CN102718264A - Method for preparing modified lithium manganate by using wet-mixing and two-step solid-phase reaction - Google Patents
Method for preparing modified lithium manganate by using wet-mixing and two-step solid-phase reaction Download PDFInfo
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- CN102718264A CN102718264A CN2012101640881A CN201210164088A CN102718264A CN 102718264 A CN102718264 A CN 102718264A CN 2012101640881 A CN2012101640881 A CN 2012101640881A CN 201210164088 A CN201210164088 A CN 201210164088A CN 102718264 A CN102718264 A CN 102718264A
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Abstract
The invention discloses a method for preparing modified lithium manganate by using a wet-mixing and two-step solid-phase reaction. The method comprises the following steps: (1) weighing lithium carbonate and aluminium hydroxide according to ratio and putting them into a vertical-type ball mill; (2) adding proper amount of water into the ball mill to start stirring and ball milling; (3) after the granularity of the lithium carbonate is grinded to certain requirements, adding electrolytic manganese dioxide in accordance with ratio and continuing to stir for a period of time; (4) discharging and drying materials in an oven; (5) smashing the materials and granulating by a granulator after dried, and putting into an atmosphere furnace to calcine for the first time; and (6) smashing the once calcined materials and calcining the materials for the second time after lithium is supplied. By employing a wet-mixing with water, the uniform degree of material mixing is greatly improved and granularity difference of reactants is reduced. By employing a secondary calcining way, surface active of particles is effectively enhanced, and many fresh interfaces on the particles are generated. The mixing method conductive to ion migration improves uniformity of material mixing, thereby promoting occurrence of solid phase reaction and improving electrochemical performance of materials.
Description
Technical field
The present invention relates to the anode material for lithium-ion batteries technical field, be specifically related to the method that material by wet type mixing-two single-step solid phase reaction prepares the modification lithium manganate.
Background technology
Advantages such as lithium ion battery is high with its WV, energy density is big, good cycle, self-discharge are little, memory-less effect.Be widely used in fields such as portable Move tool, digital product, man-made satellite, aerospace at present, also had boundless prospect in fields such as electric bicycle and automobiles.
The method of suitability for industrialized production lithium manganate mainly is a high temperature solid-state method at present.For solid-phase synthesis, the degree of uniformity of raw materials mix and particle size are the important factors that influences the synthetic performance of material, so different mixing methods may have certain influence to the degree of mixing of material and the performance of size-grade distribution and synthetic product.
Summary of the invention
Deficiency to the prior art existence; Technical problem to be solved by this invention is; Provide a kind of and can the enhanced granule surfactivity make it produce the method that material by wet type mixing-two single-step solid phase reaction that many fresh interfaces help ion migration prepares the modification lithium manganate, this method reduces reactant granularity difference, improves the homogeneity of material mixing; Promote the generation of solid state reaction, improve the chemical property of material.
For solving the problems of the technologies described above, the technical scheme that the present invention taked is: a kind of material by wet type mixing-two single-step solid phase reaction prepares the method for modification lithium manganate, may further comprise the steps:
(1), puts into agitated ball mill according to proportioning weighing Quilonum Retard and white lake;
(2), adding an amount of water in the ball mill starts and stirs the beginning ball milling;
(3), after the granularity of treating Quilonum Retard is ground to certain requirement, adds electrolytic manganese dioxide by proportioning and continue to stir for some time;
(4), blowing, it is dry that material is put into baking oven;
(5), after the completion to be dried, separate broken and granulation, put into atmosphere furnace and once calcine with tablets press;
(6), the material after will once calcining separate broken, carry out the replenishing of lithium after, secondary clacining.
Above-mentioned material by wet type mixing-two single-step solid phase reaction prepares the method for modification lithium manganate, and each reactant quality proportioning is 728: 101: 3192.
Above-mentioned material by wet type mixing-two single-step solid phase reaction prepares the method for modification lithium manganate, and amount of water is 600ml.
Above-mentioned material by wet type mixing-two single-step solid phase reaction prepares the method for modification lithium manganate, and adding electrolytic manganese dioxide continuation churning time is 30min.
Above-mentioned material by wet type mixing-two single-step solid phase reaction prepares the method for modification lithium manganate, and granulation is that the Z 150PH (PVA) with 3% is made tackiness agent, and moisture content 18% in the material, and drying temperature is 150 ℃.
Above-mentioned material by wet type mixing-two single-step solid phase reaction prepares the method for modification lithium manganate; Once calcining is in 1h, to be warming up to 350 ℃ from room temperature, under this temperature, is incubated 4h, in 1h, rises to 930 ℃ of insulation 5h again; 2h reduces to 650 ℃ of insulation 15h then, last cooling naturally; Secondary clacining is to lower the temperature naturally after in 2h, rising to 650 ℃ of insulation 26h.
The advantage that material by wet type mixing of the present invention-two single-step solid phase reaction prepares the method for modification lithium manganate is: adopt the mode that adds the water material by wet type mixing; Improved the degree that mixes of material greatly; Make reactant granularity difference reduce, adopt the mode of secondary clacining, effectively strengthened granule surface activity and made it produce the homogeneity that method for mixing that many fresh interfaces help ion migration has improved material mixing; Thereby promoted the generation of solid state reaction, improved the chemical property of material.
Description of drawings
Fig. 1 is the SEM figure of material by wet type mixing modification lithium manganate;
Fig. 2 is the XRD figure of material by wet type mixing modification lithium manganate;
Fig. 3 is a material by wet type mixing modification lithium manganate battery cycle characteristics graphic representation;
Fig. 4 is the first charge-discharge graphic representation of material by wet type mixing modification lithium manganate.
Embodiment
Below in conjunction with specific embodiment the present invention is explained further details;
Embodiment 1:
(1) weighing 693g Quilonum Retard 101g white lake is poured in the agitated ball mill.
(2) adding 600ml water begins to stir.
When (3) Quilonum Retard is ground to about D50 and is 0.6um, add electrolytic manganese dioxide 3192g, continue to stir blowing behind the 30min.
(4) separate broken in the automatic granulating machine and carry out granulation, moisture content 18% pouring into behind the dry materials with 3% Z 150PH.
(5) after 150 ℃ of dryings, carry out particle once sintered.
(6) after the once sintered completion particle is separated brokenly, is added Quilonum Retard 35g, mix and carry out secondary clacining, final powder product.
(7) powder is done XRD, SEM and electrical property analytical test, result such as Fig. 1-shown in Figure 4.
Embodiment 2:
(1) weighing 728g Quilonum Retard 101g white lake is poured in the agitated ball mill.
(2) adding 600ml water begins to stir.
When (3) Quilonum Retard is ground to about D50 and is 0.6um, add electrolytic manganese dioxide 3192g, continue to stir blowing behind the 20min.
(4) separate broken in the automatic granulating machine and carry out granulation, moisture content 16% pouring into behind the dry materials with 3% Z 150PH.
(5) after 150 ℃ of dryings, carry out particle once sintered.
(6) after the once sintered completion particle is separated brokenly, is carried out secondary clacining, final powder product.
(7) powder is done analytical test.
Embodiment 3:
(1) weighing 693g Quilonum Retard 101g white lake is poured in the agitated ball mill.
(2) adding 600ml water begins to stir.
When (3) Quilonum Retard is ground to about D50 and is 0.6um, add electrolytic manganese dioxide 3192g, continue to stir blowing behind the 5min.
(4) separate broken in the automatic granulating machine and carry out granulation, moisture content 16% pouring into behind the dry materials with 3% Z 150PH.
(5) after 150 ℃ of dryings, carry out particle once sintered.
(6) after the once sintered completion particle is separated brokenly, is added Quilonum Retard 35g, mix and carry out secondary clacining, final powder product.
(7) powder is done analytical test.
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. material by wet type mixing-two single-step solid phase reaction prepares the method for modification lithium manganate, it is characterized in that, may further comprise the steps:
(1), puts into agitated ball mill according to proportioning weighing Quilonum Retard and white lake;
(2), adding an amount of water in the ball mill starts and stirs the beginning ball milling;
(3), after the granularity of treating Quilonum Retard is ground to certain requirement, adds electrolytic manganese dioxide by proportioning and continue to stir for some time;
(4), blowing, it is dry that material is put into baking oven;
(5), after the completion to be dried, separate broken and granulation, put into atmosphere furnace and once calcine with tablets press;
(6), the material after will once calcining separate broken, carry out the replenishing of lithium after, secondary clacining.
2. material by wet type mixing-two single-step solid phase reaction according to claim 1 prepares the method for modification lithium manganate, it is characterized in that: each reactant quality proportioning is 728: 101: 3192.
3. material by wet type mixing-two single-step solid phase reaction according to claim 1 prepares the method for modification lithium manganate, it is characterized in that: amount of water is 600ml.
4. material by wet type mixing-two single-step solid phase reaction according to claim 1 prepares the method for modification lithium manganate, it is characterized in that: adding electrolytic manganese dioxide continuation churning time is 30min.
5. material by wet type mixing-two single-step solid phase reaction according to claim 1 prepares the method for modification lithium manganate, it is characterized in that: granulation is that the Z 150PH (PVA) with 3% is made tackiness agent, and moisture content 18% in the material, and drying temperature is 150 ℃.
6. material by wet type mixing-two single-step solid phase reaction according to claim 1 prepares the method for modification lithium manganate; It is characterized in that: once calcining is in 1h, to be warming up to 350 ℃ from room temperature; Under this temperature, be incubated 4h; In 1h, rise to 930 ℃ of insulation 5h again, 2h reduces to 650 ℃ of insulation 15h then, last cooling naturally; Secondary clacining is to lower the temperature naturally after in 2h, rising to 650 ℃ of insulation 26h.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103531775A (en) * | 2013-09-13 | 2014-01-22 | 东莞市天楠光电科技有限公司 | Preparation method of doped lithium-rich lithium manganese oxide cathode material |
| CN103613142A (en) * | 2013-09-16 | 2014-03-05 | 无锡晶石新型能源有限公司 | Method for producing lithium manganate through semi-dry method |
| CN114933332A (en) * | 2022-06-06 | 2022-08-23 | 安徽博石高科新材料股份有限公司 | Method for producing lithium manganate by composite raw materials |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1872702A (en) * | 2006-06-16 | 2006-12-06 | 南京航空航天大学 | Method for preparing spinel type lithium manganate in use for material of positive pole in lithium ion battery |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1872702A (en) * | 2006-06-16 | 2006-12-06 | 南京航空航天大学 | Method for preparing spinel type lithium manganate in use for material of positive pole in lithium ion battery |
Non-Patent Citations (4)
| Title |
|---|
| 《哈 尔 滨 工 业 大 学 学 报》 20080430 顾大明等 "尖晶石型锰酸锂制备及其电化学性能" 第607-610页 1-6 第40卷, 第4期 * |
| 《精细化工中间体》 20100228 贺周初等 "锂离子电池正极材料尖晶石型锰酸锂的研究进展" 第7-11页 1-6 第40卷, 第1期 * |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103531775A (en) * | 2013-09-13 | 2014-01-22 | 东莞市天楠光电科技有限公司 | Preparation method of doped lithium-rich lithium manganese oxide cathode material |
| CN103613142A (en) * | 2013-09-16 | 2014-03-05 | 无锡晶石新型能源有限公司 | Method for producing lithium manganate through semi-dry method |
| CN114933332A (en) * | 2022-06-06 | 2022-08-23 | 安徽博石高科新材料股份有限公司 | Method for producing lithium manganate by composite raw materials |
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Inventor after: Sun Qi Inventor after: Xiao Xiangqian Inventor after: Sun Huiying Inventor before: Sun Qi Inventor before: Zhang Lianjun Inventor before: Sun Huiying |
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Denomination of invention: Method for preparing modified lithium manganate by using wet-mixing and two-step solid-phase reaction Effective date of registration: 20200629 Granted publication date: 20140625 Pledgee: China Construction Bank Corporation Qingdao Zhongshan Road sub branch Pledgor: QINGDAO QIANYUN HIGH-TECH NEW MATERIAL Co.,Ltd. Registration number: Y2020370010025 |
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