CN107482202A - A kind of preparation method and applications of graphene/phosphoric acid hydrogen zirconium composite material - Google Patents
A kind of preparation method and applications of graphene/phosphoric acid hydrogen zirconium composite material Download PDFInfo
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- CN107482202A CN107482202A CN201710701421.0A CN201710701421A CN107482202A CN 107482202 A CN107482202 A CN 107482202A CN 201710701421 A CN201710701421 A CN 201710701421A CN 107482202 A CN107482202 A CN 107482202A
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- phosphoric acid
- graphene
- acid hydrogen
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- hydrogen zirconium
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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
- H01M4/364—Composites as mixtures
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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
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
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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
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
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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
The invention discloses a kind of preparation method and applications of graphene/phosphoric acid hydrogen zirconium composite material, after graphene is mixed with phosphoric acid hydrogen zirconium, the 10h of hydro-thermal reaction 2 under conditions of being 80 180 DEG C in temperature, then graphene/phosphoric acid hydrogen zirconium composite material is made through calcination processing.The graphene made from bying the use of/phosphoric acid hydrogen zirconium composite material of the invention can overcome battery material poorly conductive, the problem of Volumetric expansion is serious, with the characteristics of cyclical stability is strong, electric conductivity is strong as the negative material of lithium battery；This method has the characteristics of simple to operate, repeatability is high.
Description
Technical field
The invention belongs to technical field of lithium ion, and in particular to a kind of system of graphene/phosphoric acid hydrogen zirconium composite material
Preparation Method and its application.
Background technology
Lithium ion battery due to operating voltage is high, energy density is high, memory-less effect the advantages of and be widely used
In the small-sized movable electronics field such as video camera, mobile phone, notebook computer, and in the field such as power electric and energy-storage battery pond
Also the development prospect to attract people's attention is shown.It is but fast with the aggravation of energy crisis and portable electric appts and Electric power car
Speed increases, and commercial Li-ion battery graphite cathode material can not meet the needs of its people at present.
2004, the physicist An Deliehaimu and Constantine's Nuo Woxiao loves of Univ Manchester UK,
By simple mechanical stripping method successfully isolated from graphite can individualism two-dimentional carbonizable substance --- graphene, and
Its property is measured and characterized, shows its superior physical property, so as to start the prelude of graphene research.Two
Therefore scientist also obtains Nobel Prize in physics in 2010.Carbon as the newest form after fullerene, CNT is received
Rice material, graphene is since being reported, due to a series of novel physicochemical properties, such as ultrafast charge migration speed
Mechanical strength of degree, huge specific surface area and superelevation etc., is widely used in the electrochemical fields such as ultracapacitor, electro-catalysis.
Phosphoric acid hydrogen zirconium and the compound electric conductivity that can not only improve battery of graphene, improve its Volumetric expansion, simultaneously
Also there is good storage lithium ability, by increasing capacitance it is possible to increase the specific capacity of composite.Compared with other carbon materials, graphene has than table
The advantages that area is big, high mechanical strength, good conductivity, to SnO2、FeSb2Research Deng material shows, passes through the introducing of graphene
Its chemical property can be effectively improved.
The content of the invention
It is an object of the invention in view of the shortcomings of the prior art, providing a kind of system of graphene/phosphoric acid hydrogen zirconium composite material
Preparation Method and its application.Negative material by the use of phosphoric acid hydrogen zirconium prepared by the present invention with graphene composite material as lithium battery,
Battery material poorly conductive can be overcome, the problem of Volumetric expansion is serious, there is the spy that cyclical stability is strong, electric conductivity is strong
Point；This method has the characteristics of simple to operate, repeatability is high.
In order to achieve the above object, the technical scheme taken of the present invention is：
A kind of preparation method of graphene/phosphoric acid hydrogen zirconium composite material, specifically includes following steps：
（1）0.0080-0.0800g graphene oxide is taken to be added in 80ml solvents, mixture is put into supersonic frequency is
Supersound process 0.5-3h is carried out in 40kHz ultrasonic washing instrument, obtains graphene oxide dispersion；
（2）0.0020-0.3000g phosphoric acid hydrogen zirconium is taken to be added to step（1）In obtained graphene oxide dispersion, stirring
Uniformly；
（3）By step（2）Gained mixed solution is transferred in 100ml hydrothermal reaction kettles, under conditions of temperature is 80-180 DEG C
2-10h is reacted, reaction end treats that nature is down to room temperature, then carries out vacuum drying treatment；
（4）By step（3）Gained composite carries out calcination processing under an inert atmosphere, and calcining is cooled to room temperature after terminating, i.e.,
The graphene/phosphoric acid hydrogen zirconium composite material is made.
Step（1）The solvent is any one in deionized water, absolute ethyl alcohol, ethylene glycol and diethylene glycol.
Step（3）The vacuum drying treatment is under the conditions of temperature is 60-100 DEG C, is dried in vacuo 8-16h.
Step（4）The inert atmosphere is Ar or N2Atmosphere.
Step（4）The calcination processing process is：Heated up with 2-10 DEG C/m in heating rate, be warming up to 300-
800 DEG C, calcine 1-10h.
Graphene made from the above method/phosphoric acid hydrogen zirconium composite material is used for the negative material of lithium battery.
The present invention operation principle be：
The present invention prepares graphene/phosphoric acid hydrogen zirconium composite material using solvent-thermal method, and control solvent thermal reaction condition can obtain shape
The controllable phosphoric acid hydrogen zirconium nano material of looks, at the same in solution graphene presence, the original position of generation graphene can be made to be attached to phosphorus
Sour hydrogen zirconium surface obtains phosphoric acid hydrogen zirconium and graphene composite material, through calcination processing, enables graphene in the crystalline substance of phosphoric acid hydrogen zirconium
Lacking oxygen is formed in lattice, so as to increase carrier number and lattice defect, improves electric conductivity.The presence of graphene makes phosphoric acid hydrogen zirconium
Conductive network is formed between nano particle, is advantageous to improve the overall electric conductivity of material, while graphene coats as fexible film
On phosphoric acid hydrogen zirconium surface, the Volumetric expansion in its charge and discharge process can be buffered.
The beneficial effects of the present invention are：
The preparation method of the present invention has easy to operation, and repeatability is strong, and cost is low, it is environmentally safe the characteristics of.Profit
It can overcome battery conductive as the negative material of lithium battery with graphene composite material by the use of phosphoric acid hydrogen zirconium prepared by this method
Difference, the problem of Volumetric expansion is serious, there is the characteristics of cyclical stability is strong, electric conductivity is strong.Due to graphene have it is high
Conductance and big specific surface area, battery composite material electric conductivity can be effectively improved, while the cladding of graphene can be effective
Improve battery composite material Volumetric expansion, improve the chemical property of battery composite material, this method have it is simple to operate,
The characteristics of repeatable high, cost is cheap.
Brief description of the drawings
Fig. 1 be the composite for preparing of the present invention as lithium ion battery negative material when charge graph.
Embodiment
Below in conjunction with specific embodiment, the present invention will be further described, but the present invention is not limited only to these embodiments.
Embodiment 1
Weigh 8mg graphene oxides to be added in 80ml deionized waters, mixture is put into the ultrasonic wave that supersonic frequency is 40kHz
Supersound process 2h is carried out in cleaning device, obtains graphene oxide dispersion；Weigh 26mg phosphoric acid hydrogen zirconiums be added to it is obtained above
After being stirred in graphene oxide dispersion, above-mentioned mixed solution is transferred in 100ml hydrothermal reaction kettles, is in temperature
2h is reacted in the environment of 180 DEG C, reaction end treats that nature is down to room temperature, then under the conditions of temperature is 60 DEG C, vacuum drying
15h；Gained composite under an ar atmosphere, is risen to after 300 DEG C with 2 DEG C/min heating rate and calcines 10h after drying, and is calcined
After end naturally cools to room temperature, graphene/phosphoric acid hydrogen zirconium composite material is obtained.Embodiment 2
Weigh 8mg graphene oxides to be added in 80ml ethanol, it is clear that mixture is put into the ultrasonic wave that supersonic frequency is 40kHz
Wash and supersound process 1h is carried out in instrument, obtain graphene oxide dispersion；Weigh 26mg phosphoric acid hydrogen zirconiums and be added to oxygen obtained above
After being stirred in graphite alkene dispersion liquid, above-mentioned mixed solution is transferred in 100ml hydrothermal reaction kettles, is 180 in temperature
2h is reacted in the environment of DEG C, reaction end treats that nature is down to room temperature, then under the conditions of temperature is 60 DEG C, is dried in vacuo 15h；Will
Gained composite under an ar atmosphere, is risen to after 700 DEG C with 10 DEG C/min heating rate and calcines 1h after drying, and calcining terminates certainly
After being so cooled to room temperature, graphene/phosphoric acid hydrogen zirconium composite material is obtained.
Embodiment 3
Weigh 8mg graphene oxides to be added in 80ml ethylene glycol, it is clear that mixture is put into the ultrasonic wave that supersonic frequency is 40kHz
Wash and supersound process 1h is carried out in instrument, obtain graphene oxide dispersion；Weigh 26mg phosphoric acid hydrogen zirconiums and be added to oxygen obtained above
After being stirred in graphite alkene dispersion liquid, above-mentioned mixed solution is transferred in 100ml hydrothermal reaction kettles, is 180 in temperature
2h is reacted in the environment of DEG C, reaction end treats that nature is down to room temperature, then under the conditions of temperature is 90 DEG C, is dried in vacuo 6h；Will
Gained composite under an ar atmosphere, is risen to after 800 DEG C with 10 DEG C/m in heating rate and calcines 1h, calcining terminates after drying
After naturally cooling to room temperature, graphene/phosphoric acid hydrogen zirconium composite material is obtained.
Embodiment 4
Weigh 80mg graphene oxides to be added in 80ml diethylene glycols, mixture is put into the ultrasound that supersonic frequency is 40kHz
Supersound process 3h is carried out in ripple cleaning device, obtains graphene oxide dispersion；Weigh 300mg phosphoric acid hydrogen zirconiums and be added to above-mentioned be made
Graphene oxide dispersion in stir after, above-mentioned mixed solution is transferred in 100ml hydrothermal reaction kettles, is in temperature
10h is reacted in the environment of 150 DEG C, reaction end treats that nature is down to room temperature, then under the conditions of temperature is 90 DEG C, vacuum drying
6h；Gained composite under an ar atmosphere, is risen to after 800 DEG C with 10 DEG C/m in heating rate and calcines 1h, forged after drying
After sintering beam naturally cools to room temperature, graphene/phosphoric acid hydrogen zirconium composite material is obtained.
Embodiment 5
Weigh 40mg graphene oxides to be added in 80ml deionized waters, mixture is put into the ultrasound that supersonic frequency is 40kHz
Supersound process 1h is carried out in ripple cleaning device, obtains graphene oxide dispersion；Weigh 150mg phosphoric acid hydrogen zirconiums and be added to above-mentioned be made
Graphene oxide dispersion in stir after, above-mentioned mixed solution is transferred in 100ml hydrothermal reaction kettles, in temperature
To react 6h in the environment of 140 DEG C, reaction end treats that nature is down to room temperature, then under the conditions of temperature is 90 DEG C, vacuum drying
6h；Gained composite will be dried in N2Under atmosphere, risen to 5 DEG C/min heating rate after 700 DEG C and calcine 5h, calcining terminates
After naturally cooling to room temperature, graphene/phosphoric acid hydrogen zirconium composite material is obtained.
Fig. 1 be the composite for preparing of the present invention as lithium ion battery negative material when charge graph.By that can be seen in figure
It is only 297mAh/g to go out pure zinc oxide initial charge specific capacity, and specific capacity is close to after charge and discharge cycles three times
0mAh/g, and the initial charge specific capacity of graphene/phosphoric acid hydrogen zirconium composite material reaches 690mAh/g, after 50 circulations
Specific capacity remains to be maintained at 250mAh/g, illustrates to obtain with preferable chemical property by suitable control reaction condition
Phosphoric acid hydrogen zirconium and graphene composite material.
The foregoing is only presently preferred embodiments of the present invention, all equivalent changes done according to scope of the present invention patent with
Modification, it should all belong to the covering scope of the present invention.
Claims (7)
- A kind of 1. preparation method of graphene/phosphoric acid hydrogen zirconium composite material, it is characterised in that：Specifically include following steps：（1）Take 0.0080-0.0800g graphene oxide to be added in 80ml solvents, be ultrasonically treated 0.5-3h, obtain oxidation stone Black alkene dispersion liquid；（2）0.0020-0.3000g phosphoric acid hydrogen zirconium is taken to be added to step（1）In obtained graphene oxide dispersion, stirring is equal It is even；（3）By step（2）Gained mixed solution is transferred in 100ml hydrothermal reaction kettles, under conditions of temperature is 80-180 DEG C 2-10h is reacted, reaction end treats that nature is down to room temperature, then carries out vacuum drying treatment；（4）By step（3）Gained composite carries out calcination processing under an inert atmosphere, and calcining is cooled to room temperature after terminating, i.e., The graphene/phosphoric acid hydrogen zirconium composite material is made.
- 2. the preparation method of graphene according to claim 1/phosphoric acid hydrogen zirconium composite material, it is characterised in that：Step（1） Described in solvent be deionized water, absolute ethyl alcohol, ethylene glycol and diethylene glycol in any one.
- 3. the preparation method of graphene according to claim 1/phosphoric acid hydrogen zirconium composite material, it is characterised in that：Step（1） In supersonic frequency be 40kHZ.
- 4. the preparation method of graphene according to claim 1/phosphoric acid hydrogen zirconium composite material, it is characterised in that：Step（3） The technological parameter of middle vacuum drying treatment is：60-100 DEG C of drying temperature, drying time 8-16h.
- 5. the preparation method of graphene according to claim 1/phosphoric acid hydrogen zirconium composite material, it is characterised in that：Step（4） Described in inert atmosphere be Ar or N2Atmosphere.
- 6. the preparation method of graphene according to claim 1/phosphoric acid hydrogen zirconium composite material, it is characterised in that：Step（4） Middle calcination processing process is：Heated up with 2-10 DEG C/min heating rate, be warming up to 300-800 DEG C, calcine 1-10h.
- 7. the application of graphene/phosphoric acid hydrogen zirconium composite material, its feature made from a kind of preparation method as claimed in claim 1 It is：The graphene/phosphoric acid hydrogen zirconium composite material is used for the negative material of lithium battery.
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| CN201710701421.0A CN107482202A (en) | 2017-08-16 | 2017-08-16 | A kind of preparation method and applications of graphene/phosphoric acid hydrogen zirconium composite material |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109364870A (en) * | 2018-10-22 | 2019-02-22 | 天津工业大学 | A kind of resistance to extreme condition layered phosphates foamed material and its preparation method and application |
| CN114243039A (en) * | 2022-02-28 | 2022-03-25 | 浙江高成绿能科技有限公司 | High-temperature-resistant composite carrier, catalyst for fuel cell and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
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2017
- 2017-08-16 CN CN201710701421.0A patent/CN107482202A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
Non-Patent Citations (1)
| Title |
|---|
| HUI QIAO等: ""One-pot synthesis of spring-like superstructures consisting of layered tin(IV) hydrogen phosphate nanodisks"", 《CHEM.COMMUN.》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109364870A (en) * | 2018-10-22 | 2019-02-22 | 天津工业大学 | A kind of resistance to extreme condition layered phosphates foamed material and its preparation method and application |
| CN114243039A (en) * | 2022-02-28 | 2022-03-25 | 浙江高成绿能科技有限公司 | High-temperature-resistant composite carrier, catalyst for fuel cell and preparation method thereof |
| CN114243039B (en) * | 2022-02-28 | 2022-05-27 | 浙江高成绿能科技有限公司 | High-temperature-resistant composite carrier, catalyst for fuel cell and preparation method of catalyst |
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Application publication date: 20171215 |