CN103682301A - Preparation method of nanometer lithium titanate covered with double highly-conductive materials - Google Patents
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Abstract
The invention provides a preparation method of nanometer lithium titanate covered with double highly-conductive materials. Through a sol-gel method, a La[0.5]Sr[0.5]Sc[0.1]Mn[0.9]O3/C-Li4Ti5O12 anode material is prepared by a step of blending a soluble Li compound and a soluble Ti compound according to a molar ratio of Li/Ti=0.8-1.0, adding into an alcohol-water mixed solvent containing a hydrolysis inhibitor, adding a bi-component chelating agent, subjecting the bi-component chelating agent and metal ions to chelation under alkaline conditions, and stirring and heating to form gel; a step of dissolving a La compound, a Sr compound, a Sc compound and a Mn compound into an alcohol-water mixed solvent according to a molar ratio of La: Sr: Sc: Mn=0.5:0.5:0.1:0.9, adding the bi-component chelating agent, subjecting the bi-component chelating agent and metal ions to chelation under alkaline conditions, and stirring to form sol; a step of mixing the gel and the sol and stirring to form co-gel to obtain a sintering precursor; and a step of ball milling and calcining at 900-1150 DEG C for 5-15 h. The lithium titanate prepared by the method has good dispersion effects and excellent electrochemical performance, and the agglomeration phenomenon of nano-powder is improved significantly.
Description
Technical field
The present invention relates to a kind of preparation method of lithium ion secondary battery cathode material lithium titanate, particularly a kind of method with the coated lithium titanate of the two high conductive materials of sol-gal process preparation.
Background technology
Lithium rechargeable battery has been widely used in the fields such as mobile communication, notebook computer, video camera, camera, portable instrument as high-energy-density chemical power source, develop rapidly and become one of current most important secondary cell.Lithium ion battery gains great popularity because of advantages such as its voltage are high, energy density is high, have extended cycle life, environmental pollution is little.At present, business-like lithium ion battery negative material great majority adopt carbon negative pole material, but there are some defects in carbon negative pole material: first in discharge process with the electrolyte formation surface passivated membrane that reacts, cause the consumption of electrolyte and coulomb efficiency is lower first; The electrode potential of carbon electrode and lithium metal is close, when battery overcharge, still may and form dendrite, cause short circuit at carbon electrodes precipitating metal lithium, causes safety problem etc.Find novel ion cathode material lithium and become the focus of research.
Commercial ion cathode material lithium adopts various embedding lithium material with carbon elements mostly.There are some shortcomings in material with carbon element: has Li dendrite; First charge-discharge efficiency is lower; Have an effect and form solid electrolyte interface film with electrolyte; There is obvious voltage delay effect; Preparation method is relatively also more complicated.Compare with carbon negative pole material, alloy type negative material generally has higher specific capacity, but cycle performance is poor, and alloy type negative material has also solved the safety issue of part; Recently, spinel type lithium titanate, as a kind of novel negative material, has " zero strain ", and good cycle has good charge and discharge platform, do not react with electrolyte, and low price, the easy advantage such as preparation, becomes the focus of research gradually.But, Li
4ti
5o
12conductivity very low, be close to insulation, the poor-performing under high magnification, will be subject to great restriction if be applied to the fields such as power car, large-scale energy-storage battery.Thereby, for Li
4ti
5o
12the shortcoming of material poorly conductive, the research that improves its conductivity and high rate capability seems particularly important.At present, the simplest method is by its nanometer, reaches and shortens Li
+the evolving path, reduce Li
+diffusional resistance, slow down the object of electrode polarization, with this, tentatively promote electrode performance.This patent, by improving, is introduced bi-component chelating agent, by lithium titanate gel component-La
0.5sr
0.5sc
0.1mn
0.9o
3heating time is strictly controlled in the mixing of colloidal sol component simultaneously, will foreshorten to 3 ~ 8 h the reaction time, and by being controlled at tube furnace calcination time, particle scale is down to 150 ~ 350 nm, obtains a kind of pair of high conductive material (C-La
0.5sr
0.5sc
0.1mn
0.9o
3) the coated lithium secondary battery cathode material nanometer Li with good charge-discharge performance and cycle life
4ti
5o
12.
Summary of the invention
The object of the invention is to prepare the coated lithium secondary battery cathode material nanometer Li with good charge-discharge performance and cycle life of a kind of pair of high conductive material
4ti
5o
12.A kind of shortening Li is provided
+transmission path in battery negative pole material of lithium titanate, improve the preparation method of charge-discharge performance and cycle performance.The standby lithium titanate anode material of this legal system demonstrates excellent high rate performance and cycle performance.
A preparation method for pair lithium titanate that high conductive material is coated, is characterized in that, the concrete steps of the method are:
(1) first ethanol and water are pressed to 1:(0～0.5) volume ratio premix form mixed solution, then add acid as the inhibitor of follow-up Ti soluble compounds hydrolysis or the lytic agent of Li slightly soluble compound;
(2) by the slightly soluble of Li and Ti or soluble compound, according to mol ratio, prepare burden, join in the mixed liquor of step (1), by magnetic force heating stirrer stirring at normal temperature, until all dissolve;
(3) bi-component chelating agent is followed to water premix, water and chelating agent volume ratio are (0.5～2): 1, mix rear dropping ammoniacal liquor until chelating agent all dissolves, and then join in the mixed liquor of step (2), and add ammoniacal liquor to regulate between pH value to 7～10, continue to stir;
(4) mixed liquor until above-mentioned steps (3) is stirred into after colloidal sol, then chooses suitable time heating, continues to be stirred to brown color gel state;
(5) by the soluble compound of La, Sr, Sc and Mn, according to mol ratio, prepare burden, add and prepare in advance ethanol and water volume ratio 1:(0.01～0.5) mixed solution, by magnetic agitation to all dissolving;
(6) by bi-component chelating agent and water premix, after mixing, add ammoniacal liquor to chelating agent all to dissolve, then add in the mixed liquor of step (5), its pH value to 7～10, continue to be stirred to colloidal sol;
(7) (6) are mixed with (4), then in the convection oven of 150～250 ℃, dry 3～24 hours, obtain the lithium titanate precursor of black;
(8) lithium titanate precursor is put into high energy ball mill ball milling 1～10 hour, then put into tube furnace and calcine 900～1150 ℃ of calcinings 5～15 hours, obtain finished product carbon content 1～20% and La
0.5sr
0.5sc
0.1mn
0.9o
3coated nano barium titanate powder for lithium.
Described acid is a kind of or its combination, the wherein alcohol in nitric acid, hydrochloric acid, acetic acid, tartaric acid, oxalic acid, malic acid, citric acid, ascorbic acid, benzoic acid, salicylic acid, caffeic acid: volume ratio=1:(0.01～0.1 of acid).
Described slightly soluble or solubility Li compound are a kind of or its combination in lithium nitrate, lithium carbonate, lithium chloride, lithium acetate, lithium citrate, lithium oxalate, lithium formate, lithium lactate, isopropyl lithium alkoxide, long-chain or short-chain alkyl lithium; Described soluble T i compound is a kind of or its combination, the wherein mol ratio of Li:Ti=(0.8～1.0) in the chloride of tetra-n-butyl titanate, tetraisopropyl titanate, titanium: 1, and Ti compound wherein: volume ratio=1:(5～20 of alcohol).
Described bi-component chelating agent is triethanolamine, acetic acid, laurate, tartaric acid, citric acid, oxalic acid, gluconic acid, 2,2'-bipyridine, 1, in 10-phenanthrolene, aminotriacetic acid, diethylene-triamine pentaacetic acid, ethylenediamine, ethylenediamine tetra-acetic acid two kinds, wherein chelating agent: the mol ratio of metal ion=(1.0～3.0): 1.
Described La compound is a kind of or its combination in lanthanum nitrate, lanthanum sulfate, lanthanum acetate, citric acid lanthanum, lanthanum chloride, lanthanum oxalate, lanthanum carbonate.
Described Sr compound is a kind of or its combination in strontium nitrate, strontium chloride, strontium carbonate, strontium oxalate, strontium citrate, strontium lactate, strontium acetate.
Described Mn compound is a kind of or its combination in manganese acetate, manganese oxalate, manganese carbonate, manganese lactate, manganese nitrate, chloric acid manganese.
The heating-up temperature that described colloidal sol is converted to gel is 60～100 ℃, is chosen as colloidal sol heating time and stirs after 1～3 hour.
Described black lithium titanate precursor ball milling solvent is water, alcohol or solubilizer not, and in process, the mass ratio of ball and material is controlled as (0.5 ~ 10): 1, and the rotating speed of ball milling is controlled at 300～550 r/min, and ball milling post-drying temperature is 60～200 ℃.
In described step (8), the temperature of calcining is to heat up the program phase, and it is 2～10 ℃/min that heating rate is controlled, and heated perimeter is 900～1150 ℃, and particle size size is 150～350 nm.
The present invention adopts bi-component chelating agent, alkaline synthesis condition, can improve significantly the uniformity that reactant mixes, and can obviously improve the particle agglomeration phenomenon of material, increases the homogeneity of particle diameter.In addition, the present invention strictly controls the selection on heating time and heating opportunity, has not only controlled the hydrolysis rate of Ti compound but also has accelerated the shaping speed of gel, has shortened process cycle.Meanwhile, by lithium titanate gel and La
0.5sr
0.5sc
0.1mn
0.9o
3colloidal sol mixes, and tube furnace calcining obtains a kind of La
0.5sr
0.5sc
0.1mn
0.9o
3the Li common coated with carbon
4ti
5o
12, i.e. La
0.5sr
0.5sc
0.1mn
0.9o
3/ C-Li
4ti
5o
12, be abbreviated as LSSM/C-LTO.Product of the present invention is applied to the negative material of lithium ion battery, has superior fast charging and discharging performance and good cyclical stability.
Accompanying drawing explanation
Fig. 1 is the TEM figure of the embodiment of the present invention 1 product;
Fig. 2 is the specific discharge capacities of the embodiment of the present invention 2 products under 0.5C and 1C multiplying power.
Embodiment
The present invention is described in detail below by instantiation, but protection scope of the present invention is not limited to these examples of implementation.
Embodiment 1:
First according to volume ratio 1:0.1,300 ml ethanol and 30 ml water premixs are formed to mixed solvent, then add the HNO of 15 ml
3inhibitor as subsequent reactions; By the soluble compound compound of Li and Ti, mol ratio according to Li:Ti=4.2:5 is prepared burden, take the tetra-n-butyl titanate (analyzing pure) of 25.52g, the lithium carbonate of 2.33g (analyzing pure), join in previous alcohol water acid mixed liquor, by magnetic force heating stirrer, stir, until all dissolve; Again 20g ethylenediamine tetra-acetic acid and 30g citric acid are joined in mixed in advance metal ion solution, mix rear dropping 100 ml ammoniacal liquor and regulate pH value to 8, continue to stir; Until above-mentioned mixed liquor, be stirred into after colloidal sol, then 80 ℃ of heating are stirred to gel state; La, Sr, Sc and Mn compound are prepared burden by La:Sr:Sc:Mn=0.5:0.5:0.1:0.9 mol ratio, take 9.48 g lanthanum acetates (analyzing pure), 9.69 g strontium nitrates (analyzing pure), 13.239 g manganese acetates (analyzing pure), 1.9639 g scandium nitrates (analyzing pure), being dissolved in volume ratio is in the 300 ml ethanol and 30 ml water mixed solvents of 1:0.1, stirs, until all dissolve by magnetic force heating stirrer; Again 20 g ethylenediamine tetra-acetic acids and 30g citric acid are joined in mixed in advance metal ion solution, mix rear dropping 100 ml ammoniacal liquor and regulate pH value to 8, continue to stir, treat that above-mentioned mixed liquor is stirred into colloidal sol; The gel of above-mentioned preparation and colloidal sol are mixed, then in the convection oven of 240 ℃, dry, obtain the lithium titanate precursor that black is fluffy; Presoma is put into high energy ball mill ball milling 1～10h, and wherein the mass ratio of ball and material is 2:1, obtains the lithium titanate precursor that particle is tiny; Then the presoma of black is put into 900 ℃, tube furnace calcining, 5 h, obtained carbon content and be 15% LSSM/C-LTO.
Embodiment 2:
According to volume ratio 1:0.1,300 ml ethanol and 30 ml water premixs are formed to mixed solvent, then add the HCl of 15 ml as the inhibitor of subsequent reactions; By the soluble compound compound of Li and Ti, mol ratio according to Li:Ti=4.2:5 is prepared burden, take the tetraisopropyl titanate (analyzing pure) of 21.31g, the lithium acetate of 6.43 g (analyzing pure), join in previous alcohol water acid mixed liquor, by magnetic force heating stirrer, stir, until all dissolve; Again 20 g ethylenediamine tetra-acetic acids and 40 g citric acids are joined in mixed in advance metal ion solution, mix rear dropping 100 ml ammoniacal liquor and regulate pH value to 9, continue to stir; Until above-mentioned mixed liquor, be stirred into after colloidal sol, then 80 ℃ of heating are stirred to gel state; La, Sr, Sc and Mn compound are prepared burden by La:Sr:Sc:Mn=0.5:0.5:0.1:0.9 mol ratio, take 16.80 g lanthanum oxalates (analyzing pure), 5.27 g strontium oxalates (analyzing pure), 7.722 g manganese oxalates (analyzing pure), 1.3863 g scandium nitrates (analyzing pure), being dissolved in volume ratio is in the 300 ml ethanol and 30 ml water mixed solvents of 1:0.1, stirs, until all dissolve by magnetic force heating stirrer; Again 20 g ethylenediamine tetra-acetic acids and 40g citric acid are joined in mixed in advance metal ion solution, mix rear dropping 100 ml ammoniacal liquor and regulate pH value to 9, continue to stir, above-mentioned mixed liquor is stirred into colloidal sol; The gel of above-mentioned preparation and colloidal sol are mixed, then in the convection oven of 240 ℃, dry, obtain the lithium titanate precursor that black is fluffy; Presoma is put into high energy ball mill ball milling 1～10 h, and wherein the mass ratio of ball and material is 2:1, obtains the lithium titanate precursor that particle is tiny; Then the presoma of black is put into 1000 ℃, tube furnace calcining, 10 h, obtained carbon content and be 6% LSSM/C-LTO.
Embodiment 3:
According to volume ratio 1:0.2,300 ml ethanol and 60 ml water premixs are formed to mixed solvent, then add the HNO of 30 ml
3inhibitor as subsequent reactions; By the soluble compound compound of Li and Ti, mol ratio according to Li:Ti=4.4:5 is prepared burden, take the tetra-n-butyl titanate (analyzing pure) of 25.52 g, the lithium nitrate of 4.55 g (analyzing pure), join in previous alcohol water acid mixed liquor, by magnetic force heating stirrer, stir, until all dissolve; Again 20 g ethylenediamine tetra-acetic acids and 60 g citric acids are joined in mixed in advance metal ion solution, mix rear dropping 110ml ammoniacal liquor and regulate pH value to 7, continue to stir; Until above-mentioned mixed liquor, be stirred into after colloidal sol, then 80 ℃ of heating are stirred to gel state; La, Sr, Sc and Mn compound are prepared burden by La:Sr:Sc:Mn=0.5:0.5:0.1:0.9 mol ratio, take 9.48 g lanthanum oxalates (analyzing pure), 5.27 g strontium oxalates (analyzing pure), 13.239 g manganese oxalates (analyzing pure), 2.3768 g scandium nitrates (analyzing pure), being dissolved in volume ratio is in the 300 ml ethanol and 60 ml water mixed solvents of 1:0.2, stirs, until all dissolve by magnetic force heating stirrer; Again 20 g ethylenediamine tetra-acetic acids and 60 g citric acids are joined in mixed in advance metal ion solution, mix rear dropping 110 ml ammoniacal liquor and regulate pH value to 7, continue to stir, above-mentioned mixed liquor is stirred into colloidal sol; The gel of above-mentioned preparation and colloidal sol are mixed, then in the convection oven of 240 ℃, dry, obtain the lithium titanate precursor that black is fluffy; Lithium titanate precursor is put into high energy ball mill ball milling 1～10 h, and wherein the mass ratio of ball and material is 2:1, obtains the lithium titanate precursor that particle is tiny; Then the presoma of black is put into 1150 ℃ of Muffle furnaces calcining, 10 h, obtained carbon content and be 3% LSSM/C-LTO.
Claims (10)
1. a preparation method for the coated lithium titanate of two high conductive materials, is characterized in that, the concrete steps of the method are:
(1) first ethanol and water are pressed to 1:(0～0.5) volume ratio premix form mixed solution, then add acid as the inhibitor of follow-up Ti soluble compounds hydrolysis or the lytic agent of Li slightly soluble compound;
(2) by the slightly soluble of Li and Ti or soluble compound, according to mol ratio, prepare burden, join in the mixed liquor of step (1), by magnetic force heating stirrer stirring at normal temperature, until all dissolve;
(3) bi-component chelating agent is followed to water premix, water and chelating agent volume ratio are (0.5～2): 1, mix rear dropping ammoniacal liquor until chelating agent all dissolves, and then join in the mixed liquor of step (2), and add ammoniacal liquor to regulate between pH value to 7～10, continue to stir;
(4) mixed liquor until above-mentioned steps (3) is stirred into after colloidal sol, then chooses suitable time heating, continues to be stirred to brown color gel state;
(5) by the soluble compound of La, Sr, Sc and Mn, according to mol ratio, prepare burden, add and prepare in advance ethanol and water volume ratio 1:(0.01～0.5) mixed solution, by magnetic agitation to all dissolving;
(6) by bi-component chelating agent and water premix, after mixing, add ammoniacal liquor to chelating agent all to dissolve, then add in the mixed liquor of step (5), its pH value to 7～10, continue to be stirred to colloidal sol;
(7) (6) are mixed with (4), then in the convection oven of 150～250 ℃, dry 3～24 hours, obtain the lithium titanate precursor of black;
(8) lithium titanate precursor is put into high energy ball mill ball milling 1～10 hour, then put into tube furnace and calcine 900～1150 ℃ of calcinings 5～15 hours, obtain finished product carbon content 1～20% and La
0.5sr
0.5sc
0.1mn
0.9o
3coated nano barium titanate powder for lithium.
2. the preparation method of the coated lithium titanate of a kind of pair of high conductive material according to claim 1, it is characterized in that, described acid is a kind of or its combination, the wherein alcohol in nitric acid, hydrochloric acid, acetic acid, tartaric acid, oxalic acid, malic acid, citric acid, ascorbic acid, benzoic acid, salicylic acid, caffeic acid: volume ratio=1:(0.01～0.1 of acid).
3. the preparation method of the coated lithium titanate of a kind of pair of high conductive material according to claim 1, it is characterized in that, described slightly soluble or solubility Li compound are a kind of or its combination in lithium nitrate, lithium carbonate, lithium chloride, lithium acetate, lithium citrate, lithium oxalate, lithium formate, lithium lactate, isopropyl lithium alkoxide, long-chain or short-chain alkyl lithium; Described soluble T i compound is a kind of or its combination, the wherein mol ratio of Li:Ti=(0.8～1.0) in the chloride of tetra-n-butyl titanate, tetraisopropyl titanate, titanium: 1, and Ti compound wherein: volume ratio=1:(5～20 of alcohol).
4. the preparation method of the coated lithium titanate of a kind of pair of high conductive material according to claim 1, it is characterized in that, described bi-component chelating agent is triethanolamine, acetic acid, laurate, tartaric acid, citric acid, oxalic acid, gluconic acid, 2,2'-bipyridine, 1, in 10-phenanthrolene, aminotriacetic acid, diethylene-triamine pentaacetic acid, ethylenediamine, ethylenediamine tetra-acetic acid two kinds, wherein chelating agent: the mol ratio of metal ion=(1.0～3.0): 1.
5. the preparation method of the coated lithium titanate of a kind of pair of high conductive material according to claim 1, is characterized in that, described La compound is a kind of or its combination in lanthanum nitrate, lanthanum sulfate, lanthanum acetate, citric acid lanthanum, lanthanum chloride, lanthanum oxalate, lanthanum carbonate.
6. the preparation method of the coated lithium titanate of a kind of pair of high conductive material according to claim 1, is characterized in that, described Sr compound is a kind of or its combination in strontium nitrate, strontium chloride, strontium carbonate, strontium oxalate, strontium citrate, strontium lactate, strontium acetate.
7. the preparation method of the coated lithium titanate of a kind of pair of high conductive material according to claim 1, is characterized in that, described Mn compound is a kind of or its combination in manganese acetate, manganese oxalate, manganese carbonate, manganese lactate, manganese nitrate, chloric acid manganese.
8. the preparation method of the coated lithium titanate of a kind of pair of high conductive material according to claim 1, is characterized in that, the heating-up temperature that described colloidal sol is converted to gel is 60～100 ℃, is chosen as colloidal sol heating time and stirs after 1～3 hour.
9. the preparation method of the coated lithium titanate of a kind of pair of high conductive material according to claim 1, it is characterized in that, described black lithium titanate precursor ball milling solvent is water, alcohol or solubilizer not, in process, the mass ratio of ball and material is controlled as (0.5 ~ 10): 1, the rotating speed of ball milling is controlled at 300～550 r/min, and ball milling post-drying temperature is 60～200 ℃.
10. the preparation method of the coated lithium titanate of a kind of pair of high conductive material according to claim 1, it is characterized in that, in described step (8), the temperature of calcining is to heat up the program phase, it is 2～10 ℃/min that heating rate is controlled, heated perimeter is 900～1150 ℃, and particle size size is 150～350 nm.
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| CN114956279A (en) * | 2022-03-18 | 2022-08-30 | 苏州科技大学 | Method for preparing lanthanide series gel coagulant and application of lanthanide series gel coagulant in deep phosphorus removal |
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| CN114956279A (en) * | 2022-03-18 | 2022-08-30 | 苏州科技大学 | Method for preparing lanthanide series gel coagulant and application of lanthanide series gel coagulant in deep phosphorus removal |
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