CN1283014C - Process for preparing high density spherical nickel-cobalt lithium manganate as anode material of lithium ion cell - Google Patents
Process for preparing high density spherical nickel-cobalt lithium manganate as anode material of lithium ion cell Download PDFInfo
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- C01G45/1221—Manganates or manganites with a manganese oxidation state of Mn(III), Mn(IV) or mixtures thereof
- C01G45/1228—Manganates or manganites with a manganese oxidation state of Mn(III), Mn(IV) or mixtures thereof of the type [MnO2]n-, e.g. LiMnO2, Li[MxMn1-x]O2
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- C01G51/42—Cobaltates containing alkali metals, e.g. LiCoO2
- C01G51/44—Cobaltates containing alkali metals, e.g. LiCoO2 containing manganese
- C01G51/50—Cobaltates containing alkali metals, e.g. LiCoO2 containing manganese of the type [MnO2]n-, e.g. Li(CoxMn1-x)O2, Li(MyCoxMn1-x-y)O2
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- C01G53/44—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese
- C01G53/50—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese of the type [MnO2]n-, e.g. Li(NixMn1-x)O2, Li(MyNixMn1-x-y)O2
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- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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Abstract
The present invention discloses a method for preparing high density spherical nickel-cobalt lithium manganate as the anode material of a lithium ion cell, which belongs to the technical field of the preparation of energy source materials. The method for preparing high density spherical nickel-cobalt lithium manganate as the anode material of a lithium ion cell comprises the following steps: nickel salt, cobalt salt and manganese salt are reacted with sodium hydroxide and ammonia in water solution to synthesize a spherical or spheroid nickel-cobalt hydroxide manganese Ni<1/3>Co<1/3>Mn<1/3>(OH)<2> precursor; the precursor is uniformly mixed with lithium carbonate after the precursor is washed and dried; the spherical nickel-cobalt lithium manganate is obtained by a heat treatment with the high temperature of 750 to 950 DEG C for from 8 to 48 hours in air. The bulk density of the spherical nickel-cobalt lithium manganate prepared by the present invention is large, the average particle diameter of the spherical nickel-cobalt lithium manganate is from 3 to 7 mu m, the tap density of the spherical nickel-cobalt lithium manganate can reach from 2.25 to 2.50 g/cm<3>, and the reversible specific capacity of the spherical nickel-cobalt lithium manganate can reach from 172 to 185 mAh/g.
Description
Technical field
The invention belongs to the energy and material preparing technical field, particularly a kind of preparation method of anode material for lithium-ion batteries high density spherical nickel-cobalt LiMn2O4.
Background technology
Lithium ion battery is the green high-capacity battery of a new generation, numerous advantages such as have that voltage height, energy density are big, good cycle, self discharge are little, memory-less effect, operating temperature range are wide, be widely used in mobile phone, notebook computer, UPS, video camera, various portable power tool, electronic instrument, weaponry etc., in electric automobile, also have a good application prospect, be considered to be in 21st century national economy and the significant new high-tech product of people's lives.
Positive electrode is the important component part of lithium ion battery.At present, the maximum positive electrode of research is LiCoO
2, LiMn
2O
4, LiNiO
2LiCoO
2Be the positive electrode of unique large-scale commercial, the research comparative maturity, high comprehensive performance, but cost an arm and a leg, capacity is lower, and toxicity is bigger, has certain safety issue, and expectation will be replaced by the new material of high-performance and low-cost.Spinelle LiMn
2O
4Cost is low, and fail safe is good, but cycle performance especially high temperature cyclic performance is poor, certain dissolubility is arranged in electrolyte, storge quality is poor.LiNiO
2Cost is lower, and capacity is higher, but the preparation difficulty, there are comparatively serious safety problem in the consistency of material property and poor reproducibility.LiNi
0.8Co
0.2O
2Can regard LiNiO as
2And LiCoO
2Solid solution, have LiNiO concurrently
2And LiCoO
2Advantage, once it is believed that it is most possibly to replace LiCoO
2Novel anode material, but still have shortcomings such as synthesis condition comparatively harsh (needing oxygen atmosphere), fail safe be relatively poor, combination property haves much room for improvement.
Recently, novel ternary compound oxides nickle cobalt lithium manganate (LiNi
1/3Co
1/3Mn
1/3O
2) attracted attention by the people.In this material, Ni is+divalent, and Co is+3 valencys, and Mn is+4 valencys; During charging, Mn
4+Fixed price, Ni
2+Become Ni
4+, Co
3+Become Co
4+Studies show that this novel anode material has been concentrated LiCoO
2, LiNiO
2, LiMn
2O
4Advantage separately Deng material: cost compares LiCoO
2Reduce greatly, with LiNi
0.8Co
0.2O
2Quite, even be lower than LiNi
0.8Co
0.2O
2The voltage platform height; Reversible capacity big (160-190mAh/g); Stability Analysis of Structures, fail safe is good, is better than LiNi
0.8Co
0.8O
2, between LiNi
0.8Co
0.2O
2And LiMn
2O
4Between; Good cycle; Easily synthetic, only need in air atmosphere, can synthesize.
At present, synthetic nickle cobalt lithium manganate is about to lithium source, nickel source, cobalt source, manganese source ground and mixed together mainly by high-temperature solid phase reaction method, and calcining is synthetic under about 1000 ℃ of high temperature.There is significant disadvantages in this method, and the one, nickel, cobalt, three kinds of elements of manganese are failed full and uniform mixing, fail to give full play to effect separately.The 2nd, the powder body material that synthesizes is made up of random particle, and bulk density is low, and general tap density only is 1.6-1.8g/cm
3, than cobalt acid lithium (general tap density 2.2-2.5g/cm
3, the high 2.8-2.9g/cm that reaches
3) much lower, low bulk density makes that the volume and capacity ratio of nickle cobalt lithium manganate is more much lower than the sour lithium of cobalt, has no advantage and can say, has hindered the practical application of this material.Therefore, the bulk density and the volume and capacity ratio of raising nickle cobalt lithium manganate are significant to the practicability of nickle cobalt lithium manganate.
The bulk density of powder body material and the pattern of powder granule, particle diameter and distribution thereof are closely related.The nickle cobalt lithium manganate positive electrode of having reported both at home and abroad all is made up of random sheet or granular solid matter at present, and bulk density is low.The nickle cobalt lithium manganate powder body material of being made up of the spheric granules of rule will have higher bulk density.Moreover, spherical product also has excellent flowability, dispersiveness and processability, very helps making the coating of positive electrode slurry and electrode slice, improves the electrode slice quality.In addition, with respect to random particle, the spheric granules surface ratio of rule is easier to coat complete, even, firm decorative layer, so the spherical nickel-cobalt LiMn2O4 more is hopeful further to improve combination property by finishing.Up to now, the spherical nickel-cobalt LiMn2O4 is not seen bibliographical information as yet.
Summary of the invention
The purpose of this invention is to provide by sphere or spherical particle and form, bulk density is big, the preparation method of a kind of anode material for lithium-ion batteries high density spherical nickel-cobalt LiMn2O4 that specific capacity is high is characterized in that: earlier nickel salt, cobalt salt, manganese salt and NaOH, ammonia are reacted synthesizing spherical or class ball-shape nickel hydroxide cobalt manganese Ni in the aqueous solution
1/3Co
1/3Mn
1/3(OH)
2Presoma, evenly mix with lithium carbonate the dry back of washing, obtained the spherical nickel-cobalt LiMn2O4 in high-temperature heat treatment 8-48 hour through 750-950 ℃ in air.Concrete enforcement comprises following each step:
1) the total concentration of metal ions of preparation is nickel salt, cobalt salt, the manganese salt mixed aqueous solution of 0.6-3 mol, wherein is Ni: Co: Mn=1 in molar ratio: 1: 1.
2) compound concentration is the sodium hydrate aqueous solution of 2-10 mol.
3) compound concentration is the ammonia spirit of 2-10 mol.
4) above-mentioned nickel cobalt-manganese salt mixed aqueous solution, sodium hydrate aqueous solution, ammonia spirit are input to respectively continuously with pump in the reactor of band stirring, regulate the flow of nickel cobalt-manganese salt mixed aqueous solution and ammonia spirit, the control mol ratio is NH
3: (Ni+Co+Mn)=0.2-1.0; Regulate the flow of sodium hydrate aqueous solution simultaneously, the pH value of control reactor internal reaction liquid is 10-12.Control reaction temperature is 40-65 ℃.Mixed material nature overflow in the reactor is discharged.
5) step (4) gained material changed over to carry out Separation of Solid and Liquid in the solid-liquid separator, with the solid product of deionized water washing Separation of Solid and Liquid gained to the pH value of washings less than till 8; Product after the washing in 80-100 ℃ of dry 2-4 hour, gets ball-shape nickel hydroxide cobalt manganese in drier.
6) with mass ratio 1: 1 lithium carbonate is mixed with deionized water, and in ball mill, made slurry in ball milling 2-4 hour.
7) be Li in molar ratio: (Ni+Co+Mn)=(1-1.1): 1 ratio takes by weighing step (5) gained ball-shape nickel hydroxide cobalt manganese and step (6) gained lithium carbonate slurry mixes.
8) step (7) products therefrom is placed stove, be warming up to 750-950 ℃, constant temperature 8-48 hour, natural cooling in stove obtained the spherical nickel-cobalt LiMn2O4.
Described nickel salt is selected from one or more in nickel nitrate, nickel chloride and the nickelous sulfate.
Described cobalt salt is selected from one or more in cobalt nitrate, cobalt chloride and the cobaltous sulfate.
Described manganese salt is selected from one or more in manganese nitrate, manganese chloride and the manganese sulfate.
The invention has the beneficial effects as follows: the method for using co-precipitation in the aqueous solution is with nickel, cobalt, the homogeneous precipitation simultaneously of manganese three metal ion species, reach the even mixing of atom level, again with this presoma and lithium carbonate blend heat treatment, thereby nickel, cobalt, manganese three metal ion species also reach the even mixing of atom level in the assurance end product, give full play to effect separately, help improving the performance of material.Simultaneously, in coprecipitation process, the control reaction condition, making coprecipitated product is sphere or class sphere, and its particle size distribution is optimized, and is sphere or class sphere thereby make end product, reaches higher bulk density.Embodiment product after tested, average grain diameter is 3-7 μ m, tap density is 2.25～2.50g/cm
3With the lithium sheet is negative pole, and recording this nickle cobalt lithium manganate first discharge specific capacity at room temperature is 172～185mAh/g.
Embodiment
The invention provides by sphere or spherical particle and form, bulk density is big, the preparation method of a kind of anode material for lithium-ion batteries high density spherical nickel-cobalt LiMn2O4 that specific capacity is high.This method is earlier nickel salt, cobalt salt, manganese salt and NaOH, ammonia to be reacted synthesizing spherical or class ball-shape nickel hydroxide cobalt manganese Ni in the aqueous solution
1/3Co
1/3Mn
1/3(OH)
2Presoma, evenly mix with lithium carbonate the dry back of washing, obtained the spherical nickel-cobalt LiMn2O4 in high-temperature heat treatment 8-48 hour through 750-950 ℃ in air.Specific implementation method of the present invention comprises following each step:
1) the total concentration of metal ions of preparation is nickel salt, cobalt salt, the manganese salt mixed aqueous solution of 0.6-3 mol, wherein is Ni: Co: Mn=1 in molar ratio: 1: 1.
2) compound concentration is the sodium hydrate aqueous solution of 2-10 mol.
3) compound concentration is the ammonia spirit of 2-10 mol.
4) above-mentioned nickel cobalt-manganese salt mixed aqueous solution, sodium hydrate aqueous solution, ammonia spirit are input to respectively continuously with pump in the reactor of band stirring, regulate the flow of nickel cobalt-manganese salt mixed aqueous solution and ammonia spirit, the control mol ratio is NH
3: (Ni+Co+Mn)=0.2-1.0; Regulate the flow of sodium hydrate aqueous solution simultaneously, the pH value of control reactor internal reaction liquid is 10-12.Control reaction temperature is 40-65 ℃.Mixed material nature overflow in the reactor is discharged.
5) step (4) gained material changed over to carry out Separation of Solid and Liquid in the solid-liquid separator, with the solid product of deionized water washing Separation of Solid and Liquid gained to the pH value of washings less than till 8; Product after the washing in 80-100 ℃ of dry 2-4 hour, gets ball-shape nickel hydroxide cobalt manganese in drier.
6) with mass ratio 1: 1 lithium carbonate is mixed with deionized water, and in ball mill, made slurry in ball milling 2-4 hour.
7) be Li in molar ratio: (Ni+Co+Mn)=(1-1.1): 1 ratio takes by weighing step (5) gained ball-shape nickel hydroxide cobalt manganese and step (6) gained lithium carbonate slurry mixes.
8) step (7) products therefrom is placed stove, be warming up to 750-950 ℃, constant temperature 8-48 hour, natural cooling in stove obtained the spherical nickel-cobalt LiMn2O4.
In above-mentioned preparation method, the described nickel salt of step (1) is selected from a kind of in nickel nitrate, nickel chloride, the nickelous sulfate or several; Described cobalt salt is selected from a kind of in cobalt nitrate, cobalt chloride, the cobaltous sulfate or several; Described manganese salt is selected from a kind of in manganese nitrate, manganese chloride, the manganese sulfate or several.
Introduce embodiments of the invention below:
Embodiment 1
Preparation nickel nitrate concentration is that 1 mol, cobalt nitrate concentration are that 1 mol, manganese nitrate concentration are the nickel cobalt-manganese salt mixed aqueous solution of 1 mol, and compound concentration is the sodium hydrate aqueous solution of 10 mol, and compound concentration is the ammonia spirit of 10 mol.Respectively nickel cobalt-manganese salt mixed aqueous solution, sodium hydrate aqueous solution, ammonia spirit are input to measuring pump in the reactor of 3 liter capacities that filled with deionized water in advance and react.The flow of control nickel cobalt-manganese salt mixed aqueous solution is 120 milliliters/hour, and the flow of control ammonia spirit makes NH in the reactor
3/ (Ni+Co+Mn)=0.5.Regulate the flow of sodium hydrate aqueous solution, the pH value of control reactor internal reaction liquid is 11.5.The control reactor temperature is 45 ℃.Mixed material nature overflow in the reactor enters in the pans.After the continuous feed 50 hours, stop charging, the material in the reactor is discharged, carry out Separation of Solid and Liquid with centrifuge.With 60 ℃ deionized waters washing solid products to the pH value of washings less than till 8.With the product after the washing in drying box in 90 ℃ dry 3 hours down, obtain ball-shape nickel hydroxide cobalt manganese.Take by weighing 38.85 gram lithium carbonate (Li
2CO
3) and measure 39 milliliters of deionized waters, place the ball mill ball milling to stop after 4 hours.Taking by weighing the above-mentioned nickel hydroxide cobalt manganese that makes of 90 grams, place the lithium carbonate slurry behind the ball milling, slowly stirred 10 minutes, obtain mixed slurry, wherein is Li in molar ratio: (Ni+Co+Mn)=1: 1.Mixed slurry is put into alumina crucible, and the speed by 200 ℃/hour in muffle furnace is warming up to 800 ℃, and constant temperature 16 hours stops heating, naturally cools to room temperature in stove, obtains the spherical nickel-cobalt LiMn2O4.Recording this product average grain diameter is 4-6 μ m, and tap density is 2.40g/cm
3With the lithium sheet is negative pole, and recording this nickle cobalt lithium manganate first discharge specific capacity at room temperature is 185mAh/g.
Embodiment 2
The preparation concentration of nickel sulfate is that 0.6 mol, cobalt sulfate concentration are that 0.6 mol, manganese sulfate concentration are the nickel cobalt-manganese salt mixed aqueous solution of 0.6 mol, compound concentration is the sodium hydrate aqueous solution of 3.6 mol, and compound concentration is the ammonia spirit of 5 mol.Respectively nickel cobalt-manganese salt mixed aqueous solution, sodium hydrate aqueous solution, ammonia spirit are input to measuring pump in the reactor of 3 liter capacities that filled with deionized water in advance and react.The flow of control nickel cobalt-manganese salt mixed aqueous solution is 120 milliliters/hour, and the flow of control ammonia spirit makes to be NH in the reactor in molar ratio
3/ (Ni+Co+Mn)=0.8.Regulate the flow of sodium hydrate aqueous solution, the pH value of control reactor internal reaction liquid is 11.0.The control reactor temperature is 45 ℃.Mixed material nature overflow in the reactor enters in the pans.After the continuous feed 50 hours, stop charging, the material in the reactor is discharged, carry out Separation of Solid and Liquid with centrifuge.With 60 ℃ deionized waters washing solid products to the pH value of washings less than till 8.With the product after the washing be in the dry case in 90 ℃ dry 3 hours down, obtain ball-shape nickel hydroxide cobalt manganese.Take by weighing 38.85 gram lithium carbonate (Li
2CO
3) and measure 39 milliliters of deionized waters, place the ball mill ball milling to stop after 4 hours.Taking by weighing the above-mentioned nickel hydroxide cobalt manganese that makes of 90 grams, place the lithium carbonate slurry behind the ball milling, slowly stirred 10 minutes, obtain mixed slurry, wherein is Li in molar ratio: (Ni+Co+Mn)=1: 1.Mixed slurry is put into alumina crucible, and the speed by 200 ℃/hour in muffle furnace is warming up to 800 ℃, and constant temperature 16 hours stops heating, naturally cools to room temperature in stove, obtains the spherical nickel-cobalt LiMn2O4.Recording this product average grain diameter is 4-6 μ m, and tap density is 2.35g/cm
3With the lithium sheet is negative pole, and recording this nickle cobalt lithium manganate first discharge specific capacity at room temperature is 177mAh/g.
Embodiment 3
Preparation nickel chloride concentration is that 0.2 mol, cobalt chloride concentration are that 0.2 mol, manganese chloride concentration are the nickel cobalt-manganese salt mixed aqueous solution of 0.2 mol, compound concentration is the sodium hydrate aqueous solution of 2.0 mol, and compound concentration is the ammonia spirit of 2 mol.Respectively nickel cobalt-manganese salt mixed aqueous solution, sodium hydrate aqueous solution, ammonia spirit are input to measuring pump in the reactor of 3 liter capacities that filled with deionized water in advance and react.The flow of control nickel cobalt-manganese salt mixed aqueous solution is 120 milliliters/hour, and the flow of control ammonia spirit makes to be NH in the reactor in molar ratio
3/ (Ni+Co+Mn)=1.0.Regulate the flow of sodium hydrate aqueous solution, the pH value of control reactor internal reaction liquid is 10.5.The control reactor temperature is 45 ℃.Mixed material nature overflow in the reactor enters in the pans.After the continuous feed 50 hours, stop charging, the material in the reactor is discharged, carry out Separation of Solid and Liquid with centrifuge.With 60 ℃ deionized waters washing solid products to the pH value of washings less than till 8.With the product after the washing in drying box in 90 ℃ dry 3 hours down, obtain ball-shape nickel hydroxide cobalt manganese.Take by weighing 38.85 gram lithium carbonate (Li
2CO
3) and measure 39 milliliters of deionized waters, place the ball mill ball milling to stop after 4 hours.Taking by weighing the above-mentioned nickel hydroxide cobalt manganese that makes of 90 grams, place the lithium carbonate slurry behind the ball milling, slowly stirred 10 minutes, obtain mixed slurry, wherein is Li in molar ratio: (Ni+Co+Mn)=1: 1.Mixed slurry is put into alumina crucible, and the speed by 200 ℃/hour in muffle furnace is warming up to 800 ℃, and constant temperature 16 hours stops heating, naturally cools to room temperature in stove, obtains the spherical nickel-cobalt LiMn2O4.Recording this product average grain diameter is 4-6 μ m, and tap density is 2.30g/cm
3With the lithium sheet is negative pole, and recording this nickle cobalt lithium manganate first discharge specific capacity at room temperature is 175mAh/g.
Embodiment 4
Heat treatment temperature is 950 ℃, constant temperature 48 hours, and other condition obtains the spherical nickel-cobalt LiMn2O4 with embodiment 1.Recording this product average grain diameter is 3-5 μ m, and tap density is 2.50g/cm
3With the lithium sheet is negative pole, and recording this nickle cobalt lithium manganate first discharge specific capacity at room temperature is 172mAh/g.
Embodiment 5
Heat treatment temperature is 750 ℃, constant temperature 8 hours, and other condition obtains the spherical nickel-cobalt LiMn2O4 with embodiment 1.Recording this product average grain diameter is 5-7 μ m, and tap density is 2.25g/cm
3With the lithium sheet is negative pole, and recording this nickle cobalt lithium manganate first discharge specific capacity at room temperature is 173mAh/g.
Embodiment 6
The lithium carbonate consumption increases to 40.7 grams, is Li in molar ratio in the mixed slurry: (Ni+Co+Mn)=1.1: 1, other condition obtains the spherical nickel-cobalt LiMn2O4 with embodiment 1.Recording this product average grain diameter is 4-6 μ m, and tap density is 2.42g/cm
3With the lithium sheet is negative pole, and recording this nickle cobalt lithium manganate first discharge specific capacity at room temperature is 176mAh/g.
Comparing embodiment 1
Adopt traditional mechanical mixture-high-temperature solid phase reaction method to prepare non-spherical nickel-cobalt LiMn2O4.Take by weighing 38.85 gram lithium carbonate (Li
2CO
3), 41.65 gram nickelous carbonate (NiCO
3), 41.65 gram cobalt carbonate (CoCO
3), 40.25 gram manganese carbonate (MnCO
3), place the ball mill ball milling to stop after 24 hours.Mixed material is put into alumina crucible, and the speed by 200 ℃/hour in muffle furnace is warming up to 800 ℃, and constant temperature 16 hours stops heating, naturally cools to room temperature in stove, obtains nickle cobalt lithium manganate.Recording this product average grain diameter is 6-8 μ m, and tap density is 1.70g/cm
3With the lithium sheet is negative pole, and recording this nickle cobalt lithium manganate first discharge specific capacity at room temperature is 162mAh/g.
Claims (4)
1. the preparation method of an anode material for lithium-ion batteries high density spherical nickel-cobalt LiMn2O4 is characterized in that: earlier nickel salt, cobalt salt, manganese salt and NaOH, ammonia are reacted synthesizing spherical or class ball-shape nickel hydroxide cobalt manganese Ni in the aqueous solution
1/3Co
1/3Mn
1/3(OH)
2Presoma, evenly mix with lithium carbonate the dry back of washing, obtained the spherical nickel-cobalt LiMn2O4 in high-temperature heat treatment 8-48 hour through 750-950 ℃ in air; Concrete enforcement comprises following each step:
1) the total concentration of metal ions of preparation is nickel salt, cobalt salt, the manganese salt mixed aqueous solution of 0.6-3 mol, wherein is Ni: Co: Mn=1 in molar ratio: 1: 1;
2) compound concentration is the sodium hydrate aqueous solution of 2-10 mol;
3) compound concentration is the ammonia spirit of 2-10 mol;
4) above-mentioned nickel cobalt-manganese salt mixed aqueous solution, sodium hydrate aqueous solution, ammonia spirit are input to respectively continuously with pump in the reactor of band stirring, regulate the flow of nickel cobalt-manganese salt mixed aqueous solution and ammonia spirit, the control mol ratio is NH
3: (Ni+Co+Mn)=0.2-1.0; Regulate the flow of sodium hydrate aqueous solution simultaneously, the pH value of control reactor internal reaction liquid is 10-12; Control reaction temperature is 40-65 ℃; Mixed material nature overflow in the reactor is discharged;
5) step (4) gained material changed over to carry out Separation of Solid and Liquid in the solid-liquid separator, with the solid product of deionized water washing Separation of Solid and Liquid gained to the pH value of washings less than till 8; Product after the washing in 80-100 ℃ of dry 2-4 hour, gets ball-shape nickel hydroxide cobalt manganese in drier;
6) with mass ratio 1: 1 lithium carbonate is mixed with deionized water, and in ball mill, made slurry in ball milling 2-4 hour;
7) be Li in molar ratio: (Ni+Co+Mn)=(1-1.1): 1 ratio takes by weighing step (5) gained ball-shape nickel hydroxide cobalt manganese and step (6) gained lithium carbonate slurry mixes;
8) step (7) products therefrom is placed stove, be warming up to 750-950 ℃, constant temperature 8-48 hour, natural cooling in stove obtained the spherical nickel-cobalt LiMn2O4.
2. the preparation method of nickle cobalt lithium manganate according to claim 1 is characterized in that described nickel salt is selected from one or more in nickel nitrate, nickel chloride or the nickelous sulfate.
3. the preparation method of nickle cobalt lithium manganate according to claim 1 is characterized in that described cobalt salt is selected from one or more in cobalt nitrate, cobalt chloride or the cobaltous sulfate.
4. the preparation method of nickle cobalt lithium manganate according to claim 1 is characterized in that described manganese salt is selected from one or more in manganese nitrate, manganese chloride or the manganese sulfate.
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