CN104051713B - A kind of preparation method of micro-nano spherical composite ferric lithium phosphate material - Google Patents

A kind of preparation method of micro-nano spherical composite ferric lithium phosphate material Download PDF

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CN104051713B
CN104051713B CN201410311902.7A CN201410311902A CN104051713B CN 104051713 B CN104051713 B CN 104051713B CN 201410311902 A CN201410311902 A CN 201410311902A CN 104051713 B CN104051713 B CN 104051713B
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陈晗
白宁波
张优良
向楷雄
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Hunan University of Technology
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    • H—ELECTRICITY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • 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
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    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
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Abstract

The preparation method that the invention discloses a kind of micro-nano spherical lithium ferric phosphate composite positive pole material。Preparation method is as follows: by the lithium compound of solubility, iron compound and phosphate by lithium, ferrum, phosphorus atomic ratio be that 1:1:1 mixing is dissolved in deionized water formation solution, solution is joined in the mixed liquor of binding agent, stirring is uniformly mixed liquid。Then in oil bath pan, add appropriate conduction oil, oil bath is put into a beaker equipped with high temperature heat conductive oil, Homogeneous phase mixing liquid is instilled with certain speed in the beaker of high temperature heat conductive oil with certain mixing speed, react completely and be filtrated to get ferric lithium phosphate precursor, finally by the forerunner's high temperature carbonization in an inert atmosphere after washing and synthesis, form a kind of micro-nano spherical lithium ferric phosphate composite positive pole material with high-tap density。

Description

A kind of preparation method of micro-nano spherical composite ferric lithium phosphate material
Technical field
The present invention relates to a kind of cell positive material and preparation thereof, particularly relate to positive electrode of a kind of secondary lithium battery or power source battery and preparation method thereof。
Background technology
Lithium ion battery, since the nineties appearance in last century, has been considered as the choosing of the ideal of high power capacity, high power battery because of its high-energy-density, good cycle performance and charged protective capability。In lithium ion battery, positive electrode make consumption very big, which increase the production cost of lithium ion battery。At present, the material as anode material for lithium-ion batteries is mainly lithium-containing transition metal oxide, including LiMO(M=Co, Ni, Mn of layer structure) and the LiMn of spinel-type2O4。But, these materials are due to price (LiCoO2), safety (LiNiO2), high-temperature electrochemical properties (LiMn2O4) etc. reason make them be subject to many restrictions in the application aspect of high-capacity battery。Therefore, find new cheap, function admirable positive electrode active materials and become the emphasis of Study on Li-ion batteries。
Goodenough group reported first in 1997 LiFePO 4 (LiFePO4) chemical property。Hereafter, the research used as anode active material of lithium ion battery becomes focus。LiFePO4Reversible theoretical specific capacity up to 170mAh/g；Charge and discharge current potential is 3.4V(vs.Li+/ Li), lower than the decomposition voltage of most of electrolyte, there is good safety。LiFePO4Cycle performance and good thermal stability, particularly when high temperature, cycle performance is more preferably；What is more important, its abundant raw material source, being compatible with the environment property is good。With LiCoO2、LiNiO2And LiMn2O4Difference, LiFePO4Having stable olivine-type crystal structure, Li insertion extraction is reacted at LiFePO4And FePO4Close biphase of unit cell dimension carries out；In charge and discharge process, the change in volume of material is little, and the contraction of volume, expansion be both not result in the destruction of crystal structure, without the conductive network that impact is made up of binding agent and conductive agent, adds the service life of battery。Therefore, LiFePO4It it is considered as a kind of desirably anode material for lithium-ion batteries。
LiFePO4Belong to the polyanionic compound of olivine structural, due to its crystal structure, LiFePO4There is relatively low electronic conductivity and lithium ion diffusion coefficient, hinder its business-like application to a certain extent。At present, LiFePO is improved4The effective way of chemical property mainly has carbon cladding and high volence metal ion two kinds of methods of doping。Carbon cladding can improve LiFePO4Intergranular electric conductivity, can reduce again LiFePO4The size of granule, and then improve LiFePO4Macroscopical chemical property。But carbon cladding there is also following problem: first, amorphous carbon is difficult to be uniformly distributed between particles, and the stability of properties of product is difficult to ensure that；Secondly, the addition of amorphous carbon, make tap density be decreased obviously, this makes LiFePO4The improvement of performance and the raising of tap density can not organically be united。When adopting the method for high volence metal ion doping, metal ion improves LiFePO after entering lattice4Crystal structure so that it is electronic conductivity obtains the raising of essence, thus improving its macroscopic view chemical property, but how to make high volence metal ion enter precisely into LiFePO4Crystal enter lithium position or ferrum position, be current problem more rambunctious。
Summary of the invention
The technical problem to be solved in the present invention is to overcome the deficiencies in the prior art, it is provided that a kind of micro-nano spherical LiFePO with high-tap density4The preparation method of/C composite positive pole, this preparation method technique is simple, processing ease, less costly。
For solving above-mentioned technical problem, the technical scheme that the present invention proposes is a kind of LiFePO4The preparation method of/C composite positive pole, it is characterized in that: with high temperature heat conductive oil for reaction medium, with high molecular polymer for binding agent, instill after dissolving mixing with the lithium compound of solubility, iron compound and phosphate equipped with in the large beaker of conduction oil quickly stirring react, and by product high temperature carbonization under an inert atmosphere be synthetically formed with micro-nano spherical composite positive pole。The lithium compound of solubility, iron compound and phosphatic lithium ion, ferrum or ferrous ion, phosphate anion are called effective ion。
In technique scheme, described high temperature heat conductive oil is one or more in JARYTHERM-DBT type conduction oil, SERIOLA-1510 type conduction oil, SERIOLA-320 type conduction oil, SERIOLA-350 type conduction oil, WD-400 type conduction oil, AH-345 type conduction oil, dibenzyl toluene high temperature heat conductive oil。
In technique scheme, the structure of described composite is with Polyethylene Glycol or polyvinyl alcohol for binding agent and carbon source, the presoma of reacted generation in high temperature oil bath, at high temperature carbonization, is synthetically formed the micro-nano spherical LiFePO with superperformance4/ C composite。
In technique scheme, the temperature of described high temperature oil bath is 200 DEG C ~ 500 DEG C。
In technique scheme, mixed solution instill the speed in high temperature heat conductive oil be 20-100 drip/minute。
In technique scheme, during reaction, stir speed (S.S.) is 150-1000r/min。
In technique scheme, reaction is to carry out in equipped with the large beaker of conduction oil。
The present invention provides a kind of and has micro-nano spherical LiFePO4The preparation method of/C composite positive pole, it is characterized in that: by the lithium compound of solubility, iron compound and phosphate press lithium, ferrum, the atomic ratio of phosphorus is that 1:1:1 mixing is dissolved in deionized water, add polyvinyl alcohol, polyacrylic acid, one or more in Polyethylene Glycol are as binding agent, ultrasonic disperse is uniform, then pass through in beaker mixed solution uniformly instilled containing high temperature heat conductive oil and react, the presoma filtration washing that will be obtained by reacting, last high temperature carbonization and synthesis in an inert atmosphere, formed with high molecular polymer for binding agent and carbon source, there is the micro-nano spherical LiFePO of high-tap density4/ C composite positive pole。The preparation method of the present invention mainly makes ion react in high temperature heat conductive oil, generates LiFePO4Granule also makes LiFePO by binding agent4Granule bonds, and then carries out carbonization and synthesis, with high polymer for binding agent and carbon source, is formed and has high-tap density and micro-nano spherical LiFePO4/ C composite positive pole。
In above-mentioned preparation method, described high temperature heat conductive oil is one or more in JARYTHERM-DBT type conduction oil, SERIOLA-1510 type conduction oil, SERIOLA-320 type conduction oil, SERIOLA-350 type conduction oil, WD-400 type conduction oil, AH-345 type conduction oil, dibenzyl toluene high temperature heat conductive oil。
In above-mentioned preparation method, described reaction temperature in conduction oil controls at 200 DEG C ~ 500 DEG C, until precipitation no longer produces。
In above-mentioned preparation method, described mixed solution instill the speed in high temperature heat conductive oil be 20-100 drip/minute。In above-mentioned preparation method, during described reaction, stir speed (S.S.) is 150-1000r/min。
Compared with prior art, it is an advantage of the current invention that: the present invention utilizes the high molecular polymers such as Polyethylene Glycol, polyvinyl alcohol, Kynoar as binding agent and carbon source, and ion reacts in high temperature heat conductive oil；Secondly, the present invention generates the LiFePO with olivine structural4Microgranule, simultaneously because the effect of binding agent obtains the high-density spherical LiFePO with carbon cladding4/ C composite positive pole。The present invention has spherical LiFePO4/ C composite positive pole is relative to pure LiFePO4Positive electrode, its tap density is greatly improved, and improves its volume and capacity ratio simultaneously。This structure makes LiFePO4There is good chemical property。The present invention has the micro-nano spherical LiFePO of high-tap density4/ C composite positive pole is under 0.2 multiplying power during discharge and recharge, under room temperature, first discharge specific capacity is up to 159～167mAh/g, and under 5C multiplying power during discharge and recharge, under room temperature, first discharge specific capacity is up to 125～135mAh/g, after 500 times circulate, its capability retention reaches more than 90.4%。The preparation method technique of the present invention is simple, easily operation, less costly, for obtaining the LiFePO of above-mentioned function admirable4/ C composite positive pole provides effective way。
Detailed description of the invention
The invention will be further described by the following examples。
Embodiment 1
It is that the Quilonorm (SKB) of 1:1:1, ferrous acetate and ammonium dihydrogen phosphate are dissolved in deionized water using the mol ratio as synthesis material, it is subsequently adding the Polyethylene Glycol of synthesis material gross mass 5% as binding agent, mix homogeneously under ultrasound wave, instill equipped with in the beaker of conduction oil with the speed of 2.0ml/min, the oil bath temperature of conduction oil is 250 DEG C, and its mixing speed is 150r/min。After question response is complete, precipitation filtered and use deionized water cyclic washing, in high-purity argon gas atmosphere, being then sequentially carried out carbonization and synthesis, obtain that there is micro-nano spherical LiFePO4/ C composite positive pole。Wherein, the temperature of carbonization and synthesis controls at 550 DEG C, and the time is 12h。
Gained there is micro-nano spherical LiFePO4/ C composite positive pole is under 0.2C multiplying power during discharge and recharge, and under room temperature, first discharge specific capacity is up to 159mAh/g；Under 5C multiplying power during discharge and recharge, under room temperature, first discharge specific capacity is up to 132mAh/g, and after 500 times circulate, capability retention is 91.3%。
Embodiment 2
It is that the lithium gluconate of 1:1:1, ferrous acetate and diammonium phosphate are dissolved in deionized water using the mol ratio as synthesis material, it is subsequently adding the Polyethylene Glycol of synthesis material gross mass 10% as binding agent, mix homogeneously under ultrasound wave, instill equipped with in the beaker of conduction oil with the speed of 1.5ml/min, the oil bath temperature of conduction oil is 250 DEG C, and its mixing speed is 150r/min。After question response is complete, precipitation filtered and use deionized water cyclic washing, in high-purity argon gas atmosphere, being then sequentially carried out carbonization and synthesis, obtain that there is micro-nano spherical LiFePO4/ C composite positive pole。Wherein, the temperature of carbonization and synthesis controls at 650 DEG C, and the time is 18h。
Gained there is micro-nano spherical LiFePO4/ C composite positive pole is under 0.2C multiplying power during discharge and recharge, and under room temperature, first discharge specific capacity is up to 167mAh/g；Under 5C multiplying power during discharge and recharge, under room temperature, first discharge specific capacity is up to 135mAh/g, and after 500 times circulate, capability retention is 94.4%。
Embodiment 3
It is that the lithium formate of 1:1:1, Ferrous gluconate and ammonium dihydrogen phosphate are dissolved in deionized water using the mol ratio as synthesis material, it is subsequently adding the Polyethylene Glycol of synthesis material gross mass 5% as binding agent, mix homogeneously under ultrasound wave, instill equipped with in the beaker of conduction oil with the speed of 2.0ml/min, the oil bath temperature of conduction oil is 300 DEG C, and its mixing speed is 150r/min。After question response is complete, precipitation filtered and use deionized water cyclic washing, in high-purity argon gas atmosphere, being then sequentially carried out carbonization and synthesis, obtain that there is micro-nano spherical LiFePO4/ C composite positive pole。Wherein, the temperature of carbonization and synthesis controls at 650 DEG C, and the time is 24h。
Gained there is micro-nano spherical LiFePO4/ C composite positive pole is under 0.2C multiplying power during discharge and recharge, and under room temperature, first discharge specific capacity is up to 163mAh/g；Under 5C multiplying power during discharge and recharge, under room temperature, first discharge specific capacity is up to 133mAh/g, and after 500 times circulate, capability retention is 92.1%。
Embodiment 4
It is that the Quilonorm (SKB) of 1:1:1, ferrous lactate and ammonium phosphate are dissolved in deionized water using the mol ratio as synthesis material, it is subsequently adding the polyvinyl alcohol of synthesis material gross mass 5% as binding agent, mix homogeneously under ultrasound wave, instill equipped with in the beaker of conduction oil with the speed of 1.5ml/min, the oil bath temperature of conduction oil is 200 DEG C, and its mixing speed is 200r/min。After question response is complete, precipitation filtered and use deionized water cyclic washing, in high-purity argon gas atmosphere, being then sequentially carried out carbonization and synthesis, obtain that there is micro-nano spherical LiFePO4/ C composite positive pole。Wherein, the temperature of carbonization and synthesis controls at 550 DEG C, and the time is 24h。
The LiFePO with nanometer spherical of gained4/ C composite positive pole is under 0.2C multiplying power during discharge and recharge, and under room temperature, first discharge specific capacity is up to 159mAh/g；Under 5C multiplying power during discharge and recharge, under room temperature, first discharge specific capacity is up to 125mAh/g, and after 500 times circulate, capability retention is 90.4%。
Embodiment 5
It is that the lithium nitrate of 1:1:1, ferric nitrate and ammonium dihydrogen phosphate are dissolved in deionized water using the mol ratio as synthesis material, it is subsequently adding the polyvinyl alcohol of synthesis material gross mass 10% as binding agent, mix homogeneously under ultrasound wave, instill equipped with in the beaker of conduction oil with the speed of 2.0ml/min, the oil bath temperature of conduction oil is 200 DEG C, and its mixing speed is 300r/min。After question response is complete, precipitation filtered and use deionized water cyclic washing, in high pure nitrogen atmosphere, being then sequentially carried out carbonization and synthesis, obtain that there is micro-nano spherical LiFePO4/ C composite positive pole。Wherein, the temperature of carbonization and synthesis controls at 700 DEG C, and the time is 12h。
Gained there is micro-nano spherical LiFePO4/ C composite positive pole is under 0.2C multiplying power during discharge and recharge, and under room temperature, first discharge specific capacity is up to 160mAh/g；Under 5C multiplying power during discharge and recharge, under room temperature, first discharge specific capacity is up to 127mAh/g, and after 500 times circulate, capability retention is 91.8%。
Embodiment 6
It is that the lithium nitrate of 1:1:1, ferric nitrate and diammonium phosphate are dissolved in deionized water using the mol ratio as synthesis material, it is subsequently adding the Kynoar of synthesis material gross mass 5% as binding agent, mix homogeneously under ultrasound wave, instill equipped with in the beaker of conduction oil with the speed of 2.0ml/min, the oil bath temperature of conduction oil is 100 DEG C, and its mixing speed is 300r/min。After question response is complete, precipitation filtered and use deionized water cyclic washing, in high pure nitrogen atmosphere, being then sequentially carried out carbonization and synthesis, obtain that there is micro-nano spherical LiFePO4/ C composite positive pole。Wherein, the temperature of carbonization and synthesis controls at 800 DEG C, and the time is 2h。
Gained there is micro-nano spherical LiFePO4/ C composite positive pole is under 0.2C multiplying power during discharge and recharge, and under room temperature, first discharge specific capacity is up to 160mAh/g；Under 5C multiplying power during discharge and recharge, under room temperature, first discharge specific capacity is up to 125mAh/g, and after 500 times circulate, capability retention is 90.9%。
Embodiment 7
Propanoic acid lithium, ferrous acetate and ammonium dihydrogen phosphate that mol ratio is 1:1:1 as synthesis material is dissolved in deionized water, it is subsequently adding the Kynoar of synthesis material gross mass 10% as binding agent, mix homogeneously under ultrasound wave, instill equipped with in the beaker of conduction oil with the speed of 2.0ml/min, the oil bath temperature of conduction oil is 300 DEG C, and its mixing speed is 350r/min。After question response is complete, precipitation filtered and use deionized water cyclic washing, in high pure nitrogen atmosphere, being then sequentially carried out carbonization and synthesis, obtain that there is micro-nano spherical LiFePO4/ C composite positive pole。Wherein, the temperature of carbonization and synthesis controls at 650 DEG C, and the time is 18h。
Gained there is micro-nano spherical LiFePO4/ C composite positive pole is under 0.2C multiplying power during discharge and recharge, and under room temperature, first discharge specific capacity is up to 166mAh/g；Under 5C multiplying power during discharge and recharge, under room temperature, first discharge specific capacity is up to 135mAh/g, and after 500 times circulate, capability retention is 95.3%。
Embodiment 8
It is that the Quilonorm (SKB) of 1:1:1, ferrous acetate and ammonium dihydrogen phosphate are dissolved in deionized water using the mol ratio as synthesis material, it is subsequently adding the Kynoar of synthesis material gross mass 10% as binding agent, mix homogeneously under ultrasound wave, instill equipped with in the beaker of conduction oil with the speed of 1.0ml/min, the oil bath temperature of conduction oil is 200 DEG C, and its mixing speed is 300r/min。After question response is complete, precipitation filtered and use deionized water cyclic washing, in high pure nitrogen atmosphere, being then sequentially carried out carbonization and synthesis, obtain that there is micro-nano spherical LiFePO4/ C composite positive pole。Wherein, the temperature of carbonization and synthesis controls at 600 DEG C, and the time is 36h。
Gained there is micro-nano spherical LiFePO4/ C composite positive pole is under 0.2C multiplying power during discharge and recharge, and under room temperature, first discharge specific capacity is up to 161mAh/g；Under 5C multiplying power during discharge and recharge, under room temperature, first discharge specific capacity is up to 132mAh/g, and after 500 times circulate, capability retention is 92.6%。
Embodiment 9
It is that the Quilonorm (SKB) of 1:1:1, ferrous acetate and ammonium dihydrogen phosphate are dissolved in deionized water using the mol ratio as synthesis material, it is subsequently adding the polyacrylic acid of synthesis material gross mass 5% as binding agent, mix homogeneously under ultrasound wave, instill equipped with in the beaker of conduction oil with the speed of 1.5ml/min, the oil bath temperature of conduction oil is 300 DEG C, and its mixing speed is 350r/min。After question response is complete, precipitation filtered and use deionized water cyclic washing, in high pure nitrogen atmosphere, being then sequentially carried out carbonization and synthesis, obtain that there is micro-nano spherical LiFePO4/ C composite positive pole。Wherein, the temperature of carbonization and synthesis controls at 700 DEG C, and the time is 18h。
Gained there is micro-nano spherical LiFePO4/ C composite positive pole is under 0.2C multiplying power during discharge and recharge, and under room temperature, first discharge specific capacity is up to 160mAh/g；Under 5C multiplying power during discharge and recharge, under room temperature, first discharge specific capacity is up to 130mAh/g, and after 500 times circulate, capability retention is 91.7%。
Embodiment 10
It is that the Lithium hydrate of 1:1:1, ferrous gluconate and ammonium phosphate are dissolved in deionized water using the mol ratio as synthesis material, it is subsequently adding the polyacrylic acid of synthesis material gross mass 5% as binding agent, mix homogeneously under ultrasound wave, instill equipped with in the beaker of conduction oil with the speed of 1.0ml/min, the oil bath temperature of conduction oil is 200 DEG C, and its mixing speed is 250r/min。After question response is complete, precipitation filtered and use deionized water cyclic washing, in high pure nitrogen atmosphere, being then sequentially carried out carbonization and synthesis, obtain that there is micro-nano spherical LiFePO4/ C composite positive pole。Wherein, the temperature of carbonization and synthesis controls at 700 DEG C, and the time is 10h。
Gained there is micro-nano spherical LiFePO4/ C composite positive pole is under 0.2C multiplying power during discharge and recharge, and under room temperature, first discharge specific capacity is up to 160mAh/g；Under 5C multiplying power during discharge and recharge, under room temperature, first discharge specific capacity is up to 131mAh/g, and after 500 times circulate, capability retention is 90.9%。
Inventors state that, the present invention illustrates detailed process equipment and the technological process of the present invention by above-described embodiment, but the invention is not limited in above-mentioned detailed process equipment and technological process, namely do not mean that the present invention has to rely on above-mentioned detailed process equipment and technological process could be implemented。The equivalence of each raw material of product of the present invention, it will be clearly understood that any improvement in the present invention, is replaced and the interpolation of auxiliary element, concrete way choice etc. by person of ordinary skill in the field, all falls within protection scope of the present invention and open scope。

Claims (9)

1. a spherical LiFePO with high-tap density4The preparation method of/C composite positive pole, it is characterized in that: by the lithium compound of solubility, iron compound and phosphate by lithium, ferrum, phosphorus atomic ratio be that 1:1:1 mixing is dissolved in deionized water formation solution, solution is joined in the mixed liquor of binding agent, stir the liquid that is uniformly mixed；Then in oil bath pan, add appropriate conduction oil, oil bath is put into a beaker equipped with high temperature heat conductive oil, Homogeneous phase mixing liquid is instilled with certain speed in the beaker of high temperature heat conductive oil with certain mixing speed, react completely and be filtrated to get ferric lithium phosphate precursor, finally by the presoma high temperature carbonization in an inert atmosphere after washing and synthesis, form a kind of micro-nano spherical lithium ferric phosphate composite positive pole material with high-tap density。
2. there is the spherical LiFePO of high-tap density according to claim 14The preparation method of/C composite positive pole, it is characterised in that: binding agent is one or more in Kynoar, polyvinyl alcohol, polyacrylic acid, Polyethylene Glycol。
3. there is the spherical LiFePO of high-tap density according to claim 14The preparation method of/C composite positive pole, it is characterised in that: react under the beaker of high temperature heat conductive oil, generate spherical precursor。
4. there is the spherical LiFePO of high-tap density according to claim 14The preparation method of/C composite positive pole, it is characterised in that: the temperature of high temperature oil bath is at 200 DEG C～500 DEG C。
5. there is the spherical LiFePO of high-tap density according to claim 14The preparation method of/C composite positive pole, it is characterized in that: described composite positive pole is the micro-nano spherical composite ferric lithium phosphate material with high-tap density, the diameter of compound material ball is at 2-8 micron, composite is made up of the granule of 30-100 nanometer, and has uniform nano-carbon layer uniformly to connect between nano-particle。
6. there is the spherical LiFePO of high-tap density according to claim 14The preparation method of/C composite positive pole, it is characterised in that: the oil that high temperature oil bath uses is one or more in JARYTHERM-DBT type conduction oil, SERIOLA-1510 type conduction oil, SERIOLA-320 type conduction oil, SERIOLA-350 type conduction oil, WD-400 type conduction oil, AH-345 type conduction oil, dibenzyl toluene high temperature heat conductive oil。
7. there is the spherical LiFePO of high-tap density according to claim 14The preparation method of/C composite positive pole, it is characterised in that: mixed solution instill the speed in conduction oil be 20-100 drip/minute。
8. there is the spherical LiFePO of high-tap density according to claim 14The preparation method of/C composite positive pole, it is characterised in that: mixing speed when mixed solution reacts in high temperature heat conductive oil is 150-1000r/min。
9. there is the spherical LiFePO of high-tap density according to claim 14The preparation method of/C composite positive pole, it is characterised in that: it is carry out in equipped with the beaker of high temperature heat conductive oil that presoma is formed。
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