CN100389513C - Method for preparing spherical lithium manganate - Google Patents
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- CN100389513C CN100389513C CNB2004100962597A CN200410096259A CN100389513C CN 100389513 C CN100389513 C CN 100389513C CN B2004100962597 A CNB2004100962597 A CN B2004100962597A CN 200410096259 A CN200410096259 A CN 200410096259A CN 100389513 C CN100389513 C CN 100389513C
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Abstract
The present invention relates to a method for preparing new spherical lithium manganate used as the material of the positive electrode of a lithium ion battery. The method adopts spherical manganese oxalate prepared by an overflow method as a precursor for preparing the spherical lithium manganate, and the manganese oxalate and lithium carbonate or lithium hydroxide are mixed into mash. The spherical lithium manganate is prepared through drying and calcining. The method of the present invention prepares the spherical lithium manganate with fine patterns and is beneficial to surface decoration and modification. Thereby, the specific capacity of the lithium manganate and the cycle performance at a high temperature are enhanced.
Description
[technical field]
The present invention relates to a kind of preparation method of spherical lithium manganate, particularly relate to a kind of preparation method who is used as the spherical lithium manganate of anode material for lithium-ion batteries.
[background technology]
Can mainly contain the intercalation compounds that forms by lithium and transition metal as the material of lithium ion cell positive, for example the Li of stratiform
xMO
2Structure and spinel-type Li
xM
2O
4The oxide of structure (transition metal such as M=Co, Ni, Mn, Cr), wherein studying more is LiNiO
2, LiCoO
2And LiMn
2O
4At present, the commercialization lithium ion battery almost all uses LiCoO
2Make positive electrode, LiCoO
2Specific energy height, good cycle, preparation technology simple, but security performance is relatively poor and the costing an arm and a leg of cobalt, resource-constrained, pollution are big, therefore is badly in need of seeking substitution material.LiNiO
2Though its specific energy is higher, moderate, its cycle performance is not good, the synthetic technology difficulty is big, and application is restricted.LiMn2O4 LiMn
2O
4Compare with above-mentioned two kinds of materials, have aboundresources, cheap (price of manganese only for cobalt 1/20th) and advantage such as pollution-free, especially the LiMn2O4 fail safe of spinel structure is good, the overcharging resisting performance is good, Stability Analysis of Structures, preparation are easy, is one of the most rising positive electrode of lithium ion battery; But because the specific capacity of LiMn2O4 is lower, high temperature (55 ℃) cycle performance is relatively poor, and microscopic appearance is poor, to its coat, modification intractability such as doping is bigger, thereby limited its development.
The preparation method of traditional LiMn2O4 is that electrolytic manganese dioxide and lithium carbonate or lithium hydroxide is mixed, carries out roasting then at a certain temperature.The pattern of LiMn2O4 is kept the pattern of electrolytic manganese dioxide basically, and the pattern of electrolytic manganese dioxide is mainly determined by disintegrating process, present crushing level is difficult to guarantee manganese dioxide pattern rule globulate, and uniformity is very poor, particle surface has the attachment (see figure 1), thereby cause the pattern of LiMn2O4 relatively poor, be unfavorable for LiMn2O4 is carried out coating modification.
CN1447464A discloses a kind of preparation method of lithium ion battery anode material spherical LiMn2O4, this method comprises: compound concentration is the manganese salt solution of 0.5～3 mol, compound concentration is the alkaline aqueous solution of 2～6 mol, prepare to contain and be selected from ammonia, ethylenediamine, oxalic acid, at least a complexing agent aqueous solution in the citric acid, be input to above-mentioned three kinds of solution in the reactor of band stirring respectively continuously with pump then, the flow of control manganese salt solution and complexing agent aqueous solution is to control the mol ratio of the two, it is 9～11 that the flow of adjusting alkaline aqueous solution makes the pH value of reactor internal reaction liquid, control reaction temperature is 40～60 ℃ and reacts, mixed material nature overflow in the reactor is discharged, carry out then Separation of Solid and Liquid and with the gained solids wash to the pH value less than 8, with the washing after the product drying obtain spherical Mn
3O
4The spherical mangano-manganic oxide that obtains is mixed with lithium hydroxide or lithium carbonate, then mixture is obtained the spherical lithium manganate product through 700～800 ℃ of high-temperature heat treatment.The mol ratio of wherein said complexing agent and Mn is respectively: NH
3/ Mn=0.2～0.5, ethylenediamine/Mn=0.1～0.3, oxalic acid/Mn=0.05～0.2, citric acid/Mn=0.01～0.1.
Above-mentioned CN1447464A disclosed method is by with manganese salt OH
-(alkaline aqueous solution) precipitation, obtain spherical mangano-manganic oxide after drying as the presoma of preparation anode material for lithium-ion batteries with spherical lithium manganate, wherein when carrying out precipitation reaction with alkaline aqueous solution, the course of reaction less stable, need to control the pH value of reaction solution to obtain having the mangano-manganic oxide presoma of better sphericity more accurately, if the pH value departs from control range, the product pattern is difficult to guarantee.In addition, the consumption of the complexing agent that uses in this method is on the low side, thereby might make precipitation reaction carry out to such an extent that make the sphericity of product and particle size distribution bad too soon.
[summary of the invention]
The preparation method who the purpose of this invention is to provide a kind of spherical lithium manganate that is used as anode material for lithium-ion batteries newly, this method adopts the spherical manganese oxalate of preparing in advance as the presoma for preparing spherical lithium manganate, can prepare the good spherical lithium manganate of pattern, help it is carried out finishing and modification, thus the specific capacity and the high temperature cyclic performance of raising LiMn2O4.
The preparation method who is used as the spherical lithium manganate of anode material for lithium-ion batteries provided by the invention may further comprise the steps:
(1) compound concentration is the manganese salt solution of 0.5～5 mol;
(2) compound concentration is the oxalic acid or the oxalates aqueous solution of 0.5～3 mol;
(3) compound concentration is the complexing agent aqueous solution of 0.5～3 mol;
(4) above-mentioned manganese salt solution, oxalic acid or the oxalates aqueous solution and complexing agent aqueous solution are injected into respectively in the reactor of band stirring continuously, make the mol ratio of reaction system be controlled to be C by the injection rate of regulating these three kinds of solution
2O
4 -/ Mn
2+=1.9～2.5 and complexing agent/Mn
2+=0.2～5, control reaction temperature is 50～80 ℃, and the precipitated product nature overflow in the reactor is discharged;
(5) material that step (4) gained reaction back overflow is discharged carries out Separation of Solid and Liquid, the gained solid is washed with water and drying, obtains spherical manganese oxalate presoma;
(6) be that medium is made pastel in grinding in ball grinder with lithium carbonate or lithium hydroxide with the non-solubility organic solvent;
(7) with the spherical manganese oxalate presoma of step (5) gained and step (6) gained lithium carbonate or lithium hydroxide pastel according to Li: Mn=(0.9～1.1): 2 mixed in molar ratio is even, then oven dry removal solvent;
(8) with step (7) gained mixture 650～900 ℃ roasting temperature 1～20 hour, preferred 3～15 hours, obtain the spherical lithium manganate product.
In above-mentioned preparation method according to the present invention, the described manganese salt of step (1) can be water-soluble all manganese salt, for example manganese nitrate, manganese sulfate, manganese chloride etc.
In above-mentioned preparation method, the described oxalate solution of step (2) can be water-soluble oxalate solution, as sodium oxalate, potassium oxalate, ammonium oxalate etc.
In above-mentioned preparation method, the described complexing agent of step (3) can be energy and Mn
2+Form the complexing agent of complex compound, these complexing agents are known to a person of ordinary skill in the art, and for example, this complexing agent can be to be selected from a kind of in ethylenediamine, acetate and the acetylacetone,2,4-pentanedione.This complexing agent and Mn
2+Ratio can determine according to complexation equilibrium principle or actual needs by those of ordinary skills, for example, elected during with above-mentioned complexing agent, preferably, the mol ratio of complexing agent and manganese may be controlled to ethylenediamine/Mn=1～2.5, acetate/Mn=0.5～5, acetylacetone,2,4-pentanedione/Mn=0.2～1 in step (4) reaction system.
In above-mentioned preparation method, the C of step (4) reaction system
2O
4 -/ Mn
2+It is C that mol ratio is controlled at stoichiometric proportion
2O
4 -/ Mn
2+Mol ratio=2 o'clock should be most preferred, but one of ordinary skill in the art will appreciate that and be offset this stoichiometry a little, especially when oxalate is excessive a little, can implement the present invention fully.Therefore, the mol ratio of reaction system may be controlled to C in the step of the inventive method (4)
2O
4 -/ Mn
2+=1.9～2.5.
In above-mentioned preparation method, described manganese salt solution of step (1) and the described enveloping agent solution of step (3) can be injected in the reactor in step (4) continuously with the form of mixed solution.
In above-mentioned preparation method, the described non-solubility organic solvent of step (6) is meant the organic solvent that can not dissolve lithium carbonate or lithium hydroxide, and the present invention has no particular limits it, preferably low-carbon (LC) alcohols, more preferably ethanol.The consumption of non-solubility organic solvent has no particular limits described in the step (6), can make lithium carbonate or lithium hydroxide can form uniform pastel and can evenly mix when this pastel mixes with the manganese oxalate presoma and be unlikely to too that thickness is as the criterion.
In above-mentioned preparation method, Li in the step (7): the Mn mol ratio is preferably according to stoichiometric 1: 2, but what one of ordinary skill in the art will appreciate that is, be offset this stoichiometry a little, for example as previously described according to Li: Mn=(0.9～1.1): during 2 mixed in molar ratio, can implement the present invention fully.
In addition, can carry out doping vario-property to the manganese oxalate product by in step (4) or (6) or (7), adding other suitable doped chemical.
The principle of the inventive method can be: carry out complexing by adopting complexing agent and manganese ion, make the Mn of the free state that discharges in the reaction system
2+The concentration of ion is controlled at a suitable level, as the free Mn of this suitable concn level
2+When ion and oxalate denominationby reaction generated sediment, the gained sediment can form the uniform spherical body, can prepare the spherical lithium manganate that can be used as anode material for lithium-ion batteries of good sphericity and narrow particle size distribution thus.
The preparation method of the spherical lithium manganate as anode material for lithium-ion batteries provided by the invention is because previously prepared manganese oxalate presoma epigranular, good sphericity, stable performance, adopt this manganese oxalate can prepare the good spherical lithium manganate of pattern as presoma, help it is carried out finishing and modification, thereby improve the specific capacity and the high temperature cyclic performance of LiMn2O4, and suitable suitability for industrialized production.CN1447464A compares with documents, the course of reaction good stability of the inventive method, and the pattern of product is controlled well.
[description of drawings]
Fig. 1 is scanning electron microscopy (SEM) photo of the embodiment of the invention 1 gained lithium manganate material.
Fig. 2 is the particle size distribution test result of the embodiment of the invention 1 gained lithium manganate material.
Fig. 3 is the SEM photo of the material of Comparative Examples 1 gained LiMn2O4.
Fig. 4 is the SEM photo of the material of Comparative Examples 2 gained LiMn2O4s.
Fig. 5 is the particle size distribution test result of Comparative Examples 2 gained lithium manganate materials.
[embodiment]
The following examples will be made specific description to the present invention, but it can not be interpreted as it is qualification to protection range of the present invention.
[embodiment 1]
Prepare the manganese nitrate aqueous solution of 1 mol, the oxalic acid aqueous solution of 2 mol, the ethylenediamine solution of 2 mol.It is in 10 liters the stirring reactor that these three kinds of solution are continuously pumped into the volume that installs 3 liters of deionized waters in advance with the identical speed of 6ml/min with plunger displacement pump, continuous stirring, control reaction temperature is 70 ℃, reacts 3 hours solidliquid mixtures in the post-reactor and begins the nature overflow, stops feed liquor after 10 hours, continue to stir heavyization 1 hour, collect the solidliquid mixture of reaction gained, carry out Separation of Solid and Liquid, gained solid deionized water wash, oven dry promptly gets spherical manganese oxalate presoma then.
Take by weighing lithium carbonate 200 grams and put into ball mill, to wherein adding 600 milliliters of ethanol again, ball milling 2 hours obtains a kind of pastel.It is in 1 liter the beaker that this pastel is transferred to volume fully, and to wherein according to Li: Mn=1: 2 mol ratio adds front gained manganese oxalate presoma, mixes.Gained mixture drying to remove ethanol wherein, then 750 ℃ of roastings 6 hours, behind the natural cooling, is obtained according to the spherical lithium manganate as anode material for lithium-ion batteries of the present invention.The SEM photo of gained spherical lithium manganate as shown in Figure 1, its epigranular has good sphericity as can be seen; Measure its particle size distribution with particles distribution instrument, the gained result as shown in Figure 2, products obtained therefrom has narrower particle size distribution as can be seen, average grain diameter is about 13 μ m.
With the lithium sheet is negative pole, is that active material is made positive pole with present embodiment gained spherical lithium manganate, is that electrolyte is assembled into battery with the lithium hexafluoro phosphate, discharges and recharges with the 0.2C electric current, and the first specific discharge capacity that records this battery is 125mAh/g.
[embodiment 2]
Prepare the manganese sulfate solution of 3 mol, the sodium oxalate aqueous solution of 1 mol, the ethylenediamine solution of 1.5 mol.It is in 12 liters the stirring reactor that these three kinds of solution are continuously pumped into the volume that installs 3 liters of deionized waters in advance with plunger displacement pump, the speed that pumps into is respectively: manganese sulfate solution 2ml/min, sodium oxalate solution 10ml/min, ethylenediamine solution 10ml/min, continuous stirring, control reaction temperature is 60 ℃, react the about 4 hours solidliquid mixtures in the post-reactor and begin the nature overflow, stop feed liquor after 10 hours, continue to stir heavyization 1 hour, collect the solidliquid mixture of reaction gained, carry out Separation of Solid and Liquid, gained solid deionized water wash, oven dry promptly gets spherical manganese oxalate presoma then.
Take by weighing lithium hydroxide 200 grams and put into ball mill, to wherein adding 700 milliliters of ethanol again, ball milling 2 hours obtains a kind of pastel.It is in 1 liter the beaker that this pastel is transferred to volume fully, and to wherein according to Li: Mn=1.1: 2 mol ratio adds front gained manganese oxalate presoma, mixes.Gained mixture drying to remove ethanol wherein, then 800 ℃ of roastings 5 hours, behind the natural cooling, is obtained according to the spherical lithium manganate as anode material for lithium-ion batteries of the present invention.Sem analysis shows that gained LiMn2O4 epigranular has good sphericity.
With the lithium sheet is negative pole, is that active material is made positive pole with present embodiment gained spherical lithium manganate, is that electrolyte is assembled into battery with the lithium hexafluoro phosphate, discharges and recharges with the 0.2C electric current, and the first specific discharge capacity that records this battery is 128mAh/g.
[embodiment 3]
Prepare the mixed aqueous solution of the acetate of the manganese chloride that contains 0.8 mol and 1 mol, and prepare the ammonium oxalate aqueous solution of 2.5 mol.It is in 10 liters the stirring reactor that these two kinds of solution are continuously pumped into the volume that installs 3 liters of deionized waters in advance with plunger displacement pump, the speed that pumps into is respectively: manganese chloride/acetic acid mixed solution 7.5ml/min, ammonium oxalate solution 5ml/min, continuous stirring, control reaction temperature is 55 ℃, react the about 5 hours solidliquid mixtures in the post-reactor and begin the nature overflow, stop feed liquor after 10 hours, continue to stir heavyization 1 hour, collect the solidliquid mixture of reaction gained, carry out Separation of Solid and Liquid, gained solid deionized water wash, oven dry promptly gets spherical manganese oxalate presoma then.
Take by weighing lithium hydroxide 200 grams and put into ball mill, to wherein adding 550 milliliters of ethanol again, ball milling 2 hours obtains a kind of pastel.It is in 1 liter the beaker that this pastel is transferred to volume fully, and to wherein according to Li: Mn=0.9: 2 mol ratio adds front gained manganese oxalate presoma, mixes.Gained mixture drying to remove ethanol wherein, then 650 ℃ of roastings 15 hours, behind the natural cooling, is obtained according to the spherical lithium manganate as anode material for lithium-ion batteries of the present invention.Sem analysis shows that gained LiMn2O4 epigranular has good sphericity.
With the lithium sheet is negative pole, is that active material is made positive pole with present embodiment gained spherical lithium manganate, is that electrolyte is assembled into battery with the lithium hexafluoro phosphate, discharges and recharges with the 0.2C electric current, and the first specific discharge capacity that records this battery is 123mAh/g.
Comparative Examples 1
Take by weighing lithium carbonate 200 grams and put into ball mill, to wherein adding 600 milliliters of ethanol again, ball milling 2 hours obtains a kind of pastel.It is in 1 liter the beaker that this pastel is transferred to volume fully, and to wherein according to Li: Mn=1: 2 mol ratio adds the electrolysis manganese dioxide that is purchased, and mixes.Gained mixture drying to remove ethanol wherein, then 750 ℃ of roastings 6 hours, behind the natural cooling, is obtained the LiMn2O4 sample as anode material for lithium-ion batteries as a comparison.The SEM photo of gained spherical lithium manganate as shown in Figure 3, its particle is not a spherical and very irregular as can be seen.
With the lithium sheet is negative pole, is that active material is made positive pole with this Comparative Examples gained LiMn2O4, is that electrolyte is assembled into battery with the lithium hexafluoro phosphate, discharges and recharges with the 0.2C electric current, and the first specific discharge capacity that records this battery is 115mAh/g.
Comparative Examples 2
Same procedure according to the 5th page of embodiment 1 of specification of CN1447464A makes spherical lithium manganate.The SEM photo of gained spherical lithium manganate as shown in Figure 4; Measure its particle size distribution with particles distribution instrument, the gained result as shown in Figure 5, the product sphericity is not high as can be seen, particle size distribution is not concentrated, particle has agglomeration, average grain diameter is about 12 μ m.The applicant thinks, the not high and uneven reason of particle size distribution of its sphericity might be because too low the causing of consumption of its complexing agent, because when the complexing agent consumption is too low, and the Mn of the free state that exists in the reaction system
2+The concentration of ion is very big, and precipitation reaction is carried out too rapidly, can cause the sphericity of product bad and particle size distribution is inhomogeneous.
With the lithium sheet is negative pole, is that active material is made positive pole with this Comparative Examples gained LiMn2O4, is that electrolyte is assembled into battery with the lithium hexafluoro phosphate, discharges and recharges with the 0.2C electric current, and the first specific discharge capacity that records this battery is 110mAh/g.
Claims (6)
1. preparation method as the spherical lithium manganate of anode material for lithium-ion batteries may further comprise the steps:
(1) compound concentration is the manganese salt solution of 0.5～5 mol;
(2) compound concentration is the oxalic acid or the oxalates aqueous solution of 0.5～3 mol;
(3) compound concentration is the complexing agent aqueous solution of 0.5～3 mol;
(4) above-mentioned manganese salt solution, oxalic acid or the oxalates aqueous solution and complexing agent aqueous solution are injected into respectively in the reactor of band stirring continuously, make the mol ratio of reaction system be controlled to be C by the injection rate of regulating these three kinds of solution
2O
4 -/ Mn
2+=1.9～2.5 and complexing agent/Mn
2+=0.2～5, control reaction temperature is 50～80 ℃, and the precipitated product nature overflow in the reactor is discharged;
(5) material that step (4) gained reaction back overflow is discharged carries out Separation of Solid and Liquid, the gained solid is washed with water and drying, obtains spherical manganese oxalate presoma;
(6) be that medium is made pastel in grinding in ball grinder with lithium carbonate or lithium hydroxide with the non-solubility organic solvent;
(7) with the spherical manganese oxalate presoma of step (5) gained and step (6) gained lithium carbonate or lithium hydroxide pastel according to Li: Mn=(0.9～1.1): 2 mixed in molar ratio is even, then oven dry removal solvent;
(8) with step (7) gained mixture 650～900 ℃ roasting temperature 1～20 hour, obtain the spherical lithium manganate product.
2. according to the preparation method of claim 1, wherein the described manganese salt of step (1) is manganese nitrate, manganese sulfate or manganese chloride.
3. according to the preparation method of claim 1, wherein the described oxalates of step (2) is sodium oxalate, potassium oxalate or ammonium oxalate.
4. according to the preparation method of claim 1, wherein the described complexing agent of step (3) is to be selected from a kind of in ethylenediamine, acetate or the acetylacetone,2,4-pentanedione.
5. according to the preparation method of claim 4, wherein the mol ratio of complexing agent and manganese is controlled to be ethylenediamine/Mn=1～2.5, acetate/Mn=0.5～5, or acetylacetone,2,4-pentanedione/Mn=0.2～1 in step (4) reaction system.
6. according to the preparation method of claim 1, wherein described manganese salt solution of step (1) and the described enveloping agent solution of step (3) are injected in the reactor in step (4) continuously with the form of mixed solution.
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|---|---|---|---|
| CNB2004100962597A CN100389513C (en) | 2004-11-29 | 2004-11-29 | Method for preparing spherical lithium manganate |
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Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101319373B (en) * | 2008-05-30 | 2012-02-01 | 哈尔滨工程大学 | Production method of orderly arranged manganese oxide |
| CN101335348B (en) * | 2008-07-18 | 2010-06-02 | 清华大学 | Preparing method of lithium ionic cell 5V anode material spherical LiNi0.5Mn1.5O4 |
| CN101841023B (en) * | 2010-05-25 | 2012-08-29 | 上海应用技术学院 | Method for preparing spherical lithium manganate |
| CN104282889B (en) * | 2014-09-11 | 2017-05-03 | 浙江南都电源动力股份有限公司 | Preparation method of manganese oxalate feed liquor and spinel lithium manganate |
| CN107840793B (en) * | 2017-10-26 | 2021-04-20 | 北京科技大学 | Preparation method of special-shaped monodisperse zinc oxalate powder |
| CN113061910B (en) * | 2021-03-22 | 2021-11-12 | 长沙学院 | Electrolytic manganese dioxide and preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000149943A (en) * | 1998-11-05 | 2000-05-30 | Toyota Central Res & Dev Lab Inc | Process for lithium manganese compound oxide for lithium secondary battery positive active material |
| CN1447464A (en) * | 2003-04-26 | 2003-10-08 | 清华大学 | Method for preparing spherical lighium manganate anode material of lighium ion batteries |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000149943A (en) * | 1998-11-05 | 2000-05-30 | Toyota Central Res & Dev Lab Inc | Process for lithium manganese compound oxide for lithium secondary battery positive active material |
| CN1447464A (en) * | 2003-04-26 | 2003-10-08 | 清华大学 | Method for preparing spherical lighium manganate anode material of lighium ion batteries |
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