CN105826526A - Preparation method of MgO-ZnO-graphene composite material and application thereof in batteries - Google Patents
Preparation method of MgO-ZnO-graphene composite material and application thereof in batteries Download PDFInfo
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- CN105826526A CN105826526A CN201610164325.2A CN201610164325A CN105826526A CN 105826526 A CN105826526 A CN 105826526A CN 201610164325 A CN201610164325 A CN 201610164325A CN 105826526 A CN105826526 A CN 105826526A
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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
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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
- 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
- H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
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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
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
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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
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a preparation method of an MgO-ZnO-graphene composite material and application thereof in batteries.The composite material is prepared through a hydrothermal method.Test results show that the MgO-ZnO-graphene composite material can obtain higher first-time reversible specific capacity, and the capacity retention ratio of the composite material is kept to be 90% or above and the stability is good after 100 times of charging and discharging cycles.Thus it can be seen that the MgO-ZnO-graphene composite material has excellent charge-discharge cycle performance, the performance may be related to the weight part ratio of Zinc(NO3)2.6H2O to MgCl2 6H2O in a preparation method, and when the weight part ratio of the Zinc(NO3)2.6H2O to the MgCl2 6H2O is 7-9 to 1, the performance is best.
Description
Technical field
The invention belongs to energy field, relate to graphene battery material, be specifically related to a kind of MgO-ZnO-graphene composite material
Preparation method and application in the battery.
Background technology
Transition metal oxide, as 2～3 times that its theoretical specific capacity of lithium ion battery negative material is commercialization graphite, is current
The ideal candidates material of lithium ion battery for electric vehicle.Wherein zinc oxide (ZnO) compared with other metal-oxides (MO,
M=Fe, Co, Ni, V etc.), there is preparation cheap, easy and wider Zn-Li reaction potential (0～0.5V) etc.
Advantage, but ZnO is the most relatively fewer as the research of lithium ion battery negative material, except there is metal-oxide at Li+Embed/
Outside the common disadvantage that during abjection, bulk effect is big, electronics transport capacity poor for ZnO be also affect its application one important
Factor.There is scholar once to prepare the ZnO negative material of Herba Taraxaci shape, porous flake, attempt from special nanostructured ZnO
Storage lithium ability improves.Some scholar is then devoted to ZnO and other metals and metal-oxide is doped or is combined, and refers to
Go out mixed-metal oxides chemical property and be better than pure ZnO negative material.In addition, ZnO is combined with material with carbon element
Compare both the above method there is higher application potential, first material with carbon element to improve the conductivity of ZnO, and leading of being formed
Electric network can effectively buffer the bulk effect of ZnO, and secondly material with carbon element itself can improve the storage lithium ability of composite further.
The Electrochemical Properties of carbonization glucose, graphite and CNT and ZnO composite is it has been reported that and new carbon
Graphene is but the most just starting starting with the storage lithium performance study of ZnO composite.
Graphene is as a kind of novel low-dimensional material with carbon element, and under room temperature, electron mobility reaches 1.5 × 104cm2/ (V s), resistivity is about
10-6Ω cm, by its compound with metal-oxide can the electrical conductivity of significant increase respective electrode material, and then improve its discharge and recharge
And cycle performance；Meanwhile, Graphene theoretical specific surface area is up to 2630m2/ g, in conjunction with the conductive network shape structure of its " pliable and tough "
The material that can effectively suppress metal-oxide in charge and discharge process again to cause because of change in volume expands, efflorescence and gathering, and strengthens
And the conductive contact between collector and electrolyte.Additionally, Li+If adsorb in graphene sheet layer both sides, its theoretical specific capacity simultaneously
Up to 744mAh/g, the storage lithium specific capacity of composite can be improved further.Scholar is had to use two-step method first to prepare ZnO/
Graphene oxide, under 400 DEG C of reducing atmospheres, roasting obtains ZnO/ Graphene afterwards, and the compound of Graphene effectively improves ZnO
Chemical property.
But, the mankind are more and more higher for the performance requirement of battery, and current technology has been limited, it is necessary to exploitation performance
The most superior battery and relevant electrode material.
Summary of the invention
It is an object of the invention to provide the preparation method of a kind of MgO-ZnO-graphene composite material and answering in the battery thereof
With, for the battery that processability is excellent.
The above-mentioned purpose of the present invention is achieved by techniques below scheme:
The preparation method of a kind of MgO-ZnO-graphene composite material, comprises the steps:
Step S1, by Zn (NO3)2·6H2O and MgCl2·6H2The mixture of O is scattered in graphene oxide solution, ammonia
Regulation pH=11；The weight of described mixture is equal in weight with graphene oxide, Zn (NO in described mixture3)2·6H2O and
MgCl2·6H2The weight ratio of O is 7～9:1；
Step S2, moves into mixed liquor in stainless steel cauldron, 160～200 DEG C of reactions 8～12h, naturally cools to room temperature；
Step S3, is vacuum dried 10～14h at 50～70 DEG C after cleaning with deionized water.
Further, in the preparation method of described MgO-ZnO-graphene composite material, in described mixture
Zn(NO3)2·6H2O and MgCl2·6H2The weight ratio of O is 8:1.
Further, in the preparation method of described MgO-ZnO-graphene composite material, oxygen in described graphene oxide solution
The concentration of functionalized graphene is 0.5mg/mL.
Further, preparation method step S2 of described MgO-ZnO-graphene composite material is: moved into by mixed liquor stainless
In steel reactor, 180 DEG C of reaction 10h, naturally cool to room temperature.
Further, preparation method step S3 of described MgO-ZnO-graphene composite material is: after cleaning with deionized water
12h it is vacuum dried at 60 DEG C.
The application in the battery of above-mentioned MgO-ZnO-graphene composite material.
Advantages of the present invention:
The MgO-ZnO-graphene composite material that the present invention provides has the charge-discharge performance of excellence, and this performance may be with
Zn (NO in preparation method3)2·6H2O and MgCl2·6H2The weight ratio of O is relevant, as Zn (NO3)2·6H2O and
MgCl2·6H2When the weight ratio of O is between 7～9:1, performance is best.
Detailed description of the invention
Further illustrate the essentiality content of the present invention below in conjunction with embodiment, but do not limit scope with this.To the greatest extent
The present invention is explained in detail by pipe with reference to preferred embodiment, it will be understood by those within the art that, can be to the present invention
Technical scheme modify or equivalent, without deviating from the spirit and scope of technical solution of the present invention.
In the present invention, graphene oxide uses the Hummers method of improvement to prepare, and sees document Hummers, W.S., Jr.；
Offeman,R.E.J.Am.Chem.Soc.1958,80,1339。
The preparation of embodiment 1:MgO-ZnO-graphene composite material
Step S1, by 100mg Zn (NO3)2·6H2O and MgCl2·6H2It is 200ml that the mixture of O is scattered in concentration
In 0.5mg/mL graphene oxide solution, ammonia regulation pH=11；Zn (NO in described mixture3)2·6H2O and MgCl2·6H2O
Weight ratio be 8:1；
Step S2, moves into mixed liquor in stainless steel cauldron, 180 DEG C of reaction 10h, naturally cools to room temperature；
Step S3, is vacuum dried 12h with deionized water at 60 DEG C after cleaning.
The preparation of embodiment 2:MgO-ZnO-graphene composite material
Step S1, by 100mg Zn (NO3)2·6H2O and MgCl2·6H2It is 200ml that the mixture of O is scattered in concentration
In 0.5mg/mL graphene oxide solution, ammonia regulation pH=11；Zn (NO in described mixture3)2·6H2O and MgCl2·6H2O
Weight ratio be 7:1；
Step S2, moves into mixed liquor in stainless steel cauldron, 180 DEG C of reaction 10h, naturally cools to room temperature；
Step S3, is vacuum dried 12h with deionized water at 60 DEG C after cleaning.
The preparation of embodiment 3:MgO-ZnO-graphene composite material
Step S1, by 100mg Zn (NO3)2·6H2O and MgCl2·6H2It is 200ml that the mixture of O is scattered in concentration
In 0.5mg/mL graphene oxide solution, ammonia regulation pH=11；Zn (NO in described mixture3)2·6H2O and MgCl2·6H2O
Weight ratio be 9:1；
Step S2, moves into mixed liquor in stainless steel cauldron, 180 DEG C of reaction 10h, naturally cools to room temperature；
Step S3, is vacuum dried 12h with deionized water at 60 DEG C after cleaning.
The preparation of embodiment 4:MgO-ZnO-graphene composite material
Step S1, by 100mg Zn (NO3)2·6H2O and MgCl2·6H2It is 200ml that the mixture of O is scattered in concentration
In 0.5mg/mL graphene oxide solution, ammonia regulation pH=11；Zn (NO in described mixture3)2·6H2O and MgCl2·6H2O
Weight ratio be 6:1；
Step S2, moves into mixed liquor in stainless steel cauldron, 180 DEG C of reaction 10h, naturally cools to room temperature；
Step S3, is vacuum dried 12h with deionized water at 60 DEG C after cleaning.
The preparation of embodiment 5:MgO-ZnO-graphene composite material
Step S1, by 100mg Zn (NO3)2·6H2O and MgCl2·6H2It is 200ml that the mixture of O is scattered in concentration
In 0.5mg/mL graphene oxide solution, ammonia regulation pH=11；Zn (NO in described mixture3)2·6H2O and MgCl2·6H2O
Weight ratio be 10:1；
Step S2, moves into mixed liquor in stainless steel cauldron, 180 DEG C of reaction 10h, naturally cools to room temperature；
Step S3, is vacuum dried 12h with deionized water at 60 DEG C after cleaning.
Embodiment 6: effect example, electro-chemical test
Sample embodiment 1～5 prepared is as active substance, according to active substance: acetylene black: Kynoar (PVDF) quality
Ratio than 8: 1: 1 is ground uniformly in N-Methyl pyrrolidone (NMP), is then coated onto on Copper Foil, and 80 DEG C of vacuum are done
Dry 12h.With Cellgard-2400 type polypropylene screen as barrier film, 1M LiPF6Ethylene carbonate (EC) and dimethyl carbonate
(DMC) (volume ratio is 1: 1) solution is electrolyte, and metal lithium sheet is to electrode, at H2O、O2The content hands less than 0.5ppm
Casing is assembled into CR2032 type button half-cell.New Weir CT-3008 tester is used to test under 0.05A/g electric current density
Its charge-discharge performance, charging/discharging voltage interval is 0.01～2.5V (vs Li+/ Li), use Shanghai occasion China CHI660E type electrochemistry work
Be circulated volt-ampere and ac impedance measurement as station, sweep interval is 0.01～2.5V (vs Li+/Li), sweep speed is 0.1mV/s,
Frequency range is 10-2～105Hz。
Test result is following (under 50mA/g current density condition):
| Sample | Reversible specific capacity (mAh g first-1) | Capability retention (%) after 100 charge and discharge cycles |
| Embodiment 1 | 1180 | 99 |
| Embodiment 2 | 1060 | 94 |
| Embodiment 3 | 1040 | 92 |
| Embodiment 4 | 350 | 57 |
| Embodiment 5 | 370 | 63 |
Test result shows, the MgO-ZnO-graphene composite material that the present invention provides can obtain the most reversible higher specific volume
Amount, and after 100 charge and discharge cycles, capability retention more than 90%, good stability.As can be seen here, the present invention
There is provided MgO-ZnO-graphene composite material have excellence charge-discharge performance, this performance may with in preparation method
Zn(NO3)2·6H2O and MgCl2·6H2The weight ratio of O is relevant, as Zn (NO3)2·6H2O and MgCl2·6H2O
Weight ratio between 7～9:1 time, performance is best.
The effect of above-described embodiment indicates that the essentiality content of the present invention, but does not limit protection scope of the present invention with this.
It will be understood by those within the art that, technical scheme can be modified or equivalent, and not take off
Essence and protection domain from technical solution of the present invention.
Claims (6)
1. the preparation method of a MgO-ZnO-graphene composite material, it is characterised in that comprise the steps:
Step S1, by Zn (NO3)2·6H2O and MgCl2·6H2The mixture of O is scattered in graphene oxide solution, ammonia
Regulation pH=11；The weight of described mixture is equal in weight with graphene oxide, Zn (NO in described mixture3)2·6H2O and
MgCl2·6H2The weight ratio of O is 7～9:1；
Step S2, moves into mixed liquor in stainless steel cauldron, 160～200 DEG C of reactions 8～12h, naturally cools to room temperature；
Step S3, is vacuum dried 10～14h at 50～70 DEG C after cleaning with deionized water.
The preparation method of MgO-ZnO-graphene composite material the most according to claim 1, it is characterised in that: described mixed
Zn (NO in compound3)2·6H2O and MgCl2·6H2The weight ratio of O is 8:1.
The preparation method of MgO-ZnO-graphene composite material the most according to claim 2, it is characterised in that: described oxygen
In functionalized graphene solution, the concentration of graphene oxide is 0.5mg/mL.
The preparation method of MgO-ZnO-graphene composite material the most according to claim 3, it is characterised in that step S2
For: mixed liquor is moved in stainless steel cauldron, 180 DEG C of reaction 10h, naturally cool to room temperature.
The preparation method of MgO-ZnO-graphene composite material the most according to claim 4, it is characterised in that step S3
For: at 60 DEG C, it is vacuum dried 12h with deionized water after cleaning.
6. the arbitrary described MgO-ZnO-graphene composite material of Claims 1 to 5 application in the battery.
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| CN201610164325.2A CN105826526A (en) | 2016-03-22 | 2016-03-22 | Preparation method of MgO-ZnO-graphene composite material and application thereof in batteries |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2021087852A1 (en) * | 2019-11-07 | 2021-05-14 | 安徽锦华氧化锌有限公司 | Nano zinc oxide composite material used as negative electrode material of lithium-ion battery |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014047930A1 (en) * | 2012-09-29 | 2014-04-03 | East China University Of Science And Technology | Methods and compositions for making metal oxide-graphene composites |
| CN103985873A (en) * | 2014-05-19 | 2014-08-13 | 陕西科技大学 | Method of improving cycling stability of negative electrode material for lithium ion battery |
| CN104022268A (en) * | 2014-05-30 | 2014-09-03 | 陕西科技大学 | Preparation method of zinc oxide /graphene composite material for lithium ion battery |
| CN105047871A (en) * | 2015-06-18 | 2015-11-11 | 哈尔滨工业大学 | Doped lithium ion battery anode material and preparation method thereof |
| CN105336935A (en) * | 2015-12-01 | 2016-02-17 | 天津师范大学 | Preparing method and application of ZnO-Graphene lithium ion battery cathode material |
-
2016
- 2016-03-22 CN CN201610164325.2A patent/CN105826526A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014047930A1 (en) * | 2012-09-29 | 2014-04-03 | East China University Of Science And Technology | Methods and compositions for making metal oxide-graphene composites |
| CN103985873A (en) * | 2014-05-19 | 2014-08-13 | 陕西科技大学 | Method of improving cycling stability of negative electrode material for lithium ion battery |
| CN104022268A (en) * | 2014-05-30 | 2014-09-03 | 陕西科技大学 | Preparation method of zinc oxide /graphene composite material for lithium ion battery |
| CN105047871A (en) * | 2015-06-18 | 2015-11-11 | 哈尔滨工业大学 | Doped lithium ion battery anode material and preparation method thereof |
| CN105336935A (en) * | 2015-12-01 | 2016-02-17 | 天津师范大学 | Preparing method and application of ZnO-Graphene lithium ion battery cathode material |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2021087852A1 (en) * | 2019-11-07 | 2021-05-14 | 安徽锦华氧化锌有限公司 | Nano zinc oxide composite material used as negative electrode material of lithium-ion battery |
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