CN108767217A - A kind of orienting stephanoporate LiFePO4-graphene composite material and preparation method thereof - Google Patents
A kind of orienting stephanoporate LiFePO4-graphene composite material and preparation method thereof Download PDFInfo
- Publication number
- CN108767217A CN108767217A CN201810463023.4A CN201810463023A CN108767217A CN 108767217 A CN108767217 A CN 108767217A CN 201810463023 A CN201810463023 A CN 201810463023A CN 108767217 A CN108767217 A CN 108767217A
- Authority
- CN
- China
- Prior art keywords
- lifepo4
- composite material
- graphene composite
- orienting stephanoporate
- solution
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- 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
-
- 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
-
- 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
-
- 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
-
- 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
-
- 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 present invention relates to a kind of orienting stephanoporate LiFePO4-graphene composite materials and preparation method thereof.Its technical solution is：By molysite: the mass ratio of graphene oxide is 1: graphene oxide is added in the molysite aqueous solution of a concentration of 0.5~2mol/L by (0.2~2.6), ultrasonic agitation, obtained solution I.By molysite: the amount ratio of the substance of phosphoric acid is 1: 1, is added phosphoric acid in solution I, stir, obtained solution II.By molysite: the amount ratio of the substance of lithium salts is 1: 1, and Aqueous Lithium Salts are added in solution II, it is stirred by ultrasonic, obtained solution III.Solution III is freezed in directional freezing device, it is dry in vacuum freeze drier, it is kept the temperature under the conditions of protective atmosphere and 600~750 DEG C, furnace cooling obtains orienting stephanoporate LiFePO4-graphene composite material.Present invention process is simple and convenient to operate, with short production cycle and morphology controllable；Made product is in three-dimensional orientation porous structure, aperture and pore wall thickness uniform, controllable, electrochemical performance.
Description
Technical field
The invention belongs to LiFePO4-graphene composite material technical fields.More particularly to a kind of orienting stephanoporate ferric phosphate
Lithium-graphene composite material and preparation method thereof.
Background technology
Currently, energy conservation and environmental protection becomes the theme in epoch, it is gradual that solar energy, wind energy, tide energy etc. clean reborn type energy
Replace the high pollutions non-renewable energy such as traditional coal, oil, natural gas, however, but there is discontinuities for these novel energies
With instable defect, its practical application is caused to be restricted, therefore, energy conversion and efficient storage is carried out to the renewable sources of energy
Become particularly important.As efficient energy conversion device, lithium ion battery (LIB) is widely used to the energy, dynamic field
And the field 3C electronic products (Computer, Communication and Consumer Electronic), its performance and cost
Depend primarily on positive electrode.Wherein, olivine-type LiFePO4 is because theoretical specific capacity is high, at low cost, cyclical stability and peace
Full the advantages that haveing excellent performance, shows one's talent in numerous positive electrodes.However, lower ion diffusion rates and electronic conductivity
The performance for hindering LiFePO4 high rate performance greatly limits use of the LiFePO 4 material in power battery field, for
The modification of LiFePO4 inherent shortcoming, Chinese and overseas scholars have carried out many work.
Currently, the modification mode of LiFePO4 mainly have particle size nanosizing, porous topographic design, carbon coating, sun from
Son doping etc., wherein lithium iron phosphate particles nanosizing can be obviously improved to the specific discharge capacity of material.But nano-particle
Chemism is higher, easily reunites, and is unfavorable for promoting the cyclical stability of material.It is three-dimensional mutually compared with nanosizing LiFePO4
The LiFePO4 of porous structure is expected to because of its larger specific surface area, higher volume energy density and power density in power electric
It is used widely in pond field.Currently, preparation generally use soft template method, hard template method and the non-template of porous calcium phosphate iron lithium
Method.
Non-template method synthesis technology is simply and easy to operate, but the hole formed is mostly confusing；Used in soft template method
Template removal is convenient, and the LiFePO4 electric conductivity that the agraphitic carbon generated after template pyrolysis can be promoted, however, ferric phosphate
Lithium crystallization temperature is higher, and soft template is just decomposed at a lower temperature, therefore, it is impossible to continue to support porous under high temperature
Easily there is hole and caves in phenomenon in structure.
The template used rigidity of hard template method is big, hole can be avoided to cave in problem well, and from being conducive to prepare three-dimensional porous
Material, but the template needed for hard template method need to be prepared in advance, virtually so that technique is complicated, increase material
Synthesis cost, and template removal is not thorough, and is easily introduced byproduct.
Invention content
The present invention is directed to overcome prior art defect, it is therefore an objective to provide a kind of simple for process, easy to operate, with short production cycle
With the preparation method of orienting stephanoporate LiFePO4-graphene composite material of morphology controllable；The orienting stephanoporate prepared with this method
LiFePO4-graphene composite material is in three-dimensional orientation porous structure, and aperture and pore wall thickness uniform, controllable, chemical property are excellent
It is different.
To achieve the above object, the technical solution adopted by the present invention comprises the concrete steps that：
(1) molysite is pressed: the mass ratio of graphene oxide is 1: the graphene oxide is added to by (0.2~2.6)
In the molysite aqueous solution of a concentration of 0.5~2mol/L, 0.5~1.5h is stirred by ultrasonic, obtains solution I.
(2) it presses the molysite: the amount ratio of the substance of phosphoric acid is 1: 1, and the phosphoric acid is added in the solution I, stirs
20~40min obtains solution II.
(3) molysite is pressed: the amount ratio of the substance of lithium salts is 1: 1, and the Aqueous Lithium Salts of a concentration of 4mol/L are added to
In the solution II, 30~40min is stirred by ultrasonic, obtains solution III.
(4) solution III is placed in directional freezing device, 20~40min is freezed, in vacuum freeze drier
Dry 36~72h, obtains column xerogel.
(5) the column xerogel is placed in tube-type atmosphere furnace, 8 is kept the temperature under the conditions of protective atmosphere and 600~750 DEG C
~10h, furnace cooling obtain orienting stephanoporate LiFePO4-graphene composite material.
Orienting stephanoporate LiFePO4-the graphene composite material is orienting stephanoporate structure, and hole aligns, hole
Hole wall is accumulated by lithium iron phosphate nano particle and graphene to be formed, and nano-pore is distributed in the hole wall of hole.
The molysite is one kind in ironic citrate, two oxalic acid hydrates ferrous iron and green vitriol.
The lithium salts is one kind in lithium dihydrogen phosphate, two water lithium acetates and Lithium hydroxide monohydrate.
The directional freezing device includes low temperature resistant container, copper post and pipe；In the bottom centre position of low temperature resistant container
Place is provided with copper post, and the copper post is the entirety that big cylinder and small cylinder coaxial line form, solid on the cylindrical surface of small cylinder
Surely there is pipe, sealing ring is equipped between the annular surface of copper post and the lower face of pipe；In use, liquid nitrogen is housed in low temperature resistant container,
The solution III is placed in pipe.
The protective atmosphere be argon gas or be the mixed gas of nitrogen and hydrogen or be argon gas and hydrogen mixed gas.
Due to the adoption of the above technical scheme, the present invention has following product compared with the existing technology for preparing LiFePO 4 material
Pole effect：
1, the present invention, can be to prepared orienting stephanoporate LiFePO4-stone by the addition of change graphene oxide
The aperture of black alkene composite material and the thickness of hole wall carry out Effective Regulation, and prepared orienting stephanoporate LiFePO4-graphene is multiple
Condensation material aperture is 135~175nm, and pore wall thickness is 15~35nm.
2, the three-dimensional orientation porous structure of orienting stephanoporate LiFePO4-graphene composite material prepared by the present invention is ice
Crystalline substance is along temperature gradient direction oriented growth, then structure that is vacuum dried and being formed.Liquid nitrogen in low-temperature resistant plastic container
Low temperature is reached to the intersection of copper post and solution III via copper post, solution III starts to crystallize in interface, forms small ice crystal, and edge
The surface of temperature gradient direction oriented growth to III, pipe is avoided that III ambient outside temperature of solution to being generated in refrigerating process
Influence, ensure orientation refrigerating process ice-crystal growth consistency.
The porous structure of three-dimensional orientation can effectively facilitate infiltration of the electrolyte to electrode material, be provided for lithium ion transport
The channel of orientation shortens ion diffusion path.Two-dimensional graphene thin slice is embedded in porous hole wall lamella, serves as LiFePO4
The bridge of electronics transfer between nano particle, and larger specific surface area can also provide more reactivity sites for ion, have
Conducive to the specific capacity and high rate performance of promotion material.Meanwhile the presence of nano-pore can effectively alleviate charge and discharge on hole wall lamella
In the process caused by volume expansion material structure destruction.
3, the present invention using directional freezing device and combines subsequent drying and heat treatment process to can be prepared by orienting stephanoporate
LiFePO4-graphene composite material.Without additionally preparing template, meanwhile, it can be sloughed well by vacuum freeze drying
The ice crystal of oriented growth, during heat treatment, three-dimensional orientation porous structure can also be maintained well.
Therefore, present invention process be simple and convenient to operate, with short production cycle and morphology controllable；Prepared orienting stephanoporate phosphorus
Sour iron lithium-graphene composite material is in three-dimensional orientation porous structure, and aperture and pore wall thickness uniform, controllable, chemical property are excellent
It is different.
Description of the drawings
Fig. 1 is the structural schematic diagram for a kind of directional freezing device of the present invention；
Fig. 2 is the use state diagram of directional freezing device shown in Fig. 1；
Fig. 3 is a kind of XRD diagram of orienting stephanoporate LiFePO4-graphene composite material prepared by the present invention；
Fig. 4 is the low range SEM figures of orienting stephanoporate LiFePO4-graphene composite material shown in Fig. 3；
Fig. 5 is the high magnification SEM figures of orienting stephanoporate LiFePO4-graphene composite material shown in Fig. 3.
Specific implementation mode
The invention will be further described with reference to the accompanying drawings and detailed description, not to the limit of its protection domain
System.
Embodiment 1
A kind of orienting stephanoporate LiFePO4-graphene composite material and preparation method thereof.The preparation method is：
(1) molysite is pressed: the mass ratio of graphene oxide is 1: the graphene oxide is added to by (0.2~1.0)
In the molysite aqueous solution of a concentration of 0.5~2mol/L, 0.5~1.5h is stirred by ultrasonic, obtains solution I.
(2) it presses the molysite: the amount ratio of the substance of phosphoric acid is 1: 1, and the phosphoric acid is added in the solution I, stirs
20~40min obtains solution II.
(3) molysite is pressed: the amount ratio of the substance of lithium salts is 1: 1, and the Aqueous Lithium Salts of a concentration of 4mol/L are added to
In the solution II, 30~40min is stirred by ultrasonic, obtains solution III.
(4) solution III is placed in directional freezing device, 20~40min is freezed, in vacuum freeze drier
Dry 36~48h, obtains column xerogel.
(5) the column xerogel is placed in tube-type atmosphere furnace, 8 is kept the temperature under the conditions of protective atmosphere and 600~650 DEG C
~10h, furnace cooling obtain orienting stephanoporate LiFePO4-graphene composite material.
Orienting stephanoporate LiFePO4-the graphene composite material is orienting stephanoporate structure, and hole aligns, hole
Hole wall is accumulated by lithium iron phosphate nano particle and graphene to be formed, and nano-pore is distributed in the hole wall of hole.
As shown in Figure 1, the directional freezing device includes low temperature resistant container (3), copper post (2) and pipe (1).Low temperature resistant
Copper post (2) is provided at the bottom centre position of container (3), the copper post (2) is that big cylinder and small cylinder coaxial line form
Entirety, be fixed with pipe (1) on the cylindrical surface of small cylinder, be equipped between the annular surface and the lower face of pipe (1) of copper post (2)
Sealing ring.As shown in Fig. 2, in use, being equipped with liquid nitrogen (4) in low temperature resistant container (3), the solution III (5) is placed in pipe (1)
It is interior.
The molysite is ironic citrate；The lithium salts is lithium dihydrogen phosphate；The protective atmosphere is argon gas.
Fig. 3 is a kind of XRD diagram of orienting stephanoporate LiFePO4-graphene composite material manufactured in the present embodiment；Fig. 4 is figure
The low range SEM figures of product shown in 3；Fig. 5 is the high magnification SEM figures of product shown in Fig. 3.As seen from Figure 3, product is pure
Phase lithium iron phosphate material, no miscellaneous peak.Prepared orienting stephanoporate LiFePO4-graphene is compound it can be seen from Fig. 4 and Fig. 5
Material even aperture distribution, hole wall lamellar spacing are about 18.8nm, and nano-pore aperture is about 161.8nm.
Orienting stephanoporate LiFePO4-graphene composite material manufactured in the present embodiment is pure phase LiFePO 4 material, orientation
Porous calcium phosphate iron lithium-graphene composite material even aperture distribution, aperture are 155~175nm, and pore wall thickness is 15~25nm.
Embodiment 2
A kind of orienting stephanoporate LiFePO4-graphene composite material and preparation method thereof.The preparation method is：
(1) molysite is pressed: the mass ratio of graphene oxide is 1: the graphene oxide is added to by (1.0~1.8)
In the molysite aqueous solution of a concentration of 0.5~2mol/L, 0.5~1.5h is stirred by ultrasonic, obtains solution I.
(2) it presses the molysite: the amount ratio of the substance of phosphoric acid is 1: 1, and the phosphoric acid is added in the solution I, stirs
20~40min obtains solution II.
(3) molysite is pressed: the amount ratio of the substance of lithium salts is 1: 1, and the Aqueous Lithium Salts of a concentration of 4mol/L are added to
In the solution II, 30~40min is stirred by ultrasonic, obtains solution III.
(4) solution III is placed in directional freezing device, 20~40min is freezed, in vacuum freeze drier
Dry 48~60h, obtains column xerogel.
(5) the column xerogel is placed in tube-type atmosphere furnace, 8 is kept the temperature under the conditions of protective atmosphere and 650~700 DEG C
~10h, furnace cooling obtain orienting stephanoporate LiFePO4-graphene composite material.
Orienting stephanoporate LiFePO4-the graphene composite material is orienting stephanoporate structure, and hole aligns, hole
Hole wall is accumulated by lithium iron phosphate nano particle and graphene to be formed, and nano-pore is distributed in the hole wall of hole.
The directional freezing device and its use are the same as embodiment 1.
The molysite is that two oxalic acid hydrates are ferrous；The lithium salts is two water lithium acetates；The protective atmosphere is nitrogen and hydrogen
The mixed gas of gas.
Orienting stephanoporate LiFePO4-graphene composite material manufactured in the present embodiment is pure phase LiFePO 4 material, orientation
Porous calcium phosphate iron lithium-graphene composite material even aperture distribution, aperture are 145~165nm, and pore wall thickness is 20~30nm.
Embodiment 3
A kind of orienting stephanoporate LiFePO4-graphene composite material and preparation method thereof.The preparation method is：
(1) molysite is pressed: the mass ratio of graphene oxide is 1: the graphene oxide is added to by (1.8~2.6)
In the molysite aqueous solution of a concentration of 0.5~2mol/L, 0.5~1.5h is stirred by ultrasonic, obtains solution I.
(2) it presses the molysite: the amount ratio of the substance of phosphoric acid is 1: 1, and the phosphoric acid is added in the solution I, stirs
20~40min obtains solution II.
(3) molysite is pressed: the amount ratio of the substance of lithium salts is 1: 1, and the Aqueous Lithium Salts of a concentration of 4mol/L are added to
In the solution II, 30~40min is stirred by ultrasonic, obtains solution III.
(4) solution III is placed in directional freezing device, 20~40min is freezed, in vacuum freeze drier
Dry 60~72h, obtains column xerogel.
(5) the column xerogel is placed in tube-type atmosphere furnace, 8 is kept the temperature under the conditions of protective atmosphere and 700~750 DEG C
~10h, furnace cooling obtain orienting stephanoporate LiFePO4-graphene composite material.
Orienting stephanoporate LiFePO4-the graphene composite material is orienting stephanoporate structure, and hole aligns, hole
Hole wall is accumulated by lithium iron phosphate nano particle and graphene to be formed, and nano-pore is distributed in the hole wall of hole.
The directional freezing device and its use are the same as embodiment 1.
The molysite is green vitriol；The lithium salts is Lithium hydroxide monohydrate；The protective atmosphere be argon gas and
The mixed gas of hydrogen.
Orienting stephanoporate LiFePO4-graphene composite material manufactured in the present embodiment is pure phase LiFePO 4 material, orientation
Porous calcium phosphate iron lithium-graphene composite material even aperture distribution, aperture are 135~155nm, and pore wall thickness is 25~35nm.
Present embodiment has following good effect compared with the existing technology for preparing LiFePO 4 material：
1, present embodiment, can be to prepared orienting stephanoporate phosphoric acid by the addition of change graphene oxide
The aperture of iron lithium-graphene composite material and the thickness of hole wall carry out Effective Regulation, and made product is the LiFePO of pure phase4Material
Material, product are 3-D ordered multiporous structure, hole aligned orderly, uniform pore diameter.Aperture is 135~175nm, pore wall thickness 15
~35nm.
2, the three-dimensional orientation of orienting stephanoporate LiFePO4-graphene composite material prepared by present embodiment is porous
Structure is ice crystal along temperature gradient direction oriented growth, then structure that is vacuum dried and being formed.Mounted in low-temperature resistant plastic container
(3) low temperature is reached the intersection of copper post (2) and solution III (5) by the liquid nitrogen (4) in via copper post (2), and solution III (5) is at interface
Place starts to crystallize, and forms small ice crystal, and along temperature gradient direction oriented growth to the surface of III (5), pipe (1) is avoided that molten
Influence of liquid III (5) the ambient outside temperature to being generated in refrigerating process ensures the consistency of orientation refrigerating process ice-crystal growth.
The porous structure of three-dimensional orientation can effectively facilitate infiltration of the electrolyte to electrode material, be provided for lithium ion transport
The channel of orientation shortens ion diffusion path.Two-dimensional graphene thin slice is embedded in porous hole wall lamella, serves as LiFePO4
The bridge of electronics transfer between nano particle, and larger specific surface area can also provide more reactivity sites for ion, have
Conducive to the specific capacity and high rate performance of promotion material.Meanwhile the presence of nano-pore may effectively alleviate charge and discharge on hole wall lamella
In electric process caused by volume expansion material structure destruction.
3, present embodiment using directional freezing device and combines subsequent drying and heat treatment process can be prepared by
Orienting stephanoporate LiFePO4-graphene composite material.Without additionally preparing template, meanwhile, it can be very by vacuum freeze drying
The good ice crystal for sloughing oriented growth, during heat treatment, three-dimensional orientation porous structure can also be maintained well.
Therefore, present embodiment is simple for process, easy to operate, with short production cycle and morphology controllable；Prepared determines
It is in three-dimensional orientation porous structure, aperture and pore wall thickness uniform, controllable, electrochemistry to porous calcium phosphate iron lithium-graphene composite material
It has excellent performance.
Claims (6)
1. a kind of preparation method of orienting stephanoporate LiFePO4-graphene composite material, it is characterised in that the preparation method is：
(1) molysite is pressed: the mass ratio of graphene oxide is 1: the graphene oxide is added to concentration by (0.2~2.6)
In the molysite aqueous solution of 0.5~2mol/L, 0.5~1.5h to be stirred by ultrasonic, obtains solution I；
(2) molysite is pressed: the amount ratio of the substance of phosphoric acid is 1: 1, and the phosphoric acid is added in the solution I, stirring 20~
40min obtains solution II；
(3) it presses the molysite: the amount ratio of the substance of lithium salts is 1: 1, the Aqueous Lithium Salts of a concentration of 4mol/L is added to described
In solution II, 30~40min is stirred by ultrasonic, obtains solution III；
(4) solution III is placed in directional freezing device, freezes 20~40min, it is dry in vacuum freeze drier
36~72h obtains column xerogel；
(5) the column xerogel is placed in tube-type atmosphere furnace, under the conditions of protective atmosphere and 600~750 DEG C keep the temperature 8~
10h, furnace cooling obtain orienting stephanoporate LiFePO4-graphene composite material.
2. the preparation method of orienting stephanoporate LiFePO4-graphene composite material according to claim 1, it is characterised in that
The molysite is one kind in ironic citrate, two oxalic acid hydrates ferrous iron and green vitriol.
3. the preparation method of orienting stephanoporate LiFePO4-graphene composite material according to claim 1, it is characterised in that
The lithium salts is one kind in lithium dihydrogen phosphate, two water lithium acetates and Lithium hydroxide monohydrate.
4. the preparation method of orienting stephanoporate LiFePO4-graphene composite material according to claim 1, it is characterised in that
The directional freezing device includes low temperature resistant container (3), copper post (2) and pipe (1)；Bottom centre in low temperature resistant container (3)
Copper post (2) is provided at position, the copper post (2) is the entirety that big cylinder and small cylinder coaxial line form, in small cylinder
Cylindrical surface be fixed with pipe (1), between the annular surface and the lower face of pipe (1) of copper post (2) be equipped with sealing ring；In use, resistance to
Liquid nitrogen (4) is housed, the solution III (5) is placed in pipe (1) in low-temperature (low temperature) vessel (3).
5. the preparation method of orienting stephanoporate LiFePO4-graphene composite material according to claim 1, it is characterised in that
The protective atmosphere be argon gas or be the mixed gas of nitrogen and hydrogen or be argon gas and hydrogen mixed gas.
6. a kind of orienting stephanoporate LiFePO4-graphene composite material, it is characterised in that the orienting stephanoporate LiFePO4-graphite
Alkene composite material is the system according to any one of the Claims 1 to 5 item orienting stephanoporate LiFePO4-graphene composite material
Orienting stephanoporate LiFePO4-graphene composite material prepared by Preparation Method；
Orienting stephanoporate LiFePO4-the graphene composite material is orienting stephanoporate structure, and hole aligns, the hole wall of hole
It is accumulated and is formed by lithium iron phosphate nano particle and graphene, nano-pore is distributed in the hole wall of hole.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810463023.4A CN108767217B (en) | 2018-05-15 | 2018-05-15 | Directional porous lithium iron phosphate-graphene composite material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810463023.4A CN108767217B (en) | 2018-05-15 | 2018-05-15 | Directional porous lithium iron phosphate-graphene composite material and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108767217A true CN108767217A (en) | 2018-11-06 |
| CN108767217B CN108767217B (en) | 2021-04-16 |
Family
ID=64007748
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810463023.4A Active CN108767217B (en) | 2018-05-15 | 2018-05-15 | Directional porous lithium iron phosphate-graphene composite material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108767217B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109273707A (en) * | 2018-11-13 | 2019-01-25 | 武汉科技大学 | A kind of Nano Carbon ternary material and preparation method thereof |
| CN115265088A (en) * | 2022-06-24 | 2022-11-01 | 中国科学院空间应用工程与技术中心 | Directional freezing equipment and aerogel preparation method |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101941693A (en) * | 2010-08-25 | 2011-01-12 | 北京理工大学 | Graphene aerogel and preparation method thereof |
| CN102941042A (en) * | 2012-10-25 | 2013-02-27 | 北京理工大学 | Graphene/metal oxide hybrid aerogel, preparation method and applications thereof |
| CN105895865A (en) * | 2014-12-12 | 2016-08-24 | 江南大学 | Graphene/lithium salt composite material |
| CN106920931A (en) * | 2017-03-02 | 2017-07-04 | 武汉科技大学 | Loaded mesoporous lithium iron phosphate nano piece composite of graphene aerogel and preparation method thereof |
-
2018
- 2018-05-15 CN CN201810463023.4A patent/CN108767217B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101941693A (en) * | 2010-08-25 | 2011-01-12 | 北京理工大学 | Graphene aerogel and preparation method thereof |
| CN102941042A (en) * | 2012-10-25 | 2013-02-27 | 北京理工大学 | Graphene/metal oxide hybrid aerogel, preparation method and applications thereof |
| CN105895865A (en) * | 2014-12-12 | 2016-08-24 | 江南大学 | Graphene/lithium salt composite material |
| CN106920931A (en) * | 2017-03-02 | 2017-07-04 | 武汉科技大学 | Loaded mesoporous lithium iron phosphate nano piece composite of graphene aerogel and preparation method thereof |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109273707A (en) * | 2018-11-13 | 2019-01-25 | 武汉科技大学 | A kind of Nano Carbon ternary material and preparation method thereof |
| CN109273707B (en) * | 2018-11-13 | 2021-05-04 | 武汉科技大学 | Nano carbon composite ternary material and preparation method thereof |
| CN115265088A (en) * | 2022-06-24 | 2022-11-01 | 中国科学院空间应用工程与技术中心 | Directional freezing equipment and aerogel preparation method |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108767217B (en) | 2021-04-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Jin et al. | Facile synthesis of Fe-MOF/RGO and its application as a high performance anode in lithium-ion batteries | |
| Zhang et al. | Mesoporous Fe2O3 nanoparticles as high performance anode materials for lithium-ion batteries | |
| CN104993125B (en) | A kind of lithium ion battery negative material Fe3O4The preparation method of/Ni/C | |
| CN106229505A (en) | A kind of high-density spherical nano lithium iron phosphate material and preparation method thereof and the lithium ion battery comprising it | |
| CN106099110B (en) | A method of making carbon source using algae and prepares Li-S cell positive materials | |
| CN106025241B (en) | It is composite porous and preparation method thereof that graphene aerogel loads LiFePO4 | |
| CN106654192B (en) | Tin sulfide/graphene sodium-ion battery composite negative electrode material and preparation method thereof | |
| CN103579624B (en) | Modified lithium battery graphite crucible waste material negative material and preparation method thereof and application | |
| CN102044666A (en) | Method for preparing lithium iron phosphate composite material for lithium cells | |
| CN103326007A (en) | Preparation method and application of three-dimensional graphene-based stannic oxide composite material | |
| CN104882607A (en) | Anima bone base type graphene lithium ion battery negative electrode material and preparation method thereof | |
| CN103219491A (en) | Copper sulfide anode and preparation method thereof | |
| CN104466104A (en) | Germanium-graphene composite cathode material for lithium ion battery and preparation method thereof | |
| CN107601579B (en) | The preparation method and its resulting materials of a kind of high-performance porous C o-Mn-O nanometer sheet material and application | |
| CN104157832A (en) | Preparation method for electrode material of ferroferric oxide/carbon composite lithium ion battery | |
| CN109449390A (en) | A kind of iron oxide/graphene aerogel composite negative pole material and preparation method thereof | |
| CN106672935A (en) | Preparation method of nitrogen-doped hollow porous carbon | |
| CN105576220A (en) | Preparation method of porous carbon-coated lithium iron phosphate anode material | |
| CN104292100B (en) | Terephthalic acid calcium is as the application of lithium ion battery negative material | |
| CN105244503A (en) | Method for preparing graphene-grading-modification spherical sodium-ion battery electrode material | |
| CN104577126A (en) | Method for preparing MWCNT@a-C@Co9S8 composite electrode material with uniform morphology and application of material in lithium electrode | |
| CN103413918B (en) | A kind of synthetic method of anode material for lithium ion battery cobalt phosphate lithium | |
| CN104466110A (en) | Preparation method of high-performance lithium ion battery negative electrode material | |
| CN108767217A (en) | A kind of orienting stephanoporate LiFePO4-graphene composite material and preparation method thereof | |
| CN106532001A (en) | Preparation method of nitrogen-doping carbon substrate-supported Fe3O4 composite material sodium-ion battery negative electrode material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |