CN105047879B - A kind of combination electrode material and preparation method thereof - Google Patents
A kind of combination electrode material and preparation method thereof Download PDFInfo
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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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Abstract
The invention provides a kind of preparation method of combination electrode material, the method with lithium dihydrogen phosphate, two oxalic acid hydrate ferrous irons, lithium carbonate, vanadic oxide, titanium dioxide, manganese acetate for raw material, the phenol type substances such as phloroglucin are carbon source, prepare high-performance combination electrode material by the solid phase technique combined with high temperature sintering of adulterating.Preparation method's preparation process provided by the invention is simple, convenient, easy to operate, with short production cycle, and equipment requirement is low, is beneficial to its industrialized development and applies; And the LiFePO4 combination electrode material prepared has the advantages such as excellent electrochemical performance, high stability, high cycle performance, be mainly used in the various lithium ion batteries such as energy storage device, electric tool class, lightweight electric powered vehicles, mini-plant, compact electric apparatus, portable power source.
Description
Technical field
The invention belongs to the manufacture field of electrode, relate to a kind of combination electrode material and preparation method thereof, be specifically related to a kind of LiFePO4 combination electrode material and preparation method thereof.
Background technology
High-performance iron phosphate lithium combination electrode material is a kind of Olivine-type Cathode Material in Li-ion Batteries.This novel anode material has concentrated LiCoO
2, LiNiO
2, LiMn
2o
4and the respective advantage of derivative positive electrode: not containing noble element, resource extreme enrichment; Operating voltage moderate (3.4V); Platform identity is good, and voltage pole is steady, can match in excellence or beauty with stabilized voltage power supply; Theoretical capacity 170mAh/g; Stability Analysis of Structures, security performance is splendid, and O and P, with strong covalent bond strong bonded, makes material be difficult to analyse oxygen and decomposes; High-temperature behavior and thermal stability are obviously better than other known positive electrode; Good cycle; Good with most of electrolyte system compatibility, storge quality is good; Nontoxic, be real green material.Can be applicable to energy storage device, as the energy storage device of solar energy, wind energy generating plant, UPS UPS, electric tool class, if electric drill, weeder etc., lightweight electric powered vehicles, mini-plant are as various lithium ion batteries such as Medical Devices, electric bicycle, toy, compact electric apparatus, portable power sources, has a extensive future.AyMPO is disclosed first from Japanese ATT in 1996
4(A is alkali metal, the combination that M is both CoFe: LiFeC
opO
4) olivine structural anode material of lithium battery after, within 1997, Texas, USA founds the seminar such as university John.B.Goodenough, has also then reported LiFePO
4the characteristic of lithium of reversibly moving into, the U.S. and Japan coincidentally deliver olivine structural (LiMPO
4), make this material receive great attention, and cause research widely and develop rapidly.
At present, the preparation method of LiFePO4 mainly contains solid phase method, liquid phase method, sol-gel process, microwave method etc., the applicable laboratory sample preparations such as liquid phase method, sol-gel process, microwave method, research and development, be not suitable for large-scale industrial production, solid phase method has easy and simple to handle, the manageable advantage of process, is applicable to large-scale production, be beneficial to industrialized development and apply, but mostly preparation process is complicated, cost is high.
Summary of the invention
The problem to be solved in the present invention is to provide that a kind of preparation process is easy, abundant raw material source, and cost is low, safety and environmental protection, capacity are high, the preparation method of the high-performance iron phosphate lithium combination electrode material of good cycle.
For achieving the above object, of the present invention adopted technical scheme is: with lithium dihydrogen phosphate, ferrous oxalate, lithium carbonate, vanadic oxide, titanium dioxide, manganese acetate for raw material, the phenol such as phloroglucin, resorcinol or phenol are carbon source, through three-dimensional high-speed concussion ball mill mechanical activation, use two warm area rotary furnace sintering to prepare high-performance combination electrode material.
Three-dimensional high-speed concussion ball mill substantially increases speed and the efficiency of grinding, and two warm area rotary furnace makes the homogeneity sintering rear material better.
Doping vanadic oxide, titanium dioxide, manganese acetate, vanadium ion, titanium ion, the doping of manganese ion iron position create cation vacancy by charge compensation mechanism, be conducive to the diffusion of lithium ion, Doped ions may produce microcell lattice structure defects simultaneously, reduce the band gap of bulk material, thus effectively improve the conductivity of material.
The phenol such as phloroglucin is used to carry out in-situ carbon as carbon source coated, very practical for the chemical property improving LiFePO4 combination electrode material, effectively can improve the high rate performance of ferric phosphate lithium positive electrode.
This technical scheme specifically comprises the following steps:
(1) by lithium dihydrogen phosphate, two oxalic acid hydrate ferrous irons, lithium carbonate, vanadic oxide, titanium dioxide, manganese acetate be the ratio mixing of 1:0.97 ~ 1:0 ~ 0.02:0 ~ 0.01:0 ~ 0.01:0 ~ 0.01 in molar ratio, then add any one in phloroglucin, phenol or resorcinol as carbon source in the ratio of 10g/mol lithium dihydrogen phosphate;
(2) three-dimensional high-speed concussion ball mill is adopted to carry out ball milling mixing to raw material, in ball grinder, ball load is no more than 1/3rd of tank cumulative volume, raw material total amount is no more than 1/3rd of tank cumulative volume, and Ball-milling Time is 1 ~ 2 hour, and shimmy frequency is 800 ~ 1100 revs/min;
(3) two warm area rotary furnace is used to carry out high temperature sintering to the material after ball milling; setting boiler tube rotating speed is less than 3 revs/min; intermittent time is 1 minute; first nitrogen is led to 20 ~ 30 minutes before sintering; nitrogen flow rate is 0.14L/min under standard state, passes into pure nitrogen gas protection in sintering process, and nitrogen flow is 0.05L/min; sintering temperature is 600 ~ 800 DEG C, obtains the combination electrode material of pure phase after sintering.
Wherein, preferred reaction condition is, in described step (1), the mol ratio of elemental lithium and ferro element is greater than 1;
In described step (1), the mol ratio of lithium dihydrogen phosphate, two oxalic acid hydrate ferrous irons, lithium carbonate, vanadic oxide, titanium dioxide, manganese acetate is 1:0.97:0.01:0.01:0.01:0.01;
In described step (2), the ball grinder material of three-dimensional high-speed concussion ball mill is nylon or polytetrafluoroethylene, and the material of mill ball is agate;
The rotary furnace of the three-dimensional high-speed concussion ball mill used in described step (2) can 360 degree of rotations, and are welded with lifting blade in boiler tube;
In described step (2), in ball grinder, ball load is 1/3rd of tank cumulative volume, and raw material total amount accounts for 1/3rd of tank cumulative volume, and Ball-milling Time is 1.5 hours, and shimmy frequency is 1000 revs/min;
First lead to nitrogen 30 minutes before sintering in described step (3), two warm area rotary furnace is that batch (-type) rotates, and rotating speed is 2 revs/min, and the intermittent time is 1 minute, and sintering time is 10 hours.
Through inventor's experimental studies have found that for many years, in described step (1), lithium will little over amount, and lithium has a small amount of volatilization in high-temperature sintering process.
Described step (1) adds phloroglucin, phenol or resorcinol, and to carry out in-situ carbon as carbon source coated, can prevent from being oxidized in ferrous iron sintering process, without noxious substance generation after sintering, also can improve the conductivity of material.
Described step (2) selects three-dimensional high-speed concussion ball mill to carry out ball mill mixing to raw material, high speed vibration ball mill is in three dimensions high speed rotating and vibrations, substantially increase grinding efficiency, substantially increase speed and the efficiency of ball milling relative to common ball mill.
Described step (2) uses the material selecting ball grinder to be nylon or polytetrafluoroethylene, and the mill ball selecting agate material to make, avoids mixing of metal ion.
Before described step (3) sintering, logical 20 ~ 30 minutes nitrogen, is the air in emptying boiler tube, prevents side reaction from occurring; Use two warm area rotary furnace to sinter, after sintering, the homogeneity of material is better.
The advantage that the present invention has and good effect are:
(1) to be adulterated the technique combined with easy fired by solid phase, use three-dimensional high-speed concussion ball mill to carry out ball mill mixing to raw material, two warm area rotary furnace sintering prepares high-performance combination electrode material, and preparation process is simple, convenient, easy to operate;
(2) three-dimensional high-speed concussion ball mill substantially increases speed and the efficiency of grinding, and use two warm area rotary furnace to sinter raw material, the electrode material prepared has better homogeneity, and the particle diameter of material is more homogeneous;
(3) material selecting ball grinder is nylon or polytetrafluoroethylene, and the material selecting mill ball is agate, avoids mixing of metal ion;
(4) adulterate vanadic oxide, titanium dioxide, manganese acetate, vanadium ion, titanium ion, the doping of manganese ion iron position create cation vacancy by charge compensation mechanism, be conducive to the diffusion of lithium ion, Doped ions may produce microcell lattice structure defects simultaneously, reduce the band gap of bulk material, thus effectively improve the conductivity of material;
(5) phenol such as phloroglucin is used to carry out in-situ carbon as carbon source coated, very practical for the chemical property improving LiFePO4 combination electrode material, effectively can improve the high rate performance of ferric phosphate lithium positive electrode.
Embodiment
Below by embodiment the present invention be specifically described and illustrate:
Embodiment one
(1) by lithium dihydrogen phosphate, two oxalic acid hydrate ferrous irons, lithium carbonate, vanadic oxide, titanium dioxide, manganese acetate be the ratio mixing of 1:1:0:0:0:0 in molar ratio, then 10g/mol lithium dihydrogen phosphate adds phloroglucin as carbon source in proportion;
(2) three-dimensional high-speed concussion ball mill is adopted to carry out ball milling mixing to raw material, the material selecting ball grinder is polytetrafluoroethylene, select the mill ball that agate material is made, in ball grinder, ball load is 1/3rd of tank cumulative volume, raw material total amount accounts for 1/3rd of tank cumulative volume, Ball-milling Time is 1.5 hours, and shimmy frequency is 1000 revs/min;
(3) two warm area rotary furnace put into by the material after ball milling, sinter in a nitrogen atmosphere, first nitrogen is led to 30 minutes before sintering, nitrogen flow rate is 0.14L/min, and in sintering process, nitrogen flow rate is 0.05L/min under standard state, and setting rotary furnace is that batch (-type) rotates, rotating speed is 2 revs/min, intermittent time is 1 minute, and sintering temperature is 800 DEG C, sinters the combination electrode material obtaining pure phase after 10 hours.
The pure phase combination electrode material prepared by above-mentioned steps, meso-position radius is 4.82 μm, and under 1C discharge-rate, first discharge specific capacity reaches 148.5mAh/g, and the chemical property of material after 300 times that circulates is substantially undamped.
Embodiment two
(1) by lithium dihydrogen phosphate, two oxalic acid hydrate ferrous irons, lithium carbonate, vanadic oxide, titanium dioxide, manganese acetate be the ratio mixing of 1:1:0.01:0:0:0 in molar ratio, then 10g/mol lithium dihydrogen phosphate adds phloroglucin as carbon source in proportion;
(2) three-dimensional high-speed concussion ball mill is adopted to carry out ball milling mixing to raw material, the material selecting ball grinder is polytetrafluoroethylene, select the mill ball that agate material is made, in ball grinder, ball load is 1/3rd of tank cumulative volume, raw material total amount accounts for 1/3rd of tank cumulative volume, Ball-milling Time is 1.5 hours, and shimmy frequency is 1000 revs/min;
(3) two warm area rotary furnace put into by the material after ball milling, sinters in a nitrogen atmosphere, and first lead to nitrogen 30 minutes before sintering, nitrogen flow rate is 0.14L/min, and in sintering process, nitrogen flow rate is 0.05L/min under standard state.Setting rotary furnace is that batch (-type) rotates, and rotating speed is 2 revs/min, and the intermittent time is 1 minute, and sintering temperature is 800 DEG C, sinters the combination electrode material obtaining pure phase after 10 hours.
The pure phase combination electrode material prepared by above-mentioned steps, meso-position radius is 3.57 μm, and under 1C discharge-rate, first discharge specific capacity reaches 149.3mAh/g, and the chemical property of material after 300 times that circulates is substantially undamped.
Embodiment three
(1) by lithium dihydrogen phosphate, two oxalic acid hydrate ferrous irons, lithium carbonate, vanadic oxide, titanium dioxide, manganese acetate be the ratio mixing of 1:1:0.02:0:0:0 in molar ratio, then 10g/mol lithium dihydrogen phosphate adds phloroglucin as carbon source in proportion;
(2) three-dimensional high-speed concussion ball mill is adopted to carry out ball milling mixing to raw material, the material selecting ball grinder is polytetrafluoroethylene, select the mill ball that agate material is made, in ball grinder, ball load is 1/3rd of tank cumulative volume, raw material total amount accounts for 1/3rd of tank cumulative volume, Ball-milling Time is 1.5 hours, and shimmy frequency is 1000 revs/min;
(3) two warm area rotary furnace put into by the material after ball milling, sinter in a nitrogen atmosphere, first nitrogen is led to 30 minutes before sintering, nitrogen flow rate is 0.14L/min, and in sintering process, nitrogen flow rate is 0.05L/min under standard state, and setting rotary furnace is that batch (-type) rotates, rotating speed is 2 revs/min, intermittent time is 1 minute, and sintering temperature is 800 DEG C, sinters the combination electrode material obtaining pure phase after 10 hours.
The pure phase combination electrode material prepared by above-mentioned steps, meso-position radius is 3.75 μm, and under 1C discharge-rate, first discharge specific capacity reaches 145.6mAh/g, and the chemical property of material after 300 times that circulates is substantially undamped.
Embodiment four
(1) by lithium dihydrogen phosphate, two oxalic acid hydrate ferrous irons, lithium carbonate, vanadic oxide, titanium dioxide, manganese acetate be the ratio mixing of 1:1:0:0.01:0.01:0.01 in molar ratio, then 10g/mol lithium dihydrogen phosphate adds phloroglucin as carbon source in proportion;
(2) three-dimensional high-speed concussion ball mill is adopted to carry out ball milling mixing to raw material, the material selecting ball grinder is polytetrafluoroethylene, select the mill ball that agate material is made, in ball grinder, ball load is 1/3rd of tank cumulative volume, raw material total amount accounts for 1/3rd of tank cumulative volume, Ball-milling Time is 1.5 hours, and shimmy frequency is 1000 revs/min;
(3) two warm area rotary furnace put into by the material after ball milling, sinters in a nitrogen atmosphere, and first lead to nitrogen 30 minutes before sintering, nitrogen flow rate is 0.14L/min, and in sintering process, nitrogen flow rate is 0.05L/min under standard state.Setting rotary furnace is that batch (-type) rotates, and rotating speed is 2 revs/min, and the intermittent time is 1 minute, and sintering temperature is 800 DEG C, sinters the combination electrode material obtaining pure phase after 10 hours.
The combination electrode material of the pure phase prepared by above-mentioned steps, meso-position radius is 3.81 μm, and under 1C discharge-rate, first discharge specific capacity reaches 150mAh/g, and the chemical property of material after 300 times that circulates is substantially undamped.
Embodiment five
(1) by lithium dihydrogen phosphate, two oxalic acid hydrate ferrous irons, lithium carbonate, vanadic oxide, titanium dioxide, manganese acetate be the ratio mixing of 1:1:0.01:0.01:0.01:0.01 in molar ratio, then 10g/mol lithium dihydrogen phosphate adds phloroglucin as carbon source in proportion;
(2) three-dimensional high-speed concussion ball mill is adopted to carry out ball milling mixing to raw material, the material selecting ball grinder is polytetrafluoroethylene, select the mill ball that agate material is made, in ball grinder, ball load is 1/3rd of tank cumulative volume, raw material total amount accounts for 1/3rd of tank cumulative volume, Ball-milling Time is 1.5 hours, and shimmy frequency is 1000 revs/min;
(3) two warm area rotary furnace put into by the material after ball milling, sinters in a nitrogen atmosphere, and first lead to nitrogen 30 minutes before sintering, nitrogen flow rate is 0.14L/min, and in sintering process, nitrogen flow rate is 0.05L/min under standard state.Setting rotary furnace is that batch (-type) rotates, and rotating speed is 2 revs/min, and the intermittent time is 1 minute, and sintering temperature is 800 DEG C, sinters the combination electrode material obtaining pure phase after 10 hours.
The combination electrode material of the pure phase prepared by above-mentioned steps, meso-position radius is 2.85 μm, and under 1C discharge-rate, first discharge specific capacity reaches 154mAh/g, and the chemical property of material after 300 times that circulates is substantially undamped.
Embodiment six
(1) by lithium dihydrogen phosphate, two oxalic acid hydrate ferrous irons, lithium carbonate, vanadic oxide, titanium dioxide, manganese acetate be the ratio mixing of 1:1:0.01:0.01:0.01:0.01 in molar ratio, then 10g/mol lithium dihydrogen phosphate adds phenol as carbon source in proportion;
(2) three-dimensional high-speed concussion ball mill is adopted to carry out ball milling mixing to raw material, the material selecting ball grinder is polytetrafluoroethylene, select the mill ball that agate material is made, in ball grinder, ball load is 1/3rd of tank cumulative volume, raw material total amount accounts for 1/3rd of tank cumulative volume, Ball-milling Time is 1.5 hours, and shimmy frequency is 1000 revs/min;
(3) two warm area rotary furnace put into by the material after ball milling, sinters in a nitrogen atmosphere, and first lead to nitrogen 30 minutes before sintering, nitrogen flow rate is 0.14L/min, and in sintering process, nitrogen flow rate is 0.05L/min under standard state.Setting rotary furnace is that batch (-type) rotates, and rotating speed is 2 revs/min, and the intermittent time is 1 minute, and sintering temperature is 800 DEG C, sinters the combination electrode material obtaining pure phase after 10 hours.
The combination electrode material of the pure phase prepared by above-mentioned steps, meso-position radius is 2.95 μm, and under 1C discharge-rate, first discharge specific capacity reaches 150.5mAh/g, and the chemical property of material after 300 times that circulates is substantially undamped.
Embodiment seven
(1) by lithium dihydrogen phosphate, two oxalic acid hydrate ferrous irons, lithium carbonate, vanadic oxide, titanium dioxide, manganese acetate be the ratio mixing of 1:1:0.01:0.01:0.01:0.01 in molar ratio, then 10g/mol lithium dihydrogen phosphate adds resorcinol as carbon source in proportion;
(2) three-dimensional high-speed concussion ball mill is adopted to carry out ball milling mixing to raw material, the material selecting ball grinder is nylon, select the mill ball that agate material is made, in ball grinder, ball load is 1/3rd of tank cumulative volume, raw material total amount accounts for 1/3rd of tank cumulative volume, Ball-milling Time is 1.5 hours, and shimmy frequency is 1000 revs/min;
(3) two warm area rotary furnace put into by the material after ball milling, sinters in a nitrogen atmosphere, and first lead to nitrogen 30 minutes before sintering, nitrogen flow rate is 0.14L/min, and in sintering process, nitrogen flow rate is 0.05L/min under standard state.Setting rotary furnace is that batch (-type) rotates, and rotating speed is 2 revs/min, and the intermittent time is 1 minute, and sintering temperature is 800 DEG C, sinters the combination electrode material obtaining pure phase after 10 hours.
The combination electrode material of the pure phase prepared by above-mentioned steps, meso-position radius is 2.89 μm, and under 1C discharge-rate, first discharge specific capacity reaches 151.5mAh/g, and the chemical property of material after 300 times that circulates is substantially undamped.
From above experimental data, to be adulterated the technique combined with high temperature sintering by solid phase, during with phloroglucin, phenol or resorcinol for carbon source, the combination electrode material prepared has excellent chemical property, uniform particle diameter; And during using phloroglucin as carbon source, under 1C discharge-rate, first discharge specific capacity can up to 154mAh/g, the chemical property of material after 300 times that circulates is substantially undamped.
Claims (9)
1. a preparation method for combination electrode material, comprises following processing step:
(1) by lithium dihydrogen phosphate, two oxalic acid hydrate ferrous irons, lithium carbonate, vanadic oxide, titanium dioxide, manganese acetate be the ratio mixing of 1:0.97:0.01:0.01:0.01:0.01 in molar ratio, then add any one in phloroglucin, phenol or resorcinol as carbon source in the ratio of 10g/mol lithium dihydrogen phosphate;
(2) three-dimensional high-speed concussion ball mill is adopted to carry out ball milling mixing to raw material, in ball grinder, ball load is no more than 1/3rd of tank cumulative volume, raw material total amount is no more than 1/3rd of tank cumulative volume, and Ball-milling Time is 1 ~ 2 hour, and shimmy frequency is 800 ~ 1100 revs/min;
(3) two warm area rotary furnace is used to carry out high temperature sintering to the material after ball milling; setting boiler tube rotating speed is less than 3 revs/min; intermittent time is 1 minute; first nitrogen is led to 20 ~ 30 minutes before sintering; nitrogen flow rate is 0.14L/min under standard state, passes into pure nitrogen gas protection in sintering process, and nitrogen flow is 0.05L/min; sintering temperature is 600 ~ 800 DEG C, obtains the combination electrode material of pure phase after sintering.
2. the preparation method of combination electrode material according to claim 1, is characterized in that: in described step (1), the mol ratio of elemental lithium and ferro element is greater than 1.
3. the preparation method of combination electrode material according to claim 1, is characterized in that: the carbon source in described step (1) is phloroglucin.
4. the preparation method of combination electrode material according to claim 1, is characterized in that: in described step (2), the ball grinder material of three-dimensional high-speed concussion ball mill is nylon or polytetrafluoroethylene, and the material of mill ball is agate.
5. the preparation method of combination electrode material according to claim 1, is characterized in that: the rotary furnace 360 degree rotation of the three-dimensional high-speed concussion ball mill used in described step (2), and is welded with lifting blade in boiler tube.
6. the preparation method of combination electrode material according to claim 1, it is characterized in that: in described step (2), in ball grinder, ball load is 1/3rd of tank cumulative volume, raw material total amount accounts for 1/3rd of tank cumulative volume, and Ball-milling Time is 1.5 hours, and shimmy frequency is 1000 revs/min.
7. the preparation method of combination electrode material according to claim 1, is characterized in that: first lead to nitrogen 30 minutes before sintering in described step (3), sintering time is 10 hours.
8. the preparation method of combination electrode material according to claim 1, is characterized in that: the two warm area rotary furnace of described step (3) is that batch (-type) rotates, and rotating speed is 2 revs/min, and the intermittent time is 1 minute.
9. a combination electrode material, is characterized in that: the method preparation according to any one of claim 1-8.
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