CN1333179A - Wet chemical synthesizing method for lithium-manganese oxide - Google Patents
Wet chemical synthesizing method for lithium-manganese oxide Download PDFInfo
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- CN1333179A CN1333179A CN 00113534 CN00113534A CN1333179A CN 1333179 A CN1333179 A CN 1333179A CN 00113534 CN00113534 CN 00113534 CN 00113534 A CN00113534 A CN 00113534A CN 1333179 A CN1333179 A CN 1333179A
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- lithium
- manganese oxide
- lithium manganese
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Abstract
The wet chemical synthesis method of lithium-manganese oxide belongs to the field of inorganic non-metallic material and wet clemistry, and is characterized by that the manganese hydroxide is used as raw material in aqueous solution, in the presence of excess lithium compound the oxidant is added so as to insert lithium into crystal lattice of manganese oxide to synthesize intermediate state Li1 plus or minus XMn2O4, then making high-temp. treatment so as to obtain the invented spinelle type Li1 plus or minusXMn2O4 with complete crystal form, stable structure and uniform component. Said invention is simple in production process, low in cost, can control technological parameters to prepare Li1 plus or minusXMn2O4 with different lithium content, uniform chemical component and phase component and excellent chemical properties.
Description
The present invention relates to a kind of wet chemical synthesis of lithium manganese oxide.
Lithium manganese oxide is a kind of aboundresources, environmental friendliness, and the anode material for lithium-ion batteries with very big potential advantages.Its preparation method is divided into high temperature solid phase synthesis and wet-chemical synthesis method.High temperature solid phase synthesis is a raw material with Quilonum Retard and electrolytic manganese dioxide, fire through the solid-phase grinding mixing-high temperature (500～900 ℃) of repeated multiple times and to form, slow in more loaded down with trivial details and its preparation process of flow process because of solid phase diffusion speed, batch mixing is difficult to evenly, products therefrom exists at aspects such as structure, composition, size-grade distribution than big difference, thereby cause its chemical property wayward, capacity is lower.The wet-chemical synthesis method is produced lithium manganese oxide and is had special advantages, and the mixing of lithium, manganese can be carried out on molecule and atom level level, the product of the uniform component that is easy to get, and its initial cycle capacity and reversible cycle capacity are higher relatively.The wet-chemical synthesis method mainly comprises sol-gel method and hydrothermal method etc.Sol-gel method is reducing synthesis temperature, when shortening the reaction times, has improved the phase purity of synthetic product, and stoichiometric relation can be controlled preferably, but its flow process is longer, operate more loaded down with trivial detailsly, and needs the expensive organic reagent of consumption; Hydrothermal method is with MnO
2Be raw material, earlier with MnO
2Thermolysis becomes MnO
3Again with LiOHH
2O carries out hydro-thermal reaction, synthetic stratiform LiMnO
2, contain Li
2MnO
3Deng dephasign, phase purity is not high enough.
The objective of the invention is to provides a kind of new wet chemical synthesis for the preparation of anode material for lithium-ion batteries-lithium manganese oxide, controls the chemical ingredients and the phase composition of lithium manganese oxide effectively, improves its homogeneity, improves its chemical property; Meanwhile, reduce reagent cost, simplify low temperature wet and learn synthesis technique.
The present invention is a raw material with the manganous hydroxide in the aqueous solution, under the condition that has excessive lithium compound to exist, adds oxygenant, utilizes the changeable characteristic of manganese valence state, shows off Mn (OH)
2In Mn
2+Oxidation also has when the cenotype generation, and Li is embedded in the lattice of Mn oxide, and one-step synthesis lithium manganese oxide intermediate makes complete in crystal formation, constitutionally stable lithium manganese oxide (Li through thermal treatment again
1 ± xMn
2O
4).
Main processes of the present invention and parameter are as follows:
1. low-temperature mixed oxidation
At Mn (OH)
2Add excessive lithium compound or mixture (with solid or aqueous solution form) and the oxygenant (with gas or solid or aqueous solution form) of lithium compound and KOH, NaOH in the suspension, at 10～95 ℃, under stirring velocity 200～700rpm, reaction 0.5～12h, filter and with drying after pure water or ethanol or the methanol wash, make chemical ingredients evenly, the Li/Mn atomic ratio is between 0.4～0.7 Li
1 ± xMn
2O
4Intermediate.Above-mentioned lithium compound is meant any or multiple mixture in Quilonum Retard, lithium chloride, lithium hydroxide, the lithium acetate etc.Above-mentioned oxygenant is meant one or more the mixture in Potcrate, potassium hypochlorite, potassium permanganate, hydrogen peroxide, oxygen, the air etc.
2. high-temperature heat treatment
The lithium manganese oxide intermediate that step 1 is made is contained in corundum crucible and is placed retort furnace or tube furnace, under air atmosphere, fires 3～15h under 200～850 ℃, makes that crystalline structure is complete, phase composition and the uniform spinel type Li of chemical ingredients
1 ± xMn
2O
4
Characteristics of the present invention are: 1. the lithium-inserting amount of synthetic product can be controlled flexibly by the adjustment of processing parameter; 2. the chemical constitution of synthetic product, phase composition and even particle size distribution and be easy to control; 3. required reagent is cheap and easy to get, and cost is low; 4. the preparation method is simple, and technical process is short, and operation is easy to control, easily realizes industrialization.
Description of drawings:
Fig. 1: process flow diagram of the present invention.
Embodiment 1:Mn (OH)
216g, water 80ml is in 50 ℃ of following and 18gLiOHH
2After O mixes, add 120ml H
2O
2(30%wt.), stirring reaction 2h filters, washs and oven dry, gets the lithium manganese oxide intermediate and contains Li 3.78%, and Mn56.92%, Li/Mn atomic ratio are 0.53.This lithium manganese oxide intermediate is warming up to 300 ℃ of constant temperature with the speed of 2 ℃/min and fires 15h in air atmosphere, cooling then, and products therefrom is analyzed its thing through X-ray diffraction and is coordinated and be divided into spinel type LiMn
2O
4, crystalline structure is complete.
Embodiment 2:Mn (OH)
28.9g water 100ml after the LiCl solution 100ml of 2mol/l mixes, adds KMnO
4Solution 50ml (contains 7.5gKMnO
4), in 70 ℃ of following stirring reaction 0.5h, filter, wash and oven dry, get the lithium manganese oxide intermediate and contain Li 3.53%, Mn60.26%, Li/Mn atomic ratio are 0.46.This lithium manganese oxide intermediate is warming up to 700 ℃ of constant temperature with the speed of 5 ℃/min and fires 3h in air atmosphere, cooling then, and products therefrom is analyzed its thing through X-ray diffraction and is coordinated and be divided into spinel type LiMn
2O
4, crystalline structure is complete.
Embodiment 3:Mn (OH)
2130g, water 1000ml, adding 100g LiAc under 95 ℃, logical dioxygen oxidation 12h filters, washs also and dry, and gets the lithium manganese oxide intermediate and contains Li 4.81%, and Mn57.42%, Li/Mn atomic ratio are 0.66.This lithium manganese oxide intermediate is warming up to 500 ℃ of constant temperature with the speed of 3 ℃/min and fires 8h in air atmosphere, cooling then, and products therefrom is analyzed its thing through X-ray diffraction and is coordinated and be divided into spinel type LiMn
2O
4, crystalline structure is complete.
Embodiment 4:Mn (OH)
28g, water 100ml adds 15gLi successively under 70 ℃
2CO, and 5gKClO
3, blowing air oxidation 12h filters, washs and oven dry, gets the lithium manganese oxide intermediate and contains Li 3.58%, and Mn57.98%, Li/Mn atomic ratio are 0.49.This lithium manganese oxide intermediate is warming up to 850 ℃ of constant temperature with the speed of 10 ℃/min and fires 12h in air atmosphere, cooling then, and products therefrom is analyzed its thing through X-ray diffraction and is coordinated and be divided into spinel type LiMn
2O
4, crystalline structure is complete.
Embodiment 5:Mn (OH)
232g, water 200ml adds 30gLiClH
2Behind the mixing solutions 300ml that O and 20gKOH are made into, add 250mlH down in 70 ℃
2O
2(30%wt), behind the stirring reaction 1.5h, filter, wash and oven dry, get the lithium manganese oxide intermediate and contain Li 3.86%, Mn56.48%, Li/Mn atomic ratio are 0.54.This lithium manganese oxide intermediate is warming up to 200 ℃ of constant temperature with the speed of 2 ℃/min and fires 5h in air atmosphere, cooling then, and products therefrom is analyzed its thing through X-ray diffraction and is coordinated and be divided into spinel type LiMn
2O
4, crystalline structure is complete.
Claims (4)
1. wet chemical method for preparing lithium manganese oxide, it is characterized in that: with the manganous hydroxide is raw material, when in the aqueous solution, having lithium compound to exist, with oxygenant with Mn (OH)
2Oxidation one-step synthesis lithium manganese oxide intermediate prepares spinel lithium manganese oxide through high-temperature heat treatment again,
A〉reaction conditions of synthetic lithium manganese oxide intermediate is: the lithium compound consumption is 1～12 times of theoretical amount, the oxygenant consumption is 1～15 times of theoretical amount, and solid-to-liquid ratio is 1: 5～20, and temperature is 10～95 ℃, stirring velocity is 200～700rpm, and the reaction times is 0.5～12h;
B〉the heat treated condition of lithium manganese oxide intermediate is: in air atmosphere, the control temperature increasing schedule is 2～10 ℃/min, and thermostat temperature is 200～850 ℃, constant temperature time 3～15h.
2. method according to claim 1 is characterized in that: described manganous hydroxide raw material comprises that with manganous salt and manganese metal be the manganous hydroxide that reactant was generated.
3. method according to claim 1 is characterized in that: described lithium compound is a lithium chloride, lithium hydroxide, Quilonum Retard, lithium acetate, the mixture of one or more in the lithium nitrate.
4. method according to claim 1 is characterized in that: described oxygenant is a Potcrate, potassium hypochlorite, potassium permanganate, hydrogen peroxide, oxygen, airborne one or more mixture.
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| Application Number | Priority Date | Filing Date | Title |
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| CNB001135341A CN1167609C (en) | 2000-07-11 | 2000-07-11 | Wet chemical synthesizing method for lithium-manganese oxide |
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| CN1167609C CN1167609C (en) | 2004-09-22 |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1297487C (en) * | 2002-04-11 | 2007-01-31 | 日矿马铁利亚股份有限公司 | Lithium-containing complex oxide and its producing method |
| CN1330579C (en) * | 2005-04-12 | 2007-08-08 | 武汉理工大学 | Preparation of spinel type Li-Mn-oxide lithium ion screening materials by hydrothermal method |
| CN100391855C (en) * | 2005-07-08 | 2008-06-04 | 中南大学 | Method for preparing manganiferous oxide |
| CN101807686A (en) * | 2010-03-30 | 2010-08-18 | 兰州金里能源科技有限公司 | Preparation method of spinel type lithium manganate with high crystallinity used in lithium ion battery |
| CN102275994A (en) * | 2011-05-24 | 2011-12-14 | 南昌航空大学 | Oxidation-activation method for regeneration and reuse of manganese oxide waste residue in organic synthesis |
| CN104966832A (en) * | 2015-06-02 | 2015-10-07 | 中国科学院青海盐湖研究所 | Method for electrochemical-chemical reaction preparation of metal oxide or multi-metal oxide electrode material |
| CN105567325A (en) * | 2014-10-11 | 2016-05-11 | 中国科学院大连化学物理研究所 | Spinel compound-carbonate mixture system for solar energy photo-thermal chemical conversion, preparation and application thereof |
| CN110898794A (en) * | 2019-12-13 | 2020-03-24 | 中国科学院青海盐湖研究所 | Preparation method of lithium ion sieve |
-
2000
- 2000-07-11 CN CNB001135341A patent/CN1167609C/en not_active Expired - Fee Related
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1297487C (en) * | 2002-04-11 | 2007-01-31 | 日矿马铁利亚股份有限公司 | Lithium-containing complex oxide and its producing method |
| CN1330579C (en) * | 2005-04-12 | 2007-08-08 | 武汉理工大学 | Preparation of spinel type Li-Mn-oxide lithium ion screening materials by hydrothermal method |
| CN100391855C (en) * | 2005-07-08 | 2008-06-04 | 中南大学 | Method for preparing manganiferous oxide |
| CN101807686A (en) * | 2010-03-30 | 2010-08-18 | 兰州金里能源科技有限公司 | Preparation method of spinel type lithium manganate with high crystallinity used in lithium ion battery |
| CN102275994A (en) * | 2011-05-24 | 2011-12-14 | 南昌航空大学 | Oxidation-activation method for regeneration and reuse of manganese oxide waste residue in organic synthesis |
| CN102275994B (en) * | 2011-05-24 | 2013-04-10 | 南昌航空大学 | Oxidation-activation method for regeneration and reuse of manganese oxide waste residue in organic synthesis |
| CN105567325A (en) * | 2014-10-11 | 2016-05-11 | 中国科学院大连化学物理研究所 | Spinel compound-carbonate mixture system for solar energy photo-thermal chemical conversion, preparation and application thereof |
| CN105567325B (en) * | 2014-10-11 | 2018-09-21 | 中国科学院大连化学物理研究所 | It is a kind of for the catalytic removal of nox of solar energy thermochemical study and the mixture system of carbonate and its preparation and application |
| CN104966832A (en) * | 2015-06-02 | 2015-10-07 | 中国科学院青海盐湖研究所 | Method for electrochemical-chemical reaction preparation of metal oxide or multi-metal oxide electrode material |
| CN110898794A (en) * | 2019-12-13 | 2020-03-24 | 中国科学院青海盐湖研究所 | Preparation method of lithium ion sieve |
| CN110898794B (en) * | 2019-12-13 | 2023-02-07 | 中国科学院青海盐湖研究所 | Preparation method of lithium ion sieve |
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