CN102569776A - Preparation method of spinel type lithium manganese oxide for spherical high-voltage anode material - Google Patents
Preparation method of spinel type lithium manganese oxide for spherical high-voltage anode material Download PDFInfo
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Abstract
The invention discloses a preparation method of spinel type lithium manganese oxide for a spherical high-voltage anode material. The preparation method comprises the following steps of: preparing the spinel type lithium manganese oxide for the spherical high-voltage anode material by utilizing a hydrothermal-solid-phase two-step method; uniformly mixing a nickel source, a manganese source and a doped element chemical solution with a sodium/ammonium carbonate solution; adding surfactant into the mixed solution and preparing under a hydrothermal condition to prepare a spherical lithium manganese carbonate sediment; washing and drying, and then sintering to obtain a spherical lithium manganese oxide; mixing the oxide with a lithium source by liquid-phase ball milling, and drying; and finally, sintering to obtain an anode active material. According to the preparation method disclosed by the invention, the synthesis method is simple, the process is easy to control and the doped elements are introduced; physical and chemical properties of the material are optimized and the grain size of the material is uniform; and the discharge capacity is high and the multiplying power performance is good.
Description
Technical field
The present invention relates to a kind of spherical high-voltage anode material spinel-type LiM
xNi
0.5-xMn
1.5O
4The preparation method of (M=Mg, Fe, Co, Ru, Zn, Ti, Cr, Ce, La, 0≤x≤0.05) belongs to the high-performance lithium ion battery technical field.
Background technology
Be accompanied by global energy crisis and environmental pollution that automobile brings, national governments all successively drop into the development that huge fund strengthens new-energy automobile, and New-energy electric vehicle and hybrid vehicle become the developing direction of following automobile.Current driving force mainly contains three kinds with battery: plumbic acid, ni-mh and lithium dynamical battery.See that from the development trend in future lithium-ion-power cell will become main flow, have broad application prospects.Correspondingly, the requirement that must keep pace with the times of the research and development of the critical material-positive electrode of lithium-ion-power cell.
At present the more electrokinetic cell of research mainly concentrates on the manganate cathode material for lithium of cobalt acid lithium, lithium nickelate and spinel-type of LiFePO 4, the stratiform of olivine-type.But the voltage of the relative graphite of above material all is lower than 4V, and the power of battery receives certain restriction.Discover the substituted manganate cathode material for lithium LiNi of nickel
xMn
2-xO
4Has 4.5V with upper mounting plate.Wherein, to have the LiNi of 4.7V voltage platform
0.5Mn
1.5O
4Middle part manganese is replaced by nickel to be stablized the structure of its spinelle and has suppressed manganic ginger-Taylor effect, makes the cycle performance of material improve greatly.Recently, the lithium titanate anode material with excellent cycle performance has received great attention, and still, the relative lithium of this material higher current potential (1.5V) has limited itself and the coupling of main flow positive electrode (like LiFePO4, LiMn2O4) at present.In addition, along with the successful exploitation of novel electrolyte systems such as the successful development of electrolyte and ionic liquid, making high-voltage anode material move towards industrialization becomes possibility.Based on above 3 points, spinel-type LiNi
0.5Mn
1.5O
4Positive electrode is just becoming the focus of research.
The synthetic method of spinelle nickel LiMn2O4 mainly contains: solid phase method, sol-gel, high-temperature molten salt method, latex seasoning, ullrasonic spraying high-temperature decomposition, polymer high-temperature decomposition and the precipitation method.The synthetic LiNi that mixes ruthenium of solid phase method is disclosed like patent US20110229763A1
0.5Mn
1.5O
4Chemical property, the head of material is put specific capacity and is merely 116mAh/g.Patent US20080107968A1 discloses and has utilized solid phase method carbonate to prepare LiNi
0.5Mn
1.5O
4Because it contains the Mn of higher amount
3+, so its 4.1V platform is very obvious, and cycle performance is poor.Contain nickel oxide impurity in the high pressure material that Y.S.Lee (Electrochem. Comm. 4 989) prepares with sol-gel process, greatly reduce the electrical property of material.J.Gao (
J.Electrochem.Soc.7.A 899 (2010)) prepare the micron-size spherical presoma with the carbonate coprecipitation method.It is 136.8mAh/g that the high voltage nickel LiMn2O4 0.2C head that roasting obtains is put capacity, and the 100 all capability retentions that circulate are more than 95%.The preparation method of the disclosed high-voltage lithium ion anode material nickel of patent CN101640266 LiMn2O4, under hydrothermal condition, preparing thickness is nano level sheet high voltage material, has good high rate performance, discharge capacity is 70% of 1C under the 10C.Shortcomings such as the synthetic nickel manganate cathode material for lithium that obtains of the method in first three document exists that reaction is insufficient, batch mixing is inhomogeneous, technology is wayward, granule-morphology and size are wayward, then both to synthesize the material property that obtains obviously good than the above two.This is because spheric granules has bigger specific surface, wide lithium ion takes off embedding passage and high tap density; Under the hydrothermal condition, reaction raw materials can fully mix, and reacts more abundant, and the product homogeneity is good, and therefore narrow diameter distribution can obtain having the high energy density and the material of big multiplying power discharging.
Summary of the invention
The objective of the invention is to problems such as the batch mixing that exists in the above synthetic method are uneven, product purity is not high, the pattern of batch stability and particle and size are wayward; Provide that a kind of cost is lower, technology is simple and capacity and cycle performance all satisfy the high-voltage anode material preparation method of lithium-ion-power cell requirement; Under the prerequisite that guarantees big multiplying power discharging and high cyclical stability, obtain the spinelle nickel manganate cathode material for lithium of a kind of discharge platform about 4.7V.
The present invention adopts following technical scheme to achieve these goals:
The preparation method of spherical high-voltage anode material spinelle nickel LiMn2O4 is characterized in that may further comprise the steps:
(1) solution preparation:
Take by weighing nickel source, manganese source and doping element compound by a certain percentage, be dissolved in the deionized water, stirring obtains its mixed solution A, and wherein the mol ratio of material is Mn:Ni:M=1.5: (0.5-x): x, 0≤x≤0.05;
The carbonate that takes by weighing a certain amount of sodium/ammonium is dissolved in the deionized water, is configured to the solution B of 1mol/L;
Take by weighing certain amount of surfactant, it is dissolved in the solvent, stir, obtain solution C;
(2) under stirring condition, solution B slowly is added dropwise in the mixed solution A, after dropwising; Then solution C is added above mixed solution, the mol ratio of control slaine, carbanion, surfactant is 1:1.05:0.4-0.6, at room temperature stirs 2-3 hour; Transfer in the hydrothermal reaction kettle; Reaction is 10-12 hour under 80-120 ℃ of condition, and centrifugation obtains the spherical carbonate deposition, and washing is also dry;
(3) spherical carbonate that obtains in the step (2) is deposited under the 350-450 ℃ of condition in the air roasting 5-7 hour, obtains the presoma Ni, Mn oxide;
(4) take by weighing Li source compound and presoma Ni, Mn oxide, both mol ratios are 1-1.02:2, are medium with the solvent, press ball milling solid content ball mill mixing 6-8 hour of 30-70%, then at 75-85 ℃ down after dry 2-3 hour; In 700-900 ℃ of following air roasting 12-48 hour again, obtain positive electrode active materials LiMxNi0.5-xMn1.5O4, M=Mg, Fe; Co, Ru, Zn, Ti; Cr, Ce, La, 0≤x≤0.05.
The preparation method of described spherical high-voltage anode material spinelle nickel LiMn2O4 is characterized in that: described manganese source is one or more the mixture in manganese sulfate, manganese nitrate, the manganese acetate.
The preparation method of described spherical high-voltage anode material spinelle nickel LiMn2O4 is characterized in that: described nickel source is one or more the mixture in nickelous sulfate, nickel nitrate, the nickel acetate.
The preparation method of described spherical high-voltage anode material spinelle nickel LiMn2O4 is characterized in that: described doping element compound is one or more the mixture in the sulfuric acid, nitric acid, acetate of magnesium, iron, cobalt, zinc, titanium, chromium, cerium, lanthanum.
The preparation method of described spherical high-voltage anode material spinelle nickel LiMn2O4 is characterized in that: described surfactant is one or more among dodecyl sodium sulfate, cetyl-tributyl ammonium bromide, the polyethylene pyrroles.
The preparation method of described spherical high-voltage anode material spinelle nickel LiMn2O4 is characterized in that: described lithium source is one or more the mixture in lithium carbonate, lithium acetate, lithium nitrate, the lithium hydroxide.
The preparation method of described spherical high-voltage anode material spinelle nickel LiMn2O4 is characterized in that: described step (4) solvent is one or several the mixture in deionized water, absolute ethyl alcohol and the acetone.
Profitable fruit of the present invention:
(1) the present invention adopts the spherical Ni, Mn oxide presoma that Hydrothermal Preparation obtains, and the homogeneity of product is very good; (2) doped chemical of introducing improves the circulation and the high rate performance of material effectively; (3) building-up process is simple, and technology is easy to control, is very suitable for suitability for industrialized production.
Description of drawings
Fig. 1 embodiment 1 sample XRD figure spectrum.
The charging and discharging curve of Fig. 2 embodiment 1 sample.
The SEM collection of illustrative plates of SEM collection of illustrative plates (b) embodiment 1 sample of Fig. 3 (a) embodiment 1 precursor samples.
The cycle performance of Fig. 4 embodiment 5 samples.
Embodiment
Embodiment 1:
Take by weighing 4.53g manganese sulfate, 2.106g nickelous sulfate, 0.234g cobaltous sulfate, add the solution that deionized water is configured to 1mol/L; Other takes by weighing 5.4g sodium carbonate, is dissolved in the solution that forms 1mol/L in the deionized water; Then under stirring condition; Slowly sodium carbonate liquor is splashed in the above hybrid metal ion solution; Take by weighing the 0.544g dodecyl sodium sulfate again, it joined in the above mixed solution in batches, at room temperature stir 3 hours after; Regulate pH value and be after 8 that it is transferred in the hydrothermal reaction kettle of polytetrafluoroethylene of 100mL, reacted 10 hours down at 120 ℃; Centrifugation, cakes with deionized water washing 5 times 100 ℃ of air dryings 12 hours, obtains carbonate deposition 5.10g.
Take by weighing carbonate deposition 2.22g, place alumina crucible, in Muffle furnace,, obtain the Ni, Mn oxide 1.34g that cobalt mixes in 400 ℃ of roastings 5 hours.
Take by weighing above Ni, Mn oxide 26.8g and 14.8g lithium carbonate, place the planetary ball mill jar, add the 50mL absolute ethyl alcohol as medium, ball mill mixing 8 hours; Drying is 2 hours under 80 ℃, and roasting obtained positive electrode active materials LiNi in 12 hours in 800 ℃ of following air
0.48Co
0.02Mn
1.5O
4(1:1:1, electrolyte V/V) are that negative pole is assembled into 2016 button cells with the lithium metal, and test obtains its 0.2C head and puts and be 143mAh/g on Land charge-discharge test appearance to adopt EC:EMC:DMC.
Embodiment 2:
Take by weighing 5.4g manganese nitrate, 2.43g nickel nitrate, 0.27g cobalt nitrate, add the solution that deionized water is configured to 1mol/L; Other takes by weighing 5.4g sodium carbonate, is dissolved in the solution that forms 1mol/L in the deionized water; Then under stirring condition; Slowly sodium carbonate liquor is splashed in the above hybrid metal ion solution; Take by weighing the 0.544g dodecyl sodium sulfate again, it joined in the above mixed solution in batches, at room temperature stir 3 hours after; Regulate pH value and be after 8 that it is transferred in the hydrothermal reaction kettle of polytetrafluoroethylene of 100mL, reacted 10 hours down at 120 ℃; Centrifugation, cakes with deionized water washing 5 times 100 ℃ of air dryings 12 hours, obtains carbonate deposition 5.10g.
Take by weighing carbonate deposition 2.22g, place alumina crucible, in Muffle furnace,, obtain the Ni, Mn oxide 1.34g that cobalt mixes in 400 ℃ of roastings 5 hours.
Take by weighing above Ni, Mn oxide 26.8g and 14.8g lithium carbonate, place the planetary ball mill jar, add the 50mL absolute ethyl alcohol as medium, ball mill mixing 8 hours; Drying is 2 hours under 80 ℃, and roasting obtained positive electrode active materials LiNi in 12 hours in 800 ℃ of following air
0.48Co
0.02Mn
1.5O
4(1:1:1, electrolyte V/V) are that negative pole is assembled into 2016 button cells with the lithium metal, and test obtains its 0.2C head and puts and be 140mAh/g on Land charge-discharge test appearance to adopt EC:EMC:DMC.
Embodiment 3:
Take by weighing 4.53g manganese sulfate, 2.43g nickel nitrate, 0.234g cobaltous sulfate, add the solution that deionized water is configured to 1mol/L; Other takes by weighing 5.4g sodium carbonate, is dissolved in the solution that forms 1mol/L in the deionized water; Then under stirring condition; Slowly sodium carbonate liquor is splashed in the above hybrid metal ion solution; Take by weighing the 0.544g dodecyl sodium sulfate again, it joined in the above mixed solution in batches, at room temperature stir 3 hours after; Regulate pH value and be after 8 that it is transferred in the hydrothermal reaction kettle of polytetrafluoroethylene of 100mL, reacted 10 hours down at 120 ℃; Centrifugation, cakes with deionized water washing 5 times 100 ℃ of air dryings 12 hours, obtains carbonate deposition 4.89g.
Take by weighing carbonate deposition 2.22g, place alumina crucible, in Muffle furnace,, obtain the Ni, Mn oxide 1.34g that cobalt mixes in 400 ℃ of roastings 5 hours.
Take by weighing above Ni, Mn oxide 26.8g and 14.8g lithium carbonate, place the planetary ball mill jar, add the 50mL absolute ethyl alcohol as medium, ball mill mixing 8 hours; Drying is 2 hours under 80 ℃, and roasting obtained positive electrode active materials LiNi in 12 hours in 800 ℃ of following air
0.48Co
0.02Mn
1.5O
4(1:1:1, electrolyte V/V) are that negative pole is assembled into 2016 button cells with the lithium metal, and test obtains its 0.2C head and puts and be 140mAh/g on Land charge-discharge test appearance to adopt EC:EMC:DMC.
Embodiment 4:
Take by weighing 5.4g manganese nitrate, 2.43g nickel nitrate, 0.135g cobalt nitrate, 0.3255 cerous nitrate, add the solution that deionized water is configured to 1mol/L.Other takes by weighing 5.4g sodium carbonate, is dissolved in the solution that forms 1mol/L in the deionized water.Then under stirring condition; Slowly sodium carbonate liquor is splashed in the above hybrid metal ion solution; Take by weighing the 0.544g dodecyl sodium sulfate again, it joined in the above mixed solution in batches, at room temperature stir 3 hours after; Regulate pH value and be after 8 that it is transferred in the hydrothermal reaction kettle of polytetrafluoroethylene of 100mL, reacted 10 hours down at 120 ℃; Centrifugation, cakes with deionized water washing 5 times 100 ℃ of air dryings 12 hours, obtains carbonate deposition 5.10g.
Take by weighing carbonate deposition 2.22g, place alumina crucible, in Muffle furnace,, obtain the Ni, Mn oxide 1.5g of cobalt, cerium doping in 400 ℃ of roastings 5 hours.
Take by weighing above Ni, Mn oxide 30g and 14.8g lithium carbonate, place the planetary ball mill jar, add the 50mL absolute ethyl alcohol as medium, ball mill mixing 8 hours; Drying is 2 hours under 80 ℃, and roasting obtained positive electrode active materials LiNi in 12 hours in 800 ℃ of following air
0.48Co
0.01Ce
0.01Mn
1.5O
4(1:1:1, electrolyte V/V) are that negative pole is assembled into 2016 button cells with the lithium metal, and test obtains its 0.2C head and puts and be 136mAh/g on Land charge-discharge test appearance to adopt EC:EMC:DMC.
Embodiment 5:
Take by weighing 3.48 manganese acetates, 1.566g nickel acetate, 0.174g cobalt acetate, add the solution that deionized water is configured to 1mol/L, other takes by weighing the 4.8g ammonium carbonate, is dissolved in the solution that forms 1mol/L in the deionized water.Then under stirring condition; Slowly sal volatile is splashed in the above hybrid metal ion solution; Take by weighing the 0.544g dodecyl sodium sulfate again, it joined in the above mixed solution in batches, at room temperature stir 3 hours after; It is transferred in the hydrothermal reaction kettle of polytetrafluoroethylene of 100mL, 120 ℃ of reactions 10 hours down; Centrifugation, cakes with deionized water washing 5 times 100 ℃ of air dryings 12 hours, obtains carbonate deposition 5.2g.
Take by weighing carbonate deposition 2.22g, place alumina crucible, in Muffle furnace,, obtain the Ni, Mn oxide 1.34g that cobalt mixes in 400 ℃ of roastings 5 hours.
Take by weighing above Ni, Mn oxide 26.8g and 14.8g lithium carbonate, place the planetary ball mill jar, add 50mL acetone as medium, ball mill mixing 8 hours.Drying is 2 hours under 80 ℃, and roasting obtained positive electrode active materials LiNi in 12 hours in 800 ℃ of following air
0.48Co
0.02Mn
1.5O
4(1:1:1, electrolyte V/V) are that negative pole is assembled into 2016 button cells with the lithium metal, and test obtains its 0.2C head and puts and be that 142mAh/g, the 0.2C 50 all capability retentions that circulate are 95% on Land charge-discharge test appearance to adopt EC:EMC:DMC.
Embodiment 6:
Change the dodecyl sodium sulfate among the embodiment 1 into the polyethylene pyrroles, other condition is identical, makes LiNi
0.48Co
0.02Mn
1.5O
4, (1:1:1, electrolyte V/V) are that negative pole is assembled into 2016 button cells with the lithium metal, and test obtains its 0.2C head and puts and be 139mAh/g on Land charge-discharge test appearance to adopt EC:EMC:DMC.
Embodiment 7:
The temperature of the second step sintering among the embodiment 5 is transferred to 900 ℃; Adopt EC:EMC:DMC (1:1:1; V/V) electrolyte; With the lithium metal is that negative pole is assembled into 2016 button cells, and test obtains its 0.2C head and puts and be that 142mAh/g, the 0.2C 50 all capability retentions that circulate are 97% on Land charge-discharge test appearance.
Claims (7)
1. the preparation method of a spherical high-voltage anode material spinelle nickel LiMn2O4 is characterized in that may further comprise the steps:
(1) solution preparation:
Take by weighing nickel source, manganese source and doping element compound by a certain percentage, be dissolved in the deionized water, stirring obtains its mixed solution A, and wherein the mol ratio of material is Mn:Ni:M=1.5: (0.5-x): x, 0≤x≤0.05;
The carbonate that takes by weighing a certain amount of sodium/ammonium is dissolved in the deionized water, is configured to the solution B of 1mol/L;
Take by weighing certain amount of surfactant, it is dissolved in the solvent, stir, obtain solution C;
(2) under stirring condition, solution B slowly is added dropwise in the mixed solution A, after dropwising; Then solution C is added above mixed solution, the mol ratio of control slaine, carbanion, surfactant is 1:1.05:0.4-0.6, at room temperature stirs 2-3 hour; Transfer in the hydrothermal reaction kettle; Reaction is 10-12 hour under 80-120 ℃ of condition, and centrifugation obtains the spherical carbonate deposition, and washing is also dry;
(3) spherical carbonate that obtains in the step (2) is deposited under the 350-450 ℃ of condition in the air roasting 5-7 hour, obtains the presoma Ni, Mn oxide;
(4) take by weighing Li source compound and presoma Ni, Mn oxide, both mol ratios are 1-1.02:2, are medium with the solvent, press ball milling solid content ball mill mixing 6-8 hour of 30-70%, then at 75-85 ℃ down after dry 2-3 hour; In 700-900 ℃ of following air roasting 12-48 hour again, obtain positive electrode active materials LiMxNi0.5-xMn1.5O4, M=Mg, Fe; Co, Ru, Zn, Ti; Cr, Ce, La, 0≤x≤0.05.
2. the preparation method of spherical high-voltage anode material spinelle nickel LiMn2O4 according to claim 1 is characterized in that: described manganese source is one or more the mixture in manganese sulfate, manganese nitrate, the manganese acetate.
3. the preparation method of spherical high-voltage anode material spinelle nickel LiMn2O4 according to claim 1 is characterized in that: described nickel source is one or more the mixture in nickelous sulfate, nickel nitrate, the nickel acetate.
4. the preparation method of spherical high-voltage anode material spinelle nickel LiMn2O4 according to claim 1 is characterized in that: described doping element compound is one or more the mixture in the sulfuric acid, nitric acid, acetate of magnesium, iron, cobalt, zinc, titanium, chromium, cerium, lanthanum.
5. the preparation method of spherical high-voltage anode material spinelle nickel LiMn2O4 according to claim 1 is characterized in that: described surfactant is one or more among dodecyl sodium sulfate, cetyl-tributyl ammonium bromide, the polyethylene pyrroles.
6. the preparation method of spherical high-voltage anode material spinelle nickel LiMn2O4 according to claim 1 is characterized in that: described lithium source is one or more the mixture in lithium carbonate, lithium acetate, lithium nitrate, the lithium hydroxide.
7. the preparation method of spherical high-voltage anode material spinelle nickel LiMn2O4 according to claim 1 is characterized in that: described step (4) solvent is one or several the mixture in deionized water, absolute ethyl alcohol and the acetone.
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