JPH0335250B2 - - Google Patents
Info
- Publication number
- JPH0335250B2 JPH0335250B2 JP58064699A JP6469983A JPH0335250B2 JP H0335250 B2 JPH0335250 B2 JP H0335250B2 JP 58064699 A JP58064699 A JP 58064699A JP 6469983 A JP6469983 A JP 6469983A JP H0335250 B2 JPH0335250 B2 JP H0335250B2
- Authority
- JP
- Japan
- Prior art keywords
- manganese dioxide
- present
- active material
- manganese
- battery
- 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.)
- Expired - Lifetime
Links
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 38
- 239000011149 active material Substances 0.000 claims description 7
- YMKHJSXMVZVZNU-UHFFFAOYSA-N manganese(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YMKHJSXMVZVZNU-UHFFFAOYSA-N 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 238000000034 method Methods 0.000 description 13
- 239000002245 particle Substances 0.000 description 4
- 239000006183 anode active material Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000007796 conventional method Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000011255 nonaqueous electrolyte Substances 0.000 description 3
- 238000005979 thermal decomposition reaction Methods 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000004687 hexahydrates Chemical class 0.000 description 2
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 229910018378 Mn(NO3)2-6H2O Inorganic materials 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 description 1
- 229910001486 lithium perchlorate Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- -1 polypropylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 239000007858 starting material Substances 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)
- Inorganic Compounds Of Heavy Metals (AREA)
Description
【発明の詳細な説明】
(イ) 産業上の利用分野
本発明は電池用二酸化マンガン活物質の製法に
関する。DETAILED DESCRIPTION OF THE INVENTION (a) Field of Industrial Application The present invention relates to a method for producing a manganese dioxide active material for batteries.
(ロ) 従来技術
乾電池、アルカリ乾電池、非水電解液電池に代
表されるように陽極活物質として二酸化マンガン
が広く一般的に使用されている。そして二酸化マ
ンガンの製法についても種々の方法が知られてい
る。(b) Prior Art Manganese dioxide is widely and commonly used as a positive electrode active material, as typified by dry batteries, alkaline dry batteries, and non-aqueous electrolyte batteries. Various methods are also known for producing manganese dioxide.
(ハ) 発明の目的
本発明の目的とするところは、特に硝酸マンガ
ン・６水和物を出発物質とし、これを熱分解して
二酸化マンガンを得る方法に着目し、電池性能向
上に寄与する二酸化マンガンの製法を提案するこ
とにある。(c) Purpose of the Invention The purpose of the present invention is to focus on a method of obtaining manganese dioxide by thermally decomposing it using manganese nitrate hexahydrate as a starting material. The purpose is to propose a method for manufacturing manganese.
(ニ) 発明の構成
本発明の要旨とするところは、硝酸マンガン・
６水和物を密閉容器内において170〜300℃の温度
範囲で熱分解することを特徴とする電池用二酸化
マンガン活物質の製法にある。(d) Structure of the invention The gist of the present invention is that manganese nitrate.
The present invention provides a method for producing a manganese dioxide active material for batteries, which comprises thermally decomposing a hexahydrate in a closed container at a temperature of 170 to 300°C.
(ホ) 実施例
以下本発明の一実施例につき非水電池用陽極の
場合を例にとり詳述する。(e) Example An example of the present invention will be described in detail below, taking the case of an anode for a non-aqueous battery as an example.
硝酸マンガン・６水和物［Mn（NO3）2・6H2O］
を密閉容器内に入れ250℃で２時間、熱分解し分
解生成物を粉砕して後200メツシユパスを行い二
酸化マンガン活物質粉末を得る。ここで密閉容器
内の雰囲気としては酸化雰囲気、還元雰囲気を問
合ない。又熱処理温度については硝酸マンガン・
６水和物が熱分解する170〜300℃の温度範囲であ
れば良く、熱処理温度に応じて熱処理時間が考慮
される。 Manganese nitrate hexahydrate [Mn(NO 3 ) 2 6H 2 O]
The mixture is placed in a sealed container and thermally decomposed at 250°C for 2 hours to crush the decomposition products, followed by 200 mesh passes to obtain manganese dioxide active material powder. Here, it does not matter whether the atmosphere inside the closed container is an oxidizing atmosphere or a reducing atmosphere. Regarding heat treatment temperature, manganese nitrate/
The temperature range of 170 to 300° C. at which the hexahydrate is thermally decomposed is sufficient, and the heat treatment time is taken into consideration depending on the heat treatment temperature.
本実施例においては、非水電池の陽極活物質と
して適用するため、水分除去の目的で上記二酸化
マンガン活物質を更に350〜430℃で５時間熱処理
した。 In this example, the manganese dioxide active material was further heat-treated at 350 to 430° C. for 5 hours for the purpose of removing moisture in order to be applied as an anode active material of a non-aqueous battery.
ついで、この二酸化マンガン活物質85重量部、
誘電剤としてのアセチレンブラツク10重量部及び
結着剤としてのフツ素樹脂粉末５重量部を混合し
て陽極合剤とし、このうち50ｇを秤量し成型圧３
トン／cm2で直径20Φの集電リングに加圧成型した
後、更に300℃で真空乾燥して陽極とする。 Next, 85 parts by weight of this manganese dioxide active material,
10 parts by weight of acetylene black as a dielectric agent and 5 parts by weight of fluororesin powder as a binder were mixed to make an anode mixture.
After being pressure-molded into a current collector ring with a diameter of 20Φ at a pressure of tons/cm 2 , it is further vacuum-dried at 300°C to form an anode.
陰極はリチウム圧延板を直径20Φに打抜いたも
のを用い、又電解液はプロピレンカーボネートと
1.2ジメトキシエタンとの等体積混合溶媒に過塩
素酸リチウムを１モル／溶解したものでありポ
リプロピレン不織布よりなるセパレータに含浸し
て用い本発明に係る非水電解液電池(A)を作成し
た。尚、電池寸法は外径25Φ、高さ2.8mmであつ
た。 The cathode used was a lithium rolled plate punched out to a diameter of 20Φ, and the electrolyte was propylene carbonate.
A nonaqueous electrolyte battery (A) according to the present invention was prepared by dissolving 1 mol/mol of lithium perchlorate in a mixed solvent with 1.2 dimethoxyethane in an equal volume and impregnating it into a separator made of polypropylene nonwoven fabric. The battery dimensions were an outer diameter of 25Φ and a height of 2.8 mm.
一方、本発明法による優位性を調べるために、
硝酸マンガン・６水和物を開放容器内において
250℃で熱分解して得た二酸化マンガンを活物質
とすることを除いて、他は実施例と同様の方法で
比較電池(B)を作成した。 On the other hand, in order to investigate the superiority of the method of the present invention,
Manganese nitrate hexahydrate in an open container
A comparative battery (B) was produced in the same manner as in the example except that manganese dioxide obtained by thermal decomposition at 250°C was used as the active material.
第１図及び第２図はこれら電池の放電特性比較
図であり、第１図は室温下における5.6KΩ定負荷
放電特性、第２図は室温下における560Ω定負荷
放電特性を夫々示す。 Figures 1 and 2 are comparison diagrams of the discharge characteristics of these batteries; Figure 1 shows the 5.6KΩ constant load discharge characteristics at room temperature, and Figure 2 shows the 560Ω constant load discharge characteristics at room temperature.
(ヘ) 発明の効果
第１図及び第２図より明白なるように、本発明
法により得た二酸化マンガンを陽極活物質として
用いた電池(A)は比較電池(B)に比して電池性能が改
善されている。本発明による効果を考察するに、
本発明法の如く硝酸マンガン・６水和物を密閉容
器内で170〜300℃で加熱分解した二酸化マンガン
の粒径は10μ程度であるのに対し従来の如く開放
溶器内で熱分解して得た二酸化マンガンの粒径は
100μ程度であり、本発明法によればより微粒状
の二酸化マンガンが得られた。これは密閉容器内
での熱分解であるため、分解時の生成ガス（例え
ばNO2）によつて圧力下で行われるため熱分解
反応が急速に進行しているためであると考えられ
る。(f) Effects of the invention As is clear from Figures 1 and 2, the battery (A) using manganese dioxide obtained by the method of the present invention as an anode active material has better battery performance than the comparative battery (B). has been improved. Considering the effects of the present invention,
The particle size of manganese dioxide obtained by thermally decomposing manganese nitrate hexahydrate at 170 to 300°C in a closed container as in the method of the present invention is about 10μ, whereas the particle size of manganese dioxide obtained by thermally decomposing it in an open vessel as in the conventional method The particle size of the obtained manganese dioxide is
The particle diameter was approximately 100μ, and the method of the present invention yielded finer manganese dioxide. This is thought to be because the thermal decomposition is carried out in a closed container under pressure due to the gas produced during decomposition (for example, NO 2 ), so that the thermal decomposition reaction progresses rapidly.
その結果、二酸化マンガンの見掛密度は本発明
法では3.7±0.1ｇ・cm-3であるのに対し従来法で
は3.3±0.1ｇ・cm-3であり本発明法の方が大きく
容量の増加が計れる。 As a result, the apparent density of manganese dioxide was 3.7 ± 0.1 g cm -3 in the method of the present invention, whereas it was 3.3 ± 0.1 g cm -3 in the conventional method, and the capacity increase was greater in the method of the present invention. can be measured.
又、夫々の方法で得た二酸化マンガンを用いて
作成した陽極の比抵抗は本発明法では0.4Ω・cm
であるのに対し、従来法では7.5Ω・cmであつた。
よつて、本発明法により得た二酸化マンガンを用
いれば電地電圧の向上も計れる。 In addition, the specific resistance of the anode made using manganese dioxide obtained by each method is 0.4Ω・cm using the method of the present invention.
In contrast, in the conventional method, it was 7.5Ω·cm.
Therefore, by using manganese dioxide obtained by the method of the present invention, it is possible to improve the earth voltage.
第１図及び第２図は本発明法により得た二酸化
マンガンを陽極活物質とする非水電解液電池(A)と
比較電池(B)との放電特性比較図を夫々示す。
FIGS. 1 and 2 respectively show comparison diagrams of the discharge characteristics of a non-aqueous electrolyte battery (A) using manganese dioxide obtained by the method of the present invention as an anode active material and a comparative battery (B).
Claims (1)
て170〜300℃の温度範囲で熱分解することを特徴
とする電池用二酸化マンガン活物質の製法。1. A method for producing a manganese dioxide active material for batteries, which comprises thermally decomposing manganese nitrate hexahydrate in a closed container at a temperature range of 170 to 300°C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58064699A JPS59190225A (en) | 1983-04-12 | 1983-04-12 | Preparation of active material of manganese dioxide for cell |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58064699A JPS59190225A (en) | 1983-04-12 | 1983-04-12 | Preparation of active material of manganese dioxide for cell |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS59190225A JPS59190225A (en) | 1984-10-29 |
| JPH0335250B2 true JPH0335250B2 (en) | 1991-05-27 |
Family
ID=13265652
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP58064699A Granted JPS59190225A (en) | 1983-04-12 | 1983-04-12 | Preparation of active material of manganese dioxide for cell |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS59190225A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101786666B (en) * | 2010-02-10 | 2012-02-22 | 彭天剑 | lithium manganate anode material and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS57135727A (en) * | 1981-02-09 | 1982-08-21 | Nec Corp | Preparation of manganese dioxide |
-
1983
- 1983-04-12 JP JP58064699A patent/JPS59190225A/en active Granted
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS57135727A (en) * | 1981-02-09 | 1982-08-21 | Nec Corp | Preparation of manganese dioxide |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS59190225A (en) | 1984-10-29 |
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