CN103367724A - Lithium iron phosphate cell material with core-shell structure, and preparation method thereof - Google Patents
Lithium iron phosphate cell material with core-shell structure, and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a lithium iron phosphate cell material with a core-shell structure, and a preparation method thereof. The formula of the material is C1/Li1-xMxFePO4/C2, wherein x=0-0.1, M represents a metallic element doped at lithium position, C1 is a carbon core which is a nanometer carbosphere coated in a lithium iron phosphate bulk phase, and C2 is organic cracked carbon coating the material surface. The preparation method comprises: firstly preparing organic polymer microballoon or inorganic carbosphere of ferric phosphate both in nanometer degrade, then adding lithium source, organic carbon source and a doping metallic compound, taking alcohol as a dispersant, grinding and mixing uniformly, drying, and roasting at the atmosphere of high-purity nitrogen to obtain the lithium iron phosphate cell material with the core-shell structure. The preparation method is simple in technology and suitable for large-scale industrialized production, and the prepared lithium iron phosphate by the method is high in utilization rate of active substances and high in specific capacity.
Description
Technical field
The present invention relates to ferric phosphate lithium cell material of a kind of nucleocapsid structure and preparation method thereof, particularly having prepared a kind of kernel is the nucleocapsid structure ferric phosphate lithium cell material that nano-sized carbon microballoon, surface coat organic cracking carbon, belongs to the anode material for lithium-ion batteries correlative technology field.
Background technology
Since the research teams such as the vertical Goodenough of university of Texas, USA in 1997 have reported LiFePO
4After having the characteristic that invertibity ground embeds lithium ion, LiFePO4 as Olivine-type Cathode Material in Li-ion Batteries by extensive concern.Realized first batch production to LiFePO 4 material in calendar year 2001, along with going deep into of research, the modification technologies such as carbon coating and carbon thermal reduction, ion doping, nanometer are applied among the preparation technology of LiFePO4 gradually, improved the conductivity of LiFePO4, the performance of LiFePO 4 material is significantly promoted, entered immediately the stage of producing in enormous quantities.LiFePO4 has been widely applied to the every field such as electric automobile, electric bicycle, electric tool, energy-storage battery and communication base station at present.
Although after the PROCESS FOR TREATMENT such as the coating of LiFePO 4 material process carbon, ion doping, performance has had obvious improvement, but the problem that the enclosed pasture efficient of LiFePO 4 material is lower never well solves, first charge-discharge efficiency has a negative impact to indexs such as the actual specific capacity of material, energy densities about 90%.A.S. Andersson and J.O.Thomas are studied analysis to the charge-discharge mechanism of LiFePO4 theoretically, adopt " tire model " and " mosaic model " to explain that there is the basic reason of defective in material, point out: material can be at inactive " nuclear " of material internal formation behind first charge-discharge, lithium ion in the nuclear can not be deviate from and again embed, thereby has caused the lower first enclosed pasture efficient of material.For anode material for lithium-ion batteries, active material utilization is higher, and specific capacity is just higher, and efficient also must be higher first, so nonactive proportion is more few better.LiFePO4 is behind the modification technologies such as overdoping, coating, nanometer, although performance is obviously improved, but the problem that active material utilization is on the low side never well solves, the ratio of material actual specific capacity and theoretical specific capacity is generally between 82%～90%, be difficult to surpass 92%, become the technical barrier that LiFePO 4 material is needed solution badly.
Summary of the invention
The object of the invention is to overcome the deficiency of prior art, a kind of ferric phosphate lithium cell material with nucleocapsid structure and preparation method thereof is provided, is intended to reduce the ratio of nonactive " nuclear ", promote active material utilization, improve first discharging efficiency, thereby improve the specific discharge capacity of LiFePO4.
Purpose of the present invention can reach by following measure: a kind of ferric phosphate lithium cell material of nucleocapsid structure, the structure expression that it is characterized in that material is C
1/ Li
1-xM
xFePO
4/ C
2, x=0～0.1 wherein, M is the metallic element that mixes in the lithium position, C
1Being the carbon kernel, is to be wrapped in the nano-sized carbon microballoon of LiFePO4 body in mutually, C
2For being coated on the organic cracking carbon of material surface.
A kind of ferric phosphate lithium cell material preparation method of nucleocapsid structure is characterized in that it comprises the steps:
The first step adds surfactant A in dispersant (absolute ethyl alcohol or deionized water)
1, A
1Addition be 0.1%～2% of dispersant quality, then add nano inorganic carbosphere or nanometer organic polymer particulate and abundant ultrasonic dispersion, get dispersion liquid B.Then iron salt solutions with deionized water configuration 1～3 mol/L joins iron salt solutions among the dispersion liquid B, adds surfactant A by theoretical 0.2%～2% of the ferric phosphate quality that generates simultaneously
2, stir 0.5～3h, then continuing in the situation about stirring, slowly add phosphate solution according to the ratio of mol ratio Fe:P=0.98～1.02, in whole course of reaction, by dripping the ammonia spirit of 0.5～2 mol/L, hierarchy of control pH value is between 2～3.If the divalence source of iron needs by adding H than the excessive 1%-10% of theoretical amount
2O
2, to guarantee that ferrous iron is oxidized to trivalent entirely.After dripping, continues phosphate solution to stir 1～5h, ripening 2～6h then, and more after filtration, washing, drying, obtaining having nucleocapsid structure and kernel is sphere or the class ball shape ferric phosphate of nanometer organic polymer or DIC.
Second step, the ferric phosphate that adopts the first step to obtain, Li:Fe=0.9～1 takes by weighing the lithium source in molar ratio, and organic carbon source is pressed 15～20% of raw material total weight and added, take alcohol as dispersant, above-mentioned each component raw material grinding, mixing, drying are obtained precursor powder, be raised to 650～820 ℃ with the programming rate of 1～10 ℃/min from room temperature and carry out high-temperature roasting under high pure nitrogen atmosphere, insulation 2～10h is cooled to room temperature naturally, through pulverizing, sieving, obtain the ferric phosphate lithium cell material.
Described soluble ferric iron salt is a kind of in ferrous sulfate, ferric nitrate, iron chloride, the ferric acetate.
The metallic compound of described doping is a kind of in magnesium oxide, magnesium hydroxide, vanadic oxide, titanium dioxide, niobium pentaoxide, niobium oxalate, yittrium oxide, chrome green, the ammonium molybdate.
Described surfactant A
1, A
2Be respectively a kind of in dodecyl sodium sulfate, benzalkonium chloride, polysorbate, polyethers, super branched polyurethane, polyvingl ether, the polymine etc., the two can be different.
Described phosphate is a kind of in ammonium dihydrogen phosphate, diammonium hydrogen phosphate, the ammonium phosphate.
Described nano inorganic carbon particulate is a kind of in acetylene black, petroleum coke, the nano carbon microsphere, the nanometer organic high polymer microsphere is a kind of in polyethylene, polystyrene, polyimides, polymethyl methacrylate, Merlon, polypropylene, the nylon micro-sphere, and its addition is 1～3% of the LiFePO4 weight that generates.
Described lithium source is a kind of in lithium carbonate, lithium hydroxide, lithium acetate, the lithium oxalate.
Described organic carbon source is a kind of in glucose, sucrose, starch, cellulose, the organic resin.
Surfactant unite use, realized the controlledly synthesis of ferric phosphate precipitation: surfactant A
1Effect be to make iron ion at nano inorganic or organic high polymer microsphere surface enrichment, A
2Effect be formation complex compound with iron ion, reduce to greatest extent the content of iron ion in solution, thereby guarantee that ferric phosphate is deposited in nano inorganic or organic high polymer microsphere Surface Creation, reduction along with nano inorganic organic polymer Surface Fe ion concentration, thereby control ferric phosphate precipitation simultaneously can also be according to A take carbon particulate as nucleus growth
2Amount regulate the generating rate of ferric phosphate.
When take the nanometer organic high polymer microsphere as the ferric phosphate kernel, in the process of follow-up roasting synthesizing iron lithium phosphate, meeting lysisin situ, carbonization become the nano inorganic microballoon, can realize the synchronous carbonization of carbon nuclear and carbon shell.
The present invention can produce following good effect compared with the prior art:
(1) to adopt synthetic a kind of kernel be the LiFePO 4 material of the nucleocapsid structure of carbon in the present invention, utilize the conduction of carbon kernel to conduct mutually short path derivation by body the electronics of material inner surface, greatly improved the conduction velocity of electronics in LiFePO4 body phase;
(2) Pintsch process by organic carbon source forms carbon coating layer on its surface, has improved the conduction velocity of electronics between lithium iron phosphate particles;
(3) by the conduction of inside and outside two-layer carbon passage to electronics, the LiFePO4 electronic conductivity that the method is prepared is the lifting of the order of magnitude.
By the control of above technical matters, make the LiFePO 4 material conductivity of being synthesized reach 10
-1More than the S/cm, first charge-discharge efficiency significantly promotes, and reaches more than 96%, and the 0.2C specific discharge capacity reaches 159 mAh/g, and active material utilization reaches 93.5%, and multiplying power, circulation, the low temperature performance of material also have clear improvement simultaneously.
Description of drawings
Fig. 1 is that the present invention prepares nucleocapsid structure LiFePO4 C
1/ Li
1-xM
xFePO
4/ C
2The process schematic diagram.
Fig. 2 is the nucleocapsid structure LiFePO4 C of the embodiment of the invention 1 preparation
1/ Li
0.99Ti
0.01FePO
4/ C
2The XRD collection of illustrative plates.
Fig. 3 is the high power lithium iron phosphate C of the embodiment of the invention 1 preparation
1/ Li
0.99Ti
0.01FePO
4/ C
2Button cell respectively with the charging and discharging curve of 0.2C, 0.5C, voltage range 2.5～4.1V (vs. Li), 1C calculates according to 150mA/g.
Fig. 4 is the 18650 cylindrical battery charge and discharge cycles curves that the product of embodiment 1 is made, voltage range 2.0～3.65V.
Embodiment
Embodiment 1
The first step is measured the 500ml deionized water, adds the 0.5g dodecyl sodium sulfate, then adds the petroleum coke powder of 0.789g nanometer, and ultrasonic dispersion 2h gets the deionized water dispersion liquid of nanometer petroleum coke.Get 135gFeCl
36H
2O and 0.15g polyethers F-6 are dissolved in the 500ml deionized water, then join in the above-mentioned dispersion liquid, with the speed stirring 0.5h of 600r/min.Then continuing under the prerequisite that stirs, the ammonium dihydrogen phosphate 204ml that slowly adds 2.5 mol/L according to the ratio of mol ratio Fe:P=0.98, drip simultaneously the ammonia spirit of 0.5 mol/L with glue head dropper, hierarchy of control pH value is 2, continue to stir 0.5h, then static ripening 2h, more after filtration, washing, drying, getting kernel is the class ball shape ferric phosphate of nanometer petroleum coke particulate.
Second step take the class ball shape ferric phosphate of first step preparation as source of iron, takes by weighing Li
2CO
318.287g, titanium dioxide 0.399g, glucose 13.95g take alcohol as dispersant, grinds 2h with above-mentioned each component raw material, drying obtains precursor powder, be raised to 650 ℃ with the programming rate of 1 ℃/min from room temperature and carry out high-temperature roasting under high pure nitrogen atmosphere, insulation 10h is cooled to room temperature naturally, through pulverizing, sieving, obtain the ferric phosphate lithium cell material.
LiFePO 4 material degree of crystallinity with this embodiment preparation is good, and its X ray diffracting spectrum as shown in Figure 1, and is consistent with the standard spectrogram of LiFePO4.
The electrochemical property test of material is tested by the following method, and take iron phosphate powder of the present invention as positive active material, the lithium sheet is negative pole, is assembled into the CR2025 button cell and tests.Positive pole consists of 80% active material, 10% conductive carbon, 10%PVDF; Electrolyte is the LiPF of 1mol/L
6(EC+DMC), in glove box, finish assembling.The battery testing temperature is 25 ℃, and the system of discharging and recharging is: with the 0.2C constant current charge to 4.1V, then with the 4.1V constant voltage charge to electric current less than 0.005mA, leave standstill 2min, constant-current discharge is to 2.5V again.Button cell is tested as shown in Figure 2, and the 0.2C first charge-discharge efficiency reaches 98.6%, and specific capacity reaches 158mAh/g, and active material utilization reaches 92.9%, 0.5C specific capacity and reaches 156.2Ah/g.It is also very excellent that this embodiment makes the 18650 cylindrical battery test material cycle performances that LiFePO4 makes, and voltage range 1200 capability retentions that circulate when 2.0～3.65V reach 95.4%.
Embodiment 2
The first step is measured the 500ml absolute ethyl alcohol, adds the 8g polysorbate, stirs, and then adds 4.638g nano pipe/polyhenylethylene microballoon, and ultrasonic dispersion 3h gets the absolute ethyl alcohol dispersion liquid of polystyrene.Take by weighing 404g ferric nitrate and 2.956g polysorbate and be dissolved in the 600ml deionized water, fully dissolving and mixing add in the above-mentioned dispersion liquid, with the speed stirring 3h of 500r/min.Then under the prerequisite that stirs, the ammonium dibasic phosphate solution 490ml that slowly adds 2 mol/L according to the ratio of mol ratio Fe:P=1.02, drip simultaneously the ammonia spirit of 2 mol/L with glue head dropper, hierarchy of control pH value is 3, continue to stir 1h, then static ripening 2h more after filtration, washing, drying, gets the ball shape ferric phosphate that kernel is the nano pipe/polyhenylethylene particulate.
Second step, the ferric phosphate that adopts the first step to obtain takes by weighing 23.461g LiOH again, 34.982g cellulose, take alcohol as dispersant, above-mentioned each component raw material is fully ground, mix, obtain precursor powder after the drying, be raised to 820 ℃ with the programming rate of 10 ℃/min from room temperature and carry out high-temperature roasting under high pure nitrogen atmosphere, insulation 2h is cooled to room temperature naturally, through pulverizing, sieving, obtain the ferric phosphate lithium cell material.
According to the method for testing of embodiment 1, the LiFePO 4 material button cell test 0.2C specific discharge capacity of this embodiment preparation reaches 157mAh/g, and active material utilization reaches 92.3%.The material high rate performance of this embodiment preparation is also very outstanding, and 18650 cylindrical batteries of making are in the voltage range of 2.0～3.65V, and specific capacity reaches 123 mAh/g during with the 10C multiplying power discharging.
Embodiment 3
The first step is measured the 500ml deionized water, adds the 0.8g benzalkonium chloride, then adds 1.68g nanometer polymethyl methacrylate powder and abundant ultrasonic dispersion, gets the deionized water dispersion liquid of nanometer polymethyl methacrylate.Take by weighing 278g ferrous sulfate and 1.4g polymine and be dissolved in the 500ml deionized water, then add the hydrogen peroxide of 120ml 30%, stir, join in the above-mentioned dispersion liquid, with the speed stirring 3h of 300r/min.Then under the prerequisite that stirs, the ammonium phosphate solution 500ml that slowly adds 2 mol/L according to the ratio of mol ratio Fe:P=1, drip simultaneously the ammonia spirit of 0.8mol/L with glue head dropper, hierarchy of control pH value is 2.6, continue to stir 3h, then static ripening 6h more after filtration, washing, drying, gets the ball shape ferric phosphate that kernel is nanometer polymethyl methacrylate particulate.
Second step, the ferric phosphate that adopts the first step to obtain takes by weighing the 62.70g lithium acetate, 38.34g starch, 4.553 gV
2O
5Take alcohol as dispersant, above-mentioned each component raw material grinding, mixing, drying are obtained precursor powder, under high pure nitrogen atmosphere, be raised to 760 ℃ with the programming rate of 6 ℃/min from room temperature and carry out high-temperature roasting, insulation 8h, naturally be cooled to room temperature, through pulverizing, sieving, obtain the ferric phosphate lithium cell material.
According to the method for testing of embodiment 1, its specific discharge capacity of LiFePO 4 material button cell 0.2C charge-discharge test of this embodiment preparation is 159mAh/g, and it is 156.8mAh/g that active material utilization reaches 93.5%, 0.5C specific discharge capacity.
Embodiment 4
The first step is measured the 500ml deionized water, adds the 1.2g polyvingl ether, then adds 3.21g nanometer polycarbonate powder and abundant ultrasonic dispersion, gets the deionized water dispersion liquid of nanometer Merlon.Take by weighing 270g ferric trichloride and 1.5g benzalkonium chloride and be dissolved in the 300ml deionized water, with the speed stirring 2.5h of 450r/min.Then under the prerequisite that stirs, the ammonium dihydrogen phosphate 300ml that slowly adds 3.3mol/L according to the ratio of mol ratio Fe:P=1.01, drip simultaneously the ammonia spirit of 0.8mol/L with glue head dropper, hierarchy of control pH value is 2.7, continue to stir 2h, then static ripening 3.5h more after filtration, washing, drying, gets the ball shape ferric phosphate that kernel is nanometer Merlon particulate.
Second step, the ferric phosphate that adopts the first step to obtain takes by weighing the 35.112g lithium carbonate, the 29.82g cellulose, 3.163g titanium dioxide, take alcohol as dispersant, above-mentioned each component raw material grinding, mixing, drying are obtained precursor powder, under high pure nitrogen atmosphere, be raised to 780 ℃ with the programming rate of 3 ℃/min from room temperature and carry out high-temperature roasting, insulation 8.5h, naturally be cooled to room temperature, through pulverizing, sieving, obtain the ferric phosphate lithium cell material.
According to the method for testing of embodiment 1, the LiFePO 4 material button cell 0.2C first charge-discharge efficiency of this embodiment preparation reaches 98.2%, and specific discharge capacity is 158.5mAh/g, and active material utilization reaches 93.2%.Its nucleocapsid structure has improved the transmittability of electronics greatly, and the cryogenic property of material is also very superior, and 18650 cylindrical battery low-temperature tests show that-20 ℃/20 ℃ 1/3C specific discharge capacity ratio is 72.6%.
Above embodiment is described preferred implementation of the present invention; be not that scope of the present invention is limited; design under the prerequisite of spirit not breaking away from the present invention; various distortion and improvement that the common engineers and technicians in this area make technical scheme of the present invention all should fall in the definite protection range of claims of the present invention.
Claims (9)
1. the ferric phosphate lithium cell material of a nucleocapsid structure, the structure expression that it is characterized in that material is C
1/ Li
1-xM
xFePO
4/ C
2, x=0～0.1 wherein, M is the metallic element that mixes in the lithium position, C
1Being the carbon kernel, is to be wrapped in the nano-sized carbon microballoon of LiFePO4 body in mutually, C
2For being coated on the organic cracking carbon of material surface.
2. the ferric phosphate lithium cell material preparation method of a kind of nucleocapsid structure claimed in claim 1 is characterized in that it comprises the steps:
The first step adds surfactant A in dispersant (absolute ethyl alcohol or deionized water)
1, A
1Addition be 0.1%～2% of dispersant quality, then add nano inorganic carbosphere or nanometer organic polymer particulate and abundant ultrasonic dispersion, get dispersion liquid B; Then iron salt solutions with deionized water configuration 1～3 mol/L joins iron salt solutions among the dispersion liquid B, adds surfactant A by theoretical 0.2%～2% of the ferric phosphate quality that generates simultaneously
2, stir 0.5～3h, then continuing in the situation about stirring, slowly add phosphate solution according to the ratio of mol ratio Fe:P=0.98～1.02, in whole course of reaction, by dripping the ammonia spirit of 0.5～2 mol/L, hierarchy of control pH value is between 2～3; If the divalence source of iron needs by adding H than the excessive 1%-10% of theoretical amount
2O
2, to guarantee that ferrous iron is oxidized to trivalent entirely; After dripping, continues phosphate solution to stir 1～5h, ripening 2～6h then, and more after filtration, washing, drying, obtaining having nucleocapsid structure and kernel is sphere or the class ball shape ferric phosphate of nanometer organic polymer or DIC;
Second step, the ferric phosphate that adopts the first step to obtain, Li:Fe=0.9～1 takes by weighing the lithium source in molar ratio, and organic carbon source is pressed 15～20% of raw material total weight and added, take alcohol as dispersant, above-mentioned each component raw material grinding, mixing, drying are obtained precursor powder, be raised to 650～820 ℃ with the programming rate of 1～10 ℃/min from room temperature and carry out high-temperature roasting under high pure nitrogen atmosphere, insulation 2～10h is cooled to room temperature naturally, through pulverizing, sieving, obtain the ferric phosphate lithium cell material.
3. the ferric phosphate lithium cell material preparation method of a kind of nucleocapsid structure according to claim 2 is characterized in that described soluble ferric iron salt is a kind of in ferrous sulfate, ferric nitrate, iron chloride, the ferric acetate.
4. the ferric phosphate lithium cell material preparation method of a kind of nucleocapsid structure according to claim 2, the metallic compound that it is characterized in that described doping are a kind of in magnesium oxide, magnesium hydroxide, vanadic oxide, titanium dioxide, niobium pentaoxide, niobium oxalate, yittrium oxide, chrome green, the ammonium molybdate.
5. the ferric phosphate lithium cell material preparation method of a kind of nucleocapsid structure according to claim 2 is characterized in that described surfactant A
1, A
2Be respectively a kind of in dodecyl sodium sulfate, benzalkonium chloride, polysorbate, polyethers, super branched polyurethane, polyvingl ether, the polymine etc., the two can be different.
6. the ferric phosphate lithium cell material preparation method of a kind of nucleocapsid structure according to claim 2 is characterized in that described phosphate is a kind of in ammonium dihydrogen phosphate, diammonium hydrogen phosphate, the ammonium phosphate.
7. the ferric phosphate lithium cell material preparation method of a kind of nucleocapsid structure according to claim 2, it is characterized in that described nano inorganic carbon particulate is a kind of in acetylene black, petroleum coke, the nano carbon microsphere, the nanometer organic high polymer microsphere is a kind of in polyethylene, polystyrene, polyimides, polymethyl methacrylate, Merlon, polypropylene, the nylon micro-sphere, and its addition is 1～3% of the LiFePO4 weight that generates.
8. the ferric phosphate lithium cell material preparation method of a kind of nucleocapsid structure according to claim 2 is characterized in that described lithium source is a kind of in lithium carbonate, lithium hydroxide, lithium acetate, the lithium oxalate.
9. a kind of high power lithium iron phosphate cell material preparation method according to claim 2 is characterized in that described organic carbon source is a kind of in glucose, sucrose, starch, cellulose, the organic resin.
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| CN105428617A (en) * | 2015-11-16 | 2016-03-23 | 山东精工电子科技有限公司 | Iron phosphate carbon sphere synchronous synthesis and internal-external conductive carbon modified lithium iron phosphate preparation method |
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