CN103441264A - Method for reducing dissolution of manganese in lithium manganate in electrolyte solution - Google Patents
Method for reducing dissolution of manganese in lithium manganate in electrolyte solution Download PDFInfo
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- CN103441264A CN103441264A CN2013104055812A CN201310405581A CN103441264A CN 103441264 A CN103441264 A CN 103441264A CN 2013104055812 A CN2013104055812 A CN 2013104055812A CN 201310405581 A CN201310405581 A CN 201310405581A CN 103441264 A CN103441264 A CN 103441264A
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Abstract
The invention particularly relates to a method for reducing the dissolution of manganese in lithium manganate serving as a cathode material of a lithium ion battery in an electrolyte solution. The method for reducing the dissolution of manganese in lithium manganate serving as the cathode material of the lithium ion battery in an electrolyte solution comprises the following steps: by taking lithium carbonate and manganese dioxide as raw materials, firstly, carrying out ball milling on the raw materials in a dry milling mode, wherein the ball milling speed is 110-230 r/min; then, calcining the obtained product at a temperature of 500-780 DEG C, and cooling the obtained product so as to obtain the lithium manganate serving as the cathode material of the lithium ion battery. According to the invention, through taking lithium carbonate and manganese dioxide as the raw materials and by using the ball-milling treatment method, the particle size of a manganese source can be reduced, the specific surface area and the surface energy can be increased, the dissolution of manganese ions in the electrolyte solution can be reduced, the modification on lithium manganate serving as the cathode material of the lithium ion battery can be realized, and the cycle performance of the battery can be improved, therefore, the method provides a beneficial support for the preparation of a high-stability power battery.
Description
(1) technical field
The present invention relates to a kind of lithium cell anode material lithium manganate, particularly a kind ofly reduce in lithium cell anode material lithium manganate the method that manganese dissolves in electrolyte.
(2) background technology
Lithium ion battery is the new generation of green battery, have operating voltage and energy density high, have extended cycle life, volume is little, the remarkable advantage such as lightweight, once coming out, just develop rapidly.The lithium ion anode material LiMn2O4 is the novel anode material grown up after cobalt acid lithium, with the sour lithium of cobalt, compares, and has aboundresources, the distinguishing feature that cheap, environmentally friendly, fail safe is good.Spinel-type LiMn
2o
4there is unique three-dimensional tunnel structure, be conducive to Li
+embedding and deviate from.As anode material for lithium-ion batteries, LiMn
2o
4having higher power and energy density, favored in the electric automobile field, is the unique practical positive electrode of current Vehicular dynamic battery.
In recent years, to the research of LiMn2O4, be the emphasis of domestic and international development of new anode material for lithium-ion batteries always.But LiMn
2o
4the subject matter of application is that under high temperature, circulating battery is used capacity attenuation very fast.Trace it to its cause, mainly contain the dissolving of manganese, decomposition and the Jahn-Teller effect of electrolyte.For the research of this problem and the exploration of solution route, be the main contents of current Study on Li-ion batteries using.In recent years, people mainly improve LiMn by doping and surface coating method
2o
4chemical property, doping can suppress Jahn-Teller distortion (ginger-Taylor's distortion) to a certain extent, reduces LiMn
2o
4capacity attenuation speed.The surface coating can reduce the contact area of material and electrolyte, suppresses the dissolving of manganese in electrolyte, improves LiMn
2o
4cycle performance.But still there is various problems in these methods, as complicated process of preparation, condition are harsh, the cycle is long, be difficult to large-scale production and production cost is high.
(3) summary of the invention
In order to make up the deficiencies in the prior art, the invention provides a kind of method that manganese dissolves in electrolyte that reduces in lithium cell anode material lithium manganate, lithium cell anode material lithium manganate prepared by the method has reduced the dissolving of manganese in electrolyte, has improved the chemical property of lithium manganate battery.
The present invention is achieved through the following technical solutions:
A kind ofly reduce in lithium cell anode material lithium manganate the method that manganese dissolves in electrolyte, its special character is: comprise the following steps: take lithium carbonate and manganese dioxide as raw material, at first adopt dry grinding mode ball milling, ball milling speed is 110-230 r/ min, then at 500-780 ℃, calcined, with the cooling lithium cell anode material lithium manganate that obtains of stove.
The method that in reduction lithium cell anode material lithium manganate of the present invention, manganese dissolves in electrolyte, its ratio of grinding media to material is 10-2:1, Ball-milling Time is 0.5-8h.
The method that in reduction lithium cell anode material lithium manganate of the present invention, manganese dissolves in electrolyte, heat treatment process is the programming rate intensification with 3-5 ℃/min, and sintering temperature is 760-800 ℃, and sintering time is 10h.
The invention has the beneficial effects as follows: it is that raw material adopts the ball-milling treatment method that lithium carbonate and manganese oxide are take in the present invention, reduced manganese source particle diameter, specific area and surface energy have been increased, technique is simple, realize the modification to lithium cell anode material lithium manganate, reduced the dissolving of manganese ion in electrolyte in the LiMn2O4, suppressed the Jahn-Teller distortion, improve the cycle performance of battery, for the electrokinetic cell for preparing high stability, provide favourable support.
(4) accompanying drawing explanation
The x-ray diffraction pattern of LiMn2O4 prepared for different time ball milling raw material by accompanying drawing 1;
Accompanying drawing 2 is local X-ray diffraction enlarged drawing in accompanying drawing 1;
The SEM figure of LiMn2O4 sample prepared for artificial milling time 0.5h by accompanying drawing 3;
Accompanying drawing 4 is schemed for the SEM of LiMn2O4 sample prepared by Ball-milling Time 2h;
Accompanying drawing 5 is schemed for the SEM of LiMn2O4 sample prepared by Ball-milling Time 4h;
Accompanying drawing 6 is schemed for the SEM of LiMn2O4 sample prepared by Ball-milling Time 6h;
Accompanying drawing 7 is schemed for the SEM of LiMn2O4 sample prepared by Ball-milling Time 8h;
Accompanying drawing 8 is for preparing front 30 the cycle performance curves of LiMn2O4.
(5) embodiment
Embodiment 1
Take lithium carbonate and manganese dioxide as raw material, and Li:Mn=1:2 accurately takes raw material in molar ratio, carries out the mechanical ball mill on planetary ball mill, and ratio of grinding media to material is respectively 10:1,8:1,6:1,4:1,2:1, and rotating speed is 200 r/ min, ball milling 6h.By the sample of preparation, be transferred to respectively in corundum crucible, in resistance furnace, under air atmosphere, heat-treat: first with the speed of 5 ℃/min, be warming up to 500 ℃ and be incubated 3h, after cooling, grind a little, powder after pre-burning is scattered, again Preburning material is warming up to 780 ℃ and be incubated 10h with the speed of 3 ℃/min, after cooling with stove, obtain sample.
Table 1 is 200 r/ min for embodiment 1 at rotating speed, the d50 of the sample that Ball-milling Time makes while being 6h, and as can be seen from Table 1, ratio of grinding media to material is larger on the grinding efficiency impact.
Table-1 ratio of grinding media to material is on the impact of raw material particle size size
Embodiment 2
Take lithium carbonate and manganese dioxide as raw material, and Li:Mn=1:2 accurately takes raw material in molar ratio, carries out the mechanical ball mill on planetary ball mill, and ratio of grinding media to material is 4:1, and rotating speed is respectively 110,140,170,200,230r/ min, ball milling 6h.By the sample of preparation, be transferred to respectively in corundum crucible, in resistance furnace, under air atmosphere, heat-treat: first with the speed of 5 ℃/min, be warming up to 500 ℃ and be incubated 3h, cooling rear grinding, make the powder after pre-burning scattered, again Preburning material is warming up to 780 ℃ and be incubated 10 h with the speed of 3 ℃/min, after cooling with stove, obtain sample.
Table 2 carries out the mechanical ball mill for embodiment 2 on planetary ball mill, ratio of grinding media to material is 4:1, the d50 of the sample that ball milling 6h makes, as can be seen from Table 2, the rotating speed of ball mill is larger on the grinding efficiency impact, when drum's speed of rotation hour, grinding efficiency is poor, and along with rotating speed improves, grinding efficiency improves rapidly, but, when drum's speed of rotation surpasses 200 r/ min, grinding efficiency descends.
The impact of table-2 rotating speeds on the raw material particle size size
Embodiment 3
Take lithium carbonate and manganese oxide as raw material; Li:Mn=1:2 accurately takes raw material in molar ratio; underhand polish respectively, mechanical ball milling (underhand polish, mechanical ball milling are the abrasive material mode); this underhand polish is to carry out in the agate mortar; the machinery ball milling is to carry out on planetary ball mill; ratio of grinding media to material is 4:1, and rotating speed is 200 r/ min, and Ball-milling Time is respectively 2h, 4h, 6h, 8h; The underhand polish time is 0.5 h.By ball milling and underhand polish sample, be transferred to respectively in corundum crucible, in resistance furnace, under air atmosphere, heat-treat: first with the speed of 5 ℃/min, be warming up to 500 ℃ and be incubated 3 h, after cooling, grind a little, powder after pre-burning is disperseed, again Preburning material is warming up to 780 ℃ and be incubated 10 h with the speed of 3 ℃/min, after cooling with stove, obtain sample.
Table 3 carries out the mechanical ball mill in embodiment 3 on planetary ball mill, the d50 that drum's speed of rotation 200 r/ min ratios of grinding media to material are the sample that makes of 4:1, as can be seen from Table 3, Ball-milling Time is larger on the grinding efficiency impact, along with the prolongation of Ball-milling Time, d50 reduces gradually, but when Ball-milling Time surpasses 6h, particle diameter reduces Speed Reduction, and grinding efficiency descends.
The impact of-3 abrasive material times of table on the raw material particle size size
Embodiment 4
Take lithium carbonate and manganese oxide as raw material; Li:Mn=1:2 accurately takes raw material in molar ratio; underhand polish respectively, mechanical ball milling (underhand polish, mechanical ball milling are the abrasive material mode); this underhand polish is to carry out in the agate mortar; the machinery ball milling is to carry out on planetary ball mill; ratio of grinding media to material is 8:1, and rotating speed is 200 r/ min, respectively ball milling 2h, 4h, 6h, 8h; The underhand polish time is 0.5 h.By ball milling and underhand polish sample, be transferred to respectively in corundum crucible, in resistance furnace, under air atmosphere, heat-treat: first with the speed of 5 ℃/min, be warming up to 500 ℃ and be incubated 3h, after cooling, grind a little, powder after pre-burning is scattered, again Preburning material is warming up to 780 ℃ and be incubated 10 h with the speed of 3 ℃/min, after cooling with stove, obtain sample.
Table 4 is the meltage of manganese in electrolyte in the LiMn2O4 sample that in embodiment 4 prepared by the different time abrasive material.As can be seen from Table 4, the LiMn2O4 granularity synthetic due to the powder of underhand polish is large, specific area is little, the solubility of manganese is little, but the de-embedding difficulty of lithium ion, the LiMn2O4 meltage obtained along with the prolongation of powder Ball-milling Time descends gradually, reaches minimum during 6h, has so just greatly improved the cycle performance of battery.When Ball-milling Time continues to extend to 8h, the meltage of manganese increases, and this is that specific area is large because the granularity of LiMn2O4 is little, has increased the contact area with electrolyte, causes the dissolving aggravation of Mn in electrolyte, and the sample capacity decay is accelerated.
Table-4 raw material balls are consumed time on the impact that in the LiMn2O4 sample, manganese dissolves in electrolyte
From accompanying drawing 1, the X-ray diffractogram of the LiMn2O4 sample of the preparation that above-mentioned different Ball-milling Time obtains all meets spinel lithium manganate standard diagram (35-0782), can find out the change generation certain deviation of the angle of diffraction along with Ball-milling Time from the X-ray diffraction partial enlarged drawing of accompanying drawing 2 simultaneously.Can find out that in accompanying drawing 3 the LiMn2O4 particle diameter after underhand polish differs greatly, particle is inhomogeneous, from accompanying drawing 4-7, and along with the prolongation of Ball-milling Time, lithium manganate particle size continuous decrease, particle diameter is more even.The cycle performance figure of LiMn2O4 prepared for above-mentioned different Ball-milling Time raw materials by accompanying drawing 8, as can be seen from Fig., lithium carbonate and manganese oxide have the highest specific capacity and best capability retention through the sample of 6h ball milling, the specific discharge capacity that reaches first the 30th circulation is respectively 129.3mAh/ g and 122.8mAh/ g, and capability retention is 94.9%.
Claims (3)
1. one kind is reduced in lithium cell anode material lithium manganate the method that manganese dissolves in electrolyte, it is characterized in that: comprise the following steps: take lithium carbonate and manganese dioxide as raw material, at first adopt dry grinding mode ball milling, ball milling speed is 110-230 r/ min, then calcined at 500-780 ℃, obtained lithium cell anode material lithium manganate after cooling.
2. the method that in reduction lithium cell anode material lithium manganate according to claim 1, manganese dissolves in electrolyte is characterized in that: its ratio of grinding media to material is 10-2:1, and Ball-milling Time is 0.5-8h.
3. the method that in reduction lithium cell anode material lithium manganate according to claim 1 and 2, manganese dissolves in electrolyte, it is characterized in that: heat treatment process heats up for the programming rate with 3-5 ℃/min, sintering temperature is 760-800 ℃, and sintering time is 10h.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103904321A (en) * | 2014-03-31 | 2014-07-02 | 华南理工大学 | High-temperature solid-phase preparation method of lithium ion battery negative electrode material |
| CN104600281A (en) * | 2014-12-30 | 2015-05-06 | 山东神工海特电子科技有限公司 | Preparation method of lithium manganate material and method for preparing battery from lithium manganate material |
| CN108203118A (en) * | 2016-12-17 | 2018-06-26 | 赖愉文 | A kind of novel LiMn2O4Electrode material and its preparation process |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5874058A (en) * | 1995-10-06 | 1999-02-23 | Kerr-Mcgee Chemical Llc | Method of preparing Li1+x MN2-x O4 for use as secondary battery electrode |
| US20060046142A1 (en) * | 2004-08-26 | 2006-03-02 | Masahiro Kasai | Complex oxide materials and cathode materials for lithium ion battery |
| CN103151516A (en) * | 2013-04-01 | 2013-06-12 | 山东轻工业学院 | Modified lithium manganate positive material for lithium ion battery and preparation method thereof |
-
2013
- 2013-09-09 CN CN2013104055812A patent/CN103441264A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5874058A (en) * | 1995-10-06 | 1999-02-23 | Kerr-Mcgee Chemical Llc | Method of preparing Li1+x MN2-x O4 for use as secondary battery electrode |
| US20060046142A1 (en) * | 2004-08-26 | 2006-03-02 | Masahiro Kasai | Complex oxide materials and cathode materials for lithium ion battery |
| CN103151516A (en) * | 2013-04-01 | 2013-06-12 | 山东轻工业学院 | Modified lithium manganate positive material for lithium ion battery and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| 寇丹等: "球磨条件对由电解Mn02制备的LiMn204的结构、形貌和性能的影响", 《化工科技》 * |
| 梁兴华等: "汽车动力电池正极材料锰酸锂球磨工艺研究", 《广西工学院学报》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103904321A (en) * | 2014-03-31 | 2014-07-02 | 华南理工大学 | High-temperature solid-phase preparation method of lithium ion battery negative electrode material |
| CN103904321B (en) * | 2014-03-31 | 2016-06-22 | 华南理工大学 | The high-temperature solid phase preparation method of lithium ion battery negative material LiMn2O4 |
| CN104600281A (en) * | 2014-12-30 | 2015-05-06 | 山东神工海特电子科技有限公司 | Preparation method of lithium manganate material and method for preparing battery from lithium manganate material |
| CN108203118A (en) * | 2016-12-17 | 2018-06-26 | 赖愉文 | A kind of novel LiMn2O4Electrode material and its preparation process |
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Application publication date: 20131211 |