CN103633317A - Material containing nickel, titanium and manganese and optimum synthesis thereof - Google Patents
Material containing nickel, titanium and manganese and optimum synthesis thereof Download PDFInfo
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- CN103633317A CN103633317A CN201310702919.0A CN201310702919A CN103633317A CN 103633317 A CN103633317 A CN 103633317A CN 201310702919 A CN201310702919 A CN 201310702919A CN 103633317 A CN103633317 A CN 103633317A
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- solid
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- complexing agent
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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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/003—Titanates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G45/00—Compounds of manganese
- C01G45/12—Manganates manganites or permanganates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/40—Nickelates
- C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
- C01G53/44—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese
-
- 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
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
-
- 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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- 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
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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
- 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
Abstract
The invention relates to a rock salt solid solution material for an anode material for a lithium ion battery, and belongs to the technical field of application of anode materials for lithium ion batteries. The molecular formula is as follows: 0.4NiO.0.6Li2Ti0.5Mn0.5O3. The invention aims at optimizing of pH value and calcination temperature and discussing best synthesis technological conditions. The lithium ion battery made of the anode material synthesized by the technological conditions has good performance and large circulation capacity. A preparation method for the material comprises the following steps: sequentially dissolving Li, Mn, Ni and Ti into deionized water according to condition that the atomic ratio of Li:Ni:Mn:Ti is 1.2:0.4:0.3:0.3; adding a complexing agent so as to regulate the pH value of the solution; pretreating; roasting at different temperatures so as to prepare the required anode material.
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 optimization thereof are synthetic.
Background technology
From generation nineteen ninety, first Japanese Sony Corporation successfully realizes lithium ion battery after commercialization, and lithium ion battery is widely used in electronic product field.Be different from traditional storage battery, the material system of lithium ion battery is very abundant, as positive electrode has cobalt acid lithium (LiCoO
2), LiMn2O4 (LiMn
2o
4), ternary material (LiNi
xco
1-x-ymn
yo
2) and LiFePO4 (LiFePO
4) etc., negative material has graphite, hard carbon, lithium titanate (LiTi
5o
12) etc., associated materials has been combined to form abundant lithium ion battery series of products.Compare with other traditional storage battery, its specific energy is high, large current discharging capability strong, have extended cycle life, and energy storage efficiency can reach more than 90%, these characteristics have determined that it will have a good application prospect aspect new-energy automobile, quality of power supply adjusting and small distributed power station.But anode material for lithium-ion batteries is the bottleneck of restriction lithium ion battery development, and it is determining the performance of lithium ion battery, price and development thereof.The LiCoO being widely studied at present
2, LiMn
2o
4, LiNi
xco
1-x-ymn
yo
2deng respectively there being advantage.Solid-solution material lithium ion anode material is current study hotspot.But general solid-solution material poor heat stability, for large-scale lithium ion battery safety problem, become hidden danger, cannot normally be used in large-scale electrokinetic cell, this has seriously restricted the range of application of solid-solution material, and positive electrode based on NiTi system because its Heat stability is good becomes very promising power battery anode material, but this type of material capacity is lower, and cycle performance is poor.
Summary of the invention
In order to address the above problem, we have adopted sol-gal process optimization to synthesize 0.4NiO0.6Li
2ti
0.5mn
0.5o
3.Employing citric acid is complexing agent.Citric acid is ternary weak acid, it has three carboxyls and a hydroxyl, the coordination balance that simultaneously has the ionization equilibrium of citric acid and it and metal ion in the forming process of colloidal sol, different pH values can affect the degree of ionization of citric acid, forms different complexs.Therefore must control certain pH value just can obtain stable metal ion citric acid complex.Three different pH scopes of this experimental selection (2～3,5～6,7～8) are carried out synthetic 0.4NiO0.6Li
2ti
0.5mn
0.5o
3sample.
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 and forms: 0.4NiO0.6Li
2ti
0.5mn
0.5o
3.
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) by nickel salt, the soluble-salt of manganese salt and lithium salts is dissolved in deionized water, by the mol ratio of metal total ion concentration and complexing agent, be to add complexing agent at 1: 1, more dropwise add titanium salt, make Li/ (Ni+Mn+Ti)=1.2/ (0.4:0.3:0.3), after stirring fully mixes it, put it in the water-bath of 70 ℃, then add complexing agent, the pH value of regulator solution, slowly stir evaporating water, form xerogel; By xerogel ageing 24h in air, be placed on subsequently in baking oven and at 120 ℃, be dried 15h, after taking out, grind into powder becomes this material presoma.
(2) by the presoma making prior to 450 ℃ of pre-burning 5h, cooling rear grinding, then at different roasting temperatures, treat that material cooled obtains solid-solution material 0.4NiO0.6Li by grinding
2ti
0.5mn
0.5o
3
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 greatly improved the thermal stability of solid-solution material.And due to this material, make with low costly, manufacturing process repeatability is high, and batch good stability can meet the demand to solid-solution material fail safe on market.
Accompanying drawing explanation
The XRD figure of Fig. 1 embodiment 1
The first charge-discharge curve of Fig. 2 embodiment 1
The discharge cycles curve of Fig. 3 embodiment 1
DSC curve after the initial charge of Fig. 4 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:
By 12.33g nickel acetate, 9.11g manganese acetate and 15.17g lithium acetate are dissolved in deionized water, add 56.81g citric acid, slowly splash into 12.77g butyl titanate, with absolute ethyl alcohol, clean the small beaker of dress butyl titanate, cleaning fluid is added in above-mentioned mixed liquor in the lump, stirring puts it into after it is fully mixed in the water-bath of 75 ℃, add citric acid, through pH test paper, measure, the pH of mixed liquor is between 2～3, slowly stir evaporating water, form xerogel, by after xerogel ageing 24h, dry 12h at 120 ℃ in baking oven, after taking out, grind into powder becomes presoma.By presoma prior to 450 ℃ of pre-burning 5h, cooling rear grinding, then calcine 10h respectively at 550 ℃, 650 ℃, 750 ℃, treat material cooled by grinding, sieving obtains solid-solution material 0.4NiO0.6Li
2ti
0.5mn
0.5o
3.XRD figure (Fig. 1) display material of material is rock salt structure solid-solution material.Under the normal temperature of material, in first charge-discharge figure, (Fig. 2) can see, material is under 2.5-4.8V, at 650 ℃, the chemical property of sample is best, the initial charge specific capacity of 0.1C is 190.9mAh/g, first discharge specific capacity is 128mAh/g, after circulation in 30 weeks, capacity is 108.4mAh/g, and circulation conservation rate is 84.69% (Fig. 3).As shown in Figure 4, it is higher that exothermic peak plays peak temperature to DSC curve after initial charge, and thermal stability is high compared with other solid-solution materials.
Embodiment 2:
By 12.33g nickel acetate, 9.11g manganese acetate and 15.17g lithium acetate are dissolved in deionized water, add 56.81g citric acid, slowly splash into 12.78g butyl titanate, with absolute ethyl alcohol, clean the small beaker of dress butyl titanate, cleaning fluid is added in above-mentioned mixed liquor in the lump, stirring puts it into after it is fully mixed in the water-bath of 75 ℃, add citric acid, after mixing, with ammoniacal liquor, regulate between pH value to 5～6 of mixed liquor, slowly stir, evaporating water, form xerogel, xerogel ageing 20h, xerogel is dried in baking oven to 12h at 110 ℃, after taking out, grind into powder becomes presoma.By presoma prior to 450 ℃ of pre-burning 5h, cooling rear grinding, then calcine 10h respectively at 550 ℃, 650 ℃, 750 ℃, treat material cooled by grinding, sieving obtains solid-solution material 0.4NiO0.6Li
2ti
0.5mn
0.5o
3.The XRD figure display material of material is rock salt structure solid-solution material.Under the normal temperature of material, in first charge-discharge figure, can see, material is under 2.5-4.8V, at 650 ℃, the chemical property of sample is best, the initial charge specific capacity of 0.1C is 184.3mAh/g, first discharge specific capacity is 114.3mAh/g, after circulation in 30 weeks, capacity attenuation is to 87.5mAh/g, and circulation conservation rate is 76.6%.
Embodiment 3:
By 12.33g nickel acetate, 9.11g manganese acetate and 15.17g lithium acetate are dissolved in deionized water, add 56.81g citric acid, slowly splash into 12.78g butyl titanate, with absolute ethyl alcohol, clean the small beaker of dress butyl titanate, cleaning fluid is added in above-mentioned mixed liquor in the lump, stirring puts it into after it is fully mixed in the water-bath of 75 ℃, add citric acid, after mixing, with ammoniacal liquor, regulate between pH value to 7～8 of mixed liquor, slowly stir evaporating water, form xerogel, xerogel ageing 24h, xerogel is dried in baking oven to 15h at 120 ℃, after taking out, grind into powder becomes presoma.By presoma prior to 450 ℃ of pre-burning 5h, cooling rear grinding, then calcine 10h respectively at 550 ℃, 650 ℃, 750 ℃, treat material cooled by grinding, sieving obtains solid-solution material 0.4NiO0.6Li
2ti
0.5mn
0.5o
3.The XRD figure display material of material is rock salt structure solid-solution material.Under the normal temperature of material, in first charge-discharge figure, can see, material is under 2.5-4.8V, at 650 ℃, the chemical property of sample is best, initial charge specific capacity during 0.1C is 193.8mAh/g, first discharge specific capacity is 106.8mAh/g, after circulation in 30 weeks, capacity attenuation is to 72.9mAh/g, and circulation conservation rate is 68.3%.
In sum, rock salt structure solid-solution material 0.4NiO0.6Li
2ti
0.5mn
0.5o
3under different pH values and different sintering temperature, there is certain difference normal temperature discharge capacity aspect.Aspect thermal stability, performance is excellent, because itself structure is rock salt structure material, so at high temperature phase transformation substantially can not occur, Li
2tiO
3support structure effect obtained embodiment, its thermal stability obtains greatly improving compared with other solid-solution materials.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 application demand high to thermal stability 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 (9)
1. for a solid-solution material for anode material for lithium-ion batteries, it is characterized in that thering is following molecular formula and form: 0.4NiO0.6Li
2ti
0.5mn
0.5o
3.
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 2.5V-4.8V.
4. the preparation method of solid-solution material claimed in claim 1, the concrete steps of described method are as follows:
(1) by nickel salt, the soluble-salt of manganese salt and lithium salts is dissolved in deionized water, by the mol ratio of metal total ion concentration and complexing agent, be to add complexing agent at 1: 1, more dropwise add titanium salt, make Li: N: Mn: Ti=1.2: 0.4: 0.3: 0.3, after stirring fully mixes it, put it in the water-bath of 70 ℃, then add complexing agent, the pH value of regulator solution, slowly stir evaporating water, form xerogel; By xerogel ageing 24h in air, be placed on subsequently in baking oven and at 120 ℃, be dried 15h, after taking out, grind into powder becomes this material presoma.
(2) by the presoma making prior to 450 ℃ of pre-burning 5h, cooling rear grinding, then at different roasting temperatures, treat that material cooled obtains solid-solution material 0.4NiO0.6Li by grinding
2ti
0.5mn
0.5o
3.
5. preparation method 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 titanium salt is butyl titanate.
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 manganese salt is manganese acetate.
9. preparation method according to claim 4, is characterized in that, described complexing agent is citric acid.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310702919.0A CN103633317A (en) | 2013-12-13 | 2013-12-13 | Material containing nickel, titanium and manganese and optimum synthesis thereof |
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|---|---|---|---|
| CN201310702919.0A CN103633317A (en) | 2013-12-13 | 2013-12-13 | Material containing nickel, titanium and manganese and optimum synthesis thereof |
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| CN103633317A true CN103633317A (en) | 2014-03-12 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105322150A (en) * | 2015-11-26 | 2016-02-10 | 中信大锰矿业有限责任公司大新锰矿分公司 | Preparation technology of modified positive material lithium nickel manganese oxide for lithium-ion battery |
| 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 |
|---|---|---|---|---|
| JP2013206559A (en) * | 2012-03-27 | 2013-10-07 | Tdk Corp | Active material and lithium ion secondary battery including the same |
| CN103904309A (en) * | 2012-12-24 | 2014-07-02 | 天津工业大学 | Solid solution material containing nickel titanium manganese and preparation method thereof |
-
2013
- 2013-12-13 CN CN201310702919.0A patent/CN103633317A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2013206559A (en) * | 2012-03-27 | 2013-10-07 | Tdk Corp | Active material and lithium ion secondary battery including the same |
| CN103904309A (en) * | 2012-12-24 | 2014-07-02 | 天津工业大学 | Solid solution material containing nickel titanium manganese and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| 殷昊曦: "层状正极材料xNiO•（1-x）Li2TiO3（0≤X≤1）的合成与性能研究", 《万方数据库》 * |
| 殷昊曦: "层状正极材料xNiO•（1-x）Li2TiO3（0≤X≤1）的合成与性能研究", 《万方数据库》, 8 October 2013 (2013-10-08) * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105322150A (en) * | 2015-11-26 | 2016-02-10 | 中信大锰矿业有限责任公司大新锰矿分公司 | Preparation technology of modified positive material lithium nickel manganese oxide for lithium-ion battery |
| 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: 20140312 |