CN103296266A - Cu-doped lithium zinc titanate negative electrode material and preparation method thereof - Google Patents
Cu-doped lithium zinc titanate negative electrode material and preparation method thereof Download PDFInfo
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- CN103296266A CN103296266A CN201310203735XA CN201310203735A CN103296266A CN 103296266 A CN103296266 A CN 103296266A CN 201310203735X A CN201310203735X A CN 201310203735XA CN 201310203735 A CN201310203735 A CN 201310203735A CN 103296266 A CN103296266 A CN 103296266A
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Abstract
The invention relates to an electrode material and a preparation method thereof, and in particular relates to a Cu-doped lithium zinc titanate negative electrode material and a preparation method thereof. The Cu-doped lithium zinc titanate negative material is characterized by having a molecular formula of Li2Zn1-xCuxTi3O8, wherein x is more than 0 and less than or equal to 0.15. The preparation method comprises the following steps of: weighing a titanium source, a lithium source, a zinc source and a copper source, uniformly mixing and then drying; and sintering at 750 DEG C for 5 hours, then naturally cooling to the room temperature, and grinding. After Cu is doped, Cu<2+> can be distributed at a tetrahedron position and an octahedron position in a ratio of 3:2, so that the arrangement of ions in the material generates changes slightly, and the stability of a crystal structure of the material during charging and discharging is improved.
Description
Technical field:
The present invention relates to a kind of electrode material and preparation method thereof, be specifically related to zinc titanate cathode of lithium material of 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 present business-like lithium ion battery adopts various embedding lithium material with carbon elements mostly, and this is that it is higher to insert the lithium capacity because carbon electrode is lower with respect to the discharge platform of lithium metal.But because it is very approaching to insert the current potential of the current potential of carbon electrode behind the lithium and lithium metal, less than 0.1V vs Li/Li
+, when over-charging of battery, lithium metal may be separated out and forms Li dendrite in carbon electrodes, thereby causes short circuit; And most electrolyte is unstable under this current potential, and electrolyte easily decomposes at electrode surface, produces combustible gas mixture, exists potential safety hazard; In addition, Li in the carbon electrode
+Insertion will cause 10% volume deformation, cause intergranular discontinuous, cause the loose of electrode/electrolyte and electrode/collector interface with peel off.These factors are all impelling researchers that original negative material is modified and study on the modification, and constantly seek function admirable, preparation technology's new type lithium ion battery negative material simple and with low cost.
Spinelle Li
4Ti
5O
12And relevant titanium oxide etc. is owing to having excellent cycle performance and advantage such as nontoxic, safe becomes more promising negative material.But, Li
4Ti
5O
12Theoretical capacity have only half of graphite, and embedding lithium current potential is higher, thereby the negative material of exploitation with good circulation performance and 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, have a series of advantage,, good cycle big as specific capacity, high rate performance are more high; Wherein the Li of 1:1 and Zn are positioned at the four sides position of crystal structure, and the Li of 1:3 and Ti are positioned at the octahedral position, because bond distance's difference causes crystal structure to produce certain distortion, thereby causes the cycle performance of this material relatively poor.Therefore, be badly in need of improving the material property of zinc titanate lithium, remedy the deficiency of existence.
Summary of the invention:
The object of the present invention is to provide zinc titanate lithium material of modification and preparation method thereof, improve the stability of the crystal structure of this material in charge and discharge process.
The zinc titanate cathode of lithium material of doped with Cu, its molecular formula is Li
2Zn
1-xCu
xTi
3O
8, 0＜x≤0.15 wherein.
One of the method process of zinc titanate cathode of lithium material of making above-mentioned doped with Cu is as follows:
Step 1: weigh titanium source, lithium source, zinc source and copper source, mix the back oven dry,
Step 2: naturally cool to room temperature at 750 ℃ of sintering after 5 hours, grind;
Described titanium source is H
2Ti
3O
7The nanometer rods precursor, described lithium source is lithium carbonate, and described zinc source is zinc acetate, and described copper source is copper acetate.
Two processes of method of zinc titanate cathode of lithium material of making above-mentioned doped with Cu are as follows:
Step 1: the H that takes by weighing 1 mass parts
2Ti
3O
7The Li of nanometer rods precursor, 0.287 mass parts
2CO
3, add absolute ethyl alcohol, mix; Take by weighing the Zn (CH of 0.852* (1-x) mass parts then
3COO)
22H
2Cu (the CH of O and 0.78*x mass parts
3COO)
2H
2O adds in the above-mentioned solution;
Step 2: with above-mentioned solution evaporate to dryness under 70 ℃ of stirring conditions, grind;
Step 3: the previous step product is placed Muffle furnace, be warming up to 750 ℃ with 3 ℃/min, keep obtaining after 5 hours Cu doped titanic acid zinc lithium product.
The present invention is with respect to the advantage of prior art:
(1) after the doped with Cu, Cu
2+Can distribute in tetrahedron and the octahedral position ratio with 3:2, make in the material arranging of each ion that small change takes place, 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, the production efficiency height.
(3) the zinc titanate cathode of lithium material that the Cu for preparing mixes has jumbo characteristics.
(4) the zinc titanate cathode of lithium material that the Cu for preparing mixes has excellent cycle performance.
(5) the material preparation can be carried out in air or inert atmosphere, is preferably in air and carries out, and can reduce preparation cost.
Description of drawings:
Fig. 1 is X-ray diffraction (XRD) collection of illustrative plates that embodiment 1-3 and Comparative Examples prepare product, and among the figure, abscissa represents intensity, and ordinate represents intensity.
Fig. 2 is scanning electron microscopy (SEM) image of embodiment 2 preparation products;
Fig. 3 prepares the cycle performance resolution chart of the simulated battery of product for embodiment 1-3 and Comparative Examples; Among the 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 H
2Ti
3O
7, 0.287 the gram Li
2CO
3Insert in the beaker, add the 20ml absolute ethyl alcohol, mix, weigh 0.809 gram Zn (CH
3COO)
22H
2O and 0.039 gram Cu (CH
3COO)
2H
2O adds in the above-mentioned solution, with above-mentioned solution evaporate to dryness under 70 ℃ of stirring conditions, grinds, and places Muffle furnace, is warming up to 750 ℃ with 3 ℃/min, keeps obtaining after 5 hours Cu doped titanic acid zinc lithium product.
Weigh 0.7 this product of gram, it is mixed according to the ratio of mass ratio 70:20:10 with acetylene black and PVDF, be coated on the Copper Foil after stirring, place vacuum drying chamber, in 120 ℃ of following vacuumizes 24 hours, by roll-in, punching, obtain electrode slice; , form simulated battery and carry out electrochemical property test for being electrolyte to the EC:DEC:EMC solution of electrode, 1M LiPF6 with metal lithium sheet.When this sample discharges and recharges under 0.2A/ gram electric current, first discharge specific capacity is the 313.1mAh/ gram, circulating, specific discharge capacity is the 217.1mAh/ gram after 5 times, circulate that specific discharge capacity is the 202.8mAh/ gram after 100 times, and the capability retention that the 5th to 100 time circulates is 93.41%.
Embodiment 2:
X=0.1, molecular formula is: Li
2Zn
0.9Cu
0.1Ti
3O
8, preparation process is as follows:
Weigh 1 gram H
2Ti
3O
7, 0.287 the gram Li
2CO
3Insert in the beaker, add the 20ml absolute ethyl alcohol, mix, weigh 0.767 gram Zn (CH
3COO)
22H
2O and 0.078 gram Cu (CH
3COO)
2H
2O adds in the above-mentioned solution, with above-mentioned solution evaporate to dryness under 70 ℃ of stirring conditions, grinds, and places Muffle furnace, is warming up to 750 ℃ with 3 ℃/min, keeps obtaining after 5 hours Cu doped titanic acid zinc lithium product.
Weigh 0.7 this product of gram, it is mixed according to the ratio of mass ratio 70:20:10 with acetylene black and PVDF, be coated on the Copper Foil after stirring, place vacuum drying chamber, in 120 ℃ of following vacuumizes 24 hours, by roll-in, punching, obtain electrode slice; , form simulated battery and carry out electrochemical property test for being electrolyte to the EC:DEC:EMC solution of electrode, 1M LiPF6 with metal lithium sheet.When this sample discharges and recharges under 0.2A/ gram electric current, first discharge specific capacity is the 348.4mAh/ gram, circulating, specific discharge capacity is the 234.4mAh/ gram after 5 times, circulate that specific discharge capacity is that 213.7mAh/ restrains after 100 times, and the 5th to 100 time recycle ratio capability retention is 91.16%.
Embodiment 3:
X=0.15, molecular formula is: Li
2Zn
0.85Cu
0.15Ti
3O
8, preparation process is as follows:
Weigh 1 gram H
2Ti
3O
7, 0.287 the gram Li
2CO
3Insert in the beaker, add the 20ml absolute ethyl alcohol, mix, weigh 0.724 gram Zn (CH
3COO)
22H
2O and 0.116 gram Cu (CH
3COO)
2H
2O adds in the above-mentioned solution, with above-mentioned solution evaporate to dryness under 70 ℃ of stirring conditions, grinds, and places Muffle furnace, is warming up to 750 ℃ with 3 ℃/min, keeps obtaining after 5 hours Cu doped titanic acid zinc lithium product.
Weigh 0.7 this product of gram, it is mixed according to the ratio of mass ratio 70:20:10 with acetylene black and PVDF, be coated on the Copper Foil after stirring, place vacuum drying chamber, in 120 ℃ of following vacuumizes 24 hours, by roll-in, punching, obtain electrode slice; With metal lithium sheet for to electrode, 1M LiPF6 the EC:DEC:EMC(volume ratio=1:1:1) solution is electrolyte, form simulated battery and carry out electrochemical property test.When this simulated battery discharges and recharges under 0.2A/ gram electric current, first discharge specific capacity is the 328.7mAh/ gram, circulating, specific discharge capacity is the 213.9mAh/ gram after 5 times, circulate that specific discharge capacity is that 207.6mAh/ restrains after 100 times, and the 5th to 100 time recycle ratio capability retention is 97.05%.
Comparative Examples:
X=0, molecular formula is: Li
2ZnTi
3O
8, preparation process is as follows:
Weigh 1 gram H
2Ti
3O
7, 0.287 the gram Li
2CO
3Insert in the beaker, add the 20ml absolute ethyl alcohol, mix, weigh 0.852 gram Zn (CH
3COO)
22H
2O adds in the above-mentioned solution, with above-mentioned solution evaporate to dryness under 70 ℃ of stirring conditions, grinds, and places Muffle furnace, is warming up to 750 ℃ with 3 ℃/min, keeps obtaining after 5 hours Cu doped titanic acid zinc lithium product.
Weigh 0.7 this product of gram, it is mixed according to the ratio of mass ratio 70:20:10 with acetylene black and PVDF, be coated on the Copper Foil after stirring, place vacuum drying chamber, in 120 ℃ of following vacuumizes 24 hours, by roll-in, punching, obtain electrode slice; With metal lithium sheet for to electrode, form simulated battery and carry out electrochemical property test.When this sample discharges and recharges under 0.2A/ gram electric current, first discharge specific capacity is 260.4mAh/ gram, circulates subsequently that specific discharge capacity reaches maximum after 38 times, is the 184.3mAh/ gram, circulating, specific discharge capacity is the 162.8mAh/ gram after 100 times, and capability retention is 88.33%.
Claims (3)
1. the zinc titanate cathode of lithium material of doped with Cu is characterized in that, its molecular formula is Li
2Zn
1-xCu
xTi
3O
8, 0＜x≤0.15 wherein.
2. the zinc titanate cathode of lithium preparation methods of the described doped with Cu of claim 1 is characterized in that,
Step 1: weigh titanium source, lithium source, zinc source and copper source, mix the back oven dry,
Step 2: naturally cool to room temperature at 750 ℃ of sintering after 5 hours, grind;
Described titanium source is H
2Ti
3O
7The nanometer rods precursor, described lithium source is lithium carbonate, and described zinc source is zinc acetate, and described copper source is copper acetate.
3. the zinc titanate cathode of lithium preparation methods of the described doped with Cu of claim 1 is characterized in that:
Step 1: the H that takes by weighing 1 mass parts
2Ti
3O
7The Li of nanometer rods precursor, 0.287 mass parts
2CO
3, add absolute ethyl alcohol, mix; Take by weighing the Zn (CH of 0.852* (1-x) mass parts then
3COO)
22H
2Cu (the CH of O and 0.78*x mass parts
3COO)
2H
2O adds in the above-mentioned solution;
Step 2: with above-mentioned solution evaporate to dryness under 70 ℃ of stirring conditions, grind;
Step 3: the previous step product is placed Muffle furnace, be warming up to 750 ℃ with 3 ℃/min, keep obtaining after 5 hours Cu doped titanic acid zinc lithium product.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN105789580A (en) * | 2016-03-21 | 2016-07-20 | 福建师范大学 | Preparation method for copper-doped lithium zinc titanate nano particles and application thereof |
| CN110581273A (en) * | 2019-09-18 | 2019-12-17 | 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 |
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|---|---|---|---|---|
| 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 as anode active substance |
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2013
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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 as anode active substance |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN105789580A (en) * | 2016-03-21 | 2016-07-20 | 福建师范大学 | Preparation method for copper-doped lithium zinc titanate nano particles and application 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 |
| CN110581273A (en) * | 2019-09-18 | 2019-12-17 | 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 |
| 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 |
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| CN103296266B (en) | 2015-09-30 |
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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 |