CN1264233C - Method for preparing spherical lighium manganate anode material of lighium ion batteries - Google Patents

Method for preparing spherical lighium manganate anode material of lighium ion batteries Download PDF

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CN1264233C
CN1264233C CNB031229301A CN03122930A CN1264233C CN 1264233 C CN1264233 C CN 1264233C CN B031229301 A CNB031229301 A CN B031229301A CN 03122930 A CN03122930 A CN 03122930A CN 1264233 C CN1264233 C CN 1264233C
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aqueous solution
spherical
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complexing agent
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CN1447464A (en
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姜长印
万春荣
应皆荣
何向明
陈史勤
李维
蔡砚
王要武
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Tsinghua University
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Inorganic Chemistry (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The present invention relates to a method for preparing the spherical lithium manganate anode material of a lithium ion battery, which belongs to the technical field of energy source materials, and the method for preparing the spherical lithium manganate anode material of a lithium ion battery is characterized in that the method for preparing the spherical lithium manganate anode material of a lithium ion battery comprises the following steps: manganese salt aqueous solution with the concentration of 0.5 to 3 m/l and alkaline aqueous solution with the concentration of 2 to 6 mol/l are reacted with one kind, two kinds or more than two kinds of the aqueous solution of ammonia, ethylene diamine, oxalic acid and citric acid to generate spherical mangano-manganic oxide; the mangano-manganic oxide is mixed with lithium hydroxide or lithium carbonate after the mangano-manganic oxide is washed and dried; the spherical lithium manganate is obtained by a heat treatment with the high temperature of 700 to 800 DEG C. The spherical lithium manganate material prepared by the method for preparing the spherical lithium manganate anode material of a lithium ion battery has high electrode specific capacity, and the tap density of the spherical lithium manganate material can be raised to from 2.2 to 2.5 g. cm#+[-3]. The cyclical stability of the material can be improved by doping other elements (such as Co and Cr), good conditions for further surface modification and modification are provided, and the present invention has very large application value.

Description

The preparation method of lithium ion battery anode material spherical LiMn2O4
Technical field
The present invention relates to a kind of preparation method of lithium ion battery anode material spherical LiMn2O4, belong to the energy and material technical field.
Background technology
At present, commercial anode material for lithium-ion batteries mainly is LiCoO 2,, limited the further reduction of lithium ion battery cost because the price of Co is more expensive.For many years, people are devoted to research and develop more cheap positive electrode always.Wherein, LiMn 2O 4Be considered to the most promising alternative LiCoO 2One of material, and the application of existing small lot.LiMn 2O 4As anode material for lithium-ion batteries, has aboundresources, low price; Toxicity is little, and is harmless substantially to environment; Bulk effect is good, and (lithium ion battery adopts material with carbon element to make negative pole, and carbon negative pole volume in charging process can expand LiCoO 2, LiNiO 2In charging process, also to expand, and LiMn 2O 4Volume can shrink during charging, is suitable for making rectangular cell with carbon negative pole coupling); Need not over-charge protective, advantage such as fail safe is good.But, with LiCoO 2Compare LiMn 2O 4Lower (the LiCoO of specific capacity 2Specific discharge capacity be generally 140mAhg -1About, tap density can reach 2.4gcm -3More than; And LiMn 2O 4Specific discharge capacity be 120mAhg -1About, present commercially available LiMn 2O 4Tap density be 1.8～2.0gcm -3).In addition, LiMn 2O 4Cycle performance variation under high temperature (greater than 50 ℃).Above-mentioned drawbacks limit LiMn 2O 4Practical application.The present invention has developed a kind of high-density spherical LiMn 2O 4, the tap density of product can be brought up to 2.2～2.5gcm -3Owing to be spherical morphology, will help the finishing and the modification of material, and finishing and modification are to improve LiMn 2O 4The effective means of high-temperature behavior.
Summary of the invention
The purpose of this invention is to provide a kind of tap density height, electrode specific capacity height, technology is simple, is applicable to the preparation method of the lithium ion battery anode material spherical LiMn2O4 of suitability for industrialized production.
The preparation method of a kind of lithium ion battery anode material spherical LiMn2O4 that the present invention proposes, it is characterized in that: this method comprises following each step successively:
(1) compound concentration is the manganese salt solution of 0.5～3 mol;
(2) compound concentration is the alkaline aqueous solution of 2～6 mol;
(3) preparation complexing agent aqueous solution;
(4) be input to above-mentioned manganese salt solution, alkaline aqueous solution and complexing agent aqueous solution in the reactor of band stirring respectively continuously with pump, the flow of control manganese salt solution and complexing agent aqueous solution, promptly control the mol ratio of complexing agent and Mn, it is 9～11 that the flow of adjusting aqueous alkali makes the pH value of reactor internal reaction liquid, control reaction temperature is 40～60 ℃, and the 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 is dry in drier, gets spherical Mn 3O 4
(6) take by weighing a certain amount of LiOHH 2O is ball milling in ball mill, is medium with the absolute ethyl alcohol;
(7) in Li: the ratio of Mn=0.9～1.1: 2 (mol ratio), the spherical Mn of the step that takes by weighing (5) gained 3O 4Mix with the LiOH slurry of step (6) gained;
(8) place stove to be warming up to 700～800 ℃ step (7) products therefrom, constant temperature, natural cooling in stove obtains spherical LiMn 2O 4
In above-mentioned preparation method, the described manganese salt of step (1) is any in manganese sulfate, the manganese nitrate; In the manganese salt solution of step (1), also can add Co 2+Or Cr 3+Ion, adding proportion are Co/Mn=0.04～0.1 mol ratio, Cr/Mn=0.01～0.02 mol ratio.
In above-mentioned preparation method, the described alkaline aqueous solution of step (2) is any in sodium hydrate aqueous solution, the potassium hydroxide aqueous solution.
In above-mentioned preparation method, the described complexing agent of step (3) is one or two or more kinds the mixing in ammonia, ethylenediamine, oxalic acid, the citric acid.
In above-mentioned preparation method, the mol ratio of described 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.
In above-mentioned preparation method, the also available Li of step (6) 2CO 3, ball milling Li 2CO 3The time be medium with the deionized water.
Preparation LiMn2O4 LiMn provided by the present invention 2O 4Technology have the following advantages: technology is simple, prepared spherical lithium manganate material electrode specific capacity height, the tap density of product can be brought up to 2.2～2.5gcm -3(Co for example, doping Cr) can improve the cyclical stability of material, and for further finishing and modification provide advantageous conditions, have very big using value by other element.Owing to be spherical morphology, will help the finishing and the modification of material, thereby can effectively improve LiMn 2O 4High-temperature behavior.
Description of drawings
Fig. 1 is the microstructure photograph of material of the present invention.
Embodiment
The present invention will be further described below in conjunction with embodiment:
The invention provides a kind of preparation lithium ion battery anode material spherical LiMn 2O 4Technology, its concrete implementation step is as follows:
(1) manganese salt solution of preparation 0.5～3 mol, manganese salt can be selected manganese sulfate or manganese nitrate for use; Can add Co in the manganese salt solution 2+Or Cr 3+Ion, adding proportion (mol ratio) is: Co/Mn=0.04～0.1, Cr/Mn=0.01～0.02;
(2) compound concentration is the NaOH or the potassium hydroxide aqueous solution of 2～6 mol;
(3) prepare complexing agent aqueous solution respectively, selectable complexing agent comprises: ammonia, ethylenediamine, oxalic acid, citric acid;
(4) be input to one or both aqueous solution in above-mentioned manganese salt solution, sodium hydrate aqueous solution and ammonia, ethylenediamine, oxalic acid, the citric acid in the reactor of band stirring respectively continuously with pump, the flow of control manganese salt solution and complexing agent aqueous solution is respectively the mol ratio of complexing agent and Mn: 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, it is 9～11 that the flow of adjusting sodium hydrate aqueous solution makes the pH value of reactor internal reaction liquid, control reaction temperature is 40～60 ℃, and the 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 ℃ times dry 2～4 hours, gets spherical Mn in drier 3O 4
(6) take by weighing a certain amount of LiOHH 2O or Li 2CO 3Ball milling is 1～2 hour in ball mill, ball milling LiOHH 2Be medium with the absolute ethyl alcohol during O, ball milling Li 2CO 3The time be medium with the deionized water;
(7) in Li: the ratio of Mn=0.9～1.1: 2 (mol ratio) takes by weighing the spherical Mn of a certain amount of step (5) gained 3O 4LiOH or Li with step (6) gained 2CO 3Slurry mixes;
(8) step (7) products therefrom is placed aluminium oxide or zirconia crucible, be warming up to 750 ℃ in Muffle furnace, constant temperature 20 hours stops heating, naturally cools to room temperature in stove, obtains spherical LiMn 2O 4
Introduce embodiments of the invention below:
Embodiment 1
Compound concentration is the MnSO of 2.5 mol 4The aqueous solution, preparation contains 5 mol NaOH and 1 mol NH 3Mixed aqueous solution.With measuring pump respectively with MnSO 4, NaOH and NH 3Mixed aqueous solution be input in the reactor of 3 liter capacities that filled with deionized water in advance and react.Control MnSO 4Aqueous solution flow is 120 milliliters/hour, regulates NaOH and NH 3The flow of Heshui solution to make the pH value of reactor internal reaction liquid be 9.5 ± 0.1.The control reactor temperature is 45 ℃.Solidliquid mixture material nature overflow in the reactor enters in the receiving tank.After the continuous feed 20 hours, stop charging, the material in the reactor is discharged, carry out Separation of Solid and Liquid with centrifuge.Reach till 7～8 with the pH value of 60 ℃ deionized water washing solid products to washings.With the product after the washing in drying box in 80～100 ℃ dry 3～4 hours down, obtain spherical Mn 3O 4Take by weighing 27.5 gram LiOHH 2O is also measured 10 milliliters of absolute ethyl alcohols, places the ball mill ball milling to stop after 1 hour.Take by weighing the above-mentioned Mn that makes of 100 grams 3O 4, place the LiOH slurry behind the ball milling, slowly stirred 5 minutes, obtain mixed slurry.Mixed slurry is put into alumina crucible, and the speed by 100 ℃/hour in Muffle furnace is warming up to 750 ℃, and constant temperature 20 hours stops heating, naturally cools to room temperature in stove, obtains spherical LiMn 2O 4Product.Recording this product average grain diameter is 8～10 μ m, and tap density is 2.30gcm -3With the lithium sheet is negative pole, records this LiMn 2O 4First discharge specific capacity at room temperature is 124mAhg -1
Embodiment 2
Prepare spherical Mn by embodiment 1 identical condition 3O 4Take by weighing 24.2 gram Li 2CO 3And measure 10 milliliters of deionized waters, place the ball mill ball milling to stop after 1 hour.Take by weighing the above-mentioned Mn that makes of 100 grams 3O 4, put into the Li behind the ball milling 2CO 3In the slurry, slowly stirred 5 minutes, obtain mixed slurry.Mixed slurry is put into alumina crucible, and the speed by 100 ℃/hour in Muffle furnace is warming up to 750 ℃, and constant temperature 20 hours stops heating, naturally cools to room temperature in stove, obtains spherical LiMn 2O 4Product.Recording this product average grain diameter is 8～10 μ m, and tap density is 2.28gcm -3With the lithium sheet is negative pole, records this LiMn 2O 4First discharge specific capacity at room temperature is 121mAhg -1
Embodiment 3
Mn (NO with 2.5 mol 3) 2The aqueous solution substitutes MnSO 4The aqueous solution, other condition is identical with embodiment 1, prepares spherical LiMn 2O 4Product.Recording this product average grain diameter is 8～10 μ m, and tap density is 2.31gcm -3With the lithium sheet is negative pole, records this LiMn 2O 4First discharge specific capacity at room temperature is 127mAhg -1
Embodiment 4
Compound concentration is the MnSO of 2.5 mol 4The aqueous solution, preparation contains 5 mol NaOH, 1 mol NH 3Mixed aqueous solution with 0.4 mol ethylenediamine.With measuring pump respectively with MnSO 4The aqueous solution, NaOH, NH 3Being input to the volume that has filled with deionized water in advance with the mixed aqueous solution of ethylenediamine is to react in 3 liters of reactors.Control MnSO 4Aqueous solution flow is 120 milliliters/hour, regulates NaOH, NH 3Making the pH value of reactor internal reaction liquid with the flow of the mixed aqueous solution of ethylenediamine is 9.5 ± 0.1.The control reactor temperature is 45 ℃.Other condition is identical with embodiment 1, prepares spherical LiMn 2O 4Product.Recording this product average grain diameter is 10～15 μ m, and tap density is 2.38gcm -3With the lithium sheet is negative pole, records this LiMn 2O 4First discharge specific capacity at room temperature is 125mAhg -1
Embodiment 5
Prepare spherical Mn by embodiment 4 identical conditions 3O 4Take by weighing 24.2 gram Li 2CO 3And measure 10 milliliters of deionized waters, place the ball mill ball milling to stop after 1 hour.Take by weighing the above-mentioned Mn that makes of 100 grams 3O 4, put into the Li behind the ball milling 2CO 3In the slurry, slowly stirred 5 minutes, obtain mixed slurry.Mixed slurry is put into alumina crucible, and the speed by 100 ℃/hour in Muffle furnace is warming up to 800 ℃, and constant temperature 20 hours stops heating, naturally cools to room temperature in stove, obtains spherical LiMn 2O 4Product.Recording this product average grain diameter is 10～15 μ m, and tap density is 2.34gcm -3With the lithium sheet is negative pole, records this LiMn 2O 4First discharge specific capacity at room temperature is 123mAhg -1
Embodiment 6
Mn (NO with 2.5 mol 3) 2The aqueous solution substitutes MnSO 4The aqueous solution, other condition is identical with embodiment 4, prepares spherical LiMn 2O 4Product.Recording this product average grain diameter is 10～15 μ m, and tap density is 2.36gcm -3With the lithium sheet is negative pole, records this LiMn 2O 4First discharge specific capacity at room temperature is 126mAhg -1
Embodiment 7
Compound concentration is the MnSO of 2.5 mol 4The aqueous solution, preparation contains 5 mol NaOH and 1 mol NH 3Mixed aqueous solution, prepare the oxalic acid aqueous solution of 0.5 mol.With measuring pump respectively with MnSO 4, NaOH and NH 3Mixed aqueous solution and oxalic acid aqueous solution be input to 3 liter capacities that filled with deionized water in advance reactor in react.Control MnSO 4Aqueous solution flow is 120 milliliters/hour, and the oxalic acid aqueous solution flow is 60 milliliters/hour, regulates NaOH and NH 3The flow of mixed aqueous solution to make the pH value of reactor internal reaction liquid be 10.5.The control reactor temperature is 40 ℃.Other condition is identical with embodiment 1, prepares spherical LiMn 2O 4Product.Recording this product average grain diameter is 8～10 μ m, and tap density is 2.37gcm -3With the lithium sheet is negative pole, records this LiMn 2O 4First discharge specific capacity at room temperature is 126mAhg -1
Embodiment 8
Prepare spherical Mn by embodiment 7 identical conditions 3O 4Take by weighing 24.2 gram Li 2CO 3And measure 10 milliliters of deionized waters, place the ball mill ball milling to stop after 1 hour.Take by weighing the above-mentioned Mn that makes of 100 grams 3O 4, put into the Li behind the ball milling 2CO 3In the slurry, slowly stirred 5 minutes, obtain mixed slurry.Mixed slurry is put into alumina crucible, and the speed by 100 ℃/hour in Muffle furnace is warming up to 710 ℃, and constant temperature 20 hours stops heating, naturally cools to room temperature in stove, obtains spherical LiMn 2O 4Product.Recording this product average grain diameter is 8～10 μ m, and tap density is 2.32gcm -3With the lithium sheet is negative pole, records this LiMn 2O 4First discharge specific capacity at room temperature is 124mAhg -1
Embodiment 9
Mn (NO with 2.5 mol 3) 2The aqueous solution substitutes MnSO 4The aqueous solution, other condition is identical with embodiment 7, prepares spherical LiMn 2O 4Product.Recording this product average grain diameter is 8～10 μ m, and tap density is 2.33gcm -3With the lithium sheet is negative pole, records this LiMn 2O 4First discharge specific capacity at room temperature is 127mAhg -1
Embodiment 10
Compound concentration is the MnSO of 2.5 mol 4The aqueous solution, preparation contains 5 mol NaOH and 1 mol NH 3Mixed aqueous solution, prepare the aqueous citric acid solution of 0.2 mol.With measuring pump respectively with MnSO 4, NaOH and NH 3Mixed aqueous solution and aqueous citric acid solution are input in the reactor of 3 liter capacities that filled with deionized water in advance and react.Control MnSO 4Aqueous solution flow is 120 milliliters/hour, and the aqueous citric acid solution flow is 40 milliliters/hour, regulates NaOH and NH 3The flow of mixed aqueous solution to make the pH value of reactor internal reaction liquid be 10.5 ± 0.1.The control reactor temperature is 45 ℃.Other condition is identical with embodiment 1, prepares spherical LiMn 2O 4Product.Recording this product average grain diameter is 6～8 μ m, and tap density is 2.21gcm -3With the lithium sheet is negative pole, records this LiMn 2O 4First discharge specific capacity at room temperature is 128mAhg -1
Embodiment 11
Prepare spherical Mn by embodiment ten identical conditions 3O 4Take by weighing 24.2 gram Li 2CO 3And measure 10 milliliters of deionized waters, place the ball mill ball milling to stop after 1 hour.Take by weighing the above-mentioned Mn that makes of 100 grams 3O 4, put into the Li behind the ball milling 2CO 3In the slurry, slowly stirred 5 minutes, obtain mixed slurry.Mixed slurry is put into alumina crucible, and the speed by 100 ℃/hour in Muffle furnace is warming up to 750 ℃, and constant temperature 20 hours stops heating, naturally cools to room temperature in stove, obtains spherical LiMn 2O 4Product.Recording this product average grain diameter is 6～8 μ m, and tap density is 2.2gcm -3With the lithium sheet is negative pole, records this LiMn 2O 4First discharge specific capacity at room temperature is 125mAhg -1
Embodiment 12
Mn (NO with 2.5 mol 3) 2The aqueous solution substitutes MnSO 4The aqueous solution, other condition is identical with embodiment 10, makes each spherical LiMn 2O 4Product.Recording this product average grain diameter is 6～8 μ m, and tap density is 2.23gcm -3With the lithium sheet is negative pole, records this LiMn 2O 4First discharge specific capacity at room temperature is 129mAhg -1
Embodiment 13
Compound concentration is the MnSO of 2.5 mol 4The aqueous solution, preparation contains 5 mol NaOH and 1 mol NH 3Mixed aqueous solution, preparation contains the mixed aqueous solution of 0.25 mol oxalic acid and 0.1 mol citric acid.With measuring pump respectively with MnSO 4, NaOH and NH 3Mixed aqueous solution and the mixed aqueous solution of oxalic acid and citric acid be input to 3 liter capacities that filled with deionized water in advance reactor in react.Control MnSO 4Aqueous solution flow is 120 milliliters/hour, and the flow of oxalic acid and citric acid mixed aqueous solution is 60 milliliters/hour, regulates NaOH and NH 3The flow of mixed aqueous solution to make the pH value of reactor internal reaction liquid be 9.5 ± 0.1.The control reactor temperature is 45 ℃.Other condition is identical with embodiment 1, prepares spherical LiMn 2O 4Product.Recording this product average grain diameter is 8～10 μ m, and tap density is 2.45gcm -3With the lithium sheet is negative pole, records this LiMn 2O 4First discharge specific capacity at room temperature is 124mAhg -1
Embodiment 14
Prepare 2.5 mol MnSO 4With 0.125 mol CoSO 4Mixed aqueous solution alternate embodiment 1 in the MnSO of 2.5 mol 4The aqueous solution, other condition is identical with embodiment 1, prepares spherical LiMn 2O 4Product.Recording this product average grain diameter is 8～10 μ m, and tap density is 2.30gcm -3With the lithium sheet is negative pole, records this LiMn 2O 4First discharge specific capacity at room temperature is 122mAhg -1
Embodiment 15
Prepare 2.5 mol MnSO 4With 0.025 mol Cr (NO 3) 2Mixed aqueous solution alternate embodiment 1 in the MnSO of 2.5 mol 4The aqueous solution, other condition is identical with embodiment 1, prepares spherical LiMn 2O 4Product.Recording this product average grain diameter is 8～10 μ m, and tap density is 2.28gcm -3With the lithium sheet is negative pole, records this LiMn 2O 4First discharge specific capacity at room temperature is 120mAhg -1

Claims (7)

1, the preparation method of lithium ion battery anode material spherical LiMn2O4 is characterized in that: this method comprises following each step successively:
(1) compound concentration is the manganese salt solution of 0.5～3 mol;
(2) compound concentration is the alkaline aqueous solution of 2～6 mol;
(3) preparation complexing agent aqueous solution;
(4) be input to above-mentioned manganese salt solution, alkaline aqueous solution and complexing agent aqueous solution in the reactor of band stirring respectively continuously with pump, the flow of control manganese salt solution and complexing agent aqueous solution, promptly control the mol ratio of complexing agent and Mn, 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 the 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 is dry in drier, gets spherical Mn 3O 4
(6) take by weighing a certain amount of LiOHH 2O is ball milling in ball mill, is medium with the absolute ethyl alcohol;
(7) in Li: the ratio of Mn=0.9～1.1: 2 mol ratio takes by weighing the spherical Mn of step (5) gained 3O 4Mix with the LiOH slurry of step (6) gained;
(8) place stove to be warming up to 700～800 ℃ step (7) products therefrom, constant temperature, natural cooling in stove obtains spherical LiMn 2O 4
2, according to the described preparation method of claim 1, it is characterized in that: the described manganese salt of step (1) is any in manganese sulfate, the manganese nitrate.
3, according to the described preparation method of claim 1, it is characterized in that: in the manganese salt solution of step (1), add Co 2+Or Cr 3+Ion, adding proportion are Co/Mn=0.04～0.1 mol ratio, Cr/Mn=0.01～0.02 mol ratio.
4, according to the described preparation method of claim 1, it is characterized in that: the described alkaline aqueous solution of step (2) is any in sodium hydrate aqueous solution, the potassium hydroxide aqueous solution.
5, according to the described preparation method of claim 1, it is characterized in that: the described complexing agent of step (3) is one or two or more kinds the mixing in ammonia, ethylenediamine, oxalic acid, the citric acid.
6, according to the described preparation method of claim 5, it is characterized in that: the mol ratio of described 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.
7, according to the described preparation method of claim 1, it is characterized in that: step (6) is used Li 2CO 3, ball milling Li 2CO 3The time be medium with the deionized water.
CNB031229301A 2003-04-26 2003-04-26 Method for preparing spherical lighium manganate anode material of lighium ion batteries Expired - Fee Related CN1264233C (en)

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CN100435960C (en) * 2005-12-19 2008-11-26 比亚迪股份有限公司 Electrode slurry mixing process
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
CN101857277B (en) * 2010-06-13 2012-04-04 浙江亿利泰钴镍材料有限公司 Preparation method of cobalt oxide for lithium battery and product prepared by the same
CN102034977A (en) * 2010-11-10 2011-04-27 湘西自治州兴湘科技开发有限责任公司 Preparation method of positive-pole materials (lithium manganate and doped lithium manganate) of lithium ion battery
CN102491424A (en) * 2011-11-28 2012-06-13 佛山市邦普循环科技有限公司 Preparation method for sol-gel of lithium-rich lithium manganese oxide cathode material of lithium ion battery
CN102820462A (en) * 2012-08-24 2012-12-12 安徽亚兰德新能源材料股份有限公司 Preparation process of anode material lithium manganate of spherical structure for lithium ion battery
CN103000878B (en) * 2012-12-17 2015-05-13 湖南佳飞科技发展有限公司 Gradient doped type lithium-ion cathode material and method for preparing same
CN104064743B (en) * 2013-03-19 2016-04-06 南通瑞翔新材料有限公司 A kind of preparation method of lithium battery manganese-based anode material
CN108455676B (en) * 2018-03-28 2021-02-09 山东省科学院能源研究所 Preparation method of nano spinel lithium manganate serving as lithium ion battery cathode material
CN117105275B (en) * 2023-10-23 2024-01-12 湘潭电化科技股份有限公司 Spherical manganous-manganic oxide and preparation method and application thereof

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