CN104157840B - The preparation method of a kind of lithium ion battery graphene coated silica nanometer pipe composite negative pole material - Google Patents
The preparation method of a kind of lithium ion battery graphene coated silica nanometer pipe composite negative pole material Download PDFInfo
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- CN104157840B CN104157840B CN201410399928.1A CN201410399928A CN104157840B CN 104157840 B CN104157840 B CN 104157840B CN 201410399928 A CN201410399928 A CN 201410399928A CN 104157840 B CN104157840 B CN 104157840B
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The preparation method of a kind of lithium ion battery graphene coated silica nanometer pipe composite negative pole material, step is as follows: zinc oxide nano rod is distributed in ethanolic soln by (1), add water, ammoniacal liquor and teos solution successively, obtain zinc oxide/silica core-shell nanometer rod; (2) product by step (1) is distributed in sodium chloride aqueous solution, adds PDDA modification; (3) product and the graphene oxide of step (2) are distributed in the aqueous solution, drip and add sodium borohydride, obtain the zinc oxide/silica core-shell nanometer rod of graphene coated; (4) it is distributed in excessive acid solution by the product of step (3) dissolved oxygen zinc nanometer rod, obtains described composite negative pole material. The present invention take zinc oxide nano rod as template, the process being removed template by silicon-dioxide and graphene coated again prepares graphene coated silica nanometer pipe matrix material, and prepared matrix material has high charge-discharge specific storage, long circulation life and high rate capability.
Description
Technical field
The present invention relates to the preparation method of a kind of lithium ion battery negative material, particularly relate to the preparation method of a kind of graphene coated silica nanometer pipe composite negative pole material.
Background technology
Silica-base material has, such as elemental silicon, silicon-base alloy and Si oxide, the security that high theoretical specific capacity becomes reconciled, and can be used as the desirable equivalent material of lithium ion battery commercialization carbon negative pole material. Wherein, the oxide compound of silicon particularly silicon-dioxide have that preparation is easy, cost is low and advantages of environment protection, one of research focus having become silicon based anode material. But, the volume change that earth silicon material is huge in removal lithium embedded process can cause the efflorescence of electrode materials, lose electrical contact and the quick decay of specific storage. In addition, the specific conductivity of block earth silicon material is lower and Si-O bond close can be relatively big, what this was all unfavorable for that lithium ion deintercalation reacts carries out fast.
Silicon-dioxide is prepared into nanostructure, particularly nano tube structure can alleviate the problems referred to above to a certain extent, and this is owing to nanotube has bigger surf zone, shorter lithium ion diffusion length, stronger stress relief ability and an electric charge transmission path tieed up. But in charge and discharge process, the structure of nanotube can be destroyed, single silica nanometer pipe is difficult to obtain good performance of lithium ion battery. Carbon material, particularly two-dimensional graphene material has higher electroconductibility, can effectively alleviate the volume change of silicon-dioxide in removal lithium embedded process, thus by composite modified multiplying power property and the cyclical stability being expected to improve silicon-dioxide negative material of Graphene simultaneously. But, the composite nano materials of Graphene and silicon-dioxide, the particularly preparation of graphene coated silica nanometer pipe still face very big challenge, which has limited and obtain high-performance silicon dioxide negative material by nano-structure design and Graphene modification. Therefore, the novel method seeking to prepare graphene coated silica nanometer pipe matrix material has become the task of top priority.
Summary of the invention
It is an object of the invention to provide the preparation method of a kind of lithium ion battery graphene coated silica nanometer pipe composite negative pole material, graphene coated silica nanometer pipe composite negative pole material prepared by described method has unique structure and component characteristic, thus superior storage lithium performance be can show, higher charging and discharging capacity, longer cycle life and higher multiplying power property comprised.
A preparation method for lithium ion battery graphene coated silica nanometer pipe composite negative pole material, comprises the steps:
(1) zinc oxide nano rod is distributed in ethanolic soln, adds water, ammoniacal liquor and teos solution subsequently successively, room temperature reaction 0.5 ~ 12 hour, product washing is also dry, obtain zinc oxide/silica core-shell nanometer rod;
(2) step (1) being obtained zinc oxide/silica core-shell nanometer rod is distributed in sodium chloride aqueous solution, add diallyl dimethyl ammoniumchloride (PDDA), stir 0.5 ~ 24 hour, product washing is also dry, obtain the zinc oxide/silica core-shell nanometer rod of diallyl dimethyl ammoniumchloride modification;
(3) product that step (2) obtains is distributed in the aqueous solution together with graphene oxide, stir 0.5 ~ 24 hour, drip the aqueous solution adding sodium borohydride, stir 0.5 ~ 24 hour, product washing is also dry, obtain the zinc oxide/silica core-shell nanometer rod of graphene coated;
(4) being distributed in excessive acid solution by the product that step (3) obtains, stir 0.5 ~ 24 hour, zinc oxide nano rod is also dry by product washing after dissolving, and obtains graphene coated silica nanometer pipe composite negative pole material.
In step (1), the concentration of described zinc oxide nano rod in ethanolic soln is 0.01 ~ 10 grams per liter; NH in described ammoniacal liquor3Mass percentage be 25 ~ 28%, SiO in described teos solution2Mass percentage higher than 28.0%. The volume proportion of described ethanolic soln, 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 rod and sodium-chlor is 0.01 ~ 10:1; The mass ratio of described zinc oxide/silica core-shell nanometer rod and diallyl dimethyl ammoniumchloride is 0.1 ~ 10:1.
In step (3), the mass ratio of described zinc oxide/silica core-shell nanometer rod 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 soln, sulphuric acid soln or salpeter solution.
In the present invention, room temperature is referred to that scope is 0 ~ 40oC。
The present invention has following useful technique effect:
(1) the present invention take zinc oxide nano rod as template; the process being removed template by silicon-dioxide and graphene coated again prepares graphene coated silica nanometer pipe matrix material; it is produced on a large scale, it is convenient to its commercial applications on lithium ion battery negative material.
(2) zinc oxide/silica core-shell nanometer rod is carried out modification by cationic polyelectrolyte diallyl dimethyl ammoniumchloride and makes its surface band positive electricity by the present invention, utilize electrostatic attraction effect that electronegative graphene oxide is coated to the surface of core-shell nanometer rod uniformly, again by chemical reduction subsequently and the obtained final product of removal template procedure, overcome a preparation difficult problem for graphene coated silica nanometer pipe matrix material.
(3) the present invention is by the concentration of control reaction times, reaction raw materials and ratio, it is possible to regulate the thickness of pipe of silica nanometer pipe and the ratio between Graphene and silicon-dioxide, the storage lithium performance of a step control composite system of going forward side by side.
Accompanying drawing explanation
Fig. 1: the stereoscan photograph of the obtained graphene coated silica nanometer pipe composite negative pole material of embodiment 1.
Fig. 2: the transmission electron microscope photo of the obtained graphene coated silica nanometer pipe composite negative pole material of embodiment 1.
Fig. 3: the cyclic voltammogram of the obtained graphene coated silica nanometer pipe composite negative pole material of embodiment 1.
Fig. 4: the cycle performance figure of the obtained graphene coated silica nanometer pipe composite negative pole material of embodiment 1.
Fig. 5: the high rate performance figure of the obtained graphene coated silica nanometer pipe composite negative pole material of embodiment 1.
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 lithium ion battery graphene coated silica nanometer pipe composite negative pole material, step is as follows:
(1) 0.1 gram of zinc oxide nano rod is distributed in 120 milliliters of ethanolic solns, add 20 ml waters subsequently successively, 20 milliliters of ammoniacal liquor and 60 micro-rise teos solution, room temperature reaction 1 hour, product washing is also dry, obtain zinc oxide/silica core-shell nanometer rod;
(2) product that 0.6 gram of step (1) obtains is distributed in the sodium chloride aqueous 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 washing is also dry, obtain the zinc oxide/silica core-shell nanometer rod of diallyl dimethyl ammoniumchloride modification;
(3) product 0.6 gram of step (2) obtained is distributed in 50 ml water solution together with 0.2 gram of graphene oxide, stir 6 hours, drip milliliter sodium borohydride aqueous solution for 100 grams per liters that adds 20 subsequently, stir 2 hours, product washing is also dry, obtain the zinc oxide/silica core-shell nanometer rod of graphene coated;
(4) product that step (3) obtains is distributed in excessive hydrochloric acid soln and carrys out dissolved oxygen zinc nanometer rod, stir 2 hours, product washing is also dry, obtain graphene coated silica nanometer pipe composite negative pole material.
Fig. 1 and Fig. 2 is scanning electron microscope and the transmission electron microscope photo of the graphene coated silica nanometer pipe composite negative pole material of the present embodiment synthesis respectively. The two-dimensional sheet structure of Graphene and a dimension tubular structure of silicon-dioxide in described composite negative pole material as seen from the figure, and the surface being coated on silica nanometer pipe of two-dimensional graphene homogeneous media, forming three-D nano-porous graphene coated silica nanometer pipe matrix material, these structural performances are all conducive to this composite negative pole material to show storage lithium performance preferably. Fig. 3 is the cyclic voltammogram of the graphene coated silica nanometer pipe composite negative pole material of the present embodiment synthesis. As seen from the figure, the Cyclic voltamogram of product meets the storage lithium mechanism of silicon-dioxide. Fig. 4 is the cycle performance figure of the graphene coated silica nanometer pipe composite negative pole material of the present embodiment synthesis. As seen from the figure, through 100 circulations, the specific discharge capacity of graphene coated silica nanometer pipe 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, show superior cycle performance and higher specific storage. Fig. 5 is the high rate performance figure of the graphene coated silica nanometer pipe composite negative pole material of the present embodiment synthesis. As seen from the figure, when current density is 100,200,500 and 1000 milliamperes/gram, the Average specific capacities of product is respectively 1159.1,991.5,811.1 and 628.6 MAhs/g; When current density returns to 100 milliamperes/gram from 1000 milliamperes/gram, the averaged discharge specific storage of product can return to 1160.9 MAhs/g, this illustrates the high rate performance that graphene coated silica nanometer pipe composite negative pole material has had, and can be expected to realize the commercial applications on lithium ion power cell cathode.
Embodiment 2:
A preparation method for lithium ion battery graphene coated silica nanometer pipe composite negative pole material, step is as follows:
(1) 0.01 gram of zinc oxide nano rod is distributed in 1000 milliliters of ethanolic solns, add 100 ml waters subsequently successively, 100 milliliters of ammoniacal liquor and 50 micro-rise teos solution, room temperature reaction 0.5 hour, product washing is also dry, obtain zinc oxide/silica core-shell nanometer rod;
(2) product that 0.06 gram of step (1) obtains is distributed in the sodium chloride aqueous 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 washing is also dry, obtain the zinc oxide/silica core-shell nanometer rod of diallyl dimethyl ammoniumchloride modification;
(3) product 0.06 gram of step (2) obtained is distributed in 50 ml water solution together with 0.3 gram of graphene oxide, stir 24 hours, drip milliliter sodium borohydride aqueous solution for 15 grams per liters that adds 20 subsequently, stir 0.5 hour, product washing is also dry, obtain the zinc oxide/silica core-shell nanometer rod of graphene coated;
(4) product that step (3) obtains is distributed in excessive hydrochloric acid soln and carrys out dissolved oxygen zinc nanometer rod, stir 0.5 hour, product washing is also dry, obtain graphene coated silica nanometer pipe composite negative pole material. Its result is similar with embodiment 1.
Embodiment 3:
A preparation method for lithium ion battery graphene coated silica nanometer pipe composite negative pole material, step is as follows:
(1) 0.01 gram of zinc oxide nano rod is distributed in 120 milliliters of ethanolic solns, add 35 ml waters subsequently successively, 35 milliliters of ammoniacal liquor and 30 micro-rise teos solution, room temperature reaction 4 hours, product washing is also dry, obtain zinc oxide/silica core-shell nanometer rod;
(2) product that 0.06 gram of step (1) obtains is distributed in the sodium chloride aqueous 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 washing is also dry, obtain the zinc oxide/silica core-shell nanometer rod of diallyl dimethyl ammoniumchloride modification;
(3) product 0.06 gram of step (2) obtained is distributed in 50 ml water solution together with 0.06 gram of graphene oxide, stir 12 hours, drip milliliter sodium borohydride aqueous solution for 15 grams per liters that adds 20 subsequently, stir 1 hour, product washing is also dry, obtain the zinc oxide/silica core-shell nanometer rod of graphene coated;
(4) product that step (3) obtains is distributed in excessive hydrochloric acid soln and carrys out dissolved oxygen zinc nanometer rod, stir 1 hour, product washing is also dry, obtain graphene coated silica nanometer pipe composite negative pole material. Its result is similar with embodiment 1.
Embodiment 4:
A preparation method for lithium ion battery graphene coated silica nanometer pipe composite negative pole material, step is as follows:
(1) 0.5 gram of zinc oxide nano rod is distributed in 100 milliliters of ethanolic solns, add 20 ml waters subsequently successively, 20 milliliters of ammoniacal liquor and 70 micro-rise teos solution, room temperature reaction 8 hours, product washing is also dry, obtain zinc oxide/silica core-shell nanometer rod;
(2) product that 6 grams of steps (1) obtain is distributed in the sodium chloride aqueous 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 washing is also dry, obtain the zinc oxide/silica core-shell nanometer rod of diallyl dimethyl ammoniumchloride modification;
(3) product 6 grams of steps (2) obtained is distributed in 50 ml water solution together with 0.6 gram of graphene oxide, stir 1 hour, drip milliliter sodium borohydride aqueous solution for 300 grams per liters that adds 100 subsequently, stir 12 hours, product washing is also dry, obtain the zinc oxide/silica core-shell nanometer rod of graphene coated;
(4) product that step (3) obtains is distributed in excessive hydrochloric acid soln and carrys out dissolved oxygen zinc nanometer rod, stir 12 hours, product washing is also dry, obtain graphene coated silica nanometer pipe composite negative pole material. Its result is similar with embodiment 1.
Embodiment 5:
A preparation method for lithium ion battery graphene coated silica nanometer pipe composite negative pole material, step is as follows:
(1) 1 gram of zinc oxide nano rod is distributed in 100 milliliters of ethanolic solns, add 50 ml waters subsequently successively, 50 milliliters of ammoniacal liquor and 100 micro-rise teos solution, room temperature reaction 12 hours, product washing is also dry, obtain zinc oxide/silica core-shell nanometer rod;
(2) product that 6 grams of steps (1) obtain is distributed in the sodium chloride aqueous 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 washing is also dry, obtain the zinc oxide/silica core-shell nanometer rod of diallyl dimethyl ammoniumchloride modification;
(3) product 6 grams of steps (2) obtained is distributed in 50 ml water solution together with 0.3 gram of graphene oxide, stir 0.5 hour, drip milliliter sodium borohydride aqueous solution for 300 grams per liters that adds 100 subsequently, stir 24 hours, product washing is also dry, obtain the zinc oxide/silica core-shell nanometer rod of graphene coated;
(4) product that step (3) obtains is distributed in excessive hydrochloric acid soln and carrys out dissolved oxygen zinc nanometer rod, stir 24 hours, product washing is also dry, obtain graphene coated silica nanometer pipe composite negative pole material. Its result is similar with embodiment 1.
Claims (5)
1. the lithium ion battery preparation method of graphene coated silica nanometer pipe composite negative pole material, it is characterised in that, comprise the steps:
(1) zinc oxide nano rod is distributed in ethanolic soln, adds water, ammoniacal liquor and teos solution subsequently successively, room temperature reaction 0.5 ~ 12 hour, product washing is also dry, obtain zinc oxide/silica core-shell nanometer rod;
(2) step (1) being obtained zinc oxide/silica core-shell nanometer rod is distributed in sodium chloride aqueous solution, add diallyl dimethyl ammoniumchloride, stir 0.5 ~ 24 hour, product washing is also dry, obtain the zinc oxide/silica core-shell nanometer rod of diallyl dimethyl ammoniumchloride modification;
(3) product that step (2) obtains is distributed in the aqueous solution together with graphene oxide, stir 0.5 ~ 24 hour, drip the aqueous solution adding sodium borohydride, stir 0.5 ~ 24 hour, product washing is also dry, obtain the zinc oxide/silica core-shell nanometer rod of graphene coated;
(4) being distributed in excessive acid solution by the product that step (3) obtains, stir 0.5 ~ 24 hour, zinc oxide nano rod is also dry by product washing after dissolving, and obtains graphene coated silica nanometer pipe composite negative pole material.
2. the preparation method of graphene coated silica nanometer pipe composite negative pole material according to claim 1, it is characterised in that: in step (1), the concentration of described zinc oxide nano rod in ethanolic soln is 0.01 ~ 10 grams per liter;NH in described ammoniacal liquor3Mass percentage be 25 ~ 28%, SiO in described teos solution2Mass percentage higher than 28.0%.
3. the preparation method of graphene coated silica nanometer pipe composite negative pole material according to claim 1, it is characterized in that: in step (1), the volume proportion of described ethanolic soln, 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 nanometer pipe composite negative pole material according to claim 1, it is characterised in that: in step (2), the mass ratio of described zinc oxide/silica core-shell nanometer rod and sodium-chlor is 0.01 ~ 10:1; The mass ratio of described zinc oxide/silica core-shell nanometer rod and diallyl dimethyl ammoniumchloride is 0.1 ~ 10:1.
5. the preparation method of graphene coated silica nanometer pipe 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 rod and graphene oxide is 0.2 ~ 20:1; The mass ratio of described sodium borohydride and graphene oxide is 1 ~ 100:1.
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| CN104979539B (en) * | 2015-05-14 | 2017-05-10 | 浙江大学 | Silicon-carbon composite nano-tube preparation method |
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| CN110993930B (en) * | 2019-11-22 | 2021-09-24 | 芜湖天弋能源科技有限公司 | Preparation method of graphene-coated nano-silicon composite material and application of graphene-coated nano-silicon composite material as negative electrode material of lithium ion battery |
| CN111900491A (en) * | 2020-07-31 | 2020-11-06 | 合肥佐佑信息技术有限公司 | Lithium battery cell and preparation method thereof |
| CN113437311B (en) * | 2021-05-24 | 2022-07-19 | 上海大学 | Preparation method of Pt-M spherical catalyst for fuel cell |
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