CN103579607A - Preparation method of spherical nickel-lithium manganate anode material - Google Patents
Preparation method of spherical nickel-lithium manganate anode material Download PDFInfo
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- CN103579607A CN103579607A CN201310525131.7A CN201310525131A CN103579607A CN 103579607 A CN103579607 A CN 103579607A CN 201310525131 A CN201310525131 A CN 201310525131A CN 103579607 A CN103579607 A CN 103579607A
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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
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G45/00—Compounds of manganese
- C01G45/12—Manganates manganites or permanganates
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- 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
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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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- 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 discloses a preparation method of a spherical nickel-lithium manganate anode material. The preparation method is characterized by comprising the following steps: weighing a lithium source compound, a nickel source compound and spherical manganous-manganic oxide by a mol ratio of 2:1:1; dissolving the lithium source compound and the nickel source compound in ethanol to prepare a solution of which the total concentration of metal cation is 0.1-0.3 mol/L; adding the spherical manganous-manganic oxide into the solution; heating the solution in a water bath with stirring until a paste-like mixture is formed; drying the paste-like mixture at 90-110 DEG C to obtain gray black powder; roasting the obtained powder at 750-950 DEG C for 6-36 hours; annealing at 615-675 DEG C for 2-6 hours; cooling, directly sieving, and then obtaining the nickel-lithium manganate anode material. The lithium source compound is lithium acetate or lithium nitrate, and the nickel source compound is nickel acetate or nickel nitrate. The water-bath heating temperature is 50-70 DEG C.
Description
Technical field
The invention belongs to chemical power source anode material for lithium-ion batteries technical field, is a kind of preparation method of spherical nickel manganate cathode material for lithium, particularly relates to the preparation method of high-voltage anode material nickel LiMn2O4.
Technical background
Spinel-type nickel LiMn2O4 (LiNi
0.5mn
1.5o
4) positive electrode is one of more high-energy-density positive electrode of at present research.Its discharge voltage plateau 4.7V, approximately higher by 20% than LiMn2O4, reversible capacity can reach the theoretical 147mAh/g of 130mAh/g(), approximately higher by 20% than LiMn2O4 equally, there is thus the energy density higher than LiMn2O4, more crucial is, in structurally ordered nickel LiMn2O4, Mn is all+4 valencys, has stopped the disproportionated reaction and the poplar-Taylor effect that cause, and cycle performance and high-rate discharge ability are good, the powerful replacer who is considered to thus following LiMn2O4, can be widely used in electric automobile field.
In order to promote energy content of battery density, to improve materials processing performance, current trend is the synthetic nickel lithium manganate material with spherical morphology.And the preparation of spherical nickel LiMn2O4 generally adopts coprecipitation, first co-precipitation preparation has the presoma of spherical morphology, then high temperature lithiumation is prepared spherical nickel manganate cathode material for lithium.But the preparation of spherical presoma needs the accurate parameters such as charging rate, pH value, mixing speed, reaction temperature, complexing agent consumption of controlling, and complex process, requires high to appointed condition.The author finds when carrying out the research of nickel LiMn2O4, take spherical mangano-manganic oxide as raw material, by controlling preparation condition, also can produce spherical nickel manganate cathode material for lithium.And domestic spherical mangano-manganic oxide technology of preparing is very ripe, output is huge, and more crucial is that mangano-manganic oxide is also a kind of spinel-type compound, and to prepare nickel manganate cathode material for lithium more easy as raw material to take it.
Summary of the invention
The present invention is a kind of preparation method of spherical nickel manganate cathode material for lithium, it is characterized in that: comprise the following steps:
According to the ratio of mol ratio 2:1:1, take Li source compound, nickel source compound and spherical mangano-manganic oxide, Li source compound and nickel source compound are dissolved in and in ethanol, are configured to the solution that metal cation total concentration is 0.1-0.3mol/L, in above-mentioned solution, add spherical mangano-manganic oxide, heating water bath is to forming paste mixture while stirring, after 90-110 ℃ of oven dry, obtain grey black powder, gained powder is at 750-950 ℃ of roasting 6-36h, 615-675 ℃ of annealing 2-6h, directly sieves after cooling and obtains nickel manganate cathode material for lithium.
Described Li source compound is lithium acetate or lithium nitrate, and described nickel source compound is nickel acetate or nickel nitrate.
Described water bath heating temperature is 50-70 ℃.
According to preparation method of the present invention, it is characterized in that,
According to the ratio of mol ratio 2:1:1, take Li source compound, nickel source compound and spherical mangano-manganic oxide, Li source compound and nickel source compound are dissolved in and in ethanol, are configured to the solution that metal cation total concentration is 0.1-0.2mol/L, in above-mentioned solution, add spherical mangano-manganic oxide, heating water bath is to forming paste mixture while stirring, after 95-105 ℃ of oven dry, obtain grey black powder, gained powder is at 800-900 ℃ of roasting 12-28h, 650-670 ℃ of annealing 3-5h, directly sieves after cooling and obtains nickel manganate cathode material for lithium;
Above-mentioned Li source compound is lithium acetate; Above-mentioned nickel source compound is nickel acetate; Above-mentioned water bath heating temperature is 60-65 ℃.
The present invention be take spherical mangano-manganic oxide as raw material, and through stirring simply, the operation such as oven dry, roasting can prepare spherical nickel manganate cathode material for lithium, raw material sources are abundant, technique is simple, the material tap density of synthesized is high, good processability, and chemical property is excellent.
Accompanying drawing explanation
Fig. 1 is the ESEM picture of example 1 spherical mangano-manganic oxide raw material used;
Fig. 2 is the ESEM picture of the spherical nickel manganate cathode material for lithium of example 1 preparation;
Fig. 3 is the 1C rate charge-discharge curve of the spherical nickel manganate cathode material for lithium of example 1 preparation.
Embodiment
Below by specific embodiment, the present invention is described in detail, following embodiment is only for the present invention is described, but the practical range being not intended to limit the present invention.
Embodiment 1:
According to the ratio of mol ratio 2:1:1, take lithium acetate, nickel acetate and spherical mangano-manganic oxide (mangano-manganic oxide ESEM picture as shown in Figure 1), lithium acetate and nickel acetate are dissolved in and in ethanol, are configured to the solution that metal cation total concentration is 0.1mol/L, in above-mentioned solution, add spherical mangano-manganic oxide, 50 ℃ of heating water baths are to forming paste mixture while stirring, after 90 ℃ of oven dry, obtain grey black powder, gained powder is at 750 ℃ of roasting 6h, 615 ℃ of annealing 2h, directly sieve after cooling and obtain nickel manganate cathode material for lithium.Resulting materials has been inherited the spherical morphology (Fig. 2) of mangano-manganic oxide, and the 1C of its button cell is discharge capacity 126.1mAh/g(Fig. 3 first), capability retention 100.1% circulates 100 times.
Embodiment 2:
According to the ratio of mol ratio 2:1:1, take lithium nitrate, nickel acetate and spherical mangano-manganic oxide, lithium nitrate and nickel acetate are dissolved in and in ethanol, are configured to the solution that metal cation total concentration is 0.2mol/L, in above-mentioned solution, add spherical mangano-manganic oxide, 60 ℃ of heating water baths are to forming paste mixture while stirring, after 100 ℃ of oven dry, obtain grey black powder, gained powder is at 850 ℃ of roasting 12h, and 650 ℃ of annealing 4h directly sieve after cooling and obtain nickel manganate cathode material for lithium.The 1C of resulting materials button cell is discharge capacity 128.2mAh/g first, and capability retention 100.2% circulates 100 times.
Embodiment 3:
According to the ratio of mol ratio 2:1:1, take lithium nitrate, nickel nitrate and spherical mangano-manganic oxide, lithium nitrate and lithium nitrate are dissolved in and in ethanol, are configured to the solution that metal cation total concentration is 0.3mol/L, in above-mentioned solution, add spherical mangano-manganic oxide, 70 ℃ of heating water baths are to forming paste mixture while stirring, after 110 ℃ of oven dry, obtain grey black powder, gained powder is at 950 ℃ of roasting 24h, and 675 ℃ of annealing 6h directly sieve after cooling and obtain nickel manganate cathode material for lithium.The 1C of resulting materials button cell is discharge capacity 123.2mAh/g first, and capability retention 100.3% circulates 100 times.
Claims (2)
1. a preparation method for spherical nickel manganate cathode material for lithium, is characterized in that: comprise the following steps:
According to the ratio of mol ratio 2:1:1, take Li source compound, nickel source compound and spherical mangano-manganic oxide, Li source compound and nickel source compound are dissolved in and in ethanol, are configured to the solution that metal cation total concentration is 0.1-0.3mol/L, in above-mentioned solution, add spherical mangano-manganic oxide, heating water bath is to forming paste mixture while stirring, after 90-110 ℃ of oven dry, obtain grey black powder, gained powder is at 750-950 ℃ of roasting 6-36h, 615-675 ℃ of annealing 2-6h, directly sieves after cooling and obtains nickel manganate cathode material for lithium;
Described Li source compound is lithium acetate or lithium nitrate, and described nickel source compound is nickel acetate or nickel nitrate;
Described water bath heating temperature is 50-70 ℃.
2. preparation method according to claim 1, is characterized in that: comprise the following steps:
According to the ratio of mol ratio 2:1:1, take Li source compound, nickel source compound and spherical mangano-manganic oxide, Li source compound and nickel source compound are dissolved in and in ethanol, are configured to the solution that metal cation total concentration is 0.1-0.2mol/L, in above-mentioned solution, add spherical mangano-manganic oxide, heating water bath is to forming paste mixture while stirring, after 95-105 ℃ of oven dry, obtain grey black powder, gained powder is at 800-900 ℃ of roasting 12-28h, 650-670 ℃ of annealing 3-5h, directly sieves after cooling and obtains nickel manganate cathode material for lithium;
Above-mentioned Li source compound is lithium acetate; Above-mentioned nickel source compound is nickel acetate; Above-mentioned water bath heating temperature is 60-65 ℃.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105206811A (en) * | 2015-09-23 | 2015-12-30 | 中信国安盟固利电源技术有限公司 | Wrapped and modified anode material doped with metallic oxide and preparation method of anode material |
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| US20100330429A1 (en) * | 2010-06-21 | 2010-12-30 | Ngk Insulators, Ltd. | Positive electrode active material and lithium secondary battery |
| CN102299310A (en) * | 2011-07-13 | 2011-12-28 | 奇瑞汽车股份有限公司 | Preparation method for LiNi0.5Mn1.5O4 material and lithium ion battery prepared by materials |
| CN102491422A (en) * | 2011-12-26 | 2012-06-13 | 湖南汇通科技有限责任公司 | Spherical manganic manganous oxide and its preparation method |
| CN103172117A (en) * | 2013-03-15 | 2013-06-26 | 英德佳纳金属科技有限公司 | Method for preparing mangano-manganic oxide by liquid phase oxidation |
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Patent Citations (5)
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| CN101378119A (en) * | 2008-10-06 | 2009-03-04 | 天津巴莫科技股份有限公司 | Method for preparing carbon-coating type lithium titanate for lithium ion battery |
| US20100330429A1 (en) * | 2010-06-21 | 2010-12-30 | Ngk Insulators, Ltd. | Positive electrode active material and lithium secondary battery |
| CN102299310A (en) * | 2011-07-13 | 2011-12-28 | 奇瑞汽车股份有限公司 | Preparation method for LiNi0.5Mn1.5O4 material and lithium ion battery prepared by materials |
| CN102491422A (en) * | 2011-12-26 | 2012-06-13 | 湖南汇通科技有限责任公司 | Spherical manganic manganous oxide and its preparation method |
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| CN105206811A (en) * | 2015-09-23 | 2015-12-30 | 中信国安盟固利电源技术有限公司 | Wrapped and modified anode material doped with metallic oxide and preparation method of anode material |
| CN105206811B (en) * | 2015-09-23 | 2018-09-07 | 中信国安盟固利电源技术有限公司 | A kind of positive electrode and preparation method thereof of blended metal oxide coating modification |
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Address after: 100010 Beijing, Chaoyangmen, North Street, No. 25, No. Patentee after: CHINA NATIONAL OFFSHORE OIL Corp. Patentee after: CNOOC TIANJIN CHEMICAL RESEARCH & DESIGN INSTITUTE Co.,Ltd. Patentee after: CNOOC ENERGY TECHNOLOGY & SERVICES Ltd. Address before: 100010 Beijing, Chaoyangmen, North Street, No. 25, No. Patentee before: CHINA NATIONAL OFFSHORE OIL Corp. Patentee before: CNOOC TIANJIN CHEMICAL RESEARCH & DESIGN INSTITUTE Patentee before: CNOOC ENERGY TECHNOLOGY & SERVICES Ltd. |
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Effective date of registration: 20161008 Address after: No. three road 300131 Tianjin city Hongqiao District dingzigu No. 85 Patentee after: CNOOC TIANJIN CHEMICAL RESEARCH & DESIGN INSTITUTE Co.,Ltd. Patentee after: CNOOC ENERGY TECHNOLOGY & SERVICES Ltd. Address before: 100010 Beijing, Chaoyangmen, North Street, No. 25, No. Patentee before: CHINA NATIONAL OFFSHORE OIL Corp. Patentee before: CNOOC TIANJIN CHEMICAL RESEARCH & DESIGN INSTITUTE Co.,Ltd. Patentee before: CNOOC ENERGY TECHNOLOGY & SERVICES Ltd. |