JPH01279565A - Nonaqueous solvent battery - Google Patents
Nonaqueous solvent batteryInfo
- Publication number
- JPH01279565A JPH01279565A JP63109305A JP10930588A JPH01279565A JP H01279565 A JPH01279565 A JP H01279565A JP 63109305 A JP63109305 A JP 63109305A JP 10930588 A JP10930588 A JP 10930588A JP H01279565 A JPH01279565 A JP H01279565A
- Authority
- JP
- Japan
- Prior art keywords
- manganese dioxide
- positive
- battery
- positive electrode
- active material
- 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
- 239000002904 solvent Substances 0.000 title abstract description 5
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims abstract description 57
- 239000000126 substance Substances 0.000 claims abstract description 14
- 239000006229 carbon black Substances 0.000 claims abstract description 13
- 239000004020 conductor Substances 0.000 claims abstract description 12
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 8
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims abstract description 7
- GEYXPJBPASPPLI-UHFFFAOYSA-N manganese(iii) oxide Chemical compound O=[Mn]O[Mn]=O GEYXPJBPASPPLI-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000007774 positive electrode material Substances 0.000 claims abstract description 7
- 239000011230 binding agent Substances 0.000 claims abstract description 6
- 229940099596 manganese sulfate Drugs 0.000 claims abstract description 6
- 235000007079 manganese sulphate Nutrition 0.000 claims abstract description 6
- 239000011702 manganese sulphate Substances 0.000 claims abstract description 6
- 239000013078 crystal Substances 0.000 claims abstract description 4
- 239000003125 aqueous solvent Substances 0.000 claims description 12
- 239000011149 active material Substances 0.000 claims description 9
- TYTHZVVGVFAQHF-UHFFFAOYSA-N manganese(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Mn+3].[Mn+3] TYTHZVVGVFAQHF-UHFFFAOYSA-N 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 239000011255 nonaqueous electrolyte Substances 0.000 claims description 2
- 239000000203 mixture Substances 0.000 abstract description 12
- 239000012298 atmosphere Substances 0.000 abstract description 4
- 239000003792 electrolyte Substances 0.000 abstract description 4
- 239000008188 pellet Substances 0.000 abstract description 3
- 229910001220 stainless steel Inorganic materials 0.000 abstract description 2
- 239000010935 stainless steel Substances 0.000 abstract description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 12
- 239000007788 liquid Substances 0.000 description 8
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 6
- 229910052744 lithium Inorganic materials 0.000 description 6
- 239000006230 acetylene black Substances 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 239000010439 graphite Substances 0.000 description 4
- 229910002804 graphite Inorganic materials 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- -1 polytetrafluoroethylene Polymers 0.000 description 4
- 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 description 3
- 241000872198 Serjania polyphylla Species 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 239000007773 negative electrode material Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- 238000004438 BET method Methods 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical class [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 description 2
- 229910001486 lithium perchlorate Inorganic materials 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- SPEUIVXLLWOEMJ-UHFFFAOYSA-N 1,1-dimethoxyethane Chemical compound COC(C)OC SPEUIVXLLWOEMJ-UHFFFAOYSA-N 0.000 description 1
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 description 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 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
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 229910016938 MnO2+2 Inorganic materials 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- GOPYZMJAIPBUGX-UHFFFAOYSA-N [O-2].[O-2].[Mn+4] Chemical class [O-2].[O-2].[Mn+4] GOPYZMJAIPBUGX-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 238000007323 disproportionation reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000003411 electrode reaction Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000005087 graphitization Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 229910000357 manganese(II) sulfate Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000015654 memory Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000011356 non-aqueous organic solvent Substances 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000003716 rejuvenation Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 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
- 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
-
- 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
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/502—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese for non-aqueous cells
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明は、非水溶媒電池に関し、特に正極の組成を改良
した非水溶媒電池に係わるものである。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a non-aqueous solvent battery, and particularly to a non-aqueous solvent battery in which the composition of the positive electrode is improved.
［従来の技術］
負極活物質としてリチウム、ナトリウム等の軽金属を用
いた非水溶媒電池はエネルギー密度が大きく、貯蔵特性
に優れ、かつ作動温度範囲が広いという特徴をもち、電
卓、時計、メモリのバックアップ電源として多用されて
いるが、最近、重負荷放電性能が要求されている。また
、かかる非水溶媒電池において負極活物質であるリチウ
ム、ナトリウム等の軽金属と組合わせる正極活物質の選
択は電池性能を左右するため極めて重要である。[Prior art] Nonaqueous solvent batteries that use light metals such as lithium and sodium as negative electrode active materials have high energy density, excellent storage characteristics, and a wide operating temperature range, and are used in calculators, watches, and memories. Although it is often used as a backup power source, heavy load discharge performance has recently been required. In addition, in such a non-aqueous solvent battery, the selection of a positive electrode active material to be combined with a light metal such as lithium or sodium, which is a negative electrode active material, is extremely important because it affects the battery performance.
ところで、上述した電池に使用される正極活物質として
は従来より多くの物質が検討され、その中でも二酸化マ
ンガンは比較的優れた性能を示し、化学的にも安定して
いるという長所を有するため広く用いられている。こう
した二酸化マンガンの中でも非水溶媒電池には、硫酸マ
ンガンを電解酸化して得られる電解二酸化マンガンが一
般的に使用されている。また、非水溶媒電池の正極は前
記活物質に導電材及び結着剤を添加、混合した組成のも
のが使用されている。この導電材としては、従来よりア
セチレンブラックや黒鉛等が多用されている。By the way, many materials have been considered as positive electrode active materials for use in the above-mentioned batteries, and among them, manganese dioxide has been widely used because it has relatively excellent performance and is chemically stable. It is used. Among these manganese dioxides, electrolytic manganese dioxide obtained by electrolytically oxidizing manganese sulfate is generally used in nonaqueous solvent batteries. Further, the positive electrode of a non-aqueous solvent battery is made of a composition in which a conductive material and a binder are added to and mixed with the above-mentioned active material. Conventionally, acetylene black, graphite, and the like have been frequently used as the conductive material.
［発明が解決しようとする課題］
しかしながら、活物質として電解二酸化マンガン、導電
材としてアセチレンブラック又は黒鉛ヲ用いた正極を組
込んだ非水溶媒電池では前述した重負荷放電性能の向上
に充分に対応できない問題があった。即ち、正極を構成
するために電解二酸化マンガンと共に配合されるアセチ
レンブラックは、吸液性に優れているものの、導電性が
劣る。[Problems to be Solved by the Invention] However, non-aqueous solvent batteries incorporating a positive electrode using electrolytic manganese dioxide as an active material and acetylene black or graphite as a conductive material cannot sufficiently cope with the above-mentioned improvement in heavy load discharge performance. There was a problem that I couldn't do it. That is, acetylene black, which is blended together with electrolytic manganese dioxide to constitute the positive electrode, has excellent liquid absorption properties, but is poor in electrical conductivity.
一方、黒鉛は導電性に優れているものの、吸液特性が劣
る。従って、これらを導電材として正極を構成した場合
には正極の液保持性又は導電性が低下するため、電池の
内部抵抗を低減し難く、放電性能を向上させることが困
難となる。また、両者を配合した正極でも前記欠点を解
消できない。更に、電解二酸化マンガンも正極活物質と
して必ずしも充分な特性を有しているものといえず、し
かもその製造に際しては電解に長時間要し、かつ多くの
電力を消費するため製造コストが高くなるという問題が
あった。On the other hand, although graphite has excellent conductivity, it has poor liquid absorption properties. Therefore, when a positive electrode is constructed using these conductive materials, the liquid retention or conductivity of the positive electrode is reduced, making it difficult to reduce the internal resistance of the battery and to improve the discharge performance. Further, even a positive electrode containing both of them cannot overcome the above-mentioned drawbacks. Furthermore, electrolytic manganese dioxide does not necessarily have sufficient properties as a positive electrode active material, and furthermore, its production requires a long time for electrolysis and consumes a lot of electricity, which increases production costs. There was a problem.
本発明は、上記従来の課題を解決するためになされたも
ので、雷放電性能の優れた非水溶媒電池を提供しようと
するものである。The present invention has been made to solve the above-mentioned conventional problems, and aims to provide a non-aqueous solvent battery with excellent lightning discharge performance.
［課題を解決するための手段］
本発明は、軽金属を活物質とする負極と、活物質、導電
材及び結若剤からなる正極と、非水溶媒系電解液とを具
備した非水溶媒電池において、前記正極活物質は硫酸マ
ンガン結晶を焙焼した三二酸化マンガン（Ｍｎ ２Ｏ３
）を硫酸溶液に浸漬して二酸化マンガン（ＭｎＯ２）
とし、これを水洗、乾燥、プレスして得た化学二酸化マ
ンガンがらなり、かつ前記導電材は比表面積（ＢＥＴ法
により求めた値）が９０〜１５０ｍ２／ｇのカーボンブ
ラックからなることを特徴とする非水溶媒電池である。[Means for Solving the Problems] The present invention provides a nonaqueous battery comprising a negative electrode using a light metal as an active material, a positive electrode comprising an active material, a conductive material, and a rejuvenating agent, and a nonaqueous electrolyte. , the positive electrode active material is manganese sesquioxide (Mn2O3) obtained by roasting manganese sulfate crystals.
) in sulfuric acid solution to produce manganese dioxide (MnO2).
It is characterized in that it is made of chemical manganese dioxide obtained by washing, drying, and pressing this, and that the conductive material is made of carbon black with a specific surface area (value determined by the BET method) of 90 to 150 m2/g. It is a non-aqueous solvent battery.
上記負極活物質である軽金属としては、例えばリチウム
、ナトリウム、カリウム、カルシウム、マグネシウム、
アルミニウム等を挙げることができ、特にリチウム、ア
ルミニウムが好適である。Examples of the light metal as the negative electrode active material include lithium, sodium, potassium, calcium, magnesium,
Examples include aluminum, with lithium and aluminum being particularly preferred.
上記電解液としては、例えばプロピレンカーボネート、
１．２−ジメトキシエタン、γ−ブチロラクトン、テト
ラヒドロフラン、ジオキソラン等の非水有機溶媒に過塩
素酸リチウム、ホウフッ化リチウム、塩化リチウム等の
電解質を０．２〜１．５モル／ノ溶解せしめたものが使
用される。Examples of the electrolyte include propylene carbonate,
1. Electrolyte such as lithium perchlorate, lithium borofluoride, lithium chloride, etc. dissolved in a non-aqueous organic solvent such as 2-dimethoxyethane, γ-butyrolactone, tetrahydrofuran, dioxolane, etc. at 0.2 to 1.5 mol/min. is used.
上記正極活物質として使用する化学二酸化マンガンの詳
細な製造方法は、次のとうりである。まず、硫酸マンガ
ン結晶を空気雰囲気又は空気より酸素分圧の大きい酸素
雰囲気中にて８００〜１１００℃、１０分間以上の条件
で焙焼し、硫酸マンガンを分解してＭｎ２Ｏ３を主成分
とするマンガン酸化物を調製する。つづいて、このマン
ガン酸化物を硫酸により酸処理する。これにより、次式
に示す不均化反応が起こって二酸化マンガンが生成され
る。The detailed method for producing chemical manganese dioxide used as the positive electrode active material is as follows. First, manganese sulfate crystals are roasted in an air atmosphere or an oxygen atmosphere with a higher oxygen partial pressure than air at 800 to 1100°C for 10 minutes or more to decompose the manganese sulfate and oxidize the manganese to Mn2O3 as the main component. prepare something Subsequently, this manganese oxide is acid-treated with sulfuric acid. As a result, the disproportionation reaction shown in the following formula occurs and manganese dioxide is produced.
Ｍｎ２Ｏ３ ”Ｈ２８０４−ＭｎＯ２＋Ｍｎ５Ｏ４＋Ｈ
２Ｏ月ｎ３０４ ＋２１１２８０４ →、ＭｎＯ２＋２
ＭｎＳＯ４＋２１１２Ｏ上記反応で生成したＭ２Ｏ３を
水洗、中和処理、乾燥を行なった後、得られた粉末をロ
ールプレスにより１〜１０ｔｏｎ ／ｄの圧力下で平板
状に圧縮成形し、ひきつづき所定の粒度に粉砕して化学
二酸化マンガンを製造する。Mn2O3 ”H2804-MnO2+Mn5O4+H
2O month n304 +2112804 →, MnO2+2
MnSO4+2112O After washing the M2O3 produced in the above reaction with water, neutralizing it, and drying it, the resulting powder is compression molded into a flat plate shape under a pressure of 1 to 10 tons/d using a roll press, and then pulverized to a predetermined particle size. to produce chemical manganese dioxide.
上記特定の比表面積を有するカーボンブラックは、次の
ような方法により製造される。まず、炭素原子／水素原
子が重量比で９以上の液状炭化水素を炉内で気体状の分
子状酸素及び水蒸気の存在下で部分酸化して合成ガスを
生成させると共に、カーボンを副生させる。ここに用い
る液状炭化水素としては、例えばナフサの熱分解油（エ
チレンヘビーエンド）、芳香族系炭化水素にカーボンを
混合したもの（カーボンオイル）、芳香族系炭化水素に
Ｃ重油などを混合した混合オイル等を挙げることができ
る。前記水蒸気は、目的とするカーボンを副生させるた
めに液状炭化水素１ トンに対しテ２Ｏ０〜８００ Ｋ
’ｊ、好ましくハ４ｏｏ〜８ｏｏ幻使用する。前記炉内
の温度は、１２Ｏ０−１４５０’ｃ、好ましくは１３０
０〜１４５０℃とし、反応時の圧力は１０〜８０気圧、
好ましくは２５〜８０気圧にする。つづいて、前記副生
カーボンを窒素雰囲気下、３００〜９０（１’Ｃで０．
５〜３時間乾燥し、更に不活性ガス雰囲気下、１０００
〜３０００℃で０．５〜５時間加熱処理することにより
前記特定の比表面積を有するカーボンブラックを製造す
る。Carbon black having the above specific specific surface area is produced by the following method. First, a liquid hydrocarbon having a carbon atom/hydrogen atom weight ratio of 9 or more is partially oxidized in a furnace in the presence of gaseous molecular oxygen and water vapor to generate a synthesis gas and to generate carbon as a by-product. The liquid hydrocarbons used here include, for example, naphtha pyrolysis oil (ethylene heavy end), aromatic hydrocarbons mixed with carbon (carbon oil), aromatic hydrocarbons mixed with C heavy oil, etc. Oil etc. can be mentioned. The water vapor is heated at a temperature of 0 to 800 K per 1 ton of liquid hydrocarbon in order to produce the desired carbon as a by-product.
'j, preferably use 4oo to 8oo. The temperature in the furnace is 12O0-1450'C, preferably 130
The temperature was 0 to 1450°C, and the pressure during the reaction was 10 to 80 atm.
Preferably the pressure is 25 to 80 atmospheres. Subsequently, the by-product carbon was heated to a temperature of 300 to 90% (0.5% at 1'C) under a nitrogen atmosphere.
Dry for 5 to 3 hours, and then dry for 1000 min under an inert gas atmosphere.
Carbon black having the specific surface area described above is produced by heat treatment at ~3000°C for 0.5 to 5 hours.
上記カーボンブラックの比表面積を限定した理由は、比
表面積が９０ｍ２／９未満にすると保液性が低下して放
電性能の低下を招き、かといって比表面積が１５０ｍ２
／ｇを越えると前記製造過程での加熱不足を意味し、官
能基が残存して化学二酸化マンガンを還元して容量劣化
を招く。また、かかるカーボンブラックはＪ Ｉ Ｓ
Ｋ１４９Ｂによる塩酸吸液量が２ＯＭ１５ ｇ以上であ
ることが望ましい。The reason why the specific surface area of the carbon black is limited is that if the specific surface area is less than 90 m2/9, the liquid retention property will decrease and the discharge performance will deteriorate.
If it exceeds /g, it means insufficient heating in the manufacturing process, and the functional groups remain and reduce chemical manganese dioxide, resulting in capacity deterioration. In addition, such carbon black is JIS
It is desirable that the amount of hydrochloric acid absorbed by K149B is 2OM15 g or more.
上記結着剤としては、例えばポリテトラフロロエチレン
、ポリアクリル酸、その塩類等を挙げることができる。Examples of the binder include polytetrafluoroethylene, polyacrylic acid, and salts thereof.
上記正極を構成する活物質としての化学二酸化マンガン
、導電材としてのカーボンブラック及び結着材との配合
比率は、重量比にてｇθ〜９４：５〜１５；Ｉ〜５の範
囲とすることが望ましい。こうした配合範囲を逸脱する
と、導電性の低下、放電容量劣化、成形性の低下を招く
恐れがある。The compounding ratio of chemical manganese dioxide as an active material, carbon black as a conductive material, and binder constituting the positive electrode may be in the range of gθ~94:5~15; I~5 in terms of weight ratio. desirable. Deviation from such a blending range may lead to a decrease in conductivity, discharge capacity deterioration, and moldability.
［作用］
本発明によれば、正極の主成分である活物質として特定
の原料の処理、プレス成形を施して得た比表面積の大き
い化学二酸化マンガンを用いることによって、電解質と
接する界面を大きくできるため、従来の電解二酸化マン
ガンに比べて重負荷での電極反応の進行を円滑にできる
。また、導電材として使用する特定の比表面積をもつカ
ーボンブラックはアセチレンブラックに比べて粒子表面
の黒鉛化度が進んでおり、かつ吸液特性や導電性が優れ
ている。しかも、かかるカーボンブラックは粒子表面の
官能基が少ないため、活物質である化学二酸化マンガン
の劣化を防ぐことができる。[Function] According to the present invention, the interface in contact with the electrolyte can be enlarged by using chemical manganese dioxide with a large specific surface area obtained by processing and press-molding a specific raw material as the active material that is the main component of the positive electrode. Therefore, compared to conventional electrolytic manganese dioxide, electrode reactions can proceed more smoothly under heavy loads. Further, carbon black with a specific specific surface area used as a conductive material has a higher degree of graphitization on the particle surface than acetylene black, and has excellent liquid absorption properties and conductivity. Furthermore, since such carbon black has few functional groups on the particle surface, deterioration of chemical manganese dioxide, which is an active material, can be prevented.
従って、これらの化学二酸化マンガン、カーボンブラッ
クを結着剤と共に配合した正極を構成し、電池に組込む
ことによって、重負荷放電性能を大幅に向上できる。Therefore, by constructing a positive electrode containing these chemical manganese dioxide and carbon black together with a binder and incorporating it into a battery, heavy load discharge performance can be greatly improved.
［発明の実施例］
以下、本発明をコイン形非水溶媒電池に適用した例につ
いて第１図を参照して詳細に説明する。[Embodiments of the Invention] Hereinafter, an example in which the present invention is applied to a coin-type non-aqueous solvent battery will be described in detail with reference to FIG.
図中の１は、ステンレス鋼製の正極容器であり、この容
器１内には正極合剤２が収納されている。この正極合剤
２は、既述した方法で得た化学二酸化マンガンを４００
℃で８時間空気中で加熱したものとＢＥＴ法より測定し
た比表面積が１３５ｍ２／ｇのカーボンブラックとポリ
テトラフロロエチレンとを重量比にて８７：１０：３の
割合で混合し、これを外径１６ｍ、厚さ１．７１［Ｉｌ
、重量０．８９９のペレット状に成形したものである。1 in the figure is a positive electrode container made of stainless steel, and a positive electrode mixture 2 is housed in this container 1. This positive electrode mixture 2 contains 400% of chemical manganese dioxide obtained by the method described above.
Carbon black with a specific surface area of 135 m2/g measured by the BET method and polytetrafluoroethylene were mixed in a weight ratio of 87:10:3, heated in air for 8 hours at Diameter 16m, thickness 1.71 [Il
, and was molded into pellets with a weight of 0.899.
また、前記正極合剤２上にはポリプロピレン不織布から
なるセパレータ３及び金属リチウムからなる負極４が載
置されている。前記セパレータ３には、プロピレンカー
ボネートと１．２−ジメトキシエタンの混合溶媒（重量
比で１ ＝１）に過塩素酸リチウムを１モル／ノの濃度
で溶解した電解液が含浸保持されている。前記正極容器
１の開口部にはバッキング５を介して負極容器Ｂが設け
られており、該負極容器Ｂのかしめ加工により正極容器
１、負極容器Ｂ内に前記正極合剤２、セパレータ３及び
負極４が密閉されている。このコイン形非水溶媒電池は
、外径２Ｏｕ、厚さ２．４ ｒｍの寸法を有するもので
ある。Further, on the positive electrode mixture 2, a separator 3 made of a polypropylene nonwoven fabric and a negative electrode 4 made of metallic lithium are placed. The separator 3 is impregnated with an electrolytic solution in which lithium perchlorate is dissolved in a mixed solvent of propylene carbonate and 1,2-dimethoxyethane (weight ratio: 1=1) at a concentration of 1 mol/no. A negative electrode container B is provided at the opening of the positive electrode container 1 via a backing 5, and by caulking the negative electrode container B, the positive electrode mixture 2, separator 3, and negative electrode are placed inside the positive electrode container 1, negative electrode container B. 4 is sealed. This coin-shaped non-aqueous solvent battery has an outer diameter of 2 Ou and a thickness of 2.4 rm.
比較例
電解二酸化マンガンを４００℃で８時間加熱したものと
黒鉛とポリテトラフロロエチレンとを重量比にて８７：
１０：３の割合で混合し、ベレット状に成形した正極合
剤を用いた以外、実施例と同様なコイン形非水溶媒電池
を組立てた。Comparative Example Electrolytic manganese dioxide heated at 400°C for 8 hours, graphite and polytetrafluoroethylene in a weight ratio of 87:
A coin-shaped nonaqueous solvent battery was assembled in the same manner as in the example except that a positive electrode mixture mixed at a ratio of 10:3 and molded into a pellet shape was used.
しかして、本実施例及び比較例の電池２Ｏ個について３
０日間貯蔵し、その後３００Ω負荷をかけた時の放電持
続時間（放電終止電圧２．ＯＶ）を測定した。その結果
を下記第１表に平均値として示した。Therefore, for 20 batteries in this example and comparative example, 3
The battery was stored for 0 days, and then the discharge duration (discharge end voltage 2.OV) was measured when a 300Ω load was applied. The results are shown in Table 1 below as average values.
第１表
［発明の効果］
以上詳述した如く、本発明によれば重負荷放電性能の優
れた非水溶媒電池を提供することができる。Table 1 [Effects of the Invention] As detailed above, according to the present invention, a non-aqueous solvent battery with excellent heavy load discharge performance can be provided.
第１図は本発明の一実施例を示すコイン形非水溶媒電池
の断面図である。
ｌ・・・正極容器、２・・・正極合剤、３・・・セノく
レータ、４・・・負極、５・・・バッキング、６・・・
負極容器。
出願人代理人 弁理士 鈴江武彦
第１図FIG. 1 is a sectional view of a coin-shaped non-aqueous solvent battery showing one embodiment of the present invention. l...Positive electrode container, 2...Positive electrode mixture, 3...Cenoclator, 4...Negative electrode, 5...Backing, 6...
Negative electrode container. Applicant's agent Patent attorney Takehiko Suzue Figure 1
Claims (1)
着剤からなる正極と、非水溶媒系電解液とを具備した非
水溶媒電池において、前記正極活物質は硫酸マンガン結
晶を焙焼した三二酸化マンガン（Ｍｎ２Ｏ＿３）を硫酸
溶液に浸漬して二酸化マンガン（ＭｎＯ＿２）とし、こ
れを水洗、乾燥、プレスして得た化学二酸化マンガンか
らなり、かつ前記導電材は比表面積が９０〜１５０ｍ＾
２／ｇのカーボンブラックからなることを特徴とする非
水溶媒電池。In a non-aqueous battery comprising a negative electrode made of a light metal as an active material, a positive electrode made of an active material, a conductive material, and a binder, and a non-aqueous electrolyte, the positive electrode active material is made by roasting manganese sulfate crystals. The conductive material is made of chemical manganese dioxide obtained by immersing manganese sesquioxide (Mn2O_3) in a sulfuric acid solution to obtain manganese dioxide (MnO_2), which is then washed with water, dried, and pressed, and the conductive material has a specific surface area of 90 to 150 m^.
A non-aqueous solvent battery comprising 2/g of carbon black.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63109305A JPH01279565A (en) | 1988-05-02 | 1988-05-02 | Nonaqueous solvent battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63109305A JPH01279565A (en) | 1988-05-02 | 1988-05-02 | Nonaqueous solvent battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH01279565A true JPH01279565A (en) | 1989-11-09 |
Family
ID=14506827
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63109305A Pending JPH01279565A (en) | 1988-05-02 | 1988-05-02 | Nonaqueous solvent battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01279565A (en) |
-
1988
- 1988-05-02 JP JP63109305A patent/JPH01279565A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US7491378B2 (en) | Electrode structure production process | |
| AU741721B2 (en) | Lithium manganate, method of producing the same, and lithium cell produced by the method | |
| US3536532A (en) | Primary cell for electric batteries | |
| JP3064655B2 (en) | Non-aqueous electrolyte secondary battery and method for producing positive electrode active material thereof | |
| US4405699A (en) | Manganese dioxide electrode for lithium batteries | |
| JP3221352B2 (en) | Method for producing spinel-type lithium manganese composite oxide | |
| JPWO2007142275A1 (en) | Cathode active material for non-aqueous electrolyte secondary battery and method for producing the same | |
| Pan et al. | Synthesis, characterization and electrochemical performance of battery grade NiOOH | |
| US5496664A (en) | Process for producing a positive electrode for lithium secondary batteries | |
| JPH09320588A (en) | Manufacture of lithium battery positive electrode active material, and lithium battery | |
| US6270925B1 (en) | Lithium battery | |
| Kijima et al. | Synthesis, crystal structure, and electrochemical properties of niobium-substituted hollandite-type titanium dioxides, KxTi1–yNbyO2, with different potassium content in the tunnel space | |
| JP2979826B2 (en) | Method for producing positive electrode active material for non-aqueous electrolyte secondary battery | |
| JPH10316432A (en) | Production of nickel oxyhydroxide and nonaqueous electrolytic battery | |
| JPH10321228A (en) | Positive electrode active material for lithium battery, its manufacture, and lithium battery using it | |
| JP7272052B2 (en) | Positive electrode active material for lithium ion secondary battery and method for producing the same | |
| JPH01279565A (en) | Nonaqueous solvent battery | |
| KR102558764B1 (en) | Method for manufacturing electrode active material, electrode active material, and lithium ion battery comprising the same | |
| JPH01307159A (en) | Nonaqueous solvent battery | |
| JPH0381268B2 (en) | ||
| JPH03225752A (en) | Nonaqueous solvent battery | |
| JPS5848357A (en) | Manufacture of positive electrode for organic electrolyte battery | |
| JPH03252055A (en) | Alkaline dry cell | |
| CN117293306A (en) | Lithium-rich manganese-based material and application thereof in sulfide all-solid-state battery | |
| CN117117120A (en) | Vanadium-containing self-supplementing lithium composite phosphate positive electrode material and preparation method and application thereof |