JPH02139861A - Non-aqueous electrolyte secondary battery - Google Patents
Non-aqueous electrolyte secondary batteryInfo
- Publication number
- JPH02139861A JPH02139861A JP63291163A JP29116388A JPH02139861A JP H02139861 A JPH02139861 A JP H02139861A JP 63291163 A JP63291163 A JP 63291163A JP 29116388 A JP29116388 A JP 29116388A JP H02139861 A JPH02139861 A JP H02139861A
- Authority
- JP
- Japan
- Prior art keywords
- positive electrode
- limn2o4
- aqueous electrolyte
- battery
- discharge capacity
- 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
- 239000011255 nonaqueous electrolyte Substances 0.000 title claims abstract description 14
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 12
- 229910000733 Li alloy Inorganic materials 0.000 claims abstract description 5
- 239000001989 lithium alloy Substances 0.000 claims abstract description 5
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 5
- 229910052802 copper Inorganic materials 0.000 claims abstract description 4
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 4
- 229910052709 silver Inorganic materials 0.000 claims abstract description 4
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 4
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 3
- 229910052742 iron Inorganic materials 0.000 claims abstract description 3
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 3
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 3
- 229910052700 potassium Inorganic materials 0.000 claims abstract 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 10
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 4
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 abstract description 24
- 239000000126 substance Substances 0.000 abstract 2
- 239000013543 active substance Substances 0.000 abstract 1
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 46
- 239000007774 positive electrode material Substances 0.000 description 17
- 239000002245 particle Substances 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 10
- 238000010438 heat treatment Methods 0.000 description 8
- 239000000203 mixture Substances 0.000 description 6
- 229910002983 Li2MnO3 Inorganic materials 0.000 description 5
- 229910015645 LiMn Inorganic materials 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- 239000011572 manganese Substances 0.000 description 5
- 230000007423 decrease Effects 0.000 description 4
- 229910052808 lithium carbonate Inorganic materials 0.000 description 4
- 229910011197 Li2Co Inorganic materials 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000006258 conductive agent Substances 0.000 description 3
- AMWRITDGCCNYAT-UHFFFAOYSA-L manganese oxide Inorganic materials [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 229910014143 LiMn2 Inorganic materials 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- 229910014549 LiMn204 Inorganic materials 0.000 description 1
- 229910014540 LiMn2O Inorganic materials 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 150000001786 chalcogen compounds Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 229910002102 lithium manganese oxide Inorganic materials 0.000 description 1
- VLXXBCXTUVRROQ-UHFFFAOYSA-N lithium;oxido-oxo-(oxomanganiooxy)manganese Chemical compound [Li+].[O-][Mn](=O)O[Mn]=O VLXXBCXTUVRROQ-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- -1 polypropylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- 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
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
-
- 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、非水電解質二次電池、特に、その正極の改良
に関する。DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to a non-aqueous electrolyte secondary battery, and particularly to improvements in its positive electrode.
従来の技術
リチウムまたはリチウム合金を負極とする非水電解質二
次電池の正極活物質については、これまで、Ｔｉ、Ｖ、
Ｃｒ、Ｍｏ等の層状もしくはトンネル構造を有する酸化
物及びカルコゲン化合物が知られている。これらの構造
を有する化合物では、電池の充放電により、リチウムイ
オンが化合物の層もしくはトンネル内へ出入りする。こ
のため、化合物自体の結晶格子は単に膨張、収縮するの
みで、結晶構造が著しく破壊されることがないため、二
次電池用正極活物質に適する。Conventional technology As for the positive electrode active materials of non-aqueous electrolyte secondary batteries using lithium or lithium alloy as the negative electrode, Ti, V,
Oxides and chalcogen compounds having layered or tunnel structures such as Cr and Mo are known. In compounds having these structures, lithium ions move in and out of the layer or tunnel of the compound as the battery is charged and discharged. Therefore, the crystal lattice of the compound itself simply expands and contracts, and the crystal structure is not significantly destroyed, making it suitable as a positive electrode active material for secondary batteries.
ところで、ＭｎＯ２は、高い電圧、大きい放電容量、す
なわち、高エネルギー密度を有する正極活物質として非
水電解質−次電池に適用され、小型電子機器用電源をは
じめとし広く利用されている。By the way, MnO2 is applied to nonaqueous electrolyte secondary batteries as a positive electrode active material having high voltage, large discharge capacity, that is, high energy density, and is widely used in power supplies for small electronic devices and other applications.
しかし、ＭｎＯ□はルチル型の結晶構造で上述のトンネ
ル構造を有しているにもかかわらず、充放電サイクルで
の容量減少が著しいため、二次電池用正極活物質には不
向きである。この理由は、放電にともなうＭｎＯ２粒子
自体の電子伝導性の低下と、充電の際のＭｎＯ□粒子の
収縮によるＭｎＯ２粒子とカーボンブラック等の導電剤
粒子の分離による集電不良である。特に、ＭｎＯ２粒子
と導電剤粒子の分離は、放電過程で生成したＬｉ２ＣＯ
３が絶縁体に近いため、充電過程でのＭｎＯ２粒子から
のリチウムイオンの放出を一層困難にする。However, although MnO□ has a rutile-type crystal structure and the above-mentioned tunnel structure, it is not suitable as a positive electrode active material for secondary batteries because its capacity decreases significantly during charging and discharging cycles. The reasons for this are a decrease in the electronic conductivity of the MnO2 particles themselves due to discharge, and poor current collection due to separation of the MnO2 particles and conductive agent particles such as carbon black due to shrinkage of the MnO□ particles during charging. In particular, the separation of MnO2 particles and conductive agent particles is performed using Li2CO generated during the discharge process.
3 is close to an insulator, making it more difficult to release lithium ions from the MnO2 particles during the charging process.
以上のようなＭｎＯ２の充放電サイクルでの容量減少を
防止するため、ＭｎＯ２にあらかじめＬｉを添加、加熱
し、充放電過程での結晶格子の膨張。In order to prevent the capacity reduction during charge/discharge cycles of MnO2 as described above, Li is added to MnO2 in advance and heated to cause expansion of the crystal lattice during the charge/discharge process.
収縮の度合がＭｎＯ２に比べ小さい、スピネル型の結晶
構造を有するＬｉＭｎ２Ｏ４を正極活物質に用いること
が提案されており、特に、放電容量の点から、低温で加
熱することにより得たＬｉＭｎ、、０４が好ましいとさ
れている（英国公開公報ＣＢ２１９６７８６Ａ ）。こ
の低温でのＬｉＭｎ２Ｏ４の製造法は概ね次のようであ
る。Ｌｉ２ＣＯ３とＭｎＯ２を混合し、４３０℃〜６２
０℃の温度範囲で加熱するか、または、ＬｉＩとＭｎＯ
２の混合物を３００℃で加熱後、有機溶媒で洗浄するこ
とによりＬｉＭｎ２Ｏ４を得る。ここで、加熱温度をさ
らに上昇させると結晶性の高いＬｉＭｎ２Ｏ４になるが
、この高結晶性のＬｉＭｎ２Ｏ４では放電容量が極めて
小さくなることから電池用正極活物質には適さないとさ
れている。It has been proposed to use LiMn2O4, which has a spinel-type crystal structure and has a smaller degree of shrinkage than MnO2, as a positive electrode active material. is said to be preferable (British Publication Publication CB2196786A). The method for producing LiMn2O4 at this low temperature is generally as follows. Mix Li2CO3 and MnO2 and heat from 430℃ to 62℃
Heating in the temperature range of 0°C or LiI and MnO
LiMn2O4 is obtained by heating the mixture of 2 at 300°C and washing with an organic solvent. Here, if the heating temperature is further increased, LiMn2O4 becomes highly crystalline, but this highly crystalline LiMn2O4 has an extremely small discharge capacity and is therefore not suitable as a positive electrode active material for batteries.
発明が解決しようとする課題
しかし、このような６００℃過度までの低温での製造法
で得たＬｉＭｎ２Ｏ４を正極活物質として用い、リチウ
ムまたはリチウム合金を負極に用いた電池を組み立て、
充放電サイクルをくり返した場合、リチウム負極の腐食
が著しく、サイクル寿命が短いという課題があった。こ
れは次の理由による。Problems to be Solved by the Invention However, it is difficult to assemble a battery using LiMn2O4 obtained by such a low-temperature manufacturing method of over 600°C as a positive electrode active material and lithium or a lithium alloy as a negative electrode.
When the charge and discharge cycles are repeated, the lithium negative electrode is severely corroded, resulting in a short cycle life. This is due to the following reason.
Ｌｉ２Ｃｏ、とＭｎＯ，、を混合、加熱してＬ ｉ Ｍ
ｎ２０４を得る場合、Ｌｉ、、Ｃｏ３の融点は６１８
℃であるため、Ｌｉ２Ｃｏ３がＭｎＯ２と十分に反応で
きる状態になるためにはこの融点近傍まで加熱する必要
がある。しかし、ＭｎＯ２はこのような温度ではβ型の
構造に転移するか、または、Ｌｉとの反応が著しく不活
性なＭｎ２０．に変化する。β型のＭｎＯ，、はＬｉが
ＭｎＯ□内に拡散可能なトンネル構造を有するが、Ｌｉ
を十分にＭｎＯ２内に取り込むことができない。これは
、β型ＭｎＯ□を正極活物質に用いる非水電解質−次電
池の放電容量が極端に小さいということからもうかがえ
る。したがって、Ｌｉ２Ｃｏ、とＭｎＯ２からＬｉＭｎ
、、０４を調製する場合、Ｍ ｎ Ｏ２粒子表面に過剰
なＬｉが堆積し電気化学的に不活性なＬｉ２ＭｎＯ３が
形成される一方、Ｌｉ２Ｃｏ３粒子とＭｎＯ□粒子が接
触していなかったＭｎＯ□粒子表面上は依然としてＭｎ
Ｏ２として残る。すなわち、Ｌｉ２Ｃｏ、とＭｎＯ２の
反応では、同一粒子上にＬｉ２ＭｎＯ３とＭｎＯ２が混
在したものが生成しやすい。Ｌｉ２Ｍｎ０．やＭｎＯ２
は電解質中に含まれる微量の水分により若干溶出するた
め、リチウムまたはリチウム合金負極に到達し、この結
果、負極表面上でリチウム・マンガン酸化物が形成され
ることにより、リチウム負極が腐食するため、サイクル
寿命が短くなるものである。Li2Co, and MnO, are mixed and heated to form LiM
When obtaining n204, the melting point of Li, Co3 is 618
℃, it is necessary to heat it to around this melting point in order to bring Li2Co3 into a state where it can sufficiently react with MnO2. However, at such temperatures, MnO2 transforms into a β-type structure, or MnO2 is extremely inactive in reacting with Li. Changes to β-type MnO,, has a tunnel structure in which Li can diffuse into MnO□, but Li
cannot be sufficiently incorporated into MnO2. This can be seen from the fact that the discharge capacity of a non-aqueous electrolyte secondary battery using β-type MnO□ as a positive electrode active material is extremely small. Therefore, Li2Co, and MnO2 to LiMn
,,04, excessive Li is deposited on the MnO2 particle surface to form electrochemically inactive Li2MnO3, while the MnO□ particle surface where the Li2Co3 particle and the MnO□ particle were not in contact with each other. The top is still Mn
It remains as O2. That is, in the reaction between Li2Co and MnO2, a mixture of Li2MnO3 and MnO2 is likely to be produced on the same particle. Li2Mn0. and MnO2
is slightly eluted by trace amounts of water contained in the electrolyte, and reaches the lithium or lithium alloy negative electrode.As a result, lithium manganese oxide is formed on the negative electrode surface, causing corrosion of the lithium negative electrode. This shortens the cycle life.
以上のようなＬｉ２ＭｎＯ３とＭｎＯ，、が混在しない
ＬｉＭｎ２ ｏ４を作製するためには、加熱温度を８０
０℃〜９００℃まで上昇させればよい。しかし、この場
合には、充放電容量が極めて小さくなり、電池用正極活
物質には適さない。In order to produce LiMn2o4 in which Li2MnO3 and MnO are not mixed together as described above, the heating temperature must be set to 80°C.
What is necessary is just to raise it to 0 degreeC - 900 degreeC. However, in this case, the charge/discharge capacity becomes extremely small, making it unsuitable as a positive electrode active material for batteries.
本発明はこのような従来の欠点を除去するものであり、
Ｌｉ２ＭｎＯ３やＭｎＯ２の混在がなく、リチウムまた
はリチウム負極の腐食がないために充放電サイクル寿命
が長くなり、しかも放電容量が大きいＬｉＭｎ２Ｏ４誘
導体を正極活物質に用いることで、信頼性の高い非水電
解質二次電池を提供することを目的とする。The present invention eliminates these conventional drawbacks,
Since there is no mixture of Li2MnO3 or MnO2 and there is no corrosion of lithium or lithium negative electrodes, the charge/discharge cycle life is extended, and by using LiMn2O4 derivatives with large discharge capacity as the positive electrode active material, highly reliable non-aqueous electrolyte The purpose is to provide next generation batteries.
課題を解決するための手段
本発明の非水電解質二次電池は、正極活物質に次式で表
わされるＬＩＭｎ２０４誘導体を用いることを特徴とす
る。Means for Solving the Problems The nonaqueous electrolyte secondary battery of the present invention is characterized in that a LIMn204 derivative represented by the following formula is used as a positive electrode active material.
（ＬＬ １−ｙＡｒ）ｘ・（Ｍｎ１−ｚ１３ｚｈ・ｏ４
ただし、
ＡはＮａ、に、Ｃｕ、Ａｇ、Ｚｎから選択される元素Ｂ
はＶ、Ｏｒ、Ｆｅ、Ｃｏ、Ｎｉから選択される元素１．
１≧ｘ≧０．９
０．２≧ｙ≧０．０
０．２≧ｚ≧０．０
（ｘ＝１．ｏととき、ｙ、ｚは同時に０．０にはならな
い）作用
ＬｉＭｎ２Ｏ４は立方晶系であり、Ｌｉは四つの０から
なる正四面体の中心に位置しているため、この正四面体
より抜は出して隣の正面体に拡散するには、三つの０か
らなる三角形の輪を通ることになり、著しい活性化エネ
ルギーを特徴とする特に、高い温度で加熱して得られた
Ｉ、ｊＭｎ２０４ではこの傾向が顕著であり、放電過程
でさらにリチウムイオンを挿入させようとしても、既に
正四面体に位置しているＬｉが動きにくいため、新たな
リチウムイオンが入らない。すなわち放電容量が少なく
なるのである。(LL 1-yAr)x・(Mn1-z13zh・o4
However, A is Na, and B is an element selected from Cu, Ag, and Zn.
is an element selected from V, Or, Fe, Co, and Ni.
1≧x≧0.9 0.2≧y≧0.0 0.2≧z≧0.0 (When x=1.o, y and z cannot be 0.0 at the same time) Action LiMn2O4 is cubic Li is a crystalline system, and Li is located at the center of a regular tetrahedron made of four 0's, so in order to get out of this regular tetrahedron and diffuse to the adjacent frontal body, it is necessary to use a triangular shape made of three 0's. This tendency is particularly noticeable in I,jMn204 obtained by heating at a high temperature, which is characterized by a remarkable activation energy. Since Li already located in the regular tetrahedron is difficult to move, new lithium ions cannot enter. In other words, the discharge capacity decreases.
そこで、本発明は、ＬｉＭｎ２Ｏ４のＬｉ量を加減する
ことにより、空の正四面体を増加させＬｉＭｎ２Ｏ４内
でのＬｉの拡散を容易にする。さらに、Ｌｌの一部また
はＭｎの一部を他元素で置換することで歪スピネルを作
製し、０の正四面体を歪ませＬｌの拡散を容易にする。Therefore, the present invention increases or decreases the amount of Li in LiMn2O4 to increase the number of empty regular tetrahedrons and facilitate the diffusion of Li within LiMn2O4. Furthermore, by replacing part of Ll or part of Mn with another element, a strained spinel is produced, and the regular tetrahedron of 0 is distorted to facilitate the diffusion of Ll.
したがって、このようなＬｉＭｎ２０４誘導体は、高い
温度で加熱して得ても放電容量は十分に太きい。そして
、高い温度で加熱して作製することによりＬｉ２Ｍｎ０
゜やＭｎＯ２の混在しないＬｉＭｎ２Ｏ４誘導体を得る
ことができるので、充放電サイクル寿命の長い非水電解
質二次電池が構成できる。Therefore, such a LiMn204 derivative has a sufficiently large discharge capacity even if it is obtained by heating at a high temperature. Then, Li2Mn0 is produced by heating at high temperature.
Since it is possible to obtain a LiMn2O4 derivative that does not contain ゜ or MnO2, a non-aqueous electrolyte secondary battery with a long charge/discharge cycle life can be constructed.
実施例 以下、本発明の実施例について説明する。Example Examples of the present invention will be described below.
実施例１
本発明の実施例としてＬｉ１．、Ｍｎ２０４を次のよう
にして作製した。Example 1 As an example of the present invention, Li1. , Mn204 was produced as follows.
Ｌｉ２ＧＯ，１３，３２１ｉｉ’とＭｎ３０４５０．ｏ
ｏｏｒをボールミルで混合後、空気雰囲気中、８５０℃
で６時間加熱した。さらに、この生成物を粉砕し、再び
８６０℃で１８時間加熱し、粉末にした。Li2GO,13,321ii' and Mn30450. o
After mixing oor in a ball mill, it was heated to 850℃ in an air atmosphere.
It was heated for 6 hours. Further, this product was ground and heated again at 860° C. for 18 hours to form a powder.
このＬｉ５．、Ｍｎ ２０４を正極活物質として、第２
図に示すような扁平型電池を組み立て充放電試験を行っ
た。以下、第２図に基づき説明する。This Li5. , Mn 204 as the positive electrode active material, the second
A flat battery as shown in the figure was assembled and a charge/discharge test was conducted. The explanation will be given below based on FIG. 2.
Ｌｉ、、、Ｍｎ ２０４、導電剤であるカーボンブラッ
ク、及び結着剤である四弗化エチレン樹脂粉粉末を重量
比で、７０対２０対１０の割合で混合した。この混合物
６０■をチタンエキスバンドメタルから成る正極集電体
１をスポット溶接した電池ケース２内に成型、圧着し、
正極３とした。正極板の直径は１４．３ｆｆｆｆである
。負極４には、厚さ０．３６ｍｍのリチウムシートを用
い、ステンレスメノンユから成る負極集電体６をスポッ
ト溶接した封口板６に加圧圧着した。電解液には、プロ
ピレンカーボネートとジメトキシエタンを等体積の割合
で混合したものに、１モル／′４の割合でＬ ｉ Ｃ（
Ｊ ０４を溶解したものを用いた。また、セパレータ７
にはポリプロピレン不織布を用いた。このようにして構
成した本発明の電池を人とする。Li,..., Mn 204, carbon black as a conductive agent, and tetrafluoroethylene resin powder as a binder were mixed in a weight ratio of 70:20:10. 60 cm of this mixture was molded and crimped into a battery case 2 to which a positive electrode current collector 1 made of titanium extracted band metal was spot welded.
It was set as positive electrode 3. The diameter of the positive electrode plate is 14.3ffff. A lithium sheet with a thickness of 0.36 mm was used as the negative electrode 4, and a negative electrode current collector 6 made of stainless steel meningue was pressure-bonded to a sealing plate 6 spot-welded. The electrolyte was a mixture of propylene carbonate and dimethoxyethane in equal volumes, and L i C (
A solution of J04 was used. Also, separator 7
A polypropylene nonwoven fabric was used. The battery of the present invention constructed in this manner is assumed to be a human body.
次に比較例として、Ｌｉ２００５とＭｎ３Ｏ４をＬｉ／
Ｍｎ 原子比で１７２にしたほかは、上記のＬｉ、Ｉ
Ｍｎ２０４と同様に加熱してＬｉＭｎ２Ｏ４を作製し、
同様の扁平型電池を構成した。この電池をＢとする。Next, as a comparative example, Li2005 and Mn3O4 are
Except for the Mn atomic ratio of 172, the above Li and I
LiMn2O4 is produced by heating in the same manner as Mn204,
A similar flat battery was constructed. This battery is called B.
さらに比較例として、Ｌ工２Ｃ０５とＭｎＯ２を原料と
してＬｉＭｎ２Ｏ４を作製した。Ｌｉ２ＧＯ５１０，６
２４９とγ型ＭｎＯ，，５０，０００５’をボールミル
で混合した後、４７０℃で６時間加熱した。Furthermore, as a comparative example, LiMn2O4 was produced using L-2C05 and MnO2 as raw materials. Li2GO510,6
249 and γ-type MnO, 50,0005' were mixed in a ball mill and then heated at 470° C. for 6 hours.
このようにして得たＬｉＭｎ ２０４を正極活物質とし
て、上記で述べた扁平型電池を同様に構成した。A flat battery described above was constructed in the same manner using LiMn 204 thus obtained as a positive electrode active material.
この電池をＣとする。This battery is called C.
以上のようにして構成した本発明の電池人と比較例の電
池Ｂ、Ｃにおいて、ｏ、８ ｍ Ａの定電流。In the battery of the present invention constructed as described above and the batteries B and C of the comparative example, a constant current of 8 mA was obtained.
放電下限電圧２．Ｏｖ、充電上限電圧３．８ｖの条件で
充放電試験を行った。Discharge lower limit voltage2. A charge/discharge test was conducted under the conditions of Ov and charging upper limit voltage of 3.8V.
第１図は、本発明の電池人と比較例の電池Ｂ。FIG. 1 shows a battery according to the present invention and a battery B as a comparative example.
Ｃの各充放電サイクルでの放電容量をプロットした図で
ある。第１図より、比較例の電池Ｂでは、本発明の電池
Ａに比べて、放電容量が半分未満と極めて少なく、電池
の正極活物質として適さないことがわかる。この理由は
、比較例の電池Ｂに用いたＬｉＭｎ２Ｏ４の結晶性が著
しく高く、ＬｉＭｎ２Ｏ４内でのＬｌの拡散が困難なた
めである。また、第１図より比較例の電池Ｃでは、本発
明の電池人に比べて、放電容量は同等であるが、すイク
ル寿命（放電容量が初期容量の半分になった時のサイク
ル数）が約１３０サイクルと短い。これは、比較例の電
池Ｃに用いたＬｉＭｎ２Ｏ４において、Ｌｉ２ＭｎＯ３
やＭｎＯ２が不純物として混在し、これらが電解液中の
微量の水分によって溶出し、リチウム負極を腐食するた
めである。以上のことから、本発明の電池Ａは放電容量
、サイクル寿命の両方においてすぐれることがわかる。It is a figure which plotted the discharge capacity in each charge/discharge cycle of C. From FIG. 1, it can be seen that the battery B of the comparative example has an extremely small discharge capacity of less than half that of the battery A of the present invention, and is not suitable as a positive electrode active material for a battery. The reason for this is that the crystallinity of LiMn2O4 used in Comparative Example Battery B is extremely high, making it difficult for Ll to diffuse within LiMn2O4. In addition, as shown in Figure 1, Comparative Example Battery C has the same discharge capacity as the battery of the present invention, but the cycle life (the number of cycles when the discharge capacity becomes half of the initial capacity) It is short at about 130 cycles. This is because Li2MnO3 used in LiMn2O4 used in battery C of comparative example.
This is because impurities such as MnO2 and MnO2 are mixed together as impurities, and these are eluted by a trace amount of water in the electrolytic solution and corrode the lithium negative electrode. From the above, it can be seen that the battery A of the present invention is excellent in both discharge capacity and cycle life.
実施例２
実施例１の本発明の実施例としてＬ ｉｌ、、Ｍ ｎ
２０４を作製したのと同様に表１に示したＬｉＭｎ２Ｏ
４誘導体を作製した。ここで、元素Ｎ＆、には水酸化物
として、また、元素Ｃｕ、Ａｇ、Ｚｎは酸化物として、
それぞれ、所定の量をＬｉ２ＣＯ３とＭｎ３Ｏ４ととも
に混合し加熱した。Example 2 As an example of the present invention of Example 1, L il,, M n
LiMn2O shown in Table 1 in the same way as 204 was prepared.
Four derivatives were prepared. Here, the elements N & are used as hydroxides, and the elements Cu, Ag, and Zn are used as oxides.
A predetermined amount of each was mixed with Li2CO3 and Mn3O4 and heated.
扁平型電池の構成及び充放電試験は実施例１と同様にし
て行った。The configuration of the flat battery and the charge/discharge test were conducted in the same manner as in Example 1.
（以下 余 白）
表１は、各ＬｉＭｎ２Ｏ４誘導体を正極活物質に用いた
扁平型電池の１０サイクル目の放電容量とサイクル寿命
を記載したものである。表１より、本発明のＬｉＭｎ２
Ｏ４誘導体は、放電容量、サイクル寿命の両方において
良好であることがわかる。(Left below) Table 1 lists the discharge capacity and cycle life at the 10th cycle of flat batteries using each LiMn2O4 derivative as the positive electrode active material. From Table 1, LiMn2 of the present invention
It can be seen that the O4 derivative is good in both discharge capacity and cycle life.
なお、本実施例のＬｉＭｎ、、０４誘導体を次式で表わ
すと、
（Ｌｉ、−Ｙ−Ａｙ ）１Ｍｎ２０４
放電容量、サイクル寿命の両方において特性が向上する
のは、いずれの元素人においても概ね１．１≧ｘ≧０．
９
０．２≧ｙ≧０，０
（ｘ＝１．０のときＹは０でない）
つ範囲であった。Note that the LiMn,,04 derivative of this example is expressed by the following formula: (Li, -Y-Ay)1Mn204 The characteristics of both discharge capacity and cycle life are improved in approximately 1 for each element. .1≧x≧0.
9 0.2≧y≧0,0 (Y is not 0 when x=1.0).
実施例３
実施例１の本発明の実施例としてＬｉ、、Ｉ Ｍｎ２０
４に作製したのと同様に、表２に示したＬｉＭｎ２Ｏ４
誘導体を作製した。ここで、元素Ｖ、Ｏｒ、Ｆｅ。Example 3 As an example of the present invention of Example 1, Li,,I Mn20
4, the LiMn2O4 shown in Table 2
A derivative was prepared. Here, the elements V, Or, Fe.
Ｃｏ、Ｎｉは、それぞれ酸化物として所定の量をＬｉ２
００５とＭｎ３Ｏ４とともに混合し加熱した。Co and Ni each have a predetermined amount as an oxide with Li2
005 and Mn3O4 and heated.
扁平型電池の構成及び充放電試験は実施例１同様にして
行った。The configuration of the flat battery and the charge/discharge test were conducted in the same manner as in Example 1.
（以下 余 白）
表２は、各ＬｉＭｎ２Ｏ４誘導体を正極活物質に用いた
扁平型電池の１０サイクル目の放電容量とサイクル寿命
を記載したものである。表２より、本発明のＬｉＭｎ２
Ｏ４誘導体は、放電容量、サイクル寿命の両方において
優れた特性を示すことがわかる。(Left below) Table 2 lists the discharge capacity and cycle life at the 10th cycle of flat batteries using each LiMn2O4 derivative as the positive electrode active material. From Table 2, LiMn2 of the present invention
It can be seen that the O4 derivative exhibits excellent characteristics in both discharge capacity and cycle life.
なお、本実施例のＬｉＭｎ、、０４誘導体を次式で表わ
すと、
Ｌｉ（Ｍｎ 、−１−Ｂ Ｚ）２０４
放電容量、サイクル寿命の両方において特性が向上する
のは、いずれの元素Ｂにおいても概ね０．２≧２ ＞
０．０
の範囲であった。The LiMn,,04 derivative of this example is expressed by the following formula: Approximately 0.2≧2>
It was in the range of 0.0.
以上、実施例２，３でＬｉＭｎ２Ｏ４中のＬｉまたはＭ
ｎの一部を他元素で置換することで、放電容量、サイク
ル寿命にすぐれたＬｉＭｎ、、０４誘導体を得るが、置
換する量がいずれの元素を用いても同様の特定範囲にな
る理由は、本発明のＬｉＭｎ２Ｏ４誘導体はいずれも置
換元素との固溶体と考えられ、この特定範囲外では複酸
化物が形成することに々す、特性が低下するためと考え
られる。As described above, in Examples 2 and 3, Li or M in LiMn2O4
By substituting a part of n with another element, a LiMn,.04 derivative with excellent discharge capacity and cycle life can be obtained, but the reason why the amount of substitution remains in the same specific range regardless of which element is used is as follows. The LiMn2O4 derivatives of the present invention are all considered to be solid solutions with substituting elements, and it is thought that outside this specific range, double oxides are formed and the properties deteriorate.
発明の効果
以上のように、本発明によれば、ＬｉＭｎ２Ｏ４誘導体
を正極活悔質として用いるため、放電容量サイクル寿命
の両方において優れた、信頼性の高い非水電解質二次電
池を得ることができる。Effects of the Invention As described above, according to the present invention, since a LiMn2O4 derivative is used as a positive electrode material, a highly reliable non-aqueous electrolyte secondary battery that is excellent in both discharge capacity and cycle life can be obtained. .
第１図は本発明の電池人及び比較例の電池Ｂ。
Ｃにおける各サイクルでの放電容量をプロットした図、
第２図は本発明の実施例及び比較例に用いた扁平型電池
の断面図である。
１・・・・正極集電体、２・・・・・−電池ケース、３
正極、４・・・・・負極、６・・・・・負極集電体、６
・・・封口板、７・・・・・セパレータ、８・・・・・
・ガスケット。
代理人の氏名 弁理士 粟 野 重 孝 ほか１名放電
容ｔＣｍ八に）
へ −もFIG. 1 shows a battery according to the present invention and a battery B as a comparative example. A diagram plotting the discharge capacity at each cycle in C,
FIG. 2 is a sectional view of a flat battery used in an example of the present invention and a comparative example. 1...Positive electrode current collector, 2...-Battery case, 3
Positive electrode, 4... Negative electrode, 6... Negative electrode current collector, 6
... Sealing plate, 7... Separator, 8...
·gasket. Name of agent: Patent attorney Shigetaka Awano and one other person (discharge capacity tCm8)
Claims (1)
ウムまたはリチウム合金からなる負極を構成要素とする
電池であって、前記正極は下記の組成式で表わされるＬ
ｉＭｎ＿２Ｏ＿４の誘導体であることを特徴とする非水
電解質二次電池。 （Ｌｉ＿１＿−＿ｙ・Ａ＿ｙ）＿ｘ・（Ｍｎ＿１＿−＿
ｚ・Ｂ＿ｚ）＿２・Ｏ＿４ ただし、 ＡはＮａ、Ｋ、Ｃｕ、Ａｇ、Ｚｎから選択される元素 ＢはＶ、Ｃｒ、Ｆｅ、Ｃｏ、Ｎｉから選択される元素 １．１≧ｘ≧０．９ ０．２≧ｙ≧０．０ ０．２≧ｚ≧０．０ （ｘ＝１．０のとき、ｙ、ｚは同時に０．０にはならな
い）[Scope of Claims] A battery comprising a positive electrode, a lithium ion conductive non-aqueous electrolyte, and a negative electrode made of lithium or a lithium alloy, the positive electrode having L represented by the following compositional formula.
A non-aqueous electrolyte secondary battery characterized by being a derivative of iMn_2O_4. (Li_1_-_y・A_y)_x・(Mn_1_-_
z・B_z)_2・O_4 However, A is an element selected from Na, K, Cu, Ag, and Zn B is an element selected from V, Cr, Fe, Co, and Ni 1.1≧x≧0.9 0.2≧y≧0.0 0.2≧z≧0.0 (When x=1.0, y and z cannot be 0.0 at the same time)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63291163A JPH0821382B2 (en) | 1988-11-17 | 1988-11-17 | Non-aqueous electrolyte secondary battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63291163A JPH0821382B2 (en) | 1988-11-17 | 1988-11-17 | Non-aqueous electrolyte secondary battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02139861A true JPH02139861A (en) | 1990-05-29 |
| JPH0821382B2 JPH0821382B2 (en) | 1996-03-04 |
Family
ID=17765260
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63291163A Expired - Fee Related JPH0821382B2 (en) | 1988-11-17 | 1988-11-17 | Non-aqueous electrolyte secondary battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0821382B2 (en) |
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0390185A2 (en) * | 1989-03-30 | 1990-10-03 | Matsushita Electric Industrial Co., Ltd. | Non-aqueous electrolyte secondary cell |
| JPH04106875A (en) * | 1990-08-24 | 1992-04-08 | Honda Motor Co Ltd | Positive pole active material for lithium secondary battery |
| JPH04233169A (en) * | 1990-12-28 | 1992-08-21 | Matsushita Electric Ind Co Ltd | Manufacture of positive electrode active material for nonaqueous electrolyte secondary battery |
| US5494762A (en) * | 1992-01-16 | 1996-02-27 | Nippondenso Co., Ltd. | Non-aqueous electrolyte lithium secondary cell |
| US5498764A (en) * | 1993-09-22 | 1996-03-12 | Nippondenso Co., Ltd. | Negative electrode for lithium secondary cells and lithium secondary cells using the same |
| JPH08190907A (en) * | 1995-01-10 | 1996-07-23 | Hitachi Ltd | Secondary battery |
| US5565688A (en) * | 1993-09-22 | 1996-10-15 | Nippondenso Co., Ltd. | Method for preparing an active substance of lithium secondary cells |
| US5742070A (en) * | 1993-09-22 | 1998-04-21 | Nippondenso Co., Ltd. | Method for preparing an active substance of chemical cells |
| US5962166A (en) * | 1997-08-18 | 1999-10-05 | Covalent Associates, Inc. | Ultrahigh voltage mixed valence materials |
| US6093503A (en) * | 1992-09-01 | 2000-07-25 | Nippondenso Co., Ltd. | Non-aqueous electrolyte lithium secondary cell |
| US6168888B1 (en) | 1997-06-19 | 2001-01-02 | Tosoh Corporation | Spinel-type lithium-manganese oxide containing heteroelements, preparation process and use thereof |
| US6361756B1 (en) | 1998-11-20 | 2002-03-26 | Fmc Corporation | Doped lithium manganese oxide compounds and methods of preparing same |
| US6579475B2 (en) | 1999-12-10 | 2003-06-17 | Fmc Corporation | Lithium cobalt oxides and methods of making same |
| US6794085B2 (en) | 1997-05-15 | 2004-09-21 | Fmc Corporation | Metal oxide containing multiple dopants and method of preparing same |
| JP2007053110A (en) * | 2006-10-26 | 2007-03-01 | Hitachi Maxell Ltd | Small button secondary battery |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0260056A (en) * | 1988-08-25 | 1990-02-28 | Sanyo Electric Co Ltd | Manufacture of nonaqueous secondary battery and its positive electrode active mateiral |
-
1988
- 1988-11-17 JP JP63291163A patent/JPH0821382B2/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0260056A (en) * | 1988-08-25 | 1990-02-28 | Sanyo Electric Co Ltd | Manufacture of nonaqueous secondary battery and its positive electrode active mateiral |
Cited By (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5084366A (en) * | 1989-03-30 | 1992-01-28 | Matsushita Electric Industrial Co., Ltd. | Non-aqueous electrolyte secondary cell |
| EP0390185A2 (en) * | 1989-03-30 | 1990-10-03 | Matsushita Electric Industrial Co., Ltd. | Non-aqueous electrolyte secondary cell |
| JP2561556B2 (en) * | 1990-08-24 | 1996-12-11 | 本田技研工業株式会社 | Positive electrode active material for lithium secondary battery |
| JPH04106875A (en) * | 1990-08-24 | 1992-04-08 | Honda Motor Co Ltd | Positive pole active material for lithium secondary battery |
| JPH04233169A (en) * | 1990-12-28 | 1992-08-21 | Matsushita Electric Ind Co Ltd | Manufacture of positive electrode active material for nonaqueous electrolyte secondary battery |
| US5494762A (en) * | 1992-01-16 | 1996-02-27 | Nippondenso Co., Ltd. | Non-aqueous electrolyte lithium secondary cell |
| US6093503A (en) * | 1992-09-01 | 2000-07-25 | Nippondenso Co., Ltd. | Non-aqueous electrolyte lithium secondary cell |
| US5565688A (en) * | 1993-09-22 | 1996-10-15 | Nippondenso Co., Ltd. | Method for preparing an active substance of lithium secondary cells |
| US5498764A (en) * | 1993-09-22 | 1996-03-12 | Nippondenso Co., Ltd. | Negative electrode for lithium secondary cells and lithium secondary cells using the same |
| US5742070A (en) * | 1993-09-22 | 1998-04-21 | Nippondenso Co., Ltd. | Method for preparing an active substance of chemical cells |
| JPH08190907A (en) * | 1995-01-10 | 1996-07-23 | Hitachi Ltd | Secondary battery |
| US6794085B2 (en) | 1997-05-15 | 2004-09-21 | Fmc Corporation | Metal oxide containing multiple dopants and method of preparing same |
| US6168888B1 (en) | 1997-06-19 | 2001-01-02 | Tosoh Corporation | Spinel-type lithium-manganese oxide containing heteroelements, preparation process and use thereof |
| US5962166A (en) * | 1997-08-18 | 1999-10-05 | Covalent Associates, Inc. | Ultrahigh voltage mixed valence materials |
| US6361756B1 (en) | 1998-11-20 | 2002-03-26 | Fmc Corporation | Doped lithium manganese oxide compounds and methods of preparing same |
| US6579475B2 (en) | 1999-12-10 | 2003-06-17 | Fmc Corporation | Lithium cobalt oxides and methods of making same |
| US6932922B2 (en) | 1999-12-10 | 2005-08-23 | Fmc Corporation | Lithium cobalt oxides and methods of making same |
| JP2007053110A (en) * | 2006-10-26 | 2007-03-01 | Hitachi Maxell Ltd | Small button secondary battery |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0821382B2 (en) | 1996-03-04 |
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