CN102205989A - Preparation method for cathode material LiMn2O4 of cell - Google Patents
Preparation method for cathode material LiMn2O4 of cell Download PDFInfo
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- CN102205989A CN102205989A CN2011100733899A CN201110073389A CN102205989A CN 102205989 A CN102205989 A CN 102205989A CN 2011100733899 A CN2011100733899 A CN 2011100733899A CN 201110073389 A CN201110073389 A CN 201110073389A CN 102205989 A CN102205989 A CN 102205989A
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- lithium
- preparation
- manganese dioxide
- aqueous solution
- cell positive
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Abstract
The invention discloses a preparation method for a cathode material LiMn2O4 of a cell. The preparation method comprises the following steps: dispersing solid manganese dioxide in a water solution containing lithium ions; carrying out the following reaction: 4Li<+>+MnO2+BH4<->+4OH<->=4LiMn2O4+BO2<->+H2+2H2O, when slowly dripping a water solution containing hydroboron to the water solution containing dispersed solid manganese dioxide and lithium ions; obtaining lithium-embedded manganese dioxide through carrying out filtering, washing and vacuum drying on a reaction solution when the reaction is finished; and carrying out low temperature calcination on lithium-embedded manganese dioxide. So LiMnO4 is obtained. Nano LiMn2O4 particles with uniform diameters which are prepared in the present invention have a good multiplying factor performance, and can be used in ionic cells to improve the power performance and the energy density of the cells.
Description
Technical field
The present invention relates to a kind of cell positive material LiMn
2O
4The preparation method, belong to electrochemical field.
Background technology
Along with the exhaustion day by day of petroleum resources and increasingly sharpening of environmental pollution, be that the hybrid electric automobile and the pure electric automobile of power become global much-talked-about topic with the battery.In the recent period, countries in the world have all given great support to the development of electromobile, and have formulated corresponding evolutionary operation(EVOP), and expectation is alleviated more and more serious energy dilemma and air environmental pollution problem with this.At present, large-scale lithium ion battery is considered to the automobile power cell of potentialization.Domestic and international many automobile production producer is getting down to the research of automobile-used lithium ion battery, and has realized the part commercialization.Lithium manganate having spinel structure has that Heat stability is good, overcharging resisting electricity, high rate during charging-discharging are superior, aboundresources and advantage such as environmentally friendly, and therefore it become the desirable positive electrode material of automobile-used large-scale lithium ion battery.In recent years, lithium manganate having spinel structure is generally accepted in the electromobile field, and enters the industrialization stage.For example: the electromobiles that motor corporation produced such as Toyota, Honda and daily output have all used with the spinel type mangaic acid and have been anodal lithium ion lithium cell." i-MiEV " electromobile that Mitsubishi Motors released in July, 2009 also adopts the positive electrode material of lithium manganate as lithium ion battery.
Along with the progressively development of electromobile, to the also progressively raising of performance requriements of lithium manganate having spinel structure.Starting, quickening and required superpower climbing the time in order to satisfy automobile, needing further to improve the multiplying power property of lithium manganate having spinel structure.Nanoscale and specific nanostructure then are the important channels of increasing the lithium manganate having spinel structure multiplying power property.Nanoscale can shorten lithium ion and the evolving path of electronics in discharge or process of charging effectively.Specific nanostructure then helps the transmission in electrode interior of the preparation of electrode and electronics as nano wire nanotube etc.Yet synthesizing the lithium manganate having spinel structure with nanoscale and nanostructure with conventional method is the comparison difficulty.
Existing Li
xMn
2O
4The preparation method of positive electrode material mainly contains following three classes.First kind high temperature solid-phase sintering method.This method synthesis technique is simple, only need lithium source and manganese source material thorough mixing with the chemical formula proportioning after, in 700～1000 ℃ of scopes, calcine got final product in 12～48 hours product.But the material of this method preparation, particle size is generally at tens microns, and do not possess even pattern, though can be used as the positive electrode material of lithium ion battery, but because the influence of its particle diameter and pattern, its multiplying power property can not satisfy high power lithium ion cell, especially the requirement of power cell. the second class sol-gel process.The concrete operations of this method generally be with the lithium salts of chemical formula proportioning and manganese salt under the effect of solvent and dispersion agent, be made into colloidal sol, be prepared into presoma, though then obtain sample through high-temperature calcination. the particle of this method may command material is at hundreds of nanometer or several micron, but because itself and inhomogenous pattern, make that the coating process of battery is complicated, thereby influence the integral working of battery.The 3rd class hydrothermal synthesis method. this method can prepare smaller particles size (generally in hundreds of nanometers), but because the limitation of synthetic method itself makes material not have good crystal formation, the cycle performance of material is affected.In sum, existing synthetic method is difficult to the nanometer lithium manganate LiMn for preparing the yardstick homogeneous or have ad hoc structure
2O
4
Summary of the invention
In view of the defective that above-mentioned prior art exists, the objective of the invention is to propose that a kind of technology is simple, the yardstick homogeneous, have ad hoc structure and be nano level cell positive material LiMn
2O
4The preparation method.
Purpose of the present invention will be achieved by the following technical programs:
A kind of cell positive material LiMn
2O
4The preparation method, comprise the steps:
(a) solid manganese dioxide is distributed in the aqueous solution that contains lithium ion;
(b) under powerful condition of stirring, the aqueous solution that will contain hydroborates is added drop-wise to lentamente and has above-mentionedly disperseed solid manganese dioxide and contain in the aqueous solution of lithium ion, and following reaction: 4Li takes place in this process
++ MnO
2+ BH
4 -+ 4OH
-→ 4LiMn
2O
4+ BO
2 -+ H
2+ 2H
2O;
(c) after above-mentioned reaction finishes, to reaction solution filter, washing and vacuum drying treatment, obtain the Manganse Dioxide of embedding lithium;
(d) Manganse Dioxide of the above-mentioned embedding lithium that makes is carried out low temperature calcination under 600 ℃ the condition and handles being lower than, obtain spinel lithium-manganese oxide LiMnO
2, prepared LiMnO
2Pattern be nano particle, nano wire, nanotube, sphere, class sphere or hollow ball.
Further, the form of solid manganese dioxide described in the step (a) is selected from one or more in particle, nano wire, nanotube, sphere, class sphere and the hollow ball.
Further, described form is that nanometer is linear, nanometer is tubular and the solid manganese dioxide of hollow sphere is to be prepared from by hydrothermal synthesis method or template.
Further, the aqueous solution that contains lithium ion described in the step (a) is the aqueous solution that is selected from one or more compounds in lithium hydroxide, lithium chloride, Lithium Acetate, Quilonum Retard, lithium nitrate, nitrate trihydrate lithium, Lithium Sulphate and the sulfuric acid monohydrate lithium.
Further, described hydroborates is selected from NaBH
4, KBH
4And LiBH
4In one or more.
Compared with prior art, beneficial effect of the present invention is: (1) technology is simple, starting material are easily obtained, and cost is lower; (2) resulting LiMn
2O
4Be the nano-scale particle of yardstick homogeneous, have specific structure, and have high rate performance preferably; (3) resulting LiMPO
4Be used for the power-performance that ionization cell can improve battery, improve the energy density of battery.
Following constipation closes the embodiment accompanying drawing, the specific embodiment of the present invention is described in further detail, so that technical solution of the present invention is easier to understand, grasp.
Description of drawings
Fig. 1 is LiMn among the embodiment 1
2O
4The sem photograph of nano particle;
Fig. 2 is LiMn among the embodiment 4
2O
4The sem photograph of nano wire and transmission electron microscope picture.
Embodiment
Embodiment 1
Adopt the method synthesis of nano LiMn in claims
2O
4The particle (see figure 1).Obtain LiMn
2O
4Nano particle, prepared LiMn
2O
4The granular size of nano particle is at 400～500nm.With the LiMn that makes
2O
4Nano particle, conductive agent and binding agent are then controlled certain thickness and are coated on the aluminum foil current collector according to 85: 5: 10 mixed slurry.With 1.0mol/L LiPF
6/ EC+DEC+DMC (volume ratio 1: 1: 1) is an ionogen, and the Li sheet is a negative pole, and it is barrier film that the U.S. produces Cellgard-2400 type polypropylene screen, is assembled into button cell in being full of the glove box of argon gas.On the LandCT2001A type battery test system that Jin Nuo Electronics Co., Ltd. in Wuhan produces, synthetic materials is carried out multiplying power test and cycle life test then.When 1/3C charged and discharged, the capacity of this material was 120mAh/g; When 1C charged and discharged, its capacity was 115mAh/g; When 20C charged and discharged, the capacity of this material was 85mAh/g.Under the 1C condition, charge and discharge 100 weeks of circulation, the capacity sustainment rate is 80%.
Comparative Examples 1
Adopt conventional solid phase synthesis process to prepare LiMn
2O
4Material: after grinding Manganse Dioxide and lithium salts evenly, 800～1000 ℃ of calcinings 6～48 hours down, get final product product.The granular size that obtains product is about 5um.With the LiMn that makes
2O
4Micron particle, conductive agent and binding agent are then controlled certain thickness and are coated on the aluminum foil current collector according to 85: 5: 10 mixed slurry.With 1.0mol/LLiPF
6/ EC+DEC+DMC (volume ratio 1: 1: 1) is an ionogen, and the Li sheet is a negative pole, and it is barrier film that the U.S. produces Cellgard-2400 type polypropylene screen, is assembled into button cell in being full of the glove box of argon gas.On the LandCT2001A type battery test system that Jin Nuo Electronics Co., Ltd. in Wuhan produces, synthetic materials is carried out multiplying power test and cycle life test then.When 1/3C charged and discharged, the capacity of this material was 118mAh/g; When 1C charged and discharged, its capacity was 109mAh/g; When 20C charged and discharged, the capacity of this material was 57mAh/g.Under the 1C condition, charge and discharge 100 weeks of circulation, the capacity sustainment rate is 80%.
Adopt the method synthesis of nano Li in claims
1.05Mn
1.95O
4Particle.Obtain Li
1.05Mn
1.95O
4Nano particle, prepared Li
1.05Mn
1.95O
4The granular size of nano particle is at 400～500nm.With the Li that makes
1.05Mn
1.95O
4Nano particle, conductive agent and binding agent are then controlled certain thickness and are coated on the aluminum foil current collector according to 85: 5: 10 mixed slurry.With 1.0mol/L LiPF
6/ EC+DEC+DMC (volume ratio 1: 1: 1) is an ionogen, and the Li sheet is a negative pole, and it is barrier film that the U.S. produces Cellgard-2400 type polypropylene screen, is assembled into button cell in being full of the glove box of argon gas.On the LandCT2001A type battery test system that Jin Nuo Electronics Co., Ltd. in Wuhan produces, synthetic materials is carried out multiplying power test and cycle life test then.When 1/3C charged and discharged, the capacity of this material was 109mAh/g; When 1C charged and discharged, its capacity was 103mAh/g; When 20C charged and discharged, the capacity of this material was 80mAh/g.Under the 1C condition, charge and discharge 100 weeks of circulation, the capacity sustainment rate is 95%.
Embodiment 3
Adopt the method synthesis of nano LiMg in claims
0.05Mn
1.95O
4Nano particle.Obtain LiMg
0.05Mn
1.95O
4Nano particle is with the LiMg that makes
0.05Mn
1.95O
4Nano particle, conductive agent and binding agent are then controlled certain thickness and are coated on the aluminum foil current collector according to 85: 5: 10 mixed slurry.With 1.0mol/L LiPF
6/ EC+DEC+DMC (volume ratio 1: 1: 1) is an ionogen, and the Li sheet is a negative pole, and it is barrier film that the U.S. produces Cellgard-2400 type polypropylene screen, is assembled into button cell in being full of the glove box of argon gas.On the LandCT2001A type battery test system that Jin Nuo Electronics Co., Ltd. in Wuhan produces, synthetic materials is carried out multiplying power test and cycle life test then.When 1/3C charged and discharged, the capacity of this material was 110mAh/g; When 1C charged and discharged, capacity was 106mAh/g; When 20C charged and discharged, the capacity of this material was 83mAh/g.Under the 1C condition, charge and discharge 100 weeks of circulation, the capacity sustainment rate is 94%.
Embodiment 4
Adopt the method synthesis of nano LiMn in claims
2O
4Nano wire.Obtain product LiMn
2O
4Nano wire, prepared LiMn
2O
4The diameter of nano wire is 40nm～100nm, and length is 1um～3um.With the LiMn that makes
2O
4Nano wire, conductive agent and binding agent are then controlled certain thickness and are coated on the aluminum foil current collector according to 85: 5: 10 mixed slurry.With 1.0mol/L LiPF
6/ EC+DEC+DMC (volume ratio 1: 1: 1) is an ionogen, and the Li sheet is a negative pole, and it is barrier film that the U.S. produces Cellgard-2400 type polypropylene screen, is assembled into button cell in being full of the glove box of argon gas.On the LandCT2001A type battery test system that Jin Nuo Electronics Co., Ltd. in Wuhan produces, synthetic materials is carried out multiplying power test and cycle life test then.When 1/3C charged and discharged, the capacity of this material was 118mAh/g; When 1C charged and discharged, its capacity was 110mAh/g; When 20C charged and discharged, the capacity of this material was 87mAh/g.Under the 1C condition, charge and discharge 100 weeks of circulation, the capacity sustainment rate is 90%.
Sum up the performance number of the various materials that make among the embodiment 1～4 and Comparative Examples 1 below with the form of form.
The performance perameter of the various materials that make in table 1 embodiment 1～4 and the Comparative Examples 1
Compared with prior art, beneficial effect of the present invention is: (1) technology is simple, starting material are easily obtained, and cost is lower; (2) resulting LiMn
2O
4Be the nano-scale particle of yardstick homogeneous, have specific structure, and have high rate performance preferably; (3) resulting LiMPO
4Be used for the power-performance that ionization cell can improve battery, improve the energy density of battery.
The present invention still has multiple concrete embodiment, and all employings are equal to replacement or equivalent transformation and all technical schemes of forming, all drop within the scope of protection of present invention.
Claims (5)
1. cell positive material LiMn
2O
4The preparation method, it is characterized in that: comprise the steps:
(a) solid manganese dioxide is distributed in the aqueous solution that contains lithium ion;
(b) under powerful condition of stirring, the aqueous solution that will contain hydroborates is added drop-wise to lentamente and has above-mentionedly disperseed solid manganese dioxide and contain in the aqueous solution of lithium ion, and following reaction: 4Li takes place in this process
++ MnO
2+ BH
4 -+ 4OH
-→ 4LiMn
2O
4+ BO
2 -+ H
2+ 2H
2O;
(c) after above-mentioned reaction finishes, to reaction solution filter, washing and vacuum drying treatment, obtain the Manganse Dioxide of embedding lithium;
(d) Manganse Dioxide of the above-mentioned embedding lithium that makes is carried out low temperature calcination under 600 ℃ the condition and handles being lower than, obtain spinel lithium-manganese oxide LiMnO
2
2. cell positive material LiMn according to claim 1
2O
4The preparation method, it is characterized in that: the form of solid manganese dioxide is selected from one or more in particle, nano wire, nanotube, sphere, class sphere and the hollow ball described in the step (a).
3. cell positive material LiMn according to claim 2
2O
4The preparation method, it is characterized in that: described form is that the solid manganese dioxide of nano wire, nanotube and hollow ball is to be prepared from by hydrothermal synthesis method or template.
4. cell positive material LiMn according to claim 3
2O
4The preparation method, it is characterized in that: the aqueous solution that contains lithium ion described in the step (a) is the aqueous solution that is selected from one or more compounds in lithium hydroxide, lithium chloride, Lithium Acetate, Quilonum Retard, lithium nitrate, nitrate trihydrate lithium, Lithium Sulphate and the sulfuric acid monohydrate lithium.
5. according to any described cell positive material LiMn among the claim 1-4
2O
4The preparation method, it is characterized in that: described hydroborates is selected from NaBH
4, KBH
4And LiBH
4In one or more.
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| CN2011100733899A CN102205989A (en) | 2011-03-25 | 2011-03-25 | Preparation method for cathode material LiMn2O4 of cell |
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|---|---|---|---|
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103594695A (en) * | 2012-08-13 | 2014-02-19 | 深圳华粤宝电池有限公司 | Lithium ion battery cathode material lithium manganate and preparation method thereof |
| CN103762354A (en) * | 2014-01-22 | 2014-04-30 | 中南大学 | LiNi0.5Mn1.5O4 material, preparation method thereof as well as lithium ion battery |
| CN108455674A (en) * | 2017-12-26 | 2018-08-28 | 郑州科技学院 | A kind of preparation method of spindle bodily form LiMn2O4 hollow pipe |
| CN111418094A (en) * | 2017-09-01 | 2020-07-14 | 安托法加斯塔大学 | Manganese spinel doped with magnesium, cathode material comprising same, method for preparing same and lithium ion battery comprising such spinel |
| CN114195504A (en) * | 2021-11-05 | 2022-03-18 | 中山大学 | MgAl2O4Preparation method and application of nanowire film |
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| US20100270498A1 (en) * | 2005-06-29 | 2010-10-28 | Yuan Gao | Lithium manganese compounds and methods of making the same |
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2011
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103594695A (en) * | 2012-08-13 | 2014-02-19 | 深圳华粤宝电池有限公司 | Lithium ion battery cathode material lithium manganate and preparation method thereof |
| CN103762354A (en) * | 2014-01-22 | 2014-04-30 | 中南大学 | LiNi0.5Mn1.5O4 material, preparation method thereof as well as lithium ion battery |
| CN111418094A (en) * | 2017-09-01 | 2020-07-14 | 安托法加斯塔大学 | Manganese spinel doped with magnesium, cathode material comprising same, method for preparing same and lithium ion battery comprising such spinel |
| CN108455674A (en) * | 2017-12-26 | 2018-08-28 | 郑州科技学院 | A kind of preparation method of spindle bodily form LiMn2O4 hollow pipe |
| CN108455674B (en) * | 2017-12-26 | 2021-02-26 | 郑州科技学院 | Preparation method of spindle-shaped lithium manganate hollow tube battery positive electrode material |
| CN114195504A (en) * | 2021-11-05 | 2022-03-18 | 中山大学 | MgAl2O4Preparation method and application of nanowire film |
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Application publication date: 20111005 |