JPH03291863A - Secondary cell - Google Patents
Secondary cellInfo
- Publication number
- JPH03291863A JPH03291863A JP2094464A JP9446490A JPH03291863A JP H03291863 A JPH03291863 A JP H03291863A JP 2094464 A JP2094464 A JP 2094464A JP 9446490 A JP9446490 A JP 9446490A JP H03291863 A JPH03291863 A JP H03291863A
- Authority
- JP
- Japan
- Prior art keywords
- sodium
- positive electrode
- weight
- negative electrode
- alloy
- 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
- 239000011734 sodium Substances 0.000 claims abstract description 25
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 22
- 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 claims abstract description 19
- 239000002131 composite material Substances 0.000 claims abstract description 13
- 239000007774 positive electrode material Substances 0.000 claims abstract description 11
- 229910000528 Na alloy Inorganic materials 0.000 claims description 8
- PBHYLKMSZFULFJ-UHFFFAOYSA-N [Co].[Ni].[Na] Chemical compound [Co].[Ni].[Na] PBHYLKMSZFULFJ-UHFFFAOYSA-N 0.000 claims description 6
- 239000007773 negative electrode material Substances 0.000 claims description 4
- 239000011255 nonaqueous electrolyte Substances 0.000 claims description 2
- 239000003575 carbonaceous material Substances 0.000 abstract description 8
- 229910045601 alloy Inorganic materials 0.000 abstract description 6
- 239000000956 alloy Substances 0.000 abstract description 6
- 239000006229 carbon black Substances 0.000 abstract description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 abstract description 4
- 239000000843 powder Substances 0.000 abstract description 4
- 239000000463 material Substances 0.000 abstract description 3
- 239000011149 active material Substances 0.000 abstract description 2
- 239000000835 fiber Substances 0.000 abstract description 2
- 239000011133 lead Substances 0.000 abstract description 2
- 229920000098 polyolefin Polymers 0.000 abstract description 2
- 239000011135 tin Substances 0.000 abstract description 2
- 239000004020 conductor Substances 0.000 abstract 2
- 229910052745 lead Inorganic materials 0.000 abstract 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 abstract 1
- 125000004122 cyclic group Chemical group 0.000 abstract 1
- 229910052731 fluorine Inorganic materials 0.000 abstract 1
- 239000011737 fluorine Substances 0.000 abstract 1
- 229910052759 nickel Inorganic materials 0.000 abstract 1
- 239000011347 resin Substances 0.000 abstract 1
- 229920005989 resin Polymers 0.000 abstract 1
- 229910052718 tin Inorganic materials 0.000 abstract 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 12
- 239000011230 binding agent Substances 0.000 description 8
- 238000007599 discharging Methods 0.000 description 7
- 239000003792 electrolyte Substances 0.000 description 6
- -1 polytetrafluoroethylene Polymers 0.000 description 6
- 229910000978 Pb alloy Inorganic materials 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 238000000465 moulding Methods 0.000 description 5
- WBLCSWMHSXNOPF-UHFFFAOYSA-N [Na].[Pb] Chemical compound [Na].[Pb] WBLCSWMHSXNOPF-UHFFFAOYSA-N 0.000 description 4
- 239000006258 conductive agent Substances 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 229910002804 graphite Inorganic materials 0.000 description 4
- 239000010439 graphite Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 229910052744 lithium Inorganic materials 0.000 description 4
- 229920002943 EPDM rubber Polymers 0.000 description 3
- 239000006230 acetylene black Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000008151 electrolyte solution Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- 229920000181 Ethylene propylene rubber Polymers 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 229910001413 alkali metal ion Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- ZUHZGEOKBKGPSW-UHFFFAOYSA-N tetraglyme Chemical compound COCCOCCOCCOCCOC ZUHZGEOKBKGPSW-UHFFFAOYSA-N 0.000 description 2
- 239000006234 thermal black Substances 0.000 description 2
- YFNKIDBQEZZDLK-UHFFFAOYSA-N triglyme Chemical compound COCCOCCOCCOC YFNKIDBQEZZDLK-UHFFFAOYSA-N 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 241000207199 Citrus Species 0.000 description 1
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- 229910020808 NaBF Inorganic materials 0.000 description 1
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 229910001128 Sn alloy Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- ULZXFYZRJCPOPI-UHFFFAOYSA-N [Co]=O.[Ni].[Na] Chemical compound [Co]=O.[Ni].[Na] ULZXFYZRJCPOPI-UHFFFAOYSA-N 0.000 description 1
- IQQJSTNKDJGJPH-UHFFFAOYSA-N [Ni]=O.[Na] Chemical compound [Ni]=O.[Na] IQQJSTNKDJGJPH-UHFFFAOYSA-N 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 229910021383 artificial graphite Inorganic materials 0.000 description 1
- WXCZUWHSJWOTRV-UHFFFAOYSA-N but-1-ene;ethene Chemical compound C=C.CCC=C WXCZUWHSJWOTRV-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000006231 channel black Substances 0.000 description 1
- 235000020971 citrus fruits Nutrition 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910001429 cobalt ion Inorganic materials 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 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
- 238000004880 explosion Methods 0.000 description 1
- 239000006232 furnace black Substances 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- 229910001453 nickel ion Inorganic materials 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 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
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 230000002194 synthesizing effect Effects 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
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000001947 vapour-phase growth Methods 0.000 description 1
- 238000003466 welding Methods 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
Landscapes
- Battery Electrode And Active Subsutance (AREA)
- Secondary Cells (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、電池電圧が高く、サイクル寿命が長く、かつ
充放電の際の電流効率が良好な高エネルギー密度を有す
る高性能の二次電池に関する。[Detailed Description of the Invention] [Field of Industrial Application] The present invention provides a high-performance secondary battery that has high battery voltage, long cycle life, and high energy density with good current efficiency during charging and discharging. Regarding.
近年、軽量かつエネルギー密度が高いことから、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
池が市販されているか、リチウム金属が、あまりにも活
性なため溶媒と反応し、絶縁被膜を形成し、さらにテン
ドライトの成長によって短絡し、電池内の内部／ヨード
による爆発などの危険性もあり、満足な性能のものは得
られていない。そのため、リチウムを合金化して活性を
抑制する試みもなされている。In recent years, secondary batteries that use lithium metal, an alkali metal, as the negative electrode have become commercially available due to its light weight and high energy density, or because lithium metal is so active that it reacts with solvents and forms an insulating coating. In addition, there is a risk of short-circuiting due to the growth of tendrite, and explosion due to internal iodine in the battery, so that satisfactory performance has not been obtained. Therefore, attempts have been made to suppress the activity by alloying lithium.
またナトリウムは電位かリチウムに比して０２〜０．７
Ｖ程度貴側に７フトするので、電解液との反応性か緩和
され、負極材料に適していることか知られている。ナト
リウムを用いた二次電池は、Ａｌｌｉｅｄ社、 Ａｌｌ
ｉＡｌｌｌｅｄ−３ｉ社等かすてに出願している（ＵＳ
］”４，６６８，５９６、ＵＳＰ４．７５３，８５８）
。Also, the potential of sodium is 02 to 0.7 compared to lithium.
It is known that since the V is about 7 feet to the noble side, the reactivity with the electrolyte is moderated, making it suitable as a negative electrode material. Secondary batteries using sodium are manufactured by Allied, Inc.
iAlled-3i and other companies have already applied (US
]"4,668,596, USP4.753,858)
.
また、ナトリウム合金と炭素材料とを混合した負極を用
いた二次電池は、先に本出願人が提案している。（特願
昭６３−１６９３８４）。Furthermore, the applicant has previously proposed a secondary battery using a negative electrode made of a mixture of a sodium alloy and a carbon material. (Patent application No. 63-169384).
しかしながら、上記従来のアルカリ金属、或いはアルカ
リ合金を用いた二次電池においても電解液との反応性を
完全に防止することは困難であった。However, even in the conventional secondary batteries using alkali metals or alkaline alloys, it has been difficult to completely prevent reactivity with the electrolyte.
本発明者らは、上記の問題を解決すべく、鋭意検討を行
なった結果、ナトリウムが出入し易い正極活物質が得ら
れれば、上記問題の解決に寄与すると考え、種々探索を
行なった結果、ナトリウム・ニッケル・コバルト複合酸
化物が有効なことを発見した。In order to solve the above problem, the present inventors conducted intensive studies and found that if a positive electrode active material into which sodium can easily enter and exit could be obtained, it would contribute to solving the above problem, and as a result of various searches, It was discovered that sodium-nickel-cobalt composite oxide is effective.
本発明は上記の発見に基づいてなされたもので、エネル
ギー密度が高く、サイクル特性に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 high energy density and excellent cycle characteristics.
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からなる二次電池において、
正極に下式で示すナトリウム・ニッケル・コバルト複合
酸化物を正極活物質として用い、負極にナトリウムまた
はナトリウム合金を負極活物質として用いる。In order to achieve the above object, the secondary battery of the present invention includes a positive electrode, a negative electrode, and a non-aqueous electrolyte, in which a sodium-nickel-cobalt composite oxide represented by the following formula is used as a positive electrode active material. It is used as a negative electrode, and sodium or a sodium alloy is used as the negative electrode active material.
本発明の正極に用いられるナトリウム・ニッケル酸化物
（正極活物質）は、下記の（１）式で示されるものであ
る。The sodium nickel oxide (positive electrode active material) used in the positive electrode of the present invention is represented by the following formula (1).
Ｎ ａ ０．７Ｎ ！ ｘＣ０，１−Ｘ１ｏ ｚ
−−（１）（但し、ＸはＯ＜ｘ≦０．４）
二次電池の正極に用いる場合、理由は定かでないがＸは
Ｏ＜ｘ≦０．４の範囲が最適であり、この範１［外れた
ナトリウム・ニッケル・コバルト複合酸化物を用いても
、効果が少ないことが判明した。N a 0.7N! xC0,1-X1oz
--(1) (However, X is O<x≦0.4) When used in the positive electrode of a secondary battery, although the reason is unclear, 1 [It was found that even if a sodium-nickel-cobalt composite oxide was used, the effect was small.
上記ナトリウム・ニッケル・コバルト複合酸化物は、導
電剤や結着剤と混合して成形されるが、上記ナトリウム
・ニッケル・コバルト複合酸化物の形状は粉体、特に粒
径５０μｍ以下として用いると、性能の良い正極が得ら
れる。The above-mentioned sodium-nickel-cobalt composite oxide is molded by mixing with a conductive agent and a binder, but when the above-mentioned sodium-nickel-cobalt composite oxide is used as a powder, especially as a particle size of 50 μm or less, A positive electrode with good performance can be obtained.
導電剤としては、カーボンブラック、黒鉛、炭素繊維な
どが挙げられるが、特にカーボンブラックが好ましい。Examples of the conductive agent include carbon black, graphite, and carbon fiber, with carbon black being particularly preferred.
カーボンブラックの種類は多く、ファーネスブラック
サーマルブラック、チャンネルブラック等があるが、特
に限定されるものではない。There are many types of carbon black, including furnace black.
Examples include thermal black, channel black, etc., but they are not particularly limited.
また、結着剤としては、ポリテトラフルオロエチレンに
代表されるフッ素柑脂粉、ポリオレフィン等があり、い
ずれを用いてもよいが、結着性が優れていることから、
特に繊維状のものか好適である。In addition, as a binder, there are fluorinated citrus powder represented by polytetrafluoroethylene, polyolefin, etc., and any of them may be used, but since they have excellent binding properties,
Fibrous ones are particularly suitable.
正極は上記正極活物質、導電剤、結着剤を混合、成形し
てつくられるが、上記正極活物質の含有量は、８０重量
％以上で、特に８５〜９９重量％の範囲が好ましい。正
極活物質の量が８０重量％未満では、電気容量が低下し
、また９９重量％を越えると電極嵩密度が増大し、反応
抵抗が大きくなり、同様に電気容量が低下する。炭素材
料（導電剤）は１５重量％以下、特に１〜ＩＯ重量％の
範囲が好ましい。The positive electrode is produced by mixing and molding the positive electrode active material, the conductive agent, and the binder, and the content of the positive electrode active material is preferably 80% by weight or more, particularly preferably in the range of 85 to 99% by weight. If the amount of the positive electrode active material is less than 80% by weight, the capacitance decreases, and if it exceeds 99% by weight, the electrode bulk density increases, the reaction resistance increases, and the capacitance decreases as well. The content of the carbon material (conductive agent) is preferably 15% by weight or less, particularly in the range of 1 to IO% by weight.
また、結着剤は１０重量％以下、特に１〜５重量％の範
囲か好ましい。Further, the amount of the binder is preferably 10% by weight or less, particularly in the range of 1 to 5% by weight.
上記炭素材料および結着剤の混合量は正極活物質の量を
上記範囲に保持し、かつ正極性能を考慮して上記範囲よ
り選択される。The amount of the carbon material and binder to be mixed is selected from the above range while keeping the amount of the positive electrode active material within the above range and taking into account the performance of the positive electrode.
正極は、上記３つの成分を配合し、有機溶媒を添加混練
した後、プレス成形やロール成形によって所定の形状に
成形される。成形した正極の性能を充分に発揮させるに
は、乾燥して、溶媒などを充分に除去することが重要で
ある。乾燥条件は、１５０°Ｃ以上で、減圧乾燥を２４
ｈｒ以上行なうのかよい。The positive electrode is formed by blending the above three components, adding an organic solvent and kneading, and then molding into a predetermined shape by press molding or roll molding. In order to fully demonstrate the performance of the molded positive electrode, it is important to dry it and sufficiently remove the solvent and the like. Drying conditions are 150°C or higher and vacuum drying for 24 hours.
Should I do it for more than hr?
また、本発明に用いられる負極は、充放電によってナト
リウムを効率よく出入されることか必要で、ナトリウム
と錫、或いはナトリウムと鉛の合金が用いられるか、特
にナトリウムと鉛の合金か好ましい。これは、ナトリウ
ム・鉛合金は鉛が電気化学的にナトリウムと合金化し易
い金属で、さらにナトリウムを可逆的に出入できるから
である。In addition, the negative electrode used in the present invention must be able to efficiently transfer sodium in and out during charging and discharging, and an alloy of sodium and tin or sodium and lead is preferably used, and particularly an alloy of sodium and lead is preferably used. This is because in a sodium-lead alloy, lead is a metal that easily alloys with sodium electrochemically, and furthermore, sodium can be reversibly taken in and taken out.
上記ナトリウム・鉛合金を負極に用いる場合、上記炭素
材料との複合体として用いるのが好ましい。When the above sodium-lead alloy is used for the negative electrode, it is preferably used as a composite with the above carbon material.
上記複合体負極の構成要素のうち、主として電荷を出し
入れする活物質として働くのはナトリウムであり充電で
電解液側からアルカリ金属イオンが還元されナトリウム
合金中に移動し、また放電でナトリウム合金中の一部の
ナトリウムが酸化され電解液中に移動するものと考えら
れる。Among the constituent elements of the composite negative electrode, sodium primarily acts as an active material that transfers charges.During charging, alkali metal ions are reduced from the electrolyte side and move into the sodium alloy, and during discharging, the alkali metal ions in the sodium alloy are reduced. It is thought that some sodium is oxidized and moves into the electrolyte.
上記合金の組成としては、電池の充電時の状態で、ナト
リウムと鉛のモル比は１０：１乃至１：２の範囲内が好
ましい。これは、電池の充電状態から放電状態に至るま
で、ナトリウムと鉛が合金状態を維持できるかまたは電
位的に開回路電位がナトリウム単独電位より高い電位を
示し、ナトリウムのデンドライト発生を抑制できる範囲
内であると同時に、各サイクルの充放電状態前にナトリ
ウムが負極中で枯渇状態にならない範囲内であることに
よる。As for the composition of the above-mentioned alloy, the molar ratio of sodium to lead is preferably within the range of 10:1 to 1:2 when the battery is being charged. This is within the range in which sodium and lead can maintain an alloy state from the charging state to the discharging state of the battery, or the open circuit potential can be higher than the potential of sodium alone, and the generation of sodium dendrites can be suppressed. At the same time, it is within the range that sodium does not become depleted in the negative electrode before the charge/discharge state of each cycle.
しかし、単独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、炭素材料との複合体電極にするのが良い。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。上記カーボンブラ、りには、サーマルブラック、
ファーネスブランク、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。また、その添加
量は負極重量当たり、１％ないし１５％が好ましい。However, using only a sodium alloy as an electrode does not improve the utilization rate and reversibility of the negative electrode, and it is better to use a composite electrode with a carbon material. Carbon black or graphite is suitable as the carbon material to be used. The above carbon bra, thermal black,
There are furnace blanks, 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. The amount added is preferably 1% to 15% 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く分散させて加熱溶
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−ブテンコ
ム（ＥＢＲ）、エチレン−プロピレン−ジエンコム（Ｅ
ＰＤＭ）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 thoroughly dispersing polyethylene or polypropylene fibers or powder in the electrode and welding it by heating. Further, as a more effective binder for the negative electrode material, for example, olefin copolymer rubber such as ethylene propylene rubber (EPR), ethylene-butene rubber (EBR), ethylene-propylene-diene rubber (EBR), etc.
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
、ナトリウム塩を１．２−ジメトキ／エタンとエーテル
系化合物との混合溶媒に溶解したものかよい。When such a negative electrode is used, a suitable electrolytic solution may be one in which a sodium salt is dissolved in a mixed solvent of 1,2-dimethoxy/ethane and an ether compound.
エーテル系化合物との混合系で用いる場合その種類に特
に制限はないか、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。When used in a mixed system with an ether compound, there are no particular restrictions on the type, and 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、エトキン−メト
キシエタン、タイグライム、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１１１４−３メチルジオキソラン
、ジオキサン等のエーテル化合物て、特にダイグライム
、トリグライムテトラグライムか好ましい。Examples of the non-aqueous solvent to be mixed include ether compounds such as ethquin-methoxyethane, tiglyme, triglyme, tetraglyme, pentaglyme, tetrahydrofuran, 2-methyltetrahydrofuran 1114-3 methyldioxolane, and dioxane, particularly diglyme, triglyme, and tetraglyme. Or preferable.
ナトリウム塩の具体例としては、ＮａＰＦ、やＮａＢＦ
４．ＮａＣＦ３５○Ｂ＋ Ｎ ａ Ａ ｓ Ｆ ＠＋
Ｎ ａＳ ＩＦ ｓ等を挙げることができるが、有機
溶媒への溶解度が比較的高く、電気化学的に安定な電解
質としてＮ ａ Ｐ Ｆ ｅが好適である。Specific examples of sodium salts include NaPF and NaBF.
4. NaCF35○B+ N a A s F @+
Examples include NaSIFs, but NaPFe is preferable as an electrolyte that has relatively high solubility in organic solvents and is electrochemically stable.
次に実施例、比較例を示して本発明を具体的に説明する
。Next, the present invention will be specifically explained by showing Examples and Comparative Examples.
・実施例１
正極はＮ ａ ２０２ 、Ｃ０３０４およびＮ１０を酸
素雰囲気下で加熱反応させＮ ａ ０７Ｎ ＋。３ＣＯ
０，７０、を合成し、それを粉砕した後、篩分けして粒
径５０μｍ以下の粒子を得、これを正極活物質とした。- Example 1 The positive electrode was made by heating and reacting Na 202 , C0304 and N10 in an oxygen atmosphere to form Na 07N + . 3CO
0.70 was synthesized, pulverized, and then sieved to obtain particles with a particle size of 50 μm or less, which were used as a positive electrode active material.
この正極活物質か９５重量％、アセチレンブラックが２
５重量％、テトラフルオロエチレンか２５重量％となる
ように配合し、これに有機溶剤を添加して混練した。こ
の混練したものをロールで４００μｍの厚さに圧延し、
幅４ｃｍ、長さ１３ｃｍの大きさに切り取り２００°Ｃ
て真空乾燥し正極とした。This positive electrode active material is 95% by weight, and acetylene black is 2% by weight.
5% by weight and 25% by weight of tetrafluoroethylene, an organic solvent was added thereto, and the mixture was kneaded. This kneaded material was rolled with a roll to a thickness of 400 μm,
Cut into pieces 4cm wide and 13cm long at 200°C.
It was dried in vacuum and used as a positive electrode.
また、ナトリウムと鉛とを原子比か３：１となるように
配合し、不活性ガス雰囲気下で加熱反応させ、ナトリウ
ム・鉛合金を得た。これを微細に粉砕した後、あらかじ
め用意したアセチレンブラックとＥＰＤＭの重量比が３
・１の混合物を加え、ナトリウム・鉛合金が９０％、上
記混合物が１０％になるように混ぜてプレス成形により
幅４ｃｍ長さ１５ｃｍの負極を成形した。Further, sodium and lead were mixed at an atomic ratio of 3:1 and reacted by heating under an inert gas atmosphere to obtain a sodium-lead alloy. After finely pulverizing this, the weight ratio of the acetylene black and EPDM prepared in advance was 3.
- The mixture of 1 was added and mixed so that the sodium-lead alloy was 90% and the above mixture was 10%, and a negative electrode with a width of 4 cm and a length of 15 cm was formed by press molding.
さらに１．２−ジメトキシエタンにＮ ａ Ｐ Ｆ ａ
を１．０モル／ｇの濃度に溶かしたものを電解液とした
。Furthermore, N a P F a to 1,2-dimethoxyethane
An electrolytic solution was prepared by dissolving the following to a concentration of 1.0 mol/g.
上記正極、負極、電解液、およびセパレータとしてポリ
プロピレン製マイクロポーラスフィルムを用いてＡＡ型
のシリンダー電池を組立てた。An AA type cylinder battery was assembled using the positive electrode, negative electrode, electrolytic solution, and a polypropylene microporous film as a separator.
この電池の組立直後の電圧は２．４８Ｖであった。この
電池を放電方向に電流２００ｍＡで電池電圧が１．５ｖ
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、さらに同じ電流値で放電を行い
これを数回繰り返し、このときの放電容量を調べた。The voltage of this battery immediately after assembly was 2.48V. This battery is discharged with a current of 200mA and a battery voltage of 1.5V.
Discharge until the battery voltage reaches 3.5mm at the same current value.
The battery was charged until it reached Ov, and then discharged at the same current value. This was repeated several times, and the discharge capacity at this time was examined.
最大放電容量は６２８ｍＡｈであり、充電放電における
電流効率は１００％であった。The maximum discharge capacity was 628 mAh, and the current efficiency during charging and discharging was 100%.
また、この電池の放電容量が最大値の９０％に低下する
までのサイクル数は、１２５回であった。Further, the number of cycles until the discharge capacity of this battery decreased to 90% of the maximum value was 125 times.
実施例２
正極にＮ ａ Ｏ，？Ｎ ＋ ０．４ＣＯｏ、 ｓｏ
！を用いた以外は、実施例１と同しにしてＡＡ型電池を
組み立てた。Example 2 N a O, ? at the positive electrode? N + 0.4COo, so
! An AA type battery was assembled in the same manner as in Example 1, except that AA type battery was used.
この電池５個（Ｎｏ２−１〜Ｎｏ２−５）を組み立てて
実施例１と同様の実験を行った。結果を第１表に示す。Five of these batteries (No. 2-1 to No. 2-5) were assembled and the same experiment as in Example 1 was conducted. The results are shown in Table 1.
第１表
実施例３
正極にＮ ａｏ、７Ｎ Ｉ 。、 ＋ＣＯｏ、 ６０
＊を用いた以外は実施例１と同様のものを用いてＡＡ型
電池を組立てた。この電池５個（Ｎｏ３−１〜Ｎｏ３−
５）を組み立てて実施例１と同様の実験を行った。結果
を第２表に示す。Table 1 Example 3 N ao and 7N I for the positive electrode. , +COo, 60
An AA type battery was assembled using the same battery as in Example 1 except that * was used. These 5 batteries (No. 3-1 to No. 3-
5) was assembled and the same experiment as in Example 1 was conducted. The results are shown in Table 2.
第２表
比較例１
正極にＮ ａ ０．７Ｎ ｉ ０．、Ｃｏ ｏ、５０
、を用いた以外は実施例１と同様にしてＡＡ型電池を組
み立てた。Table 2 Comparative Example 1 Positive electrode has N a 0.7 N i 0. , Co o, 50
An AA type battery was assembled in the same manner as in Example 1 except that , was used.
この電池５個（Ｎｏ４−１〜Ｎｏ４−５）を組み立てて
実施例１と同様の実験を行った。結果を第３表に示す。Five of these batteries (No. 4-1 to No. 4-5) were assembled and the same experiment as in Example 1 was conducted. The results are shown in Table 3.
第３表
第３表よりＮｉを０５に増すと、放電容量及び電池電圧
か低下することかわかった。From Table 3, it was found that when Ni was increased to 05, the discharge capacity and battery voltage decreased.
比較例２
正極にＮａ、○、とＣＯ２Ｏ３を酸素雰囲気下で加熱反
応させＮａｏ７Ｃｏ○、を合成したものを用いた以外は
、実施例１と同様にしてＡＡ型電池を組み立てた。Comparative Example 2 An AA type battery was assembled in the same manner as in Example 1, except that the cathode was made by synthesizing Nao7Co◯ by heating reaction of Na,◯, and CO2O3 in an oxygen atmosphere.
この電池５個（Ｎｏ５−１〜Ｎｏ５−５）を組み立てて
実施例１と同様の実験を行った。結果を第４表に示す。Five of these batteries (No. 5-1 to No. 5-5) were assembled and the same experiment as in Example 1 was conducted. The results are shown in Table 4.
第４表
充電終止電圧が３．ＯＶでは放電容量が低くなってしま
った。Table 4 Charging end voltage is 3. With OV, the discharge capacity became low.
上記第１表〜第４表の結果よりＮ ａ 、、７Ｎ ｉ
ｘＣＯｆｌ−１１１０２（但し、Ｏ＜ｘ≦０．４）を正
極に用いることで高容量で高エネルギー密度の二次電池
を開発することができた。From the results in Tables 1 to 4 above, N a , 7N i
By using xCOfl-11102 (O<x≦0.4) as a positive electrode, we were able to develop a secondary battery with high capacity and high energy density.
高容量充放電が可能な理由は、詳しくはわからないが酸
化ニッケルが酸化コバルトのナトリウムに対する電位を
下げる効果があり充放電電圧中（１５〜３．ＯＶ）での
容量が高くなったものと思われる。The reason why high capacity charging and discharging is possible is not known in detail, but it is thought that nickel oxide has the effect of lowering the potential of cobalt oxide relative to sodium, increasing the capacity at medium charging and discharging voltages (15 to 3.OV). .
また、Ｎｉが原子比で０．４以上になると正極電位が下
がると共に、３価のニッケルイオンが過剰に存在するた
め、コバルトサイトへ入す込ミ４価のコバルイオンによ
ってできた正孔をつぶしてしまいナトリウムイオンの吸
収ができなくなってしまうため、正極の容量低下をきた
すものと思われる。In addition, when the atomic ratio of Ni is 0.4 or more, the positive electrode potential decreases, and since trivalent nickel ions are present in excess, they enter the cobalt site and crush the holes created by tetravalent cobalt ions. This is thought to result in a decrease in the capacity of the positive electrode because sodium ions cannot be absorbed.
本発明において、酸化コバルトニッケルナトリウムを正
極に用いることにより高エネルギー密度でありさらにサ
イクル特性に優れた安定で信頼性の高い二次電池が得ら
れる。In the present invention, by using sodium cobalt nickel oxide for the positive electrode, a stable and highly reliable secondary battery with high energy density and excellent cycle characteristics can be obtained.
Claims (1)
酸化物を正極活物質として用い、負極にナトリウムまた
はナトリウム合金を負極活物質として用いることを特徴
とする二次電池。 Ｎａ＿０＿．＿７Ｎｉ＿ｘＣｏ＿（＿１＿−＿ｘ＿）Ｏ
＿２（但し、ｘは０＜ｘ≦０．４）[Scope of Claims] In a secondary battery consisting of a positive electrode, a negative electrode, and a non-aqueous electrolyte, a sodium-nickel-cobalt composite oxide shown in the formula below is used as a positive electrode active material in the positive electrode, and sodium or a sodium alloy is used in the negative electrode. A secondary battery characterized by being used as a negative electrode active material. Na_0_. _7Ni_xCo_(_1_-_x_)O
_2 (However, x is 0<x≦0.4)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2094464A JPH03291863A (en) | 1990-04-10 | 1990-04-10 | Secondary cell |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2094464A JPH03291863A (en) | 1990-04-10 | 1990-04-10 | Secondary cell |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH03291863A true JPH03291863A (en) | 1991-12-24 |
Family
ID=14111002
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2094464A Pending JPH03291863A (en) | 1990-04-10 | 1990-04-10 | Secondary cell |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH03291863A (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006179473A (en) * | 2004-11-26 | 2006-07-06 | Kyushu Univ | Positive electrode active material for nonaqueous electrolyte secondary battery |
| WO2010024304A1 (en) * | 2008-08-27 | 2010-03-04 | 住友化学株式会社 | Electrode active material and method for producing same |
| US7695868B2 (en) * | 2006-03-20 | 2010-04-13 | Sanyo Electric Co., Ltd. | Sodium ion secondary battery |
| US8709655B2 (en) | 2004-11-26 | 2014-04-29 | Sumitomo Chemical Company, Limited | Positive electrode active material for nonaqueous electrolyte secondary battery |
| US8790831B2 (en) | 2008-02-04 | 2014-07-29 | Sumitomo Chemical Company, Limited | Powder for positive electrode active material, positive active electrode active material, and sodium secondary battery |
| JP2014175243A (en) * | 2013-03-12 | 2014-09-22 | Nippon Telegr & Teleph Corp <Ntt> | Sodium secondary battery |
| US9142860B2 (en) | 2008-02-04 | 2015-09-22 | Sumitomo Chemical Company, Limited | Mixed metal oxide and sodium secondary battery |
| US10122014B2 (en) | 2008-02-04 | 2018-11-06 | Sumitomo Chemical Company, Limited | Mixed metal oxide and sodium secondary battery |
| CN108987738A (en) * | 2018-07-23 | 2018-12-11 | 合肥科晶材料技术有限公司 | A kind of technique preparing sodium stannum alloy cathode material and battery |
-
1990
- 1990-04-10 JP JP2094464A patent/JPH03291863A/en active Pending
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006179473A (en) * | 2004-11-26 | 2006-07-06 | Kyushu Univ | Positive electrode active material for nonaqueous electrolyte secondary battery |
| US8709655B2 (en) | 2004-11-26 | 2014-04-29 | Sumitomo Chemical Company, Limited | Positive electrode active material for nonaqueous electrolyte secondary battery |
| US7695868B2 (en) * | 2006-03-20 | 2010-04-13 | Sanyo Electric Co., Ltd. | Sodium ion secondary battery |
| US8790831B2 (en) | 2008-02-04 | 2014-07-29 | Sumitomo Chemical Company, Limited | Powder for positive electrode active material, positive active electrode active material, and sodium secondary battery |
| US9142860B2 (en) | 2008-02-04 | 2015-09-22 | Sumitomo Chemical Company, Limited | Mixed metal oxide and sodium secondary battery |
| US10122014B2 (en) | 2008-02-04 | 2018-11-06 | Sumitomo Chemical Company, Limited | Mixed metal oxide and sodium secondary battery |
| WO2010024304A1 (en) * | 2008-08-27 | 2010-03-04 | 住友化学株式会社 | Electrode active material and method for producing same |
| JP2010080424A (en) * | 2008-08-27 | 2010-04-08 | Sumitomo Chemical Co Ltd | Electrode active material and method for manufacturing the same |
| JP2014175243A (en) * | 2013-03-12 | 2014-09-22 | Nippon Telegr & Teleph Corp <Ntt> | Sodium secondary battery |
| CN108987738A (en) * | 2018-07-23 | 2018-12-11 | 合肥科晶材料技术有限公司 | A kind of technique preparing sodium stannum alloy cathode material and battery |
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