CN103904315A - Solid solution material containing nickel manganese and preparation method thereof - Google Patents
Solid solution material containing nickel manganese and preparation method thereof Download PDFInfo
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- CN103904315A CN103904315A CN201210568080.1A CN201210568080A CN103904315A CN 103904315 A CN103904315 A CN 103904315A CN 201210568080 A CN201210568080 A CN 201210568080A CN 103904315 A CN103904315 A CN 103904315A
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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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- 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
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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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
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- Y02E60/10—Energy storage using batteries
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Abstract
The invention provides a solid solution material with rock salt structure and used for a lithium ion battery anode material, and belongs to the technical field of application of lithium ion battery anode material. The material has a molecular formula of xNiO-(1-x)Li2MnO3, wherein x satisfies the relation of: 0.3<=x<=0.8. The solid solution material is characterized by having a disordered rock salt structure; and compared with the solid solution materials reported at present, the material has better normal temperature cycle stability, high temperature cycle stability, voltage scope approaching to that of a current lithium ion battery material system, low manufacturing cost for mass manufacture and high repeatability of the manufacture process, and is suitable for the requirements of special batteries.
Description
Technical field
The invention belongs to anode material for lithium-ion batteries technical field, particularly a kind of solid solution anode material for lithium ion battery and preparation method thereof.
Background technology
Lithium ion battery is secondary cell of new generation after lead-acid battery, nickel-cadmium cell and Ni-MH battery.Face constantly today of deterioration of lasting in short supply and environment of petroleum resources in the whole world, lithium ion battery due to have capacity high, have extended cycle life, self discharge is little, memory-less effect, the advantages such as non-environmental-pollution and security performance are good, having become one of emphasis of hi-tech development, be considered to the choosing of the ideal of high power capacity, high power battery, is the environmental protection power supply of 21 century.Rechargeable lithium ion batteries is since nineteen ninety starts commercialization, its range of application is constantly expanded, from the field of portable electronic apparatus such as mobile phone, notebook computer to electric automobile and following numerous areas such as Aero-Space, artificial satellite all will be used widely.At present, people have started to be devoted to study novel rechargeable lithium ion batteries, can be for vehicles such as mixed power electric car, chargeable hybrid electric vehicle and pure electric vehicles, thus reduce the dependence to oil and alleviate air pollution.Meet this application, lithium ion battery must possess the cycle performance that high power density, high energy density are become reconciled.Fundamentally, positive electrode, as the most important components of lithium ion battery, is the key of lithium-ion energy storage device development.Solid-solution material lithium ion anode shape material is current study hotspot.But especially there is Jahn-Teller deformation under high temperature in general solid-solution material in cyclic process, along with circulation carrying out by stratified material progressively phase transformation become rock salt structure material, material becomes coexisting phase from homogeneous phase, be accompanied by the quick decay of material property, this has seriously restricted application and the development of solid-solution material.
Summary of the invention
In order to solve the circulatory problems of solid-solution material, we have invented a kind of novel solid-solution material xNiO-(1-x) Li
2mnO
3(0.3≤x≤0.8), this kind of unordered rock salt structure of novel solid-solution material, material has formed nano-sized particles, has improved normal temperature circulation and the high-temperature behavior of solid-solution material, has increased this kind of business-like possibility of material.
In order to solve the problems of the technologies described above, the technical scheme the present invention relates to is as follows:
The solid-solution material of a kind of rock salt structure for anode material for lithium-ion batteries of the present invention, has following molecular formula composition: xNiO-(1-x) Li
2mnO
3(0.3≤x≤0.8)
The preparation method of a kind of rock salt structure solid-solution material for anode material for lithium-ion batteries of the present invention, concrete steps are as follows:
(1) be x in molar ratio by nickel salt, manganese salt and lithium salts: (1-x): 2 (1-x) wherein, the soluble-salt of 0.3≤x≤0.8 is dissolved in deionized water, then add complexing agent, making to add the mol ratio of metal ion total amount and complexing agent is 1: 1, stirring puts it into after it is fully mixed in the water-bath of 60 ℃, slowly stir evaporating water, form xerogel, xerogel is dried in baking oven to 12h at 120 ℃, after taking out, grind into powder becomes this material presoma;
(2) by the presoma making prior to 450 ℃ of pre-burning 6h, cooling rear grinding, then calcine 12h at 900 ℃, after material cooled through grinding, sieving obtains solid-solution material xNiO-(1-x) Li
2mnO
3wherein, 0.3≤x≤0.8.
Compared with prior art, the invention has the beneficial effects as follows:
Solid-solution material structure prepared by the present invention is unordered rock salt structure, and this structural design is enhanced the cyclical stability of solid-solution material and thermal stability.And make with low costly due to this material, manufacturing process repeatability is high, batch good stability, can meet the demand to solid-solution material application on market.
Accompanying drawing explanation
The XRD figure of Fig. 1 embodiment 1
The normal temperature first charge-discharge curve of Fig. 2 embodiment 1
50 ℃ of first charge-discharge curves of Fig. 3 embodiment 1
The normal temperature discharge cycles curve of Fig. 4 embodiment 1
50 ℃ of discharge cycles curves of Fig. 5 embodiment 1
Embodiment
Tell about by the following examples detailed process of the present invention, it is the convenience in order to understand that embodiment is provided, and is never restriction the present invention.
Embodiment 1:
15g nickel acetate, 34.3g manganese acetate and 18.5g lithium acetate are dissolved in deionized water, add 35g citric acid, stir in the water-bath that puts it into 60 ℃ after it is fully mixed, slowly stir evaporating water, form xerogel; Xerogel is dried in baking oven to 12h at 120 ℃, after taking out, grind into powder becomes presoma.By presoma prior to 450 ℃ of pre-burning 6h, cooling rear grinding, then calcine 12h at 900 ℃, after material cooled through grinding, sieving obtains solid-solution material 0.3NiO-0.7Li
2mnO
3.XRD figure (Fig. 1) display material of material is rock salt structure solid-solution material, does not find that other dephasigns exist.Under the normal temperature of material, in first charge-discharge figure, (Fig. 2) can see, material initial charge specific capacity of 0.1C under 2.0-4.8V is 234.3mAh/g, and first discharge specific capacity is 169.4mAh/g.Under 50 ℃ of high temperature, under 2.0-4.8V, the initial charge specific capacity of 0.1C is 352.7mAh/g, and first discharge specific capacity is 283.3mAh/g (Fig. 3).Under normal temperature 60 weeks cyclic curve (Fig. 4) can see, in former Zhou Xunhuan, material reality is in activation stage, circulation volume is basicly stable in 213mAh/g left and right after 20 weeks.In 60 cyclic curve figure (Fig. 5) under 50 ℃ of high temperature, also find that material has activation phenomenon, the more common solid-solution material of its high temperature circulation stability increases.
Embodiment 2:
25g nickel acetate, 24.5g manganese acetate and 13.2g lithium acetate are dissolved in deionized water, add 45g citric acid, stir in the water-bath that puts it into 60 ℃ after it is fully mixed, slowly stir evaporating water, form xerogel; Xerogel is dried in baking oven to 12h at 120 ℃, after taking out, grind into powder becomes presoma.By presoma prior to 450 ℃ of pre-burning 6h, cooling rear grinding, then calcine 12h at 900 ℃, after material cooled through grinding, sieving obtains solid-solution material 0.5NiO-0.5Li
2mnO
3.The XRD figure display material of material is rock salt structure solid-solution material, does not find that other dephasigns exist.Material initial charge specific capacity of 0.1C under 2.0-4.8V is 204.3mAh/g, and first discharge specific capacity is 145.8mAh/g.Under 50 ℃ of high temperature, under 2.0-4.8V, the initial charge specific capacity of 0.1C is 310.5mAh/g, and first discharge specific capacity is 223.5mAh/g.Within under normal temperature 60 weeks, circulate in that in former Zhou Xunhuan, material reality is in activation stage, circulation conservation rate is 98.7%.In 60 cyclic curve figure under 50 ℃ of high temperature, also find that material has activation phenomenon, circulation conservation rate 94%.
Embodiment 3:
34.8g nickel acetate, 14.7g manganese acetate and 8g lithium acetate are dissolved in deionized water, add 42g citric acid, stir in the water-bath that puts it into 60 ℃ after it is fully mixed, slowly stir evaporating water, form xerogel; Xerogel is dried in baking oven to 12h at 120 ℃, after taking out, grind into powder becomes presoma.By presoma prior to 450 ℃ of pre-burning 6h, cooling rear grinding, then calcine 12h at 900 ℃, after material cooled through grinding, sieving obtains solid-solution material 0.7NiO-0.3Li
2mnO
3.The XRD figure display material of material is rock salt structure solid-solution material, does not find that other dephasigns exist.Material initial charge specific capacity of 0.1C under 2.0-4.8V is 187.5mAh/g, and first discharge specific capacity is 97.4mAh/g.Under 50 ℃ of high temperature, under 2.0-4.8V, the initial charge specific capacity of 0.1C is 260.5mAh/g, and first discharge specific capacity is 185.8mAh/g.Under normal temperature, circulation in 60 weeks does not find that activation phenomenon, circulation conservation rate are 87.7% substantially.In 60 cyclic curve figure under 50 ℃ of high temperature, do not find that material has activation phenomenon, circulation conservation rate 80.5%.
Embodiment 4:
40g nickel acetate, 9.8g manganese acetate and 5.3g lithium acetate are dissolved in deionized water, add 30g citric acid, stir in the water-bath that puts it into 60 ℃ after it is fully mixed, slowly stir evaporating water, form xerogel; Xerogel is dried in baking oven to 12h at 120 ℃, after taking out, grind into powder becomes presoma.By presoma prior to 450 ℃ of pre-burning 6h, cooling rear grinding, then calcine 12h at 900 ℃, after material cooled through grinding, sieving obtains solid-solution material 0.8NiO-0.2Li
2mnO
3.The XRD figure display material of material is rock salt structure solid-solution material, does not find that other dephasigns exist.Material initial charge specific capacity of 0.1C under 2.0-4.8V is 127.5mAh/g, and first discharge specific capacity is 37.2mAh/g.Under 50 ℃ of high temperature, under 2.0-4.8V, the initial charge specific capacity of 0.1C is 160.5mAh/g, and first discharge specific capacity is 58.8mAh/g.Under normal temperature, circulation in 60 weeks does not find that activation phenomenon, circulation conservation rate are 54.7%.In 60 cyclic curve figure under 50 ℃ of high temperature, do not find that material has activation phenomenon, circulation conservation rate 40.5%, material property significantly worsens.
In sum, rock salt structure solid-solution material xNiO-(1-x) Li
2mnO
3(0.3≤x≤0.8) needs activation in normal temperature and high temperature circulation process, in activation process, capacity progressively improves, while arriving a certain value, cyclical stability is good, and because its structure is unordered rock salt structure, this material cyclical stability is better than common solid-solution material.But along with the increase of x value, this material property occurs deteriorated, need to control the span of x when preparation.This lower cost for material, manufacturing process repeatability is high, and batch good stability, is convenient to the features such as production management, can meet the application demand to high-temperature material on market.
Although in conjunction with figure, invention has been described above; but the present invention is not limited to above-mentioned embodiment; above-mentioned embodiment is only schematic; rather than restrictive; those of ordinary skill in the art is under enlightenment of the present invention; in the situation that not departing from aim of the present invention, can also make a lot of distortion, within these all belong to protection of the present invention.
Claims (8)
1. for a novel solid-solution material for anode material for lithium-ion batteries, it is characterized in that thering is following molecular formula composition: xNiO-(1-x) Li
2mnO
3wherein, 0.3≤x≤0.8.
2. solid-solution material according to claim 1, is characterized in that, the structure of described material is rock salt structure.
3. solid-solution material according to claim 1, is characterized in that, the voltage scope of application of described material is at 2.0V-4.8V.
4. the preparation method of solid-solution material claimed in claim 1, the concrete steps of described method are as follows:
(1) be x in molar ratio by nickel salt, manganese salt and lithium salts: (1-x): the soluble-salt of 2 (1-x) (0.3≤x≤0.8) is dissolved in deionized water, then add complexing agent, the mol ratio that makes metal ion total amount and complexing agent is 1: 1, stirring puts it into after it is fully mixed in the water-bath of 60 ℃, slowly stir evaporating water, form xerogel, xerogel is dried in baking oven to 12h at 120 ℃, after taking out, grind into powder becomes this material presoma;
(2) by the presoma making prior to 450 ℃ of pre-burning 6h, cooling rear grinding, then calcine 12h at 900 ℃, after material cooled through grinding, sieving obtains solid-solution material xNiO-(1-x) Li
2mnO
3, wherein, 0.3≤x≤0.8.
5. the preparation method of solid-solution material according to claim 4, is characterized in that, described nickel salt is acetate.
6. preparation method according to claim 4, is characterized in that, described manganese salt is acetate.
7. preparation method according to claim 4, is characterized in that, described lithium salts is lithium acetate.
8. preparation method according to claim 4, is characterized in that, described complexing agent is citric acid.
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| CN201210568080.1A CN103904315A (en) | 2012-12-24 | 2012-12-24 | Solid solution material containing nickel manganese and preparation method thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110372039A (en) * | 2019-07-23 | 2019-10-25 | 合肥工业大学 | A kind of method that high-valence state transition metal ions Permutations combination strategy prepares cation disorder rock salt structure positive electrode |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20000061759A (en) * | 1999-03-30 | 2000-10-25 | 김순택 | A positive active material for a lithium secondary battery and A method of preparing the same |
| CN1545158A (en) * | 2003-11-25 | 2004-11-10 | 复旦大学 | Method for preparing positive electrode material LiNi0.5Mn0.5O2 of lithium ion battery |
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- 2012-12-24 CN CN201210568080.1A patent/CN103904315A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20000061759A (en) * | 1999-03-30 | 2000-10-25 | 김순택 | A positive active material for a lithium secondary battery and A method of preparing the same |
| CN1545158A (en) * | 2003-11-25 | 2004-11-10 | 复旦大学 | Method for preparing positive electrode material LiNi0.5Mn0.5O2 of lithium ion battery |
Non-Patent Citations (1)
| Title |
|---|
| XIONG WANG ET AL: ""Fabrication and characterization of nanosized single-crystalline LiNi0.5Mn0.5O2"", 《JOURNAL OF CRYSTAL GROWTH》, vol. 267, 15 June 2004 (2004-06-15), XP004515809, DOI: doi:10.1016/j.jcrysgro.2004.03.053 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110372039A (en) * | 2019-07-23 | 2019-10-25 | 合肥工业大学 | A kind of method that high-valence state transition metal ions Permutations combination strategy prepares cation disorder rock salt structure positive electrode |
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Application publication date: 20140702 |