CN103296266B - Zinc titanate lithium titanate cathode material of doped with Cu and preparation method thereof - Google Patents
Zinc titanate lithium titanate cathode material of doped with Cu and preparation method thereof Download PDFInfo
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- CN103296266B CN103296266B CN201310203735.XA CN201310203735A CN103296266B CN 103296266 B CN103296266 B CN 103296266B CN 201310203735 A CN201310203735 A CN 201310203735A CN 103296266 B CN103296266 B CN 103296266B
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Abstract
The present invention relates to a kind of electrode material and preparation method thereof, zinc titanate lithium titanate cathode material being specifically related to a kind of doped with Cu and preparation method thereof.The zinc titanate lithium titanate cathode material of doped with Cu, is characterized in that, its molecular formula is Li
2zn
1-xcu
xti
3o
8, wherein 0<x≤0.15.Preparation method is as follows: weigh titanium source, lithium source, zinc source and copper source, mix post-drying; Room temperature is naturally cooled to after 5 hours, grinding at 750 DEG C of sintering.After doped with Cu, Cu
2+can distribute with the ratio of 3:2 at tetrahedron and octahedral position, make the arrangement of each ion in material that small change occur, improve the stability of the crystal structure of this material in charge and discharge process.
Description
Technical field:
The present invention relates to a kind of electrode material and preparation method thereof, zinc titanate lithium titanate cathode material being specifically related to a kind of doped with Cu and preparation method thereof.
Background technology:
The core technology of lithium ion battery is the lithium storage materials that can carry out reversible removal lithium embedded.The negative material of current business-like lithium ion battery adopts various embedding lithium material with carbon element mostly, and this is because carbon electrode is lower relative to the discharge platform of lithium metal, inserts lithium capacity higher.But due to the current potential of carbon electrode after slotting lithium and the current potential of lithium metal very close, be less than 0.1V vs Li/Li
+, when over-charging of battery, lithium metal may be separated out in carbon electrodes and form Li dendrite, thus causes short circuit; And most electrolyte is unstable under this current potential, electrolyte easily decomposes at electrode surface, produces combustible gas mixture, there is potential safety hazard; In addition, Li in carbon electrode
+insertion will cause the volume deformation of 10%, cause intergranular discontinuous, cause the loose of electrode/electrolyte and electrode/collector interface and peel off.These factors all impel researchers to modify and study on the modification original negative material, and constantly to find function admirable, preparation technology Novel cathode material for lithium ion battery simple and with low cost.
Spinelle Li
4ti
5o
12and relevant titanium oxide etc. becomes more promising negative material owing to having good cycle performance and the advantage such as nontoxic, safe.But, Li
4ti
5o
12theoretical capacity only have the half of graphite, and intercalation potential is higher, and thus exploitation has good circulation performance and the negative material of higher capacity remains the research emphasis in this field; Zinc titanate lithium Li
2znTi
3o
8as a kind of insert type lithium ion battery negative material, there is a series of advantage, as large in specific capacity, good cycle, high rate performance are more high; Wherein Li and Zn of 1:1 is positioned at the four sides position of crystal structure, Li and Ti of 1:3 is positioned at octahedral position, due to the difference of bond distance, causes crystal structure to produce certain distortion, thus causes the cycle performance of this material poor.Therefore, be badly in need of the material property improving zinc titanate lithium, make up the deficiency of existence.
Summary of the invention:
Zinc titanate lithium material that the object of the present invention is to provide modification and preparation method thereof, improves the stability of the crystal structure of this material in charge and discharge process.
The zinc titanate lithium titanate cathode material of doped with Cu, its molecular formula is Li
2zn
1-xcu
xti
3o
8, wherein 0<x≤0.15.
Manufacture one of the method for the zinc titanate lithium titanate cathode material of above-mentioned doped with Cu process as follows:
Step one: weigh titanium source, lithium source, zinc source and copper source, mix post-drying,
Step 2: naturally cool to room temperature at 750 DEG C of sintering after 5 hours, grinding;
Described titanium source is H
2ti
3o
7nanometer rods precursor, described lithium source is lithium carbonate, and described zinc source is zinc acetate, and described copper source is copper acetate.
Two processes manufacturing the method for the zinc titanate lithium titanate cathode material of above-mentioned doped with Cu are as follows:
Step one: the H taking 1 mass parts
2ti
3o
7the Li of nanometer rods precursor, 0.287 mass parts
2cO
3, add absolute ethyl alcohol, mix; Then Zn (the CH of 0.852* (1-x) mass parts is taken
3cOO)
22H
2cu (the CH of O and 0.78*x mass parts
3cOO)
2h
2o adds in above-mentioned solution;
Step 2: by above-mentioned solution evaporate to dryness under 70 DEG C of stirring conditions, grinding;
Step 3: previous step product is placed in Muffle furnace, is warming up to 750 DEG C with 3 DEG C/min, keeps obtaining Cu doped titanic acid zinc lithium product after 5 hours.
The present invention is relative to the advantage of prior art:
(1) after doped with Cu, Cu
2+can distribute with the ratio of 3:2 at tetrahedron and octahedral position, make the arrangement of each ion in material that small change occur, improve the stability of the crystal structure of this material in charge and discharge process.
(2) calcining heat is low, the time is short, and equipment investment is few, and energy consumption is little, and production efficiency is high.
(3) the zinc titanate lithium titanate cathode material of the Cu doping prepared has jumbo feature.
(4) the zinc titanate lithium titanate cathode material of the Cu doping prepared has excellent cycle performance.
(5) material preparation can be carried out in air or inert atmosphere, preferably carries out in atmosphere, can reduce preparation cost.
Accompanying drawing illustrates:
Fig. 1 is X-ray diffraction (XRD) collection of illustrative plates that embodiment 1-3 and comparative example prepare product, and in figure, abscissa represents intensity, and ordinate represents intensity.
Fig. 2 is scanning electron microscopy (SEM) image that embodiment 2 prepares product;
Fig. 3 is the cycle performance resolution chart that embodiment 1-3 and comparative example prepare the simulated battery of product; In figure, abscissa represents cycle-index, and ordinate represents capacity, and unit is mAhg-
1
Embodiment:
Embodiment 1:
X=0.05, molecular formula is: Li
2zn
0.95cu
0.05ti
3o
8, preparation process is as follows:
Weigh 1 gram of H
2ti
3o
7, 0.287 gram of Li
2cO
3insert in a beaker, add 20ml absolute ethyl alcohol, mix, weigh 0.809 gram of Zn (CH
3cOO)
22H
2o and 0.039 gram of Cu (CH
3cOO)
2h
2o adds in above-mentioned solution, and by above-mentioned solution evaporate to dryness under 70 DEG C of stirring conditions, grinding, is placed in Muffle furnace, is warming up to 750 DEG C with 3 DEG C/min, keep obtaining Cu doped titanic acid zinc lithium product after 5 hours.
Weigh 0.7 gram of this product, it mixed according to the ratio of mass ratio 70:20:10 with acetylene black and PVDF, be coated on Copper Foil, be placed in vacuum drying chamber after stirring, at 120 DEG C, vacuumize 24 hours, by roll-in, punching, obtains electrode slice; Be to the EC:DEC:EMC solution of electrode, 1M LiPF6 for electrolyte with metal lithium sheet, composition simulated battery carries out electrochemical property test.This sample is under 0.2A/ gram of electric current during discharge and recharge, first discharge specific capacity is 313.1mAh/ gram, the specific discharge capacity after 5 times that circulates is 217.1mAh/ gram, and the specific discharge capacity after 100 times that circulates is 202.8mAh/ gram, and the 5th is 93.41% to the capability retention of 100 circulations.
Embodiment 2:
X=0.1, molecular formula is: Li
2zn
0.9cu
0.1ti
3o
8, preparation process is as follows:
Weigh 1 gram of H
2ti
3o
7, 0.287 gram of Li
2cO
3insert in a beaker, add 20ml absolute ethyl alcohol, mix, weigh 0.767 gram of Zn (CH
3cOO)
22H
2o and 0.078 gram of Cu (CH
3cOO)
2h
2o adds in above-mentioned solution, and by above-mentioned solution evaporate to dryness under 70 DEG C of stirring conditions, grinding, is placed in Muffle furnace, is warming up to 750 DEG C with 3 DEG C/min, keep obtaining Cu doped titanic acid zinc lithium product after 5 hours.
Weigh 0.7 gram of this product, it mixed according to the ratio of mass ratio 70:20:10 with acetylene black and PVDF, be coated on Copper Foil, be placed in vacuum drying chamber after stirring, at 120 DEG C, vacuumize 24 hours, by roll-in, punching, obtains electrode slice; Be to the EC:DEC:EMC solution of electrode, 1M LiPF6 for electrolyte with metal lithium sheet, composition simulated battery carries out electrochemical property test.This sample is under 0.2A/ gram of electric current during discharge and recharge, first discharge specific capacity is 348.4mAh/ gram, the specific discharge capacity after 5 times that circulates is 234.4mAh/ gram, and the specific discharge capacity after 100 times that circulates is 213.7mAh/ gram, and the 5th is 91.16% to 100 recycle ratio capability retentions.
Embodiment 3:
X=0.15, molecular formula is: Li
2zn
0.85cu
0.15ti
3o
8, preparation process is as follows:
Weigh 1 gram of H
2ti
3o
7, 0.287 gram of Li
2cO
3insert in a beaker, add 20ml absolute ethyl alcohol, mix, weigh 0.724 gram of Zn (CH
3cOO)
22H
2o and 0.116 gram of Cu (CH
3cOO)
2h
2o adds in above-mentioned solution, and by above-mentioned solution evaporate to dryness under 70 DEG C of stirring conditions, grinding, is placed in Muffle furnace, is warming up to 750 DEG C with 3 DEG C/min, keep obtaining Cu doped titanic acid zinc lithium product after 5 hours.
Weigh 0.7 gram of this product, it mixed according to the ratio of mass ratio 70:20:10 with acetylene black and PVDF, be coated on Copper Foil, be placed in vacuum drying chamber after stirring, at 120 DEG C, vacuumize 24 hours, by roll-in, punching, obtains electrode slice; EC:DEC:EMC(volume ratio=1:1:1 so that metal lithium sheet is to electrode, 1M LiPF6) solution is for electrolyte, and composition simulated battery carries out electrochemical property test.This simulated battery is under 0.2A/ gram of electric current during discharge and recharge, first discharge specific capacity is 328.7mAh/ gram, the specific discharge capacity after 5 times that circulates is 213.9mAh/ gram, and the specific discharge capacity after 100 times that circulates is 207.6mAh/ gram, and the 5th is 97.05% to 100 recycle ratio capability retentions.
Comparative example:
X=0, molecular formula is: Li
2znTi
3o
8, preparation process is as follows:
Weigh 1 gram of H
2ti
3o
7, 0.287 gram of Li
2cO
3insert in a beaker, add 20ml absolute ethyl alcohol, mix, weigh 0.852 gram of Zn (CH
3cOO)
22H
2o adds in above-mentioned solution, and by above-mentioned solution evaporate to dryness under 70 DEG C of stirring conditions, grinding, is placed in Muffle furnace, is warming up to 750 DEG C with 3 DEG C/min, keep obtaining Cu doped titanic acid zinc lithium product after 5 hours.
Weigh 0.7 gram of this product, it mixed according to the ratio of mass ratio 70:20:10 with acetylene black and PVDF, be coated on Copper Foil, be placed in vacuum drying chamber after stirring, at 120 DEG C, vacuumize 24 hours, by roll-in, punching, obtains electrode slice; With metal lithium sheet for carrying out electrochemical property test to electrode, composition simulated battery.This sample is under 0.2A/ gram of electric current during discharge and recharge, first discharge specific capacity is 260.4mAh/ gram, and reaching maximum with specific discharge capacity after Posterior circle 38 times, is 184.3mAh/ gram, the specific discharge capacity after 100 times that circulates is 162.8mAh/ gram, and capability retention is 88.33%.
Claims (2)
1. the zinc titanate lithium titanate cathode material of doped with Cu, is characterized in that, its molecular formula is Li
2zn
1-xcu
xti
3o
8, wherein 0<x≤0.15.
2. the preparation method of the zinc titanate lithium titanate cathode material of doped with Cu described in claim 1, is characterized in that:
Step one: the H taking 1 mass parts
2ti
3o
7the Li of nanometer rods precursor, 0.287 mass parts
2cO
3, add absolute ethyl alcohol, mix; Then Zn (the CH of 0.852* (1-x) mass parts is taken
3cOO)
22H
2cu (the CH of O and 0.78*x mass parts
3cOO)
2h
2o adds in above-mentioned solution;
Step 2: by above-mentioned solution evaporate to dryness under 70 DEG C of stirring conditions, grinding;
Step 3: previous step product is placed in Muffle furnace, is warming up to 750 DEG C with 3 DEG C/min, keeps obtaining Cu doped titanic acid zinc lithium product after 5 hours.
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|---|---|---|---|---|
| CN103745833A (en) * | 2013-12-25 | 2014-04-23 | 东莞市迈科新能源有限公司 | Super capacitor battery and preparation method thereof |
| CN104577065A (en) * | 2014-12-30 | 2015-04-29 | 深圳市贝特瑞纳米科技有限公司 | Li2ZnTi3O8 compounded anode material and preparation method thereof |
| CN105789580B (en) * | 2016-03-21 | 2018-07-20 | 福建师范大学 | A kind of preparation method and applications of Copper-cladding Aluminum Bar zinc titanate lithium nano-particle |
| CN110581273B (en) * | 2019-09-18 | 2021-04-13 | 东北大学秦皇岛分校 | Zinc-position sodium-copper co-doped synergetic nitrogen-sulfur doped carbon-coated modified zinc titanate negative electrode material and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101399344A (en) * | 2007-09-25 | 2009-04-01 | 株式会社东芝 | Active materials for non-aqueous electrolyte battery and non-aqueous electrolyte battery |
| CN101786875A (en) * | 2010-01-02 | 2010-07-28 | 桂林理工大学 | Microwave medium ceramic material with low-temperature sintering spinel structure and preparation method thereof |
| CN102891304A (en) * | 2012-09-24 | 2013-01-23 | 合肥国轩高科动力能源有限公司 | Lithium titanate and lithium ion battery using lithium titanate negative electrode active material |
-
2013
- 2013-05-28 CN CN201310203735.XA patent/CN103296266B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101399344A (en) * | 2007-09-25 | 2009-04-01 | 株式会社东芝 | Active materials for non-aqueous electrolyte battery and non-aqueous electrolyte battery |
| CN101786875A (en) * | 2010-01-02 | 2010-07-28 | 桂林理工大学 | Microwave medium ceramic material with low-temperature sintering spinel structure and preparation method thereof |
| CN102891304A (en) * | 2012-09-24 | 2013-01-23 | 合肥国轩高科动力能源有限公司 | Lithium titanate and lithium ion battery using lithium titanate negative electrode active material |
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Effective date of registration: 20210823 Address after: 519000 unit 1, No. 1043 East Jiuzhou Avenue, Jida, Xiangzhou District, Zhuhai City, Guangdong Province Patentee after: Zhuhai Changxing New Energy Technology Co.,Ltd. Address before: 300072 Tianjin City, Nankai District Wei Jin Road No. 92 Patentee before: Tianjin University |
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