CN109742340A - A kind of iron manganese phosphate for lithium composite material and preparation method, application - Google Patents
A kind of iron manganese phosphate for lithium composite material and preparation method, application Download PDFInfo
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Abstract
The invention discloses a kind of preparation methods of iron manganese phosphate for lithium composite material, comprising: manganese sulfate monohydrate, ferrous sulfate heptahydrate are added in deionized water, adds ethylene glycol and stirs to get mixed solution；Phosphoric acid ethylene glycol solution is added dropwise in lithium hydroxide ethylene glycol solution and is stirred, then is added dropwise to mixed solution stirring, hydro-thermal reaction is dried to obtain LiMn0.5Fe0.5PO4Presoma；Successively lithium hydroxide, butyl titanate and lanthanum nitrate are dissolved in dehydrated alcohol and being stirred, deionized water is added, is subsequently added into LiMn0.5Fe0.5PO4Presoma stirring, hydro-thermal reaction are dried to obtain Li0.3La0.56TiO3‑LiMn0.5Fe0.5PO4Presoma；By Li0.3La0.56TiO3‑LiMn0.5Fe0.5PO4Presoma is mixed with glucose, ball milling, is calcined, cooling, and sieving obtains iron manganese phosphate for lithium composite material, and particle is smaller, particle diameter distribution is uniform, crystallinity is high, to improve the chemical property of material while reducing material preparation cost.
Description
Technical field
The present invention relates to technical field of lithium ion more particularly to a kind of iron manganese phosphate for lithium composite material and its preparation sides
Method, application.
Background technique
With the continuous growth of population in the world, the energy consumed by human lives is increasing, it is predicted that the whole world in 2100
Energy consumption will be present three times.Therefore, a large amount of fossil fuel such as petroleum, coal and natural gas etc. is by continuous exploitation benefit
With it is increasingly depleted not only resulting in fossil energy, and seriously destroy environment and ecology.In order to maintain holding for human society
Supervention exhibition, the new energy for researching and developing Novel clean are extremely urgent.Wherein, secondary cell efficiently, cleanliness without any pollution, as
The power or accessory power supply of internal-combustion engine vehicle, can effectively reduce the consumption of fuel.Compared to traditional lead storage battery and
Nickel metal hydride, lithium ion battery are with the obvious advantage in cycle life, energy density, power density and environmental-friendly performance.
Although there is certain gap with fuel cell in energy density, the life of the high manufacturing cost of fuel cell and complexity
It is difficult that production. art achieves commercialization.Therefore, lithium ion battery is the following electric car and hybrid-power battery
Ideal power power supply.
In recent years, lithium ion battery is constantly subjected to the extensive concern of scientists, and the development of lithium ion battery depends on
The research and development of positive electrode.Currently, the anode material for lithium-ion batteries being widely applied in business mainly has including layer structure
LiCoO2, spinel structure LiMn2O4With the LiFePO of olivine-type structure4.As China is to the need of lithium ion battery
It asks and increasingly increases, consumer proposes harsher requirement to the security performance of lithium ion battery.Therefore, high safety is researched and developed
Property, the good positive electrode of thermal stability be the key that improve lithium ion battery safety performance.Same LiFePO4Equally, LiMnPO4?
Belong to olivine-type structure, theoretical capacity 171mAhg-1, workbench is in 4.1V (vs.Li+/ Li) left and right, it is in mesh
Preceding commercialized electrolyte stable region, energy density 701WhKg-1, compare LiFePO4It is high by 20%.In addition, the storage of manganese is rich
Richness, therefore LiMnPO4The cost of raw material it is cheap, and LiMnPO4Synthesis condition there is no LiFePO4It is so harsh, so more
Attention is started to be placed on LiMnPO come more scientific research personnel4On.But LiMnPO4Electronic conductivity and lithium ion expand
Scattered coefficient is very low, causes the electrochemistry of material that can bring into play well, and limits its commercial applications.
Summary of the invention
Technical problems based on background technology, the invention proposes a kind of iron manganese phosphate for lithium composite material and its preparations
Method, application, raw material sources are extensive, easy to operate, controllability is good, reproducibility is high, gained iron manganese phosphate for lithium composite material granular
It is smaller, particle diameter distribution is uniform, crystallinity is high, to improve the electrochemistry of material while reducing material preparation cost
Energy.
A kind of preparation method of iron manganese phosphate for lithium composite material proposed by the present invention, comprising the following steps:
S1, will manganese sulfate monohydrate, ferrous sulfate heptahydrate be added deionized water in, add ethylene glycol be uniformly mixing to obtain it is mixed
Close solution；Phosphoric acid ethylene glycol solution is added dropwise in lithium hydroxide ethylene glycol solution and is uniformly mixing to obtain white suspension, then is dripped
Mixed solution is added to stir evenly, then carries out hydro-thermal reaction, it is cooling, it is centrifuged, washing is dried to obtain LiMn0.5Fe0.5PO4Before
Drive body；
S2, successively lithium hydroxide, butyl titanate and lanthanum nitrate are dissolved in dehydrated alcohol stirring evenly, add from
Sub- water, is subsequently added into LiMn0.5Fe0.5PO4Presoma stirring, then carries out hydro-thermal reaction, cooling, is centrifuged, and washing is dried to obtain
Li0.3La0.56TiO3-LiMn0.5Fe0.5PO4Presoma；
S3, by Li0.3La0.56TiO3-LiMn0.5Fe0.5PO4Presoma is mixed with glucose, ball milling, is subsequently placed in logical
Enter in the tube furnace of inert gas and calcine, cooling, sieving obtains iron manganese phosphate for lithium composite material.
Preferably, in S1, lithium, phosphorus, manganese, iron elemental mole ratios be 3:1:0.5:0.5.
Preferably, in S1, phosphoric acid ethylene glycol solution is added dropwise to lithium hydroxide ethylene glycol with the speed of 0.8-1.2mL/min
White suspension is uniformly mixing to obtain in solution.
Preferably, in S1, then mixed solution is added dropwise to the speed of 1.8-2.2mL/min to white suspension and is stirred
It is even.
Preferably, in S1, hydrothermal temperature is 160-200 DEG C, the hydro-thermal reaction time 6-12h.
Preferably, in S2, hydrothermal temperature is 160-200 DEG C, the hydro-thermal reaction time 24-36h.
Preferably, the Li of S20.3La0.56TiO3-LiMn0.5Fe0.5PO4In presoma, Li0.3La0.56TiO3Mass fraction
For 1-10wt%, preferably 3-5wt%.
Preferably, in S3, Li0.3La0.56TiO3-LiMn0.5Fe0.5PO4The mass ratio of presoma and glucose is 1.5-
2.5:1.
Preferably, use ethyl alcohol as dispersing agent in the mechanical milling process of S3.
Preferably, in S3, inert gas is the mixed gas of hydrogen and argon gas, and wherein the volume ratio of hydrogen and argon gas is
95:5.
Preferably, in S3, specific step is as follows for calcining: being warming up to 300-400 DEG C, calcines 2.5-3.5h, then heat up
To 580-620 DEG C, 4.8-5.2h is calcined.
A kind of iron manganese phosphate for lithium composite material that the present invention also proposes, using the preparation of the iron manganese phosphate for lithium composite material
Method is made.
Preferably, microstructure is nano bar-shape.
Above-mentioned iron manganese phosphate for lithium composite material answering as positive electrode in power lithium-ion battery proposed by the present invention
With.
Compared with prior art, beneficial effects of the present invention:
1, present invention gained iron manganese phosphate for lithium composite material grain diameter is uniform, stable structure, densification, wherein
Li0.3La0.56TiO3It is a kind of fast-ionic conductor, electronics with higher and ionic conductivity, is conducive to lithium ion and electronics exists
Conduction between electrode material and electrolyte can be improved the discharge capacity and cycle performance of active material；
2, present invention gained iron manganese phosphate for lithium composite material granular uniformity, good dispersion, crystallinity are high, obtained material
Material has nanoscale partial size and rodlike pattern, and Li0.3La0.56TiO3It restrained effectively electrode in charge and discharge process
Impedance between electrolyte interface increases, and is conducive to the chemical property for improving material；
3, present invention gained iron manganese phosphate for lithium composite material has considerable energy density, excellent high rate performance and stabilization
Cycle life so that the material with very high actual use be worth, can effectively meet the various applications of lithium ion battery
Actual requirement.
4, present invention gained iron manganese phosphate for lithium composite material theoretical capacity with higher and quick charge-discharge performance, mention
The high energy density and power density of lithium ion battery, used raw material are cheap and easy to get.
Detailed description of the invention
Fig. 1 is the XRD diagram of iron manganese phosphate for lithium composite material obtained by 1-3 of the embodiment of the present invention；Wherein a is 1 gained of embodiment
Iron manganese phosphate for lithium composite material, b are 2 gained iron manganese phosphate for lithium composite material of embodiment, and c is 3 gained iron manganese phosphate for lithium of embodiment
Composite material.
Fig. 2 is the SEM figure of iron manganese phosphate for lithium composite material obtained by 1-4 of the embodiment of the present invention；Wherein a is 1 gained of embodiment
Iron manganese phosphate for lithium composite material, b are 2 gained iron manganese phosphate for lithium composite material of embodiment, and c is 3 gained iron manganese phosphate for lithium of embodiment
Composite material；D is 4 gained iron manganese phosphate for lithium composite material of embodiment
Fig. 3 is the first charge-discharge song that battery is formed using iron manganese phosphate for lithium composite material obtained by 1-3 of the embodiment of the present invention
Line chart；Wherein a is 1 gained iron manganese phosphate for lithium composite material of embodiment, and b is 2 gained iron manganese phosphate for lithium composite material of embodiment, c
For 3 gained iron manganese phosphate for lithium composite material of embodiment.
Fig. 4 is the 5C circulation that battery is formed using iron manganese phosphate for lithium composite material obtained by 1-3 of the embodiment of the present invention
It can curve graph；Wherein a is 1 gained iron manganese phosphate for lithium composite material of embodiment, and b is 2 gained iron manganese phosphate lithium composite of embodiment
Material, c are 3 gained iron manganese phosphate for lithium composite material of embodiment.
Specific embodiment
In the following, technical solution of the present invention is described in detail by specific embodiment.
Embodiment 1
A kind of preparation method of iron manganese phosphate for lithium composite material, comprising the following steps:
S1, it 0.06mol lithium hydroxide is dissolved in 60mL ethylene glycol obtains lithium hydroxide ethylene glycol solution；It will
0.02mol phosphoric acid, which is dissolved in 30mL ethylene glycol, obtains phosphoric acid ethylene glycol solution；By 0.01mol manganese sulfate monohydrate, 0.01mol seven
Aqueous ferrous sulfate is added in 10mL deionized water, adds 60mL ethylene glycol and is uniformly mixing to obtain mixed solution；By phosphoric acid second two
Alcoholic solution is added dropwise in lithium hydroxide ethylene glycol solution with the speed of 1mL/min and is uniformly mixing to obtain white suspension, then with
The speed of 2mL/min is added dropwise to mixed solution and stirs evenly, and then carries out hydro-thermal reaction 10h, and hydrothermal temperature is 180 DEG C,
Cooling, centrifugation is respectively washed 3 times with deionized water and dehydrated alcohol, and dry 10h obtains LiMn0.5Fe0.5PO4Presoma；
S2, successively 0.00016mol lithium hydroxide, 0.00054mol butyl titanate and 0.0003mol lanthanum nitrate be dissolved in
It is stirred evenly in dehydrated alcohol, adds deionized water, be subsequently added into 3.14g LiMn0.5Fe0.5PO4Presoma stirring, then
Hydro-thermal reaction 36h is carried out, hydrothermal temperature is 180 DEG C, and cooling, centrifugation is respectively washed 3 times with deionized water and dehydrated alcohol,
Dry 10h, obtains Li0.3La0.56TiO3-LiMn0.5Fe0.5PO4Presoma；
S3, by Li0.3La0.56TiO3-LiMn0.5Fe0.5PO4Presoma is that 2:1 is mixed with glucose in mass ratio, ball
5h is ground, uses ethyl alcohol as dispersing agent in mechanical milling process, is subsequently placed in the tube furnace for the mixed gas for being passed through hydrogen and argon gas,
Wherein the volume ratio of hydrogen and argon gas is 95:5, is warming up to 350 DEG C, calcines 3h, then heats to 600 DEG C, calcines 5h, cooling,
Sieving obtains iron manganese phosphate for lithium composite material.
As shown in Figure 1, show that gained iron manganese phosphate for lithium composite material has single olivine structural through XRD detection, and
Crystallinity is high.Due to Li0.3La0.56TiO3Content is less, so without discovery Li in XRD spectrum0.3La0.56TiO3Feature
Peak.
As shown in Fig. 2, learning from SEM: the even particle size of gained iron manganese phosphate for lithium composite material is consistent, is
Nano bar-shape, and the length of nanometer rods, within the scope of 100-200nm, width is in 50-100nm or so.
Using iron manganese phosphate for lithium composite material obtained by the present embodiment as positive electrode, assembled in the glove box full of argon gas
At experiment fastening lithium ionic cell, charge and discharge cycles are carried out between 2.4-4.5V with 0.05C multiplying power.As shown in figure 3, gained phosphoric acid
The discharge capacity for the first time of manganese iron lithium composite material is 146.2mAhg-1；From fig. 4, it can be seen that under the big multiplying power of 5C for the first time
Discharge capacity is 131.3mAhg-1, and capacity is 106.4mAhg-1 after circulation 100 weeks, and capacity retention ratio 81.0% is shown
Showing the present invention has excellent high rate performance and cyclical stability.
Embodiment 2
A kind of preparation method of iron manganese phosphate for lithium composite material, comprising the following steps:
S1, it 0.06mol lithium hydroxide is dissolved in 60mL ethylene glycol obtains lithium hydroxide ethylene glycol solution；It will
0.02mol phosphoric acid, which is dissolved in 30mL ethylene glycol, obtains phosphoric acid ethylene glycol solution；By 0.01mol manganese sulfate monohydrate, 0.01mol seven
Aqueous ferrous sulfate is added in 10mL deionized water, adds 60mL ethylene glycol and is uniformly mixing to obtain mixed solution；By phosphoric acid second two
Alcoholic solution is added dropwise in lithium hydroxide ethylene glycol solution with the speed of 1mL/min and is uniformly mixing to obtain white suspension, then with
The speed of 2mL/min is added dropwise to mixed solution and stirs evenly, and then carries out hydro-thermal reaction 10h, and hydrothermal temperature is 180 DEG C,
Cooling, centrifugation is respectively washed 3 times with deionized water and dehydrated alcohol, and dry 10h obtains LiMn0.5Fe0.5PO4Presoma；
S2, successively 0.00027mol lithium hydroxide, 0.0009mol butyl titanate and 0.0005mol lanthanum nitrate be dissolved in
It is stirred evenly in dehydrated alcohol, adds deionized water, be subsequently added into 3.14g LiMn0.5Fe0.5PO4Presoma stirring, then
Hydro-thermal reaction 36h is carried out, hydrothermal temperature is 180 DEG C, and cooling, centrifugation is respectively washed 3 times with deionized water and dehydrated alcohol,
Dry 10h, obtains Li0.3La0.56TiO3-LiMn0.5Fe0.5PO4Presoma；
S3, by Li0.3La0.56TiO3-LiMn0.5Fe0.5PO4Presoma is that 2:1 is mixed with glucose in mass ratio, ball
5h is ground, uses ethyl alcohol as dispersing agent in mechanical milling process, is subsequently placed in the tube furnace for be passed through inert gas and is warming up to 350 DEG C,
3h is calcined, then heats to 600 DEG C, calcines 5h, cooling, sieving obtains iron manganese phosphate for lithium composite material.
As shown in Figure 1, show that gained iron manganese phosphate for lithium composite material has single olivine structural through XRD detection, and
Crystallinity is high.Due to Li0.3La0.56TiO3Content is less, so without discovery Li in XRD spectrum0.3La0.56TiO3Feature
Peak.
As shown in Fig. 2, learning from SEM: the even particle size of gained iron manganese phosphate for lithium composite material is consistent, is
Nano bar-shape, and the length of nanometer rods, within the scope of 100-200nm, width is in 50-100nm or so.
Using iron manganese phosphate for lithium composite material obtained by the present embodiment as positive electrode, assembled in the glove box full of argon gas
At experiment fastening lithium ionic cell, charge and discharge cycles are carried out between 2.4-4.5V with 0.05C multiplying power.As shown in figure 3, gained phosphoric acid
The discharge capacity for the first time of manganese iron lithium composite material is 154.3mAhg-1；From fig. 4, it can be seen that putting under the big multiplying power of 5C for the first time
Capacitance is 128.8mAhg-1, capacity is 106.2mAhg after recycling 100 weeks-1, capacity retention ratio 82.5%, it is shown that
Excellent high rate performance and cyclical stability.
Embodiment 3
A kind of preparation method of iron manganese phosphate for lithium composite material, comprising the following steps:
S1, it 0.06mol lithium hydroxide is dissolved in 60mL ethylene glycol obtains lithium hydroxide ethylene glycol solution；It will
0.02mol phosphoric acid, which is dissolved in 30mL ethylene glycol, obtains phosphoric acid ethylene glycol solution；By 0.01mol manganese sulfate monohydrate, 0.01mol seven
Aqueous ferrous sulfate is added in 10mL deionized water, adds 60mL ethylene glycol and is uniformly mixing to obtain mixed solution；By phosphoric acid second two
Alcoholic solution is added dropwise in lithium hydroxide ethylene glycol solution with the speed of 1mL/min and is uniformly mixing to obtain white suspension, then with
The speed of 2mL/min is added dropwise to mixed solution and stirs evenly, and then carries out hydro-thermal reaction 10h, and hydrothermal temperature is 180 DEG C,
Cooling, centrifugation is respectively washed 3 times with deionized water and dehydrated alcohol, and dry 10h obtains LiMn0.5Fe0.5PO4Presoma；
S2,0.00054mol lithium hydroxide, 0.0018mol butyl titanate and 0.001mol lanthanum nitrate be successively dissolved in nothing
It is stirred evenly in water-ethanol, adds deionized water, be subsequently added into 3.14g LiMn0.5Fe0.5PO4Presoma stirring, then into
Row hydro-thermal reaction 36h, hydrothermal temperature is 180 DEG C, cooling, and centrifugation is respectively washed 3 times with deionized water and dehydrated alcohol, is done
Dry 10h, obtains Li0.3La0.56TiO3-LiMn0.5Fe0.5PO4Presoma；
S3, by Li0.3La0.56TiO3-LiMn0.5Fe0.5PO4Presoma is that 2:1 is mixed with glucose in mass ratio, ball
5h is ground, uses ethyl alcohol as dispersing agent in mechanical milling process, is subsequently placed in the tube furnace for be passed through inert gas and is warming up to 350 DEG C,
3h is calcined, then heats to 600 DEG C, calcines 5h, cooling, sieving obtains iron manganese phosphate for lithium composite material.
As shown in Figure 1, show that gained iron manganese phosphate for lithium composite material has single olivine structural through XRD detection, and
Crystallinity is high.Due to Li0.3La0.56TiO3Content is less, so without discovery Li in XRD spectrum0.3La0.56TiO3Feature
Peak.
As shown in Fig. 2, learning from SEM: the even particle size of gained iron manganese phosphate for lithium composite material is consistent, is
Nano bar-shape, and the length of nanometer rods, within the scope of 100-200nm, width is in 50-100nm or so.
Using iron manganese phosphate for lithium composite material obtained by the present embodiment as positive electrode, assembled in the glove box full of argon gas
At experiment fastening lithium ionic cell, charge and discharge cycles are carried out between 2.4-4.5V with 0.05C multiplying power.As shown in figure 3, gained phosphoric acid
The discharge capacity for the first time of manganese iron lithium composite material is 135.2mAhg-1；From fig. 4, it can be seen that putting under the big multiplying power of 5C for the first time
Capacitance is 124.8mAhg-1, capacity is 97.7mAhg after recycling 100 weeks-1, capacity retention ratio 78.3%, it is shown that
Excellent high rate performance and cyclical stability.
Embodiment 4
A kind of preparation method of iron manganese phosphate for lithium composite material, comprising the following steps:
S1, it 0.06mol lithium hydroxide is dissolved in 60mL ethylene glycol obtains lithium hydroxide ethylene glycol solution；It will
0.02mol phosphoric acid, which is dissolved in 30mL ethylene glycol, obtains phosphoric acid ethylene glycol solution；By 0.01mol manganese sulfate monohydrate, 0.01mol seven
Aqueous ferrous sulfate is added in 10mL deionized water, adds 60mL ethylene glycol and is uniformly mixing to obtain mixed solution；By phosphoric acid second two
Alcoholic solution is added dropwise in lithium hydroxide ethylene glycol solution with the speed of 1mL/min and is uniformly mixing to obtain white suspension, then with
The speed of 2mL/min is added dropwise to mixed solution and stirs evenly, and then carries out hydro-thermal reaction 10h, and hydrothermal temperature is 180 DEG C,
Cooling, centrifugation is respectively washed 3 times with deionized water and dehydrated alcohol, and dry 10h obtains LiMn0.5Fe0.5PO4Presoma；
S2, successively 0.00027mol lithium hydroxide, 0.0009mol butyl titanate and 0.0005mol lanthanum nitrate be dissolved in
It is stirred evenly in dehydrated alcohol, adds deionized water, be subsequently added into 3.14g LiMn0.5Fe0.5PO4Presoma stirring, then
Carrying out hydro-thermal reaction for 24 hours, hydrothermal temperature is 180 DEG C, and cooling, centrifugation is respectively washed 3 times with deionized water and dehydrated alcohol,
Dry 10h, obtains Li0.3La0.56TiO3-LiMn0.5Fe0.5PO4Presoma；
S3, by Li0.3La0.56TiO3-LiMn0.5Fe0.5PO4Presoma is that 2:1 is mixed with glucose in mass ratio, ball
5h is ground, uses ethyl alcohol as dispersing agent in mechanical milling process, is subsequently placed in the tube furnace for the mixed gas for being passed through hydrogen and argon gas,
Wherein the volume ratio of hydrogen and argon gas is 95:5, is warming up to 350 DEG C, calcines 3h, then heats to 600 DEG C, calcines 5h, cooling,
Sieving obtains iron manganese phosphate for lithium composite material.
Show that gained iron manganese phosphate for lithium composite material has single olivine structural through XRD detection, and crystallinity is high.
Due to Li0.3La0.56TiO3Content is less, so without discovery Li in XRD spectrum0.3La0.56TiO3Characteristic peak.While from
Observation is learnt in SEM: the even particle size of gained iron manganese phosphate for lithium composite material is consistent, is nano bar-shape, and nanometer rods
Length within the scope of 200-300nm, width is in 50-100nm or so.
Using iron manganese phosphate for lithium composite material obtained by the present embodiment as positive electrode, assembled in the glove box full of argon gas
At experiment fastening lithium ionic cell, charge and discharge cycles are carried out between 2.4-4.5V with 0.05C multiplying power, gained iron manganese phosphate for lithium is compound
The discharge capacity for the first time of material is 143.6mAhg-1；And the discharge capacity for the first time under the big multiplying power of 5C is 125.5mAhg-1,
Capacity is 107.2mAhg after recycling 100 weeks-1, capacity retention ratio 85.4%, it is shown that excellent high rate performance and circulation is steady
It is qualitative.
Embodiment 5
A kind of preparation method of iron manganese phosphate for lithium composite material, comprising the following steps:
S1, it 0.06mol lithium hydroxide is dissolved in 60mL ethylene glycol obtains lithium hydroxide ethylene glycol solution；It will
0.02mol phosphoric acid, which is dissolved in 30mL ethylene glycol, obtains phosphoric acid ethylene glycol solution；By 0.01mol manganese sulfate monohydrate, 0.01mol seven
Aqueous ferrous sulfate is added in 10mL deionized water, adds 60mL ethylene glycol and is uniformly mixing to obtain mixed solution；By phosphoric acid second two
Alcoholic solution is added dropwise in lithium hydroxide ethylene glycol solution with the speed of 1mL/min and is uniformly mixing to obtain white suspension, then with
The speed of 2mL/min is added dropwise to mixed solution and stirs evenly, and then carries out hydro-thermal reaction 10h, and hydrothermal temperature is 180 DEG C,
Cooling, centrifugation is respectively washed 3 times with deionized water and dehydrated alcohol, and dry 10h obtains LiMn0.5Fe0.5PO4Presoma；
S2, successively 0.00027mol lithium hydroxide, 0.0009mol butyl titanate and 0.0005mol lanthanum nitrate be dissolved in
It is stirred evenly in dehydrated alcohol, adds deionized water, be subsequently added into 3.14g LiMn0.5Fe0.5PO4Presoma stirring, then
Carrying out hydro-thermal reaction for 24 hours, hydrothermal temperature is 200 DEG C, and cooling, centrifugation is respectively washed 3 times with deionized water and dehydrated alcohol,
Dry 10h, obtains Li0.3La0.56TiO3-LiMn0.5Fe0.5PO4Presoma；
S3, by Li0.3La0.56TiO3-LiMn0.5Fe0.5PO4Presoma is that 2:1 is mixed with glucose in mass ratio, ball
5h is ground, uses ethyl alcohol as dispersing agent in mechanical milling process, is subsequently placed in the tube furnace for the mixed gas for being passed through hydrogen and argon gas,
Wherein the volume ratio of hydrogen and argon gas is 95:5, is warming up to 350 DEG C, calcines 3h, then heats to 600 DEG C, calcines 5h, cooling,
Sieving obtains iron manganese phosphate for lithium composite material.
Show that gained iron manganese phosphate for lithium composite material has single olivine structural through XRD detection, and crystallinity is high.
Due to Li0.3La0.56TiO3Content is less, so without discovery Li in XRD spectrum0.3La0.56TiO3Characteristic peak.While from
Observation is learnt in SEM: the even particle size of gained iron manganese phosphate for lithium composite material is consistent, is nano bar-shape, and nanometer rods
Length within the scope of 50-100nm, width is in 50nm or so.
Using iron manganese phosphate for lithium composite material obtained by the present embodiment as positive electrode, assembled in the glove box full of argon gas
At experiment fastening lithium ionic cell, charge and discharge cycles are carried out between 2.4-4.5V with 0.05C multiplying power, gained iron manganese phosphate for lithium is compound
The discharge capacity for the first time of material is 150.4mAhg-1；And the discharge capacity for the first time under the big multiplying power of 5C is 123.5mAhg-1,
Capacity is 104.7mAhg after recycling 100 weeks-1, capacity retention ratio 84.8%, it is shown that excellent high rate performance and circulation is steady
It is qualitative.
Embodiment 6
A kind of preparation method of iron manganese phosphate for lithium composite material, comprising the following steps:
S1, it 0.06mol lithium hydroxide is dissolved in 60mL ethylene glycol obtains lithium hydroxide ethylene glycol solution；It will
0.02mol phosphoric acid, which is dissolved in 30mL ethylene glycol, obtains phosphoric acid ethylene glycol solution；By 0.01mol manganese sulfate monohydrate, 0.01mol seven
Aqueous ferrous sulfate is added in 10mL deionized water, adds 60mL ethylene glycol and is uniformly mixing to obtain mixed solution；By phosphoric acid second two
Alcoholic solution is added dropwise in lithium hydroxide ethylene glycol solution with the speed of 1mL/min and is uniformly mixing to obtain white suspension, then with
The speed of 2mL/min is added dropwise to mixed solution and stirs evenly, and then carries out hydro-thermal reaction 12h, and hydrothermal temperature is 160 DEG C,
Cooling, centrifugation is respectively washed 3 times with deionized water and dehydrated alcohol, and dry 10h obtains LiMn0.5Fe0.5PO4Presoma；
S2, successively 0.00016mol lithium hydroxide, 0.00054mol butyl titanate and 0.0003mol lanthanum nitrate be dissolved in
It is stirred evenly in dehydrated alcohol, adds deionized water, be subsequently added into 3.14g LiMn0.5Fe0.5PO4Presoma stirring, then
Hydro-thermal reaction 36h is carried out, hydrothermal temperature is 160 DEG C, and cooling, centrifugation is respectively washed 3 times with deionized water and dehydrated alcohol,
Dry 10h, obtains Li0.3La0.56TiO3-LiMn0.5Fe0.5PO4Presoma；
S3, by Li0.3La0.56TiO3-LiMn0.5Fe0.5PO4Presoma is that 2:1 is mixed with glucose in mass ratio, ball
5h is ground, uses ethyl alcohol as dispersing agent in mechanical milling process, is subsequently placed in the tube furnace for the mixed gas for being passed through hydrogen and argon gas,
Wherein the volume ratio of hydrogen and argon gas is 95:5, is warming up to 350 DEG C, calcines 3h, then heats to 600 DEG C, calcines 5h, cooling,
Sieving obtains iron manganese phosphate for lithium composite material.
Show that gained iron manganese phosphate for lithium composite material has single olivine structural through XRD detection, and crystallinity is high.
Due to Li0.3La0.56TiO3Content is less, so without discovery Li in XRD spectrum0.3La0.56TiO3Characteristic peak.While from
Observation is learnt in SEM: the even particle size of gained iron manganese phosphate for lithium composite material is consistent, is nano bar-shape, and nanometer rods
Length within the scope of 100-200nm, width is in 100nm or so.
Using iron manganese phosphate for lithium composite material obtained by the present embodiment as positive electrode, assembled in the glove box full of argon gas
At experiment fastening lithium ionic cell, charge and discharge cycles are carried out between 2.4-4.5V with 0.05C multiplying power, gained iron manganese phosphate for lithium is compound
The discharge capacity for the first time of material is 142.9mAhg-1；And the discharge capacity for the first time under the big multiplying power of 5C is 118.8mAhg-1,
Capacity is 100.3mAhg after recycling 100 weeks-1, capacity retention ratio 84.4%, it is shown that excellent high rate performance and circulation is steady
It is qualitative.
Embodiment 7
A kind of preparation method of iron manganese phosphate for lithium composite material, comprising the following steps:
S1, it 0.06mol lithium hydroxide is dissolved in 60mL ethylene glycol obtains lithium hydroxide ethylene glycol solution；It will
0.02mol phosphoric acid, which is dissolved in 30mL ethylene glycol, obtains phosphoric acid ethylene glycol solution；By 0.01mol manganese sulfate monohydrate, 0.01mol seven
Aqueous ferrous sulfate is added in 10mL deionized water, adds 60mL ethylene glycol and is uniformly mixing to obtain mixed solution；By phosphoric acid second two
Alcoholic solution is added dropwise in lithium hydroxide ethylene glycol solution with the speed of 1mL/min and is uniformly mixing to obtain white suspension, then with
The speed of 2mL/min is added dropwise to mixed solution and stirs evenly, and then carries out hydro-thermal reaction 10h, and hydrothermal temperature is 200 DEG C,
Cooling, centrifugation is respectively washed 3 times with deionized water and dehydrated alcohol, and dry 10h obtains LiMn0.5Fe0.5PO4Presoma；
S2,0.00054mol lithium hydroxide, 0.0018mol butyl titanate and 0.001mol lanthanum nitrate be successively dissolved in nothing
It is stirred evenly in water-ethanol, adds deionized water, be subsequently added into 3.14g LiMn0.5Fe0.5PO4Presoma stirring, then into
Row hydro-thermal reaction 36h, hydrothermal temperature is 200 DEG C, cooling, and centrifugation is respectively washed 3 times with deionized water and dehydrated alcohol, is done
Dry 10h, obtains Li0.3La0.56TiO3-LiMn0.5Fe0.5PO4Presoma；
S3, by Li0.3La0.56TiO3-LiMn0.5Fe0.5PO4Presoma is that 2:1 is mixed with glucose in mass ratio, ball
5h is ground, uses ethyl alcohol as dispersing agent in mechanical milling process, is subsequently placed in the tube furnace for the mixed gas for being passed through hydrogen and argon gas,
Wherein the volume ratio of hydrogen and argon gas is 95:5, is warming up to 350 DEG C, calcines 3h, then heats to 600 DEG C, calcines 5h, cooling,
Sieving obtains iron manganese phosphate for lithium composite material.
Show that gained iron manganese phosphate for lithium composite material has single olivine structural through XRD detection, and crystallinity is high.
Due to Li0.3La0.56TiO3Content is less, so without discovery Li in XRD spectrum0.3La0.56TiO3Characteristic peak.While from
Observation is learnt in SEM: the even particle size of gained iron manganese phosphate for lithium composite material is consistent, is nano bar-shape, and nanometer rods
Length within the scope of 100-200nm, width is in 50-100nm or so.
Using iron manganese phosphate for lithium composite material obtained by the present embodiment as positive electrode, assembled in the glove box full of argon gas
At experiment fastening lithium ionic cell, charge and discharge cycles are carried out between 2.4-4.5V with 0.05C multiplying power, gained iron manganese phosphate for lithium is compound
The discharge capacity for the first time of material is 138.1mAhg-1；And the discharge capacity for the first time under the big multiplying power of 5C is 122.5mAhg-1,
Capacity is 98.7mAhg after recycling 100 weeks-1, capacity retention ratio 80.6%, it is shown that excellent high rate performance and circulation is steady
It is qualitative.
The foregoing is only a preferred embodiment of the present invention, but scope of protection of the present invention is not limited thereto,
Anyone skilled in the art in the technical scope disclosed by the present invention, according to the technique and scheme of the present invention and its
Inventive concept is subject to equivalent substitution or change, should be covered by the protection scope of the present invention.
Claims (10)
1. a kind of preparation method of iron manganese phosphate for lithium composite material, which comprises the following steps:
S1, will manganese sulfate monohydrate, ferrous sulfate heptahydrate be added deionized water in, add ethylene glycol be uniformly mixing to obtain mixing it is molten
Liquid；Phosphoric acid ethylene glycol solution is added dropwise in lithium hydroxide ethylene glycol solution and is uniformly mixing to obtain white suspension, then is added dropwise to
Mixed solution stirs evenly, and then carries out hydro-thermal reaction, cooling, is centrifuged, and washing is dried to obtain LiMn0.5Fe0.5PO4Presoma；
S2, it successively lithium hydroxide, butyl titanate and lanthanum nitrate is dissolved in dehydrated alcohol stirring evenly, add deionization
Water is subsequently added into LiMn0.5Fe0.5PO4Presoma stirring, then carries out hydro-thermal reaction, cooling, is centrifuged, and washing is dried to obtain
Li0.3La0.56TiO3-LiMn0.5Fe0.5PO4Presoma；
S3, by Li0.3La0.56TiO3-LiMn0.5Fe0.5PO4Presoma is mixed with glucose, ball milling, be subsequently placed in be passed through it is lazy
Property gas tube furnace in calcine, cooling, sieving obtains iron manganese phosphate for lithium composite material.
2. the preparation method of iron manganese phosphate for lithium composite material according to claim 1, which is characterized in that in S1, lithium, phosphorus, manganese,
The elemental mole ratios of iron are 3:1:0.5:0.5.
3. the preparation method of iron manganese phosphate for lithium composite material according to claim 1 or claim 2, which is characterized in that in S1, by phosphoric acid
Ethylene glycol solution is added dropwise in lithium hydroxide ethylene glycol solution with the speed of 0.8-1.2mL/min and is uniformly mixing to obtain white suspension
Liquid；Preferably, in S1, then mixed solution is added dropwise to the speed of 1.8-2.2mL/min to white suspension and is stirred evenly.
4. the preparation method of any one of -3 iron manganese phosphate for lithium composite materials according to claim 1, which is characterized in that in S1,
Hydrothermal temperature is 160-200 DEG C, the hydro-thermal reaction time 6-12h.
5. the preparation method of any one of -4 iron manganese phosphate for lithium composite materials according to claim 1, which is characterized in that in S2,
Hydrothermal temperature is 160-200 DEG C, the hydro-thermal reaction time 24-36h.
6. the preparation method of any one of -5 iron manganese phosphate for lithium composite materials according to claim 1, which is characterized in that S2's
Li0.3La0.56TiO3-LiMn0.5Fe0.5PO4In presoma, Li0.3La0.56TiO3Mass fraction be 1-10wt%, preferably 3-
5wt%.
7. the preparation method of any one of -6 iron manganese phosphate for lithium composite materials according to claim 1, which is characterized in that in S3,
Li0.3La0.56TiO3-LiMn0.5Fe0.5PO4The mass ratio of presoma and glucose is 1.5-2.5:1；Preferably, the ball milling mistake of S3
Using ethyl alcohol as dispersing agent in journey；Preferably, in S3, inert gas is the mixed gas of hydrogen and argon gas；Preferably, S3
In, specific step is as follows for calcining: being warming up to 300-400 DEG C, calcines 2.5-3.5h, then heats to 580-620 DEG C, calcining
4.8-5.2h。
8. a kind of iron manganese phosphate for lithium composite material, which is characterized in that multiple using any one of the claim 1-7 iron manganese phosphate for lithium
The preparation method of condensation material is made.
9. iron manganese phosphate for lithium composite material according to claim 8, which is characterized in that its microstructure is nano bar-shape.
10. one kind iron manganese phosphate for lithium composite material as described in claim 8 or 9 is used as positive electrode in power lithium-ion battery
Application.
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| CN116692818A (en) * | 2023-06-30 | 2023-09-05 | 浙江工业大学 | Preparation method and application of lithium iron manganese phosphate nanorod anode material |
| CN116902951A (en) * | 2023-07-10 | 2023-10-20 | 中国石油大学(北京) | Method for preparing lithium iron manganese phosphate positive electrode material based on titanium white byproduct ferrous sulfate |
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| CN110416541A (en) * | 2019-07-12 | 2019-11-05 | 大连恒超锂业科技有限公司 | A kind of preparation method of the modified phosphate iron lithium of morphology controllable |
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| CN116692818A (en) * | 2023-06-30 | 2023-09-05 | 浙江工业大学 | Preparation method and application of lithium iron manganese phosphate nanorod anode material |
| CN116902951A (en) * | 2023-07-10 | 2023-10-20 | 中国石油大学(北京) | Method for preparing lithium iron manganese phosphate positive electrode material based on titanium white byproduct ferrous sulfate |
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