JPH03182056A - Lithium cell with highpolymer solid electrolyte - Google Patents
Lithium cell with highpolymer solid electrolyteInfo
- Publication number
- JPH03182056A JPH03182056A JP1319608A JP31960889A JPH03182056A JP H03182056 A JPH03182056 A JP H03182056A JP 1319608 A JP1319608 A JP 1319608A JP 31960889 A JP31960889 A JP 31960889A JP H03182056 A JPH03182056 A JP H03182056A
- Authority
- JP
- Japan
- Prior art keywords
- lithium
- lithium ions
- solid electrolyte
- electrode
- 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.)
- Granted
Links
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 12
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 12
- 239000007784 solid electrolyte Substances 0.000 title claims description 11
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 22
- 229910017053 inorganic salt Inorganic materials 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims abstract description 5
- 239000007787 solid Substances 0.000 claims abstract description 5
- 239000003792 electrolyte Substances 0.000 claims abstract description 4
- 239000000463 material Substances 0.000 claims abstract 2
- 229920000642 polymer Polymers 0.000 claims description 13
- 229910000733 Li alloy Inorganic materials 0.000 claims description 2
- 239000001989 lithium alloy Substances 0.000 claims description 2
- 238000009830 intercalation Methods 0.000 claims 1
- 150000002500 ions Chemical class 0.000 abstract description 5
- 239000000956 alloy Substances 0.000 abstract 1
- 229910045601 alloy Inorganic materials 0.000 abstract 1
- 238000007599 discharging Methods 0.000 abstract 1
- 239000000126 substance Substances 0.000 abstract 1
- XQHAGELNRSUUGU-UHFFFAOYSA-M lithium chlorate Chemical compound [Li+].[O-]Cl(=O)=O XQHAGELNRSUUGU-UHFFFAOYSA-M 0.000 description 3
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 description 3
- 229910001486 lithium perchlorate Inorganic materials 0.000 description 3
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Chemical compound [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 3
- 238000010586 diagram Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 230000005684 electric field Effects 0.000 description 2
- 229910003002 lithium salt Inorganic materials 0.000 description 2
- 159000000002 lithium salts Chemical class 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- 239000005518 polymer electrolyte Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical compound [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 229940005989 chlorate ion Drugs 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Electrochemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Dispersion Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Secondary Cells (AREA)
- Primary Cells (AREA)
Abstract
Description
【発明の詳細な説明】
産業上の利用分野
本発明は高分子固体電解質リチウム電池に関するもので
ある。DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to polymer solid electrolyte lithium batteries.
従来技術とその問題点
従来の高分子固体電解質リチウム電池ｔこおいては、高
分子固体電解質の伝導度が低いために、最も伝導度が高
くなる時のリチウム塩量を用い、これは添加量を種々に
変えた実験により求めていた。しかしこれでも高率放電
時の電池の放電容量が非常に小さく、問題であった。Conventional technology and its problems In conventional polymer solid electrolyte lithium batteries, since the conductivity of the polymer solid electrolyte is low, the amount of lithium salt at which the conductivity is highest is used, and this is the amount of addition. was determined through experiments with various changes. However, even with this, the discharge capacity of the battery during high rate discharge was very small, which was a problem.
発明の目的
本発明は上記従来の問題点に鑑みなされたものであり、
高率放電時の放電容量の優れた高分子固体電解質リチウ
ム電池を提供することを目的とするものである。Purpose of the Invention The present invention has been made in view of the above-mentioned conventional problems.
The object of the present invention is to provide a polymer solid electrolyte lithium battery with excellent discharge capacity during high rate discharge.
発明の構成
本発明は上記目的を遠戚するべく、
正極がリチウムイオンをインターカレー！／替ンできる
材料であり、負極がリチウムまたはリチウム合金であり
、電解質がイオン伝導度を有する有機固体高分子とリチ
ウムイオンを含む無ａ塩からなり、該リチウムイオンを
含む無機塩が交流インピーダンス法で測定した最も高い
伝導度にあるリチウムイオン濃度Ｃ対し、１／２の濃度
であることを特徴とする高分子固体電解質リチウム電池
である。Structure of the Invention In order to achieve the above object, the present invention has the following features: The positive electrode intercalates lithium ions! The negative electrode is made of lithium or a lithium alloy, the electrolyte is made of an organic solid polymer with ionic conductivity and an aluminous salt containing lithium ions, and the inorganic salt containing lithium ions is used in the alternating current impedance method. This is a polymer solid electrolyte lithium battery characterized by a lithium ion concentration 1/2 of the lithium ion concentration C at the highest conductivity measured in .
実施例
負極にリチウム箔、圧積に二酸化マンガン、高分子固体
電解質にポリエーテル系のコポリマーを架橋してネット
ワーク構造とした高分子を用いて電池を構成した。支持
塩にはリチウムパークロレイトを添加した。Example A battery was constructed using a lithium foil for the negative electrode, manganese dioxide for the pressure, and a polymer solid polymer electrolyte crosslinked with a polyether copolymer to form a network structure. Lithium perchlorate was added to the supporting salt.
＠２図にリチウムバークロレイトの添加量とイオン伝導
度の関係を示した。尚、第１図は後述のｊｇ９式と第１
０式を図示したものである。Figure @2 shows the relationship between the amount of lithium chlorate added and the ionic conductivity. In addition, Figure 1 shows the jg9 formula and the first
This is a diagram illustrating Equation 0.
第２図からリチウムバークロレイトの添加量が９Ｎ量坏
の時が最も高いイオン伝導度である。From FIG. 2, the ionic conductivity is highest when the amount of lithium chlorate added is 9N.
リチウムバークロレイトの添加量が９重量％（従来品）
と４．５重量％（本発明）の電池を各々作成した。The amount of lithium chlorate added is 9% by weight (conventional product)
and 4.5% by weight (invention), respectively.
表
各々の電池を放電４流密度１００μＡ／−と１０μＡ／
。ｄの高率放！試験と低率放電試験を実施した。この結
果を第３図に示した。本発明の電池は高率放電における
容量低下がほとんどない。Table 4 discharge current density of each battery 100μA/- and 10μA/
. d's high rate release! Tests and low rate discharge tests were conducted. The results are shown in FIG. The battery of the present invention exhibits almost no capacity loss during high rate discharge.
尚、この理由は以下の如くに考察される。The reason for this will be considered as follows.
リチウム塩としてリチウムバークロレイトを添加した高
分子固体電解質中では、電池を定電流で放電すると、リ
チウムイオン、パークロレイトイオンは以下のような移
動Ｃ関する連立微分方程式に従って移動する・
δＸ
Ｏ−−Ｄ−ｆ−ｐ−ｎＸ （Ｅｌ ＋に２）ｙ； リチ
ウムイオンの濃度
ハ； リチウムイオンの移動度
Ｄ； リチウムイオンの拡散定数
工；放電電流
Ｘ；パークロレイトイオンの濃度
μス；バークロレイトイオンの移動度
ＤＸ＝パークロレイトイオン拡散定数
Ｓ；高分子固体電解質の断面積
（３）
Ｅｌ；両［に発生する電池起電力による電場Ｅ２；両イ
オンの間で電気的中性を保つための電場消去法Ｃより未
知数を整理すると
この微分方程式は解析的には解けないので、巨視的には
リチウムイオンとパークロレイトイオンの濃度はすべて
の位置で電気的中性を保つために濃度は等しくなってい
ると近似して、濃度ｙをｘ：Ｏ〜１で積分し、最初に添
加されたリチウムイオン量Ｍ（０）から積分定数を求め
ると、
イオンの移動度と拡散定数とは比例するというアインシ
ュタインの近似法則により、−に−Ｄ
−に−Ｄ
これらを代入すると、
（６）式より、
負・正極表面のリチウムイオンの
濃度は
電池の放電容量が非常に小さいということは、定常状態
が得られないということであり、（７）式が成立できな
い、つまり負極表面でのリチウムイオン濃度が高分子固
体電解質中のリチウムイオンを受は入れられるサイトの
濃度より高くなってしまったということである。In a polymer solid electrolyte to which lithium perchlorate is added as a lithium salt, when the battery is discharged at a constant current, lithium ions and perchlorate ions move according to the following simultaneous differential equations related to movement C: δX O− -D-f-p-n Mobility of chlorate ion DX = Perchlorate ion diffusion constant S; Cross-sectional area of polymer solid electrolyte (3) El; Electric field E2 due to battery electromotive force generated between both ions; Electrical neutrality between both ions If we organize the unknowns using electric field elimination method C to maintain this differential equation, this differential equation cannot be solved analytically, so macroscopically, the concentrations of lithium ions and perchlorate ions are determined to maintain electrical neutrality at all positions. Approximating that the concentrations are equal, we integrate the concentration y over x:O~1 and find the integral constant from the initially added amount of lithium ions M(0).The ion mobility and diffusion constant According to Einstein's law of approximation that is proportional to -D - to -D Substituting these values, we can see from equation (6) that the concentration of lithium ions on the negative and positive electrode surfaces means that the discharge capacity of the battery is extremely small. This means that a steady state cannot be obtained, and equation (7) cannot be established.In other words, the lithium ion concentration at the negative electrode surface is higher than the concentration at the site in the polymer solid electrolyte that can accept lithium ions. That is to say.
交流インピーダンス法で測定した時鵡最も高い伝導度を
与えるリチウムイオン濃度が、高分子固体電解質中のリ
チウムイオンを受は入れられるサイトの最大濃度を示し
ている。この時の濃度をＭ−とすると、臨界条件は（９
）式になる。The lithium ion concentration that gives the highest conductivity when measured by the AC impedance method indicates the maximum concentration of sites that can accept lithium ions in the solid polymer electrolyte. If the concentration at this time is M-, the critical condition is (9
) becomes the formula.
また、正極表面でリチウムイオン濃度が０になっても、
熱論放電は継続できないので、その臨界条件は（１０）
式になる。Moreover, even if the lithium ion concentration becomes 0 on the surface of the positive electrode,
Since thermal discharge cannot continue, its critical condition is (10)
It becomes a ceremony.
Ｌ
Ｍ （ｍ＋ ＞ Ｍ （０１＋ ４ｅＳＤ
（９）（９）、 （１０）式を図示すると第１図の
斜線部となり、イオン伝導度の面からは、Ｍ（０）は高
い方か良いのであるから・
Ｍ （０１−Ｍ （ｍ）／ ２
発明の効果
上述した如く、本発明は高率放電時の放電容量の優れた
高分子固体電解質リチウム電池を提供することが出来る
ので、その工業的価値は極めて大である。L M (m+ > M (01+ 4eSD
(9) (9) and (10) are shown in the shaded area in Figure 1. From the perspective of ionic conductivity, the higher M(0) is, the better. M (01-M (m )/2 Effects of the Invention As described above, the present invention can provide a polymer solid electrolyte lithium battery with excellent discharge capacity during high rate discharge, and therefore has extremely great industrial value.
第１図は第９式と第１０式を図示したもの、第２図はリ
チウムパークロレイトの添加量とイオン伝４度の関係を
示したもの、第３図は本発明の電池と従来品電池の放電
特性比較図である。Figure 1 shows equations 9 and 10, Figure 2 shows the relationship between the amount of lithium perchlorate added and ion conductivity, and Figure 3 shows the battery of the present invention and the conventional battery. FIG. 3 is a comparison diagram of discharge characteristics of batteries.
Claims (1)
材料であり、負極がリチウムまたはリチウム合金であり
、電解質がイオン伝導度を有する有機固体高分子とリチ
ウムイオンを含む無機塩からなり、該リチウムイオンを
含む無機塩が交流インピーダンス法で測定した最も高い
伝導度にあるリチウムイオン濃度に対し、１／２の濃度
であることを特徴とする高分子固体電解質リチウム電池
。The positive electrode is a material capable of intercalating lithium ions, the negative electrode is lithium or a lithium alloy, and the electrolyte is composed of an organic solid polymer having ionic conductivity and an inorganic salt containing lithium ions, and the inorganic salt containing the lithium ions. A polymer solid electrolyte lithium battery characterized in that the concentration of lithium ions is 1/2 of the lithium ion concentration at the highest conductivity measured by an AC impedance method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1319608A JP3041864B2 (en) | 1989-12-08 | 1989-12-08 | Polymer solid electrolyte lithium battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1319608A JP3041864B2 (en) | 1989-12-08 | 1989-12-08 | Polymer solid electrolyte lithium battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH03182056A true JPH03182056A (en) | 1991-08-08 |
| JP3041864B2 JP3041864B2 (en) | 2000-05-15 |
Family
ID=18112176
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1319608A Expired - Fee Related JP3041864B2 (en) | 1989-12-08 | 1989-12-08 | Polymer solid electrolyte lithium battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3041864B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8447561B2 (en) | 2008-06-06 | 2013-05-21 | Canon Kabushiki Kaisha | Shape measurement method of synthetically combining partial measurements |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR102009288B1 (en) * | 2017-09-18 | 2019-08-09 | 한국정보공학 주식회사 | Apparatus for holding fishing rod |
-
1989
- 1989-12-08 JP JP1319608A patent/JP3041864B2/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8447561B2 (en) | 2008-06-06 | 2013-05-21 | Canon Kabushiki Kaisha | Shape measurement method of synthetically combining partial measurements |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3041864B2 (en) | 2000-05-15 |
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Legal Events
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