JP2009245911A - Electrolytic solution, and secondary battery using the same - Google Patents
Electrolytic solution, and secondary battery using the same Download PDFInfo
- Publication number
- JP2009245911A JP2009245911A JP2008119597A JP2008119597A JP2009245911A JP 2009245911 A JP2009245911 A JP 2009245911A JP 2008119597 A JP2008119597 A JP 2008119597A JP 2008119597 A JP2008119597 A JP 2008119597A JP 2009245911 A JP2009245911 A JP 2009245911A
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- JP
- Japan
- Prior art keywords
- lithium
- electrolytic solution
- group
- salt
- ion conductive
- 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
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- 229910052744 lithium Inorganic materials 0.000 claims abstract description 30
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 29
- 150000003839 salts Chemical class 0.000 claims abstract description 29
- 150000002500 ions Chemical class 0.000 claims abstract description 24
- 229940126062 Compound A Drugs 0.000 claims abstract description 19
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 claims abstract description 19
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- 125000004432 carbon atom Chemical group C* 0.000 claims description 15
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- ACFSQHQYDZIPRL-UHFFFAOYSA-N lithium;bis(1,1,2,2,2-pentafluoroethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)C(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)C(F)(F)F ACFSQHQYDZIPRL-UHFFFAOYSA-N 0.000 claims description 3
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- 125000001889 triflyl group Chemical group FC(F)(F)S(*)(=O)=O 0.000 claims 1
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- 239000000243 solution Substances 0.000 abstract 1
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- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 125000003866 trichloromethyl group Chemical group ClC(Cl)(Cl)* 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- 125000003258 trimethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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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- Primary Cells (AREA)
- Secondary Cells (AREA)
Abstract
Description
本発明は、発火の危険性の低い電解液及びこの電解液を用いた二次電池に関する。 The present invention relates to an electrolytic solution having a low risk of ignition and a secondary battery using the electrolytic solution.
近年多く用いられるようになったリチウム一次電池、リチウム二次電池等の蓄電デバイスにおいては、リチウムイオンが移動することにより充放電が行われる。
これら蓄電デバイスが使われる携帯用機器の小型高性能化に伴って、蓄電デバイスには高エネルギー密度化が求められている。
2. Description of the Related Art In power storage devices such as lithium primary batteries and lithium secondary batteries that have been widely used in recent years, charging and discharging are performed by movement of lithium ions.
Accompanying the miniaturization and high performance of portable devices in which these electricity storage devices are used, energy storage devices are required to have higher energy density.
これらの電池は、リチウム塩を有機溶媒に溶解した電解液が用いられており、有機溶媒としては、プロピレンカーボネート、エチレンカーボネート、γ−ブチロラクトン等の極性溶媒や、ジメチルカーボネート等の有機溶媒が用いられている。 In these batteries, an electrolytic solution in which a lithium salt is dissolved in an organic solvent is used. As the organic solvent, a polar solvent such as propylene carbonate, ethylene carbonate, and γ-butyrolactone, or an organic solvent such as dimethyl carbonate is used. ing.
これら有機溶媒は揮発性を有し、また可燃性でもあるため、環境への影響や、過熱時の発火の問題等も有する。 Since these organic solvents are volatile and flammable, they also have environmental impacts, ignition problems during overheating, and the like.
上記問題点を解決する手法の一つとして、いわゆる常温溶融塩を用いる手法も提案されている。即ち、常温溶融塩は、イオンに解離可能な塩でありながら常温で液体の化合物であり、また不揮発性のため発火の危険もないため、該常温溶融塩を溶媒とし、リチウム塩をこの常温溶融塩に溶解することによって、揮発性有機溶媒による環境への影響や安全性の問題を低減する方法が提案されている(例えば、特許文献1参照)。 As one of methods for solving the above problems, a method using a so-called room temperature molten salt has also been proposed. That is, a room temperature molten salt is a compound that is dissociable into ions but is a liquid at room temperature, and since it is non-volatile, there is no risk of ignition. There has been proposed a method for reducing environmental problems and safety problems caused by volatile organic solvents by dissolving in a salt (see, for example, Patent Document 1).
また、特定の構造のエーテル化合物を配位子として有するアルカリ金属のエーテル錯塩が提案されており、安全性を高めることが報告されている(例えば、特許文献2参照)。 Moreover, an alkali metal ether complex salt having an ether compound having a specific structure as a ligand has been proposed, and it has been reported to improve safety (for example, see Patent Document 2).
従来公知の常温溶融塩を溶媒として用いた場合には、カチオンとしてのリチウムイオンと常温溶融塩を構成するカチオンとの二種類が存在するため、電場をかけた際に、リチウムイオンの移動と常温溶融塩を構成するカチオンの移動とが競争して起きるため、電池特性が悪いという問題があった。 When a conventionally known room temperature molten salt is used as a solvent, there are two types of lithium ions as cations and cations constituting the room temperature molten salt. Since the movement of the cation constituting the molten salt occurs in competition, there is a problem that the battery characteristics are poor.
また、特許文献2に記載されている特定の構造のエーテルを配位子として有するリチウム塩のエーテル錯塩について、リチウムイオン電池特性に関する記載はなかった。我々の実験によると満足のいくリチウムイオン電池特性を得る事はできなかった。 Moreover, there was no description about the lithium ion battery characteristic about the ether complex of the lithium salt which has the ether of the specific structure described in patent document 2 as a ligand. According to our experiments, satisfactory lithium-ion battery characteristics could not be obtained.
本発明は、発火の危険性が低く、安全性を高め、さらに従来の電解液を用いたリチウムイオン電池と同等の性能を得ることが可能な、電解液及びこの電解液を用いた二次電池を提供することを目的とするものである。 The present invention relates to an electrolyte solution and a secondary battery using this electrolyte solution that can reduce the risk of ignition, increase safety, and obtain performance equivalent to that of a lithium ion battery using a conventional electrolyte solution. Is intended to provide.
本発明者等は上記課題を解決する為に鋭意検討を行った結果、特定の構造のエーテル化合物とイオン導電性塩の混合溶媒が、ある特定の混合比率において発火の危険性が低いため、安全性を高めることができ、さらに従来の電解液を用いたリチウムイオン電池と同等の電池特性を示すことを見出し、本発明を完成するに至った。 As a result of diligent studies to solve the above problems, the present inventors have found that a mixed solvent of an ether compound having a specific structure and an ion conductive salt has a low risk of ignition at a specific mixing ratio, so that it is safe. The present invention has been completed by finding that the battery characteristics can be improved and battery characteristics equivalent to those of a conventional lithium ion battery using an electrolytic solution are exhibited.
本発明は、(1)下記一般式(I)で示されるエーテル化合物Aと、イオン導電性塩Bとの混合物を含み、前記エーテル化合物Aと前記イオン導電性塩Bの混合比率が、モル比で0.4≦(A/B)<1である電解液に関する。 The present invention includes (1) a mixture of an ether compound A represented by the following general formula (I) and an ion conductive salt B, wherein the mixing ratio of the ether compound A and the ion conductive salt B is a molar ratio. And 0.4 ≦ (A / B) <1.
また、本発明は、(2)前記イオン導電性塩Bがリチウム塩であり、該リチウム塩が六フッ化リン酸リチウム(LiPF6)、四フッ化ホウ酸リチウム(LiBF4)、過塩素酸リチウム(LiClO4)、リチウムビス(トリフルオロメタンスルホニル)イミド(LiN(SO2CF3)2)、リチウムビス(ペンタフルオロエタンスルホニル)イミド(LiN(SO2C2F5)2)、トリフルオロメタンスルホン酸リチウム(LiCF3SO3)から選ばれる一種又は二種以上の混合物である上記(1)に記載の電解液に関する。 In the present invention, (2) the ion conductive salt B is a lithium salt, and the lithium salt is lithium hexafluorophosphate (LiPF 6 ), lithium tetrafluoroborate (LiBF 4 ), perchloric acid. Lithium (LiClO 4 ), lithium bis (trifluoromethanesulfonyl) imide (LiN (SO 2 CF 3 ) 2 ), lithium bis (pentafluoroethanesulfonyl) imide (LiN (SO 2 C 2 F 5 ) 2 ), trifluoromethanesulfone is one or a mixture of two or more selected from lithium acid (LiCF 3 SO 3) relating to the electrolyte according to the above (1).
また、本発明は、(3)前記リチウム塩が、リチウムビス(トリフルオロメタンスルホニル)イミド(LiN(SO2CF3)2)である上記(2)に記載の電解液に関する。
また、本発明は、(4)前記一般式(I)中のnがn=2〜6である上記(1)〜(3)のいずれか一つに記載の電解液に関する。
また、本発明は、(5)前記一般式(I)中のnがn=2であり、R1、R3がメチル基、R2がエチレン基である上記(1)〜(4)のいずれか一つに記載の電解液に関する。
The present invention also relates to (3) the electrolytic solution according to (2), wherein the lithium salt is lithium bis (trifluoromethanesulfonyl) imide (LiN (SO 2 CF 3 ) 2 ).
Moreover, this invention relates to the electrolyte solution as described in any one of said (1)-(3) whose n in said (4) said general formula (I) is n = 2-6.
Further, the present invention relates to the use of (5) wherein a general formula (I) n is n = 2 in, R 1, R 3 is a methyl group, R 2 is (1) to (4) is an ethylene group The electrolyte solution according to any one of the above.
さらに、本発明は、(6)正極及び負極と、これら正負極間に介在させたセパレーターと、電解液と、を含む二次電池において、前記電解液が、上記(1)〜(5)のいずれか一つに記載の電解液である二次電池に関する。 Furthermore, the present invention provides a secondary battery comprising (6) a positive electrode and a negative electrode, a separator interposed between the positive and negative electrodes, and an electrolytic solution, wherein the electrolytic solution is as described in (1) to (5) above. The present invention relates to a secondary battery that is the electrolytic solution according to any one of the above.
本発明の電解液は、発火の危険性が低いために安全性を高めることができ、さらに従来の電解液を用いた二次電池と同等の電池性能を得ることができる。 Since the electrolyte of the present invention has a low risk of ignition, safety can be improved, and battery performance equivalent to that of a secondary battery using a conventional electrolyte can be obtained.
(本発明の電解液)
本発明の電解液は、下記一般式(I)で示されるエーテル化合物Aと、イオン導電性塩Bとの混合物を含み、前記エーテル化合物Aと前記イオン導電性塩Bの混合比率が、モル比で0.4≦(A/B)<1である。
(Electrolytic solution of the present invention)
The electrolytic solution of the present invention contains a mixture of an ether compound A represented by the following general formula (I) and an ion conductive salt B, and the mixing ratio of the ether compound A and the ion conductive salt B is a molar ratio. 0.4 ≦ (A / B) <1.
前記イオン性導電性塩Bとしては、リチウム塩が挙げられ、リチウム電池又はリチウムイオン電池の作動電圧範囲で安定なリチウム塩であれば、特に制限はない。
本発明で用いられるリチウム塩として、具体的には、六フッ化リン酸リチウム(LiPF6)、四フッ化ホウ酸リチウム(LiBF4)、過塩素酸リチウム(LiClO4)、リチウムビス(トリフルオロメタンスルホニル)イミド(LiN(SO2CF3)2)、リチウムビス(ペンタフルオロエタンスルホニル)イミド(LiN(SO2C2F5)2)、トリフルオロメタンスルホン酸リチウム(LiCF3SO3)が挙げられる。
これらのリチウム塩は、1種単独で用いることも、2種以上混合して用いることもできる。
Examples of the ionic conductive salt B include lithium salts, and are not particularly limited as long as they are stable in the operating voltage range of a lithium battery or a lithium ion battery.
Specific examples of the lithium salt used in the present invention include lithium hexafluorophosphate (LiPF 6 ), lithium tetrafluoroborate (LiBF 4 ), lithium perchlorate (LiClO 4 ), and lithium bis (trifluoromethane). Sulfonyl) imide (LiN (SO 2 CF 3 ) 2 ), lithium bis (pentafluoroethanesulfonyl) imide (LiN (SO 2 C 2 F 5 ) 2 ), lithium trifluoromethanesulfonate (LiCF 3 SO 3 ), and the like. .
These lithium salts can be used singly or in combination of two or more.
これらの中でもリチウムビス(トリフルオロメタンスルホニル)イミドを用いると、電解液の粘度が低くなること及びエーテルへの溶解性が高いため、望ましい。
本発明で用いられるエーテル化合物Aとしての前記一般式(I)中、R1、R3は、同一又は異なる、総炭素数が1〜4の、置換基を有していてもよいアルキル基である。置換基としては、フッ素、塩素等のハロンゲン基、ニトリル基、ケトン基、アルケニル基等が挙げられる。
Among these, use of lithium bis (trifluoromethanesulfonyl) imide is desirable because the viscosity of the electrolytic solution is low and the solubility in ether is high.
In the general formula (I) as the ether compound A used in the present invention, R 1 and R 3 are the same or different alkyl groups having 1 to 4 carbon atoms, which may have a substituent. is there. Examples of the substituent include a halogenon group such as fluorine and chlorine, a nitrile group, a ketone group, and an alkenyl group.
R1又はR3として示される、置換基を有していても良い総炭素数1〜4のアルキル基として具体的には、メチル基、エチル基、n−プロピル基、sec−プロピル基、n−ブチル基、sec−ブチル基、tert−ブチル基等の無置換アルキル基;モノフルオロメチル基、トリフルオロメチル基、ペンタフルオロエチル基等のフルオロアルキル基;トリクロロメチル基、2−クロロエチル基、ペンタクロロエチル基等のクロロアルキル基;等を挙げることができる。 Specific examples of the optionally substituted alkyl group having 1 to 4 carbon atoms represented by R 1 or R 3 include methyl group, ethyl group, n-propyl group, sec-propyl group, n -Unsubstituted alkyl group such as butyl group, sec-butyl group, tert-butyl group; fluoroalkyl group such as monofluoromethyl group, trifluoromethyl group, pentafluoroethyl group; trichloromethyl group, 2-chloroethyl group, penta A chloroalkyl group such as a chloroethyl group;
炭素数が多くなるほど、粘度が上昇する傾向が強いため、前記R1又はR3が炭素数5以上のアルキル基では、イオン伝導性が低くなり、やはり本発明の目的である、良好なイオン伝導度を得ることが困難となる。なお、同じ炭素数の場合、置換基、特にハロゲン基を有するアルキル基は、エーテルとイオン導電性塩との間の相互作用が小さくなり、粘度が小さくなる傾向がある反面、難燃性の効果が小さくなる傾向がある。
従って、R1、R3としては、メチル基又はエチル基であることが好ましく、さらにはメチル基であることが好ましい。
Since the viscosity tends to increase as the number of carbon atoms increases, the ionic conductivity of the alkyl group in which R 1 or R 3 is 5 or more is low, which is also an object of the present invention, and is good ion conduction. It becomes difficult to obtain the degree. In the case of the same number of carbon atoms, the substituent, particularly the alkyl group having a halogen group, tends to reduce the interaction between the ether and the ion conductive salt and reduce the viscosity, but the effect of flame retardancy. Tends to be smaller.
Therefore, R 1 and R 3 are preferably a methyl group or an ethyl group, and more preferably a methyl group.
上記一般式(I)において、R2は、置換基を有していてもよい総炭素数が2〜4のアルキレン基であり、その主鎖を構成する炭素数は2〜4である。上記R2における主鎖の炭素数が1である化合物は、安定性が低く、室温付近では安定な化合物として得ることができない傾向がある。他方、主鎖の炭素数が5以上では、化学的安定性が低くなるばかりでなく、イオン伝導度も低下する傾向がある。R2として特に好ましくは、主鎖を構成する炭素数が2のものである。 In the general formula (I), R 2 is the total number of carbon atoms which may have a substituent is an alkylene group having 2 to 4 carbon atoms constituting the main chain is 2 to 4. The compound having 1 carbon in the main chain in R 2 has a low stability and tends not to be obtained as a stable compound near room temperature. On the other hand, when the number of carbon atoms in the main chain is 5 or more, not only the chemical stability is lowered but also the ionic conductivity tends to be lowered. R 2 is particularly preferably one having 2 carbon atoms constituting the main chain.
また、R2は、総炭素数が2〜4であれば置換されていてもよい(総炭素数は、置換基を有する場合には、該置換基の炭素原子も含む数である)。総炭素数が5以上では、やはりイオン伝導度が充分なものとならない傾向がある。 R 2 may be substituted if the total carbon number is 2 to 4 (the total carbon number is the number including the carbon atom of the substituent when it has a substituent). If the total number of carbon atoms is 5 or more, the ionic conductivity tends to be insufficient.
R2として好適な基としては、エチレン基、トリメチレン基、テトラメチレン基等の無置換アルキレン基;イソプロピレン基、イソブチレン基等のアルキル置換アルキレン基、テトラフルオロエチレン基、1,1−ジフルオロエチレン基、ヘキサフルオロトリメチレン基等のフルオロアルキレン基;テトラクロロエチレン基、1,2−ジクロロエチレン基、1,1−ジクロロエチレン基等のクロロアルキレン基等を挙げることができる。
上記一般式(I)において、nは2以上である。nが1であると、難燃性の効果が得られ難い傾向がある。nを2以上とすることで、イオン導電性塩と相互作用できるエーテル中の酸素原子の数が増えるため、難燃性の効果が得られ易い傾向がある。
R 2 is preferably an unsubstituted alkylene group such as an ethylene group, trimethylene group or tetramethylene group; an alkyl-substituted alkylene group such as an isopropylene group or isobutylene group, a tetrafluoroethylene group or a 1,1-difluoroethylene group. And fluoroalkylene groups such as hexafluorotrimethylene group; chloroalkylene groups such as tetrachloroethylene group, 1,2-dichloroethylene group and 1,1-dichloroethylene group.
In the above general formula (I), n is 2 or more. When n is 1, the flame retardancy effect tends to be hardly obtained. By setting n to 2 or more, the number of oxygen atoms in the ether that can interact with the ion conductive salt is increased, and thus there is a tendency that a flame-retardant effect is easily obtained.
本発明で用いられるエーテル化合物Aとして具体的には、エーテルを具体的に例示すると、ジエチレングリコールジメチルエーテル、ジエチレングリコールエチルメチルエーテル、トリエチレングリコールジメチルエーテル、トリエチレングリコールエチルメチルエーテル、テトラエチレングリコールジメチルエーテル、ペンタエチレングリコールジメチルエーテル、ヘキサエチレングリコールジメチルエーテル等のエチレングリコール類、エチレングリコールビス(プロピオにトリル)、ジエチレングリコールモノエチルエーテルアセテート、2−エトキシエチルイソブチレート、2−(2−エトキシエトキシ)エチルアクリレート等が挙げられる。 Specific examples of the ether compound A used in the present invention include ethers such as diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, triethylene glycol dimethyl ether, triethylene glycol ethyl methyl ether, tetraethylene glycol dimethyl ether, and pentaethylene glycol. Examples include ethylene glycols such as dimethyl ether and hexaethylene glycol dimethyl ether, ethylene glycol bis (propiotolyl), diethylene glycol monoethyl ether acetate, 2-ethoxyethyl isobutyrate, 2- (2-ethoxyethoxy) ethyl acrylate, and the like.
電解液を構成するエーテルの沸点又は引火点が高いほど、リチウム電池又はリチウムイオン電池として使用した際の発火の危険性が低くなる傾向があるため好ましい。そのため、本発明で用いられるエーテル化合物Aは、沸点が100℃以上であることが好ましく、200℃以上であることがさらに好ましい。沸点が100℃以上のエーテルとしては、ジエチレングリコールジメチルエーテル等が上げられ、沸点が200℃以上であるエーテルとしては、トリエチレングリコールジメチルエーテル等が挙げられる。 The higher the boiling point or flash point of the ether constituting the electrolytic solution is preferable because the risk of ignition when used as a lithium battery or a lithium ion battery tends to decrease. Therefore, the ether compound A used in the present invention preferably has a boiling point of 100 ° C. or higher, and more preferably 200 ° C. or higher. Examples of the ether having a boiling point of 100 ° C. or higher include diethylene glycol dimethyl ether, and examples of the ether having a boiling point of 200 ° C. or higher include triethylene glycol dimethyl ether.
エーテル化合物Aとイオン導電性塩Bの混合物の融点が室温よりも高く、室温(約25℃)において固体である場合、有機溶媒に溶解して使用することができる。
また、エーテル化合物Aとイオン導電性塩Bの混合物が室温で液体であっても、融点や粘度を下げる目的及びリチウム電池特性を向上するために有機溶媒を添加して用いても良い。
When the melting point of the mixture of the ether compound A and the ion conductive salt B is higher than room temperature and is a solid at room temperature (about 25 ° C.), it can be used by dissolving in an organic solvent.
Further, even if the mixture of the ether compound A and the ion conductive salt B is liquid at room temperature, an organic solvent may be added for the purpose of lowering the melting point and viscosity and improving the lithium battery characteristics.
上記有機溶媒としては、イオン導電性塩Bを溶解可能であるとともに、リチウム電池又はリチウムイオン電池の作動電圧範囲で安定なものであれば、特に制限はない。
有機溶媒の具体例としては、ジブチルエーテル、1,2−ジメトキシエタン、1,2−エトキシメトキシエタン、ジエチレングリコールジメチルエーテル、トリエチレングリコールジメチルエーテル、テトラエチレングリコールジメチルエーテル、ジエチレングリコールジエチルエーテル、ジエチレングリコールジブチルエーテル、グリコールエーテル類(エチルセルソルブ、エチルカルビトール、ブチルセルソルブ、ブチルカルビトール等)等の鎖状エーテル類;テトラヒドロフラン、2−メチルテトラヒドロフラン、1,3−ジオキソラン、4,4−ジメチル−1,3−ジオキサン等の環状エーテル類;γ−ブチロラクトン、γ−バレロラクトン、δ−バレロラクトン、3−メチル−1,3−オキサゾリン−2−オン等のラクトン類;N−メチルホルムアミド、N,N−ジメチルホルムアミド、N−メチルアセトアミド、N−メチルピロリジノン等のアミド類;ジエチルカーボネート、ジメチルカーボネート、エチルメチルカーボネート、プロピレンカーボネート、エチレンカーボネート、スチレンカーボネート、ビニレンカーボネート等のカーボネート類;1,3−ジメチル−2−イミダゾリジノン等のイミダゾリジノン類又はこれらの各種有機溶媒の水素原子やアルキル基がフルオロアルキル基に置換されたフッ素系溶媒等が挙げられる。
これらの非水系有機溶媒は、1種単独で用いても良く、2種以上混合して用いても良い。
The organic solvent is not particularly limited as long as it can dissolve the ion conductive salt B and is stable in the operating voltage range of the lithium battery or the lithium ion battery.
Specific examples of the organic solvent include dibutyl ether, 1,2-dimethoxyethane, 1,2-ethoxymethoxyethane, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, glycol ethers. Chain ethers such as (ethyl cellosolve, ethyl carbitol, butyl cellosolve, butyl carbitol, etc.); tetrahydrofuran, 2-methyltetrahydrofuran, 1,3-dioxolane, 4,4-dimethyl-1,3-dioxane, etc. Cyclic ethers of γ-butyrolactone, γ-valerolactone, δ-valerolactone, lactones such as 3-methyl-1,3-oxazolin-2-one; N- Amides such as tilformamide, N, N-dimethylformamide, N-methylacetamide, N-methylpyrrolidinone; carbonates such as diethyl carbonate, dimethyl carbonate, ethylmethyl carbonate, propylene carbonate, ethylene carbonate, styrene carbonate, vinylene carbonate; Examples thereof include imidazolidinones such as 1,3-dimethyl-2-imidazolidinone or fluorine-based solvents in which hydrogen atoms or alkyl groups of these various organic solvents are substituted with fluoroalkyl groups.
These non-aqueous organic solvents may be used individually by 1 type, and may be used in mixture of 2 or more types.
中でも、誘電率が大きく、電気化学的安定範囲及び使用温度範囲が広く、且つ安全性に優れるものが好ましく、例えば、エチレンカーボネート又はプロピレンカーボネートを主成分として含む混合溶媒や、エチレンカーボネート、プロピレンカーボネート、ビニレンカーボネート、ジメチルカーボネート、エチルメチルカーボネート、ジエチルカーボネート、γ―ブチロラクトン、フッ素化プロピレンカーボネート及びフッ素化γ−ブチロラクトンから選ばれる少なくとも1種の溶媒を用いることが好ましい。 Among them, those having a large dielectric constant, wide electrochemical stability range and use temperature range, and excellent safety are preferable, for example, a mixed solvent containing ethylene carbonate or propylene carbonate as a main component, ethylene carbonate, propylene carbonate, It is preferable to use at least one solvent selected from vinylene carbonate, dimethyl carbonate, ethyl methyl carbonate, diethyl carbonate, γ-butyrolactone, fluorinated propylene carbonate, and fluorinated γ-butyrolactone.
本発明の電解液を製造する方法は特に制限はないが、前記エーテル化合物Aと前記イオン導電性塩Bを特定の混合比率で反応させ、混合物を得ることにより製造する方法が反応の容易さから好適である。 The method for producing the electrolytic solution of the present invention is not particularly limited, but the method for producing the mixture by reacting the ether compound A and the ion conductive salt B at a specific mixing ratio to obtain a mixture is easy to react. Is preferred.
エーテル化合物Aとイオン導電性塩Bの混合モル比率A/Bは、0.4≦(A/B)<1であることが好ましい。この比率が1以上であると安全性が高くなる効果が薄くなり、0.4未満であると高粘度が原因でイオン伝導率が低下する恐れがある。さらに好ましくは0.4≦(A/B)<0.9であり、0.5≦(A/B)<0.8が最適である。 The mixing molar ratio A / B of the ether compound A and the ion conductive salt B is preferably 0.4 ≦ (A / B) <1. If this ratio is 1 or more, the effect of increasing safety is reduced, and if it is less than 0.4, the ionic conductivity may be lowered due to high viscosity. More preferably, 0.4 ≦ (A / B) <0.9, and 0.5 ≦ (A / B) <0.8 is optimal.
本発明の電解液の製造において、反応温度や時間は特に限定はない。一般的には、攪拌下、用いる原料エーテル化合物Aの沸点以下の温度で、エーテル化合物Aとイオン導電性塩B、及び必要により有機溶媒とを混合し、数分〜数時間で反応は完結するため、本発明においても適宜反応時間、反応温度を調整すればよい。
なお、反応が完了して混合物が得られたことを確認するには、粘度確認により行う。一定時間後に粘度が変化ないことによって確認できる。
In the production of the electrolytic solution of the present invention, the reaction temperature and time are not particularly limited. In general, the ether compound A, the ion conductive salt B, and, if necessary, an organic solvent are mixed under stirring at a temperature below the boiling point of the starting ether compound A to be used, and the reaction is completed within a few minutes to a few hours. Therefore, the reaction time and reaction temperature may be appropriately adjusted in the present invention.
In addition, in order to confirm that the reaction is completed and a mixture is obtained, the viscosity is confirmed. This can be confirmed by the fact that the viscosity does not change after a certain time.
本発明の電解液は、粘度が200000mPa・s以下であることが好ましく、3000mPa・sであることがより好ましい。ここで粘度とは、E型粘度計((株)トキメックス製「ELD」)を用いて測定した25℃での粘度をさす。粘度を上記範囲とするには、エーテル化合物Aやイオン導電性塩Bを適宜選択する、エーテル化合物Aとイオン導電性塩Bとの混合比率を調整する、又は電解液に有機溶媒を添加する等で達成できる。 The electrolyte solution of the present invention preferably has a viscosity of 200,000 mPa · s or less, and more preferably 3000 mPa · s. Here, the viscosity refers to a viscosity at 25 ° C. measured using an E-type viscometer (“ELD” manufactured by Tokimex Co., Ltd.). In order to set the viscosity within the above range, the ether compound A and the ion conductive salt B are appropriately selected, the mixing ratio of the ether compound A and the ion conductive salt B is adjusted, or an organic solvent is added to the electrolytic solution. Can be achieved.
(本発明の電解液の利用)
このようにして得られた本発明になる電解液は、リチウムイオン一次電池及びリチウムイオン二次電池の電解液、リチウム一次電池及びリチウム二次電池の電解液に好適に用いられる。この電解液を用いて、リチウムイオン一次電池、リチウムイオン二次電池、リチウム一次電池、リチウム二次電池の蓄電デバイスを構成することにより、発火の危険性が低く安全性の高い電気化学デバイスを構築することもできる。
(Use of electrolytic solution of the present invention)
The electrolyte solution according to the present invention thus obtained is preferably used for an electrolyte solution of a lithium ion primary battery and a lithium ion secondary battery, and an electrolyte solution of a lithium primary battery and a lithium secondary battery. Using this electrolyte solution, lithium ion primary batteries, lithium ion secondary batteries, lithium primary batteries, and lithium secondary battery power storage devices are constructed to build electrochemical devices with low risk of ignition and high safety You can also
電池の基本構造は、セパレーターを介して正極及び負極を対向配置し、これに非水電解液を含浸させるものであり、本発明においては、この非水電解液として、上述した本発明の電解液を用いる。 The basic structure of the battery is such that a positive electrode and a negative electrode are arranged opposite to each other via a separator and impregnated with a non-aqueous electrolyte. In the present invention, the above-described electrolyte of the present invention is used as the non-aqueous electrolyte. Is used.
リチウム電池及びリチウムイオン電池の正極に含まれる正極活物質としては、LiCoO2、LiNiO2、LiMnO2、LiMn2O4等のリチウムと遷移金属との複合酸化物、MnO2、V2O5等の遷移金属酸化物、MoS2、TiS等の遷移金属硫化物、ポリアセチレン、ポリアセン、ポリアニリン、ポリピロール、ポリチオフェン等の導電性高分子化合物、ポリ(2,5−ジメルカプト−1,3,4−チアジアゾール)等のジスルフィド化合物等が用いられる。 Examples of the positive electrode active material included in the positive electrode of the lithium battery and the lithium ion battery include composite oxides of lithium and transition metal such as LiCoO 2 , LiNiO 2 , LiMnO 2 , LiMn 2 O 4 , MnO 2 , V 2 O 5, and the like. Transition metal oxides, transition metal sulfides such as MoS 2 , TiS, conductive polymer compounds such as polyacetylene, polyacene, polyaniline, polypyrrole, polythiophene, poly (2,5-dimercapto-1,3,4-thiadiazole) A disulfide compound such as is used.
リチウム電池及びリチウムイオン電池の負極に含まれる負極活物質としては、リチウム金属、リチウムアルミニウム合金等のリチウム合金、リチウムを吸蔵・放出できる炭素質材料、黒鉛、フェノール樹脂、フラン樹脂等のコークス類、炭素繊維、ガラス状炭素、熱分解炭素、活性炭等が用いられる。 Negative electrode active materials contained in the negative electrodes of lithium batteries and lithium ion batteries include lithium alloys such as lithium metal and lithium aluminum alloys, carbonaceous materials capable of occluding and releasing lithium, cokes such as graphite, phenolic resin, and furan resin, Carbon fiber, glassy carbon, pyrolytic carbon, activated carbon and the like are used.
電極活物質を用いて帯電デバイス用電極を作製する際に、バインダと共に導電助剤を用いることが好ましく、用いられる導電助剤としては、例えば、アセチレンブラック、ケッチェンブラック等のカーボンブラック、天然黒鉛、熱膨張黒鉛、炭素繊維、導電性カーボン、酸化ルテニウム、酸化チタン、アルミニウム、ニッケル等の金属繊維等が用いられる。これらの中でも、少量の配合で所望の導電性を確保できるアセチレンブラック、ケッチェンブラックが好ましい。
なお、導電助剤は、電極活物質に対して、通常0.5〜50質量%程度配合されるが、1〜30質量%配合することがより好ましい。
When producing an electrode for a charging device using an electrode active material, it is preferable to use a conductive aid together with a binder. Examples of the conductive aid used include carbon black such as acetylene black and ketjen black, natural graphite Further, metal fibers such as thermally expanded graphite, carbon fiber, conductive carbon, ruthenium oxide, titanium oxide, aluminum, and nickel are used. Among these, acetylene black and ketjen black that can ensure desired conductivity with a small amount of blend are preferable.
In addition, although a conductive support agent is normally mix | blended about 0.5-50 mass% with respect to an electrode active material, it is more preferable to mix | blend 1-30 mass%.
帯電デバイス用電極を作製する際に導電助剤と共に用いられるバインダとしては、公知の各種バインダを用いることができる。
例えば、ポリテトラフルオロエチレン、ポリフッ化ビニリデン、カルボキシメチルセルロース、フルオロオレフィン共重合体架橋ポリマー、スチレン−ブタジエン共重合体、ポリアクリロニトリル、ポリビニルアルコール、ポリアクリル酸、ポリイミド、石油ピッチ、石炭ピッチ、フェノール樹脂等が挙げられる。
なお、帯電デバイス用電極の作製において、N−メチルピロリドン、N,N−ジメチルホルムアミド、ジメチルアセトアミド、水、アルコール類等の塗工溶媒を用いることも好ましい。
Various known binders can be used as the binder used together with the conductive auxiliary agent when the charging device electrode is produced.
For example, polytetrafluoroethylene, polyvinylidene fluoride, carboxymethyl cellulose, fluoroolefin copolymer crosslinked polymer, styrene-butadiene copolymer, polyacrylonitrile, polyvinyl alcohol, polyacrylic acid, polyimide, petroleum pitch, coal pitch, phenol resin, etc. Is mentioned.
In the production of the charging device electrode, it is also preferable to use a coating solvent such as N-methylpyrrolidone, N, N-dimethylformamide, dimethylacetamide, water, and alcohols.
帯電デバイスに用いるセパレーターとしても、公知の各種セパレーターを用いることができる。
具体例としては、紙製、ポリプロピレン製、ポリエチレン製、ガラス繊維製セパレーター等が挙げられる。
Various known separators can also be used as the separator used in the charging device.
Specific examples include paper, polypropylene, polyethylene, glass fiber separators, and the like.
ただし、電解液が高粘度である場合には、ポリプロピレン製やポリエチレン製のものを用いると濡れ性が悪くなる可能性があるため、ポリプロピレンやポリエチレン多孔体の表面をシラン且つプリング剤や樹脂等によって処理したセパレーターを用いることでセパレーターへの濡れ性を向上させることができる。 However, when the electrolyte solution has a high viscosity, the use of polypropylene or polyethylene may deteriorate the wettability, so the surface of the polypropylene or polyethylene porous body is made of silane and a pulling agent or resin. By using the treated separator, the wettability to the separator can be improved.
以下、実施例により本発明をさらに具体的に説明するが、本発明はこれらの実施例に制限するものではない。
<電解液の作製>
EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples.
<Preparation of electrolyte>
(実施例1)
2.63g(12mmol)のリチウムビス(トリフルオロメタンスルホニル)イミドに、5.09g(18mmol)のテトラエチレングリコールジメチルエーテルを加えてアルゴン雰囲気下室温で24時間攪拌し、無色透明の液体を得て、これを電解液1とした。
なお、反応が完了して混合物が得られたことを確認するには、粘度確認により行う。一定時間後に粘度が変化ないことによって確認できる。
Example 1
To 2.63 g (12 mmol) of lithium bis (trifluoromethanesulfonyl) imide, 5.09 g (18 mmol) of tetraethylene glycol dimethyl ether was added and stirred at room temperature for 24 hours under an argon atmosphere to obtain a colorless transparent liquid. Was used as electrolytic solution 1.
In addition, in order to confirm that the reaction is completed and a mixture is obtained, the viscosity is confirmed. This can be confirmed by the fact that the viscosity does not change after a certain time.
(実施例2)
10.1g(35mmol)のリチウムビス(トリフルオロメタンスルホニル)イミドに、5.66g(25mmol)のテトラエチレングリコールジメチルエーテルを加えてアルゴン雰囲気下室温で24時間攪拌し、無色透明の液体を得て、これを電解液2とした。
(Example 2)
To 10.1 g (35 mmol) of lithium bis (trifluoromethanesulfonyl) imide, 5.66 g (25 mmol) of tetraethylene glycol dimethyl ether was added and stirred at room temperature under an argon atmosphere for 24 hours to obtain a colorless transparent liquid. Was used as electrolytic solution 2.
(実施例3)
9.25g(32mmol)のリチウムビス(トリフルオロメタンスルホニル)イミドに、5.63g(25mmol)のテトラエチレングリコールジメチルエーテルを加えてアルゴン雰囲気下室温で24時間攪拌し、無色透明の液体を得て、これを電解液3とした。
(Example 3)
To 9.25 g (32 mmol) of lithium bis (trifluoromethanesulfonyl) imide, 5.63 g (25 mmol) of tetraethylene glycol dimethyl ether was added and stirred at room temperature under an argon atmosphere for 24 hours to obtain a colorless transparent liquid. Was used as electrolytic solution 3.
(比較例1)
4.85g(17mmol)のリチウムビス(トリフルオロメタンスルホニル)イミドに3.77g(17mmol)のテトラエチレングリコールジメチルエーテルを加えてアルゴン雰囲気下室温で24時間攪拌し、無色透明の液体を得て、これを電解液4とした。
(Comparative Example 1)
4.77 g (17 mmol) of tetraethylene glycol dimethyl ether was added to 4.85 g (17 mmol) of lithium bis (trifluoromethanesulfonyl) imide and stirred at room temperature for 24 hours under an argon atmosphere to obtain a colorless transparent liquid. Electrolytic solution 4 was obtained.
(比較例2)
7.01g(24mmol)のリチウムビス(トリフルオロメタンスルホニル)イミド(キシダ化学(株)製)に、2.32g(10.5mmol)のテトラエチレングリコールジメチルエーテル(東京化成工業(株)製)を加えてアルゴン雰囲気下室温で24時間攪拌し、無色透明の液体を得て、これを電解液5とした。
(Comparative Example 2)
To 7.01 g (24 mmol) of lithium bis (trifluoromethanesulfonyl) imide (manufactured by Kishida Chemical Co., Ltd.), 2.32 g (10.5 mmol) of tetraethylene glycol dimethyl ether (manufactured by Tokyo Chemical Industry Co., Ltd.) was added. The mixture was stirred at room temperature for 24 hours under an argon atmosphere to obtain a colorless and transparent liquid.
<電解液の評価>
(粘度の測定)
実施例1〜3の電解液1〜3及び比較例1及び2の電解液4、5について、E型粘度計((株)トキメック製「ELD」)を用いて25℃での粘度を測定した。
<Evaluation of electrolyte>
(Measurement of viscosity)
About the electrolytic solutions 1-3 of Examples 1-3 and the electrolytic solutions 4, 5 of Comparative Examples 1 and 2, the viscosity at 25 ° C. was measured using an E-type viscometer (“ELD” manufactured by Tokimec Co., Ltd.). .
(イオン伝導率の測定)
実施例1〜3の電解液1〜3及び比較例1及び2の電解液4、5について、電気伝導率計(東亜DKK製「CM−20J」)を用いて25℃でのイオン伝導率を測定した。
(Ion conductivity measurement)
For the electrolytic solutions 1 to 3 of Examples 1 to 3 and the electrolytic solutions 4 and 5 of Comparative Examples 1 and 2, the ionic conductivity at 25 ° C. was measured using an electric conductivity meter (“CM-20J” manufactured by Toa DKK). It was measured.
(電解液難燃性試験)
実施例1〜3の電解液1〜3及び比較例1及び2の電解液4、5について、電解液難燃性試験を行った。ガラスフィルターに各電解液を含浸し、10cmの長さの炎に調節したガスバーナーを炎の先端にガラスフィルターを置いて3秒間接した後、炎から離してガラスフィルターの燃焼の有無を確認した。この試験を3回行い、3回のうち燃焼した回数を評価した。燃焼した回数が少ないほど、蓄電デバイス用電解液として使用した際の発火の危険性が低いと判断した。
(Electrolyte flame retardant test)
The electrolyte solution flame retardancy test was performed on the electrolyte solutions 1 to 3 of Examples 1 to 3 and the electrolyte solutions 4 and 5 of Comparative Examples 1 and 2. A glass filter was impregnated with each electrolyte solution and a gas burner adjusted to a flame of 10 cm in length was placed on the tip of the flame for 3 seconds to indirect, and then separated from the flame to check whether the glass filter burned or not. . This test was performed three times, and the number of times of burning out of the three times was evaluated. It was judged that the smaller the number of burns, the lower the risk of ignition when used as an electrolyte for an electricity storage device.
(熱安定性試験)
実施例1〜3の電解液1〜3及び比較例1及び2の電解液4、5について、熱安定性試験を行った。示差熱・熱重量同時測定装置(Seiko Instruments社製、TG/DTA630)を用いて10℃/分の昇温速度で30〜300℃の温度範囲で測定した。質量減少率が5%となる温度を分解温度として評価した。
上記の粘度、イオン伝導率、電解液難燃性試験及び熱分解温度の結果を表1に示す。
(Thermal stability test)
A thermal stability test was performed on the electrolytic solutions 1 to 3 of Examples 1 to 3 and the electrolytic solutions 4 and 5 of Comparative Examples 1 and 2. It measured in the temperature range of 30-300 degreeC with the temperature increase rate of 10 degree-C / min using the differential-heat / thermogravimetric simultaneous measuring apparatus (The Seiko Instruments company make, TG / DTA630). The temperature at which the mass reduction rate was 5% was evaluated as the decomposition temperature.
Table 1 shows the results of the above viscosity, ionic conductivity, electrolyte flame retardant test and thermal decomposition temperature.
(電極特性の評価)
1)リチウム二次電池用正極の作製
正極活物質としてコバルト酸リチウム(日本化学工業(株)製、「セルシード10N」)と、導電性カーボン(電気化学工業(株)製、「HS−100」)と、バインダとしてポリフッ化ビニリデン((株)クレハ製、「PVDF#1120」)と、塗工溶媒としてN−メチルピロリドン(以下、NMP)を活物質:導電性カーボン:バインダ:NMP=94:3:3:28(固形分の質量比率)の割合で混合してペースト状にし、アルミ集電箔(日本蓄電器工業(株)製、「20CB」)に塗布し、80℃で4時間乾燥させた後、圧延してリチウム二次電池用正極電極を得た。圧延後の正極活物質の密度は2.5g/mlであった。
(Evaluation of electrode characteristics)
1) Preparation of positive electrode for lithium secondary battery Lithium cobaltate (manufactured by Nippon Chemical Industry Co., Ltd., “Cell Seed 10N”) and conductive carbon (manufactured by Electrochemical Industry Co., Ltd., “HS-100”) as a positive electrode active material ), Polyvinylidene fluoride (manufactured by Kureha Co., Ltd., “PVDF # 1120”) as a binder, and N-methylpyrrolidone (hereinafter, NMP) as a coating solvent: active material: conductive carbon: binder: NMP = 94: It was mixed at a ratio of 3: 3: 28 (mass ratio of solid content) to form a paste, applied to an aluminum current collector foil (manufactured by Nippon Electric Storage Co., Ltd., “20CB”), and dried at 80 ° C. for 4 hours. And then rolling to obtain a positive electrode for a lithium secondary battery. The density of the positive electrode active material after rolling was 2.5 g / ml.
2)リチウム二次電池の作製
対極として厚さ1mmの金属リチウムを用い、また作用極として前記で得られた正極電極を用い、両極をセパレーター(セルガード(株)製、「セルガード#2300」)を介して対向させた。上記各電解液を用いて通常の方法によってリチウム二次電池を作製した。
2) Fabrication of lithium secondary battery Using 1 mm thick metal lithium as the counter electrode and using the positive electrode obtained above as the working electrode, both electrodes were separators ("Celguard # 2300" manufactured by Celgard Co., Ltd.). Faced through. A lithium secondary battery was produced by the usual method using each of the above electrolytic solutions.
3)電極特性の評価
対極(リチウム極)に対し、0.1Cに相当する電流で4.2Vまで充電した。
放電はリチウム極に対して0.1Cに相当する電流で3.0Vまで行い、初期(初回)放電容量を測定した。またこの初期放電容量を初期充電容量で割った値を初期充放電効率(%)として算出した。その結果を表2に示す。
3) Evaluation of electrode characteristics The counter electrode (lithium electrode) was charged to 4.2 V with a current corresponding to 0.1 C.
Discharge was performed up to 3.0 V with a current corresponding to 0.1 C with respect to the lithium electrode, and the initial (initial) discharge capacity was measured. A value obtained by dividing the initial discharge capacity by the initial charge capacity was calculated as the initial charge / discharge efficiency (%). The results are shown in Table 2.
表1に示されるように本発明になる電解液は安全性に優れることが明らかである。
また、表2に示されるように、本発明になる電解液を用いた実施例1〜3のリチウム二次電池では、従来の電解液を用いたリチウム電池と同等の初期放電容量及び初期充放電効率を示すことが明らかである。
このように、本発明になる電解液を用いた場合、発火の危険性が低く、熱安定性に優れた有用な蓄電デバイス用電解液となり得ることがわかる。
As shown in Table 1, it is clear that the electrolytic solution according to the present invention is excellent in safety.
Further, as shown in Table 2, in the lithium secondary batteries of Examples 1 to 3 using the electrolytic solution according to the present invention, the initial discharge capacity and the initial charge and discharge equivalent to those of the lithium battery using the conventional electrolytic solution are used. It is clear that it shows efficiency.
Thus, it can be seen that when the electrolytic solution according to the present invention is used, the risk of ignition is low and the electrolytic solution for a power storage device having excellent thermal stability can be obtained.
Claims (6)
Priority Applications (1)
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JP2010073489A (en) * | 2008-09-18 | 2010-04-02 | Nissan Motor Co Ltd | Electrolyte excellent in thermal stability and secondary battery prepared using the same |
WO2012011507A1 (en) | 2010-07-21 | 2012-01-26 | 旭硝子株式会社 | Non-aqueous electrolyte for secondary batteries, and secondary battery |
WO2012060445A1 (en) * | 2010-11-05 | 2012-05-10 | 株式会社 村田製作所 | Secondary battery |
JP2012104268A (en) * | 2010-11-08 | 2012-05-31 | Central Res Inst Of Electric Power Ind | Lithium-ion secondary battery |
JP2012109223A (en) * | 2010-10-29 | 2012-06-07 | Yokohama National Univ | Alkali metal-sulfur secondary battery |
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US10290902B2 (en) | 2016-05-27 | 2019-05-14 | Samsung Electronics Co., Ltd. | Electrolyte for lithium metal battery, lithium metal battery including the electrolyte, and method of manufacturing the lithium metal battery |
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