CN103825017A - Preparation method of lithium manganate used as lithium ion battery cathode material and doped lithium manganate - Google Patents
Preparation method of lithium manganate used as lithium ion battery cathode material and doped lithium manganate Download PDFInfo
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- CN103825017A CN103825017A CN201410050598.5A CN201410050598A CN103825017A CN 103825017 A CN103825017 A CN 103825017A CN 201410050598 A CN201410050598 A CN 201410050598A CN 103825017 A CN103825017 A CN 103825017A
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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
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/30—Alkali metal phosphates
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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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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- 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
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- 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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Abstract
The invention discloses a preparation method of lithium manganate used as a lithium ion battery cathode material and doped lithium manganate. The preparation method comprises the following steps: mixing trimanganese tetraoxide or trimanganese tetraoxide doped with other elements with lithium carbonate according to a certain ratio through a ball-milling method, and then subjecting the mixture to processes of pre-burning, heating, annealing, mixing, sieving, and iron-removing so as to obtain the lithium manganate lithium ion battery cathode material rich in lithium and doped lithium manganate. Compared to the conventional method, the preparation method prominently improves the compacted density and cycle performance of the lithium manganate lithium ion battery cathode material.
Description
Technical field
The present invention relates to a kind of anode material for lithium-ion batteries, the present invention relates to particularly the preparation method for LiMn2O4 and the adulterated lithium manganate of anode material for lithium-ion batteries.
Background technology
Lithium ion battery has that voltage is high, energy density is high, has extended cycle life, the advantage such as self discharge is low, memory-less effect, has therefore obtained fast development and extensive use.The positive electrode of practical application is at present mainly cobalt acid lithium, ternary material, LiFePO4 and LiMn2O4.Cobalt acid lithium lacks expensive because of cobalt resource, its cost, far above negative pole, accounts for the more than 1/3rd of battery total cost, makes the large-scale application of lithium ion battery, especially be restricted in the application of electric automobiles, also there is poor heat stability and safety problem in cobalt acid lithium in addition; Ternary material price is also higher, and poor heat stability, voltage platform are low; LiFePO4 poorly conductive and density are too low; Spinel lithium manganate has with low cost and environmentally friendly advantage, but cycle performance is poor.Thereby the cycle performance that how to improve LiMn2O4 just becomes the key of anode material for lithium-ion batteries exploitation.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of preparation method of LiMn2O4 and adulterated lithium manganate for anode material for lithium-ion batteries, the LiMn2O4 that this preparation method prepares or adulterated lithium manganate pattern have unique spherical morphology and particle diameter distributes, more than conventional LiMn2O4 precursor electrolytic manganese dioxide and lower impurity and the metallic foreign body of mangano-manganic oxide, the higher long cycle performance of middle gentle high temperature, power market, more suitable middle and high end.
The present invention solves the problems of the technologies described above adopted technological means: for the preparation method of the LiMn2O4 of anode material for lithium-ion batteries, comprise the following steps:
(1) by mangano-manganic oxide and lithium compound nLi in molar ratio: nMn=1～1.40, after mixing and ball milling, in Muffle furnace in 800～900 ℃ burn 8～20 hours, obtain sintered product;
(2) by the sintered product of described step (1) in 600 ℃～650 ℃ annealing 6～12 hours, after sieving, obtain the LiMn2O4 for anode material for lithium-ion batteries of granularity D50=5～25 μ m.
The preparation method who is used for the adulterated lithium manganate of anode material for lithium-ion batteries, comprises the following steps:
(1) by mangano-manganic oxide 700-900 ℃ of oxidation, oxidation after with lithium carbonate nLi:nMn=1～1.40 in molar ratio, in Muffle furnace in 800～900 ℃ burnings 8～20 hours, obtain sintered product; Wherein, the oxidization time of described mangano-manganic oxide is 8～15 hours;
(2) in the sintered product of described step (1), add doping oxide, mixing and ball milling, then in 600 ℃～650 ℃ annealing 6～12 hours, obtains the adulterated lithium manganate for anode material for lithium-ion batteries of granularity D50=5～25 μ m after sieving.
Described doping oxide be selected from aluminium oxide and magnesian at least one; And the addition of described doping oxide is 0.01%～10% of sintered product quality.
Compared with prior art, it has following beneficial effect in the present invention:
(1) LiMn2O4 that preparation method of the present invention prepares or adulterated lithium manganate pattern have unique spherical morphology and particle diameter distributes, more than conventional LiMn2O4 precursor electrolytic manganese dioxide and lower impurity and the metallic foreign body of mangano-manganic oxide, the higher long cycle performance of middle gentle high temperature, power market, more suitable middle and high end.
(2) the present invention has significantly improved compacted density and the cycle performance of manganate lithium ion battery positive electrode.
Accompanying drawing explanation
Fig. 1 is the SEM figure of the spherical lithium manganate for preparing in embodiment 1;
Fig. 2 is the spherical lithium manganate doped SEM figure preparing in embodiment 2;
Fig. 3 is the spherical lithium manganate doped SEM figure preparing in embodiment 3;
Fig. 4 is the spherical lithium manganate doped SEM figure preparing in embodiment 4.
Embodiment
In order to understand better content of the present invention, be described further below in conjunction with specific embodiments and the drawings.Should be understood that these embodiment, only for the present invention is further described, limit the scope of the invention and be not used in.In addition should be understood that and reading after content of the present invention, person skilled in art makes some nonessential change or adjustment to the present invention, still belongs to protection scope of the present invention.,
Embodiment 1
By mangano-manganic oxide and lithium carbonate nLi in molar ratio: nMn=1～1.10, the amount of mangano-manganic oxide is 1kg, after mixing and ball milling, in Muffle furnace, burn 20 hours in 800 ℃, then in 600 ℃ of annealing 10 hours, after sieving, obtain spherical lithium manganate, surface topography SEM is shown in accompanying drawing 1.Under gained spherical lithium manganate room temperature, 1C capacity is for being 94.3mAh/g, and after 45 ℃ of 300 circulations, capability retention is 92.2%.
Embodiment 2
Mangano-manganic oxide is oxidized to 10 hours in 700-900 ℃ of air atmosphere, mangano-manganic oxide and lithium carbonate nLi in molar ratio by after oxidation: nMn=1～1.20, the amount of mangano-manganic oxide is 1kg, after mixing and ball milling, in Muffle furnace, burns 20 hours in 800 ℃, sintered product adds 0.1% aluminium oxide, mixing and ball milling, then, in 600 ℃ of annealing 10 hours, obtains spherical lithium manganate doped after sieving, granularity D50=5～25 μ m, surface topography SEM is shown in accompanying drawing 2.Under the spherical lithium manganate doped room temperature of gained, 1C capacity is for being 98.3mAh/g, and after 45 ℃ of 300 circulations, capability retention is 91%.
Embodiment 3
Mangano-manganic oxide is oxidized to 8 hours in 700-900 ℃ of air atmosphere, mangano-manganic oxide and lithium carbonate nLi in molar ratio by after oxidation: nMn=1～1.30, the amount of mangano-manganic oxide is 1kg, after mixing and ball milling, in Muffle furnace, burns 20 hours in 800 ℃, sintered product adds 0.1% magnesium oxide, mixing and ball milling, then, in 600 ℃ of annealing 10 hours, obtains spherical lithium manganate doped after sieving, granularity D50=5～25 μ m, surface topography SEM is shown in accompanying drawing 3.Under the spherical lithium manganate doped room temperature of gained, 1C capacity is for being 96.5mAh/g, and after 45 ℃ of 300 circulations, capability retention is 92.3%.
Embodiment 4
Mangano-manganic oxide is oxidized to 15 hours in 700-900 ℃ of air atmosphere, mangano-manganic oxide and lithium carbonate nLi in molar ratio by after oxidation: nMn=1～1.40, the amount of mangano-manganic oxide is 1kg, after mixing and ball milling, in Muffle furnace, burns 20 hours in 800 ℃, sintered product adds 0.1% magnesium oxide and 0.1% aluminium oxide, mixing and ball milling, then, in 600 ℃ of annealing 10 hours, obtains spherical lithium manganate doped after sieving, granularity D50=5～25 μ m, surface topography SEM is shown in accompanying drawing 4.Under the spherical lithium manganate doped room temperature of gained, 1C capacity is for being 94.7mAh/g, and after 45 ℃ of 500 circulations, capability retention is 86%.
As mentioned above, just can realize preferably the present invention.
Claims (3)
1. for the preparation method of the LiMn2O4 of anode material for lithium-ion batteries, it is characterized in that, comprise the following steps:
(1) by mangano-manganic oxide and lithium compound nLi in molar ratio: nMn=1～1.40, after mixing and ball milling, in Muffle furnace in 800～900 ℃ burn 8～20 hours, obtain sintered product;
(2) by the sintered product of described step (1) in 600 ℃～650 ℃ annealing 6～12 hours, after sieving, obtain the LiMn2O4 for anode material for lithium-ion batteries of granularity D50=5～25 μ m.
2. for the preparation method of the adulterated lithium manganate of anode material for lithium-ion batteries, it is characterized in that, comprise the following steps:
(1) by mangano-manganic oxide 700-900 ℃ of oxidation, oxidation after with lithium carbonate nLi:nMn=1～1.40 in molar ratio, in Muffle furnace in 800～900 ℃ burnings 8～20 hours, obtain sintered product;
(2) in the sintered product of described step (1), add doping oxide, mixing and ball milling, then in 600 ℃～650 ℃ annealing 6～12 hours, obtains the adulterated lithium manganate for anode material for lithium-ion batteries of granularity D50=5～25 μ m after sieving.
3. the preparation method of the adulterated lithium manganate for anode material for lithium-ion batteries according to claim 2, is characterized in that, described doping oxide be selected from aluminium oxide and magnesian at least one; And the addition of described doping oxide is 0.01%～10% of sintered product quality.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104868117A (en) * | 2015-05-11 | 2015-08-26 | 合肥国轩高科动力能源股份公司 | Modified preparation method for lithium manganate anode material of lithium-ion battery |
| CN107104233A (en) * | 2017-05-26 | 2017-08-29 | 国家纳米科学中心 | A kind of anode material for lithium-ion batteries and preparation method thereof |
| CN107681134A (en) * | 2017-09-07 | 2018-02-09 | 浙江瓦力新能源科技有限公司 | The preparation method of High-performance lithium manganate anode material |
| 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 |
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| CN102336441A (en) * | 2011-06-29 | 2012-02-01 | 金瑞新材料科技股份有限公司 | Method for preparing lithium manganate used as lithium ion battery anode material by using trimanganese tetroxide |
| JP2012517675A (en) * | 2009-02-13 | 2012-08-02 | 成都晶元新材料技術有限公司 | Cathode material for lithium ion battery to which nickel / cobalt / manganese multielements are added and method for producing the same |
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| CN102694167A (en) * | 2011-08-30 | 2012-09-26 | 中国科学院宁波材料技术与工程研究所 | Modified lithium manganate positive pole material and preparation method thereof |
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Patent Citations (7)
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104868117A (en) * | 2015-05-11 | 2015-08-26 | 合肥国轩高科动力能源股份公司 | Modified preparation method for lithium manganate anode material of lithium-ion battery |
| CN107104233A (en) * | 2017-05-26 | 2017-08-29 | 国家纳米科学中心 | A kind of anode material for lithium-ion batteries and preparation method thereof |
| CN107681134A (en) * | 2017-09-07 | 2018-02-09 | 浙江瓦力新能源科技有限公司 | The preparation method of High-performance lithium manganate anode material |
| 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 |
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Application publication date: 20140528 |