CN1767236A - Method for preparing lithium ion battery anode material LiMnxCoyNi1-x-yO2 - Google Patents

Abstract

The invention relates to a method for using layered double hydroxyl compound oxide as pioneer body to prepare alpha-NaFeO2 structure lithium ion cell LiMnxCoyNi1-x-yO2 anode material. It first prepares a cobalt-nickel-manganese layered double hydroxyl compound oxide Co-Ni-Mn-LDHs pioneer body; and then it mixes them with lithium source material and burns them at a certain temperature to obtain the electrode material.

Description

A kind of anode material for lithium-ion batteries LiMn xCo yNi 1-x-yO 2The preparation method

Technical field

The invention belongs to the lithium ion battery material preparing technical field, a kind of polynary metal oxide LiMn particularly is provided _xCo _yNi _1-x-yO ₂The preparation method of positive electrode.

Background technology

Present commercial lithium ion battery is mainly with LiCoO ₂As positive electrode, but LiCoO ₂Have price height, poisonous, anti-over-charging poor electrical performance, defectives such as actual specific capacity is on the low side, thermal stability difference, so people still constantly research and develop the new type lithium ion battery positive electrode, wherein polynary metal oxide LiMn _xCo _yNi _1-x-yO ₂Positive electrode causes people's common concern.With LiCoO ₂Material is compared, LiMn _xCo _yNi _1-x-yO ₂Positive electrode has specific capacity height, anti-over-charging good electrical property, thermal stability advantages of higher.But to polynary metal oxide LiMn _xCo _yNi _1-x-yO ₂Positive electrode, how to guarantee the even distribution in product of manganese, cobalt and nickel element, it is the key of synthetic this material, existing research work shows, synthetic method and process conditions are to the considerable influence that is evenly distributed with of manganese in the product, cobalt, nickel element, and finally have influence on the composition structure and the chemical property of product.

At document (1) Journal of The Electrochemical Society, 2003,150 (12): among the A1637, people such as S.Jouanneau adopt coprecipitation method to synthesize Ni earlier _xCo _1-2xMn _x(OH) ₂As the reaction precursor body, mix the back then with LiOH at 900～1100 ℃ of roasting temperature certain hours, obtain anode material for lithium-ion batteries Li[Ni _xCo _1-2xMn _x] O ₂But because Mn (OH) ₂, Co (OH) ₂And the solubility product constant of Ni (OH) has than big difference, therefore is difficult to guarantee the even distribution of above-mentioned three metal ion species in presoma.

At document (2) Journal of Power Sources, 2004, among the 132:150, people such as De-Cheng Li have compared spray drying process and acetate thermolysis process to synthetic Li Ni _1/3Mn _1/3Co _1/3O ₂Influence.In the acetate thermolysis process, the raw material mixing uniformity is relatively poor, is prone to the impurity phase; Adopt spray drying process; the raw material degree of mixing increases; but because presoma is a mixture; segregation phenomena easily takes place in follow-up roasting process; therefore still be difficult to guarantee the even distribution in product of manganese, cobalt and nickel element, in addition, adopt spray drying process; production cost is higher, is difficult to accomplish scale production.

Summary of the invention

The object of the present invention is to provide a kind of polynary metal oxide LiMn _xCo _yNi _1-x-yO ₂The preparation method of anode material for lithium-ion batteries distributes evenly inadequately to solve transition metal manganese in this material, cobalt, nickel, is prone to the problem of impurity phase.

Lithium ion battery LiMn of the present invention _xCo _yNi _1-x-yO ₂Positive electrode adopts has the preparation method of the cobalt-nickel-manganese layered di-hydroxyl composite metal oxidate (Co-Ni-Mn-LDHs) of good crystal formation as the reaction precursor body.Utilize metallic element equally distributed architectural feature on laminate among the LDHs, can make manganese, cobalt, nickel element reach the even distribution of molecular level; Utilize the lattice orientation effect of metallic element among the LDHs, can make that segregation does not take place transition metal ions in the roasting process, thereby can obtain the LiMn of purity height, regular crystal forms _xCo _yNi _1-x-yO ₂Positive electrode.

In addition, the present invention considers that the valence state of manganese is more and is oxidized to easily and is higher than+higher valence state of 3 valencys, by adding H in the alcaliotropism slurries ₂O ₂Oxidant controllably is oxidizing to the manganese of+divalent+3 valencys, thereby synthesizes cobalt-nickel that crystal formation is good, purity is high-manganese layered di-hydroxyl composite metal oxidate (Co-Ni-Mn-LDHs) presoma, and this also is the key link that the present invention is implemented.

The Co-Ni-Mn-LDHs presoma and the lithium source material that will have good crystal formation mix, and obtain lithium ion battery LiMn after roasting _xCo _yNi _1-x-yO ₂Positive electrode.

Concrete processing step is as follows:

A. according to the molar ratio (Co of metal cation ²⁺+ Ni ²⁺)/Mn ²⁺Be 1～4 and Co ²⁺/ Ni ²⁺Ratio be 0.5～2.0, the salt that takes by weighing solubility divalence cobalt, nickel, manganese respectively is dissolved in the deionized water and is made into [Mn ²⁺+ Co ²⁺+ Ni ²⁺] the metal ion total concentration is the mixing salt solution of 0.8～1.0mol/L; Preparation is the mixed-alkali solution of 1.4～2.0mol/L with mixing salt solution equal-volume, total concentration; Is to mix fast under 15～35 ℃ 1～2 minute above-mentioned two kinds of solution in reaction temperature; Then with slurries 50～70 ℃ of following crystallization 10～20 hours, dripping concentration during the beginning crystallization is the H of 0.1～0.2mol/L ₂O ₂Solution, H ₂O ₂Addition be 0.5～2 times of manganese element total amount in the reactant, in 1～2 hour, at the uniform velocity dropwise; Crystallization finishes the back with deionized water washing reaction product repeatedly, to filtrate pH value be 7～8,70～90 ℃ of dryings 6～12 hours in air again obtain having the stratiform Co-Ni-Mn-LDHs presoma of good crystal formation.

B. be 1.05～1.10 to take by weighing lithium source material and Co-Ni-Mn-LDHs presoma according to metal ion molar ratio Li/ (Co+Ni+Mn), it with the cyclohexane dispersant ball milling 6～12 hours in the agate jar, 60～80 ℃ of dryings were removed cyclohexane in 4～8 hours and are placed in the muffle furnace, be warming up to 450 ℃ with 5～10 ℃/minute speed, be incubated 1～3 hour, be warming up to 800 ℃～900 ℃ with 5～10 ℃/minute speed again, be incubated 10～20 hours, cool to room temperature with the furnace, obtain product α-NaFeO of the present invention ₂The LiMn of structure _xCo _yNi _1-x-yO ₂Positive electrode.

The described solubility divalent cobalt of steps A is cobalt nitrate Co (NO ₃) ₂, cobalt chloride CoCl ₂Or cobaltous sulfate CoSO ₄In a kind of, the solubility divalent nickel salt is nitric acid nickel (NO ₃) ₂, nickel chloride NiCl ₂Or nickelous sulfate NiSO ₄In a kind of, the solubility manganous salt is manganese nitrate Mn (NO ₃) ₂, manganese chloride MnCl ₂Or manganese sulfate MnSO ₄In a kind of.

The mixture solution that the described mixed-alkali solution of steps A is hydroxide and carbonate, and OH ^-With CO ₃ ^2-Mol ratio be 2～4; Hydroxide is a kind of among lithium hydroxide LiOH, NaOH NaOH, the potassium hydroxide KOH, and carbonate is sodium carbonate Na ₂CO ₃, potash K ₂CO ₃, ammonium carbonate (NH ₄) ₂CO ₃In a kind of.

In the preparation of the described stratiform presoma of steps A, the actual amount of hydroxide and carbonate is a little more than generating the required hydroxide of Co-Ni-Mn-LDHs presoma and the theoretical consumption of carbonate, thereby the slurries that make generation are alkalescence, and the pH value is 10～12, drip H when the beginning crystallization ₂O ₂Solution is to utilize H ₂O ₂In alkaline solution, be weak oxide, can and only+2 manganese can be oxidizing to+3 valencys, control H ₂O ₂Consumption, can make the molar ratio M of bivalent metal ion and trivalent metal ion ²⁺/ M ³⁺Be 2～4, to satisfy the primary condition that generates layered di-hydroxyl composite metal oxidate.

Lithium source material described in the step B is lithium carbonate Li ₂CO ₃, lithium nitrate LiNO ₃Or among the lithium hydroxide LiOH any one.

The invention has the advantages that: by the pH value and the oxidizing condition of slurries in the control crystallization process, controllably the manganese of general+divalent is oxidized to+3 valencys, have the Co-Ni-Mn-LDHs presoma of good crystal formation with formation, can make manganese, cobalt, nickel element reach the even distribution of molecular level; Utilize the lattice orientation effect of metallic element among the LDHs, can make that segregation does not take place transition metal ions in the roasting process, thereby can obtain the LiMn of purity height, regular crystal forms _xCo _yNi _1-x-yO ₂Positive electrode; In addition, the synthetic method craft that the present invention relates to is simple, and is easy to operate, is easy to realize large-scale industrial production.The method that adopts invention to provide can be prepared the electrode material (seeing comparative example table 1) with higher reversible first specific discharge capacity and favorable charge-discharge cycle performance.

Description of drawings

Fig. 1. the LiMn that utilizes Co-Ni-Mn-LDHs to obtain as the reaction precursor body _0.40Ni _0.40Co _0.20O ₂XRD spectra.Abscissa is angle 2 θ, and unit is ° (degree); Ordinate is an intensity, and unit is a.u. (absolute unit).

Embodiment

Embodiment 1:

With Mn (NO ₃) ₂, Co (NO ₃) ₂, Ni (NO ₃) ₂Mn in molar ratio ²⁺/ Co ²⁺/ Ni ²⁺=2/1/2 mixed is dissolved in the deionized water, is made into [Mn ²⁺+ Co ²⁺+ Ni ²⁺] the metal ion total concentration is the mixing salt solution of 1.0mol/L, preparation equal-volume total concentration is LiOH and the (NH of 1.8mol/L ₄) ₂CO ₃The mixed-alkali aqueous solution, and LiOH/ (NH ₄) ₂CO ₃Mol ratio be 2; Is to mix reaction 1 minute under 25 ℃ fast with above-mentioned two kinds of solution in reaction temperature; Then with slurries 70 ℃ of following crystallization 10 hours, dripping concentration during the beginning crystallization is the H of 0.1mol/L ₂O ₂Solution, H ₂O ₂Addition be 0.5 times of manganese element total amount in the reactant, in 1 hour, at the uniform velocity dropwise; Crystallization finishes the back with deionized water washing reaction product repeatedly, to filtrate pH value be 8,70 ℃ of dryings 12 hours in air again obtain having the stratiform Co-Ni-Mn-LDHs presoma of good crystal formation.

According to metal ion molar ratio Li/ (Co+Ni+Mn) is 1.05 to take by weighing Li ₂CO ₃With the Co-Ni-Mn-LDHs presoma, it with the cyclohexane dispersant ball milling 6 hours in the agate jar, 60 ℃ of dryings were removed cyclohexane in 8 hours and are placed in the muffle furnace, be warming up to 450 ℃ with 5 ℃/minute speed, be incubated 1 hour, be warming up to 800 ℃ with 5 ℃/minute speed again, be incubated 20 hours, cool to room temperature with the furnace, obtain anode material for lithium-ion batteries of the present invention.

Adopt day island proper Tianjin ICPS-7500 type inductive coupling plasma emission spectrograph to measure the content of metal ion in the product, determine that it consists of LiMn _0.40Co _0.20Ni _0.40O ₂Adopt day island proper Tianjin XRD-6000 type x-ray powder diffraction instrument (Cu K _αRadiation, λ=1.5406 ) characterize product structure, its XRD test result as shown in Figure 1, product is the single α-NaFeO of crystalline phase ₂The LiMn of structure _0.40Co _0.20Ni _0.40O ₂

Embodiment 2:

With MnSO ₄, CoSO ₄, NiSO ₄Mn in molar ratio ²⁺/ Co ²⁺/ Ni ²⁺=1/1/1 mixed is dissolved in the deionized water, is made into [Mn ²⁺+ Co ²⁺+ Ni ²⁺] the metal ion total concentration is the mixing salt solution of 0.9mol/L, preparation equal-volume total concentration is KOH and the K of 1.6mol/L ₂CO ₃The mixed-alkali aqueous solution, and KOH/K ₂CO ₃Mol ratio be 4; Is to mix reaction 2 minutes under 15 ℃ fast with above-mentioned two kinds of solution in reaction temperature; Then with slurries 50 ℃ of following crystallization 20 hours, dripping concentration during the beginning crystallization is the H of 0.2mol/L ₂O ₂Solution, H ₂O ₂Addition be 1 times of manganese element total amount in the reactant, in 2 hours, at the uniform velocity dropwise; Crystallization finishes the back with deionized water washing reaction product repeatedly, to filtrate pH value be 7.5,90 ℃ of dryings 6 hours in air again obtain having the stratiform Co-Ni-Mn-LDHs presoma of good crystal formation.

According to metal ion molar ratio Li/ (Co+Ni+Mn) is 1.10 to take by weighing LiNO ₃With the Co-Ni-Mn-LDHs presoma, it with the cyclohexane dispersant ball milling 12 hours in the agate jar, 80 ℃ of dryings were removed cyclohexane in 4 hours and are placed in the muffle furnace, be warming up to 450 ℃ with 10 ℃/minute speed, be incubated 3 hours, be warming up to 900 ℃ with 10 ℃/minute speed again, be incubated 10 hours, cool to room temperature with the furnace, obtain anode material for lithium-ion batteries of the present invention.

ICP and XRD test result show that product is the single α-NaFeO of crystalline phase ₂The LiMn of structure _1/3Co _1/3Ni _1/3O ₂

Embodiment 3:

With MnCl ₂, CoCl ₂, NiCl ₂Mn in molar ratio ²⁺/ Co ²⁺/ Ni ²⁺=1/2/2 mixed is dissolved in the deionized water, is made into [Mn ²⁺+ Co ²⁺+ Ni ²⁺] the metal ion total concentration is the mixing salt solution of 0.8mol/L, preparation equal-volume total concentration is NaOH and the Na of 1.4mol/L ₂CO ₃The mixed-alkali aqueous solution, and NaOH/Na ₂CO ₃Mol ratio be 2; Is to mix reaction 1 minute under 35 ℃ fast with above-mentioned two kinds of solution in reaction temperature; Then with slurries 60 ℃ of following crystallization 15 hours, dripping concentration during the beginning crystallization is the H of 0.1mol/L ₂O ₂Solution, H ₂O ₂Addition be 2 times of manganese element total amount in the reactant, in 1 hour, at the uniform velocity dropwise; Crystallization finishes the back with deionized water washing reaction product repeatedly, to filtrate pH value be 7,80 ℃ of dryings 10 hours in air again obtain having the stratiform Co-Ni-Mn-LDHs presoma of good crystal formation.

According to metal ion molar ratio Li/ (Co+Ni+Mn) is 1.05 to take by weighing LiOH and Co-Ni-Mn-LDHs presoma, it with the cyclohexane dispersant ball milling 8 hours in the agate jar, 70 ℃ of dryings were removed cyclohexane in 6 hours and are placed in the muffle furnace, be warming up to 450 ℃ with 10 ℃/minute speed, be incubated 2 hours, be warming up to 800 ℃ with 10 ℃/minute speed again, be incubated 15 hours, cool to room temperature with the furnace, obtain anode material for lithium-ion batteries of the present invention.

ICP and XRD test result show that product is the single α-NaFeO of crystalline phase ₂The LiMn of structure _0.20Co _0.40Ni _0.40O ₂

Embodiment 4:

With MnSO ₄, CoSO ₄, NiSO ₄Mn in molar ratio ²⁺/ Co ²⁺/ Ni ²⁺=2/2/1 mixed is dissolved in the deionized water, is made into [Mn ²⁺+ Co ²⁺+ Ni ²⁺] the metal ion total concentration is the mixing salt solution of 1.0mol/L, preparation equal-volume total concentration is LiOH and the (NH of 1.8mol/L ₄) ₂CO ₃The mixed-alkali aqueous solution, and LiOH/ (NH ₄) ₂CO ₃Mol ratio be 3; Is to mix reaction 2 minutes under 25 ℃ fast with above-mentioned two kinds of solution in reaction temperature; Then with slurries 60 ℃ of following crystallization 20 hours, dripping concentration during the beginning crystallization is the H of 0.1mol/L ₂O ₂Solution, H ₂O ₂Addition be 0.5 times of manganese element total amount in the reactant, in 1 hour, at the uniform velocity dropwise; Crystallization finishes the back with deionized water washing reaction product repeatedly, to filtrate pH value be 8,70 ℃ of dryings 12 hours in air again obtain having the stratiform Co-Ni-Mn-LDHs presoma of good crystal formation.

According to metal ion molar ratio Li/ (Co+Ni+Mn) is 1.10 to take by weighing LiNO ₃With the Co-Ni-Mn-LDHs presoma, it with the cyclohexane dispersant ball milling 8 hours in the agate jar, 60 ℃ of dryings were removed cyclohexane in 8 hours and are placed in the muffle furnace, be warming up to 450 ℃ with 10 ℃/minute speed, be incubated 2 hours, be warming up to 900 ℃ with 5 ℃/minute speed again, be incubated 10 hours, cool to room temperature with the furnace, obtain anode material for lithium-ion batteries of the present invention.

ICP and XRD test result show that product is the single α-NaFeO of crystalline phase ₂The LiMn of structure _0.40Co _0.40Ni _0.20O ₂

Embodiment 5:

With Mn (NO ₃) ₂, Co (NO ₃) ₂, Ni (NO ₃) ₂Mn in molar ratio ²⁺/ Co ²⁺/ Ni ²⁺=2/1/1 mixed is dissolved in the deionized water, is made into [Mn ²⁺+ Co ²⁺+ Ni ²⁺] the metal ion total concentration is the mixing salt solution of 0.8mol/L, preparation equal-volume total concentration is LiOH and the Na of 1.5mol/L ₂CO ₃Mixed aqueous solution, and LiOH/Na ₂CO ₃Mol ratio be 2; Is to mix reaction 2 minutes under 35 ℃ fast with above-mentioned two kinds of solution in reaction temperature; Then with slurries 60 ℃ of following crystallization 15 hours, dripping concentration during the beginning crystallization is the H of 0.1mol/L ₂O ₂Solution, H ₂O ₂Addition be 1.0 times of manganese element total amount in the reactant, in 1 hour, at the uniform velocity dropwise; Crystallization finishes the back with deionized water washing reaction product repeatedly, to filtrate pH value be 7,80 ℃ of dryings 10 hours in air again obtain having the stratiform Co-Ni-Mn-LDHs presoma of good crystal formation.

According to metal ion molar ratio Li/ (Co+Ni+Mn) is 1.05 to take by weighing Li ₂CO ₃With the Co-Ni-Mn-LDHs presoma, it with the cyclohexane dispersant ball milling 12 hours in the agate jar, 80 ℃ of dryings were removed cyclohexane in 6 hours and are placed in the muffle furnace, be warming up to 450 ℃ with 10 ℃/minute speed, be incubated 3 hours, be warming up to 850 ℃ with 5 ℃/minute speed again, be incubated 15 hours, cool to room temperature with the furnace, obtain anode material for lithium-ion batteries of the present invention.

ICP and XRD test result show that product is the single α-NaFeO of crystalline phase ₂The LiMn of structure _0.50Co _0.25Ni _0.25O ₂

Comparative Examples

Synthetic α-the NaFeO of the inventive method will be adopted ₂The LiMn of structure _xCo _yNi _1-x-yO ₂Electrode material and commercially available acetylene black conductive agent and polytetrafluoroethylene binding agent mix by the mass fraction of (85: 10: 5), and the thickness of compressing tablet to 100 μ m, in 120 ℃ of vacuum (＜1Pa) drying 24 hours.As to electrode, adopt Celgard 2400 barrier films, the LiPF of 1mol/L with metal lithium sheet ₆+ EC+DMC (EC/DMC volume ratio 1: 1) is an electrolyte, at the German M. Braun Unlab of company type dry argon gas glove box (H ₂O＜1ppm, O ₂＜be assembled into Experimental cell in 1ppm), adopt the blue electric BTI1-10 type cell tester in Wuhan to carry out electrochemical property test.α-NaFeO by embodiment of the invention acquisition ₂The LiMn of structure _xCo _yNi _1-x-yO ₂Reversible specific discharge capacity when the chemical composition of sample, electro-chemical test condition, reversible specific discharge capacity, the circulation when reversible specific discharge capacity, circulation 10 times first 35 times and the capability retention that circulates 35 times the time are shown in Table 1.Also listed the Electrochemical results of sample in document (1) and (2) in the table 1.

The composition of table 1 electrode material and chemical property

The sample title	Chemical composition	The electro-chemical test condition	Specific discharge capacity mAh/g
							Reversible first	10 times reversible	35 times reversible	Capability retention
			Embodiment 1	LiMn 0.40Co 0.20Ni 0.40O 2	2.75～4.5V vs.Li 0.2mA/cm 2	187					176	164	88％
Embodiment 2	LiMn 1/3Co 1/3Ni 1/3O 2	2.75～4.5V vs.Li 0.2mA/cm 2					186	177	165	89％
			Embodiment 3	LiMn 0.20Co 0.40Ni 0.40O 2	2.75～4.5V vs.Li 0.2mA/cm 2	192					181	167	87％
Embodiment 4	LiMn 0.40Co 0.40Ni 0.20O 2	2.75～4.5V vs.Li 0.2mA/cm 2					184	173	166	90％
			Embodiment 5	LiMn 0.50Co 0.25Ni 0.25O 2	2.75～4.5V vs.Li 0.2mA/cm 2	185					171	159	86％
Document (1)	LiMn 0.25Co 0.50Ni 0.25O 2	2.5～4.4V vs.Li 40mA/g					158	137 *		87％ *
			Document (2)	LiMn 1/3Co 1/3Ni 1/3O 2	3.0 3 hours 0.2mA/cm of～4.5V vs.Li 4.5V constant voltage charge 2	195						166	85％

Annotate: ^*Be the data that circulate 20 times the time

As can be seen from Table 1: the method that adopts invention to provide can be prepared has the higher reversible first specific discharge capacity and the electrode material of favorable charge-discharge cycle performance.

Claims (3)

1. anode material for lithium-ion batteries LiMn _xCo _yNi _1-x-yO ₂The preparation method, its processing step comprises:

A. according to the molar ratio (Co of metal cation ²⁺+ Ni ²⁺)/Mn ²⁺Be 1～4 and Co ²⁺/ Ni ²⁺Ratio be 0.5～2.0, the salt that takes by weighing solubility divalence cobalt, nickel, manganese respectively is dissolved in the deionized water and is made into [Mn ²⁺+ Co ²⁺+ Ni ²⁺] the metal ion total concentration is the mixing salt solution of 0.8～1.0mol/L;

Preparation is the mixed-alkali solution of 1.4～2.0mol/L with mixing salt solution equal-volume, total concentration, and mixed-alkali solution is the mixture solution of hydroxide and carbonate, and OH ^-With CO ₃ ^2-Mol ratio be 2～4;

Is to mix reaction 1～2 minute under 15～35 ℃ fast with above-mentioned two kinds of solution in reaction temperature, then with slurries 50～70 ℃ of following crystallization 10～20 hours, dripping concentration during the beginning crystallization is the H of 0.1～0.2mol/L ₂O ₂Solution, H ₂O ₂Addition be 0.1～2 times of manganese element total amount in the reactant, in 1～2 hour, at the uniform velocity dropwise; Crystallization finishes the back with deionized water washing reaction product repeatedly, to filtrate pH value be 7～8, again 70～90 ℃ of dryings 6～12 hours down, obtain having the stratiform Co-Ni-Mn-LDHs presoma of good crystal formation;

B. be 1.05～1.10 to take by weighing lithium source material and Co-Ni-Mn-LDHs presoma according to metal ion molar ratio Li/ (Co+Ni+Mn), it with the cyclohexane dispersant ball milling 6～12 hours in the agate jar, 60～80 ℃ of dryings 4～8 hours, removing cyclohexane is placed in the muffle furnace, be warming up to 450 ℃ with 5～10 ℃/minute speed, be incubated 1～3 hour, be warming up to 800 ℃～900 ℃ with 5～10 ℃/minute speed again, be incubated 10～20 hours, cool to room temperature with the furnace, obtain product α-NaFeO of the present invention ₂The LiMn of structure _xCo _yNi _1-x-yO ₂Positive electrode.

2. according to the described anode material for lithium-ion batteries LiMn of claim 1 _xCo _yNi _1-x-yO ₂The preparation method, it is characterized in that: the described hydroxide of steps A is a kind of among lithium hydroxide LiOH, NaOH NaOH, the potassium hydroxide KOH, and carbonate is sodium carbonate Na ₂CO ₃, potash K ₂CO ₃, ammonium carbonate (NH ₄) ₂CO ₃In a kind of; In the preparation of the described stratiform presoma of steps A, the actual amount of hydroxide and carbonate is 10～12 a little more than generating the required hydroxide of Co-Ni-Mn-LDHs presoma and the theoretical consumption of carbonate thereby make the slurry pH value of generation.

3. according to the described anode material for lithium-ion batteries LiMn of claim 1 _xCo _yNi _1-x-yO ₂The preparation method, it is characterized in that:

The described solubility divalent cobalt of steps A is cobalt nitrate Co (NO ₃) ₂, cobalt chloride CoCl ₂Or cobaltous sulfate CoSO ₄In a kind of, the solubility divalent nickel salt is nitric acid nickel (NO ₃) ₂, nickel chloride NiCl ₂Or nickelous sulfate NiSO ₄In a kind of, the solubility manganous salt is manganese nitrate Mn (NO ₃) ₂, manganese chloride MnCl ₂Or manganese sulfate MnSO ₄In a kind of;

Lithium source material described in the step B is lithium carbonate Li ₂CO ₃, lithium nitrate LiNO ₃Or among the lithium hydroxide LiOH any one.