CN103000892A - Metal doping method for lithium iron phosphate anode material - Google Patents
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- CN103000892A CN103000892A CN2012105489551A CN201210548955A CN103000892A CN 103000892 A CN103000892 A CN 103000892A CN 2012105489551 A CN2012105489551 A CN 2012105489551A CN 201210548955 A CN201210548955 A CN 201210548955A CN 103000892 A CN103000892 A CN 103000892A
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Abstract
The invention relates to a metal doping method for a lithium iron phosphate anode material. The method comprises the following steps of: (1) adding a mixture into a dispersing agent, wherein the mixture contains a Li source, a Fe source and a PO4 source which are in a molar ratio; grinding, and then adding a Mg source, a V source and a carbon source, grinding and drying; (2) performing primary sintering on the above materials; (3) adding the materials subjected to primary sintering into the dispersing agent, grinding the materials in a grinding machine, adding the carbon source for the second time, continuously grinding and drying; (4) performing secondary sintering on the materials; and (5) sintering the sintered materials subjected to secondary sintering for the third time, thus obtaining lithium iron phosphate which is completely coated with carbon and has excellent electrochemical performance. According to the method, the required raw materials do not contain rare precious metals, abundant, readily available and low in price, and the production cost is low, so the method is favorable for large-scale industrial production. The doping process is simple and easy to operate, and the equipment requirement is low. By adoption of Mg and V ion doping, the lithium iron phosphate anode material is long in cycle life, high in lithium ion diffusion coefficient, controllable in particle size distribution, high in conductive performance and high in compaction density.
Description
Technical field
The present invention relates to the modified technique of lithium battery anode, especially the metal-doped method of lithium iron phosphate positive material.
Background technology
Along with the aggravation of human environmental pollution pressure, the finiteness of primary energy urgently needs high-energy at present, low pollution, continuable green novel energy source.
Since the eighties lithium ion battery commercialization in last century, it has been observed that it is as a kind of potential quality of new forms of energy of sustainable development, but because the main prices of raw and semifnished materials costliness of lithium ion battery originally, manufacture craft is immature, has limited its development.Simultaneously, city automobile tail gas becomes the first principal element of city environmental pollution, becomes the main method that instantly solves auto-pollution as free of contamination new forms of energy power electric motor car.The power source of electric automobile mainly is lithium ion battery, and as the LiFePO of positive electrode
4Become one of preferred material.Entered since 21st century, progressively commercialization along with lithium iron phosphate positive material, because its abundant raw materials, cheap, substantially without injury, and good chemical property enjoys common people's favor to environment, even for the patent of LiFePO4, caused the LiFePO4 patent dispute of industry, in order to obtain the patent right of LiFePO4, world-famous lithium ion battery factory has played international lawsuit one after another.
LiFePO
4Positive electrode is the orthorhombic system olivine structural, belongs to polyanion type compound, and its space group is PZnb.LiFePO
4Crystal is by FeO
6Octahedron and PO
4The spatial skeleton that tetrahedron consists of.LiCoO with stratiform and spinelle
2, LiNiO
2, LiMn
2O
4Compare Deng positive electrode, it is good that polyanion type compound positive electrode has security performance, and crystal structure is stable, the advantages such as thermal stability.
At present, LiFePO
4The conductivity that material itself is relatively poor and lower lithium ion diffusion coefficient are to hinder its practical main reason always, thereby impel Chinese scholars improving LiFePO
4The aspect of conductive capability launched research.For this reason, both at home and abroad the expert can see through the method that coats, replaces, is prepared into the upgradings such as nanometer materials and overcome this shortcoming.Add conductive materials in order to improve the LiFePO that takes off behind the lithium
4Electron conduction, can be at LiFePO
4Introduce the conductive agent of good dispersion property between powder, precious metals such as carbon black or gold, silver, copper can obviously improve interparticle electric conductivity, so that LiFePO
4Utilization ratio improve, the reversible capacitance amount can reach 95% of theoretical value, even the cycle performance performance is also very good under the high current charge-discharge condition of 5C.
But LiFePO
4Material itself still exists poorly conductive and the low shortcoming of lithium ion diffusion coefficient.
Summary of the invention
The present invention proposes LiFePO
4A kind of codope different proportion Mg of anode material for lithium-ion batteries and V replace the preparation method in Fe ion room, improve the lithium ion diffusion coefficient in the lithium ion charge and discharge process.
The technical solution adopted for the present invention to solve the technical problems is: a kind of metal-doped method of lithium iron phosphate positive material comprises the steps:
(1), according to Li source, Fe source, PO
4The mixture of source mol ratio joins in the high-purity dispersant, and adds Mg source compound and V source compound after in addition ground and mixed is processed, and then for the first time adds carbon source, continues to be ground to the mixed material particle size distribution and reaches dry after the predetermined value;
(2), with said mixture material first sintering;
(3), the material of first sintering is joined in the low-purity dispersant, and in milling apparatus, carry out adding carbon source for the second time after the ground and mixed, proceed to grind, after material reaches prescribed particle size, stop to grind, then dry;
(4), with the above-mentioned material sintering second time;
(5), the material of sintering carries out for the third time sintering for the second time.
Li of the present invention source, Fe source, PO4 source mole composition ratio are: 1.000:0.854:0.954; Described dispersant is ethanol, and described high-purity dispersant is that ethanol content is not less than 95% ethanol; Described low-purity dispersant is that ethanol content is not less than 85% ethanol; Described Mg source compound and V source compound addition are: take the Li source as radix, Li source: V source: Mg source mol ratio is 1:0.03:0.02, and described Mg source compound is magnesium acetate, and the V source compound is vanadic oxide; Add carbon source the described first time is sucrose or glucose, accounts for 7% ~ 10% of lithium source quality; Adding for the first time carbon source is 1:3 with the mass ratio that adds for the second time carbon source; Described drying is to carry out under 100 ℃ ~ 120 ℃ oxygen free conditions; Described first sintering, its condition are that material is placed in the iron crucible with the chamber type sintering stove 300 ℃ ~ 600 ℃ lower insulations 2 ~ 5 hours, and pass into and process under the nitrogen protection; Described second time sintering, its condition is that material is placed in the iron crucible with the chamber type sintering stove 300 ℃ ~ 350 ℃ insulations 5 ~ 10 hours, and passes under the nitrogen protection and process; Described for the third time sintering, its condition be placed on material in the oxidation aluminum crucible and in tunnel cave with 650 ~ 730 ℃ of insulations 10 ~ 15 hours, and pass under the nitrogen protection and process; Described grinding, the time is 1～2 hour.
Lithium iron phosphate positive material of the present invention can be regulated according to its preparation technology the doping ratio of metal ion, the ground and mixed time, drying means, sintering temperatures etc. are controlled the granule-morphology of phosphoric acid iron crystalline lithium structured forerunner, make its particle size distribution controlled, can greatly improve the degree of crystallinity of lithium iron phosphate positive material, the invertibity that lithium ion embeds and deviates from, dispersed homogeneous degree, and can suppress to become ferric ion after ferrous ion is deviate from the time, produce the impact that trip path changes after the lattice smaller volume, and then improved the chemical property of lithium iron phosphate positive material.
It is better that the present invention has degree of crystallinity, and the lithium iron phosphate positive material of superior electrical property mainly obtains control by control Mg, V are compound doped.Namely add Mg, V compound by a batch mixing, then pass through high temperature sintering, Mg ion, V ion replace Fe ionic lattice room in the high temperature building-up process, obtain the high-performance lithium iron phosphate cathode material of Mg ion, V ion co-doped.
After adopting above technical scheme, the invention has the beneficial effects as follows: raw material do not contain any rare precious metal and rich and easy to get, cheap, and production cost is low, is conducive to large-scale industrial production.Its doping process is simple to operation, and is also not high to equipment requirement.Adopt have extended cycle life behind Mg, the V ion doping, particle size distribution is controlled, conducts electricity very well, tap density is high, specific capacity can reach 160mAh/g.
The invention will be further described below in conjunction with accompanying drawing.
Description of drawings
Fig. 1 is sem analysis figure of the present invention.
Fig. 2 is X-ray diffracting spectrum of the present invention.
Fig. 3 is that the present invention forms discharge curve result behind the experimental cell.
Embodiment
The metal-doped method of a kind of lithium iron phosphate positive material of the present invention, comprise the steps: (1), join in the high-purity dispersant according to the mixture of Li source, Fe source, PO4 source mol ratio, and add Mg source compound and V source compound after in addition ground and mixed is processed, then for the first time add carbon source, continue to be ground to the mixed material particle size distribution and reach dry after the predetermined value;
(2), with said mixture material first sintering;
(3), the material of first sintering is joined in the low-purity dispersant, and in milling apparatus, carry out adding carbon source for the second time after the ground and mixed, proceed to grind, after material reaches prescribed particle size, stop to grind, then dry;
(4), with the above-mentioned material sintering second time;
(5), the material of sintering carries out for the third time sintering for the second time.
Li of the present invention source, Fe source, PO4 source mole composition ratio are: 1.000:0.854:0.954; Described dispersant is ethanol, and described high-purity dispersant is that ethanol content is not less than 95% ethanol; Described low-purity dispersant is that ethanol content is not less than 85% ethanol; Described Mg source compound and V source compound addition are: take the Li source as radix, Li source: V source: Mg source mol ratio is 1:0.03:0.02, and described Mg source compound is magnesium acetate, and the V source compound is vanadic oxide; Add carbon source the described first time is sucrose or glucose, accounts for 7% ~ 10% of lithium source quality; Adding for the first time carbon source is 1:3 with the mass ratio that adds for the second time carbon source; Described drying is to carry out under 100 ℃ ~ 120 ℃ oxygen free conditions; Described first sintering, its condition are that material is placed in the iron crucible with the chamber type sintering stove 300 ℃ ~ 600 ℃ lower insulations 2 ~ 5 hours, and pass into and process under the nitrogen protection; Described second time sintering, its condition is that material is placed in the iron crucible with the chamber type sintering stove 300 ℃ ~ 350 ℃ insulations 5 ~ 10 hours, and passes under the nitrogen protection and process; Described for the third time sintering, its condition be placed on material in the oxidation aluminum crucible and in tunnel cave with 650 ~ 730 ℃ of insulations 10 ~ 15 hours, and pass under the nitrogen protection and process; Described grinding, the time is 1～2 hour.
Embodiment 1:
(1) at first lithium carbonate, ferrous oxalate, ammonium dihydrogen phosphate raw material are added purity greater than in 95% the alcohol dispersant according to mol ratio 1.000:0.854:0.954, and in addition ground and mixed is processed.Grind after 1 hour, according to Li:V
2O
5: Mg (C
2H
3O
2)
24H
2The O mol ratio is 1:0.02:0.02, and afterwards according to adding lithium carbonate: the sucrose mass ratio is that 1:0.07 adds sucrose, continues to grind after 1 hour, carries out drying under oxygen free condition.
(2) material that the first step is made carries out first sintering in nitrogen medium, temperature is 300 ℃ ~ 600 ℃, and temperature retention time is 2 hours.
(3) material that second step is made joins purity greater than in 85% alcohol dispersant, grind after 1 hour, add carbon source according to 21% of the described middle adding lithium source quality of the first step, continue to grind after 2 hours, under 100 ℃ ~ 120 ℃ oxygen free conditions, carry out drying, finished for the second time adding of C source compound.
(4) material that the 3rd step was made carries out the sintering second time in nitrogen medium, sintering temperature is set in 300 ℃ ~ 350 ℃, is incubated 5 hours.
(5) material that the 4th step was made carries out for the third time sintering in nitrogen medium, sintering temperature is set in 650 ~ 730 ℃, is incubated 12 hours, obtains carbon and coats the LiFePO4 complete, that chemical property is good.
Detect the lithium iron phosphate positive material of this case method preparation, record tap density and reach 1.51g/cm
3, as shown in Figure 1, sem analysis shows, even particle distribution.As shown in Figure 2, the X-ray diffraction test shows that this lithium iron phosphate battery positive material purity is high, and is free from foreign meter, has intact degree of crystallinity.As shown in Figure 3, this lithium iron phosphate positive material is made experimental cell in being filled with the glove box of argon gas, carry out charge-discharge test about 25 ℃, the charging/discharging voltage scope is 2.0V ~ 3.7V, and the 0.5C first discharge specific capacity of this material can reach 164mAh/g.
Embodiment 2:
(1) at first lithium carbonate, ferrous oxalate, ammonium dihydrogen phosphate raw material are added purity greater than in 95% the alcohol dispersant according to mol ratio 1.000:0.854:0.954, and in addition ground and mixed is processed.Grind after 1 hour, according to Li:V
2O
5: Mg (C
2H
3O
2)
24H
2The O mol ratio is 1:0.03:0.02, and afterwards according to adding lithium carbonate: the sucrose mass ratio is that 1:0.07 adds sucrose, continues to grind after 1 hour, carries out drying under oxygen free condition.
(2) material that the first step is made carries out first sintering in nitrogen medium, temperature is 300 ℃ ~ 600 ℃, and temperature retention time is 2 hours.
(3) material that second step is made joins purity greater than in 85% alcohol dispersant, grind after 1 hour, add carbon source according to 21% of the described middle adding lithium source quality of the first step, continue to grind after 2 hours, under 100 ℃ ~ 120 ℃ oxygen free conditions, carry out drying, finished for the second time adding of C source compound.
(4) material that the 3rd step was made carries out the sintering second time in nitrogen medium, sintering temperature is set in 300 ℃ ~ 350 ℃, is incubated 5 hours.
(5) material that the 4th step was made carries out for the third time sintering in nitrogen medium, sintering temperature is set in 650 ~ 730 ℃, is incubated 15 hours, obtains carbon and coats the LiFePO4 complete, that chemical property is good.
Detect the lithium iron phosphate positive material of this case method preparation, this lithium iron phosphate positive material records tap density and reaches 1.50g/cm
3, as shown in Figure 1, sem analysis shows, even particle distribution; As shown in Figure 2, the X-ray diffraction test shows that this lithium iron phosphate battery positive material purity is high, and is free from foreign meter, has intact degree of crystallinity; As shown in Figure 3, this lithium iron phosphate positive material is made experimental cell in being filled with the glove box of argon gas, carry out charge-discharge test about 25 ℃, the charging/discharging voltage scope is 2.0V ~ 3.7V, and the 0.5C first discharge specific capacity of this material can reach 162mAh/g.
Embodiment 3:
(1) at first lithium carbonate, ferrous oxalate, ammonium dihydrogen phosphate raw material are added purity greater than in 95% the alcohol dispersant according to mol ratio 1.000:0.854:0.954, and in addition ground and mixed is processed.Grind after 1 hour, according to Li:V
2O
5: Mg (C
2H
3O
2)
24H
2The O mol ratio is 1:0.04:0.02, and afterwards according to adding lithium carbonate: the sucrose mass ratio is that 1:0.07 adds sucrose, continues to grind after 1 hour, carries out drying under oxygen free condition.
(2) material that the first step is made carries out first sintering in nitrogen medium, temperature is 300 ℃ ~ 600 ℃, and temperature retention time is 2 hours.
(3) material that second step is made joins purity greater than in 85% alcohol dispersant, grind after 1 hour, add carbon source according to 21% of the described middle adding lithium source quality of the first step, continue to grind after 2 hours, under 100 ℃ ~ 120 ℃ oxygen free conditions, carry out drying, finished for the second time adding of C source compound.
(4) material that the 3rd step was made carries out the sintering second time in nitrogen medium, sintering temperature is set in 300 ℃ ~ 350 ℃, is incubated 5 hours.
(5) material that the 4th step was made carries out for the third time sintering in nitrogen medium, sintering temperature is set in 650 ~ 730 ℃, is incubated 12 hours, obtains carbon and coats the LiFePO4 complete, that chemical property is good.
Detect the lithium iron phosphate positive material of this case method preparation, this lithium iron phosphate positive material records tap density and reaches 1.45g/cm
3, as shown in Figure 1, sem analysis shows that grain size analysis shows, even particle distribution; As shown in Figure 2, the X-ray diffraction test shows that this lithium iron phosphate battery positive material purity is high, and is free from foreign meter, has intact degree of crystallinity; As shown in Figure 3, this lithium iron phosphate positive material is made experimental cell in being filled with the glove box of argon gas, carry out charge-discharge test about 25 ℃, the charging/discharging voltage scope is 2.0V ~ 3.7V, and the 0.5C first discharge specific capacity of this material can reach 158mAh/g.
Claims (10)
1. the metal-doped method of a lithium iron phosphate positive material, it is characterized in that: comprise the steps: (1), join in the high-purity dispersant according to the mixture of Li source, Fe source, PO4 source mol ratio, and add Mg source compound and V source compound after in addition ground and mixed is processed, then for the first time add carbon source, continue to be ground to the mixed material particle size distribution and reach dry after the predetermined value;
(2), with said mixture material first sintering;
(3), the material of first sintering is joined in the low-purity dispersant, and in milling apparatus, carry out adding carbon source for the second time after the ground and mixed, proceed to grind, after material reaches prescribed particle size, stop to grind, then dry;
(4), with the above-mentioned material sintering second time;
(5), the material of sintering carries out for the third time sintering for the second time.
2. the metal-doped method of a kind of lithium iron phosphate positive material according to claim 1, it is characterized in that: described Li source, Fe source, PO4 source mole composition ratio are: 1.000:0.854:0.954.
3. the metal-doped method of a kind of lithium iron phosphate positive material according to claim 1, it is characterized in that: described dispersant is ethanol, described high-purity dispersant is that ethanol content is not less than 95% ethanol; Described low-purity dispersant is that ethanol content is not less than 85% ethanol.
4. the metal-doped method of a kind of lithium iron phosphate positive material according to claim 1 and 2, it is characterized in that: described Mg source compound and V source compound addition are: take the Li source as radix, Li source: V source: Mg source mol ratio is 1:0.03:0.02, described Mg source compound is magnesium acetate, and the V source compound is vanadic oxide.
5. the metal-doped method of a kind of lithium iron phosphate positive material according to claim 1, it is characterized in that: add carbon source the described first time is sucrose or glucose, accounts for 7% ~ 10% of lithium source quality; Adding for the first time carbon source is 1:3 with the mass ratio that adds for the second time carbon source.
6. the metal-doped method of a kind of lithium iron phosphate positive material according to claim 1, it is characterized in that: described drying is to carry out under 100 ℃ ~ 120 ℃ oxygen free conditions.
7. the metal-doped method of a kind of lithium iron phosphate positive material according to claim 1; it is characterized in that: described first sintering; its condition is that material is placed in the iron crucible with the chamber type sintering stove 300 ℃ ~ 600 ℃ lower insulations 2 ~ 5 hours, and passes under the nitrogen protection and process.
8. the metal-doped method of a kind of lithium iron phosphate positive material according to claim 1; it is characterized in that: described second time sintering; its condition is that material is placed in the iron crucible with the chamber type sintering stove 300 ℃ ~ 350 ℃ insulations 5 ~ 10 hours, and passes under the nitrogen protection and process.
9. the metal-doped method of a kind of lithium iron phosphate positive material according to claim 1; it is characterized in that: described for the third time sintering; its condition be placed on material in the oxidation aluminum crucible and in tunnel cave with 650 ~ 730 ℃ of insulations 10 ~ 15 hours, and pass under the nitrogen protection and process.
10. the metal-doped method of a kind of lithium iron phosphate positive material according to claim 1, it is characterized in that: described grinding, the time is 1～2 hour.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20230223533A1 (en) * | 2020-06-09 | 2023-07-13 | VSPC Ltd | Method for making lithium metal phosphates |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1348230A (en) * | 2000-10-06 | 2002-05-08 | 索尼株式会社 | Nonaqueous electrolyte battery |
| US20020106564A1 (en) * | 2000-10-06 | 2002-08-08 | Tsuyoshi Okawa | Non-aqueous electrolyte secondary cell |
| CN102593447A (en) * | 2011-03-23 | 2012-07-18 | 江苏菲思特新能源有限公司 | Metal doping method of lithium iron phosphate anode material |
-
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1348230A (en) * | 2000-10-06 | 2002-05-08 | 索尼株式会社 | Nonaqueous electrolyte battery |
| US20020106564A1 (en) * | 2000-10-06 | 2002-08-08 | Tsuyoshi Okawa | Non-aqueous electrolyte secondary cell |
| CN102593447A (en) * | 2011-03-23 | 2012-07-18 | 江苏菲思特新能源有限公司 | Metal doping method of lithium iron phosphate anode material |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20230223533A1 (en) * | 2020-06-09 | 2023-07-13 | VSPC Ltd | Method for making lithium metal phosphates |
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Application publication date: 20130327 |