CN103011299A - Preparation method of lithium manganate positive material - Google Patents
Preparation method of lithium manganate positive material Download PDFInfo
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- CN103011299A CN103011299A CN2012105362160A CN201210536216A CN103011299A CN 103011299 A CN103011299 A CN 103011299A CN 2012105362160 A CN2012105362160 A CN 2012105362160A CN 201210536216 A CN201210536216 A CN 201210536216A CN 103011299 A CN103011299 A CN 103011299A
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Abstract
The invention discloses a preparation method of a lithium manganate positive material. The preparation method comprises the following steps of: uniformly dispersing spherical manganese dioxide prepared by a chemical co-precipitation method in an aqueous solution by stirring; continuously adding a prepared lithium salt solution and ammonium carbonate solution into a reactor, wherein the dropping speed, pH value, temperature and the like of a system are controlled, so that tiny lithium carbonate generated by the reaction is uniformly precipitated on the surface of manganese dioxide; performing suction filtration after finishing the reaction, sintering and crushing after drying and crushing a precipitate, thereby obtaining a spherical high-performance lithium manganate material through grading preparation. Impurity content of the used spherical manganese dioxide is less, the lithium carbonate generated by precipitating is small and uniform in particle size; the synthesized lithium manganate is spherical, narrow in particle size distribution, high in compact density, small in specific surface area, and excellent in electrochemical performance.
Description
Technical field
The present invention relates to a kind of preparation method of manganate cathode material for lithium, be used for anode material for lithium-ion batteries, belong to the new energy materials field.
Background technology
Developing rapidly of automotive industry promoted progress and the development of the industry such as global machinery, the energy, traffic, but fuel-engined vehicle is when promoting the well-being of mankind, and exhaust emissions has also caused severe contamination to the human residential environment.According to statistics, 63% of the topsoil composition from fuel-engined vehicle at present, reached the degree that strictly to be controlled and to administer, the requirement of energy shortage and environmental protection has promoted the development of electromobile and hybrid vehicle, they have special performance requriements to lithium ion battery, but present commercial lithium ion battery can't satisfy the requirement of large-scale application.Therefore, the high performance lithium electric material of exploitation preparation becomes the emphasis of current research.
Summary of the invention
For the deficiency that prior art exists, technical problem to be solved by this invention is, a kind of preparation method who obtains even particle size distribution, compacted density is high, specific surface area is little, chemical property is excellent manganate cathode material for lithium is provided.
For solving the problems of the technologies described above, the technical solution used in the present invention is: a kind of preparation method of manganate cathode material for lithium may further comprise the steps:
(1), compound concentration is the solubility lithium salts of 1.0～4.0mol/L and the mixing salt solution of doped element; Concentration is the sal volatile of 0.8～3.6mol/L; Concentration is the ammoniacal liquor of 1.0～3.0mol/L;
(2), Manganse Dioxide is divided and dispersion agent is put into water, in reaction system, drip continuously solubility lithium salts mixing solutions and the sal volatile of joining, the pH value of regulation system is 9.0～11.0,50～60 ℃ of temperature, stirring velocity 35～70r/min, make the tiny Quilonum Retard of generation be deposited on the Manganse Dioxide surface, after reaction is finished, continue to stir ageing 0.5～4h;
(3), the mixture that obtains is centrifugal, wash with water for several times, be placed on 100～250 ℃ of dryings in the vacuum drying oven;
(4), above-mentioned dried mixture is pulverized, sieve, then put into atmosphere furnace and calcine, first at 750～950 ℃ of insulation 5～10h, again at 500～700 ℃ of lower insulation 10-26h, cooling, behind the crushing and classification the finished product.
The preparation method of above-mentioned manganate cathode material for lithium, used solubility lithium salts is LiNO
3, Li
2SO
4, among LiCl, LiOH, the LiF one or more.
The preparation method of above-mentioned manganate cathode material for lithium, doped element are nitrate aqueous solution or any salts solution that is dissolvable in water water of Al, Co, Mg, Cr and rare-earth elements La etc.
The preparation method of above-mentioned manganate cathode material for lithium, used MnO
2The spherical MnO by the chemical coprecipitation preparation
2
The preparation method of above-mentioned manganate cathode material for lithium, the pH value of described reaction system is 10.0,55 ℃ of temperature, stirring velocity 60r/min, ageing 2h.
The preparation method of above-mentioned manganate cathode material for lithium, drying temperature is 150 ℃ behind the suction filtration, once calcines during sintering and selects 930 ℃ of insulation 8h, secondary clacining is selected 650 ℃ of insulation 24h.
The preparation method's of manganate cathode material for lithium of the present invention advantage is: for lithium electricity positive-material lithium manganate, in order to improve its performance, the researchist starts with from its preparation method, has taked a lot of methods such as ion doping and finishing.Wherein, ion doping refers to add the related compounds such as Al, Co, Mg, Cr and rare-earth elements La in preparation process, reduces the Jahn-Teller effect to improve cycle performance.Finishing mainly is to coat, and is to carry out in the synthetic later stage of material, namely coats one deck active substance such as Al on the surface of material
2O
3, ZnO, ZrO
2Deng.The method of the raising lithium manganate material performance that we adopt now is to start with from raw material, solves raw-material pattern, granularity and impurity etc. from the source on the impact of product.For MnO
2We prepare with chemical coprecipitation, and the Quilonum Retard that then directly generates with reaction is deposited on MnO
2The surface reaches mixed uniformly purpose.Employed spherical manganese dioxide foreign matter content is few, and the Quilonum Retard granularity that precipitation generates is little and even, and the lithium manganate pattern that is synthesized is sphere, narrow particle size distribution, compacted density is high, specific surface area is little, chemical property is good.
Description of drawings
Fig. 1 is the SEM figure of positive-material lithium manganate;
Fig. 2 is the XRD figure of positive-material lithium manganate.
Embodiment
Below in conjunction with drawings and the specific embodiments the present invention is described in further details;
Embodiment 1:
1) compound concentration is the LiNO of 3.0mol/L
3And Al (NO
3)
3(trace) solution, concentration are that the sal volatile of 0.8mol/L and the concentration of regulating pH value usefulness are the ammoniacal liquor of 3.0mol/L.
2) Manganse Dioxide and the dispersion agent with the chemical coprecipitation preparation joins in the reactor that water is housed, and opens and stirs, and stirring velocity is controlled at 60r/min, with LiNO
3Slowly continuous being added drop-wise in the reactor of solution and sal volatile, the pH value of regulation system is 9.0, temperature 50 C, stirring velocity 35r/min makes the tiny Quilonum Retard of generation be deposited on the Manganse Dioxide surface, after reaction is finished, continues to stir ageing 0.5h.Wherein, dispersion agent is wetting ability dispersion agent commonly used in the prior art, such as Macrogol 200 or 400.
3) mixture that obtains is centrifugal, wash with water 3 times, be placed on 100 ℃ of dryings in the vacuum drying oven.
4) above-mentioned dried mixture is pulverized, sieved, then put into atmosphere furnace and calcine, first at 750 ℃ of insulation 10h, again
At 500 ℃ of lower insulation 26h, cooling gets the finished product behind the crushing and classification.
Embodiment 2:
1) compound concentration is the LiNO of 3.0mol/L
3And Cr (NO
3)
3(trace) solution, concentration are that the sal volatile of 1.5mol/L and the concentration of regulating pH value usefulness are the ammoniacal liquor of 3.0mol/L.
2) Manganse Dioxide and the dispersion agent with the chemical coprecipitation preparation joins in the reactor that water is housed, and opens and stirs, and stirring velocity is controlled at 60r/min, with LiNO
3Slowly continuous being added drop-wise in the reactor of solution and sal volatile, the pH value of regulation system is 10.0,55 ℃ of temperature, 50r/min makes the tiny Quilonum Retard of generation be deposited on the Manganse Dioxide surface, after reaction is finished, continues to stir ageing 2h.
3) mixture that obtains is centrifugal, wash with water 3 times, be placed on 170 ℃ of dryings in the vacuum drying oven.
4) dried material is put into water at this, the system of adding water to becomes slightly soluble gluey, adds such as a certain amount of ZrOCl in system simultaneously
2The aqueous solution, the backward system that stirs dropwise add ammoniacal liquor to be regulated about pH to 10, forms Zr (OH)
4Colloidal sol is coated on particle surface.
5) above-mentioned dried mixture is pulverized, sieved, then put into atmosphere furnace and calcine, elder generation is at 850 ℃ of insulation 8h, and at 650 ℃ of lower insulation 24h, cooling gets the finished product behind the crushing and classification again.
Embodiment 3:
1) compound concentration is the LiNO of 4.0mol/L
3And Mg (NO
3)
2(trace) solution, concentration are that the sal volatile of 3.6mol/L and the concentration of regulating pH value usefulness are the ammoniacal liquor of 1.0mol/L.
2) Manganse Dioxide and the dispersion agent with the chemical coprecipitation preparation joins in the reactor that water is housed, and opens and stirs, and stirring velocity is controlled at 60r/min, with LiNO
3Slowly continuous being added drop-wise in the reactor of solution and sal volatile, the pH value of regulation system is 11.0, temperature 60 C, 70r/min make the tiny Quilonum Retard of generation be deposited on the Manganse Dioxide surface, after reaction is finished, continue to stir ageing 4h.
3) mixture that obtains is centrifugal, wash with water 3 times, be placed on 250 ℃ of dryings in the vacuum drying oven.
4) dried material is put into water at this, the system of adding water to becomes slightly soluble gluey, adds such as a certain amount of ZrOCl in system simultaneously
2The aqueous solution, the backward system that stirs dropwise add ammoniacal liquor to be regulated about pH to 10, forms Zr (OH)
4Colloidal sol is coated on particle surface.
5) above-mentioned dried mixture is pulverized, sieved, then put into atmosphere furnace and calcine, elder generation is at 950 ℃ of insulation 5h, and at 700 ℃ of lower insulation 10h, cooling gets the finished product behind the crushing and classification again.
Certainly, above-mentioned explanation is not to be limitation of the present invention, and the present invention also is not limited to above-mentioned giving an example; those skilled in the art; in essential scope of the present invention, the variation of making, remodeling, interpolation or replacement all should belong to protection scope of the present invention.
Claims (6)
1. the preparation method of a manganate cathode material for lithium is characterized in that, may further comprise the steps:
(1), compound concentration is the solubility lithium salts of 1.0～4.0mol/L and the mixing salt solution of doped element; Concentration is the sal volatile of 0.8～3.6mol/L; Concentration is the ammoniacal liquor of 1.0～3.0mol/L;
(2), Manganse Dioxide is divided and dispersion agent is put into water, in reaction system, drip continuously solubility lithium salts mixing solutions and the sal volatile of joining, the pH value of regulation system is 9.0～11.0,50～60 ℃ of temperature, stirring velocity 35～70r/min, make the tiny Quilonum Retard of generation be deposited on the Manganse Dioxide surface, after reaction is finished, continue to stir ageing 0.5～4h;
(3), the mixture that obtains is centrifugal, wash with water for several times, be placed on 100～250 ℃ of dryings in the vacuum drying oven;
(4), above-mentioned dried mixture is pulverized, sieve, then put into atmosphere furnace and calcine, first at 750～950 ℃ of insulation 5～10h, again at 500～700 ℃ of lower insulation 10-26h, cooling, behind the crushing and classification the finished product.
2. the preparation method of manganate cathode material for lithium according to claim 1, it is characterized in that: used solubility lithium salts is LiNO
3, Li
2SO
4, among LiCl, LiOH, the LiF one or more.
3. the preparation method of manganate cathode material for lithium according to claim 2, it is characterized in that: doped element is nitrate aqueous solution or any salts solution that is dissolvable in water water of Al, Co, Mg, Cr and rare-earth elements La etc.
4. it is characterized in that: used MnO according to claim 2 or the preparation method of 3 described manganate cathode material for lithium,
2The spherical MnO by the chemical coprecipitation preparation
2
5. the preparation method of manganate cathode material for lithium according to claim 4, it is characterized in that: the pH value of described reaction system is 10.0,55 ℃ of temperature, stirring velocity 60r/min, ageing 2h.
6. the preparation method of manganate cathode material for lithium according to claim 5, it is characterized in that: drying temperature is 150 ℃ behind the suction filtration, once calcines during sintering and selects 930 ℃ of insulation 8h, secondary clacining is selected 650 ℃ of insulation 24h.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104218238A (en) * | 2014-08-21 | 2014-12-17 | 奇瑞汽车股份有限公司 | Preparation method for lithium-enriched manganese-based cathode material |
| CN109232869A (en) * | 2018-09-13 | 2019-01-18 | 腾龙特种树脂(厦门)有限公司 | A kind of PETG modified copolyester |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1743276A (en) * | 2004-08-31 | 2006-03-08 | 比亚迪股份有限公司 | Lithium cell anode material lithium manganate preparing method |
| CN101764223A (en) * | 2009-10-14 | 2010-06-30 | 孙琦 | Doped spherical LiMn2O4 (manganese acid lithium) and preparation method thereof |
| US20120064229A1 (en) * | 2011-05-10 | 2012-03-15 | International Battery, Inc. | Polymer acids as binder and ph reducing agent for aqueous lithium-ion cells |
| CN102683667A (en) * | 2011-12-06 | 2012-09-19 | 中国科学院宁波材料技术与工程研究所 | Lithium-manganese-aluminum oxygen anode material and preparation method thereof |
-
2012
- 2012-12-13 CN CN2012105362160A patent/CN103011299A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1743276A (en) * | 2004-08-31 | 2006-03-08 | 比亚迪股份有限公司 | Lithium cell anode material lithium manganate preparing method |
| CN101764223A (en) * | 2009-10-14 | 2010-06-30 | 孙琦 | Doped spherical LiMn2O4 (manganese acid lithium) and preparation method thereof |
| US20120064229A1 (en) * | 2011-05-10 | 2012-03-15 | International Battery, Inc. | Polymer acids as binder and ph reducing agent for aqueous lithium-ion cells |
| CN102683667A (en) * | 2011-12-06 | 2012-09-19 | 中国科学院宁波材料技术与工程研究所 | Lithium-manganese-aluminum oxygen anode material and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| JUN JOHN XU ET AL.: ""Amorphous Manganese Dioxide: A High Capacity Lithium Intercalation Host"", 《ELECTROCHEMICAL AND SOLID-STATE LETTERS》, vol. 1, no. 1, 31 December 1998 (1998-12-31), pages 1 - 3, XP000864910, DOI: doi:10.1149/1.1390615 * |
| 赵铭姝等: ""锂离子蓄电池正极材料尖晶石型锰酸锂的制备"", 《电源技术》, vol. 25, no. 3, 30 June 2001 (2001-06-30), pages 246 - 249 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104218238A (en) * | 2014-08-21 | 2014-12-17 | 奇瑞汽车股份有限公司 | Preparation method for lithium-enriched manganese-based cathode material |
| CN109232869A (en) * | 2018-09-13 | 2019-01-18 | 腾龙特种树脂(厦门)有限公司 | A kind of PETG modified copolyester |
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Application publication date: 20130403 |