JPH02207464A - Secondary battery - Google Patents
Secondary batteryInfo
- Publication number
- JPH02207464A JPH02207464A JP1028249A JP2824989A JPH02207464A JP H02207464 A JPH02207464 A JP H02207464A JP 1028249 A JP1028249 A JP 1028249A JP 2824989 A JP2824989 A JP 2824989A JP H02207464 A JPH02207464 A JP H02207464A
- Authority
- JP
- Japan
- Prior art keywords
- sodium
- negative electrode
- electrode
- battery
- salt
- 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
- 229910000528 Na alloy Inorganic materials 0.000 claims abstract description 11
- 239000011230 binding agent Substances 0.000 claims abstract description 10
- 159000000000 sodium salts Chemical class 0.000 claims abstract description 10
- XHONYVFDZSPELQ-UHFFFAOYSA-N 1-methoxy-3-(trifluoromethyl)benzene Chemical compound COC1=CC=CC(C(F)(F)F)=C1 XHONYVFDZSPELQ-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 8
- 125000005210 alkyl ammonium group Chemical group 0.000 claims abstract description 5
- 239000011255 nonaqueous electrolyte Substances 0.000 claims abstract description 5
- 239000002131 composite material Substances 0.000 claims description 7
- 239000003125 aqueous solvent Substances 0.000 claims description 5
- HGBJDVIOLUMVIS-UHFFFAOYSA-N [Co]=O.[Na] Chemical compound [Co]=O.[Na] HGBJDVIOLUMVIS-UHFFFAOYSA-N 0.000 claims description 4
- 239000011734 sodium Substances 0.000 abstract description 12
- 239000003792 electrolyte Substances 0.000 abstract description 9
- 229910052708 sodium Inorganic materials 0.000 abstract description 9
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 abstract description 8
- 239000002904 solvent Substances 0.000 abstract description 6
- 230000009257 reactivity Effects 0.000 abstract description 5
- 238000006243 chemical reaction Methods 0.000 abstract description 3
- 239000011149 active material Substances 0.000 abstract description 2
- 150000003839 salts Chemical class 0.000 abstract description 2
- 229910000428 cobalt oxide Inorganic materials 0.000 abstract 1
- -1 polyethylene Polymers 0.000 description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 9
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 239000008151 electrolyte solution Substances 0.000 description 6
- 229910052744 lithium Inorganic materials 0.000 description 6
- 239000004743 Polypropylene Substances 0.000 description 5
- 229920001155 polypropylene Polymers 0.000 description 5
- 229920002943 EPDM rubber Polymers 0.000 description 4
- 239000006230 acetylene black Substances 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
- 239000012046 mixed solvent Substances 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- 230000005856 abnormality Effects 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- 150000001340 alkali metals Chemical class 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- 210000004027 cell Anatomy 0.000 description 3
- 239000002482 conductive additive Substances 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000009784 over-discharge test Methods 0.000 description 3
- ZUHZGEOKBKGPSW-UHFFFAOYSA-N tetraglyme Chemical compound COCCOCCOCCOCCOC ZUHZGEOKBKGPSW-UHFFFAOYSA-N 0.000 description 3
- 229920000181 Ethylene propylene rubber Polymers 0.000 description 2
- 229910000978 Pb alloy Inorganic materials 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 229920001940 conductive polymer Polymers 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 210000001787 dendrite Anatomy 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 239000007773 negative electrode material Substances 0.000 description 2
- 239000004745 nonwoven fabric Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000005060 rubber Substances 0.000 description 2
- 229910001415 sodium ion Inorganic materials 0.000 description 2
- SPEUIVXLLWOEMJ-UHFFFAOYSA-N 1,1-dimethoxyethane Chemical compound COC(C)OC SPEUIVXLLWOEMJ-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- HTWIZMNMTWYQRN-UHFFFAOYSA-N 2-methyl-1,3-dioxolane Chemical compound CC1OCCO1 HTWIZMNMTWYQRN-UHFFFAOYSA-N 0.000 description 1
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 description 1
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- WBLCSWMHSXNOPF-UHFFFAOYSA-N [Na].[Pb] Chemical compound [Na].[Pb] WBLCSWMHSXNOPF-UHFFFAOYSA-N 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 229910021383 artificial graphite Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- WXCZUWHSJWOTRV-UHFFFAOYSA-N but-1-ene;ethene Chemical compound C=C.CCC=C WXCZUWHSJWOTRV-UHFFFAOYSA-N 0.000 description 1
- OJIJEKBXJYRIBZ-UHFFFAOYSA-N cadmium nickel Chemical compound [Ni].[Cd] OJIJEKBXJYRIBZ-UHFFFAOYSA-N 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 150000004770 chalcogenides Chemical class 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000006232 furnace black Substances 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 229910001502 inorganic halide Inorganic materials 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Inorganic materials O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- DMDPGPKXQDIQQG-UHFFFAOYSA-N pentaglyme Chemical compound COCCOCCOCCOCCOCCOC DMDPGPKXQDIQQG-UHFFFAOYSA-N 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 239000006234 thermal black Substances 0.000 description 1
- YFNKIDBQEZZDLK-UHFFFAOYSA-N triglyme Chemical compound COCCOCCOCCOC YFNKIDBQEZZDLK-UHFFFAOYSA-N 0.000 description 1
- 238000001947 vapour-phase growth Methods 0.000 description 1
- 238000003466 welding Methods 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/40—Alloys based on alkali metals
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/621—Binders
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- 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、エネルギー密度が高く、自己放電率が小さく
、サイクル寿命が長い等、性能の良好な二次電池に関す
る。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a secondary battery with good performance such as high energy density, low self-discharge rate, and long cycle life.
従来、アルカリ金属の一つであるリチウム金属を負極に
用いた二次電池は古くから注目されており、例えば、Ｍ
、 Ｈｕｇｈｅｇ、 ｅｔ ａＬ、 Ｊ 、 Ｐｏ
ｗｅｒＳｏｕｒｃｅｓ、 １２． Ｐ８３〜１４４ （
１９８４）にその総説が載っている。その中にリチウム
金属があまりにも活性なため溶媒と反応し、さらにデン
ドライト成長を起し、負極への適用の難しさが示されて
いる。Conventionally, secondary batteries using lithium metal, which is one of the alkali metals, as a negative electrode have been attracting attention for a long time, and for example, M
, Hugheg, et al., J., Po.
werSources, 12. P83-144 (
(1984) contains a review. Among them, lithium metal is so active that it reacts with the solvent and causes dendrite growth, making it difficult to apply to negative electrodes.
その対策としてリチウム金属を合金化したり、導電性高
分子と複合化したりする試みがなされているが、これら
はＡ、Ｎ、ＤｅｙのＪ 、Ｅ ｅｌｅｃｔｒｏｃｈｅｍ
、Ｓｏｃ、、１１８．Ｎｏ、ｌＯ，ＰＬ５４７〜１５４
９ （１９７１）や、特開昭５９−１３２５７６号公報
、同６０−２６２３５１号公報、同６１２４５４７４号
公報、同６２−１４０３５８号公報等に記載されている
。As a countermeasure, attempts have been made to alloy lithium metal or composite it with conductive polymers;
,Soc,,118. No, IO, PL547-154
9 (1971), JP-A-59-132576, JP-A 60-262351, JP-A 61245474, JP-A No. 62-140358, etc.
また、ナトリウム系負極を用い、上記と同様に合金化や
導電性高分子との複合化を行っているが、これらについ
ては、Ａｌｌｉｅｄ社またはＡ１１ｉｅｄ Ｓｉｇｎ
ａｌ Ｉ ｎｃ、が出願したＵＳＰ ４，６６８，５
９６゜同４，７５３，８５８等に記載されている。In addition, sodium-based negative electrodes are alloyed or composited with conductive polymers in the same way as above, but these are manufactured by Allied or A11ied Sign.
USP 4,668,5 filed by al I nc.
96° 4,753,858, etc.
ところで、アルカリ金属を負極に用いた室温作動用二次
電池は、上記のように、各方面で研究されているにもか
かわらずアルカリ金属と電解液との反応性を完全に抑制
するに到らず、いまだ汎用の二次電池に匹敵するほどの
市場を得たものはない。By the way, as mentioned above, despite research in various fields on secondary batteries that use alkali metals as negative electrodes and operate at room temperature, it has not yet been possible to completely suppress the reactivity between the alkali metals and the electrolyte. However, there is still no product that has gained a market comparable to general-purpose secondary batteries.
しかし、一部に極小容量型（１＋ｎＡｈ乃至１０ｍＡｈ
）のリチウム系二次電池は上布されている。However, there are some extremely small capacity types (1+nAh to 10mAh).
) lithium-based secondary batteries are covered.
マタカナダのＭＯＬＩ ＥＮＥＲＧＹ ＬＩＭＩＴ
ＥＤ が正極にＭｏＳ、を用い、負極にＬｉ箔を用い
た比較的高容量（６００ｍＡｈ）の二次電池を商品化し
たが、充放電サイクルの可逆性、高速充放電特性、過放
電特性のいずれも同形状のニッケル・カドミウム系二次
電池を凌駕するに至らず、エネルギー密度が改善された
に留っており、汎用性に乏しい。Mata Canada MOLI ENERGY LIMIT
ED has commercialized a relatively high capacity (600 mAh) secondary battery using MoS for the positive electrode and Li foil for the negative electrode, but the reversibility of the charge/discharge cycle, high-speed charge/discharge characteristics, and overdischarge characteristics are not satisfactory. However, it does not outperform a nickel-cadmium secondary battery of the same shape, and its energy density is only improved, so it lacks versatility.
このＬｉ系負極が実用化されにくいのは、上記したよう
にリチウムと電解液との反応及びそれに由来するデンド
ライト成長による短絡現象が最大の原因である。The main reason why this Li-based negative electrode is difficult to put into practical use is the short-circuit phenomenon caused by the reaction between lithium and the electrolyte and the resulting dendrite growth, as described above.
リチウムをナトリウム合金に代えることで電極電位が０
．２■ないし０．４Ｖ程度貴側にシフトするので、電解
液との反応性は若干緩和されるが充分ではない。By replacing lithium with sodium alloy, the electrode potential can be reduced to 0.
．． Since the voltage is shifted to the noble side by about 2 to 0.4 V, the reactivity with the electrolyte is somewhat relaxed, but not enough.
本発明者らは、上記問題を解決すべ（鋭意研究した結果
、電極構成物質と電解液との優れた組合せを発見した。The present inventors have solved the above problem (as a result of intensive research, they have discovered an excellent combination of an electrode constituent material and an electrolyte solution.
本発明は、上記の発見に基づいてなされたもので、各種
性能の優れた二次電池を提供することを目的とする。The present invention was made based on the above discovery, and an object of the present invention is to provide a secondary battery with excellent various performances.
上記の目的を達成するため、本発明の二次電池は、正極
と負極と非水電解液とによって構成され、負極がナトリ
ウム合金と炭素材料と結着剤との複合体からなり、非水
電解液がナトリウム塩またはナトリウム塩とアルキルア
ンモニウム塩を、ｍトリフルオロメチルアニソールを３
０容１１％以上含む非水溶媒に溶解したものである。In order to achieve the above object, the secondary battery of the present invention is composed of a positive electrode, a negative electrode, and a non-aqueous electrolyte, and the negative electrode is made of a composite of a sodium alloy, a carbon material, and a binder. The solution contains sodium salt or sodium salt and alkylammonium salt, mtrifluoromethylanisole,
It is dissolved in a non-aqueous solvent containing 11% or more by volume.
また、この場合ナトリウム・コバルト酸化物を主成分と
する正極が好適に使用出来る。Further, in this case, a positive electrode containing sodium cobalt oxide as a main component can be suitably used.
本発明において、負極にナトリウム合金と炭素材料と結
着剤との複合体を用いる理由は、まずナトリウムの合金
でナトリウムの活性を低下せしめ、電解液との副反応を
抑えるとともに導電性の炭素材料を電極中にほどよく分
散させることにより、電極中に電解液を含浸させ、さら
に実効表面積を増大させ、実効電流密度を下げＱかっ、
結着剤で充放電にともなう電極の形状変化や崩壊を抑制
するためである。In the present invention, the reason why a composite of a sodium alloy, a carbon material, and a binder is used for the negative electrode is that first, the sodium alloy reduces the activity of sodium, suppresses side reactions with the electrolyte, and the conductive carbon material. By appropriately dispersing the electrode into the electrode, the electrode is impregnated with the electrolyte, further increasing the effective surface area and lowering the effective current density.
This is because the binder suppresses changes in shape and collapse of the electrodes due to charging and discharging.
上記複合体負極に用いるナトリウム合金としては、ナト
リウムと鉛の合金が適する。それは、ナトリウムの相手
金属の中で鉛が、その原子比当りの広い範囲に亘ってナ
トリウムと合金化しうるためである。すなわち、ナトリ
ウム−鉛では、ナトリウム：鉛の原子比が９５：５から
２：９８の範囲で合金化可能である。As the sodium alloy used in the composite negative electrode, an alloy of sodium and lead is suitable. This is because, among the partner metals of sodium, lead can be alloyed with sodium over a wide range of its atomic ratio. That is, with sodium-lead, alloying is possible with an atomic ratio of sodium:lead in the range of 95:5 to 2:98.
またナトリウムと鉛の合金を電極に用いた場合、電極電
位に応じてナトリウムと相手金属との原子比が設定され
、逆にその原子比によって電極電位が設定されるため、
電気化学的に組成比をコントロールしやすくなる。しか
もこの合金は、狭い範囲、即ち０．５Ｖ程度の範囲内で
ナトリウムと相手金属との組成比が大きく変化するため
、電極に用いた場合に電池を充電しても、放電しても、
広い電気容量範囲で電位平坦性が保持される。Furthermore, when an alloy of sodium and lead is used as an electrode, the atomic ratio between sodium and the other metal is set according to the electrode potential, and conversely, the electrode potential is set according to that atomic ratio.
It becomes easier to control the composition ratio electrochemically. Moreover, the composition ratio of sodium and the other metal in this alloy changes greatly within a narrow range, that is, within a range of about 0.5V, so when used as an electrode, even when a battery is charged or discharged,
Potential flatness is maintained over a wide capacitance range.
しかし、単純にナトリウム合金のみを電極として使用す
るだけでは、負極の利用率、可逆性を向上させる・には
至らず、本発明の如く炭素材料との複合体電極にする必
要がある。用いる炭素材料としては、カーボンブラック
または、黒鉛が適する。However, simply using only a sodium alloy as an electrode does not improve the utilization rate and reversibility of the negative electrode, and it is necessary to use a composite electrode with a carbon material as in the present invention. Carbon black or graphite is suitable as the carbon material to be used.
上記カーボンブラックには、サーマルブラック、ファー
ネスブラック、アセチレンブラック等があるがいずれで
もよく特に制限はない。また黒鉛としては、天然黒鉛で
も人造黒鉛でもよく、また気相成長法により合成した繊
維状黒鉛でもよい。しかし、炭素材料の量があまり多過
ぎると電極容量、密度を下げる。適した量としては負極
重量当り、３％ないし２０％がよい。The above-mentioned carbon black includes thermal black, furnace black, acetylene black, etc., but any of them may be used without any particular limitation. Further, the graphite may be natural graphite or artificial graphite, or may be fibrous graphite synthesized by a vapor phase growth method. However, if the amount of carbon material is too large, the electrode capacity and density will be reduced. A suitable amount is 3% to 20% based on the weight of the negative electrode.
さらに複合電極が使用中に崩壊しないようにするため、
結着剤を添加する必要があるが、電極や電解液との反応
性がないことが必要で、通常ポリエチレン、ポリプロピ
レンの繊維または粉体を電極中によ（分散させて加熱溶
着させて用いる。また、より効果的な負極材の結着剤と
しては、例えばオレフィン系共重合体ゴム、例えばエチ
レン−プロピレンゴム（ＥＰＲ）、エチレン−ブテンゴ
ム（ＥＢＲ） 、エチレン−プロピレン−ジエンゴム（
ＥＰＤＭ）等が挙げられるが特にＥＰＤＭが好ましい。Furthermore, to prevent the composite electrode from collapsing during use,
Although it is necessary to add a binder, it is necessary that it has no reactivity with the electrode or electrolyte, and is usually used by dispersing polyethylene or polypropylene fibers or powder into the electrode and welding it by heating. In addition, more effective binders for negative electrode materials include, for example, olefin copolymer rubbers such as ethylene-propylene rubber (EPR), ethylene-butene rubber (EBR), and ethylene-propylene-diene rubber (
EPDM), etc., and EPDM is particularly preferred.
この結着剤も多く使用すると、かえって電極性能を損な
う。適した量としては負極重量当り、１％ないし８％で
ある。If too much of this binder is used, the electrode performance will be impaired. A suitable amount is 1% to 8% based on the weight of the negative electrode.
このような、負極を用いた場合、好適な電解液としては
、ナトリウム塩またはナトリウム塩とアルキルアンモニ
ウム塩をｍ−トリフルオロメチルアニソールを３０容量
％以上含んだ溶媒に溶解したものが良い。When such a negative electrode is used, a suitable electrolytic solution is one in which a sodium salt or a sodium salt and an alkylammonium salt are dissolved in a solvent containing 30% by volume or more of m-trifluoromethylanisole.
ナトリウム塩は当然電池反応の活物質として用いられる
が、アルキルアンモニウム塩は、必要に応じて電気伝導
性付与のために支持塩として用いられる。Naturally, the sodium salt is used as an active material in the battery reaction, but the alkylammonium salt is used as a supporting salt to impart electrical conductivity, if necessary.
また、’ｍ−１−リフルオロメチルアニソールが溶媒と
して、すぐれているのは、本発明の電池に用いる負極と
の反応性が低く、極めて安定だからである。Furthermore, 'm-1-lifluoromethylanisole is excellent as a solvent because it has low reactivity with the negative electrode used in the battery of the present invention and is extremely stable.
本発明の電池用溶媒としてはｍ−）リフルオロメチルア
ニソール系化合物のみを用いても良いが、他の非水溶媒
との混合系でもよい。その場合ｍ−トリフルオロメチル
アニソールを３Ｑｖｏ１％以上含有していれば他の非水
溶媒との混合系で用いても良い。混合系で用いる場合そ
の種類に特に制限はないが、当然のことながら電極活物
質と強く反応するものは使用することはできない。As the battery solvent of the present invention, the m-)lifluoromethylanisole compound alone may be used, but it may also be a mixed system with other non-aqueous solvents. In that case, it may be used in a mixed system with other non-aqueous solvents as long as it contains m-trifluoromethylanisole in an amount of 3Qvo 1% or more. When used in a mixed system, there are no particular restrictions on the type, but as a matter of course, those that strongly react with the electrode active material cannot be used.
混合される非水溶媒としては、例えば１，２ジメトキシ
エタン、グイグライム、トリグライム、テトラグライム
、ペンタグライム、テトラヒドロフラン、２−メチルテ
トラヒドロフラン、ｌ、４３メチルジオキソラン、ジオ
キサン等のエーテル化合物、プロピレンカーボネート、
エチレンカポネート等のカーボネート類が挙げられるが
、特に１．２−ジメトキシエタン、グイグライム、テト
ラグライムが好ましい。Examples of the non-aqueous solvent to be mixed include ether compounds such as 1,2 dimethoxyethane, guy glyme, triglyme, tetraglyme, penta glyme, tetrahydrofuran, 2-methyltetrahydrofuran, l,43 methyl dioxolane, and dioxane, propylene carbonate,
Examples include carbonates such as ethylene caponate, and 1,2-dimethoxyethane, guiglyme, and tetraglyme are particularly preferred.
次いで、本発明の電池に適した正極について説明する。Next, a positive electrode suitable for the battery of the present invention will be explained.
上記適した正極とは、本発明の電池に用いる負極に対し
て少なくとも１．５■以上の電圧を有し、かつ可逆的に
ナトリウムイオンを吸蔵、放出できる物であることが必
要であり、無機酸化物としては、例えばＣｏｏ、、Ｍｎ
０ｔ、ＷＯ，、Ｍｏｂ、、Ｍ。The above-mentioned suitable positive electrode must have a voltage of at least 1.5 μ or more with respect to the negative electrode used in the battery of the present invention, and must be capable of reversibly occluding and releasing sodium ions, and must be an inorganic material. Examples of oxides include Coo, Mn
0t,WO,,Mob,,M.
Ｏｌ、■、０２等、無機カルコゲナイドとしては、例え
ばＴｉＳ、、Ｍｏ、Ｓ、、Ｎ ｉ Ｐ Ｓ Ｏ３等、無
機ハライドとしては、例えばＲｕＣＱ−１ＲｕＢｒ−１
ＦｅＯＣＱ等がある。Examples of inorganic chalcogenides include TiS, Mo, S, NiPSO3, etc., and examples of inorganic halides such as RuCQ-1RuBr-1.
There are FeOCQ, etc.
これらの中で、重量当り及び体積当りの電気容量、密度
が大きく、可逆性が良いものとしてＣ。Among these, C has high electric capacity per weight and volume, high density, and good reversibility.
Ｏ３、ＭｏＯ，、ＭｏＯ，が挙げられるが、特に、Ｃ。O3, MoO,, MoO, and especially C.
Ｏ２が好ましい。このＣｏＯ，はＮａ十を層間に含んだ
形で存在しているいわゆる層間化合物の形を取り、層間
は、Ｎａ中の量により広がったり、縮んだりする。但し
、Ｎａ中は酸素間どうしのイオン反発を抑制する働きも
あり、Ｎａ十量が増えると必ずしもホスト格子のＣ軸が
延びるとは限らず、ａ軸及びｂ軸が若干延びる程度であ
る。そのため、Ｃ００、をホストに持つナトリウム・コ
バルト酸化物の充放電に伴う形状変化は比較的小さく、
他の無機物に比べ崩壊することが少ない。さらに、ナト
リウム・コバルト酸化物は電子伝導性が大きいため、導
電助材を殆ど必要としない。そのため、少ない導電助材
量または全く導電助材を使用しなくても電極として充分
に性能が発揮される。O2 is preferred. This CoO is in the form of a so-called intercalation compound that exists in a form containing Na+ between layers, and the interlayers expand or contract depending on the amount of Na in the layer. However, Na also has the function of suppressing ion repulsion between oxygen atoms, and an increase in the amount of Na does not necessarily extend the C-axis of the host lattice, but only slightly extends the a-axis and b-axis. Therefore, the shape change due to charging and discharging of sodium cobalt oxide with C00 as host is relatively small.
It is less likely to disintegrate than other inorganic substances. Furthermore, since sodium cobalt oxide has high electronic conductivity, it hardly requires a conductive additive. Therefore, sufficient performance is exhibited as an electrode even if a small amount of conductive additive or no conductive additive is used.
次に実施例を示して本発明の二次電池を具体的に説明す
る。Next, the secondary battery of the present invention will be specifically explained with reference to Examples.
実施例１
正極はＮａ１Ｏ１とＣｏ、０４を酸素雰囲気下で加熱反
応させ、Ｎ ａｏ ７Ｃｏｏ ｔを合成し、それを粉砕
した後、予め混合しておいたアセチレンブラックとテト
ラフルオロエチレン（結着剤）の重量比が３＝１の混合
物を加尤、Ｎ ａｏ７Ｃｏｏ ｔが９５％、混合物が５
％になるように混ぜて、正極活物質とし、直径１５ｍ５
、厚さ４００μｍ程度になるよう円板状に加圧成形して
作製した。Example 1 The positive electrode was made by heating and reacting Na1O1, Co, and 04 in an oxygen atmosphere to synthesize Nao7Coot, which was pulverized, and then premixed acetylene black and tetrafluoroethylene (binder). Add a mixture with a weight ratio of 3=1, Nao7Coot is 95%, and the mixture is 5
% to form a positive electrode active material and a diameter of 15m5.
, and was produced by pressure molding into a disk shape to have a thickness of about 400 μm.
また、負極は、Ｎａとｐｂの原子比が３゜０：１゜０の
合金をよく粉砕した後、あらかじめ混合しておいたアセ
チレンブラックとＥＰＤＭ（結着剤）の重量比が３：１
の混合物を加えＮａ合金が８８％、上記混合物が１２％
になるように混ぜて負極活物質とし、直径１５ｍｍ、厚
さ３００μ園程度になるよう円板状に加圧成形して作製
した。In addition, the negative electrode was made by thoroughly grinding an alloy with an atomic ratio of Na and Pb of 3°0:1°0, and then using acetylene black and EPDM (binder) mixed in a weight ratio of 3:1.
Add a mixture of Na alloy to 88% and the above mixture to 12%.
A negative electrode active material was prepared by pressure molding the mixture into a disk shape with a diameter of 15 mm and a thickness of about 300 μm.
電解液は、ｍ−トリフルオロメチルアニソールと１．２
−ジメトキシエタンの体積比で１：１の混合溶媒にＮ
ａＰ Ｆ ｓを０．１モル／１２、Ｂ ｕ、Ｎ Ｂ Ｆ
４（テトラブチルアンモニウムテトラフルオロボレート
）を０．５モル／Ｑになるようにそれぞれ溶かしたもの
を用いた。正極と負極の間にポリプロピレン製マイクロ
ポーラスフィルムとポリプロピレン製不織布をセパレー
ターとして用い、第１図に示すような、周知のコイン型
セルを組立てた。The electrolyte contains m-trifluoromethylanisole and 1.2
- N in a mixed solvent of dimethoxyethane in a volume ratio of 1:1
aP F s 0.1 mol/12, B u, N B F
4 (tetrabutylammonium tetrafluoroborate) dissolved at a concentration of 0.5 mol/Q was used. A well-known coin-shaped cell as shown in FIG. 1 was assembled using a polypropylene microporous film and a polypropylene nonwoven fabric as separators between the positive electrode and the negative electrode.
この電池の組立直後の電圧は、２．５３Ｖであった。こ
の電池を放電方向に電流３．０ｍＡで電池電圧が２．Ｏ
Ｖになるまで放電し、次いで同じ電流値で電池電圧が３
．Ｏｖになるまで充電し、以後放電・充電を繰返えして
、この電池の放電容量及び可逆性を調べたところ、最大
放電容量は１２゜３ｓＡｈ、放電容量が最大値の６０％
に低下するまでのサイクル寿命は５７０回であった。The voltage of this battery immediately after assembly was 2.53V. This battery was discharged at a current of 3.0 mA and a battery voltage of 2.0 mA. O
Discharge until the battery voltage reaches V, then at the same current value the battery voltage increases to 3.
．． After charging the battery until it reached Ov and then repeating discharging and charging, we investigated the discharge capacity and reversibility of this battery.The maximum discharge capacity was 12°3 sAh, and the discharge capacity was 60% of the maximum value.
The cycle life until it decreased to 570 times.
さらに上記と全く同じ電池を組み立て、充電状態にして
、室温、１ケ月間放置して自己放電率を調べたところ、
５．９％であった。また正極、負極を短絡し３日間放置
後、充放電を試みたとろこ、何の異常も見られず、正常
に作動できた。Furthermore, when we assembled the exact same battery as above, left it in a charged state for one month at room temperature, and examined the self-discharge rate.
It was 5.9%. In addition, when the positive and negative electrodes were short-circuited and left for 3 days, charging and discharging was attempted, and no abnormality was observed and the battery operated normally.
実施例２
正極は市販のＭＯＯ３とアセチレンブラックとポリテト
ラフルオロエチレンを重量比で８０＋１５＝５になるよ
う混ぜて実施例１と同じように成型したものを用い、負
極は実施例１と全く同様のものを用いた。Example 2 The positive electrode was made by mixing commercially available MOO3, acetylene black, and polytetrafluoroethylene in a weight ratio of 80+15=5 and molded in the same manner as in Example 1. The negative electrode was made in the same manner as in Example 1. I used something.
また、電解液は、ｍ−トリフルオロメチルアニソールと
１．２−ジメトキシエタンの体積比が２＝１の混合溶媒
にＮａＰＦ、を０．７モル／ Ｑ、 Ｂ ｕｓＥｔＮＢ
Ｆ４（トリブチルエチルアンモニウム テトラフルオロ
ボレート）を０．７モル／Ｑになるよう溶解したものを
用いた。In addition, the electrolytic solution was a mixed solvent of m-trifluoromethylanisole and 1.2-dimethoxyethane with a volume ratio of 2=1, NaPF, 0.7 mol/Q, BusEtNB
F4 (tributylethylammonium tetrafluoroborate) dissolved at 0.7 mol/Q was used.
電池は第１図のようなコイン型セルを組み、実施例１と
同様の実験を行なった。但し、放電終止電圧のみを１．
５Ｖまで下げて行なった。The battery was a coin-shaped cell as shown in FIG. 1, and the same experiment as in Example 1 was conducted. However, only the discharge end voltage should be set to 1.
I lowered it to 5V.
その結果、最大放電電気量は１１ 、５ ｍＡ ｈ、放
電容量が最大値の６０％に低下するまでのサイクル寿命
は６３０回、自己放電率は５．８％で過放電試験を行な
っても異常を見られなかった。As a result, the maximum discharge amount of electricity was 11.5 mAh, the cycle life until the discharge capacity decreased to 60% of the maximum value was 630 times, and the self-discharge rate was 5.8%, which was abnormal even when an overdischarge test was performed. I couldn't see it.
実施例３
正極及び負極は実施例１と同じものを用い、電解液のみ
を次のようにして調製したものを用いた。Example 3 The same positive and negative electrodes as in Example 1 were used, and only the electrolytic solution prepared as follows was used.
即ち、ＮａＰＦａを１．０モル／Ｑになるよう、ｍ−ト
リフルオロメチルアニソールとグイグライムの体積比が
１＝２の混合溶媒に溶かしたものを電解液とし、第１図
のようなコイン型セルを組みたて、実施例１と同様な実
験を行なった。That is, the electrolyte was prepared by dissolving NaPFa at a concentration of 1.0 mol/Q in a mixed solvent of m-trifluoromethylanisole and guiglyme with a volume ratio of 1=2, and a coin-shaped cell as shown in Fig. 1 was prepared. An experiment similar to that in Example 1 was conducted using the following.
その結果、最大放電容量は１２．５ｓＡｈ、サイクル寿
命は６０８回、自己放電率は５．９％、また過放電試験
後に異常は見られなかった。As a result, the maximum discharge capacity was 12.5 sAh, the cycle life was 608 times, the self-discharge rate was 5.9%, and no abnormality was observed after the overdischarge test.
実施例４
正極、負極は実施例１と同じものを用い、電解液のみを
次のように調製したものを用いた。即ち、ＮａＰＦ５を
１．０モル／Ｑ、Ｂｕ４ＮＦＢＦ４を０．５モル／ｅと
なるように、ｍ−トリフルオロメチルアニソールと１．
２−ジメトキシエタンとテトラグライムの体積比が３：
４：１の混合溶媒に溶かしたものを電解液とし、第１図
に示すコイン型モルを組立て、実施１と同様な実験を行
なった。Example 4 The same positive and negative electrodes as in Example 1 were used, and only the electrolyte solution prepared as follows was used. That is, m-trifluoromethylanisole and 1.0 mol/Q of NaPF5 and 0.5 mol/e of Bu4NFBF4 were added.
The volume ratio of 2-dimethoxyethane and tetraglyme is 3:
A coin-shaped mole shown in FIG. 1 was assembled using an electrolyte solution dissolved in a 4:1 mixed solvent, and an experiment similar to that in Example 1 was conducted.
その結果、最大放電容量は、１２．５ｓＡｈ、サイクル
寿命は６２５回、自己放電率は５．８％、また、過放電
試験後に異状は認められなかった。As a result, the maximum discharge capacity was 12.5 sAh, the cycle life was 625 times, the self-discharge rate was 5.8%, and no abnormality was observed after the overdischarge test.
以上述べたように、本発明の二次電池は、エネルギー密
度が高く、サイクル寿命が長く、自己放電率も低い等、
多くの優れた性能を有するので、これを電源とする分野
に寄与することが極めて大きい。As described above, the secondary battery of the present invention has high energy density, long cycle life, low self-discharge rate, etc.
Since it has many excellent performances, it will greatly contribute to the field of using it as a power source.
第１図は実施例において、電池性能を調べるのに使用し
たコイン型二次電池の縦断面図である。
１・・・・・・正極、２・・・・・・集電用金網、３・
・・・・・ポリプロピレン製不織布、４・・・・・・ポ
リプロピレン製マイクロポーラスフィルム、５・・・・
・・絶縁バッキング、６・・・・・・負極。FIG. 1 is a longitudinal cross-sectional view of a coin-shaped secondary battery used to examine battery performance in Examples. 1...Positive electrode, 2...Wire mesh for current collection, 3.
...Polypropylene nonwoven fabric, 4...Polypropylene microporous film, 5...
...Insulating backing, 6...Negative electrode.
Claims (2)
て、負極がナトリウム合金と炭素材料と結着剤との複合
体からなり、非水電解液がナトリウム塩またはナトリウ
ム塩とアルキルアンモニウム塩を、ｍ−トリフルオロメ
チルアニソールを３０容量％以上含む非水溶媒に溶解し
たものであることを特徴とする二次電池。(1) In a secondary battery consisting of a positive electrode, a negative electrode, and a nonaqueous electrolyte, the negative electrode is made of a composite of a sodium alloy, a carbon material, and a binder, and the nonaqueous electrolyte is a sodium salt or a sodium salt and an alkyl ammonium salt. Dissolved in a non-aqueous solvent containing 30% by volume or more of m-trifluoromethylanisole.
る請求項（１）記載の二次電池。(2) The secondary battery according to claim (1), wherein the positive electrode contains sodium cobalt oxide as a main component.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1028249A JPH02207464A (en) | 1989-02-07 | 1989-02-07 | Secondary battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1028249A JPH02207464A (en) | 1989-02-07 | 1989-02-07 | Secondary battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH02207464A true JPH02207464A (en) | 1990-08-17 |
Family
ID=12243306
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1028249A Pending JPH02207464A (en) | 1989-02-07 | 1989-02-07 | Secondary battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH02207464A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0746050A1 (en) * | 1995-05-26 | 1996-12-04 | Sony Corporation | Non-aqueous electrolyte secondary battery |
| EP0757399A1 (en) * | 1995-07-25 | 1997-02-05 | Sumitomo Chemical Company, Limited | Non-aqueous electrolyte and lithium secondary battery |
| EP0851524A1 (en) * | 1996-12-27 | 1998-07-01 | Sony Corporation | Non-aqueous electrolyte secondary cell |
| KR100472511B1 (en) * | 2002-10-29 | 2005-03-10 | 삼성에스디아이 주식회사 | Lithium secondary battery without protection circuit module |
| JP2010027538A (en) * | 2008-07-24 | 2010-02-04 | Kyushu Univ | Sodium secondary battery |
-
1989
- 1989-02-07 JP JP1028249A patent/JPH02207464A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0746050A1 (en) * | 1995-05-26 | 1996-12-04 | Sony Corporation | Non-aqueous electrolyte secondary battery |
| EP0757399A1 (en) * | 1995-07-25 | 1997-02-05 | Sumitomo Chemical Company, Limited | Non-aqueous electrolyte and lithium secondary battery |
| EP0851524A1 (en) * | 1996-12-27 | 1998-07-01 | Sony Corporation | Non-aqueous electrolyte secondary cell |
| KR100472511B1 (en) * | 2002-10-29 | 2005-03-10 | 삼성에스디아이 주식회사 | Lithium secondary battery without protection circuit module |
| JP2010027538A (en) * | 2008-07-24 | 2010-02-04 | Kyushu Univ | Sodium secondary battery |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US5051325A (en) | Secondary battery | |
| CA2043779A1 (en) | Electrolyte solution sequestering agents for electrochemical cells having carbonaceous electrodes | |
| US10923768B2 (en) | Alkynyl-containing compound additive for non-aqueous electrolyte solution, and non-aqueous electrolyte solution for lithium secondary battery and lithium secondary battery which include the same | |
| EP1289044B1 (en) | Nonaqueous electrolyte secondary battery | |
| JP2000223152A (en) | Lithium ion secondary battery having extended cycle life in charge/discharge | |
| EP1391003B1 (en) | Non-aqueous electrolyte additive for improving safety and lithium ion secondary battery comprising the same | |
| JPH02207464A (en) | Secondary battery | |
| JP2965674B2 (en) | Lithium secondary battery | |
| JP2839627B2 (en) | Rechargeable battery | |
| CN114641884A (en) | Non-aqueous electrolyte solution for lithium secondary battery and lithium secondary battery comprising same | |
| JPH03196467A (en) | Secondary battery | |
| KR101511792B1 (en) | Additives of electrode active materials for enhancement of battery capacity | |
| KR20080070492A (en) | Composite anode active material, method of preparing the same, and anode and lithium battery containing the material | |
| JP3144832B2 (en) | Non-aqueous solvent secondary battery | |
| JPH05325961A (en) | Lithium battery | |
| JPH02207465A (en) | Secondary battery | |
| JPH08106920A (en) | Lithium secondary battery | |
| KR20190130483A (en) | Cathode active material and fluoride ion battery | |
| EP4210144A2 (en) | Electrolyte for lithium secondary battery and lithium secondary battery including the same | |
| JPH02207463A (en) | Secondary battery | |
| JP2898056B2 (en) | Rechargeable battery | |
| JPH0364869A (en) | Secondary cell | |
| JPH02207462A (en) | Secondary battery | |
| JPH046759A (en) | Secondary battery | |
| JPH03205767A (en) | Secondary battery |