CN106816591A - A kind of preparation method of Graphene/lithium ferric phosphate/grapheme composite positive electrode material - Google Patents
A kind of preparation method of Graphene/lithium ferric phosphate/grapheme composite positive electrode material Download PDFInfo
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- CN106816591A CN106816591A CN201710060638.8A CN201710060638A CN106816591A CN 106816591 A CN106816591 A CN 106816591A CN 201710060638 A CN201710060638 A CN 201710060638A CN 106816591 A CN106816591 A CN 106816591A
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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
- 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
- H01M4/58—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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- 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 invention discloses a kind of preparation method of Graphene/lithium ferric phosphate/grapheme composite positive electrode material, it is skeleton using three-dimensional CVD Graphenes, using lithium hydroxide, lithium nitrate, or lithium acetate is lithium source, ferrous sulfate, ferrous acetate, or ferric nitrate is source of iron, phosphoric acid, or ammonium dihydrogen phosphate is phosphoric acid root, under the catalytic action of ethylenediamine, carry out hydro-thermal reaction, the temperature of hydro-thermal reaction is 160 DEG C 220 DEG C, the hydro-thermal reaction time is 8 16 hours, then calcining obtains Graphene/lithium ferric phosphate/grapheme composite positive electrode material in 8 hours at a temperature of 400 DEG C 800 DEG C again.Positive electrode of the invention specific discharge capacity in 1C is 150.9 mAh/g, and capability retention is 97.4% after 50 circulations.Sandwich structure Graphene/lithium ferric phosphate/grapheme composite positive electrode material is prepared by the present invention, excellent electrochemical performance is expected to obtain commercial application.
Description
Technical field
The invention belongs to materialogy field, it is related to field of lithium, specifically a kind of Graphene/LiFePO4/stone
The preparation method of black alkene composite positive pole.
Background technology
Since 1997, Goodenough etc. reported the LiFePO4 with olivine structural and can serve as lithium electricity first
Since pond, lithium iron phosphate positive material just causes extensive concern and substantial amounts of research.LiFePO4 has 170mAh/g's
Theoretical specific capacity and 3.5V to lithium charging platform, with traditional LiCoO2And LiMn2O4Lithium battery material is compared, and is had
Extensively, low cost, non-environmental-pollution, good cycle, heat endurance is good for raw material sources, the advantages of security performance is protruded, is
The preferable positive electrode of power type lithium ion battery.But because of the electronic conductivity and ionic conductance of the LiFePO4 of olivine structural
It is poor, in discharge and recharge, the diffusion coefficient very little of lithium ion, the reversible discharge capacity that causes material at room temperature is smaller, circulation
Poor-performing.
The current approach for solving the above problems mainly uses carbon material to be combined with LiFePO4, and to prepare carbon-LiFePO4 multiple
Positive electrode is closed, to improve the electric conductivity of LiFePO4, and then the chemical property of material is lifted.Adv. Mater. 2010,22, it is template that mesoporous carbon CMK-3 is utilized in 4944-4948 reports, mesoporous carbon CMK-3 is added and is dissolved with CH3COOLi：
(CH3COO)2Fe：NH4H2PO4 = 1：1：In 1 solution, it is stirred overnight, dries, calcining finally gives mesoporous carbon parcel phosphoric acid
The composite of iron lithium.The method can be obtained the material of excellent electrochemical performance, but mesoporous carbon CMK-3 preparation process used
It is cumbersome, improper industrialized production.
Recent graphene composite material causes extensive concern.Graphene has conduction higher compared with traditional carbon material
Property, and Graphene good mechanical property, specific surface area are bigger.Graphene is compound with LiFePO4 to be expected to further improve LiFePO4
The performance of positive electrode.J. Mater. Chem. A, Fe (NO are used in 2013,1,135-144 reports3)3·9H2O：
NH4H2PO4： LiNO3 = 1：1：In the 1.05 addition aqueous solution, add sucrose as carbon source, be subsequently adding redox graphene,
Ultrasound 2 hours, drying, high-temperature calcination obtain the LiFePO4 of graphene modified/（Carbon+redox graphene）Composite.
The method obtains that product uniformity is good, but Graphene is physical mixed effect to the package action of lithium iron phosphate/carbon.
The content of the invention：
It is compound just the invention provides a kind of Graphene/LiFePO4/Graphene for above-mentioned technical problem of the prior art
The preparation method of pole material, the preparation method of described this Graphene/lithium ferric phosphate/grapheme composite positive electrode material will be solved
The electronic conductivity and ionic conductance of LiFePO4 are poor in lithium ion battery in the prior art, in discharge and recharge, lithium ion
Diffusion coefficient very little, cause the technical problem that reversible discharge capacity is smaller, cycle performance is poor of material at room temperature.
The invention provides a kind of preparation method of Graphene/lithium ferric phosphate/grapheme composite positive electrode material, using three-dimensional
CVD Graphenes are skeleton, are lithium source, ferrous sulfate, ferrous acetate or nitre using lithium hydroxide, lithium nitrate or lithium acetate
Sour iron is source of iron, and phosphoric acid or ammonium dihydrogen phosphate are phosphoric acid root, under the catalytic action of ethylenediamine, carry out hydro-thermal reaction, water
The temperature of thermal response is 160 DEG C -220 DEG C, and the hydro-thermal reaction time is 8-16 hours, then again at a temperature of 400 DEG C -800 DEG C
Calcining obtains Graphene/lithium ferric phosphate/grapheme composite positive electrode material for -8 hours.
Further, in lithium source, source of iron and phosphoric acid root, the mol ratio of elemental lithium, ferro element and phosphate radical is 1：1：
1。
Further, in described Graphene/lithium ferric phosphate/grapheme composite positive electrode material, the quality of LiFePO4
Degree is 70% -90%, and the mass percentage content of Graphene is 30% -10%.
Further, the mass ratio of LiFePO4 is 0.5-1 in ethylenediamine and product:1.
Further, it is protective atmosphere that argon gas is used in the high-temperature burning process.
Further, the present invention with lithium hydroxide, lithium nitrate or lithium acetate as lithium source, ferrous sulfate, ferrous acetate,
Or ferric nitrate is source of iron, phosphoric acid or ammonium dihydrogen phosphate are phosphoric acid root, in graphene oxide solution according to elemental lithium,
The mol ratio of ferro element and phosphate radical is 1：1：1 adds lithium source, source of iron and phosphoric acid root, stirs to being completely dissolved, and adds three
Vc VD Graphene skeletons, are subsequently adding ethylenediamine as catalyst, and reaction obtains the graphite of three-dimensional self assembly in water-heat process
Alkene/LiFePO4/Graphene presoma, hydrothermal temperature is 160 DEG C -220 DEG C, and the hydro-thermal reaction time is 8-16 hours, will
Obtained Graphene/LiFePO4/Graphene presoma is washed, dried, and is positioned in tube furnace, under argon atmosphere,
Calcined 2-8 hours at 400 DEG C -800 DEG C, sandwich structure Graphene/lithium ferric phosphate/grapheme composite positive electrode material is obtained, its
In, Graphene mass percentage content 30%-10% in the product, LiFePO4 mass percentage content in the product is
70% - 90%。
The present invention uses three-dimensional CVD Graphenes as the carrier of LiFePO4, the graphene oxide microplate in water-heat process
Lithium iron phosphate particles are wrapped in the surface of three-dimensional CVD Graphenes.The present invention is conducive to improving the electric conductivity of LiFePO4 and changing
The cycle life of kind material.
The present invention is compared with prior art, and its technological progress is significant.The present invention is using three-dimensional CVD（Chemical vapor deposition
Product）Graphene as skeleton, with good electric conductivity, beneficial to the performance of Graphene performance.The present invention uses one step hydro thermal method
Catalyze and synthesize LiFePO4.The present invention can be carried out preferably using the self assembly behavior of graphene oxide to lithium iron phosphate particles
Parcel, beneficial to the performance of LiFePO4 cycle performance.Test shows, using the sandwich structure Graphene/phosphorus of present invention synthesis
Sour iron lithium/grapheme composite positive electrode material, specific discharge capacity is 150.9 mAh/g during 1C, and capability retention is after 50 circulations
97.4%.Sandwich structure Graphene/lithium ferric phosphate/grapheme composite positive electrode material is prepared by the present invention, chemical property is excellent
It is good, it is expected to obtain commercial application.
Brief description of the drawings
Fig. 1 is the XRD of the Graphene/lithium ferric phosphate/grapheme composite positive electrode material prepared by embodiment 1.
Fig. 2 is the SEM figures of the Graphene/lithium ferric phosphate/grapheme composite positive electrode material prepared by embodiment 1.
Fig. 3 is the 1C charging and discharging curves of Graphene/lithium ferric phosphate/grapheme composite positive electrode material prepared by embodiment 1.
Fig. 4 is the Graphene/lithium ferric phosphate/grapheme composite positive electrode material 1C cycle performance figures prepared by embodiment 1.
Specific embodiment
Below by embodiment and with reference to accompanying drawing, the present invention is described in detail, but is not intended to limit the present invention.
The electrochemical property test condition that following examples are used for：Voltage range 2.5V~4.2V, electrolyte is 1M
LiPF6/EC: DMC(1:1).It is metal lithium sheet to electrode, charging and discharging currents are 170mA/g (1C), and test temperature is 20±2
℃。
Embodiment 1：
A kind of preparation method of sandwich structure Graphene/lithium ferric phosphate/grapheme composite positive electrode material, its original needed for preparing
Material, calculates according to the mass fraction, and its composition and consumption are as follows：
7.6 parts of lithium hydroxide
50 parts of ferrous sulfate
20.7 parts of phosphoric acid
4000 parts of 3mg/mL graphene oxide solutions
14.2 parts of ethylenediamine
Lithium hydroxide, ferrous sulfate and phosphoric acid are dissolved in graphene oxide solution first, add ethylenediamine, stirring is equal
It is even.Then mixed liquor is placed in ptfe autoclave hydro-thermal reaction 12 hours under the conditions of 220 DEG C.In hydro-thermal reaction mistake
Cheng Zhong, reacts generation lithium iron phosphate particles under the catalytic action of ethylenediamine, and simultaneous oxidation graphene microchip carries out self assembly simultaneously
Graphene film interlayer of the lithium iron phosphate particles tight that will be separated out in self assembly.Then gained composite is washed, is done
It is dry, 800 DEG C of heat treatments are then carried out under argon gas protection, heat treatment time is 6 hours, and sandwich structure Graphene/phosphorus is obtained
Sour iron lithium/grapheme composite positive electrode material.
Sandwich structure Graphene/the lithium ferric phosphate/grapheme composite positive electrode material of above-mentioned gained passes through X-ray diffractometer
（TD-3200, Dandong is sensible, Cu K α）Detected, XRD test results such as Fig. 1 of gained.It can be seen that in the collection of illustrative plates in Fig. 1
All of diffraction maximum can be demarcated as the diffraction maximum of olivine structure lithium iron phosphate, and the peak position for not having other materials occurs, table
The content of bright above-mentioned Graphene has no effect on the structure of LiFePO4.Further analysis shows, the Graphene/ferric phosphate
In lithium/grapheme composite positive electrode material, the content of LiFePO4 is 70.3%, and the content of Graphene is 29.7%.
Graphene/the lithium ferric phosphate/grapheme composite positive electrode material of above-mentioned gained, uses ESEM（SEM, Japan's electricity
Sub- 6700F）The SEM figures of gained are as shown in Figure 2.From figure 2 it can be seen that the lithium iron phosphate particles diameter of gained is in 100-200
Between nanometer, and preferably wrapped up by Graphene, this structure can be material with electric network so as to improve the electricity of material
Conductance, reaches the purpose of the chemical property for improving material.Graphene parcel lithium iron phosphate particles had both improved its electric conductivity, rose again
To corresponding protective effect, the cycle performance of material can be improved.
By the Graphene/lithium ferric phosphate/grapheme composite positive electrode material of above-mentioned gained, knob is assembled into using half-cell method
The battery of button 2016 is tested the charge-discharge performance of the battery under the multiplying power of 1C, preceding 5 discharge and recharge results such as Fig. 3 institutes
Show, from figure 3, it can be seen that the Graphene/LiFePO4/specific discharge capacity of the graphene battery positive electrode under 1C multiplying powers
It is 150.9 mAh/g.Battery carries out charge-discharge performance test under 1C multiplying powers, as shown in figure 4, its capacity after 50 circulations
It is 147 mAh/g, capability retention 97.4%.It is indicated above that Graphene/LiFePO4/the graphene battery obtained by the present invention is just
Pole material has specific discharge capacity and good cyclical stability higher, can be in field of lithium ion battery application.
Embodiment 2：
A kind of preparation method of Graphene/lithium ferric phosphate/grapheme composite positive electrode material, its raw material needed for preparing, by quality
Number is calculated, and its composition and consumption are as follows：
14.5 parts of lithium nitrate
84.8 parts of ferric nitrate
24.2 parts of phosphoric acid
4000 parts of 3mg/mL graphene oxide solutions
16.6 parts of ethylenediamine
Lithium nitrate, ferric nitrate and phosphoric acid are dissolved in graphene oxide solution first, add ethylenediamine, stirred.So
Mixed liquor is placed in ptfe autoclave hydro-thermal reaction 10 hours under the conditions of 170 DEG C afterwards.In hydrothermal reaction process,
Generation lithium iron phosphate particles are reacted under the catalytic action of ethylenediamine, simultaneous oxidation graphene microchip carries out self assembly and will separate out
Lithium iron phosphate particles tight self assembly graphene film interlayer.Then gained composite is washed, is dried, then
500 DEG C of heat treatments are carried out under argon gas protection, heat treatment time is 4 hours, Graphene/LiFePO4/Graphene is obtained and is combined
Positive electrode.
Graphene/the lithium ferric phosphate/grapheme composite positive electrode material of above-mentioned gained passes through X-ray diffractometer（TD-3200,
Dandong is sensible, Cu K α）Detected, the XRD test results of gained are similar to Fig. 1.All of diffraction maximum all can also in collection of illustrative plates
It is demarcated as the diffraction maximum of olivine structure lithium iron phosphate, the peak position for not having other materials occurs, and shows containing for above-mentioned Graphene
Amount has no effect on the structure of LiFePO4.Further analysis shows, the Graphene/LiFePO4/Graphene anode composite material
In material, the content of LiFePO4 is 73.6%, and the content of Graphene is 26.4%.
Graphene/the lithium ferric phosphate/grapheme composite positive electrode material of above-mentioned gained, uses ESEM（SEM, Japan's electricity
Sub- 6700F）The SEM figures of gained are similar to Fig. 2.The lithium iron phosphate particles diameter of gained between 100-200 nanometers, and by graphite
Alkene is preferably wrapped up, this structure can be material with electric network so as to improve the electrical conductivity of material, reach raising material
Chemical property purpose.Graphene parcel lithium iron phosphate particles had both improved its electric conductivity, and corresponding protective effect is played again,
The cycle performance of material can be improved.
By the Graphene/lithium ferric phosphate/grapheme composite positive electrode material of above-mentioned gained, knob is assembled into using half-cell method
The battery of button 2016 is tested the charge-discharge performance of the battery under the multiplying power of 1C, and specific discharge capacity is 150 mAh/g, 50
Its capacity is 146.3 mAh/g, capability retention 97.5% after secondary circulation.It is indicated above that Graphene/the phosphoric acid obtained by the present invention
Iron lithium/graphene battery positive electrode has specific discharge capacity and good cyclical stability higher, can be in lithium ion
Field of batteries application.
Embodiment 3：
A kind of preparation method of Graphene/lithium ferric phosphate/grapheme composite positive electrode material, its raw material needed for preparing, by quality
Number is calculated, and its composition and consumption are as follows：
16.5 parts of lithium acetate
43.5 parts of ferrous acetate
28.8 parts of phosphoric acid
4000 parts of 3mg/mL graphene oxide solutions
19.4 parts of ethylenediamine
Lithium acetate, ferrous acetate and phosphoric acid are dissolved in graphene oxide solution first, add ethylenediamine, stirred.
Then mixed liquor is placed in ptfe autoclave hydro-thermal reaction 8 hours under the conditions of 160 DEG C.In hydrothermal reaction process
In, generation lithium iron phosphate particles are reacted under the catalytic action of ethylenediamine, simultaneous oxidation graphene microchip carries out self assembly and incites somebody to action
Graphene film interlayer of the lithium iron phosphate particles tight of precipitation in self assembly.Then gained composite is washed, is dried,
Then 38.60 DEG C of heat treatments are carried out under argon gas protection, heat treatment time is 2 hours, and Graphene/LiFePO4/graphite is obtained
Alkene composite positive pole.
Graphene/the lithium ferric phosphate/grapheme composite positive electrode material of above-mentioned gained passes through X-ray diffractometer（TD-3200,
Dandong is sensible, Cu K α）Detected, the XRD test results of gained are similar to Fig. 1.All of diffraction maximum can be marked in collection of illustrative plates
It is set to the diffraction maximum of olivine structure lithium iron phosphate, the peak position for not having other materials occurs, and shows the content of above-mentioned Graphene
Have no effect on the structure of LiFePO4.Further analysis shows, the Graphene/lithium ferric phosphate/grapheme composite positive electrode material
In, the content of LiFePO4 is 76.4%, and the content of Graphene is 23.6%.
Graphene/the lithium ferric phosphate/grapheme composite positive electrode material of above-mentioned gained, uses ESEM（SEM, Japan's electricity
Sub- 6700F）The SEM figures of gained are similar to Fig. 2.The lithium iron phosphate particles diameter of gained between 100-200 nanometers, and by graphite
Alkene is preferably wrapped up, this structure can be material with electric network so as to improve the electrical conductivity of material, reach raising material
Chemical property purpose.Graphene parcel lithium iron phosphate particles had both improved its electric conductivity, and corresponding protective effect is played again,
The cycle performance of material can be improved.
By the Graphene/lithium ferric phosphate/grapheme composite positive electrode material of above-mentioned gained, knob is assembled into using half-cell method
The battery of button 2016 is tested the charge-discharge performance of the battery under the multiplying power of 1C, and specific discharge capacity is 149.7 mAh/g,
Its capacity is 145.6 mAh/g, capability retention 97.3% after 50 circulations.It is indicated above that Graphene/the phosphorus obtained by the present invention
Sour iron lithium/graphene battery positive electrode have specific discharge capacity and good cyclical stability higher, can lithium from
Sub- field of batteries application.
Embodiment 4：
A kind of preparation method of Graphene/lithium ferric phosphate/grapheme composite positive electrode material, its raw material needed for preparing, by quality
Number is calculated, and its composition and consumption are as follows：
16.4 parts of lithium hydroxide
108.4 parts of ferrous sulfate
44.9 parts of ammonium dihydrogen phosphate
4000 parts of 3mg/mL graphene oxide solutions
30.6 parts of ethylenediamine
Lithium hydroxide, ferrous sulfate and ammonium dihydrogen phosphate are dissolved in graphene oxide solution first, add ethylenediamine, stirred
Mix uniform.Then mixed liquor is placed in ptfe autoclave hydro-thermal reaction 16 hours under the conditions of 220 DEG C.It is anti-in hydro-thermal
During answering, generation lithium iron phosphate particles are reacted under the catalytic action of ethylenediamine, simultaneous oxidation graphene microchip is carried out from group
Graphene film interlayer of the lithium iron phosphate particles tight that fill and will separate out in self assembly.Then gained composite is washed
Wash, dry, 800 DEG C of heat treatments are then carried out under argon gas protection, heat treatment time is 8 hours, and Graphene/ferric phosphate is obtained
Lithium/grapheme composite positive electrode material.
Graphene/the lithium ferric phosphate/grapheme composite positive electrode material of above-mentioned gained passes through X-ray diffractometer（TD-3200,
Dandong is sensible, Cu K α）Detected, the XRD test results of gained are similar to Fig. 1.All of diffraction maximum can be marked in collection of illustrative plates
It is set to the diffraction maximum of olivine structure lithium iron phosphate, the peak position for not having other materials occurs, and shows the content of above-mentioned Graphene
Have no effect on the structure of LiFePO4.Further analysis shows, the Graphene/lithium ferric phosphate/grapheme composite positive electrode material
In, the content of LiFePO4 is 83.6%, and the content of Graphene is 16.4%.
Graphene/the lithium ferric phosphate/grapheme composite positive electrode material of above-mentioned gained, uses ESEM（SEM, Japan's electricity
Sub- 6700F）The SEM figures of gained are similar to Fig. 2.The lithium iron phosphate particles diameter of gained between 100-200 nanometers, and by graphite
Alkene is preferably wrapped up, this structure can be material with electric network so as to improve the electrical conductivity of material, reach raising material
Chemical property purpose.Graphene parcel lithium iron phosphate particles had both improved its electric conductivity, and corresponding protective effect is played again,
The cycle performance of material can be improved.
By the Graphene/lithium ferric phosphate/grapheme composite positive electrode material of above-mentioned gained, knob is assembled into using half-cell method
The battery of button 2016 is tested the charge-discharge performance of the battery under the multiplying power of 1C, and specific discharge capacity is 149.2 mAh/g,
Its capacity is 145 mAh/g, capability retention 97.2% after 50 circulations.It is indicated above that Graphene/the phosphoric acid obtained by the present invention
Iron lithium/graphene battery positive electrode has specific discharge capacity and good cyclical stability higher, can be in lithium ion
Field of batteries application.
Embodiment 5：
A kind of preparation method of Graphene/lithium ferric phosphate/grapheme composite positive electrode material, its raw material needed for preparing, by quality
Number is calculated, and its composition and consumption are as follows：
44.2 parts of lithium acetate
116.5 parts of ferrous acetate
77.1 parts of ammonium dihydrogen phosphate
4000 parts of 3mg/mL graphene oxide solutions
52.3 parts of ethylenediamine
Lithium acetate, ferrous acetate and ammonium dihydrogen phosphate are dissolved in graphene oxide solution first, add ethylenediamine, stirred
Uniformly.Then mixed liquor is placed in ptfe autoclave hydro-thermal reaction 11 hours under the conditions of 180 DEG C.In hydro-thermal reaction
During, generation lithium iron phosphate particles are reacted under the catalytic action of ethylenediamine, simultaneous oxidation graphene microchip carries out self assembly
And the lithium iron phosphate particles tight that will be separated out is in the graphene film interlayer of self assembly.Then gained composite is washed,
Dry, 700 DEG C of heat treatments are then carried out under argon gas protection, heat treatment time is 3 hours, and Graphene/LiFePO4/stone is obtained
Black alkene composite positive pole.
Graphene/the lithium ferric phosphate/grapheme composite positive electrode material of above-mentioned gained passes through X-ray diffractometer（TD-3200,
Dandong is sensible, Cu K α）Detected, the XRD test results of gained are similar to Fig. 1.All of diffraction maximum can be marked in collection of illustrative plates
It is set to the diffraction maximum of olivine structure lithium iron phosphate, the peak position for not having other materials occurs, and shows the content of above-mentioned Graphene
Have no effect on the structure of LiFePO4.Further analysis shows, the Graphene/lithium ferric phosphate/grapheme composite positive electrode material
In, the content of LiFePO4 is 89.7%, and the content of Graphene is 10.3%.
Graphene/the lithium ferric phosphate/grapheme composite positive electrode material of above-mentioned gained, uses ESEM（SEM, Japan's electricity
Sub- 6700F）The SEM figures of gained are similar to Fig. 2.The lithium iron phosphate particles diameter of gained between 100-200 nanometers, and by graphite
Alkene is preferably wrapped up, this structure can be material with electric network so as to improve the electrical conductivity of material, reach raising material
Chemical property purpose.Graphene parcel lithium iron phosphate particles had both improved its electric conductivity, and corresponding protective effect is played again,
The cycle performance of material can be improved.
By the Graphene/lithium ferric phosphate/grapheme composite positive electrode material of above-mentioned gained, knob is assembled into using half-cell method
The battery of button 2016 is tested the charge-discharge performance of the battery under the multiplying power of 1C, and specific discharge capacity is 148.5 mAh/g,
Its capacity is 144.2 mAh/g, capability retention 97.1% after 50 circulations.It is indicated above that Graphene/the phosphorus obtained by the present invention
Sour iron lithium/graphene battery positive electrode have specific discharge capacity and good cyclical stability higher, can lithium from
Sub- field of batteries application.
Embodiment 6：
A kind of preparation method of Graphene/lithium ferric phosphate/grapheme composite positive electrode material, its raw material needed for preparing, by quality
Number is calculated, and its composition and consumption are as follows：
29.6 parts of lithium nitrate
173.7 parts of ferric nitrate
49.5 parts of ammonium dihydrogen phosphate
4000 parts of 3mg/mL graphene oxide solutions
34 parts of ethylenediamine
Lithium nitrate, ferric nitrate and ammonium dihydrogen phosphate are dissolved in graphene oxide solution first, add ethylenediamine, stirring is equal
It is even.Then mixed liquor is placed in ptfe autoclave hydro-thermal reaction 9 hours under the conditions of 190 DEG C.In hydro-thermal reaction mistake
Cheng Zhong, reacts generation lithium iron phosphate particles under the catalytic action of ethylenediamine, and simultaneous oxidation graphene microchip carries out self assembly simultaneously
Graphene film interlayer of the lithium iron phosphate particles tight that will be separated out in self assembly.Then gained composite is washed, is done
It is dry, 600 DEG C of heat treatments are then carried out under argon gas protection, heat treatment time is 5 hours, and Graphene/LiFePO4/graphite is obtained
Alkene composite positive pole.
Graphene/the lithium ferric phosphate/grapheme composite positive electrode material of above-mentioned gained passes through X-ray diffractometer（TD-3200,
Dandong is sensible, Cu K α）Detected, the XRD test results of gained are similar to Fig. 1.All of diffraction maximum can be marked in collection of illustrative plates
It is set to the diffraction maximum of olivine structure lithium iron phosphate, the peak position for not having other materials occurs, and shows the content of above-mentioned Graphene
Have no effect on the structure of LiFePO4.Further analysis shows, the Graphene/lithium ferric phosphate/grapheme composite positive electrode material
In, the content of LiFePO4 is 85%, and the content of Graphene is 15%.
Graphene/the lithium ferric phosphate/grapheme composite positive electrode material of above-mentioned gained, uses ESEM（SEM, Japan's electricity
Sub- 6700F）The SEM figures of gained are similar to Fig. 2.The lithium iron phosphate particles diameter of gained between 100-200 nanometers, and by graphite
Alkene is preferably wrapped up, this structure can be material with electric network so as to improve the electrical conductivity of material, reach raising material
Chemical property purpose.Graphene parcel lithium iron phosphate particles had both improved its electric conductivity, and corresponding protective effect is played again,
The cycle performance of material can be improved.
By the Graphene/lithium ferric phosphate/grapheme composite positive electrode material of above-mentioned gained, knob is assembled into using half-cell method
The battery of button 2016 is tested the charge-discharge performance of the battery under the multiplying power of 1C, and discharge capacity is 149.1 mAh/g, 50
Its capacity is 145.8 mAh/g, capability retention 97.8% after secondary circulation.It is indicated above that Graphene/the phosphoric acid obtained by the present invention
Iron lithium/graphene battery positive electrode has specific discharge capacity and good cyclical stability higher, can be in lithium ion
Field of batteries application.
Embodiment 7：
A kind of preparation method of Graphene/lithium ferric phosphate/grapheme composite positive electrode material, its raw material needed for preparing, by quality
Number is calculated, and its composition and consumption are as follows：
21.8 parts of lithium hydroxide
90.4 parts of ferrous acetate
60 parts of phosphoric acid
4000 parts of 3mg/mL graphene oxide solutions
40.5 parts of ethylenediamine
Lithium hydroxide, ferrous acetate and phosphoric acid are dissolved in graphene oxide solution first, add ethylenediamine, stirring is equal
It is even.Then mixed liquor is placed in ptfe autoclave hydro-thermal reaction 12 hours under the conditions of 200 DEG C.In hydro-thermal reaction mistake
Cheng Zhong, reacts generation lithium iron phosphate particles under the catalytic action of ethylenediamine, and simultaneous oxidation graphene microchip carries out self assembly simultaneously
Graphene film interlayer of the lithium iron phosphate particles tight that will be separated out in self assembly.Then gained composite is washed, is done
It is dry, 500 DEG C of heat treatments are then carried out under argon gas protection, heat treatment time is 6 hours, and Graphene/LiFePO4/graphite is obtained
Alkene composite positive pole.
Graphene/the lithium ferric phosphate/grapheme composite positive electrode material of above-mentioned gained passes through X-ray diffractometer（TD-3200,
Dandong is sensible, Cu K α）Detected, the XRD test results of gained are similar to Fig. 1.All of diffraction maximum can be marked in collection of illustrative plates
It is set to the diffraction maximum of olivine structure lithium iron phosphate, the peak position for not having other materials occurs, and shows the content of above-mentioned Graphene
Have no effect on the structure of LiFePO4.Further analysis shows, the Graphene/lithium ferric phosphate/grapheme composite positive electrode material
In, the content of LiFePO4 is 87.1%, and the content of Graphene is 12.9%.
Graphene/the lithium ferric phosphate/grapheme composite positive electrode material of above-mentioned gained, uses ESEM（SEM, Japan's electricity
Sub- 6700F）The SEM figures of gained are similar to Fig. 2.The lithium iron phosphate particles diameter of gained between 100-200 nanometers, and by graphite
Alkene is preferably wrapped up, this structure can be material with electric network so as to improve the electrical conductivity of material, reach raising material
Chemical property purpose.Graphene parcel lithium iron phosphate particles had both improved its electric conductivity, and corresponding protective effect is played again,
The cycle performance of material can be improved.
By the Graphene/lithium ferric phosphate/grapheme composite positive electrode material of above-mentioned gained, knob is assembled into using half-cell method
The battery of button 2016 is tested the charge-discharge performance of the battery under the multiplying power of 1C, and discharge capacity is 148.7 mAh/g, 50
Its capacity is 144 mAh/g, capability retention 97% after secondary circulation.It is indicated above that Graphene/LiFePO4 obtained by the present invention/
Graphene battery positive electrode has specific discharge capacity and good cyclical stability higher, can be led in lithium ion battery
Apply in domain.
Embodiment 8：
A kind of preparation method of Graphene/lithium ferric phosphate/grapheme composite positive electrode material, its raw material needed for preparing, by quality
Number is calculated, and its composition and consumption are as follows：
24.4 parts of lithium acetate
149.5 parts of ferric nitrate
42.6 parts of ammonium dihydrogen phosphate
4000 parts of 3mg/mL graphene oxide solutions
28.7 parts of ethylenediamine
Lithium acetate, ferric nitrate and ammonium dihydrogen phosphate are dissolved in graphene oxide solution first, add ethylenediamine, stirring is equal
It is even.Then mixed liquor is placed in ptfe autoclave hydro-thermal reaction 13 hours under the conditions of 210 DEG C.In hydro-thermal reaction mistake
Cheng Zhong, reacts generation lithium iron phosphate particles under the catalytic action of ethylenediamine, and simultaneous oxidation graphene microchip carries out self assembly simultaneously
Graphene film interlayer of the lithium iron phosphate particles tight that will be separated out in self assembly.Then gained composite is washed, is done
It is dry, 600 DEG C of heat treatments are then carried out under argon gas protection, heat treatment time is 7 hours, and Graphene/LiFePO4/graphite is obtained
Alkene composite positive pole.
Graphene/the lithium ferric phosphate/grapheme composite positive electrode material of above-mentioned gained passes through X-ray diffractometer（TD-3200,
Dandong is sensible, Cu K α）Detected, the XRD test results of gained are similar to Fig. 1.All of diffraction maximum can be marked in collection of illustrative plates
It is set to the diffraction maximum of olivine structure lithium iron phosphate, the peak position for not having other materials occurs, and shows the content of above-mentioned Graphene
Have no effect on the structure of LiFePO4.Further analysis shows, the Graphene/lithium ferric phosphate/grapheme composite positive electrode material
In, the content of LiFePO4 is 82.7%, and the content of Graphene is 17.3%.
Graphene/the lithium ferric phosphate/grapheme composite positive electrode material of above-mentioned gained, uses ESEM（SEM, Japan's electricity
Sub- 6700F）The SEM figures of gained are similar to Fig. 2.The lithium iron phosphate particles diameter of gained between 100-200 nanometers, and by graphite
Alkene is preferably wrapped up, this structure can be material with electric network so as to improve the electrical conductivity of material, reach raising material
Chemical property purpose.Graphene parcel lithium iron phosphate particles had both improved its electric conductivity, and corresponding protective effect is played again,
The cycle performance of material can be improved.
By the Graphene/lithium ferric phosphate/grapheme composite positive electrode material of above-mentioned gained, knob is assembled into using half-cell method
The battery of button 2016 is tested the charge-discharge performance of the battery under the multiplying power of 1C, and discharge capacity is 149 mAh/g, 50 times
Its capacity is 144.3 mAh/g, capability retention 96.8% after circulation.It is indicated above that Graphene/the ferric phosphate obtained by the present invention
Lithium/graphene battery positive electrode has specific discharge capacity and good cyclical stability higher, can be in lithium-ion electric
Apply in pond field.
Embodiment 9：
A kind of preparation method of Graphene/lithium ferric phosphate/grapheme composite positive electrode material, its raw material needed for preparing, by quality
Number is calculated, and its composition and consumption are as follows：
19.3 parts of lithium nitrate
77.8 parts of ferrous sulfate
32.2 parts of ammonium dihydrogen phosphate
4000 parts of 3mg/mL graphene oxide solutions
21.7 parts of ethylenediamine
Lithium nitrate, ferrous sulfate and ammonium dihydrogen phosphate are dissolved in graphene oxide solution first, add ethylenediamine, stirred
Uniformly.Then mixed liquor is placed in ptfe autoclave hydro-thermal reaction 15 hours under the conditions of 180 DEG C.In hydro-thermal reaction
During, generation lithium iron phosphate particles are reacted under the catalytic action of ethylenediamine, simultaneous oxidation graphene microchip carries out self assembly
And the lithium iron phosphate particles tight that will be separated out is in the graphene film interlayer of self assembly.Then gained composite is washed,
Dry, 700 DEG C of heat treatments are then carried out under argon gas protection, heat treatment time is 5 hours, and Graphene/LiFePO4/stone is obtained
Black alkene composite positive pole.
Graphene/the lithium ferric phosphate/grapheme composite positive electrode material of above-mentioned gained passes through X-ray diffractometer（TD-3200,
Dandong is sensible, Cu K α）Detected, the XRD test results of gained are similar to Fig. 1.All of diffraction maximum can be marked in collection of illustrative plates
It is set to the diffraction maximum of olivine structure lithium iron phosphate, the peak position for not having other materials occurs, and shows the content of above-mentioned Graphene
Have no effect on the structure of LiFePO4.Further analysis shows, the Graphene/lithium ferric phosphate/grapheme composite positive electrode material
In, the content of LiFePO4 is 78.3%, and the content of Graphene is 21.7%.
Graphene/the lithium ferric phosphate/grapheme composite positive electrode material of above-mentioned gained, uses ESEM（SEM, Japan's electricity
Sub- 6700F）The SEM figures of gained are similar to Fig. 2.The lithium iron phosphate particles diameter of gained between 100-200 nanometers, and by graphite
Alkene is preferably wrapped up, this structure can be material with electric network so as to improve the electrical conductivity of material, reach raising material
Chemical property purpose.Graphene parcel lithium iron phosphate particles had both improved its electric conductivity, and corresponding protective effect is played again,
The cycle performance of material can be improved.
By the Graphene/lithium ferric phosphate/grapheme composite positive electrode material of above-mentioned gained, knob is assembled into using half-cell method
The battery of button 2016 is tested the charge-discharge performance of the battery under the multiplying power of 1C, and discharge capacity is 149.6 mAh/g, 50
Its capacity is 146 mAh/g, capability retention 97.6% after secondary circulation.It is indicated above that Graphene/the ferric phosphate obtained by the present invention
Lithium/graphene battery positive electrode has specific discharge capacity and good cyclical stability higher, can be in lithium-ion electric
Apply in pond field.
Claims (6)
1. a kind of preparation method of Graphene/lithium ferric phosphate/grapheme composite positive electrode material, it is characterised in that：Using three-dimensional CVD
Graphene is skeleton, is lithium source, ferrous sulfate, ferrous acetate or nitric acid using lithium hydroxide, lithium nitrate or lithium acetate
Iron is source of iron, and phosphoric acid or ammonium dihydrogen phosphate are phosphoric acid root, under the catalytic action of ethylenediamine, carry out hydro-thermal reaction, hydro-thermal
The temperature of reaction is 160 DEG C -220 DEG C, and the hydro-thermal reaction time is 8-16 hours, is then forged at a temperature of 400 DEG C -800 DEG C again
Burning obtains Graphene/lithium ferric phosphate/grapheme composite positive electrode material for -8 hours.
2. the preparation method of a kind of Graphene/lithium ferric phosphate/grapheme composite positive electrode material according to claim 1, its
It is characterised by：In lithium source, source of iron and phosphoric acid root, the mol ratio of elemental lithium, ferro element and phosphate radical is 1：1：1.
3. the preparation method of a kind of Graphene/lithium ferric phosphate/grapheme composite positive electrode material according to claim 1, its
It is characterised by：In described Graphene/lithium ferric phosphate/grapheme composite positive electrode material, the mass percent of LiFePO4 contains
It is 70% -90% to measure, and the mass percentage content of Graphene is 30% -10%.
4. the preparation method of a kind of Graphene/lithium ferric phosphate/grapheme composite positive electrode material according to claim 1, its
It is characterised by：The mass ratio of LiFePO4 is 0.5-1 in ethylenediamine and product:1.
5. the preparation method of a kind of Graphene/lithium ferric phosphate/grapheme composite positive electrode material according to claim 1, its
It is characterised by：It is protective atmosphere that argon gas is used in the high-temperature burning process.
6. the preparation method of a kind of Graphene/lithium ferric phosphate/grapheme composite positive electrode material according to claim 1, its
It is characterised by：With lithium hydroxide, lithium nitrate or lithium acetate as lithium source, ferrous sulfate, ferrous acetate or ferric nitrate are iron
Source, phosphoric acid or ammonium dihydrogen phosphate are phosphoric acid root, according to elemental lithium, ferro element and phosphate radical in graphene oxide solution
Mol ratio be 1：1：1 adds lithium source, source of iron and phosphoric acid root, stirs to being completely dissolved, and adds three-dimensional CVD Graphenes bone
Frame, is subsequently adding ethylenediamine as catalyst, in water-heat process reaction obtain the Graphene/LiFePO4 of three-dimensional self assembly/
Graphene presoma, hydrothermal temperature be 160 DEG C -220 DEG C, the hydro-thermal reaction time be 8-16 hours, by obtained Graphene/
LiFePO4/Graphene presoma is washed, dried, and is positioned in tube furnace, under argon atmosphere, at 400 DEG C -800 DEG C
Calcining 2-8 hours, is obtained sandwich structure Graphene/lithium ferric phosphate/grapheme composite positive electrode material, wherein, Graphene is being produced
Mass percentage content 30%-10% in thing, LiFePO4 mass percentage content in the product is 70% -90%.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107464925A (en) * | 2017-08-02 | 2017-12-12 | 商丘职业技术学院 | A kind of lithium battery and power device |
| CN108470889A (en) * | 2018-03-12 | 2018-08-31 | 澳洋集团有限公司 | A kind of preparation method of LiFePO4-graphite composite positive pole |
| CN114735688A (en) * | 2019-05-31 | 2022-07-12 | 常州第六元素材料科技股份有限公司 | Graphene oxide slurry for interlayer bonding of diamine organic matter, preparation method of graphene oxide slurry, graphene oxide film and preparation method of graphene oxide film |
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| CN103682368A (en) * | 2012-09-20 | 2014-03-26 | 中国科学院金属研究所 | Rapidly charged flexible lithium ion battery and preparation method of electrodes of rapidly charged flexible lithium ion battery |
| CN105977465A (en) * | 2016-06-29 | 2016-09-28 | 上海应用技术学院 | Method for preparing graphene/lithium iron phosphate composite anode materials |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103682368A (en) * | 2012-09-20 | 2014-03-26 | 中国科学院金属研究所 | Rapidly charged flexible lithium ion battery and preparation method of electrodes of rapidly charged flexible lithium ion battery |
| CN105977465A (en) * | 2016-06-29 | 2016-09-28 | 上海应用技术学院 | Method for preparing graphene/lithium iron phosphate composite anode materials |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107464925A (en) * | 2017-08-02 | 2017-12-12 | 商丘职业技术学院 | A kind of lithium battery and power device |
| CN108470889A (en) * | 2018-03-12 | 2018-08-31 | 澳洋集团有限公司 | A kind of preparation method of LiFePO4-graphite composite positive pole |
| CN114735688A (en) * | 2019-05-31 | 2022-07-12 | 常州第六元素材料科技股份有限公司 | Graphene oxide slurry for interlayer bonding of diamine organic matter, preparation method of graphene oxide slurry, graphene oxide film and preparation method of graphene oxide film |
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