CN102683704A - Lithium iron phosphate cathode of lithium ion battery and preparation method for lithium iron phosphate cathode - Google Patents
Lithium iron phosphate cathode of lithium ion battery and preparation method for lithium iron phosphate cathode Download PDFInfo
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- CN102683704A CN102683704A CN2012101978563A CN201210197856A CN102683704A CN 102683704 A CN102683704 A CN 102683704A CN 2012101978563 A CN2012101978563 A CN 2012101978563A CN 201210197856 A CN201210197856 A CN 201210197856A CN 102683704 A CN102683704 A CN 102683704A
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- lithium ion
- lithium iron
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 46
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 40
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 31
- 239000010439 graphite Substances 0.000 claims abstract description 31
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 7
- 239000002245 particle Substances 0.000 claims abstract description 6
- 229910010707 LiFePO 4 Inorganic materials 0.000 claims description 25
- 239000000203 mixture Substances 0.000 claims description 22
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 12
- 238000000498 ball milling Methods 0.000 claims description 7
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 6
- 229910052742 iron Inorganic materials 0.000 claims description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 5
- 229910019142 PO4 Inorganic materials 0.000 claims description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 5
- 239000010452 phosphate Substances 0.000 claims description 5
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 4
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 4
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 4
- 229910003002 lithium salt Inorganic materials 0.000 claims description 4
- 159000000002 lithium salts Chemical class 0.000 claims description 4
- 230000001681 protective effect Effects 0.000 claims description 4
- 238000010792 warming Methods 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 239000004254 Ammonium phosphate Substances 0.000 claims description 2
- 239000004277 Ferrous carbonate Substances 0.000 claims description 2
- DQMUQFUTDWISTM-UHFFFAOYSA-N O.[O-2].[Fe+2].[Fe+2].[O-2] Chemical compound O.[O-2].[Fe+2].[Fe+2].[O-2] DQMUQFUTDWISTM-UHFFFAOYSA-N 0.000 claims description 2
- MCDLETWIOVSGJT-UHFFFAOYSA-N acetic acid;iron Chemical compound [Fe].CC(O)=O.CC(O)=O MCDLETWIOVSGJT-UHFFFAOYSA-N 0.000 claims description 2
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 2
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 2
- 229910000148 ammonium phosphate Inorganic materials 0.000 claims description 2
- 235000019289 ammonium phosphates Nutrition 0.000 claims description 2
- YNQRWVCLAIUHHI-UHFFFAOYSA-L dilithium;oxalate Chemical compound [Li+].[Li+].[O-]C(=O)C([O-])=O YNQRWVCLAIUHHI-UHFFFAOYSA-L 0.000 claims description 2
- RAQDACVRFCEPDA-UHFFFAOYSA-L ferrous carbonate Chemical compound [Fe+2].[O-]C([O-])=O RAQDACVRFCEPDA-UHFFFAOYSA-L 0.000 claims description 2
- 235000019268 ferrous carbonate Nutrition 0.000 claims description 2
- 229960004652 ferrous carbonate Drugs 0.000 claims description 2
- 235000019850 ferrous citrate Nutrition 0.000 claims description 2
- 239000011640 ferrous citrate Substances 0.000 claims description 2
- 229940062993 ferrous oxalate Drugs 0.000 claims description 2
- OWZIYWAUNZMLRT-UHFFFAOYSA-L iron(2+);oxalate Chemical compound [Fe+2].[O-]C(=O)C([O-])=O OWZIYWAUNZMLRT-UHFFFAOYSA-L 0.000 claims description 2
- 229910000015 iron(II) carbonate Inorganic materials 0.000 claims description 2
- APVZWAOKZPNDNR-UHFFFAOYSA-L iron(ii) citrate Chemical compound [Fe+2].OC(=O)CC(O)(C([O-])=O)CC([O-])=O APVZWAOKZPNDNR-UHFFFAOYSA-L 0.000 claims description 2
- 239000003446 ligand Substances 0.000 claims description 2
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 2
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 2
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 2
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 11
- 230000008569 process Effects 0.000 abstract description 9
- 238000005516 engineering process Methods 0.000 abstract description 7
- 230000001976 improved effect Effects 0.000 abstract description 5
- 239000007772 electrode material Substances 0.000 abstract description 4
- 239000002131 composite material Substances 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 239000006182 cathode active material Substances 0.000 abstract 1
- 239000002482 conductive additive Substances 0.000 abstract 1
- 239000000463 material Substances 0.000 description 8
- 238000011161 development Methods 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 230000009471 action Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000006258 conductive agent Substances 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 239000002803 fossil fuel Substances 0.000 description 2
- 229910010710 LiFePO Inorganic materials 0.000 description 1
- 239000006183 anode active material Substances 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000010450 olivine Substances 0.000 description 1
- 229910052609 olivine Inorganic materials 0.000 description 1
- 229920000447 polyanionic polymer Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a lithium iron phosphate cathode of a lithium ion battery and a preparation method for the lithium iron phosphate cathode, and belongs to a preparation technology for an active cathode material of the lithium ion battery. Lithium iron phosphate particles are uniformly distributed on a thin graphite flake layer which can provide a good conductive network for lithium iron phosphate, so that the power and energy density and cycle performance of the lithium iron phosphate are improved; the thin graphite flake layer has the function of improving the electrical conductivity of the lithium iron phosphate cathode of the lithium ion battery, so that the addition of a conductive additive during preparation is not required, and the manufacture cost of the lithium iron phosphate cathode of the lithium ion battery is lowered; in addition, the lithium iron phosphate cathode of the lithium ion battery also can be used as a low-cost substitute of a lithium iron phosphate and graphene composite material in the prior art; and the preparation method for the lithium iron phosphate cathode of the lithium ion battery can be based on the conventional matured preparation process for an electrode material of the lithium ion battery, the conventional process is not required to be greatly improved, and industrial implementation cost is low.
Description
Technical field
The present invention relates to the preparing technical field of anode active material of lithium ion battery, relate in particular to a kind of lithium iron (II) phosphate anode of lithium ion battery and preparation method thereof.
Background technology
The world today, the fossil fuel quasi-tradition energy is day by day exhausted, and in the process of combustion of fossil fuel, the problem of environmental pollution of generation is also serious day by day.The harmonious sustainable development of the energy, resource, environment and human society becomes the focus of social concerns, and the harmonious development of seek renewable and clean energy resource, seeking human and environment progressively becomes the theme in epoch.In the process of new energy development, the storage of energy green high-efficient and transfer become a key issue.Have high power density and high-energy-density, pollution-free, reusable lithium ion battery and become the object of national governments and scientific research institution's common concern.
Positive electrode is the important component part of lithium ion battery, and the performance of material property directly influences the power of lithium ion battery, the performance of energy characteristics.LiFePO
4Be a kind of polyanion phosphate of olivine structural, Material Thermodynamics is stable, and is safe and reliable, is one of current anode material for lithium-ion batteries of greatest concern.LiFePO
4Have also that nontoxic, environmentally friendly, abundant raw material, capacity and coulombic efficiency are high, charge and discharge platform steadily, specific capacity and specific power advantages of higher, so this material is very suitable for the large-sized battery application very responsive to fail safe, cycle life, power characteristic, use cost etc.
But LiFePO
4Electronic conductivity and the not good reason of ions diffusion rate restricted its dynamic performance and range of application always.To these problems, researchers carry out modification to these positive electrodes, and method mainly contains coating, mixes, reduces the nanometer technologies such as particle diameter of material.It is to improve LiFePO that carbon coats
4One of modified method that material property is the most frequently used, carbon coats not only can improve LiFePO
4The electronic conductivity of material can also effectively be controlled LiFePO
4Grain growth, be the effective means of obtaining nano particle, improving the lithium ion diffusivity.Wherein, grapheme material has caused the revolution of scientific circles since 2004 come to light, and through the compound or simple mixing of Graphene with different electrode materials, great facilitation has been played in the performance raising of material; It is compound to utilize Graphene and LiFePO 4 to carry out, to the performance of LiFePO 4 all have greatly improved effect (L. Wang, H.B. Wang, Z.H. Liu, C. Xiao; S.M. Dong, P.X. Han, Z.Y. Zhang, X.Y. Zhang, C.F. Bi; G.L. Cui, Solid State Ionics 181 (2010) 1685. X.F. Zhou, F. Wang, Y.M. Zhu and Z.P. Liu; J. Mater. Chem. 21 (2011) 3353. Y. Ding, Y. Jiang, F. Xua, J. Yin; H. Ren, Q. Zhuo, Z. Long and P. Zhang, Electrochem. Commun. 12 (2010) is 10.).Chinese patent CN 201010281627.0 discloses anode material for lithium-ion batteries of a kind of nanostructure and preparation method thereof, makes full use of the characteristic of Graphene and other positive electrodes, has prepared the excellent anode composite material of chemical property.Yet it is in practical application, utilize Graphene and LiFePO 4 to carry out compound preparation method and realize that industrialized preparation cost is higher, and simple inadequately.
Summary of the invention
Technical problem to be solved by this invention is to the above-mentioned deficiency that exists in the prior art; A kind of have higher power and energy density are provided; And the lithium iron (II) phosphate anode of lithium ion battery of excellent cycle performance and preparation method thereof, more be prone to realize industrialization and reduce preparation cost greatly.
For realizing above-mentioned purpose; A kind of lithium iron (II) phosphate anode of lithium ion battery of the present invention; Comprise LiFePO 4 particle and thin layer graphite; Said LiFePO 4 is evengranular to be distributed on the said thin layer graphite flake layer, and the mass ratio of said LiFePO 4 particle and thin layer graphite is (100 ~ 1): 1, and wherein said thin layer graphite is the graphene film of 20-200 layer for the sheet number of plies.
For realizing above-mentioned purpose, the preparation method of a kind of lithium iron (II) phosphate anode of lithium ion battery of the present invention comprises the steps:
A), according to Li:Fe:PO
4 3-=(1 ~ 1.3): (1 ~ 1.3): 1 mol ratio, get oxide, phosphate or the phosphorylated ligand resulting mixture of lithium salts, ferrous salt or iron, and mixture is joined in the ball mill;
B), in ball mill, add thin layer graphite, the quality of said thin layer graphite and steps A) in the mixture quality ratio be 1: (100 ~ 1), and in ball mill, add big mill ball and little mill ball; Wherein, (gross mass of big mill ball and little mill ball): mixture gross mass in (thin layer graphite and steps A))=(1 ~ 30): 1, the diameter of said big mill ball is 1.0 ~ 1.5 cm, the diameter of said little mill ball is 0.1 ~ 0.8 cm;
C), with thin layer graphite and steps A) in mixture ball milling in the ball mill of the rotating speed of 100 ~ 500r/min obtain head product after 1 ~ 24 hour;
D) with step C) head product that obtains adds in the tube furnace; Under the protection of protective gas; After said tube furnace is warming up to 300 ~ 400 ℃ of constant temperature 1-10 hours with the programming rate of 1 ~ 50 ℃/min; Programming rate with 1 ~ 50 ℃/min was warming up to 500 ~ 800 ℃ of constant temperature 2 ~ 20 hours again, behind the natural cooling, can obtain lithium iron (II) phosphate anode of lithium ion battery.
In steps A) described in lithium salts be a kind of or any several kinds mixture in lithium carbonate, lithium oxalate, lithium acetate, the lithium hydroxide.
In steps A) described in ferrous salt or the oxide of iron be a kind of or any several kinds mixture in ferrous carbonate, ferrous oxalate, ferrous citrate, ferrous acetate, ferrous oxide, di-iron trioxide, the tri-iron tetroxide.
In steps A) described in phosphate be a kind of or any several kinds mixture in ammonium phosphate, ammonium hydrogen phosphate, the ammonium dihydrogen phosphate.
At step D) described in protective gas be nitrogen or rare gas.
For realizing above-mentioned purpose, the preparation method of a kind of lithium iron (II) phosphate anode of lithium ion battery of the present invention comprises the steps:
A), be (100 ~ 1) with thin layer graphite according to mass ratio with LiFePO 4: 1 joins in the ball mill after mixing;
B), in ball mill, add big mill ball and little mill ball; Wherein, (gross mass of big mill ball and little mill ball): quality=(1 ~ 30) of mixture steps A): 1, the diameter of said big mill ball is 1.0 ~ 1.5 cm, the diameter of said little mill ball is 0.1 ~ 0.8 cm;
C), with steps A) in mixture ball milling in the ball mill of the rotating speed of 100 ~ 500r/min can obtain lithium iron (II) phosphate anode of lithium ion battery after 1 ~ 24 hour.
The present invention and prior art relatively have following beneficial effect:
(1), said LiFePO 4 is evengranular is distributed on the said thin layer graphite flake layer, thin layer graphite can be LiFePO 4 the favorable conductive network is provided, and has improved power and the energy density and the cycle performance of LiFePO 4;
(2), because thin layer graphite has castering action to the conductivity of said lithium iron (II) phosphate anode of lithium ion battery; Make said lithium iron (II) phosphate anode of lithium ion battery in preparation, can add any conductive agent, reduced the lithium iron (II) phosphate anode of lithium ion battery manufacturing cost;
(3), simultaneously said lithium iron (II) phosphate anode of lithium ion battery also can be used as a kind of low-cost substitute of LiFePO 4 and graphene composite material in the prior art; The preparation method of said lithium iron (II) phosphate anode of lithium ion battery can rely on the ripe preparation technology of existing lithium ion battery electrode material, need not existing technology is done big improvement, and the industrializing implementation cost is low.
Embodiment
For further understanding characteristic of the present invention, technological means and the specific purposes that reached, function, the present invention is described in further detail below in conjunction with embodiment.
Embodiment 1
The thin layer graphite of getting 3.0g LiFePO 4 and 0.4g joins in the ball mill; And to add diameter to ball mill be the big mill ball of 1.2 cm and the little mill ball that diameter is 0.4cm; Big mill ball is 1:3 with the number ratio of little mill ball, and big mill ball and little mill ball gross mass are 87.4g; The mixture of LiFePO 4 and thin layer graphite ball milling in the ball mill of the rotating speed of 400r/min was obtained lithium iron (II) phosphate anode of lithium ion battery after 10 hours.
Embodiment 2
Get the LiAc2H of 1.02g
2The FeC of O, 1.80g
2O
42H
2The NH of O, 1.15g
4H
2PO
4Join in the ball mill with the thin layer graphite mixture of 0.4g; And be the little mill ball of 0.4cm to wherein adding big mill ball and the diameter that diameter is 1.2 cm; Big mill ball is 1:3 with the number ratio of little mill ball, and big mill ball is 87.4g with the number of little mill ball than gross mass; With LiAc2H
2O, FeC
2O
42H
2O, NH
4H
2PO
4And thin layer graphite obtained head product in 10 hours with the rotating speed ball milling of 400r/min; Head product is put into tube furnace, and under protection of nitrogen gas, said tube furnace is heated to 350 ℃ of constant temperature 10h with the programming rate of 5 ℃/min; Programming rate with 5 ℃/min is heated to 600 ℃, constant temperature 10h again; Natural cooling promptly obtains lithium iron (II) phosphate anode of lithium ion battery.
Embodiment 3
Present embodiment is identical with embodiment 1 process, and just the consumption with thin layer graphite changes 1.1g into.
Embodiment 4
Present embodiment is identical with embodiment 1 process, and just the number ratio with big mill ball and little mill ball changes 1:10 into.
Embodiment 5
Present embodiment is identical with embodiment 1 process, and just the gross mass with big mill ball and little mill ball changes 100g into.
Embodiment 6
Present embodiment is identical with embodiment 1 process, and just the rotating speed with ball mill changes 500r/min into.
Embodiment 7
Present embodiment is identical with embodiment 1 process, just changes the ball milling time into 24 hours.
Embodiment 8
Present embodiment is identical with embodiment 2 processes, and being said tube furnace is heated to 400 ℃ of constant temperature 5h with the programming rate of 10 ℃/min, and the programming rate with 10 ℃/min is heated to 700 ℃ of constant temperature 12h again.
In sum, LiFePO 4 of the present invention is evengranular to be distributed on the said thin layer graphite flake layer, and thin layer graphite can be LiFePO 4 the favorable conductive network is provided, and has improved power and the energy density and the cycle performance of LiFePO 4; Because thin layer graphite has castering action to the conductivity of said lithium iron (II) phosphate anode of lithium ion battery; Make said lithium iron (II) phosphate anode of lithium ion battery in preparation, can add any conductive agent, reduced the lithium iron (II) phosphate anode of lithium ion battery manufacturing cost; Simultaneously said lithium iron (II) phosphate anode of lithium ion battery also can be used as a kind of low-cost substitute of LiFePO 4 and graphene composite material in the prior art; The preparation method of said lithium iron (II) phosphate anode of lithium ion battery can rely on the ripe preparation technology of existing lithium ion battery electrode material, need not existing technology is done big improvement, and the industrializing implementation cost is low.
The above embodiment has only expressed several kinds of execution modes of the present invention, and it describes comparatively concrete and detailed, but can not therefore be interpreted as the restriction to claim of the present invention.Should be pointed out that for the person of ordinary skill of the art under the prerequisite that does not break away from the present invention's design, can also make some distortion and improvement, these all belong to protection scope of the present invention.Therefore, the protection range of patent of the present invention should be as the criterion with accompanying claims.
Claims (8)
1. lithium iron (II) phosphate anode of lithium ion battery; It is characterized in that: comprise LiFePO 4 particle and thin layer graphite; Said LiFePO 4 is evengranular to be distributed on the said thin layer graphite flake layer, and the mass ratio of said LiFePO 4 particle and thin layer graphite is (100 ~ 1): 1.
2. require described a kind of lithium iron (II) phosphate anode of lithium ion battery according to right 1, it is characterized in that: said thin layer graphite is the graphene film of 20-200 layer for the sheet number of plies.
3. require the preparation method of described a kind of lithium iron (II) phosphate anode of lithium ion battery according to right 1 ~ 2, it is characterized in that, comprise the steps:
A), according to Li:Fe:PO
4 3-=(1 ~ 1.3): (1 ~ 1.3): 1 mol ratio, get oxide, phosphate or the phosphorylated ligand resulting mixture of lithium salts, ferrous salt or iron, and mixture is joined in the ball mill;
B), in ball mill, add thin layer graphite, the quality of said thin layer graphite and steps A) in the mixture quality ratio be 1: (100 ~ 1), and in ball mill, add big mill ball and little mill ball; Wherein, (gross mass of big mill ball and little mill ball): mixture gross mass in (thin layer graphite and steps A))=(1 ~ 30): 1, the diameter of said big mill ball is 1.0 ~ 1.5 cm, the diameter of said little mill ball is 0.1 ~ 0.8 cm;
C), with thin layer graphite and steps A) in mixture ball milling in the ball mill of the rotating speed of 100 ~ 500r/min obtain head product after 1 ~ 24 hour;
D) with step C) head product that obtains adds in the tube furnace; Under the protection of protective gas; After said tube furnace is warming up to 300 ~ 400 ℃ of constant temperature 1-10 hours with the programming rate of 1 ~ 50 ℃/min; Programming rate with 1 ~ 50 ℃/min was warming up to 500 ~ 800 ℃ of constant temperature 2 ~ 20 hours again, behind the natural cooling, can obtain lithium iron (II) phosphate anode of lithium ion battery.
4. require the preparation method of described a kind of lithium iron (II) phosphate anode of lithium ion battery according to right 3, it is characterized in that: it is characterized in that: in steps A) described in lithium salts be a kind of or any several kinds mixture in lithium carbonate, lithium oxalate, lithium acetate, the lithium hydroxide.
5. require the preparation method of described a kind of lithium iron (II) phosphate anode of lithium ion battery according to right 3, it is characterized in that: in steps A) described in ferrous salt or the oxide of iron be a kind of or any several kinds mixture in ferrous carbonate, ferrous oxalate, ferrous citrate, ferrous acetate, ferrous oxide, di-iron trioxide, the tri-iron tetroxide.
6. require the preparation method of described a kind of lithium iron (II) phosphate anode of lithium ion battery according to right 3, it is characterized in that: in steps A) described in phosphate be a kind of or any several kinds mixture in ammonium phosphate, ammonium hydrogen phosphate, the ammonium dihydrogen phosphate.
7. require the preparation method of described a kind of lithium iron (II) phosphate anode of lithium ion battery according to right 3, it is characterized in that: at step D) described in protective gas be nitrogen or rare gas.
8. require the preparation method of described a kind of lithium iron (II) phosphate anode of lithium ion battery according to right 1 ~ 2, it is characterized in that, comprise the steps:
A), be (100 ~ 1) with thin layer graphite according to mass ratio with LiFePO 4: 1 joins in the ball mill after mixing;
B), in ball mill, add big mill ball and little mill ball; Wherein, (gross mass of big mill ball and little mill ball): quality=(1 ~ 30) of mixture steps A): 1, the diameter of said big mill ball is 1.0 ~ 1.5 cm, the diameter of said little mill ball is 0.1 ~ 0.8 cm;
C), with steps A) in mixture ball milling in the ball mill of the rotating speed of 100 ~ 500r/min can obtain lithium iron (II) phosphate anode of lithium ion battery after 1 ~ 24 hour.
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| CN102306783A (en) * | 2011-09-14 | 2012-01-04 | 哈尔滨工业大学 | Multi-layer graphene/lithium iron phosphate intercalated composite material, preparation method thereof, and lithium ion battery adopting multi-layer grapheme/lithium iron phosphate intercalated composite material as anode material |
| WO2012023464A1 (en) * | 2010-08-19 | 2012-02-23 | Semiconductor Energy Laboratory Co., Ltd. | Electrical appliance |
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| CN101562248A (en) * | 2009-06-03 | 2009-10-21 | 龚思源 | Graphite composite lithium ion battery anode material lithium iron phosphate and preparation method thereof |
| WO2012023464A1 (en) * | 2010-08-19 | 2012-02-23 | Semiconductor Energy Laboratory Co., Ltd. | Electrical appliance |
| CN101950801A (en) * | 2010-09-21 | 2011-01-19 | 新疆金盛科达有色金属新材料有限责任公司 | A kind of preparation method of lithium-ion battery cathode material LiFePO4/C |
| CN102306783A (en) * | 2011-09-14 | 2012-01-04 | 哈尔滨工业大学 | Multi-layer graphene/lithium iron phosphate intercalated composite material, preparation method thereof, and lithium ion battery adopting multi-layer grapheme/lithium iron phosphate intercalated composite material as anode material |
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