JPH01258410A - Energy storage device using non-aqueous electrolyte - Google Patents
Energy storage device using non-aqueous electrolyteInfo
- Publication number
- JPH01258410A JPH01258410A JP63085183A JP8518388A JPH01258410A JP H01258410 A JPH01258410 A JP H01258410A JP 63085183 A JP63085183 A JP 63085183A JP 8518388 A JP8518388 A JP 8518388A JP H01258410 A JPH01258410 A JP H01258410A
- Authority
- JP
- Japan
- Prior art keywords
- storage device
- energy storage
- aqueous electrolyte
- electrolyte energy
- carbon atoms
- 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.)
- Pending
Links
- 238000004146 energy storage Methods 0.000 title claims description 19
- 239000011255 nonaqueous electrolyte Substances 0.000 title claims description 18
- 125000003118 aryl group Chemical group 0.000 claims abstract description 20
- 150000001875 compounds Chemical class 0.000 claims abstract description 17
- 150000003839 salts Chemical class 0.000 claims abstract description 16
- 239000003792 electrolyte Substances 0.000 claims abstract description 14
- 238000009833 condensation Methods 0.000 claims abstract description 10
- 230000005494 condensation Effects 0.000 claims abstract description 10
- 229910052751 metal Inorganic materials 0.000 claims abstract description 6
- 239000002184 metal Substances 0.000 claims abstract description 6
- 239000003960 organic solvent Substances 0.000 claims abstract description 6
- 229910001420 alkaline earth metal ion Inorganic materials 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims abstract description 4
- 239000000126 substance Substances 0.000 claims abstract 3
- 229920000642 polymer Polymers 0.000 claims description 13
- 125000004432 carbon atom Chemical group C* 0.000 claims description 12
- 125000000217 alkyl group Chemical group 0.000 claims description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 9
- 229910052799 carbon Inorganic materials 0.000 claims description 7
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims description 6
- 125000003709 fluoroalkyl group Chemical group 0.000 claims description 6
- 229910052736 halogen Inorganic materials 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 229910052698 phosphorus Inorganic materials 0.000 claims description 5
- 229910001413 alkali metal ion Inorganic materials 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 125000004437 phosphorous atom Chemical group 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical group CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 3
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims 3
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims 2
- 238000002441 X-ray diffraction Methods 0.000 claims 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims 1
- 229910003002 lithium salt Inorganic materials 0.000 claims 1
- 159000000002 lithium salts Chemical group 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 9
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 abstract 1
- 239000013543 active substance Substances 0.000 abstract 1
- 229910052796 boron Inorganic materials 0.000 abstract 1
- 229910021645 metal ion Inorganic materials 0.000 abstract 1
- -1 halogen ion Chemical class 0.000 description 10
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 8
- 210000004027 cell Anatomy 0.000 description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 4
- 239000007772 electrode material Substances 0.000 description 4
- 229910052744 lithium Inorganic materials 0.000 description 4
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 239000003990 capacitor Substances 0.000 description 3
- 238000010000 carbonizing Methods 0.000 description 3
- 239000005011 phenolic resin Substances 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 2
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 229930003836 cresol Natural products 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 239000004745 nonwoven fabric Substances 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- KWVVTSALYXIJSS-UHFFFAOYSA-L silver(ii) fluoride Chemical compound [F-].[F-].[Ag+2] KWVVTSALYXIJSS-UHFFFAOYSA-L 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- KPZGRMZPZLOPBS-UHFFFAOYSA-N 1,3-dichloro-2,2-bis(chloromethyl)propane Chemical compound ClCC(CCl)(CCl)CCl KPZGRMZPZLOPBS-UHFFFAOYSA-N 0.000 description 1
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- 229910000733 Li alloy Inorganic materials 0.000 description 1
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- AQTIRDJOWSATJB-UHFFFAOYSA-K antimonic acid Chemical compound O[Sb](O)(O)=O AQTIRDJOWSATJB-UHFFFAOYSA-K 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 150000001786 chalcogen compounds Chemical class 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 239000007849 furan resin Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 1
- 239000001989 lithium alloy Substances 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910001425 magnesium ion Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920001197 polyacetylene Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229910001414 potassium ion Inorganic materials 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000012047 saturated solution Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 125000002256 xylenyl group Chemical group C1(C(C=CC=C1)C)(C)* 0.000 description 1
Classifications
-
- 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
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明は高特性・高信頼性を有する非水電解液エネルギ
ー貯蔵装置に関するものである。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a non-aqueous electrolyte energy storage device having high characteristics and high reliability.
［従来の技術］
近年、小型大容量コンデンサとして■活性炭酸いは活性
炭繊維を用いた電気二重層コンデンサが例えばメモリバ
ックアップ電源として急速に需要が伸長している。[Prior Art] In recent years, the demand for electric double layer capacitors using activated carbon fiber or activated carbon fiber as a small-sized, large-capacity capacitor, for example, as a memory backup power source, has been rapidly increasing.
また■負極にリチウム或いはリチウム合金正極に活性炭
等を用いた有極性電気二重層コンデンサに関しても随所
で報告が成され、また実用に供されている。Additionally, (2) polar electric double layer capacitors using lithium or lithium alloy as the negative electrode and activated carbon as the positive electrode have been reported and put into practical use.
また■正極材料に例えばＴｊＳｚ、 ＭＯ３１，Ｖａｎ
ｓなどの金属カルコゲン化合物、酸化物等を用いて二次
電池化する試みも提案され一部実用化されている。In addition, for example, TjSz, MO31, Van
Attempts to make secondary batteries using metal chalcogen compounds such as s, oxides, etc. have also been proposed and some have been put into practical use.
また■負極材料としてリチウムをより軽量化且つ無公害
化するために導電性高分子化合物のポリアセチレンを用
いる報告も成されている。There have also been reports of the use of polyacetylene, a conductive polymer compound, as a negative electrode material in order to make lithium lighter and less polluting.
［発明が解決しようとする課題］
しかしながら、■に示されたものは放電容量が小さく実
際の使用において長期間のバックアップが出来ない欠点
があった。[Problems to be Solved by the Invention] However, the device shown in (2) has a drawback that the discharge capacity is small and it cannot be backed up for a long period of time in actual use.
又■に示されたものは、充電時の負極へのリチウム析出
過程でデンドライト状に析出することにより、電池の内
部短絡や活物質の脱落による充放電効率の低下が欠点と
なっていた。In addition, the battery shown in (2) has the disadvantage that lithium is deposited in the form of dendrites during the process of depositing lithium on the negative electrode during charging, resulting in internal short circuits in the battery and drop-off of the active material, resulting in a decrease in charging and discharging efficiency.
又■に示されたものは、材料によっては容量の小さいも
の或は充放電サイクル特性の劣るものがあり、テバイス
としての特性は不完全である欠点を有していた。Moreover, the devices shown in (2) had the disadvantage that, depending on the material, some had a small capacity or had poor charge/discharge cycle characteristics, and the characteristics as a device were incomplete.
又、■に示されたものは、材料の安定性に乏しく、自己
放電が著しい欠点を有していた。Furthermore, the material shown in (3) had the disadvantage of poor material stability and significant self-discharge.
［課題を解決するための手段］
本発明は前述の諸欠点を解決すべくなされたものであり
、正極及び負極が芳香族系縮合高分子化合物の炭素化物
からなり、電解液が一般式 （１）で表わされる第４級
オニウム塩及び／又は一般式 ＋Ｉ＋１で表わされる金
属塩を有機溶媒に溶解したものからなることを特徴とす
る非水電解液エネルギー貯蔵装置。[Means for Solving the Problems] The present invention has been made to solve the above-mentioned drawbacks, and the positive electrode and the negative electrode are made of a carbonized aromatic condensation polymer compound, and the electrolyte has the general formula (1 1. A non-aqueous electrolyte energy storage device comprising a quaternary onium salt represented by the following formula and/or a metal salt represented by the general formula +I+1 dissolved in an organic solvent.
（１） （Ｉｌｌ
ただし、前記一般式（１）において、ＡはＮまたはＰを
示し、 Ｌ、 Ｌ、 Ｒｓ、およびＲ４は、それぞれ水
素原子（すべてがＨであることはない）、または炭素数
１−１５のアルキル基もしくは炭素数６〜１５のアリー
ル（ａｒｙｌ）基を示し、ｘ″〜はＢＦ：、 ＰＦ６．
ＣＩＯ；、ＡｇＦ２． ＳｂＦ；。(1) (Ill) However, in the general formula (1) above, A represents N or P, and L, L, Rs, and R4 are each a hydrogen atom (not all of them are H) or a carbon number It represents a 1-15 alkyl group or an aryl group having 6-15 carbon atoms, and x''~ is BF:, PF6.
CIO;, AgF2. SbF;.
ＡｌＣｌ；、またはＲｒＳＯ； （Ｒｅは炭素数１〜８
のフルオロアルキル基）ハロゲンイオン、 Ｎｏ；（以
上は ｎ＝１）、ＳＯａ”−（ｎ＝ ２）または ｐｏ
、”−（ｎ＝３）を示す。AlCl; or RrSO; (Re is 1 to 8 carbon atoms
fluoroalkyl group) halogen ion, No; (n = 1), SOa''- (n = 2) or po
, ”-(n=3).
又、前記一般式（１１）において、Ｍ＠＋はアルカリ金
属イオン（ｍ−１）又はアルカリ土類金属イオン（ｍ・
２）を示し、ｘ″−はＢＦ；、 ＰＦ；。In addition, in the general formula (11), M@+ is an alkali metal ion (m-1) or an alkaline earth metal ion (m.
2), where x″- is BF;, PF;.
Ｃｌ０ａ、 ＡｓＦ；、 ＳｂＦ；、 ＡｌＣｌ
；、 ＲｒＳＯ； （Ｒｒは炭素数１〜８のフルオ
ロアルキル基）、ハロゲンイオン、Ｎ０＝（以上はｎ＝
１）、ＳＯａ”−（ｎ＝ ２）、ＰＯ４’−（ｎ＝ ３
）を示す。Cl0a, AsF;, SbF;, AlCl
;, RrSO; (Rr is a fluoroalkyl group having 1 to 8 carbon atoms), halogen ion, N0= (n=
1), SOa''-(n=2), PO4'-(n=3
) is shown.
本発明の非水電解液エネルギー貯蔵装置の電極材料の原
料となる芳香族系縮合高分子化合物としては、例えばフ
ェノール樹脂、フラン樹脂などがあるが、フェノール、
キシレノール、クレゾール等のフェノール性水酸基を有
する芳香族系縮合高分子化合物と、ホルムアルデヒド、
アセトアルデヒド等のアルデヒド類の縮合したフェノー
ル樹脂が好ましい。Examples of the aromatic condensation polymer compound that is a raw material for the electrode material of the non-aqueous electrolyte energy storage device of the present invention include phenol resin and furan resin.
Aromatic condensation polymer compounds having phenolic hydroxyl groups such as xylenol and cresol, and formaldehyde,
Phenol resins in which aldehydes such as acetaldehyde are condensed are preferred.
本発明の電極材料は、上記芳香族系縮合高分子化合物を
、炭素化して得られたものであり、水素／炭素の原子比
が０．３５以下、好ましくは０．１以下であり、かつＸ
線回折法により求めた炭素の（０θ２）面の面間隔が３
．３７Å以上、好ましくは３．４０Å以上でかつ３．８
０Å以下であるものである。このような材料を得るため
の、芳香族系縮合高分子化合物の炭素化の方法は、その
高分子化合物を真空中または窒素、アルゴン等の不活性
雰囲気中で熱処理することである。熱処理の温度は原料
高分子化合物によって異なるが、７５０〜３０００℃で
あることが好ましい。The electrode material of the present invention is obtained by carbonizing the aromatic condensation polymer compound, and has a hydrogen/carbon atomic ratio of 0.35 or less, preferably 0.1 or less, and
The spacing of the (0θ2) plane of carbon determined by line diffraction is 3
．． 37 Å or more, preferably 3.40 Å or more and 3.8 Å or more
The thickness is 0 Å or less. A method for carbonizing an aromatic condensed polymer compound to obtain such a material is to heat-treat the polymer compound in vacuum or in an inert atmosphere such as nitrogen or argon. The temperature of the heat treatment varies depending on the raw material polymer compound, but is preferably 750 to 3000°C.
さらに、これを電極とする場合、芳香族系縮合高分子化
合物をあらかじめフィルム、板、布 □等の使用に
適した形状とした後、炭素化して電極としてもよいし、
その高分子化合物を炭素化した後粉砕して粉末として、
必要ならば適宜バインダー等を添加して好ましい形状に
成形してもよい。Furthermore, if this is to be used as an electrode, the aromatic condensation polymer compound may be shaped into a film, plate, cloth, etc. in advance, and then carbonized to form the electrode.
The polymer compound is carbonized and then ground into powder.
If necessary, a binder or the like may be added to form a desired shape.
正極と負極は、上記の芳香族系縮合高分子化合物を炭素
化して得られた電極材料であれば、正負極共に同材料で
あっても異材料であってもよい。The positive and negative electrodes may be made of the same material or different materials as long as they are electrode materials obtained by carbonizing the aromatic condensation polymer compound described above.
本発明で用いる電解液の溶質としては （１）式及び／
又は （ＩＩ）式で示される化合物を用いることが重要
である。As the solute of the electrolyte used in the present invention, the formula (1) and /
It is important to use a compound represented by formula (II).
上記電解質の一般式（１）で、（）内はテトラアルキル
オニウム又はテトラアリールオニウムを表す。ここで、
窒素原子或いはリン原子に結合される４個のアルキル基
又はアリール基は、同一のものからなる対称型のオニウ
ム塩であってもよく、また少なくとも２個以上が異なる
ものから非対称型のオニウム塩であってもよい。アルキ
ル基は、炭素数が好ましくは１〜４の低級アルキル基が
適当である。アリール基は、１〜２個のベンヤン核を有
するものが好ましく、特にはフェニル基が好ましい。ア
ルキル基とアリール基がリン原子に結合しているテトラ
アルキル、アリールオニウム塩であってもよい。In the general formula (1) of the electrolyte, the parentheses represent tetraalkylonium or tetraarylonium. here,
The four alkyl groups or aryl groups bonded to the nitrogen atom or phosphorus atom may be a symmetric onium salt consisting of the same group, or an asymmetric onium salt consisting of at least two different groups. There may be. The alkyl group is preferably a lower alkyl group having 1 to 4 carbon atoms. The aryl group preferably has 1 to 2 Benyan nuclei, and particularly preferably a phenyl group. It may also be a tetraalkyl or arylonium salt in which an alkyl group and an aryl group are bonded to a phosphorus atom.
上記対称型第４級オニウムとしては、好ましくはテトラ
メチルオニウム、テトラエチルオニウム、テトラプロピ
ルオニウム、テトラブチルオニウム、ジメチルジエチル
オニウムなどが溶解性及び入手性の点から好ましい。The symmetrical quaternary onium is preferably tetramethylonium, tetraethylonium, tetrapropylonium, tetrabutylonium, dimethyldiethylonium, etc. from the viewpoint of solubility and availability.
一方、非対称型第４級オニウム塩°におけるＲ１〜Ｒ４
の組合わせとしては、たとえばメチルトリエチル、ジメ
チルジエチル、エチルトリメチル、ジエチルジブチル、
プロピルトリブチル、トリフェニルエチルなどの基があ
げられるがこれらに限定されるものではない。これらの
中で、ジメチルジエチル、エチルトリメチル、ブチルト
リフェニルなどの基が、溶媒に対する溶解性および利用
可能性の面から特に好ましい。On the other hand, R1 to R4 in the asymmetric quaternary onium salt °
Examples of combinations include methyltriethyl, dimethyldiethyl, ethyltrimethyl, diethyldibutyl,
Examples include, but are not limited to, groups such as propyltributyl and triphenylethyl. Among these, groups such as dimethyldiethyl, ethyltrimethyl, and butyltriphenyl are particularly preferred in terms of solubility in solvents and availability.
さらに前記一般式（１）においてｘｌｌ−とじては、４
フツ化ホウ酸（ｏＦ；） 、 ６フツ化リン酸（ＰＦ；
） 、過塩素酸（ＣＩロー）、６フツ化ヒ酸（ＡｓＦ；
）、６フツ化アンチモン酸（ＳｂＦ；）、４塩化アルミ
ン酸（ＡＩＣＩ；） 、ＲｆＳＯ； （Ｒ，は炭素数ｌ
〜８好ましくは１〜４のフルオロアルキル基）ハロゲン
イオン（Ｆ−、ＣＩ−、Ｂｒ−、Ｉ−） 、硝酸（ＮＯ
；）、硫酸（８口、ａ−）又はリン酸（ＰＯ４”−１が
好適である。Furthermore, in the general formula (1), xll- means 4
Boric acid fluoride (oF;), phosphoric acid hexafluoride (PF;
), perchloric acid (CI low), arsenic hexafluoride (AsF;
), antimonic acid hexafluoride (SbF;), aluminic acid tetrachloride (AICI;), RfSO; (R is the number of carbon atoms
~8 preferably 1 to 4 fluoroalkyl groups) halogen ion (F-, CI-, Br-, I-), nitric acid (NO
;), sulfuric acid (8 ports, a-) or phosphoric acid (PO4''-1) are preferred.
上記電解質の一般式 （１１）で１Ｍ′″＋はアルカリ
金属イオン（ｍ−１）またはアルカリ土類金属イオン（
ｍ・２）を表す。アルカリ金属イオンとしてはリチウム
イオン（Ｌｉ”） 、ナトリウムイオン（Ｎａ”） 、
カリウムイオン（Ｋ＋）が好ましく、リチウムイオンが
特に好ましい。アルカリ土類金属イオンとしては、マグ
ネシウムイオン（Ｍｇ”）、カルシウムイオン（（ａ
２ ＊ ）が好ましい。In the general formula (11) of the electrolyte above, 1M'''+ is an alkali metal ion (m-1) or an alkaline earth metal ion (
m・2). Alkali metal ions include lithium ion (Li”), sodium ion (Na”),
Potassium ions (K+) are preferred, and lithium ions are particularly preferred. Examples of alkaline earth metal ions include magnesium ion (Mg”), calcium ion ((a
2*) is preferred.
また、上記一般式 （ＩＩ）のｘ’−は、一般式（１１
と同様に、４フツ化ホウ酸（ＢＦ；） 、 ６フツ化°
リン酸（ｐＦ、）、過塩素酸＋ｃ＋ｏ；）、６フツ化ヒ
Ｆａ （Ａ、Ｆ；）、６フツ化７ンチモンＭ （ＳｂＦ
４） 、４塩化アルミン酸（Ａ＋ｃ＋；＋ 、ｓｏ；
（Ｒｒは炭素数１〜８、好ましくは１〜４のフルオロア
ルキル基）ハロゲンイオン （Ｆ−、ＣＩ−、Ｂｒまた
は１−）、硝酸（ＮＯ；）、硫酸（ＳＯ４”−１または
リン酸（ＰＯ，−）が好適である。Furthermore, x'- in the above general formula (II) is represented by the general formula (11
Similarly, boric acid tetrafluoride (BF;), hexafluoride °
Phosphoric acid (pF, ), perchloric acid + c + o;
4) , tetrachloroaluminic acid (A+c+;+ , so;
(Rr is a fluoroalkyl group having 1 to 8 carbon atoms, preferably 1 to 4 carbon atoms), halogen ion (F-, CI-, Br or 1-), nitric acid (NO;), sulfuric acid (SO4''-1 or phosphoric acid ( PO, -) is preferred.
かかる溶質の電解液中の濃度としては、０．１〜３．０
Ｍ／氾、特に０．５〜１．５Ｍ／βとすることが好まし
い。該濃度が低すぎる場合には、内部抵抗の増大に伴い
損失が増大し、一方、高ずぎる場合には寒冷時における
溶質の析出に伴う安定性の低下などの不都合を生ずるお
それがある。The concentration of such solute in the electrolyte is 0.1 to 3.0.
M/flood, particularly preferably 0.5 to 1.5 M/β. If the concentration is too low, loss increases due to an increase in internal resistance, while if it is too high, problems such as a decrease in stability due to precipitation of solutes in cold weather may occur.
本発明において、有機溶媒の種類は特に限定されること
がなく、従来より公知ないしは周知のものが種々採用可
能であり、電気化学的に安定な非水溶媒である炭酸プロ
ピレン、γ−ブチロラクトン、アセトニトリル、ジメチ
ルホルムアミド、１．２−ジメトキシエタン、スルホラ
ンあるいはニトロメタンの単独または混合物が好ましい
。かかる溶媒は実質的に無水の状態で使用することが好
ましい。In the present invention, the type of organic solvent is not particularly limited, and various conventionally known or well-known ones can be used, and electrochemically stable non-aqueous solvents such as propylene carbonate, γ-butyrolactone, and acetonitrile can be used. , dimethylformamide, 1,2-dimethoxyethane, sulfolane or nitromethane alone or in mixtures are preferred. Preferably, such solvents are used in a substantially anhydrous state.
なかでも、炭酸プロピレン、γ−ブチロラクトンまたは
スルホランの単独または混合物が好ましい。Among these, propylene carbonate, γ-butyrolactone, or sulfolane alone or in mixtures are preferred.
前述の負極及び正極を装置の形状に合せて加工、成形し
、両電極間に多孔質のセパレータを挟み、前記のような
電解液を含浸または満たしてケース中に密閉することに
よって本発明による非水電解液エネルギー貯蔵装置が得
られる。The above-mentioned negative electrode and positive electrode are processed and molded to match the shape of the device, a porous separator is sandwiched between the two electrodes, the electrolytic solution as described above is impregnated or filled, and the case is sealed. A water electrolyte energy storage device is obtained.
多孔質セパレータとしては、たとえば、ポリプロピレン
繊維不織布、ガラス繊維混抄不織布などが好適である。As the porous separator, for example, polypropylene fiber nonwoven fabric, glass fiber mixed paper nonwoven fabric, etc. are suitable.
また、セパレータの厚みは５０〜２００μｍが適当であ
り、１００〜１５０μｍとするのが特に好適である。Further, the thickness of the separator is suitably 50 to 200 μm, and particularly preferably 100 to 150 μm.
［実施例］
以下、本発明の実施例および比較例を図面に基づいて具
体的に説明する。[Example] Examples and comparative examples of the present invention will be specifically described below based on the drawings.
実施例１〜４０、比較例１〜７
クレゾール樹脂、ｐ−ｔａｒｔ−ブチルフェノール樹脂
及びフェノール樹脂について、それぞれ第１表に示した
温度で窒素雰囲気中で加熱して熱分解させ、樹脂の炭素
化を行い、Ａ−Ｆの６種類の材料を得た。得られた炭素
材料を微粉末に粉砕して電極材料とした。これらの材料
の水素・／炭素原子比及び（００２１面の面間隔を第１
表に示した。Examples 1 to 40, Comparative Examples 1 to 7 Cresol resin, p-tart-butylphenol resin, and phenol resin were heated and thermally decomposed in a nitrogen atmosphere at the temperatures shown in Table 1 to carbonize the resins. Six types of materials A to F were obtained. The obtained carbon material was ground into fine powder to obtain an electrode material. The hydrogen/carbon atomic ratio and (0021 plane spacing) of these materials are
Shown in the table.
これらの電極用炭素粉末９０重量％、ポリエチレン粉末
１０重量％をＶ型ブレシダー中で混合した。この混合物
を厚さ０．６ｍｍ 、直径Ｉ ５ｍｍのベレットにプレ
ス成型形して正極ｌ及び負極２とした。90% by weight of these carbon powders for electrodes and 10% by weight of polyethylene powders were mixed in a V-shaped blender. This mixture was press-molded into pellets with a thickness of 0.6 mm and a diameter I of 5 mm to form a positive electrode 1 and a negative electrode 2.
このようにして作製した正極１と負極２とを繊維不織布
よりなるセパレータ３を介してステンレス鋼製のキャッ
プ４及びステンレス鋼製の缶５からなる外装容器に収納
する。次に、ユニットセル中に電解液を注入して、正極
１、負極２、及びユニットセル３中に電解液を十分に含
浸させた後、ポリプロピレン製バッキング６を介してキ
ャップ４及び缶５の小部をかしめて封口した。The positive electrode 1 and negative electrode 2 thus produced are housed in an outer container consisting of a cap 4 made of stainless steel and a can 5 made of stainless steel, with a separator 3 made of a nonwoven fiber fabric interposed therebetween. Next, the electrolyte is injected into the unit cell to sufficiently impregnate the positive electrode 1, the negative electrode 2, and the unit cell 3, and then the cap 4 and the can 5 are inserted through the polypropylene backing 6. I caulked the part and sealed it.
前述のようにして作製した非水電解液エネルギー貯蔵装
置のユニットセルを使用し、第２表に示すようなオニウ
ム塩、アルカリ金属塩、アルカリ土類金属塩を溶質とし
た種々の電解液を濃度 １．ｏｌＪｉ又は飽和溶液とし
て用いた各セルについて、２．８■の電圧を印加したと
きの初期容量および内部抵抗を測定した後、引続いてこ
のセルに２．８■の電圧を印加しながら７０℃で１００
Ｄ時間貯蔵した後の容量を測定し、初期容量からの容量
劣化率（％）を算出した。これらの測定結果を第２表に
示した。Using the unit cell of the nonaqueous electrolyte energy storage device prepared as described above, various electrolytes containing onium salts, alkali metal salts, and alkaline earth metal salts as solutes as shown in Table 2 were prepared at different concentrations. 1. For each cell used as olJi or saturated solution, the initial capacity and internal resistance were measured when a voltage of 2.8μ was applied, and then the cell was heated at 70°C while applying a voltage of 2.8μ. 100
The capacity after storage for D hours was measured, and the rate of capacity deterioration (%) from the initial capacity was calculated. The results of these measurements are shown in Table 2.
第１表Table 1
第゛１図は本発明による非水電解液エネルギー貯蔵装置
の一実施例を示す部分断面図である。
１・・・正極
２・・・負極
３・・・セパレータ
４・・・キャップ
５・・・缶
６・・・バッキングFIG. 1 is a partial sectional view showing an embodiment of a non-aqueous electrolyte energy storage device according to the present invention. 1...Positive electrode 2...Negative electrode 3...Separator 4...Cap 5...Can 6...Backing
Claims (11)
化物からなり、電解液が一般式（Ｉ）で表わされる第４
級オニウム塩及び／又は 一般式（ＩＩ）で表わされる金属塩を有機溶媒に溶解し
たものからなることを特徴とする非水電解液エネルギー
貯蔵装置。 ▲数式、化学式、表等があります▼（Ｉ）▲数式、化学
式、表等があります▼（ＩＩ） ただし、前記一般式（Ｉ）において、Ａは ＮまたはＰを示し、Ｒ＿１，Ｒ＿２，Ｒ＿３，およびＲ
＿４は、それぞれ水素原子（すべてがＨであることはな
い）、または炭素数１〜１５のアルキル基もしくは炭素
数６〜１５のアリール（ａｒｙｌ）基を示し、Ｘ＾ｎ＾
−はＢＦ＿４＾−，ＰＦ＿６＾−ＣｌＯ＿４＾−，Ａｓ
Ｆ＿４＾−，ＳｂＦ＿６＾−，ＡｌＣｌ＿４＾−，Ｒ＿
ｆＳＯ＿３＾−（Ｒ＿ｆは炭素数１〜８のフルオロアル
キル基）ハロゲンイオン，ＮＯ＿３＾−（以上はｎ＝１
）、ＳＯ＿４＾２＾−（ｎ＝２）またはＰＯ＿４＾３＾
−（ｎ＝３）を示す。 又、前記一般式（ＩＩ）において、Ｍ＾ｍ＾＋はアルカ
リ金属イオン（ｍ＝１）又はアルカリ土類金属イオン（
ｍ＝２）を示し、Ｘ＾ｎ＾−はＢＦ＿４＾−，ＰＦ＿６
＾−，ＣｌＯ＿４＾−，ＡｓＦ＿６＾−，ＳｂＦ＿６＾
−，ＡｌＣｌ＿４＾−，Ｒ＿ｆＳＯ＿３＾−（Ｒ＿ｆは
炭素数１〜８のフルオロアルキル基）、ハロゲンイオン
、ＮＯ＿３＾−（以上はｎ＝１）、ＳＯ＿４＾２＾−（
ｎ＝２）、ＰＯ＿４＾３＾−（ｎ＝３）を示す。(1) The positive electrode and the negative electrode are made of a carbonized aromatic condensed polymer compound, and the electrolyte is a
1. A non-aqueous electrolyte energy storage device comprising a class onium salt and/or a metal salt represented by general formula (II) dissolved in an organic solvent. ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(II) However, in the general formula (I) above, A represents N or P, R_1, R_2, R_3, and R
_4 each represents a hydrogen atom (not all of them are H), an alkyl group having 1 to 15 carbon atoms, or an aryl group having 6 to 15 carbon atoms, and
- is BF_4^-, PF_6^-ClO_4^-, As
F_4^-, SbF_6^-, AlCl_4^-, R_
fSO_3^- (R_f is a fluoroalkyl group having 1 to 8 carbon atoms) halogen ion, NO_3^- (n = 1
), SO_4^2^- (n=2) or PO_4^3^
-(n=3) is shown. In addition, in the general formula (II), M^m^+ is an alkali metal ion (m=1) or an alkaline earth metal ion (
m=2), and X^n^- is BF_4^-, PF_6
^-, ClO_4^-, AsF_6^-, SbF_6^
-, AlCl_4^-, R_fSO_3^- (R_f is a fluoroalkyl group having 1 to 8 carbon atoms), halogen ion, NO_3^- (n = 1), SO_4^2^-(
n=2), PO_4^3^-(n=3).
た種類のアルキル基またはアリール基が窒素又はリン原
子に結合している非対称型である請求項１記載の非水電
解液エネルギー貯蔵装置。(2) The non-aqueous electrolyte energy storage device according to claim 1, wherein the quaternary onium salt is an asymmetric type in which at least two different types of alkyl groups or aryl groups are bonded to nitrogen or phosphorus atoms.
はアリール基が窒素又はリン原子に結合している対称型
である請求項１記載の非水電解液エネルギー貯蔵装置。(3) The non-aqueous electrolyte energy storage device according to claim 1, wherein the quaternary onium salt is of a symmetrical type in which the same type of alkyl group or aryl group is bonded to a nitrogen or phosphorus atom.
ル基である請求項１〜３のいずれかに記載の非水電解液
エネルギー貯蔵装置。(4) The non-aqueous electrolyte energy storage device according to any one of claims 1 to 3, wherein the alkyl group is a lower alkyl group having 1 to 4 carbon atoms.
である請求項１〜３のいずれかに記載の非水電解液エネ
ルギー貯蔵装置。(5) The nonaqueous electrolyte energy storage device according to any one of claims 1 to 3, wherein the aryl group has 1 to 2 benzene nuclei.
＾−またはＢＦ＿４＾−である請求項１記載の非水電解
液エネルギー貯蔵装置。(6) X^n^- is R_fSO_3^-, ClO_4
The non-aqueous electrolyte energy storage device according to claim 1, wherein the non-aqueous electrolyte energy storage device is ^- or BF_4^-.
解液エネルギー貯蔵装置。(7) The non-aqueous electrolyte energy storage device according to claim 1, wherein the metal salt is a lithium salt.
ラクトン、スルホランまたはこれらの混合物である請求
項１〜６のいずれかに記載の非水電解液エネルギー貯蔵
装置。(8) The nonaqueous electrolyte energy storage device according to any one of claims 1 to 6, wherein the organic solvent is propylene carbonate, γ-butyrolactone, sulfolane, or a mixture thereof.
である請求項１〜７のいずれかに記載の非水電解液エネ
ルギー貯蔵装置。(9) The concentration of solute in the electrolyte is 0.1 to 3.0 M/l
The nonaqueous electrolyte energy storage device according to any one of claims 1 to 7.
／炭素の原子比が０．３５以下であって、Ｘ線回折法に
より求めた炭素の（００２）面の面間隔が３．３７Å以
上を有する請求項１記載の非水電解液エネルギー貯蔵装
置。(10) The carbonized product of the aromatic condensation polymer compound has a hydrogen/carbon atomic ratio of 0.35 or less, and the interplanar spacing of the (002) plane of carbon determined by X-ray diffraction method is 3.37 Å. The non-aqueous electrolyte energy storage device according to claim 1, having the above.
酸基を有する芳香族炭化水素化合物と、ホルムアルデヒ
ドの縮合物である請求項１記載の非水電解液エネルギー
貯蔵装置。(11) The non-aqueous electrolyte energy storage device according to claim 1, wherein the aromatic condensation polymer compound is a condensate of an aromatic hydrocarbon compound having a phenolic hydroxyl group and formaldehyde.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63085183A JPH01258410A (en) | 1988-04-08 | 1988-04-08 | Energy storage device using non-aqueous electrolyte |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63085183A JPH01258410A (en) | 1988-04-08 | 1988-04-08 | Energy storage device using non-aqueous electrolyte |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH01258410A true JPH01258410A (en) | 1989-10-16 |
Family
ID=13851546
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63085183A Pending JPH01258410A (en) | 1988-04-08 | 1988-04-08 | Energy storage device using non-aqueous electrolyte |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01258410A (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04206917A (en) * | 1990-11-30 | 1992-07-28 | Mitsui Petrochem Ind Ltd | Electric double layer capacitor |
| JPH06163080A (en) * | 1992-11-19 | 1994-06-10 | Sanyo Electric Co Ltd | Secondary battery |
| EP0749173A1 (en) * | 1995-06-14 | 1996-12-18 | Furukawa Denchi Kabushiki Kaisha | A lithium secondary battery |
| US5601949A (en) * | 1992-11-19 | 1997-02-11 | Sanyo Electric Co., Ltd. | Ion conductive material for secondary battery |
| JP2002063934A (en) * | 2000-08-18 | 2002-02-28 | Mitsubishi Chemicals Corp | Electrolytic solution and electrochemical element using it |
| KR100439163B1 (en) * | 1997-12-30 | 2004-09-18 | 주식회사 효성생활산업 | Lithium secondary battery capable of inhibiting decrease in initial discharge capacity and in charge/discharge efficiency and improving cycle life and safety by using anionic additive |
| JP2016521006A (en) * | 2013-04-24 | 2016-07-14 | コミッサリア ア レネルジー アトミーク エ オ ゼネルジ ザルタナテイヴ | Electrochemical supercapacitor device produced from an electrolyte solution comprising at least one salt produced from an alkali element other than lithium as the conductive salt |
-
1988
- 1988-04-08 JP JP63085183A patent/JPH01258410A/en active Pending
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04206917A (en) * | 1990-11-30 | 1992-07-28 | Mitsui Petrochem Ind Ltd | Electric double layer capacitor |
| JPH06163080A (en) * | 1992-11-19 | 1994-06-10 | Sanyo Electric Co Ltd | Secondary battery |
| EP0602782A1 (en) * | 1992-11-19 | 1994-06-22 | Sanyo Electric Co., Limited. | Secondary battery |
| US5601949A (en) * | 1992-11-19 | 1997-02-11 | Sanyo Electric Co., Ltd. | Ion conductive material for secondary battery |
| EP0749173A1 (en) * | 1995-06-14 | 1996-12-18 | Furukawa Denchi Kabushiki Kaisha | A lithium secondary battery |
| KR100439163B1 (en) * | 1997-12-30 | 2004-09-18 | 주식회사 효성생활산업 | Lithium secondary battery capable of inhibiting decrease in initial discharge capacity and in charge/discharge efficiency and improving cycle life and safety by using anionic additive |
| JP2002063934A (en) * | 2000-08-18 | 2002-02-28 | Mitsubishi Chemicals Corp | Electrolytic solution and electrochemical element using it |
| JP2016521006A (en) * | 2013-04-24 | 2016-07-14 | コミッサリア ア レネルジー アトミーク エ オ ゼネルジ ザルタナテイヴ | Electrochemical supercapacitor device produced from an electrolyte solution comprising at least one salt produced from an alkali element other than lithium as the conductive salt |
| JP2019071464A (en) * | 2013-04-24 | 2019-05-09 | コミッサリア ア レネルジー アトミーク エ オ ゼネルジ ザルタナテイヴ | Electrochemical super capacitor device made from electrolyte including at least one salt made from alkaline element other than lithium as conductive salt |
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