JPS62139266A - Polymer solid electrolyte - Google Patents
Polymer solid electrolyteInfo
- Publication number
- JPS62139266A JPS62139266A JP27891985A JP27891985A JPS62139266A JP S62139266 A JPS62139266 A JP S62139266A JP 27891985 A JP27891985 A JP 27891985A JP 27891985 A JP27891985 A JP 27891985A JP S62139266 A JPS62139266 A JP S62139266A
- Authority
- JP
- Japan
- Prior art keywords
- peo
- molecular weight
- polyethylene oxide
- mixture
- ionic conductivity
- 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.)
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Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M6/00—Primary cells; Manufacture thereof
- H01M6/14—Cells with non-aqueous electrolyte
- H01M6/18—Cells with non-aqueous electrolyte with solid electrolyte
- H01M6/181—Cells with non-aqueous electrolyte with solid electrolyte with polymeric electrolytes
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- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Primary Cells (AREA)
Abstract
Description
【発明の詳細な説明】
〔発明の利用分野〕
本発明は高分子電解質に係り、特に電池および他の電気
化学デバイス用材料として好適な高分子固体電解質に関
するものである。DETAILED DESCRIPTION OF THE INVENTION [Field of Application of the Invention] The present invention relates to polymer electrolytes, and particularly to solid polymer electrolytes suitable as materials for batteries and other electrochemical devices.
ポリエチレンオキシド（Ｐ Ｅ Ｏ、＋ＣＨｘ−ＣＨｚ
−０池）とアルカリ金属塩とからなる錯体が高いアルカ
リイオン伝導性を示すことはピー・バアシスタ（Ｐ。Polyethylene oxide (P E O, +CHx-CHz
P. Baasista (P. -0ike) and an alkali metal salt exhibit high alkali ion conductivity.
Ｖａｓｈｉｓｔａ）ら（ファースト・イオン・トランス
ポート・イン・ソリッド（Ｆａｓｔ Ｉｏｎ Ｔｒａｎ
ｓｐｏｒｔ １ｎＳｏｌｉｄ） １３１頁（１９７９）
）により報告された。それ以来１本系あるいは関連系か
らなる高分子電解質に関して、そのイオン伝導機構、構
造などの純学術的観点、あるいは電池などの電気化学デ
バイスへの応用面から活発に研究されている。Vashista et al. (Fast Ion Transport in Solid)
sport 1nSolid) 131 pages (1979)
) reported by. Since then, polymer electrolytes consisting of single or related systems have been actively researched from purely academic viewpoints such as their ionic conduction mechanism and structure, and from the viewpoint of application to electrochemical devices such as batteries.
高分子固体電解質は高分子特有の柔軟性、粘弾性を具備
しているため、電極とのイオン電子交換過程で生じる体
積変化に順応できるなどの機械的性質が無機固体電解質
に比べて優れている。また。Solid polymer electrolytes have flexibility and viscoelasticity unique to polymers, so they have superior mechanical properties compared to inorganic solid electrolytes, such as being able to adapt to changes in volume that occur during the ion-electron exchange process with electrodes. . Also.
高分子のもつ良加工性から薄膜化が容易であるなどの特
徴を有する。このため、高分子固体電解質は高エネルギ
ー密度電池、特に薄膜電池用の固体電解質材流として注
目をあびている。しかしながら、高分子固体電解質は一
般に無機物と比較してイオン伝導度が小さく、その応用
が遅れている。It has characteristics such as being easy to form into thin films due to the good processability of polymers. For this reason, solid polymer electrolytes are attracting attention as a solid electrolyte material for high energy density batteries, especially thin film batteries. However, polymer solid electrolytes generally have lower ionic conductivity than inorganic materials, and their application has been delayed.
以上が高いイオン伝導性を有する高分子固体電解質の開
発がまたれる所以である。These are the reasons why solid polymer electrolytes with high ionic conductivity are being developed.
ポリエチレンオキシド（ＰＥＯ）と種々のアルカリ金属
塩（ＬｉＣＦｓＳＯａ、 ＬｉＩ ｔ ＬｉＣｌ０ａ、
ＮａＩＮａＣＦａＳＯａ、 ＫＣＦ８ＳＯａなど）か
らなる錯体も高温（１００℃付近）において１０−”〜
１０−”Ｓ ／ ｍと比較的高いイオン伝導度を有する
が、６０℃以下の温度で急激にイオン伝導度が低下し、
室温では１０−’Ｓ／ｍ以下と小さいという欠点があっ
た。Polyethylene oxide (PEO) and various alkali metal salts (LiCFsSOa, LiI t LiClOa,
Complexes consisting of NaINaCFaSOa, KCF8SOa, etc.) also exhibit 10-”~
It has a relatively high ionic conductivity of 10-”S/m, but the ionic conductivity decreases rapidly at temperatures below 60°C.
It has the disadvantage that it is as small as 10-'S/m or less at room temperature.
本発明はこの問題を解決するために、室温で高いイオン
伝導性を有する高分子固体電解質を提供することにある
。The present invention aims to solve this problem by providing a solid polymer electrolyte that has high ionic conductivity at room temperature.
従来、ポリエチレンオキシド（ＰＥＯ）とアルカリ金属
塩からなる高分子錯体固体電解質は、分子量６０，００
０あるいは４，０００，０００などの高分子のＰＥＯと
アルカリ金属塩をアセトニトリルＣＨｓＣＮなどの有機
溶媒に溶解し、キャスティング塗布法によりフィルムと
して得られている。これらのイオン伝導度は６０℃近傍
を境にして急変する現象が観察される。すなわち、６０
℃以上ではイオン伝導の活性化エネルギーが小さく比較
的大きなイオン伝導度（例えば１００℃で１０−２〜１
Ｏ−ＩＳ ／ ｍ ）を示すのに対して、６０℃より低
温では、活性化エネルギーが大きくなりイオン伝導度が
急激に低下し、室温で１０−’Ｓ／ｍ以下と極めて小さ
な値しか示さない。Conventionally, polymer complex solid electrolytes made of polyethylene oxide (PEO) and alkali metal salts have a molecular weight of 60.00.
Polymer PEO such as 0 or 4,000,000 and an alkali metal salt are dissolved in an organic solvent such as acetonitrile CHsCN, and a film is obtained by a casting coating method. A phenomenon is observed in which these ionic conductivities suddenly change around 60°C. That is, 60
Above ℃, the activation energy of ion conduction is small and the ionic conductivity is relatively large (for example, 10-2 to 1 at 100℃).
On the other hand, at temperatures lower than 60°C, the activation energy increases and the ionic conductivity decreases rapidly, showing only an extremely small value of 10-'S/m or less at room temperature. .
このイオン伝導度が急変する温度６０℃はＰＲＯ（分子
量１０，０００以上）の融点に相当していることから、
イオン伝導度が６０℃以上で大きくなるのは、融解状態
のＰＥＯ構造領域の存在に起因するものと考えられる。Since the temperature at which the ionic conductivity suddenly changes at 60°C corresponds to the melting point of PRO (molecular weight 10,000 or more),
The reason why the ionic conductivity increases at 60° C. or higher is considered to be due to the presence of the PEO structure region in a molten state.
そこで、室温で高いイオン伝導度をもつＰＥ０−アルカ
リ塩錯体を得る方策として、融点の低い低分子量（ｉｏ
ｏｏ以下）のＰＥＯを原料に用いることが当然考えられ
る。しかしながら、この低分子量のＰＥＯは液体であり
、そのままでは固体状の高分子電解質を形成することが
できない。Therefore, as a measure to obtain a PE0-alkaline salt complex with high ionic conductivity at room temperature, low molecular weight (io
Naturally, it is conceivable to use PEO of 0 or less) as a raw material. However, this low molecular weight PEO is a liquid and cannot form a solid polymer electrolyte as it is.
以上の考察結果、高分子（分子量１ｏｏｏｏ以上）と低
分子（分子量１０００以下）の混合物からなるＰＥＯを
用いることにより、高分子領域で固体状のマトリックス
を形成し、その中に存在する低分子のＰＥＯが室温にお
けるイオン伝導の向上に寄与することをねらったもので
ある。その結果、室温で高いイオン伝導度を有する高分
子固体電解質を作成することに成功した。As a result of the above considerations, by using PEO consisting of a mixture of high molecules (molecular weight of 1000 or more) and low molecules (molecular weight of 1000 or less), a solid matrix is formed in the high molecular region, and the low molecules present in it are The purpose is for PEO to contribute to improving ionic conduction at room temperature. As a result, they succeeded in creating a solid polymer electrolyte with high ionic conductivity at room temperature.
高分子のものと低分子のものの混合比率は、全高分子化
合物のうち、高分子のものが９５〜１０重量％が好まし
く、９０〜３０重量％がより好ましい。The mixing ratio of high molecular weight compounds and low molecular weight compounds is preferably 95 to 10% by weight, more preferably 90 to 30% by weight of all the high molecular weight compounds.
以下、本発明を実施例を用いて詳細に説明する。 Hereinafter, the present invention will be explained in detail using Examples.
実施例１
ポリエチレンオキシド（ＰＥＯ）とトリフルオロメタン
スルホン酸リチウム（ＬｉＣＦｓＳＯ＋）とからなる錯
体簿膜に関する実施例を示す。本錯体の組成は一般式（
Ｐ Ｅ Ｏ）ｘＬｊＣＦａＳＯｓで表わされ、ＸはＰＥ
Ｏ単位分子中の酸素（０）とリチウム（Ｌｉ）の原子比
０／Ｌｉである。Example 1 An example regarding a complex film made of polyethylene oxide (PEO) and lithium trifluoromethanesulfonate (LiCFsSO+) is shown. The composition of this complex is expressed by the general formula (
P E O) x LjCFaSOs, where X is P E
The atomic ratio of oxygen (0) and lithium (Li) in the O unit molecule is 0/Li.
出発原料に平均分子量６００，０００のＰＥＯと平均分
子量１０００のＰＥＯおよびＬｉＣＦ＋ｓＳＯδ粉末を
用いた。PEO with an average molecular weight of 600,000, PEO with an average molecular weight of 1000, and LiCF+sSOδ powder were used as starting materials.
これらの原料を所望組成になるように秤量し、アセトニ
トリルとＣｌ１ａＣＮに溶解後、マグネテイックスター
ラで４８時間撹伴した。この時、ＰＥ０（６００，００
０） ＰＥＯ（１０００） （７）割合は５対１、アセ
トニトリル溶液の濃度は４ｗｔ％であった。この溶液を
石英などの基板上にキャスティングし、その後溶媒を窒
素ガスフロー中でゆっくり蒸発させ、さらに真空下（〜
１０−’Ｐ ａ ）で１５０℃、２４時間処理し、溶媒
を完全に除去した。得られた膜は白濁色の緻密なもので
あった。また、赤外線吸収スペクトルを調べた結果、隔
解状態および結晶状態のＰＥＯにみられる特徴的な赤外
バンドが共に観察されることから、本薄膜は結晶状態と
融解状態の領域が共存した構造になっていることが推定
される。These raw materials were weighed so as to have the desired composition, dissolved in acetonitrile and Cl1aCN, and then stirred with a magnetic stirrer for 48 hours. At this time, PE0(600,00
0) PEO (1000) (7) The ratio was 5:1 and the concentration of the acetonitrile solution was 4 wt%. This solution is cast onto a substrate such as quartz, after which the solvent is slowly evaporated in a nitrogen gas flow and further under vacuum (~
10-'Pa) at 150°C for 24 hours to completely remove the solvent. The obtained film was cloudy and dense. In addition, as a result of examining the infrared absorption spectrum, characteristic infrared bands seen in both the interphase and crystalline states of PEO were observed, indicating that this thin film has a structure in which crystalline and molten states coexist. It is presumed that this is the case.
以上のようにして得た薄膜試料（厚さ〜１μｍ）につい
て、その表面上に金のくし型電極を蒸着法で形成し、イ
ンピーダンスアナライザーを用い５Ｈｚ〜１３ＭＨｚで
インピーダンスを測り、Ｃｏ１ｅ−Ｃｏ１．ａプロット
からイオン伝導度を求めた。その結果を第１表に示す。Regarding the thin film sample (thickness ~ 1 μm) obtained as described above, a gold comb-shaped electrode was formed on the surface by vapor deposition, and the impedance was measured at 5 Hz to 13 MHz using an impedance analyzer. The ionic conductivity was determined from the a plot. The results are shown in Table 1.
本発明の製造法により得た（ Ｐ Ｅ Ｏ）ｘＬｉｃＦ
ｓｓＯｇ薄膜のイオン伝導度は、従来法で得た試料のよ
うな６０℃以下における急激な低下はなく、室温におい
ても］０−８〜１０”Ｓ／ｍの値を有し、組成を選ぶこ
とにより、例えば９＜ ｘ ＜ ３０では２Ｘ１０−”
８７ｍにもなる。このイオン伝導度の値は従来の高分子
ＰＥＯ（例えば分子量６００，０００）だけを用いて形
成した試料に比べて、３〜４桁大きく、固体電解質膜と
しても最大の部類に属する。(PEO)xLicF obtained by the production method of the present invention
The ionic conductivity of the ssOg thin film does not drop sharply below 60°C unlike samples obtained by conventional methods, and has a value of 0-8 to 10"S/m even at room temperature. For example, for 9< x < 30, 2X10-”
It reaches 87 meters. This value of ionic conductivity is 3 to 4 orders of magnitude higher than that of a sample formed using only conventional polymeric PEO (for example, molecular weight 600,000), and is among the highest among solid electrolyte membranes.
実施例２
実施例１と同じＰＥＯとＬｊ、ＣＦｉＳＯａからなる錯
体において、出発原料のＰ Ｅ Ｏ（６００，０００）
とＰＥ０（１０００）の割合を３対１にした場合の実施
例を述べる。Example 2 In the same complex as in Example 1, consisting of PEO, Lj, and CFiSOa, starting material P E O (600,000)
An example will be described in which the ratio of PE0 (1000) and PE0 (1000) is set to 3:1.
試料作成法は実施例１とまったく同じであった。The sample preparation method was exactly the same as in Example 1.
得られた試料も実施例１と同様、構造的には結晶状態と
融解状態が共存したものから成りたっていることが赤外
スペク１〜ルから明らかになった。It was revealed from the infrared spectra that the obtained sample was structurally composed of a coexistence of a crystalline state and a molten state, as in Example 1.
この試料について、実施例１と同じ方法でイオン伝導度
を測定した結果、それは第１表に示すような室温におい
て〜１０−”８７ｍとかなり大きな値を示した。The ionic conductivity of this sample was measured in the same manner as in Example 1, and as shown in Table 1, it showed a fairly large value of ~10-''87m at room temperature.
実施例３
上記実施例と同様Ｐ Ｅ Ｏ−ＬｉＣＦａＳＯｇ系錯体
において、Ｐ Ｅ Ｏ（６００，０００）とＰＥＯ（１
０００）の割合が１対１のＰＥＯ混合物から作成した試
料に関する実施例を述べる。Example 3 Similar to the above example, in the P E O-LiCFaSOg complex, P E O (600,000) and PEO (1
An example is given for a sample made from a PEO mixture with a 1:1 ratio of 000).
試料作成法ならびに得られた膜の状態および構造は実施
例１，２とほぼ同じであった。また、イオン伝導度も第
１表に示すごとく、室温で〜１Ｏ−２Ｓ ／ ｍの値を
示し、実施例１，２と大差なかった。The sample preparation method and the state and structure of the obtained film were almost the same as in Examples 1 and 2. Further, as shown in Table 1, the ionic conductivity showed a value of ~1O-2S/m at room temperature, which was not much different from Examples 1 and 2.
実施例１〜３では、出発原料に平均分子量６００ 、０
００と１０００のＰＥＯの混合物を用いたが、これに限
るわけでなく、分子量ｔｏ、ｏｏｏ以上のＰＥ０（例え
ば２０，０００．３００，０００．９００，０００．４
，０００，０００あるいは５，０００，０００など）と
分子量１０００以下のもの（例えば６００，４００など
）の混合物を用いても、本実施例とほぼ同等の性質を有
する（ Ｐ Ｅ Ｏ）ｘＬｉｃＦａｓＯ＋高分子固体電
解質が得られる。In Examples 1 to 3, the starting materials had an average molecular weight of 600,0
A mixture of PEO of 00 and 1000 was used, but it is not limited to this.
,000,000 or 5,000,000) and those having a molecular weight of less than 1000 (for example, 600,400), the polymer has almost the same properties as this example (P E O)xLicFasO + polymer. A solid electrolyte is obtained.
実施例４〜６
ポリエチレンオキシド（ＰＥＯ）とヨウ化リチウム（Ｌ
ｉＩ）からなる高分子錯体を本発明の製造法により作成
した実施例を述べる。Examples 4-6 Polyethylene oxide (PEO) and lithium iodide (L
An example in which a polymer complex consisting of iI) was prepared by the production method of the present invention will be described.
出発原料に平均分子量４，０００，０００ノＰ Ｅ Ｏ
トロ００のＰＥＯおよびＬｉＩを用いた。これらを所望
組成になるように秤量後、アセトニトリルに溶解し、実
施例１と同じプロセスでキャスティング膜を形成した。The starting material contains PEO with an average molecular weight of 4,000,000
Toro 00 PEO and LiI were used. After weighing these to have the desired composition, they were dissolved in acetonitrile, and a cast film was formed using the same process as in Example 1.
この時ノＰ Ｅ Ｏ（４，０００，０００） トＰ Ｅ
Ｏ（６００）の割合は４：１（実施例４）、２：１（
実施例５）および１：１（実施例６）であった。また、
本実施例で選んだ組成は一般式（ＰＥＯ）ｘＬｉＩにお
いて、！＝３．６，９，１．８．６０であった。At this time, P E O (4,000,000) P E
The ratio of O(600) was 4:1 (Example 4), 2:1 (
Example 5) and 1:1 (Example 6). Also,
The composition selected in this example is the general formula (PEO)xLiI, ! = 3.6, 9, 1.8.60.
得られた膜はいずれの試料の場合も無色透明で緻密なも
のであり、赤外線吸収スペクトルの測定結果から、基本
的には（ＰＥＯ）ｘＬｉＩ錯体がらなっており、かつ部
分的に融解状態のＰＥＯの構造領域を有することが認め
られた。The obtained films were colorless, transparent, and dense in all cases, and from the measurement results of infrared absorption spectra, they basically consisted of a (PEO)xLiI complex, and were partially composed of PEO in a molten state. It was recognized that the structure has a structural area of .
これらの薄膜試料に関して、上記実施例と同じ方法で求
めたイオン伝導度は第１表に示すように１０−４〜１０
１とがなり大きな値を示した。Regarding these thin film samples, the ionic conductivity determined by the same method as in the above example was 10-4 to 10, as shown in Table 1.
1, indicating a large value.
このように、本発明の方法により作成した（ＰＥＯ）ｘ
ＬｉＩ錯体は、従来法で形成した試料のような６０℃（
ＰＥＯの融点（分子量１０，０００以上））以下でイオ
ン伝導度が急激に低化するような現象がみられず、室温
でも極めて高いイオン伝導性を示す。Thus, (PEO)x produced by the method of the present invention
The LiI complex was heated at 60°C (like the sample formed by the conventional method).
No phenomenon in which the ionic conductivity suddenly decreases below the melting point of PEO (molecular weight 10,000 or more) is observed, and the ionic conductivity is extremely high even at room temperature.
以上の実施例ではＰＥＯとＬＩＣＦｓＳＯｓあるいはＬ
ｉＩを組合せた系について述べたが、別にこれらに限る
わけでなく、ＰＥＯと他のＬｉ塩（例えばＬｉＢＦａ、
ＬｉＣｌＯ４など）あるいは他のアルカリ金属塩（例
えばＮａＣＦ３５Ｏａ、 ＮａＩ、 ＫＣＦａＳＯ４な
ど）とからなる錯体、また、ＰＥＯ以外のポリエーテル
（例えば、ポリプロピレンオキシド、ポリエチレンサク
シネートなど）とアルカリ金属塩とからなる錯体、ひい
てはアルカリ金属塩と、錯体を形成するような高分子電
解質の場合も、本発明を適用することにより、室温で高
いイオン伝導度を有する高分子固体電解質を得ることが
可能である。In the above embodiments, PEO and LICFsSOs or L
Although a system combining iI has been described, the system is not limited to these, and PEO and other Li salts (e.g. LiBFa,
(LiClO4, etc.) or other alkali metal salts (e.g., NaCF35Oa, NaI, KCFaSO4, etc.); complexes consisting of polyethers other than PEO (e.g., polypropylene oxide, polyethylene succinate, etc.) and alkali metal salts; Furthermore, even in the case of a polymer electrolyte that forms a complex with an alkali metal salt, by applying the present invention, it is possible to obtain a polymer solid electrolyte that has high ionic conductivity at room temperature.
（ｌＯ）
〔発明の効果〕
以上述べてきたように、ポリエチレンオキシド（ＰＥＯ
）とアルカリ金属塩からなる高分子錯体において、出発
原料のＰＥＯに分子量１０，０００以上の高分子と１０
００以下の低分子の混合物を用いたことを特徴とする本
発明に係る高分子固体電解質の製造法によれば、従来お
こなわれていた高分子（分子量６００，０００．４，０
００，０００など）のＰＥＯのみを用いて形成した試料
にみられるようなイオン伝導度の６０℃以下における急
激な低下はなく、室温においても１０−８〜１０”−”
Ｓ／ｍと極めて高いイオン伝導度を有する高分子固体電
解質を提供することができる。(lO) [Effects of the invention] As stated above, polyethylene oxide (PEO)
) and an alkali metal salt, a polymer with a molecular weight of 10,000 or more and 10
According to the method for producing a polymer solid electrolyte according to the present invention, which is characterized by using a mixture of low molecular weight molecules having a molecular weight of 600,000.
There is no sudden drop in ionic conductivity below 60°C, as seen in samples formed using only PEO (e.g.
A solid polymer electrolyte having an extremely high ionic conductivity of S/m can be provided.
したがって、本発明により得た高分子固体電解質は室温
動作の電池をはじめとする各種電気化学デバイス用の固
体電解質材料として好適であり、特に高分子の特徴であ
る機械的強度、良加工性を生かした応用が期待される。Therefore, the solid polymer electrolyte obtained according to the present invention is suitable as a solid electrolyte material for various electrochemical devices including batteries that operate at room temperature, and in particular takes advantage of the mechanical strength and good processability that are characteristics of polymers. It is expected that it will have many applications.
Claims (1)
おいて、ポリエチレンオキシドに分子量１０，０００以
上の高分子と分子量１，０００以下の低分子の混合物を
用いたことを特徴とする高分子固体電解質。1. A solid polymer electrolyte, characterized in that, in a complex consisting of polyethylene oxide and an alkali metal salt, a mixture of a polymer having a molecular weight of 10,000 or more and a low molecule having a molecular weight of 1,000 or less is used for polyethylene oxide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27891985A JPS62139266A (en) | 1985-12-13 | 1985-12-13 | Polymer solid electrolyte |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27891985A JPS62139266A (en) | 1985-12-13 | 1985-12-13 | Polymer solid electrolyte |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS62139266A true JPS62139266A (en) | 1987-06-22 |
Family
ID=17603915
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP27891985A Pending JPS62139266A (en) | 1985-12-13 | 1985-12-13 | Polymer solid electrolyte |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62139266A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03129603A (en) * | 1989-10-13 | 1991-06-03 | Matsushita Electric Ind Co Ltd | Solid electrolyte |
| EP0628848A1 (en) * | 1992-12-28 | 1994-12-14 | Tonen Corporation | Electrochromic device |
| US5424150A (en) * | 1992-12-01 | 1995-06-13 | Sumitomo Chemical Company, Ltd. | Polymeric solid electrolyte |
| US7820908B2 (en) * | 2003-10-01 | 2010-10-26 | Korea Institute Of Science And Technology | Solid state dye-sensitized solar cell employing composite polymer electrolyte |
| ES2944407A1 (en) * | 2021-12-20 | 2023-06-20 | M Torres Disenos Ind S A Unipersonal | SOLID ELECTROLYTE, ITS MANUFACTURING METHOD, AND ITS IMPREGNATION METHOD (Machine-translation by Google Translate, not legally binding) |
-
1985
- 1985-12-13 JP JP27891985A patent/JPS62139266A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03129603A (en) * | 1989-10-13 | 1991-06-03 | Matsushita Electric Ind Co Ltd | Solid electrolyte |
| US5424150A (en) * | 1992-12-01 | 1995-06-13 | Sumitomo Chemical Company, Ltd. | Polymeric solid electrolyte |
| EP0628848A1 (en) * | 1992-12-28 | 1994-12-14 | Tonen Corporation | Electrochromic device |
| EP0628848A4 (en) * | 1992-12-28 | 1995-12-20 | Tonen Corp | Electrochromic device. |
| US7820908B2 (en) * | 2003-10-01 | 2010-10-26 | Korea Institute Of Science And Technology | Solid state dye-sensitized solar cell employing composite polymer electrolyte |
| ES2944407A1 (en) * | 2021-12-20 | 2023-06-20 | M Torres Disenos Ind S A Unipersonal | SOLID ELECTROLYTE, ITS MANUFACTURING METHOD, AND ITS IMPREGNATION METHOD (Machine-translation by Google Translate, not legally binding) |
| WO2023118631A1 (en) * | 2021-12-20 | 2023-06-29 | M. Torres Diseños Industriales, S.A. U. | Solid electrolyte, manufacturing method and impregnation method thereof |
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