CN104617251A - Preparation method for graphene/spinel LiMn2O4 nanometer composite material - Google Patents
Preparation method for graphene/spinel LiMn2O4 nanometer composite material Download PDFInfo
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- CN104617251A CN104617251A CN201410744294.9A CN201410744294A CN104617251A CN 104617251 A CN104617251 A CN 104617251A CN 201410744294 A CN201410744294 A CN 201410744294A CN 104617251 A CN104617251 A CN 104617251A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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- Y02E60/10—Energy storage using batteries
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Abstract
A preparation method for a graphene/spinel LiMn2O4 nanometer composite material belongs to the field of preparation of lithium ion batteries cathode materials. Aiming at the problems that at present spinel LiMn2O4 is capable of improving the cycle performance through body doping and surface coating, but the price is reduction of specific capacity of an active material, the preparation method for the graphene/spinel LiMn2O4 nanometer composite material with high specific capacity and excellent electric cycle performance is provided. The preparation method employs a sol-gel process and a graphite oxide reduction process for preparing spinel LiMn2O4 nanocrystalline and graphene nanosheet, and employs a freeze drying process for preparing the graphene/spinel LiMn2O4 nanometer composite material. The preparation method is simple in process, and by preparing an electrode from the graphene/spinel LiMn2O4 nanometer composite material, the discharge specific capacity is 124.30 mAh*g<-1>, and the corresponding capacity maintenance rate is 96.66% after cycling is performed for 100 times, and good electrochemical performances are provided.
Description
Technical field
The invention belongs to anode material for lithium-ion batteries preparation field.
Background technology
Lithium ion battery is with its high-energy-density, long circulation life and advantages of environment protection, becoming " green battery of 21 century " is the indispensable parts of portable type electronic product, especially the electrokinetic cell of emerging strategic energy-saving and emission-reduction industry-New-energy electric vehicle most application prospect given priority to future of country.Electric automobile lithium ion battery used, except having the technical indicators such as high-energy, high power, long-life, also should possess the features such as safe and reliable and low cost, and positive electrode is then the key factor of limiting lithium ion electrokinetic cell development.Spinelle LiMn
20
4the advantages such as, cost low, fail safe good, non-environmental-pollution, easily preparation abundant with its raw material resources, become the first-selected positive electrode of lithium dynamical battery, but the problems such as from practical application, its capacity attenuation is fast, high power charging-discharging are then the bottlenecks of its application of restriction.Although pass through spinelle LiMn
20
4carry out bulk phase-doped and Surface coating and can improve its cycle performance to a certain extent, but with the chemical property that can not significantly improve material that the specific capacity reducing active material is cost.
Summary of the invention
The object of this invention is to provide the high Graphene/spinelle LiMn that electric cycle performance is excellent simultaneously of a kind of specific capacity
2o
4nano-composite materials method.
The present invention is achieved by the following technical programs: a kind of Graphene/spinelle LiMn
2o
4nano-composite materials method, comprise 1. Graphene preparations: disperseed by graphite oxide deionized water, the mixed liquor containing stannic oxide/graphene nano layer is obtained with processor for ultrasonic wave vibration, afterwards using the brown oxidation Graphene mixed liquor round-bottomed flask of falling people of acquisition. add hydrazine hydrate as reducing agent, mixed liquor refluxes at 100 DEG C, the color of solution gradually becomes black, finally mixed liquor is filtered, cleaning, obtain the cake shape filter cake of black, grapheme material powder is obtained after drying, finally be positioned in tube furnace, 500 DEG C of calcination 2h under nitrogen protection, 2. nano spinel LiMn
20
2prepared by positive electrode: with citric acid, manganese salt, lithium salts etc. by preparing nano spinel LiMn
20
2the stoichiometric proportion metering of electrode material, add distilled water, be stirred to sample to dissolve completely, beaker is placed in water-bath, and be heated to 80 DEG C, reactant reacts, use magnetic stirrer simultaneously. until form light yellow loose shape solid, sample is dried 12h at 120 DEG C, and at 350 DEG C, calcination 3 h. mills after cooling in porcelain alms bowl afterwards, obtains LiMn
2o
4presoma, presoma is proceeded in crucible, is placed in Muffle furnace 750 DEG C of calcination 12h, sample in stove naturally cool, after cooling, sample is milled and sieves and obtain nano spinel LiMn
20
2electrode material, 3. Graphene/spinelle LiMn
20
4nano-composite materials: by the Graphene of preparation and the brilliant LiMn of nanometer point
20
4positive electrode dissolves in deionized water. and carrying out energy oscillations 24h. with processor for ultrasonic wave, to put into refrigerator freezing, moves into freeze drier afterwards and carry out freeze drying and namely obtain Graphene/spinelle LiMn
20
4nano composite material.
In described Graphene preparation process, described graphite oxide is adopt the Hummers legal system improved standby.
The present invention has following beneficial effect:
Preparation process is simple, the Graphene/spinelle LiMn of preparation
2o
4nano composite material, its specific discharge capacity is 124.30 mAhg
-1, after circulating 100 weeks, corresponding capability retention is 96.66%, has good chemical property.
Embodiment
Below in conjunction with specific embodiment, the present invention will be further described.
Specific embodiment: preparation process of the present invention is: comprise 1. Graphene preparations: adopt oxidation-reduction method to be disperseed by graphite oxide deionized water, described graphite oxide is adopt the Hummers legal system improved standby, the mixed liquor containing stannic oxide/graphene nano layer is obtained with processor for ultrasonic wave vibration, afterwards using the brown oxidation Graphene mixed liquor round-bottomed flask of falling people of acquisition. add hydrazine hydrate as reducing agent, mixed liquor refluxes at 100 DEG C, the color of solution gradually becomes black, finally mixed liquor is filtered, cleaning, obtain the cake shape filter cake of black, grapheme material powder is obtained after drying, finally be positioned in tube furnace, 500 DEG C of calcination 2h under nitrogen protection, 2. nano spinel LiMn
20
2prepared by positive electrode: adopt sol-gal process with citric acid, manganese salt, lithium salts etc. by preparing nano spinel LiMn
20
2the stoichiometric proportion metering of electrode material, add distilled water, be stirred to sample to dissolve completely, beaker is placed in water-bath, and be heated to 80 DEG C, reactant reacts, use magnetic stirrer simultaneously. until form light yellow loose shape solid, sample is dried 12h at 120 DEG C, and at 350 DEG C, calcination 3 h. mills after cooling in porcelain alms bowl afterwards, obtains LiMn
2o
4presoma, presoma is proceeded in crucible, is placed in Muffle furnace 750 DEG C of calcination 12h, sample in stove naturally cool, after cooling, sample is milled and sieves and obtain nano spinel LiMn
20
2electrode material, 3. Graphene/spinelle LiMn
20
4nano-composite materials: by the Graphene of preparation and the brilliant LiMn of nanometer point
20
4positive electrode dissolves in deionized water. and carrying out energy oscillations 24h. with processor for ultrasonic wave, to put into refrigerator freezing, moves into freeze drier afterwards and carry out freeze drying and namely obtain Graphene/spinelle LiMn
20
4nano composite material.
Make electrode; form by the mass percent of the composite material of 80% and the polyvinylidene fluoride binder of 20%: in the glove box of argon shield, assemble three electrode simulated batteries and 2032 type button cells; with metal lithium sheet as reference electrode with to electrode, electrolyte is 1molL
-1liPF
6-EC:DEC:DMC (1:1:1, V/V/V)
Constant current charge-discharge test is carried out on high accuracy battery analyzer, and current density is 0.1C, adopts electrochemical workstation to carry out cyclic voltammetric and electrochemical impedance spectroscopy test, sweep speed 0.1 mVS
-1.The test frequency of scanning voltage 3.3 ~ 4.3 V. electrochemical impedance spectroscopy is 105Hz ~ 10
-2hz, the AC signal amplitude of applying is 5mV.Before testing impedance, electrode to polarize 1h under the polarization potential of setting.
The Graphene prepared after tested/spinelle LiMn
2o
4nano composite material, its specific discharge capacity is 124.30mAhg
-1, after circulating 100 weeks, corresponding capability retention is 96.66%, has good chemical property
above content is the further description done the present invention in conjunction with concrete execution mode, can not assert that specific embodiment of the invention is confined to these explanations.For general technical staff of the technical field of the invention, without departing from the inventive concept of the premise, some simple deduction or replace can also be made, all should be considered as belonging to protection scope of the present invention.
Claims (2)
1. Graphene/spinelle LiMn
2o
4nano-composite materials method, it is characterized in that: comprise 1. Graphene preparations: disperseed by graphite oxide deionized water, the mixed liquor containing stannic oxide/graphene nano layer is obtained with processor for ultrasonic wave vibration, afterwards using the brown oxidation Graphene mixed liquor round-bottomed flask of falling people of acquisition. add hydrazine hydrate as reducing agent, mixed liquor refluxes at 100 DEG C, the color of solution gradually becomes black, finally mixed liquor is filtered, cleaning, obtain the cake shape filter cake of black, grapheme material powder is obtained after drying, finally be positioned in tube furnace, 500 DEG C of calcination 2h under nitrogen protection, 2. nano spinel LiMn
20
2prepared by positive electrode: with citric acid, manganese salt, lithium salts etc. by preparing nano spinel LiMn
20
2the stoichiometric proportion metering of electrode material, add distilled water, be stirred to sample to dissolve completely, beaker is placed in water-bath, and be heated to 80 DEG C, reactant reacts, use magnetic stirrer simultaneously. until form light yellow loose shape solid, sample is dried 12h at 120 DEG C, and at 350 DEG C, calcination 3 h. mills after cooling in porcelain alms bowl afterwards, obtains LiMn
2o
4presoma, presoma is proceeded in crucible, is placed in Muffle furnace 750 DEG C of calcination 12h, sample in stove naturally cool, after cooling, sample is milled and sieves and obtain nano spinel LiMn
20
2electrode material, 3. Graphene/spinelle LiMn
20
4nano-composite materials: by the Graphene of preparation and the brilliant LiMn of nanometer point
20
4positive electrode dissolves in deionized water. and carrying out energy oscillations 24h. with processor for ultrasonic wave, to put into refrigerator freezing, moves into freeze drier afterwards and carry out freeze drying and namely obtain Graphene/spinelle LiMn
20
4nano composite material.
2. Graphene/spinelle LiMn as claimed in claim 1
2o
4nano-composite materials method, is characterized in that: in described Graphene preparation process, and described graphite oxide is adopt the Hummers legal system improved standby.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410744294.9A CN104617251A (en) | 2014-12-09 | 2014-12-09 | Preparation method for graphene/spinel LiMn2O4 nanometer composite material |
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|---|---|---|---|
| CN201410744294.9A CN104617251A (en) | 2014-12-09 | 2014-12-09 | Preparation method for graphene/spinel LiMn2O4 nanometer composite material |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108318551A (en) * | 2017-12-29 | 2018-07-24 | 北京科技大学 | A kind of hercynite composite material, hercynite composite material modified glassy carbon electrode and its preparation method and application |
| CN113851626A (en) * | 2021-09-23 | 2021-12-28 | 宁夏大学 | Element-doped and graphene-coated layered manganese-based sodium-ion battery positive electrode material and preparation method thereof |
-
2014
- 2014-12-09 CN CN201410744294.9A patent/CN104617251A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108318551A (en) * | 2017-12-29 | 2018-07-24 | 北京科技大学 | A kind of hercynite composite material, hercynite composite material modified glassy carbon electrode and its preparation method and application |
| CN108318551B (en) * | 2017-12-29 | 2019-06-11 | 北京科技大学 | A kind of hercynite composite material, hercynite composite material modified glassy carbon electrode and its preparation method and application |
| CN113851626A (en) * | 2021-09-23 | 2021-12-28 | 宁夏大学 | Element-doped and graphene-coated layered manganese-based sodium-ion battery positive electrode material and preparation method thereof |
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Application publication date: 20150513 |