ポリマー微粒子である平均分子量７０万のポ
リメタクリル酸メチル（ＰＭＭＡ）微粒子４重量部を用
い、上記と同様の方法により機械的エネルギーによって
前記Ｖ2Ｏ5微粒子の表面にＰＭＭＡ微粒子を打ち込み、
固定化した。そして、このようにして得られたＶ2Ｏ5粒
子１０４重量部に水溶液分散型フッ素樹脂結着剤７重量
部を混合しスラリー状にした後、このスラリーをマルチ
コーターにより集電体であるアルミニウム箔４上に８０
μｍの厚みで塗布した。そして、正極が半乾燥状態にあ
るとき、２本ローラーにより６０μｍの厚みまで加圧し
圧縮してその後乾燥させた。この正極の多孔度は３３％
であった。First, 100 parts by weight of V 2 O 5 fine particles and 2 parts by weight of acetylene black conductive agent fine particles are prepared, and V 2 O 5 is supplied by mechanical energy using a high-speed airflow impact method, specifically, a hybridization system. Acetylene black fine particles were implanted on the surface of the fine particles and fixed. Then, the surface-treated V 2 O 5 fine particles 102
Parts by weight and 4 parts by weight of polymethylmethacrylate (PMMA) fine particles having an average molecular weight of 700,000, which are polymer fine particles, are used to implant PMMA fine particles on the surface of the V 2 O 5 fine particles by mechanical energy in the same manner as above. ,
Immobilized. Then, 104 parts by weight of the V 2 O 5 particles thus obtained are mixed with 7 parts by weight of an aqueous solution-dispersible fluororesin binder to form a slurry, and the slurry is made into an aluminum current collector by a multi-coater. 80 on foil 4
It was applied with a thickness of μm. Then, when the positive electrode was in a semi-dried state, it was pressed by a two-roller roller to a thickness of 60 μm, compressed, and then dried. The porosity of this positive electrode is 33%
Met.
【００２１】ついで、この正極を円盤状に打ち抜き、炭
酸プロピレンと炭酸エチレンの等体積混合溶媒にＬｉＰ
Ｆ6を１モル／ｌの濃度で溶解させた電解液の所定量を
前記正極内に注液し、減圧含浸の後７０℃にて加熱して
前記ＰＭＭＡ微粒子に前記電解液を吸収させてゲル状に
した。ゲル中のポリマー濃度は約１５重量％であった。Then, the positive electrode was punched out into a disk shape, and LiP was added to a mixed solvent of equal volume of propylene carbonate and ethylene carbonate.
A predetermined amount of an electrolytic solution in which F 6 was dissolved at a concentration of 1 mol / l was poured into the positive electrode, impregnated under reduced pressure, and heated at 70 ° C. to allow the PMMA fine particles to absorb the electrolytic solution and gel. I made it. The polymer concentration in the gel was about 15% by weight.
【００２２】また、ポリマー電解質５は、前記ポリマー
微粒子と前記電解液を、ポリマー濃度が約１５重量％と
なるように混合した後、９０℃で加熱してゾル状とした
ものを徐冷してゲル状とし、これを円盤状に打ち抜いて
前記正極３の上に載置した。The polymer electrolyte 5 is prepared by mixing the polymer fine particles and the electrolyte solution so that the polymer concentration becomes about 15% by weight, and then heating at 90 ° C. to form a sol, which is gradually cooled. A gel was formed, which was punched into a disk shape and placed on the positive electrode 3.
【００２３】その他の構成は（実施例１）と同様にし、
この電池を本発明の電池Ｃとした。電池試験についても
（実施例１）と同様にして行った。Other configurations are the same as those in the first embodiment,
This battery was designated as Battery C of the present invention. The battery test was performed in the same manner as in (Example 1).
【００２４】［実施例４］Ｖ2Ｏ5微粒子１００重量部と
アセチレンブラック導電剤微粒子２重量部を準備し、高
速乾式粉砕機、具体的には圧縮力とせん断力を利用した
メカノフュージョンシステムを用い、このときの機械的
エネルギーによってＶ2Ｏ5微粒子の表面にアセチレンブ
ラック微粒子を打ち込み、固定化した。Example 4 100 parts by weight of V 2 O 5 fine particles and 2 parts by weight of acetylene black conductive agent particles were prepared, and a high speed dry pulverizer, specifically, a mechanofusion system utilizing compression force and shearing force was used. By using the mechanical energy at this time, acetylene black fine particles were implanted and fixed on the surface of the V 2 O 5 fine particles.
【００２５】ついで、この表面処理を施したＶ2Ｏ5微粒
子１０２重量部とＰＭＭＡ微粒子４重量部を用い、上記
と同様のメカノフュージョンシステムを使用し、機械的
エネルギーによって前記Ｖ2Ｏ5微粒子表面にＰＭＭＡ微
粒子を打ち込み、固定化した。Next, 102 parts by weight of the surface-treated V 2 O 5 fine particles and 4 parts by weight of PMMA fine particles were used, and the same mechanofusion system as described above was used, and mechanical energy was applied to the surface of the V 2 O 5 fine particles. PMMA fine particles were injected into and fixed.
【００２６】その他の構成は（実施例３）と同様にし、
この電池を本発明の電池Ｄとした。電池試験についても
（実施例３）と同様にして行った。The other structure is the same as that of the third embodiment,
This battery was designated as Battery D of the present invention. The battery test was performed in the same manner as in (Example 3).
【００２７】［比較例１］比較の正極は以下のようにし
て作製した。[Comparative Example 1] A comparative positive electrode was prepared as follows.
【００２８】まずＶ2Ｏ5微粒子１００重量部にアセチレ
ンブラック導電剤微粒子を単に混合し、この混合粉体の
比抵抗値を測定して電池にしたときに必要なアセチレン
ブラック微粒子の添加量を検討したところ１０重量部が
最低限必要であることがわかった。First, 100 parts by weight of V 2 O 5 fine particles are simply mixed with acetylene black conductive agent fine particles, and the specific resistance value of the mixed powder is measured to examine the amount of acetylene black fine particles to be added when the battery is used. It was found that 10 parts by weight was the minimum required.
【００２９】そして、Ｖ2Ｏ5微粒子１００重量部とアセ
チレンブラック微粒子１０重量部を混合して合剤を作製
し、この合剤に、炭酸プロピレンと炭酸エチレンの等体
積混合溶媒にＬｉＰＦ6を１モル／ｌの濃度で溶解させ
た電解液８０重量部と架橋剤ポリエチレングリコールジ
アクリレート１８重量部とトリメチロールプロパントリ
アクリレート２重量部および熱重合開始剤アゾビスイソ
ブチロニトリル（ＡＩＢＮ）０．５重量部からなる混合
溶液を混合した。ついで、この混合物をアルミニウム箔
上に８０μｍの厚みで塗布し、８０℃密封下にて熱硬化
法により正極をゲル化させた後、円盤状に打ち抜きケー
ス内面に載置して正極を作製した。Then, 100 parts by weight of V 2 O 5 fine particles and 10 parts by weight of acetylene black fine particles are mixed to prepare a mixture, and this mixture is mixed with 1 volume of LiPF 6 in an equal volume mixed solvent of propylene carbonate and ethylene carbonate. 80 parts by weight of an electrolytic solution dissolved at a concentration of mol / l, 18 parts by weight of a cross-linking agent polyethylene glycol diacrylate, 2 parts by weight of trimethylolpropane triacrylate and 0.5 parts of a thermal polymerization initiator azobisisobutyronitrile (AIBN). A mixed solution consisting of parts by weight was mixed. Then, this mixture was applied on an aluminum foil in a thickness of 80 μm, and the positive electrode was gelated by a thermosetting method while being sealed at 80 ° C., and then punched in a disk shape to be placed on the inner surface of the case to prepare a positive electrode.
【００３０】その他の構成は（実施例１）と同様にし、
これを比較の電池Ｅとした。また、電池試験についても
（実施例１）と同様にして行った。Other configurations are the same as those in (Example 1),
This was designated as Comparative Battery E. The battery test was also performed in the same manner as in (Example 1).
【００３１】［比較例２］Ｖ2Ｏ5微粒子１００重量部と
アセチレンブラック１０重量部からなる混合合剤に対
し、水溶液分散型フッ素樹脂結着剤７重量部およびポリ
マー微粒子であるカルボキシメチルセルロース２．５重
量部を混合してスラリー状にした後、このスラリーをマ
ルチコーターにより集電体であるアルミニウム箔４上に
１００μｍの厚みで塗布した。[Comparative Example 2] 7 parts by weight of an aqueous solution-dispersible fluororesin binder and carboxymethyl cellulose as polymer particles were added to a mixture of 100 parts by weight of V 2 O 5 particles and 10 parts by weight of acetylene black. After mixing 5 parts by weight to form a slurry, the slurry was applied to the aluminum foil 4 serving as a current collector with a thickness of 100 μm by a multi-coater.
【００３２】そして、この正極が半乾燥状態にあると
き、２本ローラーにより７０μｍの厚みまで加圧圧縮し
乾燥させた。正極の多孔度は３６％であった。Then, when this positive electrode was in a semi-dried state, it was pressed and compressed to a thickness of 70 μm by two rollers and dried. The porosity of the positive electrode was 36%.
【００３３】この正極を円盤状に打ち抜いた後、炭酸プ
ロピレンと炭酸エチレンの等体積混合溶媒にＬｉＰＦ6
を１モル／ｌの濃度で溶解させた電解液を所定量、前記
電極上に注液し、減圧含浸後７０℃で加熱して前記電解
液をゲル化し固定した。ゲル中のポリマー濃度は約１５
重量％であった。After punching this positive electrode into a disk shape, LiPF 6 was added to an equal volume mixed solvent of propylene carbonate and ethylene carbonate.
A predetermined amount of an electrolyte solution in which was dissolved at a concentration of 1 mol / l was poured on the electrode, impregnated under reduced pressure, and heated at 70 ° C. to gel and fix the electrolyte solution. Polymer concentration in gel is about 15
% By weight.
【００３４】ポリマー電解質５は前記ポリマー微粒子と
前記電解液をポリマー濃度が約１５重量％となるように
混合し、９０℃で加熱してゾル状にしたものを徐冷によ
りゲル状とし、これを円盤上に打ち抜いたものを前記正
極３上に載置した。As the polymer electrolyte 5, the polymer fine particles and the electrolyte solution are mixed so that the polymer concentration is about 15% by weight, and the mixture is heated at 90 ° C. to form a sol, which is gradually cooled to form a gel. What was punched out on a disk was placed on the positive electrode 3.
【００３５】そして、この他の構成は（実施例１）と同
様にし、これを比較の電池Ｆとした。また、電池試験に
ついても（実施例１）と同様にして行った。The other structure was the same as in (Example 1), and this was used as a comparative battery F. The battery test was also performed in the same manner as in (Example 1).
【００３６】ついで、本発明の電池Ａ〜Ｄおよび比較の
電池Ｅ、Ｆを用いて測定したインピーダンス値（ただ
し、１ｋＨｚにて測定した電池３個の平均値）を（表
１）に示す。The impedance values measured using the batteries A to D of the present invention and the comparative batteries E and F (however, the average value of three batteries measured at 1 kHz) are shown in (Table 1).
【００３７】[0037]
【表１】 [Table 1]
【００３８】また、図２にこれらの電池の充放電サイク
ル寿命を示す。（表１）および図２に示したように、本
発明の電池では正極の活物質粒子の表面に導電剤粒子や
ポリマー粒子が埋め込み固定化されているので、正極内
の電子伝導度やリチウムイオン伝導度が向上し、インピ
ーダンス値が小さくなり電池の充放電サイクル寿命が向
上した。なお、本実施例では正極活物質にＶ2Ｏ5を用い
たが、これ以外にリチウム電池に通常用いられる正極活
物質であるＬｉｘＭｎＯ 2（０≦ｘ≦０．５）やＬｉＣ
ｏＯ2、ＬｉＮｉＯ2、ＬｉＭｎ2Ｏ4などであってもよ
い。また、正極活物質以外に負極活物質に適用してもよ
い。FIG. 2 shows the charge / discharge cycle of these batteries.
Indicates the service life. As shown in (Table 1) and FIG.
In the battery of the invention, conductive agent particles or
Since the polymer particles are embedded and fixed in the positive electrode,
The electronic conductivity and lithium ion conductivity of the
This reduces the impedance value and improves the battery's charge / discharge cycle life.
I went up. In this embodiment, the positive electrode active material is VTwoOFiveUsing
However, in addition to this, the positive electrode active normally used in lithium batteries
The substance LixMnO Two(0 ≦ x ≦ 0.5) and LiC
oOTwo, LiNiOTwo, LiMnTwoOFourEven if
Yes. In addition to the positive electrode active material, it may be applied to the negative electrode active material.
Yes.
【００３９】導電剤にはアセチレンブラックを用いたが
他のカーボンブラックやグラファイトなど他の炭素材あ
るいはそれらの混合物であってもよく、ポリマー粒子に
ついてもポリエチレンオキサイドやポリプロピレンオキ
サイド等の従来から用いられているポリマー粒子を用い
ても同様の効果が得られた。Although acetylene black is used as the conductive agent, other carbon materials such as carbon black and graphite, or a mixture thereof may be used, and the polymer particles are conventionally used such as polyethylene oxide and polypropylene oxide. The same effect was obtained by using polymer particles.
【００４０】さらに、活物質粒子に導電剤粒子等を打ち
込む際には、ハイブリダイゼーションシステムやメカノ
フージョンシステムを用いたが、これ以外にも粒子間に
主に圧縮力やせん断力による機械的エネルギーを作用さ
せるシステムであれば同様の効果が得られる。Further, a hybridizing system and a mechanofusion system were used when driving the conductive material particles and the like into the active material particles. In addition to this, mechanical energy mainly due to compressive force or shearing force is applied between the particles. The same effect can be obtained if the system is operated.
【００４１】また、電解液の溶質にはＬｉＰＦ6を用い
たが、ＬｉＣＦ3ＳＯ3、ＬｉＣｌＯ4、ＬｉＮ（ＣＦ3Ｓ
Ｏ2）2、ＬｉＡｓＦ6、ＬｉＢＦ4など他のリチウム塩で
あってもよい。Although LiPF 6 was used as the solute of the electrolytic solution, LiCF 3 SO 3 , LiClO 4 , and LiN (CF 3 S) were used.
Other lithium salts such as O 2 ) 2 , LiAsF 6 and LiBF 4 may be used.
【００４２】また、リチウム電池用負極には金属リチウ
ムを用いたが、これ以外にリチウムを含む化合物、例え
ばＬｉＡｌ合金やＣxＬｉ（リチウムを吸蔵した炭素あ
るいは黒鉛）などであってもよい。Further, although metallic lithium was used for the negative electrode for the lithium battery, other compounds containing lithium such as LiAl alloy and C x Li (carbon or graphite occluding lithium) may be used.
【００４３】[0043]
【発明の効果】以上のように、本発明の電池では電極の
活物質粒子の表面に導電剤粒子やポリマー粒子が機械的
エネルギーによって埋め込み固定化されているので、電
極内の電子伝導性やリチウムイオン伝導性を向上させる
ことができ、この結果、電池のインピーダンスを小さく
して電池容量や充放電サイクル寿命を向上させることが
できる。As described above, in the battery of the present invention, the conductive material particles and the polymer particles are embedded and fixed by mechanical energy on the surface of the active material particles of the electrode. Ion conductivity can be improved, and as a result, battery impedance can be reduced and battery capacity and charge / discharge cycle life can be improved.
【図１】本発明のポリマー電解質・リチウム電池の断面
図FIG. 1 is a sectional view of a polymer electrolyte / lithium battery of the present invention.
【図２】本発明と比較の電池の充放電サイクル寿命を示
す図FIG. 2 is a diagram showing charge / discharge cycle life of a battery according to the present invention and a battery for comparison.
１ ケース ２ 封口板 ３ Ｖ2Ｏ5正極 ４ アルミニウム箔 ５ ポリマー電解質 ６ 金属リチウム負極 ７ ガスケット1 Case 2 Sealing Plate 3 V 2 O 5 Positive Electrode 4 Aluminum Foil 5 Polymer Electrolyte 6 Metal Lithium Negative Electrode 7 Gasket
───────────────────────────────────────────────────── フロントページの続き (72)発明者 江田 信夫 大阪府門真市大字門真1006番地 松下電器 産業株式会社内 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Nobuo Eda 1006 Kazuma Kadoma, Kadoma City, Osaka Matsushita Electric Industrial Co., Ltd.
Claims (4)
電解質からなる電極を備え、 前記活物質粒子の表面には少なくとも導電剤粒子が機械
的エネルギーによって埋め込まれているポリマー電解質
・リチウム電池。1. A polymer electrolyte / lithium battery comprising an electrode composed of active material particles, conductive agent particles and a gel polymer electrolyte, wherein at least conductive agent particles are embedded on the surface of the active material particles by mechanical energy.
電解質からなる電極を備え、 前記活物質粒子の表面には、導電剤粒子とゲル状ポリマ
ー電解質を構成するポリマー粒子が機械的エネルギーに
よって埋め込まれている請求項１記載のポリマー電解質
・リチウム電池。2. An electrode comprising an active material particle, a conductive agent particle and a gel-like polymer electrolyte, wherein the conductive material particle and the polymer particle constituting the gel-like polymer electrolyte are formed on the surface of the active material particle by mechanical energy. The polymer electrolyte / lithium battery according to claim 1, which is embedded.
液が吸収され、膨潤または溶解し、架橋してゲル状にな
る請求項２記載のポリマー電解質・リチウム電池。3. The polymer electrolyte / lithium battery according to claim 2, wherein an electrolytic solution in which a lithium salt is dissolved in polymer particles is absorbed, swells or dissolves, and is crosslinked to form a gel.
ポリマー粒子の間に主に圧縮力、せん断力を作用させ
て、機械的エネルギーによって活物質粒子の表面に前記
導電剤粒子または／およびポリマー粒子を埋め込むポリ
マー電解質・リチウム電池用電極の製造法。4. An active material particle and / or a conductive agent particle or / and a polymer particle are mainly subjected to a compressive force or a shearing force, and mechanical energy causes the surface of the active material particle to have the conductive agent particle and / or the conductive agent particle. A method for manufacturing a polymer electrolyte / lithium battery electrode in which polymer particles are embedded.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17983595A JP3622276B2 (en) | 1995-07-17 | 1995-07-17 | Polymer electrolyte / lithium battery and method of manufacturing the electrode |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17983595A JP3622276B2 (en) | 1995-07-17 | 1995-07-17 | Polymer electrolyte / lithium battery and method of manufacturing the electrode |
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| Publication Number | Publication Date |
|---|---|
| JPH0935705A true JPH0935705A (en) | 1997-02-07 |
| JP3622276B2 JP3622276B2 (en) | 2005-02-23 |
Family
ID=16072736
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP17983595A Expired - Fee Related JP3622276B2 (en) | 1995-07-17 | 1995-07-17 | Polymer electrolyte / lithium battery and method of manufacturing the electrode |
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| JP2005135872A (en) * | 2003-10-31 | 2005-05-26 | Hitachi Maxell Ltd | Electrode material for nonaqueous secondary battery, its manufacturing method, and nonaqueous secondary battery using it |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2011129528A (en) * | 1997-02-04 | 2011-06-30 | Mitsubishi Electric Corp | Method of manufacturing lithium ion secondary battery |
| JP4561041B2 (en) * | 2002-03-28 | 2010-10-13 | Ｔｄｋ株式会社 | Lithium secondary battery |
| JP2004006285A (en) * | 2002-03-28 | 2004-01-08 | Tdk Corp | Lithium secondary battery |
| JP2005135872A (en) * | 2003-10-31 | 2005-05-26 | Hitachi Maxell Ltd | Electrode material for nonaqueous secondary battery, its manufacturing method, and nonaqueous secondary battery using it |
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| JP2010504624A (en) * | 2006-09-25 | 2010-02-12 | エルジー・ケム・リミテッド | Non-aqueous electrolyte and electrochemical device including the same |
| WO2008038930A1 (en) | 2006-09-25 | 2008-04-03 | Lg Chem, Ltd. | Non-aqueous electrolyte and electrochemical device comprising the same |
| EP2070150A4 (en) * | 2006-09-25 | 2012-05-02 | Lg Chemical Ltd | Non-aqueous electrolyte and electrochemical device comprising the same |
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| US9722253B2 (en) | 2006-09-25 | 2017-08-01 | Lg Chem, Ltd. | Non-aqueous electrolyte and electrochemical device comprising the same |
| JP2012054071A (en) * | 2010-08-31 | 2012-03-15 | Sekisui Chem Co Ltd | Lithium ion conductive material, lithium ion conductive electrolyte membrane, lithium ion conductive electrolyte membrane-electrode assembly and lithium ion polymer battery |
| CN114122350A (en) * | 2021-10-28 | 2022-03-01 | 汕头大学 | Polymer electrolyte-electrode composite material and preparation method and application thereof |
| CN114122350B (en) * | 2021-10-28 | 2023-06-02 | 汕头大学 | Polymer electrolyte-electrode composite material and preparation method and application thereof |
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