CN1466234A - Method for making positive electrode material LiMn2O4 powder of secondary cell - Google Patents

Method for making positive electrode material LiMn2O4 powder of secondary cell Download PDF

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Publication number
CN1466234A
CN1466234A CNA021231125A CN02123112A CN1466234A CN 1466234 A CN1466234 A CN 1466234A CN A021231125 A CNA021231125 A CN A021231125A CN 02123112 A CN02123112 A CN 02123112A CN 1466234 A CN1466234 A CN 1466234A
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solution
predecessor
powder
limn
sintering
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王天佑
刘如熹
吴齐昇
陈荣显
杨家谕
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XINGNENG HIGH SCIENCE AND TECHNOLOGY Co Ltd
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XINGNENG HIGH SCIENCE AND TECHNOLOGY Co Ltd
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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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • 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
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
    • 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

This invention relates to a method for processing LiMn2O4 powder of secondary Li battery positive material which is prepared by citrate gel method. The start materials are lithiumnitrate and Mn nitrate with citric acid as the mixer, pH is adjusted to 6-7 with etylenediamine to make it to organic amine salt, then to decompose the said citrate gel by heat to remove the organic material and to be sintered for 24 hors between 300-800 deg.c with oxygen in and the got product is Li Mn2O4 powder in spinel structure without other impurities having the properties of uniform particle diameter distribution and good crystallization.

Description

A kind of manufacturing positive pole material of secondary lithium battery LiMn 2O 4The method of powder
Invention field
The present invention relates to a novel LiMn who makes positive pole material of secondary lithium battery 2O 4The characteristics such as the method for powder is to adopt the preparation of citrate gel method, and is different from general conventional solid-state reaction method, and the powder tool particle diameter of gained is evenly distributed and crystallinity is good, and a simple and easy and manufacture method cheaply is provided.
Background technology
Along with the development that science and technology is maked rapid progress, the exploitation of the energy is the topic that receives much concern always.The improvement of electronic component, consumption electronic products have been driven, as mobile phone, notebook computer, digital camera, digital video recorder, PDA(Personal Digital Assistant) etc., towards light, thin, short, little trend development, energy resource system-the battery of this electronic product then becomes the key major part of these tens billion of first industry developments.
Because lithium rechargeable battery has the characteristics such as high voltage, high-energy-density and long-acting circulation, is discussed widely and studies in recent years.And lithium ion secondary battery anode material mainly is divided into LiCoO 2System, LiNiO 2System and LiMn 2O 4System, with regard to energy density, cost and environmental protection, manganese and oxygen compound is the most potential.
Tradition LiMn 2O 4Powder is synthesized with solid state reaction, yet, the initiation material difference, the sintering temperature that forms Single spinel is also thereupon different; And along with the material of different sintering temperature gained, its lattice paprmeter, surface area, particle size etc., all difference to some extent.Moreover it has the LiMn of sintering gained 2O 4The shortcomings such as diameter of particle skewness, sintering temperature height (needing more than 650～700 ℃) and the control of Li/Mn mole ratio are difficult for cause with this LiMn 2O 4Powder is that the electrical property difference of lithium rechargeable battery of positive electrode is at a distance of very big.
For above shortcoming, be necessary to propose an effective improvement method, and this is one of the object of the invention.
Summary of the invention
An object of the present invention is to provide the LiMn of a manufacturing positive pole material of secondary lithium battery 2O 4The method of powder.In a specific embodiment of the present invention, be to adjust the pH value to the citrate gel method of 6-7 with ethylenediamine, the gel of gained behind 300-800 ℃ oxygen atmosphere sintering, can get the good LiMn of quality after thermal decomposition 2O 4Powder.
The present invention can improve the LiMn with solid state reaction sintering gained 2O 4The shortcoming of diameter of particle skewness, and can under low temperature, synthesize the thin and uniform LiMn of tool Single spinel 2O 4Powder, and be in solution, to carry out when making, so reaction is evenly, the better metering ratio of product tool, the advantage such as comprehensive above-mentioned and be conducive to use on the industry.
Brief description of drawings
The thermogravimetric analysis collection of illustrative plates of Fig. 1 illustration gel predecessor of the present invention;
The heating differential analysis collection of illustrative plates of Fig. 2 illustration gel predecessor of the present invention;
Fig. 3 illustration according to the predecessor of comparing embodiment 1 through after the thermal decomposition under the air atmosphere of different temperatures 24 hours X-ray diffraction light spectrogram of sintering (wherein metal ion molal quantity in the predecessor and citric acid mole ratio are 1: 0.55);
Fig. 4 illustration according to the predecessor of comparing embodiment 1 through after the thermal decomposition under the air atmosphere of different temperatures sintering 24 hours, its image photo (wherein metal ion molal quantity in the predecessor and citric acid mole ratio are 1: 0.55) through the sweep electron microscope gained;
Fig. 5 illustration according to the predecessor of comparing embodiment 2 through after the thermal decomposition under the air atmosphere of different temperatures 24 hours X-ray diffraction light spectrogram of sintering (wherein metal ion molal quantity in the predecessor and citric acid mole ratio are 1: 1);
Fig. 6 illustration according to the predecessor of comparing embodiment 2 through after the thermal decomposition under the air atmosphere of different temperatures sintering 24 hours, by the image photo (wherein metal ion molal quantity in the predecessor and citric acid mole ratio are 1: 1) of sweep electron microscope gained;
Fig. 7 illustration according to the predecessor of the embodiment of the invention through after the thermal decomposition under the oxygen atmosphere of different temperatures 24 hours X-ray diffraction light spectrogram of sintering (wherein metal ion molal quantity in the predecessor and citric acid mole ratio are 1: 1);
Fig. 8 illustration according to the predecessor of the embodiment of the invention through after the thermal decomposition under the oxygen atmosphere of different temperatures sintering 24 hours, its image photo (wherein metal ion molal quantity in the predecessor and citric acid mole ratio are 1: 1) through the sweep electron microscope gained; And
The surface area of illustrated embodiment is relative with sintering temperature among comparing embodiment and the embodiment according to the present invention schemes for Fig. 9 illustration, wherein (a) is according to comparing embodiment 1, is shown in sintering under the air atmosphere (metal ion molal quantity and citric acid mole ratio are 1: 0.55); (b) be according to comparing embodiment 2, be shown in sintering under the air atmosphere (metal ion molal quantity and citric acid mole ratio are 1: 1); And (c) be according to embodiment, be shown in sintering under the oxygen atmosphere (metal ion molal quantity and citric acid mole ratio are 1: 1).
The description of the specific embodiment
The invention provides the LiMn of a manufacturing positive pole material of secondary lithium battery 2O 4The method of powder, it comprises following step:
(I) provide a solution that comprises lithium compound and manganese compound;
(II) add a pincers mixture to this solution;
(III) add organic base to this solution to adjust the pH value of solution, make the formation organic slat solution;
(IV) heat this organic slat solution, make to generate the gel predecessor;
(V) heating forms LiMn with this gel predecessor of thermal decomposition 2O 4The powder predecessor;
(VI) this LiMn of sintering under oxygen atmosphere 2O 4The powder predecessor forms the LiMn that can be used as positive pole material of secondary lithium battery 2O 4Powder.
In the inventive method, lithium compound is Nitrates or the acetic acid salt that is selected from lithium, and manganese compound is nitrites or the acetic acid salt that is selected from manganese, and the solvent that collocation forms solution is a water.In addition, the compound of lithium and manganese also can be selected from the alkoxide of lithium and manganese respectively, and collocation forms the solvent of solution can select alcohols for use.Wherein the mole ratio of the lithium of lithium compound and manganese compound and manganese is between 1: 1.8 to 1: 2.2.In a preferred embodiment of the present invention, the solution of lithium compound and manganese compound is lithium nitrate (LiNO 3) and Mn nitrate (Mn (NO 3) 2) aqueous solution.
In the inventive method, behind the solution that forms lithium and manganese compound, other adds a pincers mixture to this solution, and wherein this pincers mixture is the compound that contains carboxyl and hydroxyl simultaneously, the preferably is a citric acid, and its molal quantity is 1: 1 with whole metal ion mole ratios.
Moreover in order to help the formation of follow-up gel predecessor, other adds organic base in above-mentioned solution, uses the pH value of adjusting solution.Organic base can be selected from ethylenediamine or triethylamine, and the preferably is ethylenediamine, makes the formation organic slat solution.The pH value is between 5.0 to 8.0, and better person is between 6.0 to 7.0.
In order to generate the gel predecessor, must this organic slat solution of heating, to remove moisture until generate the gel predecessor.This heating steps preferably is heated between 80 ℃-140 ℃.
Then, heating is with this gel predecessor of thermal decomposition, and formation LiMn 2O 4The powder predecessor.In thermal decomposition gel predecessor step, the addition of pincers mixture is played an important role, and very few organic substance will cause gel predecessor dysoxidation, and hole increases and powder footpath skewness between powder and too much organic substance easily causes.In a specific embodiment, heating is to be heated between 280 ℃ to 400 ℃ with thermal decomposition gel predecessor.
At last, this LiMn of sintering under oxygen atmosphere 2O 4The powder predecessor.Sintering temperature is between 300 ℃ to 800 ℃, and sintering time is between 2 to 48 hours.Last formed LiMn 2O 4Powder namely can be used as the positive electrode of serondary lithium battery.
Owing to utilize known citrate gel method, prepared LiMn in Cryogenic air atmosphere technology 2O 4Powder easily produces Mn 2O 3Impurity, and by sintering under the oxygen atmosphere, can improve this shortcoming, and the LiMn of tool Single spinel 2O 4Powder, and its particle diameter distribution is also more even, hereat can (300-800 ℃) synthesize high-quality LiMn under broad sintering temperature 2O 4Powder.Comparing embodiment 1[is with the synthetic LiMn of citrate gel method 2O 4Powder, sintering under air atmosphere (metal ion molal quantity and citric acid mole ratio are 1: 0.55)]
Get respectively 2.28 gram LiNO 3Reach 16.7 gram Mn (NO 3) 24H 2O (be Li: the Mn mole is 1: 2), after in 40mL water, stirring fully dissolving, add again citric acid 11.6 grams as the pincers mixture, after treating that fully dissolving mixes, adjust the pH value to 6.0-7.0 with ethylenediamine, this solution is dewatered in 110～120 ℃ of heating with bath oiling, and formation yellowish-brown gel predecessor, with this gel predecessor in 300 ℃ air thermal decomposition 2 hours to remove organic matter, its predecessor is ground follow-up in air atmosphere, be warming up to 300 with 5 ℃ of per minutes respectively, 500,650,800 ℃ of sintering 24 hours are cooled to room temperature succeeded by 5 ℃ of per minutes, and obtain the LiMn that different temperatures is synthesized 2O 4Powder.
Fig. 1 and Fig. 2 are respectively the thermogravimetric analysis and the heating differential analysis of gel predecessor, due to the thermogravimetric loss in 110 ℃ that can get is evaporated for gel predecessor surface crystallization water absorbs heat, because surface crystallization water is with the physical adsorption way bond, cause its bond ability strong, therefore need heating greater than 100 ℃, and 280-340 ℃ thermal loss is due to organic class burning exothermic reaction in the gel.So the gel of gained of the present invention, thermal decomposition is 2 hours in 280 ℃ to 400 ℃ air, can remove the organic substance part.
Fig. 3 is through 24 hours the X-ray diffraction light spectrogram of sintering under the air atmosphere of different temperatures of the predecessor after the thermal decomposition.Experimental result is known predecessor under air atmosphere thus, along with the increase of sintering temperature, and the also relative increase of its crystallinity, but when 500 ℃ of sintering, its product has Mn 2O 3Impurity exist.
Fig. 4 is through 24 hours the sweep electron microscope image photo of sintering under the air atmosphere of different temperatures of the predecessor after the thermal decomposition.Scheme as can be known thus the LiMn that is synthesized 2O 4Powder is granular surface morphology, and its particle diameter also increases with the increase of sintering temperature.Comparing embodiment 2[is with the synthetic LiMn of citrate gel method 2O 4Powder, sintering under air atmosphere (metal ion molal quantity and citric acid mole ratio are 1: 1)]
Get respectively 1.00 gram LiNO 3Reach 7.28 gram Mn (NO 3) 24H 2O (be Li: the Mn mole is 1: 2), after in 10mL water, stirring fully dissolving, add again citric acid 9.13 grams as the pincers mixture, after treating that fully dissolving mixes, adjust the pH value to 6.0-7.0 with ethylenediamine, this solution is dewatered in 110～120 ℃ of heating with bath oiling, and formation yellowish-brown gel predecessor, with this gel predecessor in 300 ℃ air thermal decomposition 2 hours to remove organic matter, its predecessor is ground follow-up in air atmosphere, be warming up to 300 with 5 ℃ of per minutes respectively, 500,650,800 ℃ of sintering 24 hours are cooled to room temperature succeeded by 5 ℃ of per minutes, and obtain the LiMn that different temperatures is synthesized 2O 4Powder.
Fig. 5 is that predecessor is with different temperatures X-ray diffraction light spectrogram of 24 hours of sintering under air atmosphere.Experimental result is known predecessor sintering is after 24 hours in 500 ℃ air atmosphere thus, and its product also still has Mn 2O 3Impurity exists, but compares with comparing embodiment 1, obviously reduces many.
Fig. 6 is through 24 hours the sweep electron microscope image photo of sintering under the air atmosphere of different temperatures of the predecessor after the thermal decomposition.Thus figure as can be known, synthesize LiMn 2O 4Powder is granular surface morphology, and its particle diameter also increases with the increase of sintering temperature.Embodiments of the invention are [with the synthetic LiMn of citrate gel method 2O 4Powder, sintering under oxygen atmosphere (metal ion molal quantity and citric acid mole ratio are 1: 1)]
Get respectively 1.00 gram LiNO 3Reach 7.30 gram Mn (NO 3) 24H 2O (be Li: the Mn mole is 1: 2), after in 10mL water, stirring fully dissolving, add again citric acid 9.15 grams as the pincers mixture, after treating that fully dissolving mixes, adjust the pH value to 6.0-7.0 with ethylenediamine, this solution is dewatered in 110～120 ℃ of heating with bath oiling, and formation yellowish-brown gel predecessor, with this gel predecessor in 300 ℃ air thermal decomposition 2 hours to remove organic matter, its predecessor is ground follow-up in oxygen atmosphere, be warming up to 300 with 5 ℃ of per minutes respectively, 500,650,800 ℃ of sintering 24 hours are cooled to room temperature succeeded by 5 ℃ of per minutes, and the LiMn that synthesizes of different temperatures 2O 4Powder.
Fig. 7 is with different temperatures X-ray diffraction light spectrogram of 24 hours of sintering under oxygen atmosphere through the predecessor after the thermal decomposition.Experimental result is known predecessor sintering under the oxygen atmosphere of different temperatures thus, all can form the LiMn of tool Single spinel 2O 4Powder exists and there are other impurity, and along with the increase of sintering temperature, its crystallinity also increases.
Fig. 8 is through 24 hours the sweep electron microscope image photo of sintering under the oxygen atmosphere of different temperatures of the predecessor after the thermal decomposition.Scheme as can be known thus the LiMn that the inventive method is synthesized 2O 4Powder is graininess, and is evenly distributed.The particle diameter of its particle is than being little under comparing embodiment 1 and 2 relative conditons in addition.
Fig. 9 schemes for the surface area of illustrated embodiment among the present invention is relative with sintering temperature, and wherein (a) is shown in sintering under the air atmosphere (metal ion molal quantity and citric acid mole ratio are 1: 0.55); (b) be shown in sintering under the air atmosphere (metal ion molal quantity and citric acid mole ratio are 1: 1); (c) be shown in sintering under the oxygen atmosphere (metal ion molal quantity and citric acid mole ratio are 1: 1).Reach (b) more as can be known LiMn by (a) 2O 4The surface area of powder increases with the citric acid addition, this that is in gel with the increase of citric acid amount, can form more short grained LiMn 2O 4Powder.With the increase of sintering temperature, the surface area of powder diminishes in addition, and promptly particle becomes big.And by (b) and (c) more as can be known when the oxygen atmosphere sintering, can increase LiMn 2O 4The surface area of powder can synthesize thinner LiMn 2O 4Powder.
Comprehensively above-mentioned, be 1: 1 by control metal ion and citric acid mole ratio, again with the pH value of ethylenediamine adjustment solution to 6-7, formed amine salt is beneficial to the formation of gel.The thermal decomposition in 300 ℃ air of this gel can form single-phase and the tiny and uniform LiMn of particle after 2 hours in 300-800 ℃ oxygen 2O 4Powder.
By disclosed method, can be effectively in the synthetic LiMn with single-phase and thin and uniform particle diameter of relative low temperature 2O 4Powder can significantly promote the effect of making the serondary lithium battery positive electrode material.
Specific embodiments of the invention have described in detail as above, just it should be understood that, are not breaking away from various changes and the change of doing under disclosed spirit and the scope, all are Protectors that the present invention is intended to.

Claims (15)

1, a kind of LiMn that makes positive pole material of secondary lithium battery 2O 4The method of powder, it comprises the following steps:
(I) provide a solution that comprises lithium compound and manganese compound;
(II) add a pincers mixture to this solution;
(III) add organic base to this solution, to adjust the pH value of solution, make the formation organic slat solution;
(IV) heat this organic slat solution, make to generate the gel predecessor;
(V) heating forms LiMn with this gel predecessor of thermal decomposition 2O 4The powder predecessor;
(VI) this LiMn of sintering under oxygen atmosphere 2O 4The powder predecessor forms the LiMn that can be used as positive pole material of secondary lithium battery 2O 4Powder.
2, according to the process of claim 1 wherein that this lithium compound is Nitrates or acetic acid salt or the alkoxide that is selected from lithium in step (I).
3, according to the process of claim 1 wherein that this manganese compound is nitrites or acetic acid salt or the alkoxide that is selected from manganese in step (I).
4, according to the process of claim 1 wherein that in step (I) this lithium compound and the lithium of manganese compound and the mole ratio of manganese are 1: 1.8 to 1: 2.2.
5, according to the process of claim 1 wherein that this pincers mixture is for containing the compound of carboxyl and hydroxyl simultaneously in step (II).
6, according to the process of claim 1 wherein that this pincers mixture is a citric acid in step (II).
7, according to the method for claim 6, wherein the citric acid molal quantity is 1: 1 with whole lithium manganese metal ion mole ratios.
8, according to the process of claim 1 wherein that the organic base in step (III) is to be selected from ethylenediamine and triethylamine.
9, according to the process of claim 1 wherein that the pH value of solution is to be adjusted between 5.0 to 8.0 in step (III).
10, according to the process of claim 1 wherein that the pH value of solution is to be adjusted between 6.0 to 7.0 in step (III).
11, be that this organic slat solution of heating is to remove moisture up to generating the gel predecessor according to the process of claim 1 wherein in step (IV).
12, according to the method for claim 11, wherein in step (IV) be this organic slat solution to 80 of heating ℃ to 140 ℃ between.
13, according to the process of claim 1 wherein that in step (V) in heating with this gel predecessor of thermal decomposition is to carry out under 280 ℃ to 400 ℃ of temperature.
14, according to the process of claim 1 wherein that the temperature of sintering is between 300 ℃ to 800 ℃ in step (VI).
15, according to the process of claim 1 wherein that the time of sintering is between 2 to 24 hours in step (VI).
CNA021231125A 2002-06-07 2002-06-07 Method for making positive electrode material LiMn2O4 powder of secondary cell Pending CN1466234A (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101807686A (en) * 2010-03-30 2010-08-18 兰州金里能源科技有限公司 Preparation method of spinel type lithium manganate with high crystallinity used in lithium ion battery
CN102244237A (en) * 2011-06-10 2011-11-16 北京理工大学 Method for synthesizing cathodic material of high-capacity lithium ion battery
CN103606719A (en) * 2013-12-02 2014-02-26 河南师范大学 Method for preparing lithium manganate cathode material by taking waste lithium ion batteries as raw material
CN106784788A (en) * 2016-12-23 2017-05-31 安徽工业大学 One kind prepares porous LiMn by template of carbon ball2O4Method

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101807686A (en) * 2010-03-30 2010-08-18 兰州金里能源科技有限公司 Preparation method of spinel type lithium manganate with high crystallinity used in lithium ion battery
CN102244237A (en) * 2011-06-10 2011-11-16 北京理工大学 Method for synthesizing cathodic material of high-capacity lithium ion battery
CN102244237B (en) * 2011-06-10 2016-08-03 北京理工大学 A kind of synthetic method of anode material for lithium ion battery with high power capacity
CN103606719A (en) * 2013-12-02 2014-02-26 河南师范大学 Method for preparing lithium manganate cathode material by taking waste lithium ion batteries as raw material
CN103606719B (en) * 2013-12-02 2016-01-27 河南师范大学 A kind of take waste and old lithium ion battery as the method that manganate cathode material for lithium prepared by raw material
CN106784788A (en) * 2016-12-23 2017-05-31 安徽工业大学 One kind prepares porous LiMn by template of carbon ball2O4Method

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