JPS63210028A - Method for synthesizing lithium manganese oxide solid solution - Google Patents
Method for synthesizing lithium manganese oxide solid solutionInfo
- Publication number
- JPS63210028A JPS63210028A JP62043550A JP4355087A JPS63210028A JP S63210028 A JPS63210028 A JP S63210028A JP 62043550 A JP62043550 A JP 62043550A JP 4355087 A JP4355087 A JP 4355087A JP S63210028 A JPS63210028 A JP S63210028A
- Authority
- JP
- Japan
- Prior art keywords
- oxide
- solid solution
- heating
- salt
- transition metal
- 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
- 239000006104 solid solution Substances 0.000 title claims description 34
- 229910002102 lithium manganese oxide Inorganic materials 0.000 title claims description 12
- VLXXBCXTUVRROQ-UHFFFAOYSA-N lithium;oxido-oxo-(oxomanganiooxy)manganese Chemical compound [Li+].[O-][Mn](=O)O[Mn]=O VLXXBCXTUVRROQ-UHFFFAOYSA-N 0.000 title claims description 12
- 238000000034 method Methods 0.000 title claims description 6
- 230000002194 synthesizing effect Effects 0.000 title claims description 5
- 239000011572 manganese Substances 0.000 claims abstract description 57
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 25
- 150000003624 transition metals Chemical class 0.000 claims abstract description 25
- 238000010438 heat treatment Methods 0.000 claims abstract description 18
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 15
- 150000003839 salts Chemical class 0.000 claims abstract description 15
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052760 oxygen Inorganic materials 0.000 claims description 19
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 16
- 239000001301 oxygen Substances 0.000 claims description 16
- 229910052748 manganese Inorganic materials 0.000 claims description 15
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 9
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 6
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 4
- 229910017052 cobalt Inorganic materials 0.000 claims 1
- 239000010941 cobalt Substances 0.000 claims 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims 1
- 239000000203 mixture Substances 0.000 abstract description 3
- 238000002156 mixing Methods 0.000 abstract description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 abstract 4
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 abstract 2
- 229910001947 lithium oxide Inorganic materials 0.000 abstract 2
- 229910044991 metal oxide Inorganic materials 0.000 abstract 2
- 239000007787 solid Substances 0.000 abstract 2
- 230000007704 transition Effects 0.000 abstract 2
- 239000013543 active substance Substances 0.000 abstract 1
- ZJRWDIJRKKXMNW-UHFFFAOYSA-N carbonic acid;cobalt Chemical compound [Co].OC(O)=O ZJRWDIJRKKXMNW-UHFFFAOYSA-N 0.000 abstract 1
- 229910000001 cobalt(II) carbonate Inorganic materials 0.000 abstract 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 abstract 1
- 229910052808 lithium carbonate Inorganic materials 0.000 abstract 1
- 229910003002 lithium salt Inorganic materials 0.000 abstract 1
- 239000011656 manganese carbonate Substances 0.000 abstract 1
- 235000006748 manganese carbonate Nutrition 0.000 abstract 1
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 abstract 1
- 230000015572 biosynthetic process Effects 0.000 description 14
- 238000003786 synthesis reaction Methods 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 10
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000007774 positive electrode material Substances 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 229910002091 carbon monoxide Inorganic materials 0.000 description 3
- 239000011651 chromium Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229910015645 LiMn Inorganic materials 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 229910015118 LiMO Inorganic materials 0.000 description 1
- 229910014689 LiMnO Inorganic materials 0.000 description 1
- 101100513612 Microdochium nivale MnCO gene Proteins 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000008240 homogeneous mixture Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 1
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- CFJRPNFOLVDFMJ-UHFFFAOYSA-N titanium disulfide Chemical compound S=[Ti]=S CFJRPNFOLVDFMJ-UHFFFAOYSA-N 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 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
-
- 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
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)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明はリチウムマンガン酸化物固溶体の合成法に関す
る。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method for synthesizing a lithium manganese oxide solid solution.
最近、Ｌ ｉ Ｍ ｎ Ｏｘ（リチウムマンガン酸化物
）などのＬｉＭＯバリチウム遷移金属酸化物）が高エネ
ルギー密度を期待できるリチウム電池の正極活物質とし
て注目を受けている。Recently, LiMO (barium transition metal oxides such as LiMnOx (lithium manganese oxide)) has been attracting attention as a positive electrode active material for lithium batteries that can be expected to have high energy density.
しかし、ＬｉＭｎ０．の場合は、供給する酸素の量を反
応に必要な量に限定しながら合成しなければならなかっ
た。これは、ＬｉＭｎ０．の場合、ＬｉＣｏ０．などと
は異なり、開放された酸化雰囲気で加熱すると、Ｍｎ（
マンガン）が容易に酸化されてＭｎ （■）になり、例
えばＬｉＭｎｚＯｎなどのＬＩＭＯ，と異なる結晶構造
になるため、供給する酸素量を限定してＭｎ （ＩＶ）
の生成を防止する必要があるからである。However, LiMn0. In this case, it was necessary to carry out the synthesis while limiting the amount of oxygen supplied to the amount necessary for the reaction. This is LiMn0. If LiCo0. When heated in an open oxidizing atmosphere, Mn (
Manganese) is easily oxidized to Mn (■), resulting in a crystal structure different from that of LIMO, such as LiMnzOn.
This is because it is necessary to prevent the generation of
そのような事情から、これまでは、ＬｉｚＯ□とＭｎＯ
を真空封管して、Ｌｉｇｈｔの熱分解によって生じるＯ
！のみによりＭｎ（ｎ）ＯをＭ ｎ （Ｉｌｌ）に酸化
してＬｉＭｎ０．を合成していた（Ｊ、Ａｍ、Ｃｈｅｍ
。Due to such circumstances, until now LizO□ and MnO
is vacuum-sealed, and the O produced by the thermal decomposition of Light is removed.
! Mn(n)O is oxidized to Mn(Ill) by only LiMn0. was synthesized (J, Am, Chem
.
Ｓｏｃ、、 ７８．３２５５（１９５６）） 。Soc, 78.3255 (1956)).
しかし、この方法は、真空封管のため、合成に手間がか
かり、またＬｉｇｈｔという過酸化物を用いるため危険
であるという問題があった。However, this method has problems in that it is time-consuming to synthesize because it uses a vacuum-sealed tube, and it is dangerous because it uses a peroxide called Light.
本発明は、従来、ＬｉＭｎ０１の合成に際して真空封管
により供給する酸素量を制限しなければならないという
制約を受けたり、また取扱いにおいても危険を伴ったと
いう事実に鑑み、例えばリチウム電池の正極活物質とし
て用いる場合にＬｉＭ ｎ Ｏｔよりもむしろ有用なリ
チウムマンガン酸化物固溶体を前述のような制約や危険
性を招くことなく合成することを目的とする。In view of the fact that conventionally, LiMn01 was synthesized using a vacuum-sealed tube to limit the amount of oxygen supplied, and the handling was also dangerous, the present invention was developed as a positive electrode active material for lithium batteries, for example. The object of the present invention is to synthesize a lithium manganese oxide solid solution that is more useful than LiM n Ot when used as a lithium manganese oxide without incurring the limitations and risks described above.
本発明は、マンガンの酸化物または加熱により酸化物に
なる塩と、マンガン以外の第一遷移金属の酸化物または
加熱により酸化物になる塩と、リチウムの酸化物または
加熱により酸化物になる塩とを混合し、酸素供給量を制
限しない開放された雰囲気で加熱することによって、リ
チウム電池用の正極活物質としてＬｉＭｎ０ｉよりもむ
しろ有用な、式（１）
％式％（１）
（式中、Ｍはマンガン以外の第一遷移金属であり、ｙは
０．１以上で１未満である）で示されるリチウムマンガ
ン酸化物固溶体を、供給する酸素量を制限することなく
得られるようにしたものである。The present invention provides an oxide of manganese or a salt that becomes an oxide when heated, an oxide of a first transition metal other than manganese or a salt that becomes an oxide when heated, and an oxide of lithium or a salt that becomes an oxide when heated. By mixing and heating in an open atmosphere that does not limit the amount of oxygen supply, the formula (1) % formula % (1) (wherein M is a first transition metal other than manganese, and y is 0.1 or more and less than 1), which can be obtained without limiting the amount of oxygen supplied. be.
上記式（りにおいてＭで示されるマンガン以外の第一遷
移金属としては、コバル１−（Ｃｏ）、ニッケル（Ｎｉ
）、チタン（Ｔｉ）、バナジウム（Ｖ）、クロム（Ｃｒ
）、鉄（Ｆ ｅ）などがあげられる。The first transition metals other than manganese represented by M in the above formula include cobal-1-(Co), nickel (Ni
), titanium (Ti), vanadium (V), chromium (Cr
), iron (Fe), etc.
本発明において、マンガンと、マンガン以外の第一遷移
金属Ｍと、リチウムとを、それぞれ酸化物または加熱に
より酸化物になる塩の状態で反応に供するが、上記加熱
により酸化物になる塩としては、例えば炭酸塩、酢酸塩
などがあげられる。In the present invention, manganese, the first transition metal M other than manganese, and lithium are subjected to the reaction in the form of an oxide or a salt that becomes an oxide upon heating, but the salt that becomes an oxide upon heating is Examples include carbonates and acetates.
特に炭酸塩の状態で反応に供すると、加熱により脱炭酸
し、その際に微粒子化するので、各反応成分の混合状態
がより一層均−になるので好ましい結果が得られる。な
お、酸化物としては、Ｍｎの場合はＭｎ０１Ｍ ｎ ！
Ｏｓ、Ｍｎ、Ｏ，などが用いられ、遷移金属Ｍの場合
はＭＯ１Ｍ２０１、Ｍ ｓ Ｏａなどが用いられ、Ｌｉ
の場合はＬｉ、Ｏなどが用いられる。Particularly, when the reaction is carried out in the form of a carbonate, it is decarboxylated by heating and is turned into fine particles at that time, so that the mixed state of each reaction component becomes even more uniform, so that favorable results can be obtained. In addition, in the case of Mn, as an oxide, Mn01M n!
Os, Mn, O, etc. are used, and in the case of transition metal M, MO1M201, M s Oa, etc. are used, and Li
In this case, Li, O, etc. are used.
反応は酸素供給量を制限しない開放された雰囲気で行わ
れるが、この酸素供給量を制限しない開放された雰囲気
は、たとえ大気中より酸素が希薄な雰囲気であってもよ
（、むしろ遷移金属Ｍの固溶化量が少なかったり、ある
いは反応温度が低い場合には、上記酸素が希薄な雰囲気
の方が大気中よりも目的とする固溶体をより安定して得
ることができるという特徴がある。The reaction takes place in an open atmosphere that does not limit the amount of oxygen supplied, but this open atmosphere that does not limit the amount of oxygen supplied may be an atmosphere where oxygen is rarer than in the atmosphere (in fact, transition metal M When the amount of solid solution is small or the reaction temperature is low, the above-mentioned oxygen-poor atmosphere has the characteristic that the desired solid solution can be obtained more stably than in the air.
本発明においては、Ｍｎと、Ｍｎ以外の第一遷移金属Ｍ
と、リチウムとを、それぞれ酸化物または加熱により酸
化物になる塩の状態で反応に供するが、このようにＭｎ
以外の第一遷移金属Ｍを含ませた３成分系で反応させる
ことにより、ＣＯなとのＭｎ以外の第一遷移金属ＭがＭ
ｎと固溶化することになって、酸素の供給量を限定しな
い酸素雰囲気中で加熱しても、通常の条件下では酸化さ
れやすいＭｎの価数があがらずＭ ｎ （［［［）の酸
化物が合成されるようになるものと考えられる。In the present invention, Mn and a first transition metal other than Mn
and lithium are subjected to the reaction in the form of an oxide or a salt that becomes an oxide upon heating, but in this way, Mn
By reacting in a three-component system containing a first transition metal M other than Mn, the first transition metal M other than Mn such as CO
Even when heated in an oxygen atmosphere where the amount of oxygen supplied is not limited, the valence of Mn, which is easily oxidized under normal conditions, does not increase. It is thought that things will be synthesized.
上記のようにＭｎが酸化されにくくなる理由は、現在の
ところ必ずしも明確ではないが、ＣＯなとの遷移金属Ｍ
がＭｎに固溶化することにより、Ｍｎや遷移金属Ｍが３
価の状態であるＬｉ（ＭｎＭ）０３の結晶構造が安定化
し、それによってＭｎも３価の状態でとどまるようにな
るからであると考えられる。The reason why Mn becomes difficult to oxidize as mentioned above is not necessarily clear at present, but transition metal Mn such as CO
By forming a solid solution in Mn, Mn and transition metal M become 3
This is thought to be because the crystal structure of Li(MnM)03 in a valent state is stabilized, and as a result, Mn also remains in a trivalent state.
本発明において、弐〇〇中、つまりＬｉ（Ｍｎ１−ｙＭ
ｙ）Ｏｘ中のｙの値を０．１以上で１未満（つまり、０
．１≦ｙ〈１）にするが、これはｙが０．１より小さい
と、Ｍｎと遷移金属Ｍとの固溶化が充分に生じず、した
がって、供給する酸素量を制限しない開放された酸素雰
囲気中では、ＬｉＭｎ０．はもとよりリチウムマンガン
酸化物固溶体が得られなくなるからである、そして、Ｌ
ｉ Ｍｏｗ（ＭはＣｏ。In the present invention, 200 medium, that is, Li (Mn1-yM
y) Set the value of y in Ox to 0.1 or more and less than 1 (that is, 0
．． 1≦y<1), but this is because if y is smaller than 0.1, solid solution formation of Mn and transition metal M will not occur sufficiently, so an open oxygen atmosphere that does not limit the amount of oxygen to be supplied is required. Among them, LiMn0. This is because it becomes impossible to obtain a lithium manganese oxide solid solution, and L
i Mow (M is Co.
ＮｉなどのＭｎ以外の第一遷移金属）を開放された酸素
雰囲気中で合成しうろことから、ｙは１未満であればそ
の上限値は存在しないと考えられるからである。This is because if y is less than 1, it is considered that there is no upper limit because y (first transition metals other than Mn such as Ni) may be synthesized in an open oxygen atmosphere.
本発明においては、前述のように、Ｍｎと、Ｍｎ以外の
第一遷移金属Ｍと、リチウムとを炭酸塩の状態で反応に
供することが好ましいが、この際、Ｍｎと遷移金属Ｍと
は前もって炭酸塩として共沈させることにより混合して
おくことが好ましい。In the present invention, as described above, it is preferable to subject Mn, the first transition metal M other than Mn, and lithium to the reaction in the carbonate state. It is preferable to mix them by co-precipitating them as carbonates.
これは共沈させることによって、Ｍｎの炭酸塩と遷移金
属Ｍの炭酸塩が均一に混合するからである。This is because the Mn carbonate and the transition metal M carbonate are uniformly mixed by coprecipitation.
なお、上記のように共沈させる場合、得られる炭酸塩は
、特に厳しく管理された条件下でないかぎり、塩基性炭
酸塩となりやすい、それ故、本発明において炭酸塩とは
、塩基性炭酸塩をも含む概念である。In addition, when co-precipitating as described above, the carbonate obtained tends to become a basic carbonate unless under particularly strictly controlled conditions. Therefore, in the present invention, carbonate refers to a basic carbonate. It is a concept that also includes
上記のようにＭｎと遷移金属Ｍとを水溶液中で炭酸塩と
して共沈させるには、例えばＭｎの水溶性塩（例えば、
Ｍｎの塩化物）と遷移金属Ｍの水溶性塩（例えば、遷移
金属Ｍの塩化物）を炭酸ガスを飽和した純水に溶解し、
この溶液に例えばＮａＨｃｏ、やｐＪａｚｃＯｓなどの
可溶性炭酸塩を加え、それらを反応させることによって
行われる。In order to coprecipitate Mn and the transition metal M as a carbonate in an aqueous solution as described above, for example, a water-soluble salt of Mn (e.g.
chloride of Mn) and a water-soluble salt of transition metal M (for example, chloride of transition metal M) are dissolved in pure water saturated with carbon dioxide gas,
This is carried out by adding soluble carbonates such as NaHco and pJazcOs to this solution and reacting them.
加熱温度としては、８００〜１２００℃を採用するのが
好ましいが、これは８００℃未満ではＭｎと遷移金属Ｍ
との固溶化が起こりにくく、一方、１２００°Ｃを超え
るとＬｉの揮発による損失が多くなって定量的な反応生
成物が得られにくくなるからである。It is preferable to adopt a heating temperature of 800 to 1200°C, but if it is lower than 800°C, Mn and transition metal M
On the other hand, if the temperature exceeds 1200°C, the loss due to Li volatilization increases, making it difficult to obtain a quantitative reaction product.
なお、Ｍｎに添加するＧｏなどの遷移金属Ｍの量が多く
なると、反応は上記範囲内での温度の低い側でも確実に
実施できるようになる。Note that when the amount of transition metal M such as Go added to Mn is increased, the reaction can be carried out reliably even at the lower temperature within the above range.
加熱後の冷却は、特に限定されるものではないが、急冷
による方が冷却の間での予定外の相分離（固溶化したも
のが分離する）が生じるおそれがないので好ましい。Cooling after heating is not particularly limited, but rapid cooling is preferable because there is no risk of unexpected phase separation (separation of solid solution) during cooling.
本発明においては、得られるリチウムマンガン酸化物固
溶体をＬ ｉ （Ｍ ｎ ｌ−ｙ Ｍ ｙ ） Ｏｚで
示したが、（Ｍｎｌ−ｙＭｙ）部分が若干過剰になりＬ
ｉに対して等量販上（通常５％以下の範囲で）になる場
合もあるし、また、酸素欠陥が生じて０３の部分が０２
−δ、ツまりＬ ｉ （Ｍ ｎ １−ｙ Ｍｙ ）０２
−δ（δ≦０．３）になることもあるが、本発明におけ
る式（１）で示されるリチウムマンガン酸化物固溶体は
それらの場合も含むものである。In the present invention, the obtained lithium manganese oxide solid solution is expressed as L i (Mnl-yMy) Oz, but the (Mnl-yMy) portion is slightly excessive and L
There are cases where the sales volume is equal to i (usually within a range of 5% or less), and oxygen defects occur and the 03 part becomes 02
−δ, Tsumari Li (M n 1-y My ) 02
-δ (δ≦0.3), and the lithium manganese oxide solid solution represented by formula (1) in the present invention includes such cases.
そして、本発明によって合成される式（１）で示される
リチウムマンガン酸化物固溶体は、リチウム電池の正極
活物質として用いた場合、電池電圧が３．９〜４．６
Ｖ （Ｌ ｉが０〜１の範囲で変動するので、それに伴
って電池電圧も変動する）と二硫化チタンや二硫化モリ
ブデンなどの硫化物系活物質を用いた電池（通常、電池
電圧が３ｖ以下）より高く、高エネルギー密度が期待で
きる。また、ＬｉＭｎＯｘよりも、例えばＬ ｉ（Ｍｎ
１−ｙ Ｃｏｙ）０：では充放電時の分極が少なく、充
放電時の電池電圧の変化が小さくなるので、正極活物質
としてむしろ有用である。このように分極が小さくなる
のは、Ｃｏが固溶化することにより、Ｌｉ＋イオンの拡
散が速くなるためであると考えられる。When the lithium manganese oxide solid solution represented by formula (1) synthesized according to the present invention is used as a positive electrode active material of a lithium battery, the battery voltage is 3.9 to 4.6.
V (as Li varies in the range of 0 to 1, the battery voltage also varies accordingly) and batteries using sulfide active materials such as titanium disulfide and molybdenum disulfide (usually, the battery voltage is 3 V). (below), and high energy density can be expected. In addition, for example, Li(Mn
1-y Coy)0: has little polarization during charging and discharging, and the change in battery voltage during charging and discharging is small, so it is rather useful as a positive electrode active material. The reason why the polarization becomes small in this way is considered to be because the diffusion of Li + ions becomes faster due to the formation of a solid solution of Co.
（実施例〕 つぎに実施例をあげて本発明をさらに詳細に説明する。(Example〕 Next, the present invention will be explained in more detail by giving examples.
実施例１
遷移金属としてＣｏを選び、Ｌｉ（ＭｎＣＯ）Ｏｘ固溶
体を合成した。ｃｏとＭｎとのモル比は１ｏ＝９０（つ
まり、Ｃｏ／Ｍｎ−１０／９０（モル比））である。Example 1 Co was selected as the transition metal, and a Li(MnCO)Ox solid solution was synthesized. The molar ratio of co and Mn is 1o=90 (that is, Co/Mn-10/90 (molar ratio)).
合成によって得られた固溶体を式（１）にしたがって表
示すると、Ｌ ｉ（Ｍｎｏ、ｑＣｏｏ、＋）Ｏｘである
。When the solid solution obtained by synthesis is expressed according to formula (1), it is Li(Mno, qCoo, +)Ox.
合成方法は次に示すとおりである。The synthesis method is as follows.
まず、ＭｎとＣｏとがＣｏ／Ｍｎ＝１０／９０（モル比
）になる割合でＭｎ Ｃｌ ・４ ＨｉＯとＣＯＣｌ！
・６Ｈ，０を炭酸ガスを飽和した純水に溶解し、濃度４
重量％のＮ ａ ＨＣＯｓ水溶液を加え、２時間放置し
て、ＭｎとＣｏを炭酸塩として共沈させて均一な混合物
とし、得られた沈澱物を濾過、水洗した後、アルゴン中
１４０℃で５日間乾燥した。First, Mn Cl 4 HiO and COCl! in a ratio of Mn and Co such that Co/Mn=10/90 (molar ratio).
・Dissolve 6H,0 in pure water saturated with carbon dioxide gas to a concentration of 4
Aqueous NaHCOs solution of % by weight was added and left to stand for 2 hours to co-precipitate Mn and Co as carbonates to form a homogeneous mixture.The resulting precipitate was filtered, washed with water, and incubated at 140°C in argon for 5 hours. Dry for days.
つぎに、上記ＭｎとＣｏとの共沈物とＬｉ、ＣＯ８とを
モル比１：１の割合で混合し、空気中（Ｎｇｌｏｘ−８
０／２０）、１２００℃で３時間加熱したのち、エア・
クエンチ（加熱したサンプルを２５℃の大気中に取り出
し急冷する方法）することによって合成を行った。加熱
にあたって試料を収容するのに使用したボートはＡｌｔ
ｏｓを主成分とするものである。また、合成温度のみを
１０００℃に変えて他は上記と同一条件下での合成も行
った。Next, the coprecipitate of Mn and Co, Li, and CO8 were mixed at a molar ratio of 1:1, and the mixture was mixed in the air (Nglox-8
0/20), after heating at 1200℃ for 3 hours,
Synthesis was performed by quenching (a method in which a heated sample is taken out into the atmosphere at 25° C. and rapidly cooled). The boat used to house the sample during heating was Alt.
The main component is os. Further, synthesis was also carried out under the same conditions as above except that only the synthesis temperature was changed to 1000°C.
さらに、上記ではＬｉｇＣＯｓを当量用いて合成を行っ
たが、加熱中におけるリチウムの揮発による損失を補う
ため、ＬｉｉＣＯ８を１．５倍等量仕込んだ合成も行っ
た。Further, in the above, synthesis was carried out using an equivalent amount of LigCOs, but in order to compensate for loss due to volatilization of lithium during heating, synthesis was also carried out using 1.5 times the equivalent amount of LiiCO8.
実施例２
Ｃｏ／Ｍｎ比を３０／７０ （モル比）とした以外は、
実施例１と同様にしてＬ Ｌ （Ｍｎ Ｃｏ）Ｏｘ固溶
体を合成した０合成された固溶体を式（りにしたがって
表示すると、Ｌ ｉ （Ｍｎｏ、ｔＣＯｏ、１）Ｏｘで
ある。Example 2 Except that the Co/Mn ratio was 30/70 (molar ratio),
A L L (Mn Co)Ox solid solution was synthesized in the same manner as in Example 1. The synthesized solid solution is represented by the formula (L i (Mno, tCOo, 1)Ox).
実施例３
Ｃｏ／Ｍｎ比を５０１５０ （モル比）とした以外は、
実施例１と同様にしてＬｉ（ＭｎＣｏ）Ｏ，固溶体を合
成した０合成された固溶体を式（１）にしたがって表示
すると、Ｌ ｉ （Ｍｎａ、ｓＣｏｏ、５）Ｏｘである
。Example 3 Except that the Co/Mn ratio was 50150 (molar ratio),
A Li(MnCo)O solid solution was synthesized in the same manner as in Example 1. When the synthesized solid solution is expressed according to formula (1), it is L i (Mna, sCoo, 5)Ox.
実施例４
Ｃｏ／Ｍｎ比をＴｏ／３０ （モル比）とした以外は、
実施例１と同様にしてＬｉ（ＭｎＣｏ）０！固溶体を合
成した０合成された固溶体を式（１）にしたがって表示
すると、Ｌ ｉ（Ｍｎｏ、５ＣＯｏ、ｙ）Ｏｔである。Example 4 Except that the Co/Mn ratio was To/30 (molar ratio),
In the same manner as in Example 1, Li(MnCo)0! 0 Synthesized solid solution When the synthesized solid solution is expressed according to formula (1), it is L i (Mno, 5COo, y)Ot.
実施例５
Ｃｏ／Ｍｎ比を８０／２０ （モル比）とした以外は、
実施例１と同様にしてＬｉ（ＭｎＣｏ）Ｏ，固溶体を合
成した０合成された固溶体を式（りにしたがって表示す
ると、Ｌ ｉ （Ｍｎｏ、ｉＣＯｏ、ｍ）Ｏｘである。Example 5 Except that the Co/Mn ratio was 80/20 (molar ratio),
A Li(MnCo)O solid solution was synthesized in the same manner as in Example 1. When the synthesized solid solution is expressed according to the formula (R), it is L i (Mno, iCOo, m)Ox.
比較例Ｉ
Ｃｏを固溶させずにＣｏ／Ｍｎ比を０／１００とした以
外は実施例１と同様にして合成を行った。Comparative Example I Synthesis was carried out in the same manner as in Example 1 except that Co was not dissolved in solid solution and the Co/Mn ratio was set to 0/100.
比較例２
Ｃｏを１００モル％とし、Ｃｏ／Ｍｎ比を１００１０と
した以外は実施例１と同様にして合成を行った。Comparative Example 2 Synthesis was carried out in the same manner as in Example 1 except that Co was 100 mol % and the Co/Mn ratio was 10010.
上記のように合成した実施例１〜５および比較例１〜２
の物質についてＸ線回折像を測定し、合成した物質の同
定を行った。測定は５０ｋＶ、１５０ｍＡ、、Ｃｕター
ゲットのＸ線源を用いて、４” ／ｓｉｎのスキャン速
度で２θ＝７〜１００°の範囲を測定することによって
行った。その結果を第１表に示す。Examples 1 to 5 and Comparative Examples 1 to 2 synthesized as above
The synthesized substance was identified by measuring the X-ray diffraction image of the substance. The measurements were carried out using an X-ray source of 50 kV, 150 mA, and a Cu target in the range of 2θ=7 to 100° at a scan rate of 4"/sin. The results are shown in Table 1.
第１表に示すように、Ｃｏを添加しなかった比較例１
（Ｃｏ ／Ｍ ｎ ＝Ｏ／１００）では、ＬｉＭｎ０．
なる物質は合成されず、ＬｉＭｎ、Ｏ，となり、Ｍｎは
高い価数まで酸化されていた。As shown in Table 1, Comparative Example 1 in which Co was not added
(Co /M n =O/100), LiMn0.
The substance was not synthesized and became LiMn, O, and Mn was oxidized to a high valence.
これに対し、Ｃｏを少量添加した実施例１（Ｃ。In contrast, Example 1 (C) in which a small amount of Co was added.
／ Ｍ ｎ −１０／９０）では、Ｌｉ（ＭｎＣｏ）Ｏ
ｓ固溶体となり、Ｍｎの価数は３価で高くならなかった
。/Mn-10/90), Li(MnCo)O
s solid solution, and the valence of Mn was trivalent and did not become high.
以上のような結果から判断すると、固溶化してＬＬ（Ｍ
ｎｌ−ｙ Ｃｏｙ）ＯｘとなるためのＣｏの下限量は、
Ｃｏ ／Ｍ ｎ−０／１００〜１０／９０の間であり、
少なくともＣｏ／Ｍｎを１０／９０（モル比）にしてお
けば、酸素雰囲気中でも、目的とする固溶体が得られる
と考えられる。Judging from the above results, LL(M
The lower limit amount of Co to become nl-y Coy)Ox is:
Co/M n- is between 0/100 and 10/90,
It is believed that by setting Co/Mn to at least 10/90 (molar ratio), the desired solid solution can be obtained even in an oxygen atmosphere.
Ｃｏの添加量を増加した実施例２〜５では、いずれもＬ
ｉ（Ｍｎ量１−ｙＣｏｙ）Ｏｔとなり、またＣＯを１０
０モル％にした比較例２でも、Ｌ ｉ Ｃ’ｏ Ｏｓが
得られたことから、Ｍｎが３価を保ち得るＣＯの添加量
の上限値は存在しないと考えられる。In Examples 2 to 5, in which the amount of Co added was increased, L
i (Mn amount 1-yCoy) Ot, and CO 10
Since L i C'o Os was obtained even in Comparative Example 2 where the concentration was 0 mol %, it is considered that there is no upper limit for the amount of CO added that can maintain the trivalence of Mn.
なお、上記第１表に示す結果は、Ｌｉ、ＣＯ，の仕込量
を多くして加熱中のＬｉの揮発による損失を補った時の
ものである。Ｌｉ１ＣＯｓを当量仕込んだ場合は、Ｃｏ
／Ｍｎ比５０１５０よりＭｎ量の多い実施例１．２．３
では、ＬｉＭｎ、０．がわずかながら生じた。これは加
熱中にＬｉが揮発してしまうためと考えられる。したが
って、安定してＬｉ（Ｍ ｎ １−ｙ Ｍｙ ）Ｏｘ系
の固溶体を得るには、Ｌｉ。The results shown in Table 1 above were obtained when the amounts of Li and CO were increased to compensate for the loss due to the volatilization of Li during heating. When an equivalent amount of Li1COs is charged, Co
Example 1.2.3 with higher Mn content than /Mn ratio 50150
Now, LiMn, 0. occurred to a small extent. This is considered to be because Li volatilizes during heating. Therefore, in order to stably obtain a Li(Mn1-yMy)Ox-based solid solution, Li.
ＣＯｓを等量より過剰に用いるのが好ましいといえる。It can be said that it is preferable to use COs in excess of the equivalent amount.
また、Ｌｉ、ＣＯ，が多くなっても反応上は特に弊害が
生じないと考えられる。Further, even if Li and CO are increased, it is thought that no particular adverse effects will occur in terms of the reaction.
また、合成温度の下限値は明らかでないが、ＣＯがＭｎ
より等量販上の実施例３〜５では、合成温度を８００°
Ｃに下げても安定してＬｉ（ＭｎＣｏ）０！固溶体を合
成することができた。Also, although the lower limit of the synthesis temperature is not clear, CO
In Examples 3 to 5, where the volume is more equivalent, the synthesis temperature was set to 800°.
Li(MnCo) remains stable even when lowered to C! We were able to synthesize a solid solution.
つぎに、六方晶系に属するＬｉ（ＭｎＣｏ）Ｏ□固溶体
の格子定数Ｃ６、ａｌｌをそれぞれ（００６）、（１１
０）面のピーク値より算出した。その結果を第１図に示
す、これに使用した試料は合成温度１２００℃で合成さ
れたものである。Next, the lattice constants C6 and all of the Li(MnCo)O□ solid solution belonging to the hexagonal system are (006) and (11
Calculated from the peak value of 0) plane. The results are shown in FIG. 1. The sample used was synthesized at a synthesis temperature of 1200°C.
第１図に示すように、Ｃｏ量の増加に伴ってＣ０、ａ、
はほぼ直線的に減少し、均一に固溶していく様子がわか
る。これは、Ｃｏ３＋のイオン半径がＭｎ３＋のイオン
半径に比べて０．０５人程小さいことから定量的に説明
できる。As shown in Fig. 1, as the amount of Co increases, C0, a,
It can be seen that the amount decreases almost linearly and becomes a uniform solid solution. This can be quantitatively explained because the ionic radius of Co3+ is smaller by about 0.05 people than the ionic radius of Mn3+.
以上、実施例では、第一遷移金属としてＣｏを用いて説
明したが、ＣＯに代えて、Ｔｉ、Ｖ、、Ｃｒ、Ｆｅ、Ｎ
ｉなどを用いてもよい。In the above examples, Co was used as the first transition metal, but instead of CO, Ti, V, Cr, Fe, N
i, etc. may also be used.
以上説明したように、本発明では、ＭｎにＣＯなどの第
一遷移金属を固溶化させることにより、供給する酸素量
を限定しない開放された酸素雰囲気中での反応によって
、Ｌ Ｌ （Ｍｎ １−ｙ Ｍｙ ）Ｏｘで示されるす
“チウムマンガン酸化物固溶体を容易に合成することが
できるようになった。これによって従来ＬｉＭｎ０ｚを
合成するにあたって真空封管により供給する酸素量の制
限をしなければならなかったり、あるいは危険を伴った
などの問題が解決され、リチウム電池の正極活物質とし
てＬｉ Ｍ ｎ Ｏ！よりもむしろ有用なＬｉＭｎＯｘ
類値化合物を容易に合成できるようになった。As explained above, in the present invention, L L (Mn 1- It has become possible to easily synthesize a lithium manganese oxide solid solution represented by y My )Ox.As a result, when synthesizing LiMn0z, it was necessary to limit the amount of oxygen supplied using a vacuum sealed tube. LiMnOx, which is more useful than LiMnO! as a positive electrode active material for lithium batteries, solves problems such as lack of or danger.
Similar compounds can now be easily synthesized.
第１図は本発明により合成したＬｉ（Ｍｎｌ−ｙＣｏ
ｙ）Ｏｘ系固溶体の格子定数ａｌｌ、ｃｌｌ値を示す図
である。Figure 1 shows Li (Mnl-yCo) synthesized according to the present invention.
y) A diagram showing the lattice constants all and cll values of an Ox-based solid solution.
Claims (3)
塩と、マンガン以外の第一遷移金属の酸化物または加熱
により酸化物になる塩と、リチウムの酸化物または加熱
により酸化物になる塩とを混合し、酸素供給量を制限し
ない開放された雰囲気で加熱して、式（Ｉ） Ｌｉ（Ｍｎ＿１＿−＿ｙＭ＿ｙ）Ｏ＿２（Ｉ）（式中、
Ｍはマンガン以外の第一遷移金属であり、ｙは０．１以
上で１未満である） で示されるリチウムマンガン酸化物固溶体を合成するこ
とを特徴とするリチウムマンガン酸化物固溶体の合成法
。(1) An oxide of manganese or a salt that becomes an oxide when heated, an oxide of a first transition metal other than manganese or a salt that becomes an oxide when heated, and an oxide of lithium or a salt that becomes an oxide when heated. are mixed and heated in an open atmosphere without restricting the amount of oxygen supplied to obtain the formula (I) Li(Mn_1_-_yM_y)O_2(I) (wherein,
M is a first transition metal other than manganese, and y is 0.1 or more and less than 1.
特許請求の範囲第１項記載のリチウムマンガン酸化物固
溶体の合成法。(2) The method for synthesizing a lithium manganese oxide solid solution according to claim 1, wherein the salt that becomes an oxide upon heating is a carbonate.
の範囲第１項または第２項記載のリチウムマンガン酸化
物固溶体の合成法。(3) The method for synthesizing a lithium manganese oxide solid solution according to claim 1 or 2, wherein M in formula (I) is cobalt.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62043550A JPH07112929B2 (en) | 1987-02-25 | 1987-02-25 | Synthesis method of lithium manganese oxide solid solution |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62043550A JPH07112929B2 (en) | 1987-02-25 | 1987-02-25 | Synthesis method of lithium manganese oxide solid solution |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63210028A true JPS63210028A (en) | 1988-08-31 |
| JPH07112929B2 JPH07112929B2 (en) | 1995-12-06 |
Family
ID=12666863
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0265061A (en) * | 1988-08-30 | 1990-03-05 | Sanyo Electric Co Ltd | Nonaqueous secondary battery |
| JPH02199770A (en) * | 1989-01-27 | 1990-08-08 | Fuji Elelctrochem Co Ltd | Nonaqueous electrolyte secondary battery |
| EP0421421A1 (en) * | 1989-10-06 | 1991-04-10 | Matsushita Electric Industrial Co., Ltd. | Non aqueous electrolyte secondary battery |
| JPH04267053A (en) * | 1991-02-21 | 1992-09-22 | Yuasa Corp | Lithium secondary battery |
| JPH04282561A (en) * | 1991-03-11 | 1992-10-07 | Matsushita Electric Ind Co Ltd | Nonaqueous electrolyte secondary battery |
| WO1994022767A1 (en) * | 1993-04-01 | 1994-10-13 | Fuji Chemical Industry Co., Ltd. | METHOD OF PRODUCTION OF LiM3+O2 OR LiMn2O4 AND LiNi3+O2 AS POSITIVE POLE MATERIAL OF SECONDARY CELL |
| JPH0837007A (en) * | 1994-05-16 | 1996-02-06 | Tosoh Corp | Lithium-containing transition metal composite oxide, and its manufacture and use |
| US5700442A (en) * | 1994-06-21 | 1997-12-23 | Commissariat A L'energie Atomique | Insertion compounds based on manganese oxide usable as the positive electrode active material in a lithium battery |
| WO2000030977A1 (en) * | 1998-11-20 | 2000-06-02 | Fmc Corporation | Multiple doped lithium manganese oxide compounds and methods of preparing same |
| JP2009514180A (en) * | 2005-11-15 | 2009-04-02 | ザ ジレット カンパニー | Primary lithium ion electrochemical cell |
-
1987
- 1987-02-25 JP JP62043550A patent/JPH07112929B2/en not_active Expired - Lifetime
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0265061A (en) * | 1988-08-30 | 1990-03-05 | Sanyo Electric Co Ltd | Nonaqueous secondary battery |
| JPH02199770A (en) * | 1989-01-27 | 1990-08-08 | Fuji Elelctrochem Co Ltd | Nonaqueous electrolyte secondary battery |
| EP0421421A1 (en) * | 1989-10-06 | 1991-04-10 | Matsushita Electric Industrial Co., Ltd. | Non aqueous electrolyte secondary battery |
| US5147738A (en) * | 1989-10-06 | 1992-09-15 | Matsushita Electric Industrial Co., Ltd. | Nonaqueous electrolyte secondary battery |
| JPH04267053A (en) * | 1991-02-21 | 1992-09-22 | Yuasa Corp | Lithium secondary battery |
| JPH04282561A (en) * | 1991-03-11 | 1992-10-07 | Matsushita Electric Ind Co Ltd | Nonaqueous electrolyte secondary battery |
| WO1994022767A1 (en) * | 1993-04-01 | 1994-10-13 | Fuji Chemical Industry Co., Ltd. | METHOD OF PRODUCTION OF LiM3+O2 OR LiMn2O4 AND LiNi3+O2 AS POSITIVE POLE MATERIAL OF SECONDARY CELL |
| US5648057A (en) * | 1993-04-01 | 1997-07-15 | Fuji Chemical Industry Co., Ltd. | Process for producing LiM3+ O2 or LiMn2 O4 and LiNi+ O2 for use in positive electrode of secondary battery |
| JPH0837007A (en) * | 1994-05-16 | 1996-02-06 | Tosoh Corp | Lithium-containing transition metal composite oxide, and its manufacture and use |
| US5700442A (en) * | 1994-06-21 | 1997-12-23 | Commissariat A L'energie Atomique | Insertion compounds based on manganese oxide usable as the positive electrode active material in a lithium battery |
| WO2000030977A1 (en) * | 1998-11-20 | 2000-06-02 | Fmc Corporation | Multiple doped lithium manganese oxide compounds and methods of preparing same |
| US6361756B1 (en) | 1998-11-20 | 2002-03-26 | Fmc Corporation | Doped lithium manganese oxide compounds and methods of preparing same |
| JP2009514180A (en) * | 2005-11-15 | 2009-04-02 | ザ ジレット カンパニー | Primary lithium ion electrochemical cell |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH07112929B2 (en) | 1995-12-06 |
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