CN103337628B - A kind of synthetic method of positive material nano lithium manganese phosphate of lithium ion battery - Google Patents
A kind of synthetic method of positive material nano lithium manganese phosphate of lithium ion battery Download PDFInfo
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- CN103337628B CN103337628B CN201310241541.9A CN201310241541A CN103337628B CN 103337628 B CN103337628 B CN 103337628B CN 201310241541 A CN201310241541 A CN 201310241541A CN 103337628 B CN103337628 B CN 103337628B
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Abstract
The present invention discloses a kind of solvent process for thermosynthesizing of positive material nano lithium manganese phosphate of lithium ion battery.Two ethanolic solutions respectively containing lithium source, phosphoric acid root first mix by the method, add the ethanolic solution containing manganese source again, stir, then organic additive is added, finally, pour mixed liquor into reactor, sealing, with the ramp to 140 of 1 DEG C/min ~ 5 DEG C/min DEG C ~ 155 DEG C, heated at constant temperature 6h ~ 24h.It is capsule shape, sheet or cube shaped nanoscale LiMnPO that the inventive method can obtain pattern
4, have equipment investment little, technological process is simple, and pollute little, energy consumption is low, morphology controllable, the advantage that product granularity is little.
Description
Technical field
The invention belongs to electrochemical power source field of material preparation, be specifically related to a kind of LiMnPO of lithium rechargeable battery
4positive electrode and synthetic method thereof.
Background technology
Lithium rechargeable battery has been widely used in the portable sets such as mobile phone, digital camera, laptop computer.The stratiform lithium-containing transition metal oxide LiCoO of commercialization use at present
2have the problems such as the low and price of fail safe is higher, following electrochemical energy devices needs to have high-energy-density and high security and has the electrode material of inexpensive property and environment friendly simultaneously concurrently.Olivine-type LiMPO
4(M=Fe, Mn, Ni) positive electrode cost is low, and thermal stability is high.LiFePO
4be 3.45V to lithium voltage, after thousands of charge/discharge cycle, even also keep stable when overcharge and raised temperature.And Mn
3+/ Mn
2+relative to Li
+the electrode potential of/Li is 4.1V, and promoter manganese also has rich content, environmental friendliness, cheap advantage; LiMnPO
4(701Wh/kg=171mAh/g × 4.1V) has and compares LiFePO
4the theoretical energy density that (586Wh/kg=170mAh/g × 3.45V) is higher, and in the stability range of common non-water organic electrolyte; But due to LiMnPO
4the reason such as the scantling prepared of the design feature of self and conventional high-temperature sintering process is bigger than normal, causes the electrical conductivity performance of material internal poor, Li
+at LiMnPO
4in diffusion rate very low, significantly limit LiMnPO
4chemical property.
Nowadays the LiMnPO of nanostructure
4material, as nanoparticle, nanometer rods, nano-plates, nanometer sheet etc. to have obtained the attention of researcher as anode material for lithium-ion batteries.Size and the pattern of material have material impact to chemical property, synthesis nano and the material of specific morphology can improve electronic conductivity and the ionic conductivity of material well.
Solvent-thermal method effectively can control the morphological modification on nanometer level.In solvent thermal reaction, one or more presomas dissolve in a solvent, and under liquid phase or super critical condition, reactant dispersion in the solution, and becomes ground relatively vivaciously, and reaction occurs, and product slowly generates; This process is relatively simple and be easy to control, and effectively can prevent volatilization and the presoma of preparation to air-sensitive of noxious substance in enclosed system; Compared with solid phase method and sol-gel process, there is the advantage that reaction temperature is low, crystal growth abundant, product is mutually pure, scantling is little, and product batch good stability, easy volume production, raw material are cheap and easy to get.
In liquid phase environment, the kind of solvent and additive greatly can affect microscopic appearance and the size of product, and these two kinds of features can produce direct impact to the performance parameter of material; Ethanol is a kind of excellent organic solvent, has the advantage that boiling point is low, cost is low, soluble organism kinds is many.Adopt solvent-thermal method, with ethanol as solvent, just can be obtained the nanometer LiMnPO of all kinds of pattern by the kind changing organic additive simply
4, in other patent, have no report.
Summary of the invention
The object of the present invention is to provide a kind of synthetic method of nano lithium manganese phosphate of lithium, this synthetic method is solvent-thermal process method, specifically carries out according to the following steps:
(1) stoichiometrically, lithium source, manganese source, phosphoric acid root are dissolved in industrial alcohol or absolute ethyl alcohol respectively, obtain clarification unsaturated solution,
The stoichiometric proportion of lithium source, manganese source, phosphoric acid root is, Li:Mn:P mol ratio=1 ~ 1.5:1:1 ~ 1.2,
Wherein, lithium source is selected from lithium acetate, lithium nitrate or both mixtures; Manganese source is selected from manganese acetate, manganese nitrate or both mixtures; Phosphoric acid root is phosphoric acid,
In the clarification unsaturated solution obtained, the concentration of lithium ion is 0.25 ~ 0.35mol/L, and the concentration of manganese ion is 0.25 ~ 0.29mol/L, and the concentration of phosphate radical is 0.25 ~ 0.29mol/L;
(2) by the two solution mixing containing lithium source, phosphoric acid root of gained in step (1), stir,
Here mixing, can add the dropwise that gained in step (1) contains lithium source in the solution containing phosphoric acid root, or is added in the solution containing lithium source by the dropwise containing phosphoric acid root, or directly mixed by two solution;
(3) solution containing manganese source of gained in step (1) is mixed with gained solution in step (2), stirs,
Here mixing, can add the dropwise containing manganese source in step (2) in gained solution, or is added in the solution containing manganese source by gained dropwise in step (2), or is directly mixed by two solution;
(4) in step (3) gained solution, organic additive is added, mixing and stirring,
Organic additive is, liquid or the solid-state organic additive dissolving in industrial alcohol or absolute ethyl alcohol, be selected from unitary or polynary liquid alcohol or solid alcohol, the aliphatic acid dissolving in industrial alcohol or absolute ethyl alcohol, polyvinylpyrrolidone, ethylenediamine, urea, phenol, carbon tetrachloride, octadecylamine, Qu Latong, tween or triethanolamine
In this step, add organic additive, after mixing and stirring, the volume of the mixed solution of final gained is 7/6 ~ 2/1 with the ratio of the volume of the mixed solution of gained in step (3);
(5) pour step (4) gained solution into reactor, sealing, with the ramp to 140 of 1 DEG C/min ~ 5 DEG C/min DEG C ~ 155 DEG C, heated at constant temperature 6h ~ 24h, products therefrom centrifugation, with deionized water and ethanol washing, filters, dry.
The present invention is with ethanol as solvent, and the alternative of organic additive kind is high.Adopt that method products obtained therefrom purity provided by the invention is high, size is little, be conducive to the migration path shortening electronics and lithium ion; Further, the technological parameter of this method easily controls, and flow process is short, and preparation cost is low, by changing the kind of organic additive simply, just can obtain the lithium manganese phosphate with specific morphology, having expanded the research work of nanoscale lithium manganese phosphate preparation field further.
Accompanying drawing explanation
Fig. 1 is LiMnPO
4xRD figure, wherein: a is standard LiMnPO
4(standard card number: JCPDSNo.33-0803), b is embodiment 1, c be embodiment 2, d is embodiment 3.
Fig. 2 is the made LiMnPO of the embodiment of the present invention 1
4tEM figure.
Fig. 3 is the made LiMnPO of the embodiment of the present invention 2
4tEM figure.
Fig. 4 is the made LiMnPO of the embodiment of the present invention 3
4tEM figure.
Embodiment
To be described in more detail the present invention by specific embodiment below, but protection scope of the present invention is not limited to these embodiments.
Embodiment 1:
(1) get 2mmol manganese nitrate, 2.2mmol lithium nitrate and 2mmol phosphoric acid and be respectively dissolved in 7mL industrial alcohol, stirring and dissolving;
(2) then phosphoric acid solution is directly poured in lithium nitrate solution, and be constantly uniformly mixed;
(3) pour manganese nitrate solution in the mixed liquor then obtained to step (2), continue to stir;
(4) getting 12mL PEG400 again pours in the mixed liquor that step (3) obtains, mixing and stirring;
(5) pour in the polytetrafluoroethylene autoclave of 50mL by step (4) gained solution, sealing, with the ramp to 150 DEG C of 2 DEG C/min, heated at constant temperature 12h, naturally cools to room temperature, product centrifugation, by deionized water and ethanol washes clean, filter, dry.
Embodiment 2:
(1) get 2mmol manganese acetate, 2mmol lithium acetate and 2mmol phosphoric acid and be respectively dissolved in 8mL absolute ethyl alcohol, stirring and dissolving;
(2) then in phosphoric acid solution, dropwise add lithium acetate solution, and be constantly uniformly mixed;
(3), in the mixed liquor then obtained to step (2), dropwise add manganese acetate solution, continue to stir;
(4) add octadecylamine in the mixed liquor obtained to step (3), after mixing and stirring, the cumulative volume of gained solution is 36mL;
(5) pour in the polytetrafluoroethylene autoclave of 50mL by step (4) gained solution, sealing, with the ramp to 155 DEG C of 3 DEG C/min, heated at constant temperature 15h, naturally cools to room temperature, product centrifugation, by deionized water and ethanol washes clean, filter, dry.
Embodiment 3:
(1) get 2mmol manganese acetate, 2.4mmol lithium nitrate and 2mmol phosphoric acid and be respectively dissolved in 7mL absolute ethyl alcohol, stirring and dissolving;
(2) then phosphoric acid solution is dropwise joined in lithium nitrate solution, and be constantly uniformly mixed;
(3), in the mixed liquor then obtained to step (2), pour manganese acetate solution into, continue to stir;
(4) getting 14mL oleic acid again pours in the mixed liquor that step (3) obtains, mixing and stirring;
(5) step (4) gained solution is poured in the polytetrafluoroethylene autoclave of 50mL, sealing, with the ramp to 145 DEG C of 3 DEG C/min, heated at constant temperature 10h; Naturally cool to room temperature, product centrifugation, by deionized water and ethanol washes clean, filter, dry.
Claims (1)
1. a synthetic method for positive material nano lithium manganese phosphate of lithium ion battery, is characterized in that: described synthetic method is,
(1) get 2mmol manganese nitrate, 2.2mmol lithium nitrate and 2mmol phosphoric acid and be respectively dissolved in 7mL industrial alcohol, stirring and dissolving;
(2) then phosphoric acid solution is directly poured in lithium nitrate solution, and be constantly uniformly mixed;
(3) pour manganese nitrate solution in the mixed liquor then obtained to step (2), continue to stir;
(4) getting 12mL PEG400 again pours in the mixed liquor that step (3) obtains, mixing and stirring;
(5) pour in the polytetrafluoroethylene autoclave of 50mL by step (4) gained solution, sealing, with the ramp to 150 DEG C of 2 DEG C/min, heated at constant temperature 12h, naturally cools to room temperature, product centrifugation, by deionized water and ethanol washes clean, filter, dry;
Described synthetic method or be,
(1) get 2mmol manganese acetate, 2mmol lithium acetate and 2mmol phosphoric acid and be respectively dissolved in 8mL absolute ethyl alcohol, stirring and dissolving;
(2) then in phosphoric acid solution, dropwise add lithium acetate solution, and be constantly uniformly mixed;
(3), in the mixed liquor then obtained to step (2), dropwise add manganese acetate solution, continue to stir;
(4) add octadecylamine in the mixed liquor obtained to step (3), after mixing and stirring, the cumulative volume of gained solution is 36mL;
(5) pour in the polytetrafluoroethylene autoclave of 50mL by step (4) gained solution, sealing, with the ramp to 155 DEG C of 3 DEG C/min, heated at constant temperature 15h, naturally cools to room temperature, product centrifugation, by deionized water and ethanol washes clean, filter, dry.
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Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103682308A (en) * | 2013-11-28 | 2014-03-26 | 东北大学 | Method for preparing lithium-ion battery material LiNi<0.5>Mn<1.5-x>Ca<x>O<4> |
| CN104701539B (en) * | 2013-12-07 | 2017-12-19 | 天津赫维科技有限公司 | A kind of method that wet chemistry method prepares manganese-lithium phosphate anode material |
| CN103730656A (en) * | 2013-12-12 | 2014-04-16 | 天津大学 | Method for preparing lithium manganese phosphate nano-cluster |
| CN105098178B (en) * | 2014-04-29 | 2017-06-13 | 江苏华东锂电技术研究院有限公司 | The preparation method of lithium manganese phosphate and manganese phosphate lithium/carbon composite material |
| CN103996853A (en) * | 2014-05-28 | 2014-08-20 | 天津大学 | Method for preparing nano lithium manganese phosphate material with uniform size |
| CN104183845B (en) * | 2014-08-21 | 2016-04-27 | 浙江大学 | A kind of lithium manganese phosphate nano particle and preparation method thereof |
| CN104852046B (en) * | 2015-04-08 | 2017-01-18 | 浙江大学 | Nanometer piece shaped LMFP material, and manufacturing method and application thereof |
| CN105118993A (en) * | 2015-08-06 | 2015-12-02 | 天津大学 | Method for preparing rod-shaped nanometer lithium manganese phosphate material |
| CN105118992B (en) * | 2015-08-06 | 2018-01-12 | 天津大学 | The method for preparing high dispersive lithium manganese phosphate nano material |
| CN105140514A (en) * | 2015-08-06 | 2015-12-09 | 天津大学 | Method for preparing small-size nanometer lithium manganese phosphate material |
| CN105633405A (en) * | 2016-04-11 | 2016-06-01 | 天津大学 | Preparation method of lithium manganese phosphate nanorod |
| CN110518218A (en) * | 2019-09-04 | 2019-11-29 | 衢州学院 | New energy electrode material of lithium battery and production method based on 3D printing |
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Effective date of registration: 20201207 Address after: 213161, 27-7, Changzhou village, Hutang Town, Wujin District, Jiangsu Patentee after: Changzhou Fuda Amperex Technology Ltd. Address before: Gehu Lake Road Wujin District 213164 Jiangsu city of Changzhou province No. 1 Patentee before: CHANGZHOU University |