JPH0240860A - Nonaqueous electrolytic secondary battery and manufacture of positive electrode active material used thereto - Google Patents
Nonaqueous electrolytic secondary battery and manufacture of positive electrode active material used theretoInfo
- Publication number
- JPH0240860A JPH0240860A JP63191887A JP19188788A JPH0240860A JP H0240860 A JPH0240860 A JP H0240860A JP 63191887 A JP63191887 A JP 63191887A JP 19188788 A JP19188788 A JP 19188788A JP H0240860 A JPH0240860 A JP H0240860A
- Authority
- JP
- Japan
- Prior art keywords
- manganese dioxide
- positive electrode
- active material
- crystals
- electrode active
- 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.)
- Granted
Links
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 19
- 238000004519 manufacturing process Methods 0.000 title claims description 5
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims abstract description 80
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims abstract description 35
- 239000013078 crystal Substances 0.000 claims abstract description 31
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 11
- GLXDVVHUTZTUQK-UHFFFAOYSA-M lithium hydroxide monohydrate Substances [Li+].O.[OH-] GLXDVVHUTZTUQK-UHFFFAOYSA-M 0.000 claims description 15
- PQVSTLUFSYVLTO-UHFFFAOYSA-N ethyl n-ethoxycarbonylcarbamate Chemical compound CCOC(=O)NC(=O)OCC PQVSTLUFSYVLTO-UHFFFAOYSA-N 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 14
- 229940040692 lithium hydroxide monohydrate Drugs 0.000 claims description 14
- 239000011255 nonaqueous electrolyte Substances 0.000 claims description 9
- 229910000733 Li alloy Inorganic materials 0.000 claims description 5
- 239000001989 lithium alloy Substances 0.000 claims description 5
- 239000000463 material Substances 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 5
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 3
- 239000006258 conductive agent Substances 0.000 abstract description 3
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 3
- 230000008961 swelling Effects 0.000 abstract 1
- 238000007599 discharging Methods 0.000 description 10
- 230000007423 decrease Effects 0.000 description 6
- 239000003792 electrolyte Substances 0.000 description 6
- 239000011149 active material Substances 0.000 description 5
- 238000000034 method Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 150000001786 chalcogen compounds Chemical class 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- -1 polypropylene Polymers 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000004809 Teflon Substances 0.000 description 2
- 229920006362 Teflon® Polymers 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- HEPLMSKRHVKCAQ-UHFFFAOYSA-N lead nickel Chemical compound [Ni].[Pb] HEPLMSKRHVKCAQ-UHFFFAOYSA-N 0.000 description 2
- 239000005486 organic electrolyte Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 description 1
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- JFBZPFYRPYOZCQ-UHFFFAOYSA-N [Li].[Al] Chemical compound [Li].[Al] JFBZPFYRPYOZCQ-UHFFFAOYSA-N 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 229940000489 arsenate Drugs 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910001540 lithium hexafluoroarsenate(V) Inorganic materials 0.000 description 1
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 1
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- CFJRPNFOLVDFMJ-UHFFFAOYSA-N titanium disulfide Chemical compound S=[Ti]=S CFJRPNFOLVDFMJ-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
- H01M4/36—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
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
-
- 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、負極にリチウムあるいはリチウム合金、電解
液に有機電解液を使用した非水電解液二次電池に関する
ものであり、電解二酸化マンガンを改良した正極活物質
を使用することにより、放電電圧が高く、エネルギー密
度が大きく、充放電サイクル寿命の長い二次電池を提供
するものである。[Detailed Description of the Invention] Industrial Application Field The present invention relates to a non-aqueous electrolyte secondary battery using lithium or a lithium alloy for the negative electrode and an organic electrolyte for the electrolyte, which is an improved version of electrolytic manganese dioxide. By using a positive electrode active material, a secondary battery with high discharge voltage, high energy density, and long charge/discharge cycle life is provided.
従来の技術
負極にリチウムあるいはリチウム合金、電解液に有′Ｒ
電解液を使用した充放電可能な、いわゆる非水電解液二
次電池を得る試みは、さかんに行われており、正極活物
質としては、主に二硫化チタンや二硫化モリブデン等の
カルコゲン化合物が使用されてきた。［竹原 化学 ３
７ １６８ （１９８２）］しかし、正極にカルコゲン
化合物を使用した場合、放電電圧が低く、したがってエ
ネルギー密度は小さくなる。また、多くのカルコゲン化
合物は合成が困難で高価である。Conventional technology Lithium or lithium alloy is used in the negative electrode, and R is used in the electrolyte.
Many attempts have been made to obtain so-called non-aqueous electrolyte secondary batteries that can be charged and discharged using an electrolyte, and chalcogen compounds such as titanium disulfide and molybdenum disulfide are mainly used as positive electrode active materials. has been used. [Takehara Chemistry 3
7 168 (1982)] However, when a chalcogen compound is used in the positive electrode, the discharge voltage is low, and therefore the energy density is low. Additionally, many chalcogen compounds are difficult and expensive to synthesize.
これらの欠点を克服するために、正極活物質として各種
酸化物を使用することが検討され、その中でも電解二酸
化マンガンが、リチウムと組み合わせた場合、平均放電
電圧が２．８ｖと高いことや、工業的生産が可能で安価
なことから、二次電池への応用が期待されている。In order to overcome these drawbacks, the use of various oxides as positive electrode active materials has been considered.Among them, electrolytic manganese dioxide has a high average discharge voltage of 2.8V when combined with lithium, and has a high average discharge voltage of 2.8V. It is expected to be applied to secondary batteries because it can be produced efficiently and is inexpensive.
ところが、有機電解液中の電解二酸化マンガンを充放電
する場合の反応は、二酸化マンガン結晶中へのリチウム
イオンの出入りであるため、充放電によって二酸化マン
ガンの体積は膨脹と収縮を繰り遅し、次第に結晶構造が
崩壊することや、二酸化マンガンの結晶と導電材との接
触が悪くなって、サイクル数の増大と共に放電容量が減
少するという問題点を有していた。［Ｇ、Ｐｉｓｔｏｉ
ａ Ｊ、 Ｅｌｅ−ｃｔｒｏｃｈｅｎ、 Ｓａｃ、、
１２９１８６１ （１９８２）］この問題点を解決す
るために、二酸化マンガンに各種化合物を添加して充放
電特性を改良する試みがなされている。その中には水酸
化リチウムを使用する方法として、電解二酸化マンガン
を水酸化リチウム水溶液中に入れてマイクロ波を照射し
て二酸化マンガン中へリチウムをドープし、３５０〜４
３０°Ｃで加熱する方法［特開昭６２−１０８４５５号
公報］や、Ｌｉ０Ｈ−ＨｎＯ□焼成体が可逆性に優れて
いること［第２８間電池討論会予稿集、３ＢＯ９，Ｐ２
Ｏ３，１９８７、１１，１８〜２０］等が報告されてい
る。However, when charging and discharging electrolytic manganese dioxide in an organic electrolyte, the reaction is the movement of lithium ions into and out of manganese dioxide crystals, so the volume of manganese dioxide slows down to expand and contract due to charging and discharging, and gradually becomes crystallized. There have been problems in that the structure collapses and the contact between the manganese dioxide crystals and the conductive material deteriorates, resulting in a decrease in discharge capacity as the number of cycles increases. [G, Pistoi
a J, Ele-ctrochen, Sac,,
1291861 (1982)] In order to solve this problem, attempts have been made to improve the charge-discharge characteristics by adding various compounds to manganese dioxide. Among them, as a method of using lithium hydroxide, electrolytic manganese dioxide is placed in a lithium hydroxide aqueous solution and irradiated with microwaves to dope lithium into the manganese dioxide.
The method of heating at 30°C [JP-A-62-108455] and the fact that the Li0H-HnO□ fired body has excellent reversibility [Proceedings of the 28th Battery Symposium, 3BO9, P2]
O3, 1987, 11, 18-20] have been reported.
発明が解決しようとする課題
以上述べたように電解二酸化マンガンを使用した非水電
解液二次電池において、サイクル数の増大に伴い放電容
量が減少するという欠点を取り除くことにより、放電電
圧が高く、放電容量が大きく、エネルギー密度の大きい
二次電池を得ることが課題とされていた。Problems to be Solved by the Invention As described above, in a non-aqueous electrolyte secondary battery using electrolytic manganese dioxide, by eliminating the drawback that the discharge capacity decreases as the number of cycles increases, it is possible to achieve a high discharge voltage. The challenge has been to obtain a secondary battery with a large discharge capacity and high energy density.
課題を解決するための手段
本発明は、負極にリチウムあるいはリチウム合金を用い
た非水電解液二次電池において、正極活物質として電解
二酸化マンガンの結晶中に水酸化リチウムを含有したも
のを用いたことを特徴とする。また、前記正極活物質の
製造方法として電解二酸化マンガンに３０重量％以下の
水酸化リチウム一水塩を加え３５０°Ｃ以下の温度で加
熱することを特徴とする。Means for Solving the Problems The present invention uses electrolytic manganese dioxide crystals containing lithium hydroxide as the positive electrode active material in a non-aqueous electrolyte secondary battery using lithium or a lithium alloy for the negative electrode. It is characterized by The method for producing the positive electrode active material is characterized in that 30% by weight or less of lithium hydroxide monohydrate is added to electrolytic manganese dioxide and heated at a temperature of 350° C. or less.
作用
電解二酸化マンガンを非水電解液電池の活物質に使用す
る場合、結晶中に含まれている水分をある程度除去する
ために、一定の温度で加熱脱水する方法がとられている
。本発明は電解二酸化マンガンを加熱脱水する際、あら
かじめ電解二酸化マンガンに一定量の水酸化リチウム一
水塩（ＬｉＯＨ・Ｈ２Ｏ）を添加しておき、加熱によっ
て水酸化リチウム一水塩が分解して生成した水酸化リチ
ウムが二酸化マンガン結晶中にはいることを利用するも
のである。When electrolytic manganese dioxide is used as an active material in a non-aqueous electrolyte battery, a method of heating and dehydrating it at a constant temperature is used to remove some of the water contained in the crystals. In the present invention, when heating and dehydrating electrolytic manganese dioxide, a certain amount of lithium hydroxide monohydrate (LiOH H2O) is added to the electrolytic manganese dioxide in advance, and lithium hydroxide monohydrate is decomposed and generated by heating. This method takes advantage of the fact that lithium hydroxide is present in manganese dioxide crystals.
ただし、電解二酸化マンガンは室温では含水のγ−型結
晶椙造であり、加熱によって脱水するが、２５０℃以上
ではγ−型とβ−型の結晶構造の混合物、３５０″Ｃ以
上ではβ−型結晶構造となる。電池の充放電を行なう場
合はβ−型よりもγ−型結晶横遺の方が望ましいため、
加熱温度は３５０℃以下とする必要がある。However, electrolytic manganese dioxide is a water-containing γ-type crystal at room temperature and dehydrates when heated, but at temperatures above 250°C it becomes a mixture of γ- and β-type crystal structures, and at temperatures above 350°C it becomes a β-type crystal structure. It has a crystalline structure.When charging and discharging batteries, it is preferable to have a γ-type crystal structure rather than a β-type crystal structure.
The heating temperature needs to be 350°C or less.
本発明による正極活物質は、電解二酸化マンガンからの
水分の離脱と、水酸化リチウム一水塩の分解が同時に起
こる条件で合成される。したがって、生成物は二酸化マ
ンガン結晶中に水酸化リチウムがはいった状態となって
いるものと考えられる。そのため、二酸化マンガンが充
放電を行う場合、電気化学的なリチウムイオンの出入り
を伴うが、あらかじめ水酸化リチウムが二酸化マンガン
結晶中に入って、二酸化マンガンの結晶を充放電しない
状態においても、あらかじめ膨脹させておくので、充放
電におけるリチウムの出入りに伴う体積変化を電解二酸
化マンカン単独の場合よりも小さくし、その結果充放電
による膨脹収縮が非常に小さくなり、結晶間や導電剤と
の接触が良好な状態に保たれ、はとんどの二酸化マンガ
ンが反応に使われる。The positive electrode active material according to the present invention is synthesized under conditions where the separation of water from electrolytic manganese dioxide and the decomposition of lithium hydroxide monohydrate occur simultaneously. Therefore, the product is considered to be a state in which lithium hydroxide is contained in manganese dioxide crystals. Therefore, when manganese dioxide is charged and discharged, electrochemical lithium ions move in and out, but lithium hydroxide enters the manganese dioxide crystal in advance and expands even when the manganese dioxide crystal is not charged or discharged. As a result, the volume change due to the inflow and outflow of lithium during charging and discharging is smaller than that of electrolytic mancan dioxide alone, and as a result, expansion and contraction due to charging and discharging are extremely small, and contact between crystals and with the conductive agent is good. Manganese dioxide is used in the reaction.
また、加熱温度を３５０℃以下とすることによって、二
酸化マンガンの結晶がβ−型へと変化せず、γ−型ある
いはγ−型とβ−型の混合物という電池の充放電に有利
な結晶構造が保持されるものである。In addition, by setting the heating temperature to 350°C or lower, the crystals of manganese dioxide do not change to the β-type, and the crystal structure of the γ-type or a mixture of the γ-type and β-type is advantageous for battery charging and discharging. is maintained.
実施例 以下に本発明を好適な実施例を用いて説明する。Example The present invention will be explained below using preferred embodiments.
［１，正極活物質の合成方法コ
電解二酸化マンガン（γ−型結晶構造）粉末と、水酸化
リチウム一水塩粉末とを一定の割合で均一に混合し、ル
ツボに入れて電気炉で５時間加熱し、正極活物質Ｎ０８
１〜Ｎｏ、 １０を合成した。混合比および加熱温度は
第１表に示す通りである。[1, Synthesis method of positive electrode active material Co-electrolytic manganese dioxide (γ-type crystal structure) powder and lithium hydroxide monohydrate powder were uniformly mixed at a certain ratio, placed in a crucible, and heated in an electric furnace for 5 hours. Heating, positive electrode active material N08
1 to No. 10 were synthesized. The mixing ratio and heating temperature are as shown in Table 1.
第１表
［２，正極板の製法］
上記の正極活物質とアセチレンブラック（導電剤）とデ
ィスバージョンテフロンとを重量比で９０：８：２とな
るように混合し、ペースト状とし、ニッケルリード線を
取り付けた １０ｎｎ ｘｌｏｎｎのエキスバンドニッ
ケルグリッド上に塗布した。正極混合物の塗布量は極板
１枚当り約５０Ｉ１ｇとしな。これを加圧して均一な表
面とした後、２００℃で２０時間真空乾燥して余分の水
を脱水した。Table 1 [2. Manufacturing method of positive electrode plate] The above positive electrode active material, acetylene black (conductive agent), and dispersion Teflon are mixed in a weight ratio of 90:8:2, made into a paste, and nickel lead It was coated on a 10 nn x lonn expanded nickel grid with wires attached. The amount of the positive electrode mixture to be applied is approximately 50I1g per electrode plate. This was pressurized to make a uniform surface, and then vacuum dried at 200° C. for 20 hours to remove excess water.
［３，電池の試作と試験条件］
電池は正極板１枚と負極板１枚とで構成されている。負
極板は１０１１１×１０ＩＩｌのリチウム板にニッケル
リード線を圧着で収り付けたものである。セパレータと
してはｒＲ細孔を備えたポリプロピレンシートを使用し
、電解液としては２−メチルテトラヒドロフランに六フ
ッ化砒酸リチウム（ＬｉＡｓＦ６）を１．５１ｏｌ＃ｌ
溶解させた非水電解液を使用した。[3. Prototype production of battery and test conditions] The battery consists of one positive electrode plate and one negative electrode plate. The negative electrode plate was a 10111×10IIl lithium plate with a nickel lead wire crimped onto it. A polypropylene sheet with rR pores was used as the separator, and the electrolyte was 1.51 ol#l of lithium hexafluoroarsenate (LiAsF6) in 2-methyltetrahydrofuran.
A dissolved non-aqueous electrolyte was used.
この極板群をテフロンケースに入れ、全体をセパラブル
フラスコ中、アルゴン雰囲気に密閉して、充放電試験を
行なった。充放電試験条件は以下の通りである。This electrode plate group was placed in a Teflon case, the whole was sealed in an argon atmosphere in a separable flask, and a charge/discharge test was conducted. The charge/discharge test conditions are as follows.
温度：２５℃±２℃
電流： 充放電とも１．０ｍＡ／ｃｅｌｌ 定電流終
始電圧＝ （充電） ３．５０Ｖ 、 （放電） ２
．ＯＯＶ［４、充放電試験結果］
活物質ＮＯ６１〜Ｎｏ、６を用いた電池について、正極
活物質合成時の水酸化リチウム一水塩の添加量と、正極
活物質１にｇ当りの放電容量との関係を第１図に示す。Temperature: 25°C ± 2°C Current: 1.0mA/cell for both charging and discharging Constant current end-to-end voltage = (Charging) 3.50V, (Discharging) 2
．． OOV [4, charge/discharge test results] For batteries using active materials No. 61 to No. 6, the amount of lithium hydroxide monohydrate added during synthesis of the positive electrode active material, and the discharge capacity per gram of positive electrode active material 1. The relationship is shown in Figure 1.
ただし、放電容量はサイクル数で変化するので、以下全
て１０サイクル目の値を比較する。However, since the discharge capacity changes with the number of cycles, the values at the 10th cycle will be compared in all cases below.
放電容量は水酸化リチウム一水塩添加量が１０ｗｔ％の
とき最大となり、添加量を増すと減少する。水酸化リチ
ウム一水塩の添加量が３０ｗｔ％以下であれば、無添加
の場合に比べて放電容量は大きくなる。The discharge capacity is maximum when the amount of lithium hydroxide monohydrate added is 10 wt%, and decreases as the amount added is increased. If the amount of lithium hydroxide monohydrate added is 30 wt % or less, the discharge capacity will be larger than that without the addition.
活物質ＮＯ３３とＮ０１７〜Ｎｏ、 １０を用いた電池
について、水酸化リチウム一水塩を１（１ｗｔ％添加し
た場合の加熱温度と放電容量との関係を第２図に示す。FIG. 2 shows the relationship between heating temperature and discharge capacity when 1 (1 wt %) of lithium hydroxide monohydrate was added for batteries using active materials NO33 and NO17 to No. 10.
放電容量は３００℃加熱の場合に餞大となり、加熱温度
がこれより低くなっても、高くなっても、小さくなる。The discharge capacity becomes large when heated at 300° C., and decreases even if the heating temperature becomes lower or higher than this.
これは二酸化マンガンは室温ではγ−型結晶楕遣である
が、加熱によって脱水されて２５０〜３５０℃の範囲で
は１７β−型結晶構造に、３５０〜４５０℃の範囲では
β−型結晶構造となって３５０℃以上での加熱では、充
放電に適さない結晶構造となってしまうためであると考
えられる。したがって、正極活物質の加熱温度は、３５
０℃以下が適している。This is because manganese dioxide has a γ-type crystal ellipse at room temperature, but when it is dehydrated by heating, it becomes a 17β-type crystal structure in the range of 250 to 350°C, and a β-type crystal structure in the range of 350 to 450°C. This is thought to be because heating at 350° C. or higher results in a crystal structure that is unsuitable for charging and discharging. Therefore, the heating temperature of the positive electrode active material is 35
A temperature below 0°C is suitable.
次に活物質Ｎｏ、１ （無添加）を用いた電池とＮ００
３（水酸化リチウム一水塩１０ｗｔ％添加）を用いた電
池の充放電サイクル数による放電容量の変化を第３図に
示す。同図より水酸化リチウム一水塩を添加しないと放
電容量のサイクル数による減少は激しいが、水酸化リチ
ウム一水塩を添加した場合の放電容量変化は非常に小さ
いことがわかる。Next, a battery using active material No. 1 (no additives) and N00
FIG. 3 shows the change in discharge capacity depending on the number of charge/discharge cycles of a battery using No. 3 (addition of 10 wt % of lithium hydroxide monohydrate). It can be seen from the figure that if lithium hydroxide monohydrate is not added, the discharge capacity decreases sharply depending on the number of cycles, but when lithium hydroxide monohydrate is added, the change in discharge capacity is very small.
発明の効果
本発明による正極活物質を使用すれば、充放電反応にお
いて極板中に含まれる大部分の二酸化マンガンが反応に
関与するため、同じ重量の電解二酸化マンガンを単独で
使用した場合よりも放電容量は大きくなる。しかも放電
電圧は二酸化マンガン単独の場合同様、平均２．８ｖで
あるため、電池の放電エネルギー密度は極めて大きい。Effects of the Invention When the positive electrode active material according to the present invention is used, most of the manganese dioxide contained in the electrode plate participates in the charge/discharge reaction, so the reaction rate is greater than when the same weight of electrolytic manganese dioxide is used alone. The discharge capacity increases. Moreover, since the discharge voltage is 2.8 V on average as in the case of manganese dioxide alone, the discharge energy density of the battery is extremely high.
また、水酸化リチウムが二酸化マンガンの結晶中に入る
ために、充放電に伴う二酸化マンガン結晶の体積変化が
小さく、結晶間の接触も良好な状態に保たれることによ
って、サイクル数に伴う放電容量の減少は小さく、サイ
クル寿命の極めて長い二次電池が得られる。In addition, since lithium hydroxide enters the manganese dioxide crystal, the volume change of the manganese dioxide crystal during charging and discharging is small, and the contact between the crystals is maintained in a good state, resulting in discharge capacity that increases with the number of cycles. The decrease is small, and a secondary battery with an extremely long cycle life can be obtained.
なお、実施例においては負極にリチウム、電解液に２−
メチルテトラヒドロフン−六フ・ソ化砒酸リチウムを使
用したが、負極はリチウムを含む合金、例えばりチウム
−アルミニウム合金等も使用でき、また、電解液もリチ
ウムと直接反応しない各種有ｖ！Ａ電解液の使用も可能
であり、いずれの場合においても本発明の効果を得るこ
とができる６In addition, in the example, lithium was used in the negative electrode, and 2-
Although methyltetrahydrofuran-hexafluoride lithium arsenate was used, alloys containing lithium such as lithium-aluminum alloys can also be used for the negative electrode, and various electrolytes that do not react directly with lithium can also be used. It is also possible to use electrolyte A, and the effects of the present invention can be obtained in either case6.
第１図は、正極活物質合成時の水酸化リチウム一水塩含
有量と、その活物質を使った電池の放電容量との関係を
示す図、第２図は、正極活物質合成時の加熱温度と、電
池の放電容量との関係を示す図。第３図は、本発明によ
る電池および従来の電池の充放電サイクル数と放電容量
の関係を示した図。
にＬ熱湛廣 （で）Figure 1 shows the relationship between the lithium hydroxide monohydrate content during the synthesis of the positive electrode active material and the discharge capacity of a battery using that active material. The figure which shows the relationship between temperature and the discharge capacity of a battery. FIG. 3 is a diagram showing the relationship between the number of charge/discharge cycles and the discharge capacity of a battery according to the present invention and a conventional battery. ni L Nettanhiro (de)
Claims (1)
電解液二次電池において、正極活物質として電解二酸化
マンガン結晶中に水酸化リチウムを含有したものを用い
たことを特徴とする非水電解液二次電池。 ２、請求項１記載の非水電解液二次電池に用いる正極活
物質の製造方法であって、電解二酸化マンガンに３０重
量％以下の水酸化リチウム一水塩（ＬｉＯＨ・Ｈ＿２Ｏ
）を加え３５０℃以下の温度で加熱することを特徴とす
る非水電解液二次電池用正極活物質の製造方法。[Claims] 1. A non-aqueous electrolyte secondary battery using lithium or a lithium alloy for the negative electrode, characterized in that a material containing lithium hydroxide in electrolytic manganese dioxide crystal is used as the positive electrode active material. A non-aqueous electrolyte secondary battery. 2. A method for producing a positive electrode active material used in a non-aqueous electrolyte secondary battery according to claim 1, wherein 30% by weight or less of lithium hydroxide monohydrate (LiOH.H_2O) is added to electrolytic manganese dioxide.
) and heating at a temperature of 350° C. or lower.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63191887A JPH07105232B2 (en) | 1988-07-30 | 1988-07-30 | Non-aqueous electrolyte secondary battery and method for producing positive electrode active material used therein |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63191887A JPH07105232B2 (en) | 1988-07-30 | 1988-07-30 | Non-aqueous electrolyte secondary battery and method for producing positive electrode active material used therein |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0240860A true JPH0240860A (en) | 1990-02-09 |
| JPH07105232B2 JPH07105232B2 (en) | 1995-11-13 |
Family
ID=16282109
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63191887A Expired - Lifetime JPH07105232B2 (en) | 1988-07-30 | 1988-07-30 | Non-aqueous electrolyte secondary battery and method for producing positive electrode active material used therein |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH07105232B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5477410A (en) * | 1989-11-07 | 1995-12-19 | Canon Kabushiki Kaisha | Recording or reproducing apparatus using a stabilizing pad |
| JP2017068966A (en) * | 2015-09-29 | 2017-04-06 | 古河電池株式会社 | Positive electrode active material for lithium secondary battery and lithium secondary battery |
-
1988
- 1988-07-30 JP JP63191887A patent/JPH07105232B2/en not_active Expired - Lifetime
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5477410A (en) * | 1989-11-07 | 1995-12-19 | Canon Kabushiki Kaisha | Recording or reproducing apparatus using a stabilizing pad |
| JP2017068966A (en) * | 2015-09-29 | 2017-04-06 | 古河電池株式会社 | Positive electrode active material for lithium secondary battery and lithium secondary battery |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH07105232B2 (en) | 1995-11-13 |
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