JPH04269468A - Lithium secondary battery - Google Patents
Lithium secondary batteryInfo
- Publication number
- JPH04269468A JPH04269468A JP3054085A JP5408591A JPH04269468A JP H04269468 A JPH04269468 A JP H04269468A JP 3054085 A JP3054085 A JP 3054085A JP 5408591 A JP5408591 A JP 5408591A JP H04269468 A JPH04269468 A JP H04269468A
- Authority
- JP
- Japan
- Prior art keywords
- lithium
- active material
- positive electrode
- electrode active
- 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.)
- Granted
Links
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 36
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 239000007774 positive electrode material Substances 0.000 claims abstract description 24
- GEYXPJBPASPPLI-UHFFFAOYSA-N manganese(iii) oxide Chemical compound O=[Mn]O[Mn]=O GEYXPJBPASPPLI-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 claims abstract description 15
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 15
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000000463 material Substances 0.000 claims abstract description 6
- 239000007773 negative electrode material Substances 0.000 claims abstract description 6
- 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 14
- 238000009830 intercalation Methods 0.000 claims description 5
- 238000009831 deintercalation Methods 0.000 claims 1
- 229910052596 spinel Inorganic materials 0.000 abstract description 7
- 239000011029 spinel Substances 0.000 abstract description 7
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 22
- 239000011149 active material Substances 0.000 description 19
- 229910014135 LiMn2 O4 Inorganic materials 0.000 description 17
- 239000013078 crystal Substances 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 13
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 13
- 238000002441 X-ray diffraction Methods 0.000 description 12
- 238000010586 diagram Methods 0.000 description 11
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 6
- 239000008188 pellet Substances 0.000 description 6
- 239000007795 chemical reaction product Substances 0.000 description 5
- 230000007423 decrease Effects 0.000 description 5
- 229910052808 lithium carbonate Inorganic materials 0.000 description 5
- 239000011572 manganese Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- -1 polytetrafluoroethylene Polymers 0.000 description 5
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 230000006866 deterioration Effects 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
- 239000005486 organic electrolyte Substances 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 238000007789 sealing Methods 0.000 description 4
- 229910011562 Li2 Mn2 O4 Inorganic materials 0.000 description 3
- 239000004743 Polypropylene Substances 0.000 description 3
- 238000003795 desorption Methods 0.000 description 3
- 230000002687 intercalation Effects 0.000 description 3
- 239000010416 ion conductor Substances 0.000 description 3
- 150000002642 lithium compounds Chemical class 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 229920001155 polypropylene Polymers 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 229910032387 LiCoO2 Inorganic materials 0.000 description 2
- 229910016491 Mn2 O3 Inorganic materials 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000003411 electrode reaction Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000005516 engineering process Methods 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
- 238000010298 pulverizing process Methods 0.000 description 2
- 238000004080 punching Methods 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- SBUOHGKIOVRDKY-UHFFFAOYSA-N 4-methyl-1,3-dioxolane Chemical compound CC1COCO1 SBUOHGKIOVRDKY-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 229910010226 Li2Mn2O4 Inorganic materials 0.000 description 1
- 229910013375 LiC Inorganic materials 0.000 description 1
- 229910014139 LiMn2 O Inorganic materials 0.000 description 1
- 229910014540 LiMn2O Inorganic materials 0.000 description 1
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000000010 aprotic solvent Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 229910001540 lithium hexafluoroarsenate(V) Inorganic materials 0.000 description 1
- 229910002102 lithium manganese oxide Inorganic materials 0.000 description 1
- 229910001496 lithium tetrafluoroborate 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
- 238000000034 method Methods 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
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000003115 supporting electrolyte Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Battery Electrode And Active Subsutance (AREA)
- Secondary Cells (AREA)
Abstract
Description
【０００１】0001
【産業上の利用分野】本発明は、リチウムに対して４Ｖ
で作動するスピネル型ＬｉＭｎ２ Ｏ４ を正極活物質
とする二次電池（４Ｖ級リチウム二次電池）に関するも
のである。[Industrial Application Field] The present invention provides 4V for lithium.
The present invention relates to a secondary battery (4V class lithium secondary battery) that uses spinel-type LiMn2O4 as a positive electrode active material and operates at 4V.
【０００２】0002
【従来の技術とその課題】電子機器の急激なる小形軽量
化に伴い、その電源である電池に対して小形で軽量かつ
高エネルギー密度で、更に繰り返し充放電が可能な二次
電池の開発への要求が高まっている。これら要求を満た
す二次電池として、リチウム二次電池が最も有望である
。なぜなら、リチウム二次電池は、負極であるリチウム
の電位が極めて卑であるため、電池の電圧が高く、かつ
リチウムの体積，重量エネルギー密度が高いため、高エ
ネルギー密度の二次電池を提供できるという利点を有し
ているからである。[Prior art and its challenges] With the rapid reduction in the size and weight of electronic devices, there is a need to develop secondary batteries that are smaller, lighter, have higher energy density, and can be charged and discharged repeatedly compared to the batteries that serve as their power source. Demand is increasing. Lithium secondary batteries are the most promising secondary battery that meets these requirements. This is because lithium secondary batteries have a high battery voltage because the potential of lithium, which is the negative electrode, is extremely base, and the volume and weight energy density of lithium are high, making it possible to provide secondary batteries with high energy density. This is because it has advantages.
【０００３】リチウム二次電池の正極活物質は、研究の
結果より各種の材料が提案されいる。代表的なものとし
て、たとえばＶ２ Ｏ５ ，スピネル型ＬｉＭｎ２ Ｏ
４ ，ＬｉＣｏＯ２ 等が挙げられる。これらの中でも
、資源的に豊富でかつリチウムに対して約３Ｖという高
い電位を有するスピネル型ＬｉＭｎ２ Ｏ４ が実用性
のある活物質であるとして盛んに研究されてきた。As a result of research, various materials have been proposed as positive electrode active materials for lithium secondary batteries. Typical examples include V2 O5, spinel type LiMn2 O
4, LiCoO2, etc. Among these, spinel type LiMn2O4, which is abundant as a resource and has a high potential of about 3V relative to lithium, has been actively researched as a practical active material.
【０００４】この活物質の電極反応は次式となり、作動
電位は約３Ｖ（Ｌｉ／Ｌｉ＋ ）である。The electrode reaction of this active material is expressed by the following formula, and the operating potential is approximately 3V (Li/Li+).
【０００５】
放電反応： ＬｉＭｎ２ Ｏ４ ＋ Ｌｉ
＋ ＋ ｅ− → Ｌｉ２ Ｍｎ２ Ｏ４
充電反応： Ｌｉ２ Ｍｎ２ Ｏ４ → Ｌ
ｉＭｎ２ Ｏ４ ＋ Ｌｉ＋ ＋ ｅ−
ところが近年、スピネル型ＬｉＭｎ２ Ｏ４ は、
ＬｉＣｏＯ２ と同じく電気化学的にさらに酸化するこ
とで、リチウムに対して約４Ｖという極めて貴な電位有
するとともに、リチウムの充放電に対して可逆であるこ
とが報告さている（代表的な報告例として旭硝子工業技
術奨励会研究報告，５３，１０７（１９８８） がある
）。Discharge reaction: LiMn2 O4 + Li
+ + e- → Li2 Mn2 O4
Charging reaction: Li2 Mn2 O4 → L
iMn2 O4 + Li+ + e- However, in recent years, spinel type LiMn2 O4 is
It has been reported that by further electrochemically oxidizing LiCoO2, it has an extremely noble potential of about 4 V compared to lithium, and is reversible with respect to charging and discharging lithium (A typical example of a report is that of Asahi Glass Co., Ltd. Industrial Technology Promotion Association Research Report, 53, 107 (1988)).
【０００６】この活物質の電極反応は次式となり、作動
電位は約４Ｖ（Ｌｉ／Ｌｉ＋ ） である。The electrode reaction of this active material is expressed by the following equation, and the operating potential is approximately 4V (Li/Li+).
【０００７】
充電反応 ＬｉＭｎ２ Ｏ４ →
２ＭｎＯ２ ＋ Ｌｉ＋ ＋ ｅ−
放電反応 ２ＭｎＯ２ ＋ Ｌｉ＋
＋ ｅ− → ＬｉＭｎ２ Ｏ４
この活物質は、従来の活物質と比較して高い電位を
有していることとともに資源的に豊富でかつ安価なマン
ガン酸化物を原料としているため、リチウム二次電池の
正極活物質として最も有望であると思われる。Charging reaction LiMn2 O4 →
2MnO2 + Li+ + e-
Discharge reaction 2MnO2 + Li+
+ e- → LiMn2 O4 This active material has a higher potential than conventional active materials and is made from manganese oxide, which is an abundant resource and is inexpensive, so it is suitable for use in lithium secondary batteries. It seems to be the most promising as a positive electrode active material.
【０００８】スピネル型ＬｉＭｎ２ Ｏ４ は、一般に
マンガン酸化物とリチウム化合物とをＬｉ／Ｍｎモル比
で１／２になるよう混合した後、熱処理する事で製造で
きることが知られている。しかし、使用するマンガン酸
化物やリチウム化合物によって、電池用活物質としての
最適熱処理条件が異なることが報告されている。たとえ
ば、マンガン酸化物として二酸化マンガン（ＭｎＯ２
）、リチウム化合物として炭酸リチウム （Ｌｉ２
ＣＯ３ ） を用いる場合は、最適熱処理温度は４３０
℃〜５２０℃であると報告されている（特開昭６３−２
７４０５９ 号公報，特開平１−１７３５７４号公報）
。その従来報告に示された試験結果を図２に示すが、こ
の結果については、４３０℃未満では未反応のＬｉ２
ＣＯ３ が残り、一方５２０℃を越えると理由は不明で
あるが処理温度の上昇とともに一方的に容量が低下する
ことが実験で確かめられたとされている。It is known that spinel-type LiMn2O4 can generally be produced by mixing a manganese oxide and a lithium compound so that the Li/Mn molar ratio is 1/2 and then heat-treating the mixture. However, it has been reported that the optimum heat treatment conditions for a battery active material vary depending on the manganese oxide or lithium compound used. For example, manganese dioxide (MnO2) is a manganese oxide.
), lithium carbonate (Li2
When using CO3), the optimum heat treatment temperature is 430
It has been reported that the temperature is between 520°C and
74059, Japanese Patent Application Laid-open No. 1-173574)
. The test results shown in that previous report are shown in Figure 2, and this result shows that at temperatures below 430°C, unreacted Li2
It is said that it has been confirmed through experiments that when CO3 remains and the temperature exceeds 520°C, the capacity unilaterally decreases as the processing temperature increases, although the reason is unknown.
【０００９】ところが、最近マンガン酸化物として二酸
化マンガンを用いるよりも低級酸化マンガン （Ｍｎ２
Ｏ３ ） を用いた方が好ましいという報告がある
（特開平２−１７０３５４）。ここでは、リチウム化合
物として炭酸リチウム （Ｌｉ２ ＣＯ３ ） を用い
た場合は、５４０℃〜９５０℃が最適な熱処理温度成で
あると報告している。この理由は、５４０℃未満にする
と得られたリチウムマンガン酸化物中にＬｉ２ ＣＯ３
が残り、一方９５０℃を越えるとＭｎ３ Ｏ４ が
生成するためであるとしている。However, recently, lower manganese oxide (Mn2
There is a report that it is preferable to use O3) (Japanese Unexamined Patent Publication No. 2-170354). Here, it is reported that when lithium carbonate (Li2CO3) is used as the lithium compound, the optimum heat treatment temperature is 540°C to 950°C. The reason for this is that when the temperature is lower than 540°C, Li2CO3 is present in the lithium manganese oxide obtained.
remains, whereas when the temperature exceeds 950°C, Mn3O4 is generated.
【００１０】そこで、上記の報告に従い種々の条件でＬ
ｉＭｎ２ Ｏ４ を合成し、これら活物質を用いリチウ
ム二次電池を組み立て、４Ｖの作動領域で充放電サイク
ル試験を行った。[0010] Therefore, according to the above report, L
iMn2O4 was synthesized, a lithium secondary battery was assembled using these active materials, and a charge/discharge cycle test was conducted in a 4V operating range.
【００１１】しかしながら意外にも、これら３Ｖの作動
領域で優れた特性を示すと従来報告されている活物質を
用いた二次電池は４Ｖの作動領域では充放電サイクルの
進行に伴い充放電容量の著しい劣化が生じることがわか
った。[0011] Surprisingly, however, secondary batteries using active materials that have conventionally been reported to exhibit excellent characteristics in the 3V operating range decrease in charge/discharge capacity as the charge/discharge cycle progresses in the 4V operating range. It was found that significant deterioration occurred.
【００１２】前掲の報告（旭硝子工業技術奨励会研究報
告，５３，１０７（１９８８） ）においては、３Ｖの
作動領域では立方晶スピネル （ＬｉＭｎ２ Ｏ４
） と正方晶 （Ｌｉ２ Ｍｎ２ Ｏ４） の間で結
晶変化が起こっているのに対して、４Ｖの作動領域では
立方晶の結晶構造を保ったままリチウムの挿入放出が起
こっていると報告されている。In the above-mentioned report (Asahi Glass Industrial Technology Promotion Association Research Report, 53, 107 (1988)), cubic spinel (LiMn2 O4
) and tetragonal (Li2Mn2O4), whereas it has been reported that in the 4V operating region, intercalation and desorption of lithium occurs while maintaining the cubic crystal structure. .
【００１３】これは、リチウムの吸蔵放出に対して３Ｖ
の作動領域と４Ｖの作動領域とでは、安定な結晶層が異
なることを示唆している。すなわち、３Ｖの作動領域で
優れた特性を示す活物質は、リチウムに対して４Ｖの作
動領域においては不安定であるために上記のようなサイ
クルの進行にともなう充放電容量の著しい劣化が生じた
ものと思われる。This is 3V for intercalation and desorption of lithium.
This suggests that the stable crystal layers are different between the 4V operating region and the 4V operating region. In other words, the active material that exhibits excellent characteristics in the 3V operating range is unstable compared to lithium in the 4V operating range, resulting in significant deterioration in charge/discharge capacity as the cycle progresses as described above. It seems to be.
【００１４】本発明は、４Ｖの高電圧で、かつサイクル
特性に優れた安価なリチウム二次電池を提供することを
目的とする。[0014] An object of the present invention is to provide an inexpensive lithium secondary battery with a high voltage of 4V and excellent cycle characteristics.
【００１５】[0015]
【課題を解決するための手段】本発明によるリチウム二
次電池は、リチウムに対して４Ｖで作動するスピネル型
ＬｉＭｎ２ Ｏ４ を正極活物質とし、リチウムもしく
はリチウムイオンを吸蔵放出可能とする物質を負極活物
質とし、該正極活物質は三二酸化マンガンを含有するこ
とを特徴とする。[Means for Solving the Problems] The lithium secondary battery according to the present invention uses spinel-type LiMn2O4 that operates at 4V with respect to lithium as the positive electrode active material, and uses lithium or a substance capable of inserting and releasing lithium ions as the negative electrode active material. The positive electrode active material is characterized in that it contains manganese sesquioxide.
【００１６】[0016]
【作用】上記目的を達成するために検討した結果、三二
酸化マンガン（Ｍｎ２ Ｏ３ ）を含有していることを
特徴とするスピネル型ＬｉＭｎ２ Ｏ４ が、リチウム
に対して４Ｖの作動領域の充放電に対して安定であるこ
とが見出された。[Operation] As a result of studies to achieve the above object, spinel-type LiMn2 O4, which is characterized by containing manganese sesquioxide (Mn2 O3), has a high resistance to charging and discharging in the 4V operating range for lithium. It was found to be stable.
【００１７】この活物質はＣｕＫα線を使用したＸ線回
折において、回折角３２．９度に三二酸化マンガンの回
折ピークを有していることから同定することができる。
この活物質は、二酸化マンガン（ＭｎＯ２ ）に炭酸リ
チウム（Ｌｉ２ ＣＯ３ ）とをＬｉ／Ｍｎ原子比１／
２の割合で添加して、５００℃以上７５０℃以下の温度
で加熱焼成することにより製造することができる。This active material can be identified because it has a manganese sesquioxide diffraction peak at a diffraction angle of 32.9 degrees in X-ray diffraction using CuKα rays. This active material consists of manganese dioxide (MnO2) and lithium carbonate (Li2CO3) in a Li/Mn atomic ratio of 1/1.
It can be produced by adding 1/2 of the total amount of carbon dioxide and heating and baking at a temperature of 500° C. or higher and 750° C. or lower.
【００１８】またこの方法で得られる活物質は、リチウ
ムに対して４Ｖの作動領域では１００ｍＡｈ／ｇ以上の
放電容量と優れた容量保持特性を示すものの、３Ｖの作
動領域では従来の報告どおり放電容量が少さくサイクル
の進行にともなう放電容量の低下が著しいことがわかっ
た。Furthermore, although the active material obtained by this method exhibits a discharge capacity of 100 mAh/g or more and excellent capacity retention characteristics in the 4V operating region with respect to lithium, the discharge capacity decreases in the 3V operating region as previously reported. It was found that the discharge capacity decreased significantly as the cycle progressed.
【００１９】本発明の正極活物質を備えた電池が、４Ｖ
の作動領域で長いサイクル寿命を有する理由は明かでは
ないが、以下のように考えられる。[0019] A battery equipped with the positive electrode active material of the present invention has a voltage of 4V.
The reason for the long cycle life in the operating range is not clear, but it is thought to be as follows.
【００２０】二酸化マンガン（ＭｎＯ２ ）に炭酸リチ
ウムを添加して、５００℃以上７５０℃以下の温度で加
熱焼成することにより、三二酸化マンガン（Ｍｎ２ Ｏ
３ ）を含有したスピネル型ＬｉＭｎ２ Ｏ４ を合成
することができる。[0020] Manganese sesquioxide (Mn2 O
3) can be synthesized into spinel-type LiMn2O4.
【００２１】従来、立方晶スピネル （ＬｉＭｎ２
Ｏ４ ） と正方晶 （Ｌｉ２ Ｍｎ２ Ｏ４ ）
の間で結晶変化が起こる３Ｖの作動領域では、スピネル
型ＬｉＭｎ２ Ｏ４ 結晶中へのＭｎ２ Ｏ３ の混入
は、充放電容量とサイクル保持特性に悪影響を与えると
報告されている（特開平２−１７０３５４）。しかし、
立方晶の結晶構造を保ったままリチウムイオンの吸蔵放
出が起こる４Ｖの作動領域においては、結晶中に混入し
た三二酸化マンガンがスピネル型ＬｉＭｎ２ Ｏ４ 結
晶を安定化するものと思われ、結果として本発明の正極
活物質を備えた電池が、４Ｖの作動領域で長いサイクル
寿命を示したものと思われる。Conventionally, cubic spinel (LiMn2
O4 ) and tetragonal (Li2 Mn2 O4 )
It has been reported that in the 3V operating region where crystal changes occur between 3V and 3V, the incorporation of Mn2O3 into spinel-type LiMn2O4 crystals has an adverse effect on charge/discharge capacity and cycle retention characteristics (Japanese Patent Laid-Open No. 2-170354). . but,
In the 4V operating region where lithium ions are inserted and released while maintaining the cubic crystal structure, manganese sesquioxide mixed into the crystal is thought to stabilize the spinel-type LiMn2O4 crystal, and as a result, the present invention It appears that a battery with a positive electrode active material of 10% exhibited a long cycle life in the 4V operating region.
【００２２】またこの活物質は、比表面積および孔容積
が大きい二酸化マンガンを出発原料としていること、お
よび熱処理温度が結晶サイズの成長が起こりにくい５０
０℃〜７５０℃と比較的低温であることから、比表面積
および孔容積が大きくかつ結晶サイズが小さいという特
徴も有しているものと思われる。このような特徴を有す
る本発明の正極活物質は、４Ｖの作動領域においてリチ
ウムイオンの吸蔵・放出がスムーズに行われ、なおかつ
充放電を繰り返すことによる結晶構造の崩壊を抑制する
ことができる。その結果、充放電サイクルの進行にとも
なう容量劣化の少ない高寿命のリチウム二次電池を得る
ことができたものと思われる。In addition, this active material uses manganese dioxide, which has a large specific surface area and pore volume, as a starting material, and the heat treatment temperature is such that crystal size growth is difficult to occur.
Since the temperature is relatively low at 0° C. to 750° C., it is thought that it also has the characteristics of a large specific surface area and pore volume, and a small crystal size. The positive electrode active material of the present invention having such characteristics can smoothly insert and release lithium ions in the 4V operating region, and can suppress collapse of the crystal structure due to repeated charging and discharging. As a result, it seems possible to obtain a lithium secondary battery with a long life and little capacity deterioration as the charge/discharge cycle progresses.
【００２３】上記二酸化マンガンとしては、γ型，β型
あるいはγ−β型の二酸化マンガン等を挙げることがで
き、ナトリウム，カリウムなどの不純物含有量が低いも
のが望ましい。[0023] Examples of the above-mentioned manganese dioxide include γ-type, β-type, and γ-β-type manganese dioxide, and it is desirable that the content of impurities such as sodium and potassium is low.
【００２４】[0024]
【実施例】以下に、好適な実施例を用いて本発明を説明
する。
［実施例１］二酸化マンガンと炭酸リチウムとをＬｉ／
Ｍｎモル比で１／２にて混合・粉砕した後、１トン／ｃ
ｍ２ でφ２０ｍｍ、高さ２０ｍｍのペレットに成型し
た。この、ペレットをそれぞれ空気中において５００℃
，６５０℃および７５０℃で８時間加熱焼成した。これ
ら反応生成物はすべて、暗青色粉末でありＸ線回折パタ
ーンを調べたところそれぞれ図３，図４および図５に示
す回折パターンとなり、ＡＳＴＭ Ｎｏ．３５−７８
２ のＬｉＭｎ２Ｏ４ のデータと一致した。またすべ
ての反応生成物において、３３°付近にＭｎ２ Ｏ３
（ＡＳＴＭ Ｎｏ．３１−２８６）のピークが確認さ
れた。EXAMPLES The present invention will be explained below using preferred examples. [Example 1] Manganese dioxide and lithium carbonate were mixed with Li/
After mixing and pulverizing at a Mn molar ratio of 1/2, 1 ton/c
It was molded into pellets with a diameter of 20 mm and a height of 20 mm. These pellets were placed in air at 500°C.
, 650°C and 750°C for 8 hours. All of these reaction products were dark blue powders, and their X-ray diffraction patterns showed the diffraction patterns shown in FIGS. 3, 4, and 5, respectively, and ASTM No. 35-78
It was consistent with the LiMn2O4 data of 2. In addition, in all reaction products, Mn2O3 is present near 33°.
(ASTM No. 31-286) peak was confirmed.
【００２５】この本発明のＬｉＭｎ２ Ｏ４ 、１００
重量部に対してアセチレンブラック（導電助剤）を５重
量部、およびポリ４フッ化エチレン（結着材）を２重量
部添加してよく混練した後、１２０℃で４時間熱風乾燥
して正極合剤を調整した。そして、その正極合剤を１０
８ｍｇ ずつ秤量して３２５ メッシュのＳＵＳ３１６
製金網に包み込んで、２トン／ｃｍ２ で加圧成形して
正極とした。正極の寸法は、直径１６．０ｍｍ厚み０．
４ｍｍ 程度である。この正極を電池に組み込むまえに
再度、１２０℃で３時間真空乾燥処理を行った。[0025] LiMn2O4 of the present invention, 100
After adding 5 parts by weight of acetylene black (conductivity aid) and 2 parts by weight of polytetrafluoroethylene (binder) to the weight part and kneading them thoroughly, the positive electrode was dried with hot air at 120°C for 4 hours. The mixture was prepared. Then, the positive electrode mixture was
Weigh 8 mg each and 325 mesh SUS316
It was wrapped in a wire mesh and press-molded at 2 tons/cm2 to obtain a positive electrode. The dimensions of the positive electrode are 16.0 mm in diameter and 0.0 mm in thickness.
It is about 4mm. Before incorporating this positive electrode into a battery, vacuum drying treatment was performed again at 120° C. for 3 hours.
【００２６】負極には、リチウム金属を用いた。負極の
サイズは直径１６ｍｍ、厚み０．４ｍｍ 程度で、理論
容量は約２３０ｍＡｈ である。[0026] Lithium metal was used for the negative electrode. The size of the negative electrode is approximately 16 mm in diameter and 0.4 mm in thickness, and the theoretical capacity is approximately 230 mAh.
【００２７】セパレータにはポリプロピレンのマイクロ
ポーラスセパレータ（商品名『セルガードＫ２７４』）
及びポリプロピレンの不織布を重ねて用いて、外径２０
．０ｍｍ，高さ２．０ｍｍ の電池を作成した。[0027] The separator is a polypropylene microporous separator (trade name ``Celgard K274'').
and polypropylene non-woven fabric, with an outer diameter of 20
．． A battery with a diameter of 0 mm and a height of 2.0 mm was created.
【００２８】電解液には、エチレンカーボネイ（ＥＣ）
と４−メチル１，３−ジオキソラン （４−ＭｅＤＯＬ
）および１，３−ジオキソラン（ＤＯＬ） とをそれぞ
れ体積比５：３：２．７で混合してなる有機溶媒に電解
質として過塩素酸リチウムを１モル／リットル溶解した
ものを用いた（ＬｉＣｌＯ４ （１Ｍ）／ＥＣ＋４−Ｍ
ｅＤＯＬ＋ＤＯＬ（５：３：２．７） 混合溶媒）。[0028] The electrolyte contains ethylene carbonate (EC).
and 4-methyl 1,3-dioxolane (4-MeDOL
) and 1,3-dioxolane (DOL) in a volume ratio of 5:3:2.7, respectively, in which 1 mol/liter of lithium perchlorate was dissolved as an electrolyte (LiClO4 ( 1M)/EC+4-M
eDOL+DOL (5:3:2.7) mixed solvent).
【００２９】図１は、電池の縦断面図である。この図に
おいて１は、耐有機電解液性のステンレス鋼板をプレス
によって打ち抜き加工した正極端子を兼ねるケース、２
は同種の材料を打ち抜き加工した負極端子を兼ねる封口
板であり、その内壁には負極活物質３が圧着されている
。５は有機電解液を含浸したポリプロピレンからなるセ
パレーター、６は正極合剤であり正極端子を兼ねるケー
ス１の開口端部を内方へかしめ、ガスケット４を介して
負極端子を兼ねる封口板２の内周を締め付けることによ
り密閉封口している。FIG. 1 is a longitudinal sectional view of the battery. In this figure, 1 is a case that also serves as a positive terminal, which is made by punching an organic electrolyte-resistant stainless steel plate using a press, and 2
is a sealing plate that also serves as a negative electrode terminal, which is made by punching out the same material, and the negative electrode active material 3 is crimped onto the inner wall of the sealing plate. 5 is a separator made of polypropylene impregnated with an organic electrolyte, and 6 is a positive electrode mixture.The open end of the case 1, which also serves as a positive electrode terminal, is caulked inward, and the inside of the sealing plate 2, which also serves as a negative electrode terminal, is inserted through a gasket 4. It is sealed tightly by tightening the circumference.
【００３０】この本発明の正極活物質を用いた本電池を
それぞれ電池（Ａ），（Ｂ）および（Ｃ）とする。
［比較例１］二酸化マンガンと炭酸リチウムとをＬｉ／
Ｍｎモル比で１／２にて混合・粉砕した後、１トン／ｃ
ｍ２ でφ２０ｍｍ、高さ２０ｍｍのペレットに成型し
た。Batteries using the positive electrode active material of the present invention are referred to as batteries (A), (B), and (C), respectively. [Comparative Example 1] Manganese dioxide and lithium carbonate were mixed with Li/
After mixing and pulverizing at a Mn molar ratio of 1/2, 1 ton/c
It was molded into pellets with a diameter of 20 mm and a height of 20 mm.
【００３１】この、ペレットをそれぞれ空気中において
４５０℃および８５０℃で８時間加熱焼成した。４５０
℃での反応生成物は、茶褐色粉末であり、Ｘ線回折パタ
ーンを調べたところ図６に示す回折パターンとなり、Ａ
ＳＴＭ Ｎｏ．３５−７８２ のＬｉＭｎ２ Ｏ４
のデータと一致した。一方、８５０℃での反応生成物は
暗青色粉末であり、Ｘ線回折パターンを調べたところ図
７に示す回折パターンとなり、ＡＳＴＭＮｏ．３５−７
８２ のＬｉＭｎ２ Ｏ４ のデータと一致した。これ
ら両者の活物質ともに、３３°付近のＭｎ２ Ｏ３ （
ＡＳＴＭ Ｎｏ．３１−２８６ ）の存在を示すピー
クは確認されなかった。[0031] The pellets were heated and calcined in air at 450°C and 850°C for 8 hours, respectively. 450
The reaction product at ℃ is a brownish powder, and when the X-ray diffraction pattern was examined, it showed the diffraction pattern shown in Figure 6.
STM No. 35-782 LiMn2O4
The data agreed with the data. On the other hand, the reaction product at 850°C was a dark blue powder, and when the X-ray diffraction pattern was examined, the diffraction pattern was as shown in FIG. 7, and ASTM No. 35-7
It was consistent with the data of 82 LiMn2 O4. For both of these active materials, Mn2 O3 (
ASTM No. No peak indicating the presence of 31-286) was observed.
【００３２】これらＬｉＭｎ２ Ｏ４ を、電池の正極
活物質として用いることを除いて他は、実施例１と同様
の電池を作成した。この正極活物質を用いた比較電池を
それぞれ電池（ア）および（イ）とする。
［比較例２］三二酸化マンガン（Ｍｎ２ Ｏ３ ）と炭
酸リチウムとをＬｉ／Ｍｎモル比で１／２にて混合・粉
砕した後、１トン／ｃｍ２ でφ２０ｍｍ、高さ２０ｍ
ｍのペレットに成型した。A battery was prepared in the same manner as in Example 1, except that LiMn2 O4 was used as the positive electrode active material of the battery. Comparative batteries using this positive electrode active material are referred to as batteries (A) and (B), respectively. [Comparative Example 2] Manganese sesquioxide (Mn2O3) and lithium carbonate were mixed and pulverized at a Li/Mn molar ratio of 1/2, and then 1 ton/cm2 with a diameter of 20 mm and a height of 20 m.
It was molded into pellets of m.
【００３３】この、ペレットをそれぞれ空気中において
６５０℃および８５０℃で８時間加熱焼成した。これら
反応生成物は、暗青色粉末であり、Ｘ線回折パターンを
調べたところ図８および図９に示す回折パターンとなり
、ＡＳＴＭ Ｎｏ．３５−７８２ のＬｉＭｎ２ Ｏ
４ のデータと一致した。これら両者の活物質ともに、
３３°付近のＭｎ２ Ｏ３ （ＡＳＴＭ Ｎｏ．３１
−２８６ ）の存在を示すピークは確認されなかった。[0033] The pellets were heated and calcined in air at 650°C and 850°C for 8 hours, respectively. These reaction products are dark blue powders, and when examined for X-ray diffraction patterns, the diffraction patterns are shown in FIGS. 8 and 9, and ASTM No. 35-782 LiMn2O
This was consistent with the data in 4. Both of these active materials are
Mn2O3 near 33° (ASTM No.31
-286) was not confirmed.
【００３４】このＬｉＭｎ２ Ｏ４ を、電池の正極活
物質として用いることを除いて他は、実施例１と同様の
電池を作成した。この正極活物質を用いた比較電池をそ
れぞれ電池（ウ）および（エ）とする。A battery was prepared in the same manner as in Example 1, except that this LiMn2 O4 was used as the positive electrode active material of the battery. Comparative batteries using this positive electrode active material are referred to as batteries (c) and (d), respectively.
【００３５】上記各種電池について、４．３Ｖ〜３．５
Ｖの間で１．８ｍＡの定電流で充放電を繰り返し、各サ
イクルにおける放電容量を測定した。その代表例として
、電池（Ｂ）の１０サイクル目の充放電曲線を図１０に
示す。[0035] Regarding the above various batteries, 4.3V to 3.5V
Charge and discharge were repeated at a constant current of 1.8 mA between V and the discharge capacity in each cycle was measured. As a representative example, the charge/discharge curve of battery (B) at the 10th cycle is shown in FIG.
【００３６】マンガン酸化物として二酸化マンガンを用
いて合成した活物質を備えた本発明の電池（Ａ），（Ｂ
）および（Ｃ）と、比較電池（ア），（イ），（ウ）お
よび（エ）の充放電サイクルの進行にともなう放電容量
変化を図１１に示す。Batteries (A) and (B) of the present invention equipped with an active material synthesized using manganese dioxide as a manganese oxide
) and (C), and the comparative batteries (a), (b), (c), and (d), changes in discharge capacity as the charge/discharge cycle progresses are shown in FIG.
【００３７】本発明の正極活物質を用いた本発明電池（
Ａ），（Ｂ）および（Ｃ）は、比較電池（ア），（イ）
，（ウ）および（エ）と比較してサイクルの進行にとも
なう容量低下がほとんど見られない。[0037] The battery of the present invention using the positive electrode active material of the present invention (
A), (B) and (C) are comparative batteries (A) and (B).
, (c), and (d), there is almost no decrease in capacity as the cycle progresses.
【００３８】比較電池（ア）の放電容量の小さい原因と
して、この電池活物質のスピネル型ＬｉＭｎ２ Ｏ４
結晶の生成が不十分であることが考えられる。The reason for the small discharge capacity of the comparative battery (A) is that the spinel type LiMn2O4 of this battery active material
This may be due to insufficient crystal formation.
【００３９】本発明の正極活物質を備えた電池が、優れ
たサイクル寿命を有する理由は明かではないが、以下の
ように考えられる。The reason why a battery equipped with the positive electrode active material of the present invention has an excellent cycle life is not clear, but it is thought to be as follows.
【００４０】上記の試験で、優れたサイクル寿命を示し
た本発明電池（Ａ），（Ｂ）および（Ｃ）の正極活物質
は、三二酸化マンガンを含有しているスピネル型ＬｉＭ
ｎ２ Ｏ４ である。４Ｖの作動領域において正極活物
質では、立方晶の結晶構造を保ったままリチウムイオン
の吸蔵放出が起こる。この際、結晶中に含有された三二
酸化マンガンがスピネル型ＬｉＭｎ２ Ｏ４ 結晶の崩
壊を防止するしていると考えられ、その結果三二酸化マ
ンガンを含有していない活物質を有する比較電池（イ）
，（ウ）および（エ）と比較して、本発明の正極活物質
を備えた電池が、サイクルの進行にともなう放電容量に
低下が見られなかったものと思われる。The positive electrode active materials of the batteries (A), (B) and (C) of the present invention, which showed excellent cycle life in the above test, were spinel-type LiM containing manganese sesquioxide.
n2 O4. In the 4V operating region, the positive electrode active material intercalates and desorbs lithium ions while maintaining the cubic crystal structure. At this time, it is thought that the manganese sesquioxide contained in the crystal prevents the spinel-type LiMn2O4 crystal from collapsing, and as a result, the comparative battery (a) with an active material that does not contain manganese sesquioxide
, (c), and (d), it seems that the battery equipped with the positive electrode active material of the present invention showed no decrease in discharge capacity as the cycle progressed.
【００４１】本発明の活物質は、比表面積および孔容積
が大きい二酸化マンガンを出発原料としていること、お
よび熱処理温度が結晶サイズの成長が起こりにくい５０
０℃〜７５０℃と比較的低温であることから、比表面積
および孔容積が大きくかつ結晶サイズが小さいという特
徴も有していると思われる。このような特徴を有する本
発明の正極活物質は、４Ｖの作動領域においてリチウム
イオンの吸蔵・放出がスムーズがスムーズに行われ、な
おかつ充放電を繰り返すことによる結晶構造の崩壊を抑
制することができる。その結果、充放電サイクルの進行
にともなう容量劣化の少ない高寿命のリチウム二次電池
を得ることができたものと思われる。The active material of the present invention uses manganese dioxide, which has a large specific surface area and pore volume, as a starting material, and the heat treatment temperature is such that crystal size growth is difficult to occur.
Since the temperature is relatively low at 0°C to 750°C, it is thought that it also has the characteristics of a large specific surface area and pore volume, and a small crystal size. The positive electrode active material of the present invention having such characteristics can smoothly absorb and release lithium ions in the 4V operating region, and can suppress collapse of the crystal structure due to repeated charging and discharging. . As a result, it seems possible to obtain a lithium secondary battery with a long life and little capacity deterioration as the charge/discharge cycle progresses.
【００４２】なお、上記実施例では負極活物質としてリ
チウムを用いたが、本発明の正極を使用するにあたり、
負極活物質は基本的に限定されるず、従来の有機電解液
二次電池ウムイオンを吸蔵放出可能な物質を用いること
ができる。Although lithium was used as the negative electrode active material in the above examples, when using the positive electrode of the present invention,
The negative electrode active material is basically not limited, and any conventional organic electrolyte secondary battery material capable of intercalating and releasing ions can be used.
【００４３】また、リチウムイオン伝導性物質である有
機溶媒や固体のイオン導電体も基本的に限定されず、従
来の有機電解液二次電池に用いられているものを用いる
ことができる。たとえば、有機溶媒としては非プロトン
溶媒であるエチレンカーボネイトなどの環状エステル類
およびテトラハイドロフラン，ジオキソランなどのエー
テル類があげられ、これら単独もしくは２種以上を混合
した溶媒を用いることが出来る。固体のイオン導電体と
しては、リチウムイオン導電性を有するものであれば用
いることが出来る。その代表的なものとして、ポリエチ
レンオキサイドなどがあげられる。Furthermore, the organic solvent and solid ion conductor which are lithium ion conductive substances are basically not limited, and those used in conventional organic electrolyte secondary batteries can be used. For example, organic solvents include cyclic esters such as ethylene carbonate, which are aprotic solvents, and ethers such as tetrahydrofuran and dioxolane, and these solvents may be used alone or in combination of two or more thereof. As the solid ion conductor, any material having lithium ion conductivity can be used. A typical example thereof is polyethylene oxide.
【００４４】また、このような有機溶媒あるいは固体の
イオン導電体に溶解される支持電解質も基本的に限定さ
れるものではない。たとえば、 ＬｉＡｓＦ６ ， Ｌ
ｉＣｌＯ４ ，ＬｉＢＦ４ ， ＬｉＰＦ６ ，ＬｉＣ
Ｆ３ ＳＯ３ などの１種以上を用いることができる。[0044] Furthermore, the supporting electrolyte dissolved in such an organic solvent or solid ionic conductor is not fundamentally limited. For example, LiAsF6, L
iClO4, LiBF4, LiPF6, LiC
One or more types such as F3 SO3 can be used.
【００４５】なお、前記の実施例に係る電池はいずれも
ボタン形電池であるが、円筒形，角形またはペーパー形
電池に本発明を適用しても同様の効果が得られる。Although all of the batteries according to the above embodiments are button-shaped batteries, similar effects can be obtained even if the present invention is applied to cylindrical, prismatic, or paper-shaped batteries.
【００４６】[0046]
【発明の効果】以上詳述した如く、本発明によればリチ
ウムイオンの吸蔵放出に対して可逆性の優れた４Ｖ級リ
チウム二次電池用ＬｉＭｎ２ Ｏ４を正極活物質として
用いることができ、従来の電池に比較して優れたサイク
ル寿命性能を有する高エネルギー密度の４Ｖ級リチウム
二次電池を提供することができる。As described in detail above, according to the present invention, LiMn2O4 for 4V class lithium secondary batteries, which has excellent reversibility with respect to intercalation and desorption of lithium ions, can be used as a positive electrode active material, which is different from the conventional one. It is possible to provide a high energy density 4V class lithium secondary battery that has superior cycle life performance compared to batteries.
【図１】４Ｖ級リチウム二次電池の一例であるボタン電
池の内部構造を示した図。FIG. 1 is a diagram showing the internal structure of a button battery, which is an example of a 4V class lithium secondary battery.
【図２】従来報告例を示した図[Figure 2] Diagram showing examples of conventional reports
【図３】本実施例によるＬｉＭｎ２ Ｏ４ のＸ線回折
パターンを示す線図。FIG. 3 is a diagram showing the X-ray diffraction pattern of LiMn2 O4 according to this example.
【図４】本実施例によるＬｉＭｎ２ Ｏ４ のＸ線回折
パターンを示す線図。FIG. 4 is a diagram showing the X-ray diffraction pattern of LiMn2 O4 according to this example.
【図５】本実施例によるＬｉＭｎ２ Ｏ４ のＸ線回折
パターンを示す線図。FIG. 5 is a diagram showing the X-ray diffraction pattern of LiMn2 O4 according to this example.
【図６】比較例によるＬｉＭｎ２ Ｏ４ のＸ線回折パ
ターンを示す線図。FIG. 6 is a diagram showing an X-ray diffraction pattern of LiMn2 O4 according to a comparative example.
【図７】比較例によるＬｉＭｎ２ Ｏ４ のＸ線回折パ
ターンを示す線図。FIG. 7 is a diagram showing an X-ray diffraction pattern of LiMn2 O4 according to a comparative example.
【図８】比較例によるＬｉＭｎ２ Ｏ４ のＸ線回折パ
ターンを示す線図。FIG. 8 is a diagram showing an X-ray diffraction pattern of LiMn2 O4 according to a comparative example.
【図９】比較例によるＬｉＭｎ２ Ｏ４ のＸ線回折パ
ターンを示す線図。FIG. 9 is a diagram showing an X-ray diffraction pattern of LiMn2 O4 according to a comparative example.
【図１０】実施例で作成した電池の充放電曲線を示した
図。FIG. 10 is a diagram showing charge/discharge curves of batteries created in Examples.
【図１１】本発明による電池と比較電池の充放電サイク
ルの進行にともなう放電容量変化を示した図である。FIG. 11 is a diagram showing changes in discharge capacity of a battery according to the present invention and a comparative battery as the charge/discharge cycle progresses.
１ 電池ケース ２ 封口板 ３ リチウム ４ ガスケット ５ セパレーター ６ 正極合剤 1 Battery case 2 Sealing plate 3 Lithium 4 Gasket 5 Separator 6 Positive electrode mixture
Claims (1)
ネル型ＬｉＭｎ２ Ｏ４ を正極活物質とし、リチウム
もしくはリチウムイオンを吸蔵放出可能とする物質を負
極活物質とし、該正極活物質は三二酸化マンガンを含有
することを特徴とするリチウム二次電池。Claim 1: A positive electrode active material is spinel-type LiMn2O4 that operates at 4V with respect to lithium, a negative electrode active material is a material capable of intercalating and deintercalating lithium or lithium ions, and the positive electrode active material contains manganese sesquioxide. A lithium secondary battery characterized by:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3054085A JPH0766833B2 (en) | 1991-02-25 | 1991-02-25 | Lithium secondary battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3054085A JPH0766833B2 (en) | 1991-02-25 | 1991-02-25 | Lithium secondary battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04269468A true JPH04269468A (en) | 1992-09-25 |
| JPH0766833B2 JPH0766833B2 (en) | 1995-07-19 |
Family
ID=12960782
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3054085A Expired - Lifetime JPH0766833B2 (en) | 1991-02-25 | 1991-02-25 | Lithium secondary battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0766833B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001273900A (en) * | 2000-01-21 | 2001-10-05 | Showa Denko Kk | Positive active material, method of manufacturing same, and nonaqueous secondary battery using the active material |
| JP2006012426A (en) * | 2004-06-22 | 2006-01-12 | Nichia Chem Ind Ltd | Positive electrode active material for nonaqueous electrolyte secondary battery and nonaqueous electrolyte secondary battery |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02170354A (en) * | 1988-12-22 | 1990-07-02 | Toshiba Battery Co Ltd | Manufacture of positive electrode active material for nonaqueous solvent secondary cell |
| JPH02270269A (en) * | 1989-04-11 | 1990-11-05 | Matsushita Electric Ind Co Ltd | Nonaqueous electrolyte secondary battery |
| JPH03225754A (en) * | 1990-01-30 | 1991-10-04 | Fuji Elelctrochem Co Ltd | Nonaqueous electrolytic secondary battery |
-
1991
- 1991-02-25 JP JP3054085A patent/JPH0766833B2/en not_active Expired - Lifetime
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02170354A (en) * | 1988-12-22 | 1990-07-02 | Toshiba Battery Co Ltd | Manufacture of positive electrode active material for nonaqueous solvent secondary cell |
| JPH02270269A (en) * | 1989-04-11 | 1990-11-05 | Matsushita Electric Ind Co Ltd | Nonaqueous electrolyte secondary battery |
| JPH03225754A (en) * | 1990-01-30 | 1991-10-04 | Fuji Elelctrochem Co Ltd | Nonaqueous electrolytic secondary battery |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001273900A (en) * | 2000-01-21 | 2001-10-05 | Showa Denko Kk | Positive active material, method of manufacturing same, and nonaqueous secondary battery using the active material |
| JP2006012426A (en) * | 2004-06-22 | 2006-01-12 | Nichia Chem Ind Ltd | Positive electrode active material for nonaqueous electrolyte secondary battery and nonaqueous electrolyte secondary battery |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0766833B2 (en) | 1995-07-19 |
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