CN104157840A - Preparation method of graphene coated silica nanotube composite negative electrode material for lithium ion battery - Google Patents
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Abstract
A preparation method of graphene coated silica nanotube composite negative electrode material for lithium ion batteries is as follows: (1) dispersing zinc oxide nanorods to an ethanol solution, sequentially adding water, ammonia water and a TEOS solution to obtain zinc oxide / silica core-shell nanorods; (2) dispersing the products from the step (1) in to an aqueous solution of sodium chloride, and adding PDDA for modification; (3) dispersing the products from the step (2) and the graphene oxide into an aqueous solution, dropwise adding sodium borohydride to obtain graphene coated zinc oxide / silica core-shell nanorods; and (4) dispersing the products obtained from the step (3) in an excessive amount of acid solution to dissolve zinc oxide nanorods, so as to obtain the composite negative electrode material. According to the invention, zinc oxide nanorods are used as templates, and coated by silicon dioxide and graphene, and then the template is removed, so as to prepare the graphene coated silica nanotube composite material. The prepared composite material has the performances of high discharge capacity, long cycle life and high rate capability.
Description
Technical field
The present invention relates to a kind of preparation method of lithium ion battery negative material, particularly relate to a kind of preparation method of graphene coated Silica Nanotube composite negative pole material.
Background technology
Silica-base material, as elemental silicon, silicon-base alloy and Si oxide have the fail safe that high theoretical specific capacity is become reconciled, can be used as the desirable substitution material of lithium ion battery commercialization carbon negative pole material.Wherein, the oxide of silicon particularly silicon dioxide have preparation easy, cost is low and advantages of environment protection, has become one of study hotspot of silicon based anode material.But, earth silicon material huge change in volume in removal lithium embedded process can cause electrode material efflorescence, lose the quick decay electrically contacting with specific capacity.In addition, the lower and Si-O bond of the conductivity of block earth silicon material is closed can be larger, and this is all unfavorable for carrying out fast of lithium ion deintercalation reaction.
Silicon dioxide is prepared into nanostructure, particularly nano tube structure can be alleviated the problems referred to above to a certain extent, and this is because nanotube has larger surf zone, shorter lithium ion diffusion length, stronger Stress Release ability and the electric charge transmission channel of one dimension.But in charge and discharge process, the structure of nanotube can be destroyed, single Silica Nanotube is difficult to obtain good performance of lithium ion battery.Material with carbon element, particularly two-dimentional grapheme material has higher conductivity, can effectively alleviate the change in volume of silicon dioxide in removal lithium embedded process simultaneously, thereby by composite modified multiplying power property and the cyclical stability that is expected to improve silicon dioxide negative material of Graphene.But the composite nano materials of Graphene and silicon dioxide, the particularly preparation of graphene coated Silica Nanotube still face very large challenge, this has limited by nano-structure design and Graphene modification and has obtained high-performance silicon dioxide negative material.The new method of therefore, seeking to prepare graphene coated Silica Nanotube composite material has become the task of top priority.
Summary of the invention
The object of this invention is to provide the preparation method of a kind of lithium ion battery graphene coated Silica Nanotube composite negative pole material, graphene coated Silica Nanotube composite negative pole material prepared by described method has unique structure and composition characteristic, thereby can show superior storage lithium performance, comprise higher charging and discharging capacity, longer cycle life and higher multiplying power property.
A preparation method for graphene coated Silica Nanotube composite negative pole material for lithium ion battery, comprises the steps:
(1) zinc oxide nano rod is distributed in ethanolic solution, adds successively subsequently water, ammoniacal liquor and teos solution, room temperature reaction 0.5 ~ 12 hour, washs product be dried, and obtains zinc oxide/silica core-shell nanometer rods;
(2) step (1) being obtained to zinc oxide/silica core-shell nanometer rods is distributed in sodium-chloride water solution, add diallyl dimethyl ammoniumchloride (PDDA), stir 0.5 ~ 24 hour, product is washed and is dried, obtain zinc oxide/silica core-shell nanometer rods of diallyl dimethyl ammoniumchloride modification;
(3) product step (2) being obtained is distributed in the aqueous solution together with graphene oxide, stir 0.5 ~ 24 hour, drip the aqueous solution of sodium borohydride, stir 0.5 ~ 24 hour, product is washed and is dried, obtain zinc oxide/silica core-shell nanometer rods of graphene coated;
(4) product step (3) being obtained is distributed in excessive acid solution, stirs 0.5 ~ 24 hour, and zinc oxide nano rod washs product be dried after dissolving, and obtains graphene coated Silica Nanotube composite negative pole material.
In step (1), the concentration of described zinc oxide nano rod in ethanolic solution is 0.01 ~ 10 grams per liter; NH in described ammoniacal liquor
3quality percentage composition be 25 ~ 28%, SiO in described teos solution
2quality percentage composition higher than 28.0%.The volume proportion of described ethanolic solution, water, ammoniacal liquor and teos solution is 1:0.1 ~ 0.5:0.1 ~ 0.5:0.00005 ~ 0.001.
In step (2), the mass ratio of described zinc oxide/silica core-shell nanometer rods and sodium chloride is 0.01 ~ 10:1; The mass ratio of described zinc oxide/silica core-shell nanometer rods and diallyl dimethyl ammoniumchloride is 0.1 ~ 10:1.
In step (3), the mass ratio of described zinc oxide/silica core-shell nanometer rods and graphene oxide is 0.2 ~ 20:1; The mass ratio of described sodium borohydride and graphene oxide is 1 ~ 100:1.
In step (4), described acid solution is hydrochloric acid solution, sulfuric acid solution or salpeter solution.
In the present invention, room temperature institute how is 0 ~ 40
oc.
The present invention has following useful technique effect:
(1) the present invention is taking zinc oxide nano rod as template; remove again the process of template by silicon dioxide and graphene coated and prepare graphene coated Silica Nanotube composite material; be produced on a large scale, be convenient to its commercial applications on lithium ion battery negative material.
(2) the present invention carries out modification by cationic polyelectrolyte diallyl dimethyl ammoniumchloride to zinc oxide/silica core-shell nanometer rods and makes its surface band positive electricity, utilize electrostatic attraction effect electronegative graphene oxide to be coated to uniformly to the surface of core-shell nanometer rod, make end product by electronation and removal template procedure subsequently again, overcome a preparation difficult problem for graphene coated Silica Nanotube composite material.
(3) the present invention is by controlling concentration and the ratio of reaction time, reaction raw materials, can regulate the ratio between pipe thickness and Graphene and the silicon dioxide of Silica Nanotube, the storage lithium performance of the step control composite system of going forward side by side.
Brief description of the drawings
The stereoscan photograph of the graphene coated Silica Nanotube composite negative pole material that Fig. 1: embodiment 1 makes.
The transmission electron microscope photo of the graphene coated Silica Nanotube composite negative pole material that Fig. 2: embodiment 1 makes.
The cyclic voltammogram of the graphene coated Silica Nanotube composite negative pole material that Fig. 3: embodiment 1 makes.
The cycle performance figure of the graphene coated Silica Nanotube composite negative pole material that Fig. 4: embodiment 1 makes.
The high rate performance figure of the graphene coated Silica Nanotube composite negative pole material that Fig. 5: embodiment 1 makes.
Embodiment
Describe the present invention below in conjunction with specific embodiment.Protection scope of the present invention is not limited with embodiment, but is limited by claim.
embodiment 1:
A preparation method for graphene coated Silica Nanotube composite negative pole material for lithium ion battery, step is as follows:
(1) 0.1 gram of zinc oxide nano rod is distributed in 120 milliliters of ethanolic solutions, add successively subsequently 20 ml waters, 20 milliliters of ammoniacal liquor and 60 microlitre teos solutions, room temperature reaction 1 hour, washs product be dried, and obtains zinc oxide/silica core-shell nanometer rods;
(2) product 0.6 gram of step (1) being obtained is distributed in the sodium-chloride water solution of 60 milliliter of 0.5 mol/L, add the diallyl dimethyl ammoniumchloride of 0.15 gram of positively charged, stir 1 hour, product is washed and is dried, obtain zinc oxide/silica core-shell nanometer rods of diallyl dimethyl ammoniumchloride modification;
(3) product 0.6 gram of step (2) being obtained is distributed in 50 ml water solution together with 0.2 gram of graphene oxide, stir 6 hours, drip subsequently the sodium borohydride aqueous solution of 20 milliliter of 100 grams per liter, stir 2 hours, product is washed and is dried, obtain zinc oxide/silica core-shell nanometer rods of graphene coated;
(4) product step (3) being obtained is distributed in excessive hydrochloric acid solution and carrys out dissolved oxygen zinc nanometer rods, stirs 2 hours, and product is washed and is dried, and obtains graphene coated Silica Nanotube composite negative pole material.
Fig. 1 and Fig. 2 are respectively ESEM and the transmission electron microscope photos of the synthetic graphene coated Silica Nanotube composite negative pole material of the present embodiment.The two-dimensional sheet structure of Graphene and the one dimension tubular structure of silicon dioxide in described composite negative pole material as seen from the figure, and the surface that is coated on Silica Nanotube of two-dimentional Graphene homogeneous media, form three-D nano-porous graphene coated Silica Nanotube composite material, these architectural characteristics are all conducive to this composite negative pole material and show good storage lithium performance.Fig. 3 is the cyclic voltammogram of the synthetic graphene coated Silica Nanotube composite negative pole material of the present embodiment.As seen from the figure, the storage lithium mechanism of the cyclic voltammetric characteristic conforms silicon dioxide of product.Fig. 4 is the cycle performance figure of the synthetic graphene coated Silica Nanotube composite negative pole material of the present embodiment.As seen from the figure, through 100 circulations, the specific discharge capacity of graphene coated Silica Nanotube composite negative pole material is still up to 1145.3 MAhs/g, far above the theoretical specific capacity (372 MAhs/g) of graphite cathode material, superior cycle performance and higher specific capacity are shown.Fig. 5 is the high rate performance figure of the synthetic graphene coated Silica Nanotube composite negative pole material of the present embodiment.As seen from the figure, in the time that current density is 100,200,500 and 1000 milliamperes of/gram of, the average specific capacity of product is respectively 1159.1,991.5,811.1 and 628.6 MAhs/g; In the time that current density is got back to 100 milliamperes/gram from 1000 milliamperes/gram, the average specific discharge capacity of product can return to 1160.9 MAhs/g, the high rate performance that this explanation graphene coated Silica Nanotube composite negative pole material has had, can be expected to realize the commercial applications on lithium ion power cell cathode.
embodiment 2:
A preparation method for graphene coated Silica Nanotube composite negative pole material for lithium ion battery, step is as follows:
(1) 0.01 gram of zinc oxide nano rod is distributed in 1000 milliliters of ethanolic solutions, add successively subsequently 100 ml waters, 100 milliliters of ammoniacal liquor and 50 microlitre teos solutions, room temperature reaction 0.5 hour, washs product be dried, and obtains zinc oxide/silica core-shell nanometer rods;
(2) product 0.06 gram of step (1) being obtained is distributed in the sodium-chloride water solution of 20 milliliter of 0.5 mol/L, add the diallyl dimethyl ammoniumchloride of 0.6 gram of positively charged, stir 24 hours, product is washed and is dried, obtain zinc oxide/silica core-shell nanometer rods of diallyl dimethyl ammoniumchloride modification;
(3) product 0.06 gram of step (2) being obtained is distributed in 50 ml water solution together with 0.3 gram of graphene oxide, stir 24 hours, drip subsequently the sodium borohydride aqueous solution of 20 milliliter of 15 grams per liter, stir 0.5 hour, product is washed and is dried, obtain zinc oxide/silica core-shell nanometer rods of graphene coated;
(4) product step (3) being obtained is distributed in excessive hydrochloric acid solution and carrys out dissolved oxygen zinc nanometer rods, stirs 0.5 hour, and product is washed and is dried, and obtains graphene coated Silica Nanotube composite negative pole material.Its result is similar with embodiment 1.
embodiment 3:
A preparation method for graphene coated Silica Nanotube composite negative pole material for lithium ion battery, step is as follows:
(1) 0.01 gram of zinc oxide nano rod is distributed in 120 milliliters of ethanolic solutions, add successively subsequently 35 ml waters, 35 milliliters of ammoniacal liquor and 30 microlitre teos solutions, room temperature reaction 4 hours, washs product be dried, and obtains zinc oxide/silica core-shell nanometer rods;
(2) product 0.06 gram of step (1) being obtained is distributed in the sodium-chloride water solution of 200 milliliter of 0.5 mol/L, add the diallyl dimethyl ammoniumchloride of 0.06 gram of positively charged, stir 12 hours, product is washed and is dried, obtain zinc oxide/silica core-shell nanometer rods of diallyl dimethyl ammoniumchloride modification;
(3) product 0.06 gram of step (2) being obtained is distributed in 50 ml water solution together with 0.06 gram of graphene oxide, stir 12 hours, drip subsequently the sodium borohydride aqueous solution of 20 milliliter of 15 grams per liter, stir 1 hour, product is washed and is dried, obtain zinc oxide/silica core-shell nanometer rods of graphene coated;
(4) product step (3) being obtained is distributed in excessive hydrochloric acid solution and carrys out dissolved oxygen zinc nanometer rods, stirs 1 hour, and product is washed and is dried, and obtains graphene coated Silica Nanotube composite negative pole material.Its result is similar with embodiment 1.
embodiment 4:
A preparation method for graphene coated Silica Nanotube composite negative pole material for lithium ion battery, step is as follows:
(1) 0.5 gram of zinc oxide nano rod is distributed in 100 milliliters of ethanolic solutions, add successively subsequently 20 ml waters, 20 milliliters of ammoniacal liquor and 70 microlitre teos solutions, room temperature reaction 8 hours, washs product be dried, and obtains zinc oxide/silica core-shell nanometer rods;
(2) product 6 grams of steps (1) being obtained is distributed in the sodium-chloride water solution of 40 milliliter of 0.5 mol/L, add the diallyl dimethyl ammoniumchloride of 1.2 grams of positively chargeds, stir 6 hours, product is washed and is dried, obtain zinc oxide/silica core-shell nanometer rods of diallyl dimethyl ammoniumchloride modification;
(3) product 6 grams of steps (2) being obtained is distributed in 50 ml water solution together with 0.6 gram of graphene oxide, stir 1 hour, drip subsequently the sodium borohydride aqueous solution of 100 milliliter of 300 grams per liter, stir 12 hours, product is washed and is dried, obtain zinc oxide/silica core-shell nanometer rods of graphene coated;
(4) product step (3) being obtained is distributed in excessive hydrochloric acid solution and carrys out dissolved oxygen zinc nanometer rods, stirs 12 hours, and product is washed and is dried, and obtains graphene coated Silica Nanotube composite negative pole material.Its result is similar with embodiment 1.
embodiment 5:
A preparation method for graphene coated Silica Nanotube composite negative pole material for lithium ion battery, step is as follows:
(1) 1 gram of zinc oxide nano rod is distributed in 100 milliliters of ethanolic solutions, add successively subsequently 50 ml waters, 50 milliliters of ammoniacal liquor and 100 microlitre teos solutions, room temperature reaction 12 hours, washs product be dried, and obtains zinc oxide/silica core-shell nanometer rods;
(2) product 6 grams of steps (1) being obtained is distributed in the sodium-chloride water solution of 20 milliliter of 0.5 mol/L, add the diallyl dimethyl ammoniumchloride of 0.6 gram of positively charged, stir 0.5 hour, product is washed and is dried, obtain zinc oxide/silica core-shell nanometer rods of diallyl dimethyl ammoniumchloride modification;
(3) product 6 grams of steps (2) being obtained is distributed in 50 ml water solution together with 0.3 gram of graphene oxide, stir 0.5 hour, drip subsequently the sodium borohydride aqueous solution of 100 milliliter of 300 grams per liter, stir 24 hours, product is washed and is dried, obtain zinc oxide/silica core-shell nanometer rods of graphene coated;
(4) product step (3) being obtained is distributed in excessive hydrochloric acid solution and carrys out dissolved oxygen zinc nanometer rods, stirs 24 hours, and product is washed and is dried, and obtains graphene coated Silica Nanotube composite negative pole material.Its result is similar with embodiment 1.
Claims (6)
1. a preparation method for graphene coated Silica Nanotube composite negative pole material for lithium ion battery, is characterized in that, comprises the steps:
(1) zinc oxide nano rod is distributed in ethanolic solution, adds successively subsequently water, ammoniacal liquor and teos solution, room temperature reaction 0.5 ~ 12 hour, washs product be dried, and obtains zinc oxide/silica core-shell nanometer rods;
(2) step (1) being obtained to zinc oxide/silica core-shell nanometer rods is distributed in sodium-chloride water solution, add diallyl dimethyl ammoniumchloride, stir 0.5 ~ 24 hour, product is washed and is dried, obtain zinc oxide/silica core-shell nanometer rods of diallyl dimethyl ammoniumchloride modification;
(3) product step (2) being obtained is distributed in the aqueous solution together with graphene oxide, stir 0.5 ~ 24 hour, drip the aqueous solution of sodium borohydride, stir 0.5 ~ 24 hour, product is washed and is dried, obtain zinc oxide/silica core-shell nanometer rods of graphene coated;
(4) product step (3) being obtained is distributed in excessive acid solution, stirs 0.5 ~ 24 hour, and zinc oxide nano rod washs product be dried after dissolving, and obtains graphene coated Silica Nanotube composite negative pole material.
2. the preparation method of graphene coated Silica Nanotube composite negative pole material according to claim 1, is characterized in that: in step (1), the concentration of described zinc oxide nano rod in ethanolic solution is 0.01 ~ 10 grams per liter; NH in described ammoniacal liquor
3quality percentage composition be 25 ~ 28%, SiO in described teos solution
2quality percentage composition higher than 28.0%.
3. the preparation method of graphene coated Silica Nanotube composite negative pole material according to claim 1, it is characterized in that: in step (1), the volume proportion of described ethanolic solution, water, ammoniacal liquor and teos solution is 1:0.1 ~ 0.5:0.1 ~ 0.5:0.00005 ~ 0.001.
4. the preparation method of graphene coated Silica Nanotube composite negative pole material according to claim 1, is characterized in that: in step (2), the mass ratio of described zinc oxide/silica core-shell nanometer rods and sodium chloride is 0.01 ~ 10:1; The mass ratio of described zinc oxide/silica core-shell nanometer rods and diallyl dimethyl ammoniumchloride is 0.1 ~ 10:1.
5. the preparation method of graphene coated Silica Nanotube composite negative pole material according to claim 1, it is characterized in that: in step (3), the mass ratio of described zinc oxide/silica core-shell nanometer rods and graphene oxide is 0.2 ~ 20:1; The mass ratio of described sodium borohydride and graphene oxide is 1 ~ 100:1.
6. the preparation method of graphene coated Silica Nanotube composite negative pole material according to claim 1, is characterized in that: in step (4), described acid solution is hydrochloric acid solution, sulfuric acid solution or salpeter solution.
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Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104934578A (en) * | 2015-05-21 | 2015-09-23 | 东莞市迈科新能源有限公司 | High-silica zeolite and graphene compound anode material for lithium ion battery and preparation method thereof |
| CN104979539A (en) * | 2015-05-14 | 2015-10-14 | 浙江大学 | Silicon-carbon composite nano-tube preparation method |
| CN105390687A (en) * | 2015-11-03 | 2016-03-09 | 盐城工学院 | High-performance three-dimensional carbon nanotube composite negative electrode material, preparation method therefor and application thereof |
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20110103854A1 (en) * | 2009-11-02 | 2011-05-05 | Xerox Corporation | Hyper nanocomposites (hnc) for fuser materials |
| CN102343239A (en) * | 2011-05-20 | 2012-02-08 | 四川大学 | Oxidized graphene or graphene/inorganic particle core/shell material and preparation method thereof |
| CN102646817A (en) * | 2011-02-16 | 2012-08-22 | 中国科学院金属研究所 | Graphene/metal oxide composite cathode material for lithium ion battery and preparation |
| CN102709061A (en) * | 2012-07-03 | 2012-10-03 | 电子科技大学 | Graphene-cladding manganese dioxide combination electrode material and method for producing same |
| CN102881881A (en) * | 2012-10-25 | 2013-01-16 | 中国科学院宁波材料技术与工程研究所 | Negative pole material of lithium ion battery, preparation method of material and lithium ion battery |
| CN103647064A (en) * | 2013-12-19 | 2014-03-19 | 北京师范大学 | Graphene-coating mesoporous carbon-base metal oxide as well as preparation method thereof and application |
| CN103682283A (en) * | 2012-09-24 | 2014-03-26 | 三星电子株式会社 | Composite anode active material, anode and lithium battery each including the composite anode active material, method of preparing the composite anode active material |
-
2014
- 2014-08-15 CN CN201410399928.1A patent/CN104157840B/en not_active Expired - Fee Related
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20110103854A1 (en) * | 2009-11-02 | 2011-05-05 | Xerox Corporation | Hyper nanocomposites (hnc) for fuser materials |
| CN102646817A (en) * | 2011-02-16 | 2012-08-22 | 中国科学院金属研究所 | Graphene/metal oxide composite cathode material for lithium ion battery and preparation |
| CN102343239A (en) * | 2011-05-20 | 2012-02-08 | 四川大学 | Oxidized graphene or graphene/inorganic particle core/shell material and preparation method thereof |
| CN102709061A (en) * | 2012-07-03 | 2012-10-03 | 电子科技大学 | Graphene-cladding manganese dioxide combination electrode material and method for producing same |
| CN103682283A (en) * | 2012-09-24 | 2014-03-26 | 三星电子株式会社 | Composite anode active material, anode and lithium battery each including the composite anode active material, method of preparing the composite anode active material |
| CN102881881A (en) * | 2012-10-25 | 2013-01-16 | 中国科学院宁波材料技术与工程研究所 | Negative pole material of lithium ion battery, preparation method of material and lithium ion battery |
| CN103647064A (en) * | 2013-12-19 | 2014-03-19 | 北京师范大学 | Graphene-coating mesoporous carbon-base metal oxide as well as preparation method thereof and application |
Cited By (22)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106000379A (en) * | 2015-01-05 | 2016-10-12 | 重庆文理学院 | Preparation method of graphene-based material |
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