A kind of anode material for lithium-ion batteries and preparation method thereof
Technical field:
The present invention relates to cell positive material and preparation method thereof, especially a kind of anode material for lithium-ion batteries and preparation method thereof.
Background technology:
Lithium ion battery is to begin commercial mechanism of new electrochemical power sources in 1991, have energy density height, operating voltage height, advantage such as load characteristic is good, charging rate is fast, have extended cycle life, safety non-pollution, be widely used in portable electric appts at present, annual production increases very fast.
At present, the positive electrode that is mainly used in lithium ion battery is the embedding lithium transition-metal oxide, research the earliest be to have α-sodium ferrite (α-NaFeO
2) the cobalt acid lithium (LiCoO of type layer structure
2), lithium nickelate (LiNiO
2), LiMn2O4 (LiMnO
2) and have the spinel lithium manganate (LiMn of spinel structure
2O
4) and their doped compound.The LiCoO of layer structure wherein
2Be the positive electrode of developing the earliest, though its stable performance, easily preparation, good reversibility, toxicity is big and cost an arm and a leg, thereby uses and be restricted.LiNiO
2Then synthesize difficulty and compare LiCoO because of it
2Worsely overcharge safety problem and limited its application.People expect stratiform LiMnO
2Although very high embedding lithium capacity is arranged, its crystal structure in charge and discharge process easily subsides and to the spinelle transformation of configuration, causes charge/discharge capacity to descend, and cyclicity is very poor, has restricted its practical application.
1997, people such as Goodenough proposed to have the LiFePO of olivine-type structure
4, space group is Pmna, crystal is by FeO
6Octahedron and PO
4Tetrahedron constitutes spatial skeleton, and Fe and Li then are filled in octahedral space.Fe occupies octahedra M2 (010) position at common angle, and Li then occupies octahedra M1 (100) position on common limit.FeO in the lattice
6Common angles by the bc face couples together, LiO
6Then form axial length of side chain altogether along b.A FeO
6Octahedron and two LiO
6Octahedron and a PO
4Tetrahedron is the limit altogether, the PO4 tetrahedron then with a FeO
6Octahedron and two LiO
6Octahedra limit altogether.Owing to there is not continuous FeO
6Be total to the octahedra network in limit, thus electron conduction can not be formed, simultaneously, because the PO between the octahedron
4Tetrahedron has limited the variation of lattice volume, thereby makes Li
+Embedding deviate from motion and be affected.So with traditional positive electrode stratiform LiCoO
2, LiNiO
2, LiMnO
2With spinelle LiMn
2O
4Compare LiFePO
4Have that cost is low, environmental friendliness, extremely low electronic conductivity and ions diffusion speed, charge/discharge capacity is very low under high current density, so can only discharge and recharge under minimum electric current, this has just limited its application in practice greatly.LiFePO
4The voltage platform that forms with Li/Li+ pairing greatly about about 3.5V, this be one highly beneficial with the voltage window that is worth.It has excellent cycle performance, even the decay of circulation hundreds of time capacity also is very little.Its theoretical specific capacity is 170mAh/g, has higher capacity and bigger energy density.Therefore the electronic conductivity that how to improve LIFePO4 is the focus of current chemical power source circle.The research that improves LIFePO4 conductivity at present mainly concentrates on carbon coating and metal or metal ion mixing two aspects.
Present LiFePO
4Main preparation methods be with behind 350 ℃ of following preheating 6h of raw material, under 600-800 ℃ of high temperature, calcine 24h again, this method has shortcomings such as synthesis cycle length, energy consumption height.The present invention has adopted new synthetic method, in the chemical property that has improved material, has shortened the synthetic cycle, has reduced the consumption of energy.
Summary of the invention:
The invention provides a kind of positive electrode and synthetic method thereof of lithium ion battery, be used for improving the chemical property of anode material for lithium-ion batteries LiFePO 4, mainly improve reversible capacity, cycle performance and high rate capability.
Anode material for lithium-ion batteries of the present invention is by the LiFePO of 70-90wt%
4Form with the carbon of 10-30wt%, make according to following steps:
(1) with lithium salts, microcosmic salt and ferrous oxalate mixing and ball milling, the mol ratio of described lithium, iron and P elements is 1: 1: 1,300~400 ℃ of preheatings 5~8 hours under nitrogen protection of dry back;
(2) add additive in above-mentioned mixture, the weight ratio of described mixture and additive is 3~10: 1;
(3) mixture that step (2) is obtained carries out roasting under inert gas shielding, and sintering temperature is 500~800 ℃, and roasting time is 10~24 hours;
(4) with the product compressing tablet after the roasting, put into the crucible that active carbon 10~40g is housed, again crucible is put into microwave oven, microwave power transfers to 140~700W, and the control time is 1~14 minute.
Wherein said lithium salts is lithium oxalate or lithium carbonate.
Described microcosmic salt is diammonium hydrogen phosphate or phosphoric acid dihydro amine.
Described additive is a kind of in sucrose, citric acid, polypropylene or the active carbon.
Described inert gas is a kind of in nitrogen, argon gas or the hydrogen-argon-mixed body.
The method for preparing anode material for lithium-ion batteries of the present invention, carry out according to following steps:
(1) with lithium salts, microcosmic salt and ferrous oxalate mixing and ball milling, the mol ratio of described lithium, iron and P elements is 1: 1: 1,300~400 ℃ of preheatings 5~8 hours under nitrogen protection of dry back;
(2) add additive in above-mentioned mixture, the weight ratio of described mixture and additive is 3~10: 1;
(3) mixture that step (2) is obtained carries out roasting under inert gas shielding, and sintering temperature is 500~800 ℃, and roasting time is 10~24 hours;
(4) with the product compressing tablet after the roasting, put into the crucible that active carbon 10~40g is housed, again crucible is put into microwave oven, microwave power transfers to 140~700W, and the control time is 1~14 minute.
Described lithium salts is lithium oxalate or lithium carbonate.
Described microcosmic salt is diammonium hydrogen phosphate or phosphoric acid dihydro amine.
Described additive is a kind of in sucrose, citric acid, polypropylene or the active carbon.
Described inert gas is a kind of in nitrogen, argon gas or the hydrogen-argon-mixed body.
Technical solution of the present invention has overcome shortcomings such as the synthesis cycle length, energy consumption height of prior art, improves the chemical property of LiFePO 4 in the anode material for lithium-ion batteries simultaneously, as reversible capacity, cycle performance and high rate capability.
Description of drawings:
Fig. 1 carbon encapsulated material LiFePO
4/ C sample a and pure LiFePO
4Specific discharge capacity comparison diagram under the 0.1C current density;
Fig. 2 carbon encapsulated material LiFePO
4/ C sample b and the sample a specific discharge capacity comparison diagram under the 0.1C current density;
Fig. 3 carbon encapsulated material LiFePO
4/ C sample b and the sample a specific discharge capacity comparison diagram under the 0.2C current density;
Fig. 4 carbon encapsulated material LiFePO
4/ C sample c and the sample b specific discharge capacity comparison diagram under the 0.1C current density;
Fig. 5 carbon encapsulated material LiFePO
4/ C sample c and the sample b specific discharge capacity comparison diagram under the 0.2C current density.
Embodiment:
Below in conjunction with figure and specific embodiment the invention will be further described:
Abscissa among Fig. 1 to Fig. 5 is the number of times that recycles, and ordinate is specific discharge capacity (mAh/g).The positive electrode carbon encapsulated material LiFePO for preparing lithium ion battery according to preparation method of the present invention
4/ C sample a, b and c, and three samples are compared: that the square curve description is carbon encapsulated material LiFePO among Fig. 1
4The chemical property of/C sample a, that circle point curve is described is pure LiFePO
4Chemical property.The initial capacity of sample a is 133mAh/g, is higher than pure LiFePO far away
4119mAh/g.Capacity through 40 circulation back sample a still remains on 119mAh/g.That the square curve description is carbon encapsulated material LiFePO among Fig. 2
4The chemical property of/C sample b, what circle point curve was described is the chemical property of sample a.The initial capacity that can see sample b under the 0.1C current density by Fig. 2 is a little less than sample a, but through the capacity of latter two sample that circulates several times near being about 133mAh/g, through 40 circulation back sample b and sample a mutually specific capacity almost do not decay; Sample b and sample a have good high magnification cycle performance as can be seen from Figure 3, and the capacity after sample b is stable is the 119mAh/g of 122mAh/g a little more than sample a.When obtaining the superperformance product, omitted preheating step and made that operation is easier, shortened the test period, reduced energy resource consumption, more help realizing industrialization.That the square curve description is carbon encapsulated material LiFePO among Fig. 3
4The chemical property of/C sample c, what circle point curve was described is the chemical property of sample b.The initial capacity that can see sample c under the 0.1C current density by Fig. 4 will be higher than sample b, is about 137mAh/g, but cycle performance slightly is worse than sample b.Discharge and recharge under high magnification current density condition as can be seen from Figure 5, sample c is more outstanding than sample b performance, and initial capacity still can remain on the 120mAh/g of 132mAh/g far above sample c, and has excellent cycle performance.
In battery is made, get final product according to usual way.Be dissolved in the solvent absolute ethyl alcohol as polytetrafluoroethylene (PTFE) and form slurry 70% this positive electrode of weight ratio percentage, 20% acetylene black and 10%.Slurry is evenly coated on the aluminium foil, and the thickness of coating is about 80 μ m, and it is 1cm that the electrode slice that coats is cut into big small size
2Work electrode, standby at 85 ℃ of following vacuumize 12h.Test battery adopts conventional button cell, is to electrode with metallic lithium foil, the LiPF of 1mol/L
6EC-DMC (volume ratio is 1: 1) solution be electrolyte, be assembled at drying room.Charge-discharge test adopts current constant mode to carry out, and discharging and recharging cut-ff voltage is 2.0~4.5V.
Embodiment 1
With 0.7438gLi
2CO
3, 3.5966gFeC
2O
42H
2O and 2.3234gNH
4H
2PO
4Mixing and ball milling; put into the following 350 ℃ of preheatings of tube furnace nitrogen protection 6 hours after the drying; add 0.631g sucrose in the mixture after preheating, put into 650 ℃ of roastings of tube furnace nitrogen protection 12 hours then, cooling; grind; with the product compressing tablet after the roasting, put into the crucible that the 30g active carbon is housed, again crucible is put into microwave oven; regulate microwave power to 420W, the control generated time is 3min.
Embodiment 2
With 0.7438gLi
2CO
3, 3.5966gFeC
2O
42H
2O and 2.3234gNH
4H
2PO
4Mixing and ball milling; put into the following 300 ℃ of preheatings of tube furnace argon shield 8 hours after the drying; add the 1.333g polypropylene in the mixture after preheating, put into 800 ℃ of roastings of tube furnace argon shield 10 hours then, cooling; grind; with the product compressing tablet after the roasting, put into the crucible that the 40g active carbon is housed, again crucible is put into microwave oven; regulate microwave power to 140W, the control generated time is 14min.
Embodiment 3
With 0.7438gLi
2CO
3, 3.5966gFeC
2O
42H
2O and 2.3234gNH
4H
2PO
4Mixing and ball milling; put into the hydrogen-argon-mixed body of tube furnace after the drying and protect following 400 ℃ of preheatings 5 hours; add 2.21g sucrose in the mixture after preheating, put into 500 ℃ of roastings of the hydrogen-argon-mixed body protection of tube furnace 24 hours then, cooling; grind; with the product compressing tablet after the roasting, put into the crucible that the 10g active carbon is housed, again crucible is put into microwave oven; regulate microwave power to 700W, the control generated time is 1min.
Embodiment 4
With 1.0186gLi
2C
2O
4, 3.5966gFeC
2O
42H
2O and 2.3234gNH
4H
2PO
4Mixing and ball milling; put into the following 350 ℃ of preheatings of tube furnace nitrogen protection 6 hours after the drying; add the 0.694g polypropylene in the mixture after preheating, put into 650 ℃ of roastings of tube furnace nitrogen protection 12 hours then, cooling; grind; with the product compressing tablet after the roasting, put into the crucible that the 20g active carbon is housed, again crucible is put into microwave oven; regulate microwave power to 450W, the control generated time is 10min.
Embodiment 5
With 0.7438gLi
2CO
3, 3.5966gFeC
2O
42H
2O and 2.6411g (NH
4)
2PO
4Mixing and ball milling; put into the following 350 ℃ of preheatings of tube furnace argon shield 6 hours after the drying; add the 0.997g active carbon in the mixture after preheating, put into 550 ℃ of roastings of tube furnace argon shield 20 hours then, cooling; grind; with the product compressing tablet after the roasting, put into the crucible that the 30g active carbon is housed, again crucible is put into microwave oven; regulate microwave power to 500W, the control generated time is 8min.
Embodiment 6
With 0.7438gLi
2CO
3, 3.5966gFeC
2O
42H
2O and 2.6411g (NH
4)
2PO
4Mixing and ball milling; put into the hydrogen-argon-mixed body of tube furnace after the drying and protect following 350 ℃ of preheatings 6 hours; add 1.396g sucrose in the mixture after preheating, put into 550 ℃ of roastings of the hydrogen-argon-mixed body protection of tube furnace 20 hours then, cooling; grind; with the product compressing tablet after the roasting, put into the crucible that the 40g active carbon is housed, again crucible is put into microwave oven; regulate microwave power to 550W, the control generated time is 8min.
Embodiment 7
With 1.0186gLi
2C
2O
4, 3.5966gFeC
2O
42H
2O and 2.3234gNH
4H
2PO
4Mixing and ball milling; put into the following 400 ℃ of preheatings of tube furnace nitrogen protection 6 hours after the drying; add the 1.388g active carbon in the mixture after preheating, put into 600 ℃ of roastings of tube furnace nitrogen protection 15 hours then, cooling; grind; with the product compressing tablet after the roasting, put into the crucible that the 10g active carbon is housed, again crucible is put into microwave oven; regulate microwave power to 600W, the control generated time is 5min.
Embodiment 8
With 0.7438gLi
2CO
3, 3.5966gFeC
2O
42H
2O and 2.6411g (NH
4)
2PO
4Mixing and ball milling; put into the hydrogen-argon-mixed body of tube furnace after the drying and protect following 400 ℃ of preheatings 6 hours; add 2.304g sucrose in the mixture after preheating, put into 600 ℃ of roastings of the hydrogen-argon-mixed body protection of tube furnace 15 hours then, cooling; grind; with the product compressing tablet after the roasting, put into the crucible that the 10g active carbon is housed, again crucible is put into microwave oven; regulate microwave power to 600W, the control generated time is 5min.
Embodiment 9
With 1.0186gLi
2C
2O
4, 3.5966gFeC
2O
42H
2O and 2.6411g (NH
4)
2PO
4Mixing and ball milling; put into the following 400 ℃ of preheatings of tube furnace argon shield 6 hours after the drying; add the 1.451g citric acid in the mixture after preheating, put into 600 ℃ of roastings of tube furnace argon shield 15 hours then, cooling; grind; with the product compressing tablet after the roasting, put into the crucible that the 10g active carbon is housed, again crucible is put into microwave oven; regulate microwave power to 600W, the control generated time is 5min.
Embodiment 10
With 0.7438gLi
2CO
3, 3.5966gFeC
2O
42H
2O and 2.6411g (NH
4)
2PO
4Mixing and ball milling; put into the following 400 ℃ of preheatings of tube furnace nitrogen protection 6 hours after the drying; add the 0.698g active carbon in the mixture after preheating, put into 600 ℃ of roastings of tube furnace nitrogen protection 15 hours then, cooling; grind; with the product compressing tablet after the roasting, put into the crucible that the 10g active carbon is housed, again crucible is put into microwave oven; regulate microwave power to 600W, the control generated time is 5min.