CN104577099A - Method for obtaining small-granule-coated type lithium manganate positive material by precoating - Google Patents

Method for obtaining small-granule-coated type lithium manganate positive material by precoating Download PDF

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CN104577099A
CN104577099A CN201410061614.0A CN201410061614A CN104577099A CN 104577099 A CN104577099 A CN 104577099A CN 201410061614 A CN201410061614 A CN 201410061614A CN 104577099 A CN104577099 A CN 104577099A
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lithium
coated
manganese
granule
product
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周宏明
朱玉华
李荐
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Hunan Province Zhengyuan Energy Storage Materials And Device Institute
Central South University
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Hunan Province Zhengyuan Energy Storage Materials And Device Institute
Central South 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
    • H01M4/36—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
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • 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
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • 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)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
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  • Manufacturing & Machinery (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The invention discloses a method for obtaining a small-granule-coated type lithium manganate positive material by precoating, belonging to the technical field of the positive materials of lithium-ion batteries. The method comprises the following steps of weighing a lithium salt and a manganese salt according to the chemical stoichiometric ratio of LiMn2O4, and by adopting absolute ethyl alcohol as a dispersing agent, carrying out ball milling and mixing according to a certain ball-material ratio to obtain a mixed precursor; carrying out low-temperature sintering on the precursor to obtain a pre-sintered product; and preparing a certain amount of coating solution, dropwise adding the coating solution into volatile liquid of the low-temperature pre-sintered product in sequence under continuous stirring, filtering, drying, carrying out high-temperature calcination treatment, naturally cooling to room temperature so as to obtain a needed product. According to the method of firstly precoating and then calcining is adopted for preparing the small-granule positive material of the lithium-ion battery, and by reduction of the grain size of the coated positive material, the diffusion rate of lithium ions is increased, and further the electrochemical stability of spinel lithium manganate is further improved, so that the industrialization of the spinel lithium manganate has prospect.

Description

A kind of method being obtained granule cladded type manganate cathode material for lithium by pre-coated
 
Technical field
The present invention is to anode material for lithium-ion batteries modified spinelle LiMn 2o 4the improvement of preparation method, particularly relates to that a kind of particle diameter is less, the secondary lithium battery modified spinelle LiMn of stable cycle performance 2o 4preparation method.
Background technology
Spinel-type LiMn 2o 4as anode material for lithium-ion batteries, have that operating voltage is high, security performance good, an advantage such as cheap and nontoxic pollution-free, be considered to up-and-coming anode material for lithium-ion batteries.But this material capacity attenuation in charge and discharge cycles process is very fast, and especially more than 55 DEG C, its cycle performance sharply worsens, and seriously limits development and the application of this material.
Large quantity research shows LiMn 2o 4capacity attenuation mainly due to manganese dissolving in the electrolytic solution.By metal oxide as ZnO or Al 2o 3etc. being coated on spinel-type LiMn 2o 4surface, HF can be suppressed in electrolyte positive electrode LiMn 2o 4corrosion, thus reduce the dissolving of Mn, reduce the decay of capacity in cyclic process.At spinel-type LiMn in patent CN200910080931.6 and CN200610021486.2 2o 4surface adopt compound coating metal oxide and improve lithium ion anode material LiMn by complexing agent coated metal oxide 2o 4cycle performance, although the chemical property of clad material increases, preparation process is complicated, still can not meet the industrial requirement of this material.
Summary of the invention
The object of the invention is the deficiency existed for prior art, there is provided a kind of using metal oxide as clad material, by coated pre-burning product again high-temperature calcination obtain the method for granule coating spinelle LiMn2O4, both reduced lithium ion to embed in positive electrode charge and discharge process and the distance of deintercalation, the contact area of material and electrolyte can be reduced again, thus improve the electrochemical stability of spinelle manganic acid lithium material.
The technical scheme that the present invention takes is: a kind of method being obtained granule cladded type manganate cathode material for lithium by pre-coated, is comprised the following steps:
(1) taking a certain amount of lithium salts and manganese salt, take absolute ethyl alcohol as dispersant, by after certain ratio of grinding media to material ball milling mixed number hour, ball material is separated, 80 ~ 100 DEG C dryly must mix presoma;
(2) presoma will be mixed with constant temperature 6 ~ 24h behind ramp to 400 ~ 500 of 1 ~ 10 DEG C/min DEG C, obtain low temperature presintering product;
(3) middle to (2) low temperature presintering product is scattered in volatile liquid, under continuous stirring, in this volatile solution, slowly drips a certain amount of metal salt solution and ammoniacal liquor successively, filtration, the dry product obtaining metal hydroxides pre-coated;
(4) product of metal hydroxides pre-coated in high-temperature calcination process (3), temperature controls between 700 ~ 900 DEG C, heating rate 1 ~ 10 DEG C/min, constant temperature time 6 ~ 12h, naturally cools to room temperature and obtains the coated LiMn of metal oxide 2o 4.
Obtained a method for granule cladded type manganate cathode material for lithium as claimed in claim 1 by pre-coated, it is characterized in that: described lithium salts is one or more the mixture in lithium carbonate, lithium hydroxide, lithium nitrate, lithium acetate or lithium oxalate.
Obtained a method for granule cladded type manganate cathode material for lithium as claimed in claim 1 by pre-coated, it is characterized in that: described manganese salt is one or more the mixture in electrolytic manganese dioxide, mangano-manganic oxide, manganese sesquioxide managnic oxide, manganese carbonate, manganese nitrate, manganese acetate or alkali formula manganese oxide.
Obtained a method for granule cladded type manganate cathode material for lithium as claimed in claim 1 by pre-coated, it is characterized in that: in mixing presoma, the mol ratio of lithium and manganese is 1.05:2 ~ 0.95:2;
A kind of method being obtained granule cladded type manganate cathode material for lithium by pre-coated as claimed in claim 1, it is characterized in that: the ratio of absolute ethyl alcohol and raw material is 1:1 ~ 5:1 in step (1), ratio of grinding media to material is 10:1 ~ 5:1, the rotating speed of ball mill mixing is 200 ~ 1500r/min, and Ball-milling Time is 6 ~ 16h.
Obtained a method for granule cladded type manganate cathode material for lithium as claimed in claim 1 by pre-coated, it is characterized in that: described volatile liquid is any liquid dispersibling pre-burning product, be preferably the one in absolute ethyl alcohol or water.
Obtained a method for granule cladded type manganate cathode material for lithium as claimed in claim 1 by pre-coated, it is characterized in that: slaine is in step (3) a kind of in Cs, Al, Zn, Fe, Cu, Mg, Au, Be, Bi, Ca, Co, Cr, Dy, Er, Eu, Fe, Ga, Gd, Hf, Hg, Ho, In, Lu, Mn, Pb, Pd, Pm, Pr, Pt, Pu, Rh, Ru, Sc, Sm, Sn, Tb, Te, Th, Y, Yb nitrate of, two or more elements, acetate, chloride or phosphate, sulfate etc.
Obtained a method for granule cladded type manganate cathode material for lithium as claimed in claim 1 by pre-coated, it is characterized in that: the quality of metal oxide is LiMn in step (4) 2o 40.01% ~ 5% of quality.
The present invention compared with prior art, has the following advantages:
(1) presintering can make presoma form unformed mixed oxide, for sintering is prepared further;
(2) by the method for the Surface coating one deck hydroxide high-temperature calcination again at LiMn2O4 low temperature presintering product, suppress grain growth in calcination process, subtract short grained size, thus make Li +the evolving path is short, and active material utilization is high, and multiplying power property is good, and after avoiding conventional calcination, the coated grain diameter obtained is comparatively large again, Li +diffusion inside path length, the active material near granular center is difficult to the shortcoming utilized;
(3) metal oxide coating layer can effectively by LiMn 2o 4isolate with electrolyte, reduce contact area, reduce Mn dissolving in the electrolytic solution, improve spinelle LiMn 2o 4the cycle performance of positive electrode.
(4) this method is simple, can ensure the structure of synthetic spinel material, and production technology is short, is suitable for large-scale industrial and produces, be particularly useful for the anode material for lithium-ion batteries of production large-capacity battery pack and memory-less effect.
Accompanying drawing explanation
Fig. 1 is the XRD collection of illustrative plates of embodiment 1, comparative example 1 and comparative example 5;
Fig. 2 is the Laser particle-size distribution collection of illustrative plates of embodiment 1 and comparative example 2;
Fig. 3 is the SEM picture of embodiment 1 and comparative example 1, and wherein 3a is the SEM picture of embodiment 1, and 3b is the SEM picture of comparative example 1.
Embodiment
embodiment 1lithium carbonate and electrolytic manganese dioxide are taken 50g in the ratio of Li:Mn=1:2, take absolute ethyl alcohol as medium, wherein the ratio of absolute ethyl alcohol and raw material is 5:1, ratio of grinding media to material is 10:1, with after the speed wet-milling 6h of 200r/min on ball mill, dryly must mix presoma at 80 ~ 100 DEG C.Being raised to 400 DEG C of insulation 6h by mixing presoma with the heating rate of 1 DEG C/min, cooling to obtain low temperature presintering product; Again low temperature presintering product is scattered in absolute ethyl alcohol, under constantly stirring, in this ethanol solution, slowly drip a certain amount of metal salt solution and ammoniacal liquor successively simultaneously, filtration, the dry product obtaining metal hydroxides pre-coated, be raised to 700 DEG C of insulation 6h with the speed of 1 DEG C/min again, cool to obtain the coated LiMn of metal oxide 2o 4anode material for lithium-ion batteries, wherein the quality of metal oxide is LiMn 2o 40.01% of quality.
The charge-discharge performance test of this example product: by the ratio mixing of anode material for lithium-ion batteries obtained above, conductive black, PVDF 8:1:1 in mass ratio, be coated on aluminium foil, punching cut-parts 120 DEG C of vacuumize 12h make lithium battery anode.Take metal lithium sheet as the LiPF of negative pole, 1M 6for electrolyte CELL GARD 2003 for barrier film is assembled into button cell.Carry out electrochemical property test to this spinel lithium manganese oxide anode material, charging/discharging voltage is 3.3V ~ 4.5V.The electrochemical property test of this example product the results are shown in Table 1.
comparative example 1lithium carbonate and electrolytic manganese dioxide are taken 50g in the ratio of Li:Mn=1:2, take absolute ethyl alcohol as medium, wherein the ratio of absolute ethyl alcohol and raw material is 5:1, ratio of grinding media to material is 10:1, with after the speed wet-milling 6h of 200r/min on ball mill, dryly must mix presoma at 80 ~ 100 DEG C.By mix presoma with the heating rate of 1 DEG C/min be raised to 400 DEG C insulation 6h, then with the speed of 1 DEG C/min be raised to 700 DEG C insulation 6h cool to obtain calcined product LiMn 2o 4; This calcined product is scattered in absolute ethyl alcohol, simultaneously under constantly stirring, in this ethanol solution, slowly drips a certain amount of metal salt solution and ammoniacal liquor successively, filter, the LiMn of dry metal hydroxides pre-coated 2o 4; Again in 350 DEG C of insulation 3h, cool to obtain the coated LiMn of metal oxide 2o 4anode material for lithium-ion batteries, wherein the quality of metal oxide is LiMn 2o 40.01% of quality.
The electrochemical property test of this example product is identical with embodiment 1, and test result is in table 1.
embodiment 2lithium acetate and manganese acetate are taken 70g in the ratio of Li:Mn=0.95:2, take absolute ethyl alcohol as medium, wherein the ratio of absolute ethyl alcohol and raw material is 4:1, ratio of grinding media to material is 8:1, with after the speed wet-milling 8h of 600r/min on ball mill, dryly must mix presoma at 80 ~ 100 DEG C.Being raised to 450 DEG C of insulation 12h by mixing presoma with the heating rate of 2 DEG C/min, cooling to obtain low temperature presintering product; Again low temperature presintering product is scattered in water, under constantly stirring, in this solution, slowly drip a certain amount of metal salt solution and ammoniacal liquor successively simultaneously, filtration, the dry product obtaining metal hydroxides pre-coated, be raised to 750 DEG C of insulation 8h with the speed of 2 DEG C/min again, cool to obtain the coated LiMn of metal oxide 2o 4anode material for lithium-ion batteries, wherein the quality of metal oxide is LiMn 2o 42% of quality.
The electrochemical property test of this example product is identical with embodiment 1, and test result is in table 1.
comparative example 2lithium acetate and manganese acetate are taken 70g in the ratio of Li:Mn=0.95:2, take absolute ethyl alcohol as medium, wherein the ratio of absolute ethyl alcohol and raw material is 4:1, ratio of grinding media to material is 8:1, with after the speed wet-milling 8h of 600r/min on ball mill, dryly must mix presoma at 80 ~ 100 DEG C.By mix presoma with the heating rate of 2 DEG C/min be raised to 450 DEG C insulation 12h, then with the speed of 2 DEG C/min be raised to 750 DEG C insulation 8h cool to obtain calcined product LiMn 2o 4; This calcined product is scattered in water, simultaneously under constantly stirring, in this solution, slowly drips a certain amount of metal salt solution and ammoniacal liquor successively, filter, the LiMn of dry metal hydroxides pre-coated 2o 4; Again in 350 DEG C of insulation 3h, cool to obtain the coated LiMn of metal oxide 2o 4anode material for lithium-ion batteries, wherein the quality of metal oxide is LiMn 2o 42% of quality.
The electrochemical property test of this example product is identical with embodiment 1, and test result is in table 1.
embodiment 3lithium nitrate and manganese nitrate are taken 90g in the ratio of Li:Mn=1.05:2, take absolute ethyl alcohol as medium, wherein the ratio of absolute ethyl alcohol and raw material is 3:1, ratio of grinding media to material is 6:1, with after the speed wet-milling 12h of 1000r/min on ball mill, dryly must mix presoma at 80 ~ 100 DEG C.Being raised to 500 DEG C of insulation 18h by mixing presoma with the heating rate of 5 DEG C/min, cooling to obtain low temperature presintering product; Again low temperature presintering product is scattered in absolute ethyl alcohol, under constantly stirring, in this ethanol solution, slowly drip a certain amount of metal salt solution and ammoniacal liquor successively simultaneously, filtration, the dry product obtaining metal hydroxides pre-coated, be raised to 800 DEG C of insulation 10h with the speed of 5 DEG C/min again, cool to obtain the coated LiMn of metal oxide 2o 4anode material for lithium-ion batteries, wherein the quality of metal oxide is LiMn 2o 44% of quality.
The electrochemical property test of this example product is identical with embodiment 1, and test result is in table 1.
comparative example 3lithium nitrate and manganese nitrate are taken 90g in the ratio of Li:Mn=1.05:2, take absolute ethyl alcohol as medium, wherein the ratio of absolute ethyl alcohol and raw material is 3:1, ratio of grinding media to material is 6:1, with after the speed wet-milling 12h of 1000r/min on ball mill, dryly must mix presoma at 80 ~ 100 DEG C.By mix presoma with the heating rate of 5 DEG C/min be raised to 500 DEG C insulation 18h, then with the speed of 5 DEG C/min be raised to 800 DEG C insulation 10h cool to obtain calcined product LiMn 2o 4; This calcined product is scattered in absolute ethyl alcohol, simultaneously under constantly stirring, in this ethanol solution, slowly drips a certain amount of metal salt solution and ammoniacal liquor successively, filter, the LiMn of dry metal hydroxides pre-coated 2o 4; Again in 350 DEG C of insulation 3h, cool to obtain the coated LiMn of metal oxide 2o 4anode material for lithium-ion batteries, wherein the quality of metal oxide is LiMn 2o 44% of quality.
The electrochemical property test of this example product is identical with embodiment 1, and test result is in table 1.
embodiment 4lithium hydroxide and mangano-manganic oxide are taken 99g in the ratio of Li:Mn=1.05:2, take absolute ethyl alcohol as medium, wherein the ratio of absolute ethyl alcohol and raw material is 1:1, ratio of grinding media to material is 5:1, with after the speed wet-milling 16h of 1500r/min on ball mill, dryly must mix presoma at 80 ~ 100 DEG C.Being raised to 500 DEG C of insulation 24h by mixing presoma with the heating rate of 10 DEG C/min, cooling to obtain low temperature presintering product; Again low temperature presintering product is scattered in water, under constantly stirring, in this solution, slowly drip a certain amount of metal salt solution and ammoniacal liquor successively simultaneously, filtration, the dry product obtaining metal hydroxides pre-coated, be raised to 900 DEG C of insulation 12h with the speed of 10 DEG C/min again, cool to obtain the coated LiMn of metal oxide 2o 4anode material for lithium-ion batteries, wherein the quality of metal oxide is LiMn 2o 45% of quality.
The electrochemical property test of this example product is identical with embodiment 1, and test result is in table 1.
comparative example 4lithium hydroxide and mangano-manganic oxide are taken 99g in the ratio of Li:Mn=1.05:2, take absolute ethyl alcohol as medium, wherein the ratio of absolute ethyl alcohol and raw material is 1:1, ratio of grinding media to material is 5:1, with after the speed wet-milling 16h of 1500r/min on ball mill, dryly must mix presoma at 80 ~ 100 DEG C.By mix presoma with the heating rate of 10 DEG C/min be raised to 500 DEG C insulation 24h, then with the speed of 10 DEG C/min be raised to 900 DEG C insulation 12h cool to obtain calcined product LiMn 2o 4; This calcined product is scattered in water, simultaneously under constantly stirring, in this solution, slowly drips a certain amount of metal salt solution and ammoniacal liquor successively, filter, the LiMn of dry metal hydroxides pre-coated 2o 4; Again in 350 DEG C of insulation 3h, cool to obtain the coated LiMn of metal oxide 2o 4anode material for lithium-ion batteries, wherein the quality of metal oxide is LiMn 2o 45% of quality.
The electrochemical property test of this example product is identical with embodiment 1, and test result is in table 1.
comparative example 5lithium carbonate and electrolytic manganese dioxide are taken 50g in the ratio of Li:Mn=1:2, take absolute ethyl alcohol as medium, and wherein the ratio of absolute ethyl alcohol and raw material is 1:1, ratio of grinding media to material is 5:1, with the speed wet-milling 6h of 800r/min on ball mill, dry.400 DEG C of insulation 6h are raised to the heating rate of 5 DEG C/min; After being raised to 750 DEG C of insulation 6h with the speed of 5 DEG C/min again, naturally cool to obtain product LiMn 2o 4.
The electrochemical property test of this example product is identical with embodiment 1, and test result is in table 1.
 
Capability retention at the discharge capacity first of the various cell positive material of table 1 and 55 DEG C after 50 circulations
Embodiment sequence number 0.5C is discharge capacity (mAhg first -1） Capability retention (%) after 50 circulations
Embodiment 1 98.3 22.8
Comparative example 1 106.6 25.0
Embodiment 2 100.9 12.7
Comparative example 2 104.2 23.6
Embodiment 3 99.5 12.8
Comparative example 3 98.6 27.5
Embodiment 4 98.7 16.0
Comparative example 4 87.7 38.7
Comparative example 5 96.7 33.4

Claims (8)

1. obtained a method for granule cladded type manganate cathode material for lithium by pre-coated, it is characterized in that, comprise following step:
(1) taking a certain amount of lithium salts and manganese salt, take absolute ethyl alcohol as dispersant, by after certain ratio of grinding media to material ball milling mixed number hour, ball material is separated, 80 ~ 100 DEG C dryly must mix presoma;
(2) presoma will be mixed with constant temperature 6 ~ 24h behind ramp to 400 ~ 500 of 1 ~ 10 DEG C/min DEG C, obtain low temperature presintering product;
(3) middle to (2) low temperature presintering product is scattered in volatile liquid, under continuous stirring, in this volatile solution, slowly drips a certain amount of metal salt solution and ammoniacal liquor successively, filtration, the dry product obtaining metal hydroxides pre-coated;
(4) product of metal hydroxides pre-coated in high-temperature calcination process (3), temperature controls between 700 ~ 900 DEG C, heating rate 1 ~ 10 DEG C/min, constant temperature time 6 ~ 12h, naturally cools to room temperature and obtains the coated LiMn of metal oxide 2o 4.
2. a kind of method being obtained granule cladded type manganate cathode material for lithium by pre-coated as claimed in claim 1, be is characterized in that: described lithium salts is one or more the mixture in lithium carbonate, lithium hydroxide, lithium nitrate, lithium acetate or lithium oxalate.
3. a kind of method being obtained granule cladded type manganate cathode material for lithium by pre-coated as claimed in claim 1, be is characterized in that: described manganese salt is one or more the mixture in electrolytic manganese dioxide, mangano-manganic oxide, manganese sesquioxide managnic oxide, manganese carbonate, manganese nitrate, manganese acetate or alkali formula manganese oxide.
4. a kind of method being obtained granule cladded type manganate cathode material for lithium by pre-coated as claimed in claim 1, be is characterized in that: in mixing presoma, the mol ratio of lithium and manganese is 1.05:2 ~ 0.95:2.
5. a kind of method being obtained granule cladded type manganate cathode material for lithium by pre-coated as claimed in claim 1, it is characterized in that: the ratio of absolute ethyl alcohol and raw material is 1:1 ~ 5:1 in step (1), ratio of grinding media to material is 10:1 ~ 5:1, the rotating speed of ball mill mixing is 200 ~ 1500r/min, and Ball-milling Time is 6 ~ 16h.
6. a kind of method being obtained granule cladded type manganate cathode material for lithium by pre-coated as claimed in claim 1, be is characterized in that: described volatile liquid is any liquid dispersibling pre-burning product, is preferably the one in absolute ethyl alcohol or water.
7. a kind of method being obtained granule cladded type manganate cathode material for lithium by pre-coated as claimed in claim 1, be is characterized in that: slaine is in step (3) a kind of in Cs, Al, Zn, Fe, Cu, Mg, Au, Be, Bi, Ca, Co, Cr, Dy, Er, Eu, Fe, Ga, Gd, Hf, Hg, Ho, In, Lu, Mn, Pb, Pd, Pm, Pr, Pt, Pu, Rh, Ru, Sc, Sm, Sn, Tb, Te, Th, Y, Yb nitrate of, two or more elements, acetate, chloride or phosphate, sulfate etc.
8. a kind of method being obtained granule cladded type manganate cathode material for lithium by pre-coated as claimed in claim 1, be is characterized in that: in step (4), the quality of metal oxide is LiMn 2o 40.01% ~ 5% of quality.
CN201410061614.0A 2014-02-24 2014-02-24 Method for obtaining small-granule-coated type lithium manganate positive material by precoating Pending CN104577099A (en)

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Cited By (7)

* Cited by examiner, † Cited by third party
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CN105777099A (en) * 2016-02-24 2016-07-20 中南大学 Additive for magnesium aluminate spinel sintering and application method
CN109713260A (en) * 2018-12-11 2019-05-03 中国电力科学研究院有限公司 A kind of method of modifying of Phosphate coating lithium-rich manganese-based anode material
CN110627127A (en) * 2019-08-30 2019-12-31 湖南金富力新能源股份有限公司 Lithium manganate positive electrode material and preparation method and application thereof
CN111217395A (en) * 2020-03-16 2020-06-02 陕西海恩新材料有限责任公司 High-energy-density lithium manganate cathode material and preparation method thereof
CN113921788A (en) * 2021-09-29 2022-01-11 蜂巢能源科技(马鞍山)有限公司 Coated manganese-based positive electrode material and preparation method thereof
CN114506830A (en) * 2020-11-17 2022-05-17 松山湖材料实验室 Preparation method of phosphate coated positive electrode active material
CN114775034A (en) * 2022-04-01 2022-07-22 安徽格派新能源有限公司 Preparation method of monocrystal lithium manganate cathode material

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105777099A (en) * 2016-02-24 2016-07-20 中南大学 Additive for magnesium aluminate spinel sintering and application method
CN105777099B (en) * 2016-02-24 2018-10-30 中南大学 A kind of additive and application method for magnesium aluminate spinel sintering
CN109713260A (en) * 2018-12-11 2019-05-03 中国电力科学研究院有限公司 A kind of method of modifying of Phosphate coating lithium-rich manganese-based anode material
CN110627127A (en) * 2019-08-30 2019-12-31 湖南金富力新能源股份有限公司 Lithium manganate positive electrode material and preparation method and application thereof
CN111217395A (en) * 2020-03-16 2020-06-02 陕西海恩新材料有限责任公司 High-energy-density lithium manganate cathode material and preparation method thereof
CN114506830A (en) * 2020-11-17 2022-05-17 松山湖材料实验室 Preparation method of phosphate coated positive electrode active material
CN114506830B (en) * 2020-11-17 2023-07-14 松山湖材料实验室 Preparation method of phosphate coated positive electrode active material
CN113921788A (en) * 2021-09-29 2022-01-11 蜂巢能源科技(马鞍山)有限公司 Coated manganese-based positive electrode material and preparation method thereof
CN114775034A (en) * 2022-04-01 2022-07-22 安徽格派新能源有限公司 Preparation method of monocrystal lithium manganate cathode material

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Application publication date: 20150429