CN109103444A - A kind of LiMPO4The preparation method of In-situ reaction graphene - Google Patents
A kind of LiMPO4The preparation method of In-situ reaction graphene Download PDFInfo
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- CN109103444A CN109103444A CN201811001969.5A CN201811001969A CN109103444A CN 109103444 A CN109103444 A CN 109103444A CN 201811001969 A CN201811001969 A CN 201811001969A CN 109103444 A CN109103444 A CN 109103444A
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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
- H01M4/36—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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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a kind of LiMPO4The preparation method of In-situ reaction graphene, through the method for hydro-thermal reaction under aqueous conditions, the water-based graphene oxide of addition parent synthesizes LiMPO using the microwave heating method that heating uniformity is excellent in the solution4While by graphene In-situ reaction in LiMPO4Surface quickly and effectively synthesize LiMPO on the one hand by the heat characteristic of hydrone uniform high-efficiency in microwave heating solution4/ G high electrochemical performance nano material, another invention by microwave eliminate graphene oxide in reactive species, be prepared into morphology controllable, particle size Nano grade LiMPO4/ G high electrochemical performance nano material, and its electric conductivity is further increased, and substantially reduce the reaction time, easy to operate, industrial applications prospect is extensive.In addition, further effectively controlling LiMPO as template using PEG4004The sheet-like morphology of/G, the drying means of freeze-drying effectively increase the stability of graphene two-dimensional structure.
Description
Technical field
The present invention relates to lithium ion battery electrode material preparation field more particularly to a kind of LiMPO4In-situ reaction graphene
Preparation method.
Background technique
Lithium ion battery have specific capacity is high, self discharge is small, operating temperature range is wide, voltage platform is high, have extended cycle life,
Memory-less effect, it is environmentally friendly the features such as, be widely used to the fields such as mobile phone, laptop, electric tool, and
Gradually promoted in electric car field.
The more and most commonly used positive electrode with olivine structural of research is used on electric car at present
LiFePO4, LiFePO4It is to study one of battery material burning the hotest in recent years, theoretical specific capacity is relatively high to be
170mA.h/g, discharge platform is about in 3.2V or so, since the strong P-O covalent bond of binding force in anion can form stabilization
Three dimensional chemical key, make LiFePO4Regardless of still kinetically all there is extremely strong stability in thermodynamics.Therefore relative to it
For his positive electrode, LiFePO4The characteristic of stable structure provide strong guarantee for its excellent security performance.
But LiFePO4The extremely low electric conductivity of equal phosphoric acid lithium salts, limits it and develops in the application.
At present by by graphene (abbreviation G) and LiFePO4Equal the compound of phosphoric acid lithium salts has been demonstrated effectively promote phosphorus
The chemical property of hydrochlorate such as electric conductivity, but its compound mode and preparation method are very big on the influence of the performance of material.
Organic carbon containing substances such as caramel, sucrose, cellulose etc. are generallyd use in existing complex method is blended in lithium phosphate
In salt precursor body, then carbon is compounded in by way of high-temperature calcination under reducing atmosphere the surface of phosphoric acid lithium salt particles, and it is right
The compound of graphene carry out by the way of high-temperature calcination after solid-state mixes with phosphoric acid lithium salt particles using graphene particles；Tool
There is the shortcomings that complicated for operation, to need to expend a large amount of energy and time.
And the complex method of common hydro-thermal reaction is since there are certain reactive species to be difficult to disappear in graphene oxide
It removes, influences the composite effect of itself and phosphoric acid lithium salt solution, the time of synthesis is longer, and product form is larger, and it is inhomogenous, actually
It can not obtain morphology controllable, particle is in Nano grade and LiMPO that conductivity is remarkably reinforced4/G。
How the reactive mode and condition of hydro-thermal reaction are improved to solve the above problems and be worth research.
Summary of the invention
Goal of the invention: in order to overcome defect existing in the prior art, the invention proposes a kind of LiMPO4In-situ reaction
The preparation method of graphene, have it is easy to operate, the reaction time is short, the LiMPO of synthesis4/ G morphology controllable, particle size are being received
Meter level is other, has the advantages that excellent electric conductivity.
Technical solution: in order to solve the above-mentioned technical problem, the technical scheme adopted by the invention is as follows:
A kind of LiMPO4The preparation method of In-situ reaction graphene, includes the following steps:
(1) phosphoric acid solution of 0.5-1.5mol/L is uniformly mixed with PEG400, the lithium hydroxide that 4-5mol/L is added is molten
It is reacted after liquid mixing, control Li/P molar ratio is 3:1-3.5:1, and after stirring 20-40min, graphene oxide solution is added
And saturation MSO4Solution, control M/P molar ratio are 1:1；Continue to be prepared into precursor liquid after stirring 30-60min；
(2) precursor liquid that step (1) is prepared into is placed in microwave reaction system and carries out microwave reaction, microwave reaction temperature is set
It is set to 160-200 DEG C, microwave reaction power setting is 800-1000W, reaction time 5-40min；Obtain sediment；
(3) after sediment being carried out centrifuge washing, it is freeze-dried to obtain LiMPO4；
Wherein M=FexMnyCoz；The numerical value selection range of x, y, z are 0-1, and x+y+z=1.
It is 25-40 DEG C that reaction temperature is controlled while step (1) is stirred；Under this reaction temperature, phosphoric acid solution with
The reaction efficiency of lithium hydroxide solution is higher.
More preferably, the additional amount of the PEG400 is 0.2-0.4 times of phosphoric acid solution volume.
More preferably, the additional amount control of the graphene oxide solution is that the molar ratio of graphene oxide and phosphoric acid is
0.2:1-0.6:1。
Further, the additional amount control of the graphene oxide solution is that the molar ratio of graphene oxide and phosphoric acid is
0.4:1。
Step (2) the microwave reaction time is 10-40min；Under this reaction time, graphene oxide and phosphoric acid lithium salts
Composite effect it is best, on the one hand almost without the interference of impurity, finished product LiMPO obtained4/ G morphology controllable degree is preferable, ruler
Very little form is uniform, and particle size has excellent electric conductivity in Nano grade.
Step (2) the microwave reaction time is 20min；Under this reaction time, graphene oxide and phosphoric acid lithium salts
Composite effect is best, finished product LiMPO obtained4/ G morphology controllable degree is best, and size modes are uniform, hence it is evident that it can be seen that
LiMPO4The composite construction of/G, and particle size has optimal electric conductivity in Nano grade.
More preferably, the cryogenic temperature of freeze-drying described in step (3) is -10~-30 DEG C.
More preferably, sublimation drying described in step (3) is 2h-4h.
The utility model has the advantages that a kind of LiMPO provided by the invention4The preparation method of In-situ reaction graphene, passes through hydro-thermal reaction
For the method for microwave heating under aqueous conditions, the water-based graphene oxide of addition parent uses the microwave that heating uniformity is excellent
Heating synthesizes LiMPO in the solution4While by graphene In-situ reaction in LiMPO4Surface, on the one hand add by microwave
The heat characteristic of hydrone uniform high-efficiency, quickly and effectively synthesizes LiMPO in hot solution4/ G high electrochemical performance nano material,
The reactive species in graphene oxide are eliminated in another invention by microwave, are prepared into morphology controllable, particle size in nanoscale
Other LiMPO4/ G high electrochemical performance nano material, and its electric conductivity is further increased, and substantially reduce the reaction time,
Easy to operate, industrial applications prospect is extensive.In addition, further effectively controlling LiMPO as template using PEG4004The piece of/G
Shape pattern, the drying means of freeze-drying further increase the stability of graphene two-dimensional structure.
Detailed description of the invention
Fig. 1 is the LiMPO that the embodiment of the present invention 3 is prepared4Electron microscope under the shape characteristic 100nm size of/G；
Fig. 2 is the LiMPO that the embodiment of the present invention 4 is prepared4Electron microscope under the shape characteristic 100nm size of/G；
Fig. 3 is the electricity under the shape characteristic 500nm size for the product that comparative example 1 of the present invention is prepared without microwave reaction
Mirror figure；
Fig. 4 is the XRD diagram of different time of embodiment of the present invention reaction product；
Fig. 5 is that the embodiment of the present invention and comparative example prepare finished product and carry out conductivity test data comparison schematic diagram；
Fig. 6 is that the embodiment of the present invention and comparative example prepare finished product and carry out specific capacity test data contrast schematic diagram.
Specific embodiment
Below with reference to embodiment, the present invention is described in further detail:
Embodiment 1:
A kind of LiMPO4The preparation method of In-situ reaction graphene, includes the following steps:
(1) by 30mL, the phosphoric acid solution of 0.5mol/L is uniformly mixed with 10mLPEG400, and it is full that 10mL 4.5mol/L is added
It is reacted with after lithium hydroxide solution mixing, control reaction temperature is that after being stirred 30min at 25 DEG C, 40mL is added,
The graphene oxide solution and 15mL of 0.1mol/L, the FeSO of 1mol/L4Solution；Continue stirring 30min and is prepared into precursor liquid；
(2) precursor liquid being prepared into step (1) is placed in microwave reaction system and carries out microwave reaction, microwave reaction temperature
200 DEG C are set as, microwave reaction power setting is 1000W, reaction time 5min；Obtain sediment；
(3) after sediment being carried out centrifuge washing, it is freeze-dried to prepare finished product LiFePO4/G；Cryogenic temperature is -20
DEG C, drying time 3h.Reaction equation is as follows:
3LiOH+H3PO4→Li3PO4↓+3H2O
Li3PO4+FeSO4→LiFePO4+Li2SO4
The decomposition reaction of graphene oxide in microwave reaction: GO → H2O+CO2+GH
Embodiment 2:
Other embodiments are same as Example 1, the difference is that the microwave reaction time is 10min in step (2)；
Embodiment 3:
Other embodiments are same as Example 1, the difference is that the microwave reaction time is 20min in step (2)；
Embodiment 4:
Other embodiments are same as Example 1, the difference is that the microwave reaction time is 40min in step (2)；
MSO in embodiment 1-44With FeSO4For to carry out the display of more intuitively longitudinal comparative test data, but not
It is only limitted to FeSO4, MnSO can also be used4、CoSO4Or such as Fe0.5Mn0.5SO4Etc. meeting M=FexMnyCoz；(numerical value of x, y, z select
Taking range is 0-1, and x+y+z=1) a variety of mixed sulfates in generic scope are substituted.
Embodiment 5:
A kind of LiMPO4The preparation method of In-situ reaction graphene, includes the following steps:
(1) by 10mL, the phosphoric acid solution of 1.5mol/L is uniformly mixed with 12mLPEG400, and 10mL 5mol/L saturation is added
It is reacted after lithium hydroxide solution mixing, control reaction temperature is that after being stirred 40min at 40 DEG C, 40mL is added,
The graphene oxide solution and 15mL of 0.1mol/L, the FeSO of 1mol/L4Solution；Continue stirring 60min and is prepared into precursor liquid；
(2) precursor liquid being prepared into step (1) is placed in microwave reaction system and carries out microwave reaction, microwave reaction temperature
160 DEG C are set as, microwave reaction power setting is 800W, reaction time 20min；Obtain sediment；
(3) after sediment being carried out centrifuge washing, it is freeze-dried to prepare finished product LiFePO4/G；Cryogenic temperature is -30
DEG C, drying time 4h.
Embodiment 6:
A kind of LiMPO4The preparation method of In-situ reaction graphene, includes the following steps:
(1) by 15mL, the phosphoric acid solution of 1mol/L is uniformly mixed with 6mLPEG400, and 10mL 5mol/L is added and is saturated hydrogen-oxygen
It is reacted after changing the mixing of lithium solution, control reaction temperature is that after being stirred 20min at 30 DEG C, 40mL, 0.1mol/L is added
Graphene oxide solution and 15mL, 1mol/L FeSO4Solution；Continue stirring 45min and is prepared into precursor liquid；
(2) precursor liquid being prepared into step (1) is placed in microwave reaction system and carries out microwave reaction, microwave reaction temperature
180 DEG C are set as, microwave reaction power setting is 900W, reaction time 20min；Obtain sediment；
(3) after sediment being carried out centrifuge washing, it is freeze-dried to prepare finished product LiFePO4/G；Cryogenic temperature is -10
DEG C, drying time 2h.
Comparative example 1:
A kind of preparation method for the hydro-thermal reaction composite graphite alkene not using microwave heating, includes the following steps: it
Step (1) is same as Example 1；The difference is that step (2)-(3)；It is specific as follows:
(2) precursor liquid being prepared into step (1) is placed in hydrothermal reaction kettle and carries out hydro-thermal reaction, hydrothermal temperature
200 DEG C are set as, reaction time 4h；Obtain sediment；
(3) so dry that prepare finished product combination product after sediment being carried out centrifuge washing.
Finished product test experiment:
The combination electrode material that test object is embodiment 1-4 and prepared by comparative example 1；
1) electron microscopic morphology compares:
As shown in Figure 1-3, being respectively the LiFePO prepared to embodiment 3,4 and comparative example 14/ G electrode material is in Electronic Speculum
The lower shooting for carrying out pattern photo, wherein the embodiment of Fig. 1-Fig. 2 is the photo shot under 100nm size, pair of Fig. 3
Ratio 1 is the electromicroscopic photograph shot under 500nm size.
Due to time more a length of 4h of 1 hydro-thermal reaction of comparative example, the form of combination product is larger, in the size of 100nm
The comparison that can not carry out the overall picture uniformity down is shown, and there are also some irregular big cluster structures, pattern is inhomogenous；From Fig. 1-3
As can be seen that made of 3 microwave reaction 20min of the embodiment of the present invention and 4 microwave reaction 40min of embodiment is prepared
LiFePO4/ G has pattern uniform for the material that comparative example 1 synthesizes, and particle size control is excellent within 100nm
Point；The diffusion path that particle size will lead to greatly very much lithium ion increases, and increases lithium ion diffusion time in the material, can be to leading
Electrical property brings negative impact, reduces electric conductivity to a certain extent.
In addition, passing through the electromicroscopic photograph to 3 microwave reaction 20min of Fig. 1 embodiment and 4 microwave reaction 40min of Fig. 2 embodiment
Comparing and analyzing can obtain, and embodiment 3 carries out the LiFePO of microwave reaction 20min acquisition4/ G material has more uniform shape
State, particle size is smaller, and can see LiFePO pointed by roundel as shown in figure 1 and arrow4The composite construction of/G.
2) microwave reaction time and reaction impurities are analyzed:
By the detection to different microwave reaction time products, in the presence of apparent miscellaneous in reaction solution before reacting 5min
Matter phenomenon, and impurity is substantially reduced since 5min, it is most lower shown in the XRD diagram for please referring to Fig. 4 different time reaction time product
One, face is standard appearance, and several spectrograms above respectively illustrate the impurity of reaction 5min, 10min, 20min and 40min
Disturbed condition, it can be seen that impurity interference phenomenon is unobvious when reaction 5min, and in the appearance feelings of 10min, 20min, 40min
Condition show almost free from admixture interference, then comprehensively consider reaction time too long reaction product form it is excessive to electric conductivity is brought it is negative
Face effect, therefore the present invention selects time of the 5-40min as microwave reaction, and more preferable 10-40min, to obtain best shape
The combination electrode material of state and electric conductivity.
3) microwave reaction and the hydro-thermal reaction time comparison:
The microwave reaction and hydro-thermal reaction of embodiment 1-4 comparative example 1 are recorded, it is specific as shown in table 1, it can be seen that embodiment
The 1-4 microwave reaction time controls within 40min, and the reaction time of the comparative example 1 of hydro-thermal reaction needs the length of 4h, the present invention
It has been obviously shortened the reaction time, has improved production efficiency.
4) conductivity test:
Specific test method is that the test of powdered conductive rate is carried out to composite material powder, as shown in figure 5, uniformly increasing pressure
The test of power progress conductivity reaches equilibrium state until conductivity, takes the conductivity under equilibrium state, specific structure please refers to
Table 1 is recorded.
From Fig. 5 and data recorded in table 1, it can be concluded that, the minimum conductivity of comparative example 1 is only 0.213*10-5S/
Cm, and the composite material conductive rate of 1-4 of the embodiment of the present invention is superior to the compound material of comparative example 1, wherein with micro- in embodiment 3
The composite material conductive rate that wave reacts 20min acquisition is best, is 1.376*10-5S/cm, electric conductivity has obviously in contrast
Promotion.
5) specific capacity is tested:
Specific test method is that the powder that will be obtained is used as anode, and lithium piece is made into button electricity as cathode, in blue electrical testing system
It is tested under system, the test of specific capacity is carried out under multiple cycle-indexes, original test data can refer to shown in Fig. 6, finally
Specific capacity test data result is documented in table 1.
Please refer to Fig. 6 and data recorded in table 1 it can be concluded that, the specific capacity of comparative example 1 it is minimum be only 111mAh/g,
And the composite material specific capacity of 1-4 of the embodiment of the present invention is superior to the compound material of comparative example 1, wherein with microwave in embodiment 3
It is best to react the composite material specific capacity that 20min is obtained, is 158mAh/g, it will thus be seen that the embodiment of the present invention is compound
LiFePO4Electric conductivity has and is obviously improved/G electrode material in contrast.
1 embodiment 1-4 of table can be compared with 1 reaction time of comparative example and conductivity of composite material
| Test object | Reaction time | Conductivity (S/cm) | Specific capacity (mAh/g) |
| Embodiment 1 | 5min | 0.425*10-5 | 132 |
| Embodiment 2 | 10min | 0.705*10-5 | 139 |
| Embodiment 3 | 20min | 1.376*10-5 | 158 |
| Embodiment 4 | 40min | 0.853*10-5 | 143 |
| Comparative example 1 | 4h | 0.213*10-5 | 111 |
As it can be seen from table 1 a kind of LiMPO of 1-4 of the embodiment of the present invention4The reaction of the preparation method of In-situ reaction graphene
Time, which has, to be significantly shorter, and improves production efficiency, and synthetic material finished product has more excellent electric conductivity.
Claims (9)
1. a kind of LiMPO4The preparation method of In-situ reaction graphene, it is characterised in that include the following steps:
(1) phosphoric acid solution of 0.5-1.5mol/L is uniformly mixed with PEG400, the lithium hydroxide solution that 4-5mol/L is added is mixed
Reacted after conjunction, control Li/P molar ratio be 3:1-3.5:1, stir 20-40min after, be added graphene oxide solution and
It is saturated MSO4Solution, control M/P molar ratio are 1:1；Continue to be prepared into precursor liquid after stirring 30-60min；
(2) precursor liquid that step (1) is prepared into is placed in microwave reaction system and carries out microwave reaction, microwave reaction temperature setting is
160-200 DEG C, microwave reaction power setting is 800-1000W, reaction time 5-40min；Obtain sediment；
(3) after sediment being carried out centrifuge washing, it is freeze-dried to obtain LiMPO4；
Wherein M=FexMnyCoz；The numerical value selection range of x, y, z are 0-1, and x+y+z=1.
2. LiMPO according to claim 14The preparation method of In-situ reaction graphene, it is characterised in that: step (1) carries out
It is 25-40 DEG C that reaction temperature is controlled while stirring.
3. LiMPO according to claim 14The preparation method of In-situ reaction graphene, it is characterised in that: the PEG400
Additional amount be 0.2-0.4 times of phosphoric acid solution volume.
4. LiMPO according to claim 14The preparation method of In-situ reaction graphene, it is characterised in that: the oxidation stone
The additional amount control of black alkene solution is that the molar ratio of graphene oxide and phosphoric acid is 0.2:1-0.6:1.
5. LiMPO according to claim 1 or 44The preparation method of In-situ reaction graphene, it is characterised in that: the oxidation
The additional amount control of graphene solution is that the molar ratio of graphene oxide and phosphoric acid is 0.4:1.
6. LiMPO according to claim 14The preparation method of In-situ reaction graphene, it is characterised in that: the step (2)
The microwave reaction time is 10-40min.
7. LiMPO according to claim 1 or 64The preparation method of In-situ reaction graphene, it is characterised in that: the step
(2) the microwave reaction time is 20min.
8. LiMPO according to claim 14The preparation method of In-situ reaction graphene, it is characterised in that: institute in step (3)
The cryogenic temperature for stating freeze-drying is -10~-30 DEG C.
9. LiMPO according to claim 14The preparation method of In-situ reaction graphene, it is characterised in that: institute in step (3)
Stating sublimation drying is 2h-4h.
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Application publication date: 20181228 |