CN102169992A - Lithium ferric phosphate (LiFePO4) / carbon nano tube net composite positive electrode material and preparation method thereof - Google Patents
Lithium ferric phosphate (LiFePO4) / carbon nano tube net composite positive electrode material and preparation method thereof Download PDFInfo
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- CN102169992A CN102169992A CN2011100803571A CN201110080357A CN102169992A CN 102169992 A CN102169992 A CN 102169992A CN 2011100803571 A CN2011100803571 A CN 2011100803571A CN 201110080357 A CN201110080357 A CN 201110080357A CN 102169992 A CN102169992 A CN 102169992A
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Abstract
The invention discloses a lithium ferric phosphate (LiFePO4) / carbon nano tube net composite positive electrode material and a preparation method thereof. The preparation method comprises the following steps of: (1) mixing and ball-milling a catalyst, lithium carbonate, ferrous oxalate and monoammonium phosphate which serve as raw materials, and a dispersing agent to obtain a LiFePO4 precursor; (2) preparing a carbon nano tube net precursor by using a purified carbon nano tube, loading the carbon nano tube net precursor to the catalyst which is used for connection, then placing into a tubular resistance furnace, raising temperature, introducing nitrogen, introducing hydrogen after temperature is raised to 800 to 1,000 DEG C, keeping the temperature, introducing carbon source gas at the temperature of 800 to 1,000 DEG C, and then introducing the nitrogen and cooling to room temperature so as to obtain a carbon nano tube net; and (3) preparing a LiFePO4 / carbon nano tube net composite positive electrode material precursor, pre-burning the LiFePO4 / carbon nano tube net composite positive electrode material precursor in the nitrogen atmosphere, and then keeping the temperature at 700 to 800 DEG C to prepare the LiFePO4 / carbon nano tube net composite positive electrode material.
Description
Technical field
The present invention relates to the anode material for lithium-ion batteries technical field, be specifically related to a kind of LiFePO4/carbon nano-tube network composite positive pole, also relate to its preparation method simultaneously.
Background technology
LiFePO4 (LiFePO
4) material has advantages such as cost is low, Environmental compatibility good, specific capacity is higher, good stability with it, become a kind of Postive electrode material of li-ion accumulator that has application potential.Pure ferric phosphate lithium anode material conductivity is very low, the lithium ion diffusion velocity is very little, in order to improve the electric conductivity of LiFePO4, mainly be at present in LiFePO4, to mix some conductive agents to improve the conductivity of material, conductive agent commonly used has acetylene black, carbon black, carbon fiber and carbon nano-tube.Application number is the anode material for lithium-ion batteries that discloses a kind of LiFePO4 doped carbon nanometer pipe conductive agent in 200410051045.8 the patent application, but in actual applications, doped carbon nanotubes is very easily reunited in the LiFePO4 doped carbon nanometer pipe conductive agent positive electrode, the contact probability of doped carbon nanotubes and LiFePO4 is descended greatly, therefore reduced the utilance of material and the consistency of the internal resistance of cell.A kind of preparation method is disclosed in application number is 200810013571.3 patent application, solved that carbon nano-tube just is distributed in electrode material surface in the prior art, can not form the problem of the conductive network structure of perforation continuously at material internal and surface, also solve the problem that carbon nano-tube is disperseed on the LiFePO4 surface simultaneously.But carbon nano-tube just relies on its absorption affinity to link together or carbon nano-tube directly is adsorbed on the LiFePO4 surface in the LiFePO4 doped carbon nanometer pipe conductive agent positive electrode that this preparation method prepares, gravitation between its carbon nano-tube is less, therefore the LiFePO4 doped carbon nanometer pipe conductive agent positive electrode that makes is in long-term charge and discharge process, can cause carbon nano-tube moving in material, the conductivity and the thermal diffusivity of battery are affected, so the cycle life of battery is shorter.
Summary of the invention
The object of the present invention is to provide a kind of LiFePO4/carbon nano-tube network composite positive pole.
In order to realize above purpose, the technical solution adopted in the present invention is: a kind of LiFePO4/carbon nano-tube network composite positive pole is made by following method:
(1) preparation ferric lithium phosphate precursor
With catalyst, lithium carbonate, ferrous oxalate and ammonium dihydrogen phosphate is raw material, wherein said catalyst is one or more in iron, cobalt, the nickel, the mol ratio of catalyst, lithium carbonate, ferrous oxalate and ammonium dihydrogen phosphate is a catalyst: lithium carbonate: ferrous oxalate: ammonium dihydrogen phosphate=0.05:0.5:1:1, with catalyst, lithium carbonate, ferrous oxalate and ammonium dihydrogen phosphate and dispersant, ball milling 24～48 hours in ball mill makes ferric lithium phosphate precursor afterwards;
(2) preparation carbon nano-tube network
Be mixed with spray coating liquor with carbon nano-tube after the purification process and described dispersant, spray coating liquor is sprayed on the dash receiver, after drying, obtain the carbon nano-tube network presoma after peeling off dash receiver, the catalyst that the load of carbon nano-tube network presoma is used to connect again, wherein said catalyst is an iron, cobalt, in the nickel one or more, afterwards will be the carbon nano-tube network presoma of supported catalyst place the quartz ampoule of tube type resistance furnace, in the process that heats up, in quartz ampoule, feed nitrogen, change logical hydrogen when being warming up to 800～1000 ℃, be incubated 1～2 hour, under 800～1000 ℃ of conditions, feed acetylene then, a kind of and acetylene in the methane, the gaseous mixture of a kind of and nitrogen in the methane, duration of ventilation are 1～2 hour, feed nitrogen afterwards and be cooled to room temperature, obtain carbon nano-tube network;
(3) preparation LiFePO4/carbon nano-tube network composite positive pole
In ferric lithium phosphate precursor, add carbon nano-tube network, ultrasonic afterwards being uniformly dispersed, being heated to dispersant then in 100 ℃ of waters bath with thermostatic control volatilizees fully, obtain LiFePO4/carbon nano-tube network composite positive pole presoma, LiFePO4/carbon nano-tube network composite positive pole presoma is under nitrogen atmosphere afterwards, 250～350 ℃ of pre-burnings 8～10 hours, be incubated 8～l0 hour down at 700～800 ℃ again, make LiFePO4/carbon nano-tube network composite positive pole.
Wherein, described dispersant is deionized water or absolute ethyl alcohol.
The quality of the carbon nano-tube network that adds in the ferric lithium phosphate precursor in the step (3) and the mass ratio of ferric lithium phosphate precursor are: carbon nano-tube network: ferric lithium phosphate precursor=(0.01～0.05): 1.
LiFePO4 provided by the invention/carbon nano-tube network composite positive pole, carbon nano-tube network wherein is joined together to form by chemical bond by carbon nano-tube, has stronger conductivity and network skeleton supporting role preferably.The invention solves and connect loose problem between carbon nano-tube, prepare the carbon nano-tube network that chemical bond connects, it is doped to the chemical property that can improve battery in the LiFePO4, compare with LiFePO4/carbon nano-tube positive electrode, the cell cycle life that adopts LiFePO4 provided by the invention/carbon nano-tube network composite positive pole to make has improved 20%, and internal resistance reduces by 15%.Adopt the cell that LiFePO4 provided by the invention/the carbon nano-tube network composite positive pole makes to conduct electricity very well, good heat dissipation, the cycle life of battery obviously prolongs, and the combination property of battery significantly improves.
Description of drawings
Fig. 1 is the cycle-index-discharge capacity figure of cell that LiFePO4/the carbon nano-tube network composite positive pole makes that adopts the embodiment of the invention 1 and the cell that adopts LiFePO4/carbon/carbon nano tube compound anode material to make, wherein curve 1 is the cycle-index-discharge capacity curve of the cell that adopts LiFePO4/carbon/carbon nano tube compound anode material and make, and curve 2 is the cycle-index-discharge capacity curve of the cell that LiFePO4/the carbon nano-tube network composite positive pole makes that adopts the embodiment of the invention 1.
Embodiment
The LiFePO4 that present embodiment provides/carbon nano-tube network composite positive pole is made by following method:
(1) preparation ferric lithium phosphate precursor
Take by weighing the iron of 0.05mol, the lithium carbonate of 0.5mol, the ferrous oxalate of 1mol and the ammonium dihydrogen phosphate of 1mol, in ball grinder, add the 1kg deionized water, be heated to 80 ℃, in deionized water, add iron, lithium carbonate, ferrous oxalate and ammonium dihydrogen phosphate while stirring successively, ball grinder was put into the ball mill ball milling 24 hours afterwards, made ferric lithium phosphate precursor;
(2) preparation carbon nano-tube network
Take by weighing the iron of purified processed carbon nanotubes of 72.8g and 0.05mol, afterwards carbon nano-tube is put into the ultrasonic dispersion of 300ml absolute ethyl alcohol and be mixed with spray coating liquor in 15 minutes, spray coating liquor is sprayed on the dash receiver, after drying, obtain the carbon nano-tube network presoma after peeling off dash receiver, the iron catalyst that the load of carbon nano-tube network presoma is used to connect again, afterwards will be the carbon nano-tube network presoma of supported catalyst place the quartz ampoule of tube type resistance furnace, in the process that heats up, in quartz ampoule, feed nitrogen, change logical hydrogen when being warming up to 1000 ℃, be incubated 1 hour, feed acetylene gas then under 1000 ℃ of conditions, duration of ventilation is 2 hours, feed nitrogen afterwards and be cooled to room temperature, obtain carbon nano-tube network;
(3) preparation LiFePO4/carbon nano-tube network composite positive pole
In ferric lithium phosphate precursor, add carbon nano-tube network, the quality of carbon nano-tube network and the mass ratio of ferric lithium phosphate precursor are: carbon nano-tube network: ferric lithium phosphate precursor=0.01:1, ultrasonic afterwards being uniformly dispersed, being heated to dispersant then in 100 ℃ of waters bath with thermostatic control volatilizees fully, obtain LiFePO4/carbon nano-tube network composite positive pole presoma, LiFePO4/carbon nano-tube network composite positive pole presoma is under nitrogen atmosphere afterwards, 250 ℃ of pre-burnings 10 hours, be incubated 8 hours down at 800 ℃ again, make LiFePO4/carbon nano-tube network composite positive pole.
The LiFePO4 that present embodiment provides/carbon nano-tube network composite positive pole is made by following method:
(1) preparation ferric lithium phosphate precursor
Take by weighing the cobalt of 0.03mol, the nickel of 0.02mol, the lithium carbonate of 0.5mol, the ferrous oxalate of 1mol and the ammonium dihydrogen phosphate of 1mol, in ball grinder, add the 1kg absolute ethyl alcohol, be heated to 60 ℃, in deionized water, add cobalt, nickel, lithium carbonate, ferrous oxalate and ammonium dihydrogen phosphate while stirring successively, ball grinder was put into the ball mill ball milling 48 hours afterwards, made ferric lithium phosphate precursor;
(2) preparation carbon nano-tube network
Take by weighing the purified processed carbon nanotubes of 72.8g, 0.02mol nickel, 0.03mol iron, afterwards carbon nano-tube is put into the ultrasonic dispersion of 300ml absolute ethyl alcohol and be mixed with spray coating liquor in 15 minutes, spray coating liquor is sprayed on the dash receiver, after drying, obtain the carbon nano-tube network presoma after peeling off dash receiver, the nickel that the load of carbon nano-tube network presoma is used to connect again, iron catalyst, afterwards will be the carbon nano-tube network presoma of supported catalyst place the quartz ampoule of tube type resistance furnace, in the process that heats up, in quartz ampoule, feed nitrogen, change logical hydrogen when being warming up to 800 ℃, be incubated 2 hours, feed the gaseous mixture of methane and nitrogen then under 800 ℃ of conditions, duration of ventilation is 1 hour, feed nitrogen afterwards and be cooled to room temperature, obtain carbon nano-tube network;
(3) preparation LiFePO4/carbon nano-tube network composite positive pole
In ferric lithium phosphate precursor, add carbon nano-tube network, the quality of carbon nano-tube network and the mass ratio of ferric lithium phosphate precursor are: carbon nano-tube network: ferric lithium phosphate precursor=0.05:1, ultrasonic afterwards being uniformly dispersed, being heated to dispersant then in 100 ℃ of waters bath with thermostatic control volatilizees fully, obtain LiFePO4/carbon nano-tube network composite positive pole presoma, LiFePO4/carbon nano-tube network composite positive pole presoma is under nitrogen atmosphere afterwards, 350 ℃ of pre-burnings 8 hours, be incubated 10 hours down at 700 ℃ again, make LiFePO4/carbon nano-tube network composite positive pole.
LiFePO4/carbon nano-tube network the composite positive pole that makes with embodiment 1 is as positive electrode, and Delanium adopts LiPF as negative material
6/ EC+DEC(volume ratio 1: 1) be electrolyte, Celgard 2400 films are barrier film, prepare 5AH soft-package battery A; As positive electrode, Delanium adopts LiPF as negative material with LiFePO4/carbon nano tube compound material
6/ EC+DEC(volume ratio 1: 1) be electrolyte, Celgard 2400 films are barrier film, prepare 5AH soft-package battery B, as a comparison battery.Be cycle-index and the discharge capacity relation of test battery A and battery B under the condition of 1C in multiplying power afterwards, draw cycle-index-discharge capacity curve chart, see shown in Figure 1.As can be seen from Figure 1, under about 400 times condition that all circulates, the discharge capacity of battery A and cycle-index are to compare basic identical at 0 o'clock, and the discharge capacity of battery B and cycle-index are to compare obvious decline at 0 o'clock, the cycle life of this explanation battery A obviously prolongs than battery B, and the 5AH soft-package battery A performance that LiFePO4/carbon nano-tube network composite positive pole of employing embodiment 1 makes obviously is better than 5AH soft-package battery B.
Claims (6)
1. LiFePO4/carbon nano-tube network composite positive pole is characterized in that, is made by following method:
(1) preparation ferric lithium phosphate precursor
With catalyst, lithium carbonate, ferrous oxalate and ammonium dihydrogen phosphate is raw material, wherein said catalyst is one or more in iron, cobalt, the nickel, the mol ratio of catalyst, lithium carbonate, ferrous oxalate and ammonium dihydrogen phosphate is a catalyst: lithium carbonate: ferrous oxalate: ammonium dihydrogen phosphate=0.05:0.5:1:1, with catalyst, lithium carbonate, ferrous oxalate and ammonium dihydrogen phosphate and dispersant, ball milling 24～48 hours in ball mill makes ferric lithium phosphate precursor afterwards;
(2) preparation carbon nano-tube network
Be mixed with spray coating liquor with carbon nano-tube after the purification process and described dispersant, spray coating liquor is sprayed on the dash receiver, after drying, obtain the carbon nano-tube network presoma after peeling off dash receiver, the catalyst that the load of carbon nano-tube network presoma is used to connect again, wherein said catalyst is an iron, cobalt, in the nickel one or more, afterwards will be the carbon nano-tube network presoma of supported catalyst place the quartz ampoule of tube type resistance furnace, in the process that heats up, in quartz ampoule, feed nitrogen, change logical hydrogen when being warming up to 800～1000 ℃, be incubated 1～2 hour, under 800～1000 ℃ of conditions, feed acetylene then, a kind of and acetylene in the methane, the gaseous mixture of a kind of and nitrogen in the methane, duration of ventilation are 1～2 hour, feed nitrogen afterwards and be cooled to room temperature, obtain carbon nano-tube network;
(3) preparation LiFePO4/carbon nano-tube network composite positive pole
In ferric lithium phosphate precursor, add carbon nano-tube network, ultrasonic afterwards being uniformly dispersed, being heated to dispersant then in 100 ℃ of waters bath with thermostatic control volatilizees fully, obtain LiFePO4/carbon nano-tube network composite positive pole presoma, LiFePO4/carbon nano-tube network composite positive pole presoma is under nitrogen atmosphere afterwards, 250～350 ℃ of pre-burnings 8～10 hours, be incubated 8～l0 hour down at 700～800 ℃ again, make LiFePO4/carbon nano-tube network composite positive pole.
2. LiFePO4 according to claim 1/carbon nano-tube network composite positive pole is characterized in that, described dispersant is deionized water or absolute ethyl alcohol.
3. LiFePO4 according to claim 2/carbon nano-tube network composite positive pole, it is characterized in that the quality of the carbon nano-tube network that adds in the ferric lithium phosphate precursor in the step (3) and the mass ratio of ferric lithium phosphate precursor are: carbon nano-tube network: ferric lithium phosphate precursor=(0.01～0.05): 1.
4. the preparation method of the described LiFePO4 of claim 1/carbon nano-tube network composite positive pole is characterized in that concrete steps are as follows:
(1) preparation ferric lithium phosphate precursor
With catalyst, lithium carbonate, ferrous oxalate and ammonium dihydrogen phosphate is raw material, wherein said catalyst is one or more in iron, cobalt, the nickel, the mol ratio of catalyst, lithium carbonate, ferrous oxalate and ammonium dihydrogen phosphate is a catalyst: lithium carbonate: ferrous oxalate: ammonium dihydrogen phosphate=0.05:0.5:1:1, with catalyst, lithium carbonate, ferrous oxalate and ammonium dihydrogen phosphate and dispersant, ball milling 24～48 hours in ball mill makes ferric lithium phosphate precursor afterwards;
(2) preparation carbon nano-tube network
Be mixed with spray coating liquor with carbon nano-tube after the purification process and described dispersant, spray coating liquor is sprayed on the dash receiver, after drying, obtain the carbon nano-tube network presoma after peeling off dash receiver, the catalyst that the load of carbon nano-tube network presoma is used to connect again, wherein said catalyst is an iron, cobalt, in the nickel one or more, afterwards will be the carbon nano-tube network presoma of supported catalyst place the quartz ampoule of tube type resistance furnace, in the process that heats up, in quartz ampoule, feed nitrogen, change logical hydrogen when being warming up to 800～1000 ℃, be incubated 1～2 hour, under 800～1000 ℃ of conditions, feed acetylene then, a kind of and acetylene in the methane, the gaseous mixture of a kind of and nitrogen in the methane, duration of ventilation are 1～2 hour, feed nitrogen afterwards and be cooled to room temperature, obtain carbon nano-tube network;
(3) preparation LiFePO4/carbon nano-tube network composite positive pole
In ferric lithium phosphate precursor, add carbon nano-tube network, ultrasonic afterwards being uniformly dispersed, being heated to dispersant then in 100 ℃ of waters bath with thermostatic control volatilizees fully, obtain LiFePO4/carbon nano-tube network composite positive pole presoma, LiFePO4/carbon nano-tube network composite positive pole presoma is under nitrogen atmosphere afterwards, 250～350 ℃ of pre-burnings 8～10 hours, be incubated 8～l0 hour down at 700～800 ℃ again, make LiFePO4/carbon nano-tube network composite positive pole.
5. the preparation method of LiFePO4 according to claim 4/carbon nano-tube network composite positive pole is characterized in that, described dispersant is deionized water or absolute ethyl alcohol.
6. the preparation method of LiFePO4 according to claim 5/carbon nano-tube network composite positive pole, it is characterized in that the quality of the carbon nano-tube network that adds in the ferric lithium phosphate precursor in the step (3) and the mass ratio of ferric lithium phosphate precursor are: carbon nano-tube network: ferric lithium phosphate precursor=(0.01～0.05): 1.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107910501A (en) * | 2017-11-28 | 2018-04-13 | 安徽零度新能源科技有限公司 | A kind of positive electrode sheet processing method for improving lithium battery cycle performance |
| CN111732088A (en) * | 2020-07-01 | 2020-10-02 | 中南大学 | Lithium iron phosphate precursor/carbon nanotube composite material |
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| CN101533904A (en) * | 2009-04-24 | 2009-09-16 | 长沙理工大学 | Method for preparing lithium iron phosphate/nanometer carbon composite anode material |
| CN101710615A (en) * | 2009-11-19 | 2010-05-19 | 鞍山凯信工矿设备有限公司 | Preparation method of composite cathode material of lithium iron phosphate and carbon nano-tubes |
| CN101814346A (en) * | 2010-05-22 | 2010-08-25 | 西南交通大学 | Method for preparing compact three-dimensional and macroscopical carbon nanotube network |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101533904A (en) * | 2009-04-24 | 2009-09-16 | 长沙理工大学 | Method for preparing lithium iron phosphate/nanometer carbon composite anode material |
| CN101710615A (en) * | 2009-11-19 | 2010-05-19 | 鞍山凯信工矿设备有限公司 | Preparation method of composite cathode material of lithium iron phosphate and carbon nano-tubes |
| CN101814346A (en) * | 2010-05-22 | 2010-08-25 | 西南交通大学 | Method for preparing compact three-dimensional and macroscopical carbon nanotube network |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107910501A (en) * | 2017-11-28 | 2018-04-13 | 安徽零度新能源科技有限公司 | A kind of positive electrode sheet processing method for improving lithium battery cycle performance |
| CN111732088A (en) * | 2020-07-01 | 2020-10-02 | 中南大学 | Lithium iron phosphate precursor/carbon nanotube composite material |
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Application publication date: 20110831 |