CN107623107A - A kind of method for preparing lithium manganese phosphate cell positive material - Google Patents
A kind of method for preparing lithium manganese phosphate cell positive material Download PDFInfo
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- CN107623107A CN107623107A CN201710957964.9A CN201710957964A CN107623107A CN 107623107 A CN107623107 A CN 107623107A CN 201710957964 A CN201710957964 A CN 201710957964A CN 107623107 A CN107623107 A CN 107623107A
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
A kind of method for preparing lithium manganese phosphate cell positive material, comprises the following steps：（1）Manganese source, phosphorus source, carbon source are added to ball milling in high energy ball mill；（2）5~8h is incubated in 400~600 DEG C of protection gas, manganese phosphate presoma is obtained after cooling；（3）Weigh step（2）Gained manganese phosphate presoma and lithium source, reducing agent is added, then ultrasonic vibration, 30~60min of ultrasound under the conditions of 20000~50000Hz；Can drying process after ultrasound；（4）10~15h is incubated in 550~800 DEG C of protection gas, is produced after cooling.The manganese-lithium phosphate anode material that the present invention is obtained by the method for two sections of synthesis, on the one hand can reduce the microscopic dimensions of material, so as to shorten the diffusion length of lithium ion, improve the diffusion rate of lithium ion；On the other hand, the cycle performance and high rate performance of material can be improved by synthesizing the lithium manganese phosphate of specific morphology.
Description
Technical field
The present invention relates to technical field of lithium ion, more particularly to a kind of preparation of new manganese-lithium phosphate anode material
Method.
Background technology
Manganese-lithium phosphate anode material is because with higher energy density, cost is low, environmentally friendly, good thermal stability, theory
The advantages that energy density is big and there is huge potentiality to be exploited.The theoretical specific capacity of lithium manganese phosphate is 170mAh/g, discharge platform
For 4.1V, because it has higher discharge platform, therefore lithium manganese phosphate has higher energy density.But due to manganese phosphate
Electric conductivity, the ionic diffusion coefficient of lithium are extremely low, and electronics energy gap is 2eV, belongs to insulator, causes the high rate charge-discharge of material
Performance is bad, and electro-chemical activity is poor so that the application of material has obtained certain limitation.
The content of the invention
The technical problem to be solved in the present invention is overcome the deficiencies in the prior art, there is provided one kind prepares lithium manganese phosphate battery
The method of positive electrode, manganese-lithium phosphate anode material is synthesized by preparing precursor manganese phosphate, effectively improves lithium manganese phosphate positive pole
The electro-chemical activity of material.
It is a kind of side for preparing lithium manganese phosphate cell positive material that the present invention, which solves the technical scheme that its technical problem uses,
Method, comprise the following steps：
（1）By manganese source, phosphorus source, carbon source by manganese element, P elements, carbon mol ratio be 1:1:0.25~1（It is preferred that 1:1:
0.25~0.5）Ratio be added in high energy ball mill, with 200~500rpm ball millings, 6~10h；
It if using common ball mill, can mix uneven, and the particle diameter of material can be big；
（2）Will be through step（1）The material of processing is incubated 5~8h in 400~600 DEG C of protection gas, and manganese phosphate is obtained after cooling
Presoma（MnPO4）；
（3）It is 1 by manganese phosphate presoma and elemental lithium mol ratio：1-1.1 weighs step（2）Gained manganese phosphate presoma and lithium
Source, the reducing agent equivalent to manganese phosphate presoma and lithium source gross mass 5~25% is added, then ultrasonic vibration, 20000~
30~60min of ultrasound under the conditions of 50000Hz；Can drying process after ultrasound；
Reducing agent is added in this step, first, for reducing MnPO4In manganic, second, as carbon source；If reducing agent mistake
Amount, carbon content is too high, and positive active material will be reduced, and cause battery capacity to reduce；If reducing agent is very little, MnPO4Can not
Reduced completely, the battery gram volume of gained can be caused to decline.
（4）Will be through step（3）The material of processing is incubated 10~15h in 550~800 DEG C of protection gas, is obtained after cooling
The manganese-lithium phosphate anode material of manganese-lithium phosphate anode material-carbon coating.
Further, step（1）In, the manganese source can be at least one of manganese carbonate, manganese oxalate, mangano-manganic oxide.
Further, step（1）In, phosphorus source is at least one of ammonium dihydrogen phosphate, diammonium hydrogen phosphate.
Further, step（1）In, the carbon source is at least one of glucose, sucrose, citric acid, oxalic acid.
Further, step（2）In, the protection gas is at least one of argon gas, nitrogen, carbon dioxide.
Further, step（3）In, the lithium source can be lithium carbonate, lithium hydroxide, lithium acetate, in lithium oxalate at least
It is a kind of.
Further, step（3）In, the reducing agent is at least one of glucose, sucrose, citric acid, oxalic acid.
Further, step（4）In, the protection gas is at least one of argon gas, nitrogen, carbon dioxide.
Due to LiMnPO4Electric conductivity it is extremely low, electronics energy gap is 2eV, belongs to insulator, causes the big multiplying power of material to be filled
Discharge performance is bad, and electro-chemical activity is poor.And the present invention synthesizes LiMnPO by two-stage method4, added in preparation process
Appropriate carbon coats to it；And it can not obtain if only by mechanical agitation during coating and mix homogeneous phosphoric acid
Manganese lithium precursor, therefore the present invention makes carbon coating uniform by sonic oscillation, can improve the electrochemistry of manganese-lithium phosphate anode material
Performance.
The present invention reduces raw material particle size by high-energy ball milling, reduces fermi level so that the activation energy rise of raw material；It is another
Aspect, it can be refined by sonic oscillation with diplomatic corps's polyphosphoric acid manganese presoma, allow carbon source more abundant in sintering process
The surface for being coated on lithium manganese phosphate, so as to lift the performance of material.
The manganese-lithium phosphate anode material that the present invention is obtained by the method for two sections of synthesis, on the one hand can reduce the micro- of material
Size is seen, so as to shorten the diffusion length of lithium ion, improves the diffusion rate of lithium ion；On the other hand, by synthesizing specific shape
The lithium manganese phosphate of looks can improve the cycle performance and high rate performance of material.
Brief description of the drawings
Fig. 1,2,3 correspond to manganese-lithium phosphate anode material and the XRD of standard PDF cards contrast in embodiment 1,2,3 and divided respectively
Analysis figure.
Fig. 4 be in embodiment 1,2,3 manganese-lithium phosphate anode material in 0.1C first charge-discharge curve maps（From left to right distinguish
For embodiment 1,2,3）；
Fig. 5 is the preceding 50 circle circulation figure that battery is made in the gained manganese-lithium phosphate anode material of embodiment 3；
Fig. 6 is that the high rate performance comparison diagram after battery is made with positive electrode obtained by comparative example in embodiment 3.
Embodiment
The present invention is described in further detail below in conjunction with the drawings and specific embodiments.
Comparative example
This comparative example comprises the following steps：
（1）Weigh spherical mangano-manganic oxide 0.05mol, ammonium dihydrogen phosphate 0.15mol and oxalic acid 0.025mol and be added to high energy ball
In grinding machine, 6h is stirred under 250rpm；
（2）Will be through step（1）The material of processing obtains manganese phosphate in 400 DEG C of heat-agglomerating 6h after cooling；
（3）Weigh manganese phosphate and each 0.05mol of lithium hydroxide, then by ultrasonic vibration under the conditions of 30000Hz it is ultrasonic
30min, homogeneous sample is obtained after drying；
（4）By resulting sample in atmosphere with 700 DEG C of heat-agglomerating 10h, manganese-lithium phosphate anode material is obtained after cooling,
It is named as LiMnPO4-0。
Manganese-lithium phosphate anode material obtained by this comparative example is made into button cell and carries out charge-discharge performance test, is controlled
Charging/discharging voltage scope processed is 2.5~4.5V, charging and discharging currents 0.1C, measures the electric discharge first of CR2025 type button cells
Specific capacity is 96.1mAh/g.
It is inadequate without addition reducing agent, the carbon of cladding in step 3 in this comparative example so that manufactured battery performance is bad.
Embodiment 1
The present embodiment comprises the following steps：
（1）Weigh spherical mangano-manganic oxide 0.05mol, ammonium dihydrogen phosphate 0.15mol and oxalic acid 0.025mol and be added to high energy ball
In grinding machine, ball milling 6h under 250rpm；
（2）Will be through step（1）The material of processing heat-agglomerating 6h in the case where 400 DEG C of nitrogen are protected, before obtaining manganese phosphate after cooling
Drive body（MnPO4）；
（3）Weigh step（2）Gained manganese phosphate presoma and each 0.05mol of lithium hydroxide（Totally 8.7 grams）, add glucose
0.98g, then by ultrasonic vibration, the ultrasonic 30min under the conditions of 30000Hz, homogeneous product is obtained after drying；
（4）Will be through step（3）The material of processing, with 600 DEG C of heat-agglomerating 10h, lithium manganese phosphate is being obtained just after cooling in nitrogen
Pole material, is named as LiMnPO4-1。
Button cell is made in manganese-lithium phosphate anode material obtained by the present embodiment and carries out charge-discharge performance test, is controlled
Charging/discharging voltage scope processed is 2.5~4.5V, charging and discharging currents 0.1C, measures the electric discharge first of CR2025 type button cells
Specific capacity is 120.4mAh/g.
Embodiment 2
The present embodiment comprises the following steps：
（1）Weigh spherical mangano-manganic oxide 0.05mol, ammonium dihydrogen phosphate 0.15mol, oxalic acid 0.025mol and be added to high-energy ball milling
In machine, ball grinding stirring 6h under 250rpm；
（2）Will be through step（1）The material of processing heat-agglomerating 6h in 400 DEG C of argon gas protect gas, manganese phosphate is obtained after cooling
Presoma（MnPO4）；
（3）Weigh step（2）Gained manganese phosphate presoma and each 0.05mol of lithium hydroxide, add glucose 1.96g, then
Homogeneous product is obtained after ultrasonic 30min dryings under the conditions of 30000Hz by ultrasonic vibration；
（4）Will be through step（3）The material of processing 600 DEG C of sintering 10h in argon gas, lithium manganese phosphate positive pole material is obtained after cooling
Material, is named as LiMnPO4-2。
Button cell is made in manganese-lithium phosphate anode material obtained by the present embodiment and carries out charge-discharge performance test, is controlled
Charging/discharging voltage scope processed is 2.5~4.5V, charging and discharging currents 0.1C, measures the electric discharge first of CR2025 type button cells
Specific capacity is 130.5mAh/g.
Embodiment 3
The present embodiment comprises the following steps：
（1）Weigh spherical mangano-manganic oxide 0.05mol, ammonium dihydrogen phosphate 0.15mol, oxalic acid 0.025mol and be added to high-energy ball milling
In machine, ball grinding stirring 6h under 250rpm；
（2）Will be through step（1）The material of processing heat-agglomerating 6h in the case where 400 DEG C of nitrogen are protected, before obtaining manganese phosphate after cooling
Drive body（MnPO4）；
（3）Weigh step（2）Gained manganese phosphate presoma and each 0.05mol of lithium hydroxide, add glucose 1.96g, then
Homogeneous product is obtained after ultrasonic 30min dryings under the conditions of 30000Hz by ultrasonic vibration；
（4）By step（3）Resulting product 700 DEG C of sintering 10h in argon gas, lithium manganese phosphate positive pole material is obtained after cooling
Material, is named as LiMnPO4-3。
Button cell is made in manganese-lithium phosphate anode material obtained by the present embodiment and carries out charge-discharge performance test, is controlled
Charging/discharging voltage scope processed is 2.5~4.5V, charging and discharging currents 0.1C, measures the electric discharge first of CR2025 type button cells
Specific capacity is 148.8mAh/g.
From comparative example 1 and embodiment 1-3 result, lithium manganese phosphate material, which is synthesized by two-step process, has preferably electricity
Chemical property.
Claims (9)
- A kind of 1. method for preparing lithium manganese phosphate cell positive material, it is characterised in that comprise the following steps：（1）By manganese source, phosphorus source, carbon source by manganese element, P elements, carbon mol ratio be 1:1:0.25~1 ratio adds Into high energy ball mill, with 200~500rpm ball millings, 6~10h；（2）Will be through step（1）The material of processing is incubated 5~8h in 400~600 DEG C of protection gas, and manganese phosphate is obtained after cooling Presoma；（3）It is 1 by manganese phosphate presoma and elemental lithium mol ratio：1-1.1 weighs step（2）Gained manganese phosphate presoma and lithium Source, the reducing agent equivalent to manganese phosphate presoma and lithium source gross mass 5~25% is added, then ultrasonic vibration, 20000~ 30~60min of ultrasound under the conditions of 50000Hz；Can drying process after ultrasound；（4）Will be through step（3）The material of processing is incubated 10~15h in 550~800 DEG C of protection gas, and phosphoric acid is obtained after cooling The manganese-lithium phosphate anode material of manganese lithium anode material-carbon coating.
- 2. the method according to claim 1 for preparing lithium manganese phosphate cell positive material, it is characterised in that step（1）In, Manganese element, P elements, the mol ratio of carbon are 1:1:0.25~0.5.
- 3. the method according to claim 1 or 2 for preparing lithium manganese phosphate cell positive material, it is characterised in that step（1） In, the manganese source is at least one of manganese carbonate, manganese oxalate, mangano-manganic oxide.
- 4. the method according to claim 1 or 2 for preparing lithium manganese phosphate cell positive material, it is characterised in that step（1） In, phosphorus source is at least one of ammonium dihydrogen phosphate, diammonium hydrogen phosphate.
- 5. the method according to claim 1 or 2 for preparing lithium manganese phosphate cell positive material, it is characterised in that step（1） In, the carbon source is at least one of glucose, sucrose, citric acid, oxalic acid.
- 6. the method according to claim 1 or 2 for preparing lithium manganese phosphate cell positive material, it is characterised in that step（2） In, the protection gas is at least one of argon gas, nitrogen, carbon dioxide.
- 7. the method according to claim 1 or 2 for preparing lithium manganese phosphate cell positive material, it is characterised in that step（3） In, the lithium source is at least one of lithium carbonate, lithium hydroxide, lithium acetate, lithium oxalate.
- 8. the method according to claim 1 or 2 for preparing lithium manganese phosphate cell positive material, it is characterised in that step（3） In, the reducing agent is at least one of glucose, sucrose, citric acid, oxalic acid.
- 9. the method according to claim 1 or 2 for preparing lithium manganese phosphate cell positive material, it is characterised in that step（4） In, the protection gas is at least one of argon gas, nitrogen, carbon dioxide.
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Cited By (1)
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| CN108695573A (en) * | 2018-05-30 | 2018-10-23 | 安徽南都华铂新材料科技有限公司 | A kind of electro-chemical activity restorative procedure of failure lithium manganese phosphate |
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