JPH02170354A - Manufacture of positive electrode active material for nonaqueous solvent secondary cell - Google Patents
Manufacture of positive electrode active material for nonaqueous solvent secondary cellInfo
- Publication number
- JPH02170354A JPH02170354A JP63324595A JP32459588A JPH02170354A JP H02170354 A JPH02170354 A JP H02170354A JP 63324595 A JP63324595 A JP 63324595A JP 32459588 A JP32459588 A JP 32459588A JP H02170354 A JPH02170354 A JP H02170354A
- Authority
- JP
- Japan
- Prior art keywords
- positive electrode
- active material
- lithium
- electrode active
- manganese
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 21
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- 239000002904 solvent Substances 0.000 title abstract description 5
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims abstract description 50
- 238000010438 heat treatment Methods 0.000 claims abstract description 13
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims abstract description 12
- 229940099596 manganese sulfate Drugs 0.000 claims abstract description 11
- 235000007079 manganese sulphate Nutrition 0.000 claims abstract description 11
- 239000011702 manganese sulphate Substances 0.000 claims abstract description 11
- 150000002642 lithium compounds Chemical class 0.000 claims abstract description 8
- 239000000203 mixture Substances 0.000 claims abstract description 7
- 239000003125 aqueous solvent Substances 0.000 claims description 14
- 239000013078 crystal Substances 0.000 abstract description 12
- 229910002102 lithium manganese oxide Inorganic materials 0.000 abstract description 11
- VLXXBCXTUVRROQ-UHFFFAOYSA-N lithium;oxido-oxo-(oxomanganiooxy)manganese Chemical compound [Li+].[O-][Mn](=O)O[Mn]=O VLXXBCXTUVRROQ-UHFFFAOYSA-N 0.000 abstract description 11
- 238000002156 mixing Methods 0.000 abstract description 5
- QEXMICRJPVUPSN-UHFFFAOYSA-N lithium manganese(2+) oxygen(2-) Chemical compound [O-2].[Mn+2].[Li+] QEXMICRJPVUPSN-UHFFFAOYSA-N 0.000 abstract description 4
- GEYXPJBPASPPLI-UHFFFAOYSA-N manganese(III) oxide Inorganic materials O=[Mn]O[Mn]=O GEYXPJBPASPPLI-UHFFFAOYSA-N 0.000 abstract description 4
- 239000007773 negative electrode material Substances 0.000 abstract description 4
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 2
- 150000002500 ions Chemical class 0.000 abstract description 2
- 230000007547 defect Effects 0.000 abstract 2
- 230000037431 insertion Effects 0.000 abstract 1
- 238000003780 insertion Methods 0.000 abstract 1
- 229910052596 spinel Inorganic materials 0.000 abstract 1
- 239000011029 spinel Substances 0.000 abstract 1
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 20
- 239000011572 manganese Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 229910052744 lithium Inorganic materials 0.000 description 6
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 5
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 5
- 230000006866 deterioration Effects 0.000 description 5
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- TYTHZVVGVFAQHF-UHFFFAOYSA-N manganese(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Mn+3].[Mn+3] TYTHZVVGVFAQHF-UHFFFAOYSA-N 0.000 description 3
- -1 polytetrafluoroethylene Polymers 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 229910001413 alkali metal ion Inorganic materials 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003792 electrolyte 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
- 229910052808 lithium carbonate Inorganic materials 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 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
- 238000000034 method Methods 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-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
- 229910000733 Li alloy Inorganic materials 0.000 description 1
- 229910014689 LiMnO Inorganic materials 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical group [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- KLARSDUHONHPRF-UHFFFAOYSA-N [Li].[Mn] Chemical compound [Li].[Mn] KLARSDUHONHPRF-UHFFFAOYSA-N 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000001989 lithium alloy Substances 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 150000003346 selenoethers Chemical class 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-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
Landscapes
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明は、非水溶媒二次電池に用いられる正極活物質の
製造方法に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a method for producing a positive electrode active material used in a non-aqueous solvent secondary battery.
［従来の技術及び課８］
近年、電子機器の発達に（ｆい小形で軽量かつエネルギ
ー密度が高く、更に繰返し充放電可能な二次電池の開発
が要望されている。この種の二次電池としては、負極活
物質としてリチウム又はリチウム合金を用い、正極活物
質としてモリブデン、バナジウム、チタン、ニオブなど
の酸化物、硫化物、セレン化物などが検討されている。[Prior Art and Lesson 8] In recent years, with the development of electronic devices, there has been a demand for the development of secondary batteries that are small, lightweight, have high energy density, and can be charged and discharged repeatedly. As a negative electrode active material, lithium or a lithium alloy is used, and as a positive electrode active material, oxides, sulfides, selenides, etc. of molybdenum, vanadium, titanium, niobium, etc. are being considered.
一方、二酸化マンガンは高エネルギー密度、高電圧を有
する正極活物質として非水溶媒−次電池に用いられ、実
用化されている。二酸化マンガンは、トンネル構造を有
しており、−次電池においては電池が放電することによ
ってＬｉ＋イオンが前記トンネル内に侵入し、これによ
ってＭｎＯ２結晶構造は膨脹する。このトンネル内のア
ルカリ金属イオンは容易に移動できる状態であるため、
この電池を充電状態にすると、トンネル内のＬ１＋が放
出され、それに伴ってＭｎＯ２結晶構造が収縮する。こ
のように従来の非水溶媒−次電池で使用されるＭｎＯ２
をそのまま二次電池の正極活物質として用いると、電池
の充放電に伴って結晶構造の収縮・膨脹が繰返され、こ
れによってＭｎＯ２のトンネル構造が崩れてしまい、充
放電サイクルの進行につれて充放電容量の劣化が著しく
なるという問題があった。On the other hand, manganese dioxide is used as a positive electrode active material having high energy density and high voltage in non-aqueous solvent-based batteries, and has been put into practical use. Manganese dioxide has a tunnel structure, and in a secondary battery, when the battery discharges, Li+ ions enter the tunnel, thereby expanding the MnO2 crystal structure. Since the alkali metal ions in this tunnel are easily mobile,
When this battery is brought into a charged state, L1+ in the tunnel is released, and the MnO2 crystal structure contracts accordingly. In this way, the MnO2 used in conventional nonaqueous solvent-secondary batteries
If MnO2 is used as a positive electrode active material in a secondary battery, the crystal structure will repeatedly contract and expand as the battery is charged and discharged, and this will cause the tunnel structure of MnO2 to collapse, causing the charge and discharge capacity to decrease as the charge and discharge cycle progresses. There was a problem that the deterioration of the
このようなことから、硫酸マンガンを電解酸化して得ら
れる電解二酸化マンガンにリチウム化合物（例えばＬ１
２Ｃ０５）を加え、加熱焙焼することにより製造された
リチウムマンガン酸化物を正極活物質とした非水溶媒二
次電池が知られている。しかしながら、かかる正極活物
質を用いた二次電池においても充放電サイクルの進行に
つれて充放電容量の劣化が生じるという問題があった。For this reason, lithium compounds (for example, L1
A non-aqueous solvent secondary battery is known in which a positive electrode active material is lithium manganese oxide produced by adding 2C05) and heating and roasting it. However, even in a secondary battery using such a positive electrode active material, there is a problem in that the charge/discharge capacity deteriorates as the charge/discharge cycle progresses.
本発明は、上記従来の課題を解決するためになされたも
ので、トンネル構造を有し、非水溶媒二次電池に組込ん
だ後の充放電、つまりアルカリ金属イオンの侵入・放出
に伴う結晶構造の崩れの小さいマンガンリチウム酸化物
からなる正極活物質を製造し得る方法を提供しようとす
るものである。The present invention has been made to solve the above-mentioned conventional problems, and has a tunnel structure. The present invention aims to provide a method for producing a positive electrode active material made of manganese lithium oxide with minimal structural collapse.
［課題を解決するための手段］
本発明は、硫酸マンガンを焙焼して得られる低級酸化マ
ンガン（Ｍｎ ２Ｏ３ ）にリチウム化合物を添加して
加熱焙焼せしめることを特徴とする非水溶媒二次電池用
正極活物質の製造方法である。[Means for Solving the Problems] The present invention provides a non-aqueous solvent secondary characterized in that a lithium compound is added to lower manganese oxide (Mn2O3) obtained by roasting manganese sulfate and the mixture is heated and roasted. This is a method for producing a positive electrode active material for batteries.
上記低級酸化マンガン（三二酸化マンガン）（Ｍｎ２Ｏ
３）は、硫酸マンガン（ＭｎＳＯ４）溶液を加熱濃縮し
て硫酸マンガン結晶を得、これを空気雰囲気又は空気よ
り酸素分圧の大きい酸素雰囲気中にて８００〜１１００
℃、１０分間以上の条件で焙焼することにより、硫酸マ
ンガンを分解してＭｎ３Ｏ４又はＭｎ２Ｏ３を主成分と
するマンガン酸化物を調製する。ここでＭｎ３Ｏ４を主
成分とするマンガン酸化物の場合は、例えばロータリー
キルン等により７００〜９５０℃で焙焼してＭｎ ２Ｏ
３を主成分とする低級酸化マンガンとする。The above lower manganese oxide (manganese sesquioxide) (Mn2O
3) Heat and concentrate a manganese sulfate (MnSO4) solution to obtain manganese sulfate crystals, which are then heated to a concentration of 800 to 1100 in an air atmosphere or an oxygen atmosphere with a higher oxygen partial pressure than air.
By roasting at ℃ for 10 minutes or more, manganese sulfate is decomposed to prepare manganese oxide containing Mn3O4 or Mn2O3 as a main component. Here, in the case of manganese oxide whose main component is Mn3O4, it is roasted at 700 to 950°C in a rotary kiln, etc. to produce Mn2O.
It is a lower manganese oxide whose main component is 3.
上記リチウム化合物としては、例えば炭酸リチウム（Ｌ
ｌ ２ ＣＯ３） 硝酸リチウム（ＬｉＮＯ２）等を
挙げることができる。これらいずれのリチウム塩とＭｎ
２Ｏ３との加熱焙焼後の生成物は、スピネル型のリチウ
ムマンガン化合物（Ｌ Ｉ Ｍｎ ２Ｏ４ ）のみ得ら
れる。また、前記リチウム化合物の上記低級酸化マンガ
ン（Ｍｎ２Ｏ３）への添加割合は、夫々Ｌ１及びＭｎ換
算でＭｎ：ＬＩが２ ： ０．８〜２ ： １．２の範
囲とすることが望ましい。この理由は、Ｌｌの配合比を
０．８未満にすると加熱焙焼後に得られたリチウムマン
ガン酸化物中に未反応のＭｎ２Ｏ３又はＭｎ３Ｏ４が生
成され、一方Ｌｌの配合比が！、２を越えると加熱焙焼
後に得られたリチウムマンガン酸化物中にＬｊ２Ｏが生
成され、いずれの場合もサイクル特性の劣化を招く恐れ
があるからである。As the lithium compound, for example, lithium carbonate (L
l 2 CO3), lithium nitrate (LiNO2), and the like. Any of these lithium salts and Mn
The product after heating and roasting with 2O3 is only a spinel-type lithium manganese compound (L I Mn 2O4 ). Further, the addition ratio of the lithium compound to the lower manganese oxide (Mn2O3) is preferably such that Mn:LI is in the range of 2:0.8 to 2:1.2 in terms of L1 and Mn, respectively. The reason for this is that if the blending ratio of Ll is less than 0.8, unreacted Mn2O3 or Mn3O4 will be produced in the lithium manganese oxide obtained after heating and roasting, while on the other hand, if the blending ratio of Ll is less than 0.8, , 2, Lj2O will be produced in the lithium manganese oxide obtained after heating and roasting, and in either case there is a risk of deterioration of cycle characteristics.
上記加熱焙焼温度は、５４０〜９５０℃のの温度範囲す
ることが望ましい。この理由は、５４０ ”Ｃ未満にす
ると得られたリチウムマンガン酸化物中にＬｉ ２ ｃ
ｏ３が残り、一方９５０℃を越えるとＭｎ ３０４が生
成されてサイクル特性の劣化を招く恐れがあるからであ
る。The heating and roasting temperature is preferably in the range of 540 to 950°C. The reason for this is that when the temperature is lower than 540"C, Li 2 c
This is because if o3 remains and the temperature exceeds 950° C., Mn 304 is generated, which may lead to deterioration of cycle characteristics.
［作用］
本発明によれば、硫酸マンガンを焙焼して得られる特定
の低級酸化マンガン（Ｍｎ２Ｏ３）にリチウム化合物を
添加して加熱焙焼せしめることによって、正極活物質と
してのスピネル型リチウムマンガン酸化物を製造できる
。このリチウムマンガン酸化物は、結晶構造内にＬ＋＋
イオンが侵入できる空格子点が三次元的に連なっている
ことと、電解二酸化マンガンを出発原料とすることによ
り、比表面積と孔容積が大きくなるため、該正極活物質
を導電材及び結着材に配合して得た正極を組込んだ非水
溶媒二次電池の充放電時において負極活物質であるリチ
ウムイオンの該正極の正極活物質への侵入・放出がスム
ーズに行われ、なおかつ充放電を繰返すことによる結晶
構造の崩壊を抑制できる。その結果、充放電サイクルに
よる容量劣化の少ない高寿命の非水溶媒二次電池を得る
ことができる。[Function] According to the present invention, by adding a lithium compound to a specific lower manganese oxide (Mn2O3) obtained by roasting manganese sulfate and roasting it, spinel-type lithium manganese oxide as a positive electrode active material is produced. Can manufacture things. This lithium manganese oxide has L++ in its crystal structure.
Due to the three-dimensional series of vacancies into which ions can penetrate and the use of electrolytic manganese dioxide as a starting material, the specific surface area and pore volume are increased. During charging and discharging of a non-aqueous solvent secondary battery incorporating a positive electrode obtained by blending with the above, lithium ions, which are the negative electrode active material, smoothly enter and release from the positive electrode active material of the positive electrode, and the charging and discharging process is smooth. It is possible to suppress the collapse of the crystal structure due to repeated steps. As a result, a long-life non-aqueous solvent secondary battery with little capacity deterioration due to charge/discharge cycles can be obtained.
［実施例］ 以下、本発明を第１図を参照して詳細に説明する。[Example] Hereinafter, the present invention will be explained in detail with reference to FIG.
実施例１
まず、硫酸マンガン（ＭｎＳＯ，＋）溶液を加熱濃縮し
て硫酸マンガン結晶を得、これを空気雰囲気にて９００
℃、１０分間の条件で焙焼することにより、硫酸マンガ
ンを分解してＭ１３Ｑ４又はＭｎ ２ ｏ３を主成分と
するマンガン酸化物を調製する。ここでＭｎ３Ｏ４を主
成分とするマンガン酸化物の場合は、ロータリーキルン
により８００℃で焙焼してＭｎ２Ｏ３を主成分とする低
級酸化マンガンとした。Example 1 First, manganese sulfate crystals were obtained by heating and concentrating a manganese sulfate (MnSO,
By roasting at ℃ for 10 minutes, manganese sulfate is decomposed to prepare manganese oxide containing M13Q4 or Mn2O3 as a main component. In the case of manganese oxide containing Mn3O4 as the main component, it was roasted at 800° C. in a rotary kiln to produce a lower manganese oxide containing Mn2O3 as the main component.
次いで、前記三二酸化マンガン（Ｍｎ２Ｏ３）６０ｇと
Ｌｉ ２ Ｃ０３１４ｇ （モル比率でＭｎ：Ｌｌ−２
：Ｉ）にて混合・粉砕し、空気中８５０℃、１時間加熱
焙焼し、冷却した後、再び混合・粉砕し、再度空気中で
８５０℃、２時間加熱焙焼した。この反応生成物は、青
色粉末であり、Ｘ線回折パターンを調べたところ第２図
に示す回折パターンとなり、ＡＳＴＭ ＮＯ，１８−
７３６のＬｉＭｎ２Ｏ４のデータと一致した。Next, 60 g of the manganese sesquioxide (Mn2O3) and 314 g of Li 2 C0 (in a molar ratio of Mn:Ll-2
:I), heated and roasted in air at 850°C for 1 hour, cooled, mixed and crushed again, and heated and roasted again in air at 850°C for 2 hours. This reaction product is a blue powder, and when examined for its X-ray diffraction pattern, the diffraction pattern shown in Figure 2 was obtained, and it conformed to ASTM No. 18-
736 LiMn2O4 data.
次いで、前記正極活物質としての
Ｌｉ Ｍｎ ２Ｏ４９０重量部に導電剤としてのアセチ
レンブラック１０重量部及び結若剤としてのポリテトラ
フルオロエチレン５重量部とを混合して正極合剤とし、
この合剤を圧力約２トン／ ｃｄの条件で加圧成形し、
更に１２Ｏ℃で真空中で乾燥して直径１５ 、７ ｍｍ
の正極を製造した。Next, 10 parts by weight of acetylene black as a conductive agent and 5 parts by weight of polytetrafluoroethylene as a binding agent are mixed with 490 parts by weight of Li Mn 2 O as the positive electrode active material to prepare a positive electrode mixture,
This mixture was pressure-molded at a pressure of about 2 tons/cd,
It was further dried in vacuum at 120°C to a diameter of 15.7 mm.
A positive electrode was manufactured.
次いで、前記正極を用いて第１図に示す外径２Ｏｍｍ、
厚さ２．４龍の寸法を有するボタン彫型水溶媒二次電池
を組立てた。即ち、図中の１はステンレス鋼製の正極容
器であり、この容器ｌ内には集電体２を介して前記方法
で製造した正極３が収納されている。この正極３上には
、ポリプロピレン不織布からなるセパレータ４及び金属
リチウムからなる直径１５＋ｉ曹の負極５が載置されて
いる。前記セパレータ４には、プロピレンカーボネート
と１．２−ジメトキシエタンの混合溶媒（重量比でｌ
：１）に過塩素酸リチウムを０．５モル／ｆｌの濃度で
溶解した電解液が含浸保持されている。前記正極容器ｌ
の開口部にはバッキング６を介して負極容器７が設けら
れており、該負極容器７のかしめ加工により正極容器１
、負極容器７内に前記正極３、セパレータ４及び負極５
が密閉されている。Next, using the positive electrode, an outer diameter of 20 mm as shown in FIG.
A button-shaped water-solvent secondary battery having a thickness of 2.4 mm was assembled. That is, numeral 1 in the figure is a positive electrode container made of stainless steel, and the positive electrode 3 manufactured by the above method is housed in the container 1 with a current collector 2 interposed therebetween. On this positive electrode 3, a separator 4 made of a polypropylene nonwoven fabric and a negative electrode 5 made of metallic lithium and having a diameter of 15 + i carbon dioxide are placed. The separator 4 contains a mixed solvent of propylene carbonate and 1,2-dimethoxyethane (l by weight).
:1) is impregnated with an electrolytic solution in which lithium perchlorate is dissolved at a concentration of 0.5 mol/fl. The positive electrode container l
A negative electrode container 7 is provided through the backing 6 at the opening of the negative electrode container 7, and the positive electrode container 1 is closed by caulking the negative electrode container 7.
, the positive electrode 3, separator 4 and negative electrode 5 are placed in the negative electrode container 7.
is sealed.
実施例２
実施例１と同様な三二酸化マンガン
（ｋｉｎ ２Ｏ３ ） ６０ｇと水酸化リチウム８ｇを
モル比率でＭｎ ： Ｌｌ ＝２ ：１にて混合・粉砕
し、空気中６５０℃、１時間加熱焙焼し、冷却した後、
再び混合・粉砕し、再度空気中で６５０℃、３時間加熱
焙焼した。この反応生成物は、前述した第２図と同様な
回折パターンとなり、ＡＳＴＭＮｏ、 １８−７３８の
ＬｉＭｎ２Ｏ４のデータと一致した。Example 2 60 g of manganese sesquioxide (kin2O3) similar to Example 1 and 8 g of lithium hydroxide were mixed and pulverized at a molar ratio of Mn:Ll = 2:1, and roasted in air at 650°C for 1 hour. and after cooling,
The mixture was mixed and pulverized again, and heated and roasted again in the air at 650°C for 3 hours. This reaction product had a diffraction pattern similar to that shown in FIG. 2 described above, which matched the data for LiMn2O4 of ASTM No. 18-738.
この反応生成物を実施例１と同様な処理を施して正極を
製造し、この正極を用いて第１図と同構造のボタン型非
水溶媒二次電池を組立てた。This reaction product was treated in the same manner as in Example 1 to produce a positive electrode, and a button-type nonaqueous solvent secondary battery having the same structure as that shown in FIG. 1 was assembled using this positive electrode.
比較例１
硫酸マレガンを電解酸化して得られる電解二酸化マンガ
ンとＬｉ２ＣＯ３とをモル比率にてＭｎ：Ｌｊ−２：ｌ
にて混合・粉砕し、空気中８５０℃、１時間加熱焙焼し
、冷却した後、再び混合・粉砕し、再度空気中で８５０
℃、２時間加熱焙焼して得たリチウムマンガン酸化物（
ＬｉＭｎＯ，＋）を正極活物質として用いた以外、実施
例１と同様なボタン型非水溶媒二次電池を組立てた。Comparative Example 1 Electrolytic manganese dioxide obtained by electrolytically oxidizing maleganese sulfate and Li2CO3 in a molar ratio of Mn:Lj-2:l
Mixed and pulverized in the air, heated and roasted at 850°C for 1 hour, cooled, mixed and pulverized again, and roasted again in the air at 850°C.
Lithium manganese oxide obtained by heating and roasting at ℃ for 2 hours (
A button-type non-aqueous solvent secondary battery was assembled in the same manner as in Example 1 except that LiMnO, +) was used as the positive electrode active material.
比較例２
電解二酸化マンガンを６００℃で８時間０、加熱焙焼し
て得たＭｎ２Ｏ３とＬｉ ＯＨとをモル比率にてＭｎ
： Ｌｉ＝２ ：１にて混合・粉砕し、空気中５５０℃
、１時間加熱焙焼し、冷却した後、再び混合・粉砕し、
再度空気中で５５０℃、３時間加熱焙焼して得たリチウ
ムマンガン酸化物（ＬｉＭｎＯ４）を正極活物質として
用いた以外、実施例１と同様なボタン型非水溶媒二次電
池を組立てた。Comparative Example 2 Mn2O3 obtained by heating and roasting electrolytic manganese dioxide at 600°C for 8 hours and LiOH in a molar ratio
: Mixed and pulverized at Li=2:1 and heated to 550°C in air.
After heating and roasting for 1 hour, cooling, mixing and grinding again,
A button-type nonaqueous solvent secondary battery was assembled in the same manner as in Example 1, except that lithium manganese oxide (LiMnO4) obtained by heating and roasting in air at 550° C. for 3 hours was used as the positive electrode active material.
しかして、本実施例１．２及び比較例１．２の電池につ
いて、３．５Ｖ〜２．ＯＶの間にて０．５ｍＡの定電流
で充放電を繰返し、各サイクルにおける容量維持率をＡ
Ｉ定した結果、第３図に示す特性図を得た。なお、第３
図中のＡは本実施例１の電池における特性線、Ｂは本実
施例２の電池における特性線、Ｃは比較例１の電池にお
ける特性線、Ｄは比較例２の電池における特性線である
。Therefore, for the batteries of Example 1.2 and Comparative Example 1.2, the voltage was 3.5V to 2.5V. Charge and discharge are repeated at a constant current of 0.5 mA during OV, and the capacity retention rate in each cycle is A.
As a result of the determination, the characteristic diagram shown in FIG. 3 was obtained. In addition, the third
In the figure, A is the characteristic line of the battery of Example 1, B is the characteristic line of the battery of Example 2, C is the characteristic line of the battery of Comparative Example 1, and D is the characteristic line of the battery of Comparative Example 2. .
第３図から明らかなように、本実施例の非水溶媒二次電
池は比較例の電池に比べて充放電サイクルでの容量維持
率が極めて高いことがわかる。As is clear from FIG. 3, it can be seen that the non-aqueous solvent secondary battery of this example has an extremely high capacity retention rate during charge/discharge cycles compared to the battery of the comparative example.
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、ナトリウム、カリウム、カルシウム、マグネシウ
ム、アルミニウム等の他の軽金属を用いてもよい。Although lithium was used as the negative electrode active material in the above embodiments, other light metals such as sodium, potassium, calcium, magnesium, and aluminum may also be used.
上記実施例では電解液としてプロピレンカーボネートと
１．２−ジメトキシエタンの混合溶媒に過塩素酸リチウ
ムを溶解したものを用いたが、γ−ブチロラクトン、テ
トラヒドロフラン、ジオキソラン等の非水有機溶媒に過
塩素酸リチウム、ホウフッ化リチウム、塩化リチウム等
の電解質を０．２〜１．５モル／ｇ溶解せしめたものを
使用してもよい。In the above example, an electrolyte in which lithium perchlorate was dissolved in a mixed solvent of propylene carbonate and 1,2-dimethoxyethane was used. An electrolyte such as lithium, lithium borofluoride, lithium chloride, etc. dissolved in an amount of 0.2 to 1.5 mol/g may be used.
上記実施例では結着剤としてポリテトラフルオロエチレ
ンを用いたが、その他ポリアクリル酸、その塩類を用い
てもよい。In the above embodiment, polytetrafluoroethylene was used as the binder, but polyacrylic acid and its salts may also be used.
上記実施例では、ボタン型非水溶媒二次電池を例にして
説明したが、電極がスパイラル構造を有する円筒型非水
溶媒二次電池等にも同様に適用できる。Although the above embodiments have been described using a button-type non-aqueous solvent secondary battery as an example, the present invention can be similarly applied to a cylindrical-type non-aqueous solvent secondary battery whose electrodes have a spiral structure.
［発明の効果］
以上詳述した如く、本発明によればトンネル構造を有し
、非水溶媒二次電池に組込んだ後の充放電、つまりアル
カリ金属イオンの侵入・放出に伴う結晶構造の崩れの小
さいマンガンリチウム酸化物からなる正極活物質を製造
でき、ひいては該正極活物質を用いることにより充放電
サイクルでの容量劣化の少ない高寿命、高性能の非水溶
媒二次電池を得ることができる等顕著な効果を奏する。[Effects of the Invention] As detailed above, the present invention has a tunnel structure, and the crystal structure changes during charging and discharging after being incorporated into a non-aqueous solvent secondary battery, that is, due to the entry and release of alkali metal ions. It is possible to produce a positive electrode active material made of manganese lithium oxide that does not crumble easily, and by using this positive electrode active material, it is possible to obtain a long-life, high-performance non-aqueous solvent secondary battery with little capacity deterioration during charge/discharge cycles. It has remarkable effects such as:
第１図は本発明の一実施例を示すボタン型非水溶媒二次
電池の断面図、第２図は本実施例で製造されたリチウム
マンガン酸化物のＸ線回折パターンを示す線図、第３図
は本実施例１．２及び比較例１．２の電池における充放
電サイクル数に対する容量維持率を示す特性図である。
■・・・正極容器、３・・・正極、４・・・セパレータ
、５・・・負極、７・・・負極容器。
出願人代理人 弁理士 鈴江武彦
第１図
２ｅ（Ｆｅにα）
第２図
＠ｍｄＪ！剪＠＋−ドFIG. 1 is a cross-sectional view of a button-type non-aqueous solvent secondary battery showing an example of the present invention, FIG. 2 is a diagram showing an X-ray diffraction pattern of lithium manganese oxide produced in this example, and FIG. FIG. 3 is a characteristic diagram showing the capacity retention rate with respect to the number of charge/discharge cycles in the batteries of Example 1.2 and Comparative Example 1.2. ■... Positive electrode container, 3... Positive electrode, 4... Separator, 5... Negative electrode, 7... Negative electrode container. Applicant's agent Patent attorney Takehiko Suzue Figure 1 2e (α to Fe) Figure 2 @mdJ! Scissor @+-do
Claims (1)
Ｍｎ＿２Ｏ＿３）にリチウム化合物を添加して加熱焙焼
せしめることを特徴とする非水溶媒二次電池用正極活物
質の製造方法。Lower manganese oxide obtained by roasting manganese sulfate (
A method for producing a positive electrode active material for a non-aqueous solvent secondary battery, which comprises adding a lithium compound to Mn_2O_3) and heating and roasting the mixture.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63324595A JPH02170354A (en) | 1988-12-22 | 1988-12-22 | Manufacture of positive electrode active material for nonaqueous solvent secondary cell |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63324595A JPH02170354A (en) | 1988-12-22 | 1988-12-22 | Manufacture of positive electrode active material for nonaqueous solvent secondary cell |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH02170354A true JPH02170354A (en) | 1990-07-02 |
Family
ID=18167571
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63324595A Pending JPH02170354A (en) | 1988-12-22 | 1988-12-22 | Manufacture of positive electrode active material for nonaqueous solvent secondary cell |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH02170354A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04269468A (en) * | 1991-02-25 | 1992-09-25 | Japan Storage Battery Co Ltd | Lithium secondary battery |
| JP2001122626A (en) * | 1999-08-16 | 2001-05-08 | Nippon Chem Ind Co Ltd | Lithium-manganese multi-component oxide, method for manufacturing the same, lithium secondary battery positive electrode active material and lithium secondary battery |
-
1988
- 1988-12-22 JP JP63324595A patent/JPH02170354A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04269468A (en) * | 1991-02-25 | 1992-09-25 | Japan Storage Battery Co Ltd | Lithium secondary battery |
| JP2001122626A (en) * | 1999-08-16 | 2001-05-08 | Nippon Chem Ind Co Ltd | Lithium-manganese multi-component oxide, method for manufacturing the same, lithium secondary battery positive electrode active material and lithium secondary battery |
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