CN101399341A - Producing method for large granule lithium iron phosphate battery positive pole material - Google Patents
Producing method for large granule lithium iron phosphate battery positive pole material Download PDFInfo
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- CN101399341A CN101399341A CNA2007100773160A CN200710077316A CN101399341A CN 101399341 A CN101399341 A CN 101399341A CN A2007100773160 A CNA2007100773160 A CN A2007100773160A CN 200710077316 A CN200710077316 A CN 200710077316A CN 101399341 A CN101399341 A CN 101399341A
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- Prior art keywords
- lithium
- iron phosphate
- ball milling
- lithium iron
- positive material
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- 239000000463 material Substances 0.000 title claims abstract description 41
- 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 38
- 238000000034 method Methods 0.000 title claims abstract description 13
- 239000008187 granular material Substances 0.000 title description 2
- 239000002245 particle Substances 0.000 claims abstract description 33
- 238000005245 sintering Methods 0.000 claims abstract description 28
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 18
- 238000002360 preparation method Methods 0.000 claims abstract description 16
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims abstract description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 5
- 239000010452 phosphate Substances 0.000 claims abstract description 5
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 3
- 238000000498 ball milling Methods 0.000 claims description 68
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 38
- 239000000203 mixture Substances 0.000 claims description 25
- 238000001816 cooling Methods 0.000 claims description 23
- 229910052757 nitrogen Inorganic materials 0.000 claims description 19
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 17
- 238000012216 screening Methods 0.000 claims description 14
- 238000005303 weighing Methods 0.000 claims description 12
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 9
- 229910052493 LiFePO4 Inorganic materials 0.000 claims description 7
- OVAQODDUFGFVPR-UHFFFAOYSA-N lithium cobalt(2+) dioxido(dioxo)manganese Chemical compound [Li+].[Mn](=O)(=O)([O-])[O-].[Co+2] OVAQODDUFGFVPR-UHFFFAOYSA-N 0.000 claims description 6
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 6
- 229910003002 lithium salt Inorganic materials 0.000 claims description 6
- 159000000002 lithium salts Chemical class 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-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
- 239000011261 inert gas Substances 0.000 claims description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 4
- 229940062993 ferrous oxalate Drugs 0.000 claims description 3
- OWZIYWAUNZMLRT-UHFFFAOYSA-L iron(2+);oxalate Chemical compound [Fe+2].[O-]C(=O)C([O-])=O OWZIYWAUNZMLRT-UHFFFAOYSA-L 0.000 claims description 3
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 3
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 3
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 3
- 239000004254 Ammonium phosphate Substances 0.000 claims description 2
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 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
- 239000002253 acid Substances 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
- 239000010941 cobalt Substances 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 229910000388 diammonium phosphate Inorganic materials 0.000 claims description 2
- 235000019838 diammonium phosphate 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
- 229940116007 ferrous phosphate Drugs 0.000 claims description 2
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 2
- 239000011790 ferrous sulphate Substances 0.000 claims description 2
- 238000005469 granulation Methods 0.000 claims description 2
- 230000003179 granulation Effects 0.000 claims description 2
- 229910000155 iron(II) phosphate Inorganic materials 0.000 claims description 2
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 2
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims 1
- 238000009818 secondary granulation Methods 0.000 abstract description 17
- 239000002131 composite material Substances 0.000 abstract description 10
- 238000012545 processing Methods 0.000 abstract description 5
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 2
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 2
- 239000007774 positive electrode material Substances 0.000 abstract 3
- 230000015572 biosynthetic process Effects 0.000 abstract 2
- 238000003786 synthesis reaction Methods 0.000 abstract 2
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 abstract 1
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 abstract 1
- VGYDTVNNDKLMHX-UHFFFAOYSA-N lithium;manganese;nickel;oxocobalt Chemical compound [Li].[Mn].[Ni].[Co]=O VGYDTVNNDKLMHX-UHFFFAOYSA-N 0.000 abstract 1
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 abstract 1
- 239000002994 raw material Substances 0.000 abstract 1
- 239000000047 product Substances 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 13
- 239000001307 helium Substances 0.000 description 8
- 229910052734 helium Inorganic materials 0.000 description 8
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 8
- 239000010406 cathode material Substances 0.000 description 6
- 238000001228 spectrum Methods 0.000 description 6
- 238000010532 solid phase synthesis reaction Methods 0.000 description 5
- 238000001354 calcination Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 238000011056 performance test Methods 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- LBSANEJBGMCTBH-UHFFFAOYSA-N manganate Chemical compound [O-][Mn]([O-])(=O)=O LBSANEJBGMCTBH-UHFFFAOYSA-N 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 238000000975 co-precipitation Methods 0.000 description 2
- 230000002950 deficient Effects 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 238000003980 solgel method Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000010408 sweeping Methods 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 229910013553 LiNO Inorganic materials 0.000 description 1
- 239000005030 aluminium foil Substances 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 229910001448 ferrous ion Inorganic materials 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000003223 protective agent Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000011265 semifinished product Substances 0.000 description 1
Images
Classifications
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- 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
Abstract
The invention provides a preparation method of lithium iron phosphate of a lithium-ion battery positive electrode material, the method takes ferrous salt, phosphate and a lithium source as raw materials, the synthesized material is further mixed with lithium cobalt oxide, lithium manganate, lithium nickelate or lithium nickel manganese cobalt oxide and other positive electrode materials according to a certain proportion after the preliminary synthesis of the lithium iron phosphate, and the mixed material with larger particles is prepared by secondary granulation at a certain temperature. The preparation method synthesizes the positive electrode composite material with the larger particle size by the two steps of the first sintering and the secondary granulation respectively during the synthesis process of the positive electrode material lithium iron phosphate, thereby effectively improving the processing performance and the tap density of the material and improving the volume specific capacity of the material.
Description
[technical field]
The present invention relates to the chemical cell field, relate in particular to a kind of cell positive material preparation method of large-particle lithium iron phosphate.
[background technology]
The synthetic method of lithium ion battery anode material lithium iron phosphate mainly contains high temperature solid phase synthesis, coprecipitation, sol-gel process, Pechini method etc. at present.Wherein soft chemical method complex process such as coprecipitation, sol-gel method, Pechini method are difficult for realizing industrialization, so conventional synthetic method mainly adopts high temperature solid phase synthesis.
High temperature solid phase synthesis is that lithium salts and ferrous salt are mixed according to a certain percentage, and a period of time of calcination at high temperature forms.Lithium salts commonly used in this method has lithium carbonate, lithium hydroxide, lithium nitrate, lithium acetate etc., and source of iron then be a ferrous oxalate, calcination temperature at 600 ℃～950 ℃ even more highly, calcination time is about 20～60h; Its mode of heating belongs to conventional mode of heating, is that to rely on heater (as resistance wire) that heat is delivered to by modes such as convection current, conduction or radiation material-to-be-heated, makes the material-to-be-heated a certain temperature that from outward appearance to inner essence reaches.High temperature solid phase synthesis operation and process route simplicity of design, technological parameter are easy to control, less demanding to equipment, and the material property of preparation is stable, is easy to realize large-scale industrialization production.But the high temperature solid phase synthesis LiFePO4 has the following defective usually: owing to adopted a large amount of presoma carbon as preventing the protective agent that ferrous ion is oxidized; the residual carbon that contains high-load like this in the He Cheng lithium iron phosphate positive material product; and because the existence of carbon has suppressed growing up of LiFePO4 crystal grain; though synthetic granule lithium iron phosphate positive material has rate charge-discharge performance preferably; but because the particle of material is little; thereby specific area has caused its processing characteristics relatively poor greatly; particularly slurry is difficult to cover the problem of paper tinsel; in addition also because the particle of material is little; tap density is lower, thereby the volume and capacity ratio of material is also seriously influenced.
[summary of the invention]
Goal of the invention of the present invention is for overcoming above-mentioned defective of the prior art, a kind of preparation method of cell positive material of large-particle lithium iron phosphate is provided, to reach processing characteristics and the tap density of improving cell positive material, improve the purpose of the volume and capacity ratio of positive electrode.
To achieve the above object of the invention, the cell positive material preparation method of large-particle lithium iron phosphate provided by the invention comprises following steps:
S1. the mol ratio ratio in Li:Fe:P=1～1.05:1～1.05:1～1.05 takes by weighing lithium source, ferrous salt, phosphate, mixes to be placed on and carries out ball-milling treatment in the ball grinder;
S2. the mixture behind the ball milling is sent in the sintering furnace and under 300-350 ℃ of temperature, carried out the roasting preliminary treatment;
S3. pretreated mixture once more behind the ball milling, is sent into the sintering kiln roasting 24～48h of nitrogen and/or inert gas shielding;
S4. the ball milling screening is taken out in furnace temperature cooling back; screening products obtained therefrom and the lithium salts positive electrode except that LiFePO4 are pressed the mixed ball milling of mass ratio 90:10～95:5; and then send in the sintering furnace of nitrogen and/or inert gas shielding and carry out the after baking granulation; ball milling is taken out in furnace temperature cooling back, promptly gets the cell positive material of large-particle lithium iron phosphate.
Preferably, among the above-mentioned steps S1, described lithium source is to be selected from least a in lithium carbonate, lithium hydroxide, lithium nitrate, lithium acetate, the lithium oxalate, ferrous salt is to be selected from least a in ferrous oxalate, ferrous acetate, the ferrous sulfate, and phosphate is to be selected from least a in ammonium phosphate, diammonium hydrogen phosphate, the ammonium dihydrogen phosphate.
Preferably, among the above-mentioned steps S1, the process conditions of described ball-milling treatment are that ethanol or propyl alcohol are decentralized medium, 400～600 rev/mins of ball milling speed, ball milling duration 4～6 hours.
Preferably, among the above-mentioned steps S2, the pretreated time of described roasting is 4～6 hours.
Preferably, among the above-mentioned steps S3, described sintering temperature is 600～800 ℃.
Preferably, among the above-mentioned steps S4, described lithium salts positive electrode except that LiFePO4 is cobalt acid lithium, LiMn2O4, lithium nickelate or nickle cobalt lithium manganate.
Preferably, among the above-mentioned steps S4, the process conditions of described after baking are 250～600 ℃ of temperature, roasting time 12～48 hours.
As can be seen from the above technical solutions, the preparation method of the cell positive material of large-particle lithium iron phosphate provided by the present invention, adopted secondary granulation technology to improve the conventional less shortcoming of lithium iron phosphate positive material particle diameter, both can obtain the lithium iron phosphate positive material of better high rate performance, can also improve the processing characteristics and the tap density of positive electrode effectively, improve the volume and capacity ratio of material.
[description of drawings]
Shown in Figure 1 is 4000 times of sem photographs of Comparative Examples products obtained therefrom;
Shown in Figure 2 is 4000 times of surface sweeping Electronic Speculum figure of embodiment 1 products obtained therefrom;
Shown in Figure 3 is the XRD figure spectrum of Comparative Examples products obtained therefrom;
Half-finished XRD figure spectrum when also not carrying out secondary granulation behind the 4th ball milling among the embodiment of being 1 shown in Figure 4;
Shown in Figure 5 is the XRD figure spectrum of embodiment 1 products obtained therefrom;
Shown in Figure 6 is the discharge curve of battery under different discharge-rate conditions that adopts the Comparative Examples positive electrode to make;
Shown in Figure 7 is the discharge curve of battery under different discharge-rate conditions that adopts embodiment 2 positive electrodes to make.
[embodiment]
Embodiment 1
Mol ratio ratio with Li:Fe:P=1:1.05:1 takes by weighing LiOHH
2O, FeC
2O
4And NH
4H
2PO
4, place ball grinder with 400～600 commentaries on classics/min speed ball milling 6h, after finishing mixture sent in the box type furnace and with about 350 ℃, handle 6h.Pretreated mixture is carried out sending into behind the ball milling again in the sintering furnace of nitrogen protection with 700 ℃ of roasting 24h; Take out the ball milling screening with the furnace temperature cooling; to sieve products obtained therefrom and nickle cobalt lithium manganate positive electrode according to mass ratio 95:5 mixed ball milling after; send into once more in the sintering furnace of nitrogen protection and carry out secondary granulation, temperature is controlled between 250～600 ℃, and the time is controlled between 12～48h.After the furnace temperature cooling, take out ball milling, finally obtain the iron phosphate lithium positive pole composite material of larger particles.
Mol ratio ratio with Li:Fe:P=1:1:1 takes by weighing Li
2CO
3, FeC
2O
4And NH
4H
2PO
4, place ball grinder with 400～600 commentaries on classics/min speed ball milling 6h, after finishing mixture sent in the box type furnace and with about 350 ℃, handle 6h.Pretreated mixture is carried out sending into behind the ball milling again in the sintering furnace of nitrogen protection with 700 ℃ of roasting 24h; Take out the ball milling screening with the furnace temperature cooling; to sieve products obtained therefrom and lithium cobaltate cathode material according to mass ratio 90:10 mixed ball milling after; send into once more in the sintering furnace of nitrogen protection and carry out secondary granulation, temperature is controlled between 250～600 ℃, and the time is controlled between 12～48h.After the furnace temperature cooling, take out ball milling, finally obtain the iron phosphate lithium positive pole composite material of larger particles.
Mol ratio ratio with Li:Fe:P=1:1:1 takes by weighing LiNO
3, Fe (C
2H
3O
2)
24H
2O and (NH
4)
2HPO
4, place ball grinder with 400～600 commentaries on classics/min speed ball milling 6h, after finishing mixture sent in the box type furnace and with about 350 ℃, handle 6h.Pretreated mixture is carried out sending into behind the ball milling again in the sintering furnace of nitrogen protection with 700 ℃ of roasting 24h; Take out the ball milling screening with the furnace temperature cooling; to sieve products obtained therefrom and manganate cathode material for lithium according to mass ratio 92:8 mixed ball milling after; send into once more in the sintering furnace of nitrogen protection and carry out secondary granulation, temperature is controlled between 250～600 ℃, and the time is controlled between 12～48h.After the furnace temperature cooling, take out ball milling, finally obtain the iron phosphate lithium positive pole composite material of larger particles.
Mol ratio ratio with Li:Fe:P=1:1.05:1.05 takes by weighing Li
2C
2O
4, Fe (C
2H
3O
2)
24H
2O and (NH
4)
2HPO
4, place ball grinder with 400～600 commentaries on classics/min speed ball milling 6h, after finishing mixture sent in the box type furnace and with about 330 ℃, handle 4h.Pretreated mixture is carried out sending into behind the ball milling again in the sintering furnace of helium protection with 800 ℃ of roasting 24h; Take out the ball milling screening with the furnace temperature cooling; to sieve products obtained therefrom and lithium cobaltate cathode material according to mass ratio 95:5 mixed ball milling after; send into once more in the sintering furnace of helium protection and carry out secondary granulation, temperature is controlled between 250～600 ℃, and the time is controlled between 12～48h.After the furnace temperature cooling, take out ball milling, finally obtain the iron phosphate lithium positive pole composite material of larger particles.
Embodiment 5
Mol ratio ratio with Li:Fe:P=1.05:1:1.05 takes by weighing LiC
2H
3O
2, FeSO
4(NH
4)
3PO
4, place ball grinder with 400～600 commentaries on classics/min speed ball milling 6h, after finishing mixture sent in the box type furnace and with about 300 ℃, handle 5h.Pretreated mixture is carried out sending into behind the ball milling again in the mixed gas protected sintering furnace of nitrogen and helium with 600 ℃ of roasting 24h; Take out the ball milling screening with the furnace temperature cooling; to sieve products obtained therefrom and manganate cathode material for lithium according to mass ratio 95:5 mixed ball milling after; send into once more in the mixed gas protected sintering furnace of nitrogen and helium and carry out secondary granulation; temperature is controlled between 250～600 ℃, and the time is controlled between 12～48h.After the furnace temperature cooling, take out ball milling, finally obtain the iron phosphate lithium positive pole composite material of larger particles.
Embodiment 6
Mol ratio ratio with Li:Fe:P=1.05:1.05:1 takes by weighing LiOHH
2O, FeSO
4(NH
4)
3PO
4, place ball grinder with 400～600 commentaries on classics/min speed ball milling 6h, after finishing mixture sent in the box type furnace and with about 330 ℃, handle 4h.Pretreated mixture is carried out sending into behind the ball milling again in the sintering furnace of helium protection with 800 ℃ of roasting 24h; Take out the ball milling screening with the furnace temperature cooling; to sieve products obtained therefrom and nickle cobalt lithium manganate positive electrode according to mass ratio 90:10 mixed ball milling after; send into once more in the sintering furnace of helium protection and carry out secondary granulation, temperature is controlled between 250～600 ℃, and the time is controlled between 12～48h.After the furnace temperature cooling, take out ball milling, finally obtain the iron phosphate lithium positive pole composite material of larger particles.
Embodiment 7
Mol ratio ratio with Li:Fe:P=1.05:1:1 takes by weighing LiC
2H
3O
2, FeC
2O
4And NH
4H
2PO
4, place ball grinder with 400～600 commentaries on classics/min speed ball milling 6h, after finishing mixture sent in the box type furnace and with about 300 ℃, handle 5h.Pretreated mixture is carried out sending into behind the ball milling again in the mixed gas protected sintering furnace of nitrogen and helium with 600 ℃ of roasting 24h; Take out the ball milling screening with the furnace temperature cooling; to sieve products obtained therefrom and manganate cathode material for lithium according to mass ratio 90:10 mixed ball milling after; send into once more in the mixed gas protected sintering furnace of nitrogen and helium and carry out secondary granulation; temperature is controlled between 250～600 ℃, and the time is controlled between 12～48h.After the furnace temperature cooling, take out ball milling, finally obtain the iron phosphate lithium positive pole composite material of larger particles.
Embodiment 8
Mol ratio ratio with Li:Fe:P=1:1:1.05 takes by weighing Li
2CO
3, FeSO
4(NH
4)
2HPO
4, place ball grinder with 400～600 commentaries on classics/min speed ball milling 4h, after finishing mixture sent in the box type furnace and with about 330 ℃, handle 6h.Pretreated mixture is carried out sending into behind the ball milling again in the sintering furnace of nitrogen protection with 800 ℃ of roasting 24h; Take out the ball milling screening with the furnace temperature cooling; to sieve products obtained therefrom and nickle cobalt lithium manganate positive electrode according to mass ratio 92:8 mixed ball milling after; send into once more in the sintering furnace of nitrogen protection and carry out secondary granulation, temperature is controlled between 250～600 ℃, and the time is controlled between 12～48h.After the furnace temperature cooling, take out ball milling, finally obtain the iron phosphate lithium positive pole composite material of larger particles.
Embodiment 9
Mol ratio ratio with Li:Fe:P=1:1.05:1 takes by weighing Li
2C
2O
4, Fe (C
2H
3O
2)
2(NH
4)
3PO
4, place ball grinder with 400～600 commentaries on classics/min speed ball milling 6h, after finishing mixture sent in the box type furnace and with about 300 ℃, handle 5h.Pretreated mixture is carried out sending into behind the ball milling again in the sintering furnace of nitrogen protection with 600 ℃ of roasting 24h; Take out the ball milling screening with the furnace temperature cooling; to sieve products obtained therefrom and lithium cobaltate cathode material according to mass ratio 92:8 mixed ball milling after; send into once more in the sintering furnace of nitrogen protection and carry out secondary granulation, temperature is controlled between 250～600 ℃, and the time is controlled between 12～48h.After the furnace temperature cooling, take out ball milling, finally obtain the iron phosphate lithium positive pole composite material of larger particles.
Comparative Examples
Mol ratio ratio with Li:Fe:P=1:1:1 takes by weighing LiOHH
2O, FeC
2O
4And NH
4H
2PO
4, place ball grinder with 400～600 commentaries on classics/min speed ball milling 6h, after finishing mixture sent in the box type furnace and with about 350 ℃, handle 6h.Pretreated sample is carried out sending into behind the ball milling in the sintering furnace of nitrogen protection with 700 ℃ of roasting 24h again, take out the ball milling screening with the furnace temperature cooling and obtain lithium iron phosphate positive material.
Battery is made and performance test
The positive pole that is used for electric performance test is made up of according to 80:15:5 (mass ratio) the foregoing description and synthetic sample, SP and the polyvinylidene fluoride (PVDF) of Comparative Examples, after it is mixed with machine,massing, slurry on small-sized tensile pulp machine, using aluminium foil is 16 μ m, and the slurry surface density is 8～9mg/cm
2, as to electrode, electrolyte adopts conventional lithium battery electrolytes, is assembled into half-cell and tests with metal Li.Battery pack is contained in the glove box that is full of argon shield carries out H
2O and O
2All less than 1ppm.Carry out the constant current charge and discharge with 0.1C, charging is by voltage 3.8V, and discharge is by voltage 2.0V.
The finished product battery that is used for electric performance test uses technology to carry out according to the lithium battery production of routine.
To the The performance test results of the foregoing description and Comparative Examples gained positive electrode and made battery thereof as shown in drawings, 4000 times of sem photographs of Comparative Examples products obtained therefrom, XRD figure spectrum are seen Fig. 1, Fig. 3 respectively; 4000 times of surface sweeping Electronic Speculum figure of embodiment 1 products obtained therefrom, XRD figure spectrum are seen Fig. 2, Fig. 5 respectively; Semi-finished product XRD figure spectrum when also not carrying out secondary granulation behind the 4th ball milling among the embodiment 1 is seen Fig. 4; Fig. 6, shown in Figure 7 be to be respectively the discharge curve of battery under different discharge-rate conditions that adopts the positive electrode of Comparative Examples and embodiment 2 gained to make.
Carried out through the present invention as can be known by Fig. 1 and 2 that the particle of LiFePO4 sample obviously is the reunion shape behind the secondary granulation, average particle size distribution is obviously original big.
From not changing the crystalline form of lithium iron phosphate positive material after Fig. 3,4 contrasts lithium iron phosphate positive material and nickle cobalt lithium manganate ternary material mixing and ball milling as can be seen, the dephasign peak at place such as 2 θ=20 ° belongs to ternary material in the X-ray diffractogram of Fig. 4, thereby sample is the mixture of lithium iron phosphate positive material and ternary material; From Fig. 4,5 contrasts still is two kinds of mixtures of material through sample after 700～900 ℃ of calcinings as can be seen, is just becoming more sharp-pointed through high-temperature calcination rear portion swarming.
Each embodiment and Comparative Examples gained positive electrode are made the discharge scenario of the different multiplying of battery and are added up as shown in table 1:
The discharge scenario statistics of each embodiment of table 1 and Comparative Examples different multiplying
| Sample | 1C discharge capacity/2C discharge capacity | 1C discharge capacity/5C discharge capacity |
| Comparative Examples | 95.95％ | 94.55％ |
| Embodiment 1 | 95.74％ | 94.50％ |
| |
95.64％ | 93.45％ |
| |
95.5％ | 92.4％ |
| |
96.5％ | 93.78％ |
| Embodiment 5 | 95.89％ | 93.5％ |
| Embodiment 6 | 95.5％ | 93％ |
| Embodiment 7 | 95.4％ | 92.5％ |
| Embodiment 8 | 96.23％ | 92.9％ |
| Embodiment 9 | 96.1％ | 93.98％ |
From Fig. 6 and 7 relatively, and table 1 is as can be known through after the present invention carries out secondary granulation, its multiplying power discharging property compare with the Comparative Examples of small particle diameter obviously do not reduce or even situation about increasing under, resulting sample not only particle diameter obviously increases, improved the tap density (as following table 2) of material greatly, processing characteristics strengthens.
The tap density test result of table 2 Comparative Examples and each embodiment sample
Pass through secondary granulation process of the present invention as shown in Table 2, the tap density of lithium iron phosphate positive material obviously increases, and has improved the volume and capacity ratio of material greatly.
The above embodiment has only expressed several execution mode 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 without departing from the inventive concept of the premise, 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 claims.
Claims (8)
1. the cell positive material preparation method of a large-particle lithium iron phosphate is characterized in that, comprises following steps:
S1. the mol ratio ratio in Li:Fe:P=1～1.05:1～1.05:1～1.05 takes by weighing lithium source, molysite, phosphate, mixes to be placed on and carries out ball-milling treatment in the ball grinder;
S2. the mixture behind the ball milling is sent in the sintering furnace and under 300-350 ℃ of temperature, carried out the roasting preliminary treatment;
S3. pretreated mixture once more behind the ball milling, is sent into the sintering kiln roasting 24～48h of nitrogen and/or inert gas shielding;
S4. the ball milling screening is taken out in furnace temperature cooling back; screening products obtained therefrom and the lithium salts positive electrode except that LiFePO4 are pressed the mixed ball milling of mass ratio 90:10～95:5; and then send in the sintering furnace of nitrogen and/or inert gas shielding and carry out the after baking granulation; ball milling is taken out in furnace temperature cooling back, promptly gets the cell positive material of large-particle lithium iron phosphate.
2. the cell positive material preparation method of large-particle lithium iron phosphate according to claim 1, it is characterized in that, in step S1, described lithium source is to be selected from least a in lithium carbonate, lithium hydroxide, lithium nitrate, lithium acetate, the lithium oxalate, ferrous salt is to be selected from least a in ferrous oxalate, ferrous acetate, the ferrous sulfate, and phosphate is to be selected from least a in ammonium phosphate, diammonium hydrogen phosphate, the ammonium dihydrogen phosphate.
3. the cell positive material preparation method of large-particle lithium iron phosphate according to claim 1 and 2 is characterized in that, adopts ethanol or propyl alcohol as decentralized medium in the described ball-milling treatment.
4. the cell positive material preparation method of large-particle lithium iron phosphate according to claim 1 and 2 is characterized in that, speed is 400～600 rev/mins during described ball-milling treatment, 4～6 hours time.
5. the cell positive material preparation method of large-particle lithium iron phosphate according to claim 1 is characterized in that, among the step S2, the pretreated time of described roasting is 4～6 hours.
6. the cell positive material preparation method of large-particle lithium iron phosphate according to claim 1 is characterized in that, among the step S3, described sintering temperature is 600～800 ℃.
7. the cell positive material preparation method of large-particle lithium iron phosphate according to claim 1 is characterized in that, among the step S4, described lithium salts positive electrode except that LiFePO4 is cobalt acid lithium, LiMn2O4, lithium nickelate or nickle cobalt lithium manganate.
8. the cell positive material preparation method of large-particle lithium iron phosphate according to claim 1 is characterized in that, among the step S4, the process conditions of described after baking are 250～600 ℃ of temperature, roasting time 12～48 hours.
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| CN102795611A (en) * | 2011-05-26 | 2012-11-28 | 比亚迪股份有限公司 | Preparation method of lithium iron phosphate material and lithium ion battery |
| CN103151521A (en) * | 2013-02-22 | 2013-06-12 | 中国科学院过程工程研究所 | Positive electrode material of lithium ion battery and preparing method thereof |
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| CN105355868A (en) * | 2015-10-21 | 2016-02-24 | 湖州百成电池有限公司 | Preparation method of novel iron-lithium and multi-element battery |
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| CN113086959A (en) * | 2021-02-26 | 2021-07-09 | 雅安锂盛新能企业管理中心(有限合伙) | High-compaction low-temperature lithium iron phosphate material, lithium battery positive plate and preparation method thereof |
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| CN1332462C (en) * | 2005-11-15 | 2007-08-15 | 厦门大学 | Lithium iron phosphate anode material and its preparing method |
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| CN103151521A (en) * | 2013-02-22 | 2013-06-12 | 中国科学院过程工程研究所 | Positive electrode material of lithium ion battery and preparing method thereof |
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| CN105226282A (en) * | 2015-10-26 | 2016-01-06 | 刘进 | A kind of preparation technology of LiFePO 4 material |
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| CN112047321A (en) * | 2020-09-10 | 2020-12-08 | 江西智锂科技有限公司 | Method for preparing composite phosphate lithium battery anode material |
| CN113086959A (en) * | 2021-02-26 | 2021-07-09 | 雅安锂盛新能企业管理中心(有限合伙) | High-compaction low-temperature lithium iron phosphate material, lithium battery positive plate and preparation method thereof |
| CN113086959B (en) * | 2021-02-26 | 2022-03-01 | 云南航开科技有限公司 | High-compaction low-temperature lithium iron phosphate material, lithium battery positive plate and preparation method thereof |
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