CN1702043A - Preparation of spinel type Li-Mn-oxide lithium ion screening materials by hydrothermal method - Google Patents
Preparation of spinel type Li-Mn-oxide lithium ion screening materials by hydrothermal method Download PDFInfo
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- CN1702043A CN1702043A CN 200510018537 CN200510018537A CN1702043A CN 1702043 A CN1702043 A CN 1702043A CN 200510018537 CN200510018537 CN 200510018537 CN 200510018537 A CN200510018537 A CN 200510018537A CN 1702043 A CN1702043 A CN 1702043A
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Abstract
The invention relates to a hydrothermal production method of lithium ion bolting material of lithium-manganese oxide compound, which comprises the following steps: batching lithium oxidate and manganese oxidate with mole ratio of 0.5-3.0:1; delivering it to high-pressure hydrothermal autoclave after adequate mixing and grinding; adding distilled water to the mixture and processing it under 100-24 0 DEG C with 4-96h after full mixing; after filtering and rinshing to get colature of pH=7 to 8; drying it under 40-120 DEG C and processing preparatory roasting under 300 DEG C for 2h; roasting it under 300-800 DEG C in air atmosphere for 1-24h. The invention can get spinel structure lithium-manganese oxide of good crystal perfection, stable structure, and equal component. Said lithium-manganese oxide compound ionic screened material has the advantages of high selectivity and adsorption capacity when it is used to extract lithium resource from seawater and Salt Lake. The invention has the advantages of simple manufacturing process, mild conditioned response, cheap and available material and low cost of manufacture. Said lithium-manganese oxide compound can be used as electrode material of lithium ion secondary battery.
Description
Technical field
The present invention relates to a kind of method of utilizing Hydrothermal Preparation lithium ion screening material, particularly a kind of method of utilizing the Hydrothermal Preparation Li-Mn-oxide lithium ion screening materials.
Background technology
Lithium resource is the grand strategy resource.At aspects such as Energy conversion and aeronautical and space technologies great application prospect is arranged.In recent years, along with the development of lithium battery technology, the consumption of lithium is with the speed increment of annual 7-11%.According to statistics, world's gross annual output amount of lithium in 2003 in Quilonum Retard above 100,000 tons.And the total reserves of lithium is less in the ore of land, and the exploitation of a century on the process has been on the verge of exhaustion, can not satisfy industrial demand far away.Thereby the exploitation lithium resource has become inevitable from resourceful salt lake brine.The method of exploitation salt lake brine lithium resource mainly contains the precipitator method, solvent extration and ion sieve method at present.The precipitator method are main method of present industrial application, and complicated but this method is proposed the lithium technical process, alkali consumption is bigger, and environmental pollution is serious, along with society is more and more higher to environment requirement, with the development of more and more incompatible society; In addition, Mg/Li ratio is generally higher in China's salt lake brine, and the precipitator method are difficult to effectively separate magnesium salts and lithium salts, are not suitable for the salt lake brine of high Mg/Li ratio.Need bittern is concentrated during the solvent extration extraction, and organic solvent is poisonous and high volatility, thereby production cost is higher and contaminate environment, is difficult to be suitable for.In recent years, carry lithium and can directly from the seawater of lower concentration, extract lithium resource, utilize the ion sieve method from seawater and salt lake brine, to propose the attention that lithium causes people gradually along with the proposition of Green Chemistry notion and ion sieve method.Spinel lithium manganese oxide Li
xMn
2O
4The ion(ic)sieve selectivity is good, loading capacity is big, is a kind of " green " lithium ion sorbing material of excellent property, is expected to be used for extract lithium resource from salt lake brine, GEOTHERMAL WATER and lower concentration seawater; Simultaneously, spinel lithium manganese oxide Li
xMn
2O
4Still a kind of lithium secondary battery electrode material of excellent property is the focus of various countries' scholar's research.
At present, Li
xMn
2O
4Synthetic method mainly be divided into solid phase method and liquid phase method, liquid phase method comprises Sol-gel method, liquid-phase precipitation method and hydrothermal method etc.In solid phase method, generally be mixture with Quilonum Retard and Lithium Oxide 98min powder in air atmosphere 800 ℃～900 ℃ down heating obtain LiMn
2O
4Powder (D.G.Wickham W.J.Croft, J.phys.chem.solids, 1958,7:351).In this method, the long-range velocity of diffusion of reactant particle is slow, causes the inequality of product, is unfavorable for the normal growth of crystal grain, and the high temperature sintering phenomenon can hinder reaction and carry out.Thereby the product that conventional solid-state method obtains is often impure, pattern is irregular, particle diameter is inhomogeneous, loading capacity is little, cycle performance is poor, has limited it and has proposed application in lithium and the secondary cell at salt lake brine.U.S. Pat 5135732 utilizes the Sol-gel method to synthesize lithium manganese oxide, the oxyhydroxide of lithium and ammoniacal liquor and manganese acetate is made colloidal sol, and then be converted into gel, gets spinel lithium-manganese oxide through thermal treatment again.English Patent GB2276155 utilizes liquid-phase precipitation method to obtain spinel lithium manganese oxide, and it is reacted into the target throw out with Quilonum Retard and manganese acetate, be dried again spinel lithium manganese oxide.Though these prior aries can be controlled granularity, pattern, composition even the microtexture of product, its production technique is comparatively complicated, processing condition are comparatively harsh, is unfavorable for scale operation; And the raw materials used general metallorganics of costliness of price that all needs to use, production cost is higher.
Summary of the invention
The purpose of this invention is to provide a kind of method for preparing spinel type Li-Mn-oxide lithium ion screening materials, this method raw material be simple and easy to, reaction conditions gentleness and technological process be simple, the lithium manganese oxide of preparation has pure spinel structure, chemical constitution homogeneous, epigranular, the complete and excellent property of crystal formation growth, can be used for lithium ion screening material or anode material for lithium-ion batteries.
A kind of method for preparing Li-Mn-oxide lithium ion screening materials of the present invention is a hydrothermal method, the steps include:
1st, be that 0.5～3.0: 1 batching thorough mixing grinds with lithium source substance and manganese source substance by the lithium manganese of the lithium manganese oxide Bill that rubs;
2nd, the mixture after step 1 grinding is changed in the high-pressure hydrothermal reaction kettle, add distilled water and reach hydrothermal reaction kettle volumetrical 1/2～3/4, fully stir the back at 100～240 ℃ of hydrothermal treatment consists 4～96h;
3rd, after the product that step 2 is obtained is washed to filter worry fluid pH=7～8 after filtration, dry down at 40～120 ℃;
4th, with the dried sample of step 3 earlier at 300 ℃ of following preroasting 2h, 300～800 ℃ of following roasting 1～24h in air atmosphere then promptly obtain the lithium manganese oxide ion(ic)sieve material of normal spinel structure.
The used lithium source substance of the present invention is LiOH or its crystalline hydrate.Used manganese source substance is MnO
2, Mn
2O
3, Mn
3O
4, Mn (OH)
2, the mixture of one or more among γ-MnOOH.
Method starting material of the present invention be simple and easy to and cheap, preparation technology is simple, adopt hydrothermal treatment consists at first to obtain the uniform lithium manganese oxide intermediate of component, reduced maturing temperature, saved energy consumption, resulting product have pure spinel structure and form homogeneous, size distribution is even, be used for salt lake brine and carry lithium and have selectivity height, advantage that loading capacity is big.Simultaneously, the spinel lithium manganese oxide Li that makes with this method
xMn
2O
4Also can be used as the electrode materials of lithium secondary battery, have broad application prospects.
Description of drawings
Fig. 1 spinel type Li-Mn-oxide lithium ion screening materials synthesis flow of the present invention sketch
The XRD figure spectrum of Fig. 2 embodiment 1 products therefrom
The XRD figure spectrum of Fig. 3 embodiment 2 products therefroms
The XRD figure spectrum of Fig. 4 embodiment 3 products therefroms
The XRD figure spectrum of Fig. 5 embodiment 4 products therefroms
The XRD figure spectrum of Fig. 6 embodiment 5 products therefroms
The XRD figure spectrum of Fig. 7 embodiment 6 products therefroms
XRD figure in accompanying drawing spectrum is measured on the D/MAX-RB type X-ray analyzer that Japanese RIGAKU company produces, and measures power 3KW, Cuk α radiation, and 2 θ angles are 10 °～70 °, 0.02 °/step of step-length, per step 10s.
Specific embodiments
Embodiment 1: accurate weighing analytical pure (CMD) MnO2 8.6940g, analytical pure LiOHH
2O 4.1960g, the two mixes and to change in the 50mL hydrothermal reaction kettle after grind with agate under room temperature the back, adding distil water 25mL, seal hydrothermal reaction kettle behind the powerful stirring 5min, send into 160 ℃ of constant temperature oven insulation 48h, take out the naturally cooling after-filtration, be washed with distilled water to filtrate PH=8, the gained solid is sent in the High Temperature Furnaces Heating Apparatus preroasting 2h in 300 ℃ of following air atmospheres after 100 ℃ of following dryings, sample furnace cooling behind the roasting 12h in 600 ℃ of air atmospheres again, the products therefrom epigranular detects the LiMn of spinel structure on its characteristic diffraction peak (seeing accompanying drawing 2) and the JCPDS diffraction card through XRD
2O
4Characteristic diffraction peak in full accord and peak intensity is bigger, show that product is the lithium manganese oxide of pure spinel structure.The ion(ic)sieve performance of products therefrom after testing, its loading capacity is 5.04mmol/g, is 2.24 * 10 to the partition ratio of basic metal potassium, sodium
4With 8.84 * 10
3
Embodiment 2: accurate weighing analytical pure Mn
2O
37.8940g, analytical pure LiOHH
2O 5.0352g, the two mixing back with changing in the 50mL hydrothermal reaction kettle after the agate grinding, seals hydrothermal reaction kettle behind the powerful stirring of the adding distil water 30mL 5min under room temperature, send into 140 ℃ of perseverances 3 then
Temperature baking oven insulation 72h, take out the naturally cooling after-filtration, be washed with distilled water to filtrate PH=7.5, the gained solid is sent in the High Temperature Furnaces Heating Apparatus preroasting 2h in 300 ℃ of following air atmospheres after 105 ℃ of following dryings, sample furnace cooling behind the roasting 12h in 700 ℃ of air atmospheres again, the products therefrom epigranular detects the LiMn of spinel structure on characteristic diffraction peak (seeing accompanying drawing 3) and the JCPDS diffraction card through XRD
2O
4Characteristic diffraction peak in full accord and peak intensity is bigger, show that product is the lithium manganese oxide of pure spinel structure.The ion(ic)sieve performance of products therefrom after testing, its loading capacity is 4.95mmol/g, is 1.28 * 10 to the partition ratio of basic metal potassium, sodium
4With 4.54 * 10
3
Embodiment 3: accurate weighing analytical pure γ-MnOOH 8.7940g, analytical pure LiOHH
2O 12.5880g, the two mixes and to change in the 100mL hydrothermal reaction kettle after grind with agate under room temperature the back, adding distil water 60mL, seal hydrothermal reaction kettle behind the powerful stirring 5min, send into 120 ℃ of constant temperature oven insulation 24h, take out the naturally cooling after-filtration, be washed with distilled water to filtrate PH=8, the gained solid is sent in the High Temperature Furnaces Heating Apparatus preroasting 2h in 300 ℃ of following air atmospheres after 80 ℃ of following dryings, sample furnace cooling behind the roasting 8h in 500 ℃ of air atmospheres again, the products therefrom epigranular detects the LiMn of spinel structure on characteristic diffraction peak (seeing accompanying drawing 4) and the JCPDS diffraction card through XRD
2O
4Characteristic diffraction peak in full accord and peak intensity is bigger, peak width is narrower, shows that product is the lithium manganese oxide of pure spinel structure.The ion(ic)sieve performance of products therefrom after testing, its loading capacity is 5.14mmol/g, and the partition ratio of basic metal potassium, sodium is respectively 1.47 * 10
4With 8.26 * 10
3
Embodiment 4: accurate weighing analytical pure Mn (OH)
214.9900g, analytical pure LiOHH
2O 4.1960g, the two mixes to change in the 100mL hydrothermal reaction kettle adding distil water 50mL over to after grind with agate the back under room temperature, seal hydrothermal reaction kettle behind the powerful stirring 5min, send into 240 ℃ of constant temperature oven insulation 4h, take out the naturally cooling after-filtration, be washed with distilled water to
Filtrate PH=8, the gained solid is sent in the High Temperature Furnaces Heating Apparatus preroasting 2h in 300 ℃ of following air atmospheres after 50 ℃ of following dryings, sample furnace cooling behind the roasting 24h in 300 ℃ of air atmospheres again, the products therefrom epigranular, detect the LiMn of spinel structure on characteristic diffraction peak (seeing accompanying drawing 5) and the JCPDS diffraction card through XRD
2O
4The characteristic diffraction peak unanimity, show that product is the lithium manganese oxide of pure spinel structure.The ion(ic)sieve performance of products therefrom after testing, its loading capacity is 4.12mmol/g, and the partition ratio of basic metal potassium, sodium is respectively 8.44 * 10
3With 2.35 * 10
3
Embodiment 5: accurate weighing analytical pure (CMD) MnO
210.8675g, analytical pure LiOHH
2O 4.1960g, the two mixes and to change in the 50mL hydrothermal reaction kettle after grind with agate under room temperature the back, 4 adding distil water 25mL, seal hydrothermal reaction kettle behind the powerful stirring 5min, send into 100 ℃ of constant temperature oven insulation 96h, take out the naturally cooling after-filtration, be washed with distilled water to filtrate PH=8, the gained solid is sent in the High Temperature Furnaces Heating Apparatus preroasting 2h in 300 ℃ of following air atmospheres after 80 ℃ of following dryings, sample furnace cooling behind the roasting 1h in 800 ℃ of air atmospheres again, the products therefrom epigranular detects the LiMn of spinel structure on characteristic diffraction peak (seeing accompanying drawing 6) and the JCPDS diffraction card through XRD
2O
4Characteristic diffraction peak unanimity and peak intensity bigger, show that product is the lithium manganese oxide of spinel structure.The ion(ic)sieve performance of products therefrom after testing, its loading capacity is 4.50mmol/g, and the partition ratio of basic metal potassium, sodium is respectively 5.46 * 10
3With 1.95 * 10
3
Embodiment 6: accurate weighing analytical pure Mn
3O
412.7122g, analytical pure LiOHH
2O 8.3920g, the two mixes and to change in the 100mL hydrothermal reaction kettle after grind with agate under room temperature the back, adding distil water 50mL, seal hydrothermal reaction kettle behind the powerful stirring 5min, send into 120 ℃ of constant temperature oven insulation 72h, take out the naturally cooling after-filtration, be washed with distilled water to filtrate PH=8, the gained solid is sent in the High Temperature Furnaces Heating Apparatus preroasting 2h in 300 ℃ of following air atmospheres after 80 ℃ of following dryings, sample furnace cooling behind the roasting 4h in 600 ℃ of air atmospheres again, the products therefrom epigranular detects the LiMn of spinel structure on characteristic diffraction peak (being good at accompanying drawing 7) and the JCPDS diffraction card through XRD
2O
4The characteristic diffraction peak unanimity, show that product is the lithium manganese oxide of point product stone structure.The ion(ic)sieve performance of products therefrom after testing, its loading capacity is 4.34mmol/g, and the partition ratio of basic metal potassium, sodium is respectively 1.02 * 10
4With 4.11 * 10
3
Claims (3)
1, a kind of method for preparing Li-Mn-oxide lithium ion screening materials is characterized in that hydrothermal method, the steps include:
1st, be that 0.5～3.0: 1 batching thorough mixing grinds with lithium source substance and manganese source substance by the lithium manganese of the lithium manganese oxide Bill that rubs;
2nd, the mixture after step 1 grinding is changed in the high-pressure hydrothermal reaction kettle, add distilled water and reach hydrothermal reaction kettle volumetrical 1/2～3/4, fully stir the back at 100～240 ℃ of hydrothermal treatment consists 4～96h;
3rd, after the product that step 2 is obtained is washed to filter worry fluid pH=7～8 after filtration, dry down at 40～120 ℃
4th, with the dried sample of step 3 earlier at 300 ℃ of following preroasting 2h, 300～800 ℃ of following roasting 1～24h in air atmosphere then promptly obtain the lithium manganese oxide ion(ic)sieve material of normal spinel structure.
2. the method for claim 1 is characterized in that used lithium source substance is LiOH or its crystalline hydrate.
3. the method for claim 1 is characterized in that used manganese source substance is MnO
2, Mn
2O
3, Mn
3O
4, Mn (OH)
2, the mixture of one or more among γ-MnOOH.
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| CN112216894B (en) * | 2020-10-15 | 2021-11-19 | 天齐锂业（江苏）有限公司 | Preparation method and recovery method of lithium ion sieve composite material |
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| CN113332950B (en) * | 2021-08-05 | 2021-10-15 | 苏州锦艺新材料科技有限公司 | Preparation method of lithium ion adsorbent and adsorbent precursor |
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| WO2023184656A1 (en) * | 2022-03-28 | 2023-10-05 | 贵州大龙汇成新材料有限公司 | Trimanganese tetraoxide lithium pre-embedded intermediate, preparation method therefor and use thereof |
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