CN103390750A - Method for preparing lithium iron phosphate positive material - Google Patents
Method for preparing lithium iron phosphate positive material Download PDFInfo
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- CN103390750A CN103390750A CN2013103210045A CN201310321004A CN103390750A CN 103390750 A CN103390750 A CN 103390750A CN 2013103210045 A CN2013103210045 A CN 2013103210045A CN 201310321004 A CN201310321004 A CN 201310321004A CN 103390750 A CN103390750 A CN 103390750A
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- iron phosphate
- lithium
- lithium iron
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- 239000000463 material Substances 0.000 title claims abstract description 73
- 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 26
- 238000000034 method Methods 0.000 title claims abstract description 18
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 22
- 238000005245 sintering Methods 0.000 claims abstract description 20
- 230000008021 deposition Effects 0.000 claims abstract description 19
- 230000008569 process Effects 0.000 claims abstract description 15
- 239000011247 coating layer Substances 0.000 claims abstract description 12
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000010703 silicon Substances 0.000 claims abstract description 11
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 11
- 239000007789 gas Substances 0.000 claims description 58
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 43
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 28
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 24
- 238000010438 heat treatment Methods 0.000 claims description 19
- 229910052757 nitrogen Inorganic materials 0.000 claims description 17
- 229910052786 argon Inorganic materials 0.000 claims description 15
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 14
- 238000002360 preparation method Methods 0.000 claims description 13
- 239000011248 coating agent Substances 0.000 claims description 12
- 238000000576 coating method Methods 0.000 claims description 12
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 11
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 11
- 239000011261 inert gas Substances 0.000 claims description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 9
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 9
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 9
- 238000000498 ball milling Methods 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 9
- 239000002270 dispersing agent Substances 0.000 claims description 9
- 239000006185 dispersion Substances 0.000 claims description 9
- 229940062993 ferrous oxalate Drugs 0.000 claims description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 9
- OWZIYWAUNZMLRT-UHFFFAOYSA-L iron(2+);oxalate Chemical compound [Fe+2].[O-]C(=O)C([O-])=O OWZIYWAUNZMLRT-UHFFFAOYSA-L 0.000 claims description 9
- 230000014759 maintenance of location Effects 0.000 claims description 9
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 9
- 238000001291 vacuum drying Methods 0.000 claims description 9
- 238000005019 vapor deposition process Methods 0.000 claims description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 7
- 238000013461 design Methods 0.000 claims description 7
- 229910052744 lithium Inorganic materials 0.000 claims description 7
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 claims description 6
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims description 6
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims description 6
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 claims description 6
- ABTOQLMXBSRXSM-UHFFFAOYSA-N silicon tetrafluoride Chemical compound F[Si](F)(F)F ABTOQLMXBSRXSM-UHFFFAOYSA-N 0.000 claims description 6
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 5
- 229930006000 Sucrose Natural products 0.000 claims description 5
- 239000005720 sucrose Substances 0.000 claims description 5
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 4
- 239000012298 atmosphere Substances 0.000 claims description 4
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 4
- 239000003822 epoxy resin Substances 0.000 claims description 4
- 239000008103 glucose Substances 0.000 claims description 4
- 229920001568 phenolic resin Polymers 0.000 claims description 4
- 239000005011 phenolic resin Substances 0.000 claims description 4
- 229920000647 polyepoxide Polymers 0.000 claims description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 3
- 239000004698 Polyethylene Substances 0.000 claims description 3
- PZPGRFITIJYNEJ-UHFFFAOYSA-N disilane Chemical compound [SiH3][SiH3] PZPGRFITIJYNEJ-UHFFFAOYSA-N 0.000 claims description 3
- 239000001307 helium Substances 0.000 claims description 3
- 229910052734 helium Inorganic materials 0.000 claims description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 3
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 3
- -1 polyethylene Polymers 0.000 claims description 3
- 229920000573 polyethylene Polymers 0.000 claims description 3
- 238000009413 insulation Methods 0.000 claims description 2
- 239000003595 mist Substances 0.000 claims description 2
- 238000000151 deposition Methods 0.000 abstract description 17
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 12
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 12
- 238000007599 discharging Methods 0.000 abstract description 7
- 239000011204 carbon fibre-reinforced silicon carbide Substances 0.000 abstract description 5
- 230000004048 modification Effects 0.000 abstract description 4
- 238000012986 modification Methods 0.000 abstract description 4
- 238000005229 chemical vapour deposition Methods 0.000 abstract description 2
- 239000002243 precursor Substances 0.000 abstract 2
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- 230000007547 defect Effects 0.000 abstract 1
- 238000005137 deposition process Methods 0.000 abstract 1
- 239000011164 primary particle Substances 0.000 abstract 1
- 230000001105 regulatory effect Effects 0.000 abstract 1
- 238000003786 synthesis reaction Methods 0.000 abstract 1
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 23
- 229910001873 dinitrogen Inorganic materials 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 7
- 229910052493 LiFePO4 Inorganic materials 0.000 description 5
- 239000012071 phase Substances 0.000 description 4
- 239000013078 crystal Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 229910000077 silane Inorganic materials 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 150000001485 argon Chemical class 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000003746 solid phase reaction Methods 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000008358 core component Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000006181 electrochemical material Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
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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
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Abstract
The invention discloses a method for preparing a lithium iron phosphate positive material. Aiming at overcoming the conventional modification defects of a lithium iron phosphate material, a certain amount of carbon source is added into a synthesized precursor, carbon source gas and silicon source gas are introduced in a sintering process, a SiC coating layer is uniformly deposited on the surface of the lithium iron phosphate material through a chemical vapour deposition method, and thus the lithium iron phosphate material with the uniform SiC/C coating layer on the surface is prepared. In a synthesis process, the added amount of carbon source in the precursor, and the gas inlet pressures and flows and the vapour deposition time of the carbon source gas and the silicon source gas in a vapour deposition process are regulated, so that the lithium iron phosphate material with the uniform C/SiC coating layer on the surface is obtained. The lithium iron phosphate positive material has small primary particle size, is provided with the uniform and compact C/SiC coating layer on the surface and has high tap density, better multiplying power charging and discharging performance and excellent processability, so that the lithium iron phosphate positive material has broad application prospect in the field of power lithium ion batteries.
Description
Technical field
The present invention relates to electrochemical material preparation and new energy field, relate in particular to a kind of preparation method of lithium iron phosphate positive material.
Background technology
Along with increasingly sharpening of energy crisis, new renewable resource is all being found in the whole world, and renewable resource such as solar energy, wind energy, tidal energy, geothermal energy etc. have region and drink the characteristics of timeliness.Take full advantage of these resources, need intelligent grid or large-scale energy-storage system.Lithium ion battery has good application prospect as the energy storage electromotive force.On the other hand, the exhaustion day by day of fossil energy forces people to develop hybrid electrically or pure electric vehicle, and its core component battery becomes research emphasis.Lithium ion is compared its higher energy density with other batteries, good fail safe and long useful life and standby being popular.
LiFePO 4 material is as anode material for lithium-ion batteries, and the advantage such as, Heat stability is good moderate with its abundant raw material, cheap, environmental protection, operating voltage, caused people's extensive concern.
Through years of researches development, its performance has obtained obvious improvement, and still, LiFePO4 still exists all lower problems of ionic conductance and electron conductivity, poor-performing during high power charging-discharging.Present study on the modification to LiFePO 4 material is mainly by following several modes: (1) nanometer is processed, and the crystallite dimension that reduces synthesizing iron lithium phosphate can improve the ionic conductance of LiFePO4.The crystal grain radius is less, and the solid-state diffusion process of lithium ion in ion is shorter, and lithium ion embeds just easier; (2) element doping, in material lattice introducing hetero-atoms to improve the conductivity of material, but still section is clear at present for its feasibility and working mechanism, DeGrain, also can be along with the increase volume lowering along with the element doping amount; (3) conductive doped dose, can improve the electronic conductivity of material, most of carbon coating technology that adopts, because of the material with carbon element complex forms, the LiFePO 4 material tap density after most of carbon coats can reduce greatly, and processing characteristics can be subject to certain impact.
Study on the modification about LiFePO 4 material is many, but does not also find to add carbon source to synthesize small particle diameter and have the research of the LiFePO 4 material of SiC/C carbon coating layer closely in conjunction with vapour deposition SiC in sintering process in presoma at present.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of preparation method of lithium iron phosphate positive material.
In order to solve the problems of the technologies described above, the technical solution used in the present invention is: a kind of preparation method of lithium iron phosphate positive material is characterized in that comprising the following steps:
1) according to mol ratio Li: Fe: P: C=1.02: 1: 1: 0.2～0.5 takes lithium source, ferrous oxalate, ammonium dihydrogen phosphate, organic carbon source, take alcohol or acetone as dispersant, carries out the ball milling dispersion treatment, then carries out vacuum drying treatment and obtain presoma;
2) described presoma is placed under 550 ℃ of conditions of tube furnace, carries out pre-burning under nitrogen protection, 5 ℃/minute of heating rates, temperature retention time 5 hours, the naturally cooling room temperature of being down to, carry out coarse crushing to Preburning material;
3) will be placed in tube furnace through the Preburning material of coarse crushing and carry out double sintering, the heating rate with 5 ℃/minute under inert gas shielding rises to 700-750 ℃, insulation 8-15 hour; In temperature-rise period, the inert gas inlet pressure is 0.15MPa, and flow is 0.1L/min; After temperature reaches design temperature, introduce carbon-source gas and silicon source gas and carry out the vapour deposition coating, carbon-source gas inlet pressure 0.1～0.2MPa in vapor deposition processes, flow is 0.04～0.12L/min; Silicon source gas inlet pressure 0.1～0.2MPa, flow are 0.04～0.12L/min; Regulate simultaneously inert gas inlet pressure 0.1～0.2MPa, flow is 0.04～0.12L/min; After vapour deposition time 30min-240min, close carbon-source gas and silicon source gas air inlet, keep inert gas inlet pressure 0.15MPa, flow is 0.1L/min; Complete remaining sintering process under this inert atmosphere, and naturally cool to room temperature, namely obtain having surface C/lithium iron phosphate positive material of SiC coating layer.
As preferably, step 1) the lithium source described in is the combination of a kind of in lithium carbonate, lithium hydroxide, lithium acetate, lithium fluoride or at least two kinds; Described organic carbon source is the combination of a kind of in glucose, sucrose, phenolic resins, epoxy resin or polyethylene or at least two kinds.
, step 3 preferred as another) carbon-source gas described in is the combination of a kind of in methane, ethane, ethene, acetylene, benzene, toluene or at least two kinds; Described silicon source gas be monosilane, disilane, a kind of or combination of at least two kinds in silicon tetrafluoride.
Also have one preferred, step 3) described in inert gas be the mist of a kind of in helium, nitrogen and argon gas or at least two kinds.
The invention has the beneficial effects as follows:
Be combined in presoma and add carbon source and introduce SiC by chemical vapor deposition processes in follow-up heat treatment process, effectively suppressed growing up of crystal grain in traditional solid phase reaction process, realized the layer at LiFePO 4 material coated with uniform C/SiC, this material has excellent rate charge-discharge performance and processing characteristics.
Description of drawings
The present invention is further detailed explanation below in conjunction with the drawings and specific embodiments.
Fig. 1 is the TEM figure of preparation method embodiment 3 LiFePO 4 material that obtains of lithium iron phosphate positive material of the present invention.
Fig. 2 is the SEM figure of the LiFePO 4 material that obtains in the preparation method embodiment 3 of lithium iron phosphate positive material of the present invention.
Fig. 3 be in the preparation method embodiment 3 of lithium iron phosphate positive material of the present invention the discharge curve comparison figure under LiFePO 4 material 0.2C multiplying power that obtains in the LiFePO 4 material that obtains and comparative example.
In figure, a is C/SiC vapour deposition coated LiFePO 4 for lithium ion batteries, and b is carbon-coated LiFePO 4 for lithium ion batteries, and c is SiC vapour deposition coated LiFePO 4 for lithium ion batteries, and d is the pure phase LiFePO4.
Fig. 4 is the multiplying power discharging curve chart of the LiFePO 4 material that obtains in the preparation method embodiment 3 of lithium iron phosphate positive material of the present invention.
Embodiment
Embodiment 1
1) according to mol ratio Li: Fe: P: C=1.02: take lithium carbonate, ferrous oxalate, ammonium dihydrogen phosphate, sucrose at 1: 1: 0.2, carry out the ball milling dispersion treatment take alcohol as dispersant 5 hours, then carry out vacuum drying treatment acquisition presoma; The above-mentioned dry presoma that obtains is placed under 550 ℃ of conditions of tube furnace, carries out pre-burning under nitrogen protection, 5 ℃/minute of heating rates, temperature retention time 5 hours, the naturally cooling room temperature of being down to, carry out coarse crushing to Preburning material;
2) the above-mentioned Preburning material through coarse crushing that obtains is placed in tube furnace and carries out double sintering, the heating rate with 5 ℃/minute under nitrogen protection rises to 700 ℃, is incubated 10 hours.In temperature-rise period, the nitrogen inlet pressure is 0.15MPa, and flow is 0.1L/min.After temperature reaches design temperature, introduce methane gas and monosilane gas and carry out the vapour deposition coating, methane gas inlet pressure 0.1MPa in vapor deposition processes, flow is 0.12L/min, monosilane gas inlet pressure 0.1MPa, flow is 0.12L/min, regulates simultaneously nitrogen inlet pressure 0.1MPa, and flow is 0.04L/min.After vapour deposition time 30min, close methane gas and the air inlet of monosilane gas, keep nitrogen inlet pressure 0.15MPa, flow is 0.1L/min, complete remaining sintering process under this nitrogen atmosphere, and naturally cool to room temperature, namely obtain having surface C/lithium iron phosphate positive material of SiC coating layer.The tap density of this material is 1.05g/cm
3.
Embodiment 2
1) according to mol ratio Li: Fe: P: C=1.02: take lithium carbonate, ferrous oxalate, ammonium dihydrogen phosphate, glucose at 1: 1: 0.3, carry out the ball milling dispersion treatment take acetone as dispersant 5 hours, then carry out vacuum drying treatment acquisition presoma; The above-mentioned dry presoma that obtains is placed under 550 ℃ of conditions of tube furnace, carries out pre-burning under argon shield, 5 ℃/minute of heating rates, temperature retention time 5 hours, the naturally cooling room temperature of being down to, carry out coarse crushing to Preburning material;
2) the above-mentioned Preburning material through coarse crushing that obtains is placed in tube furnace and carries out double sintering, the heating rate with 5 ℃/minute under argon shield rises to 720 ℃, is incubated 10 hours.In temperature-rise period, argon inlet pressure is 0.15MPa, and flow is 0.1L/min.After temperature reaches design temperature, introduce ethane gas and b silane gas and carry out the vapour deposition coating, ethane gas inlet pressure 0.12MPa in vapor deposition processes, flow is 0.1L/min, b silane gas inlet pressure 0.12MPa, flow is 0.1L/min, regulates simultaneously argon inlet pressure 0.1MPa, and flow is 0.08L/min.After vapour deposition time 60min, close ethane gas and b silane gas air inlet, keep argon inlet pressure 0.15MPa, flow is 0.1L/min, complete remaining sintering process under this argon gas atmosphere, and naturally cool to room temperature, namely obtain having surface C/lithium iron phosphate positive material of SiC coating layer.The tap density of this material is 1.1g/cm
3.
Embodiment 3
1) according to mol ratio Li: Fe: P: C=1.02: take lithium carbonate, ferrous oxalate, ammonium dihydrogen phosphate, phenolic resins at 1: 1: 0.35, carry out the ball milling dispersion treatment take alcohol as dispersant 5 hours, then carry out vacuum drying treatment acquisition presoma; The above-mentioned dry presoma that obtains is placed under 550 ℃ of conditions of tube furnace, carries out pre-burning under nitrogen protection, 5 ℃/minute of heating rates, temperature retention time 5 hours, the naturally cooling room temperature of being down to, carry out coarse crushing to Preburning material;
2) the above-mentioned Preburning material through coarse crushing that obtains is placed in tube furnace and carries out double sintering, the heating rate with 5 ℃/minute under nitrogen protection rises to 740 ℃, is incubated 10 hours.In temperature-rise period, the nitrogen gas inlet pressure is 0.15MPa, and flow is 0.1L/min.After temperature reaches design temperature, introduce methane gas and monosilane gas and carry out the vapour deposition coating, methane gas inlet pressure 0.12MPa in vapor deposition processes, flow is 0.08L/min, monosilane gas inlet pressure 0.12MPa, flow is 0.08L/min, regulates simultaneously nitrogen gas inlet pressure 0.1MPa, and flow is 0.1L/min.After vapour deposition time 120min, close methane gas and the air inlet of monosilane gas, keep nitrogen gas inlet pressure 0.15MPa, flow is 0.1L/min, complete remaining sintering process under this nitrogen atmosphere, and naturally cool to room temperature, namely obtain having surface C/lithium iron phosphate positive material of SiC coating layer.The tap density of this material is 1.3g/cm
3, respectively as shown in Figure 1 and Figure 2, the half-cell charging and discharging curve as shown in Figure 3 for the TEM of the LiFePO 4 material that obtains and SEM.
Embodiment 4
1) according to mol ratio Li: Fe: P: C=1.02: take lithium carbonate, ferrous oxalate, ammonium dihydrogen phosphate, epoxy resin at 1: 1: 0.5, carry out the ball milling dispersion treatment take acetone as dispersant 5 hours, then carry out vacuum drying treatment acquisition presoma; The above-mentioned dry presoma that obtains is placed under 550 ℃ of conditions of tube furnace, carries out pre-burning under argon shield, 5 ℃/minute of heating rates, temperature retention time 5 hours, the naturally cooling room temperature of being down to, carry out coarse crushing to Preburning material;
2) the above-mentioned Preburning material through coarse crushing that obtains is placed in tube furnace and carries out double sintering, the heating rate with 5 ℃/minute under argon shield rises to 740 ℃, is incubated 10 hours.In temperature-rise period, argon inlet pressure is 0.15MPa, and flow is 0.1L/min.After temperature reaches design temperature, introduce acetylene gas and silicon tetrafluoride gas and carry out the vapour deposition coating, acetylene gas inlet pressure 0.2MPa in vapor deposition processes, flow is 0.04L/min, silicon tetrafluoride gas inlet pressure 0.2MPa, flow is 0.04L/min, regulates simultaneously argon inlet pressure 0.1MPa, and flow is 0.1L/min.After vapour deposition time 220min, close acetylene gas and silicon tetrafluoride gas air inlet, keep argon inlet pressure 0.15MPa, flow is 0.1L/min, complete remaining sintering process under this argon gas atmosphere, and naturally cool to room temperature, namely obtain having surface C/lithium iron phosphate positive material of SiC coating layer.The tap density of this material is 1.1g/cm
3.
The comparative example 1
1) according to mol ratio Li: Fe: P: C=i.02: take lithium carbonate, ferrous oxalate, ammonium dihydrogen phosphate, sucrose at 1: 1: 0.35, carry out the ball milling dispersion treatment take alcohol as dispersant 5 hours, then carry out vacuum drying treatment acquisition presoma; The above-mentioned dry presoma that obtains is placed under 550 ℃ of conditions of tube furnace, carries out pre-burning under nitrogen protection, 5 ℃/minute of heating rates, temperature retention time 5 hours, the naturally cooling room temperature of being down to, carry out coarse crushing to Preburning material;
2) the above-mentioned Preburning material through coarse crushing that obtains is placed in tube furnace and carries out double sintering, the heating rate with 5 ℃/minute under the nitrogen gas protection rises to 740 ℃, is incubated 10 hours.Nitrogen During gas gas inlet pressure is 0.15MPa, and flow is 0.1L/min.And naturally cool to room temperature, namely obtain not passing through the carbon-coated LiFePO 4 for lithium ion batteries positive electrode of vapor deposition processes.The tap density of this material is 0.85g/cm
3.
The comparative example 2
1) according to mol ratio Li: Fe: P=1.02: take lithium carbonate, ferrous oxalate, ammonium dihydrogen phosphate at 1: 1, carry out the ball milling dispersion treatment take alcohol as dispersant 5 hours, then carry out vacuum drying treatment acquisition presoma; The above-mentioned dry presoma that obtains is placed under 550 ℃ of conditions of tube furnace, carries out pre-burning under nitrogen protection, 5 ℃/minute of heating rates, temperature retention time 5 hours, the naturally cooling room temperature of being down to, carry out coarse crushing to Preburning material;
2) the above-mentioned Preburning material through coarse crushing that obtains is placed in tube furnace and carries out double sintering, the heating rate with 5 ℃/minute under nitrogen protection rises to 740 ℃, is incubated 10 hours.In temperature-rise period, the nitrogen gas inlet pressure is 0.15MPa, and flow is 0.1L/min.After temperature reaches design temperature, introduce methane gas and monosilane gas and carry out the vapour deposition coating, methane gas inlet pressure 0.12MPa in vapor deposition processes, flow is 0.08L/min, monosilane gas inlet pressure 0.12MPa, flow is 0.08L/min, regulates simultaneously nitrogen gas inlet pressure 0.1MPa, and flow is 0.1L/min.After vapour deposition time 120min, close methane gas and the air inlet of monosilane gas, keep nitrogen gas inlet pressure 0.15MPa, flow is 0.1L/min, complete remaining sintering process under this nitrogen atmosphere, and naturally cool to room temperature, namely obtain having the lithium iron phosphate positive material of surperficial SiC coating layer.The tap density of this material is 1.15g/cm
3.
The comparative example 3
1) according to mol ratio Li: Fe: P=i.02: take lithium carbonate, ferrous oxalate, ammonium dihydrogen phosphate at 1: 1, carry out the ball milling dispersion treatment take alcohol as dispersant 5 hours, then carry out vacuum drying treatment acquisition presoma; The above-mentioned dry presoma that obtains is placed under 550 ℃ of conditions of tube furnace, carries out pre-burning under nitrogen protection, 5 ℃/minute of heating rates, temperature retention time 5 hours, the naturally cooling room temperature of being down to, carry out coarse crushing to Preburning material;
2) the above-mentioned Preburning material through coarse crushing that obtains is placed in tube furnace and carries out double sintering, the heating rate with 5 ℃/minute under the nitrogen gas protection rises to 740 ℃, is incubated 10 hours.Nitrogen During gas gas inlet pressure is 0.15MPa, and flow is 0.1L/min.And naturally cool to room temperature, namely obtain the pure phase lithium iron phosphate positive material that obtains through solid phase reaction.The tap density of this material is 1.0g/cm
3.
The LiFePO 4 material that obtains in above-described embodiment and comparative example is assembled into button cell, in pole piece, active material matching ratio is LiFeP04: SP: PVDF=80: 10: 10, adopt Clgard2300 type barrier film, be metal lithium sheet to electrode, discharge with 0.2C, 1C, 4C, 5C multiplying power respectively, rate of charge is fixed as 0.2C, and the charging/discharging voltage scope is 2.0-4.0V.The charging and discharging curve of the LiFePO 4 material of the C/SiC coating that embodiment 3 and comparative example 1, example 2, example 3 obtain, C coating, SiC coating and pure phase as shown in Figure 3.
Embodiment and comparative example's result show: LiFePO 4 material synthetic, by add organic carbon source in presoma, and carry out the CVD vapor deposition processes in the follow-up sintering process, on the one hand effectively suppressed growing up of crystal grain in the sintering process, the LiFePO4 that has synthesized small particle diameter, realized on the other hand the C/CSi on LiFePO 4 material surface is closely coated, efficiently solved the low problem of simple carbon-coated LiFePO 4 for lithium ion batteries material tap density.Compare with carbon-coated LiFePO 4 for lithium ion batteries, vapour deposition SiC coating and pure phase LiFePO 4 material, have higher specific discharge capacity and excellent multiplying power discharging property.
In above-described embodiment, organic carbon source is to the situation of having enumerated sucrose, and the experimental result of selecting other organic carbon sources such as glucose, phenolic resins, epoxy resin and polyethylene and this organic carbon source to produce is similar; In embodiment, the lithium source, to the situation of having enumerated lithium carbonate, selects other lithium sources such as lithium hydroxide, lithium acetate, lithium fluoride to produce similar experimental result to lithium carbonate; Select other carbon-source gas such as methane, ethane, ethene, acetylene, benzene, toluene to produce similar experimental result; select other silicon source gas such as disilane, silicon tetrafluoride produced similar experimental result, select other protective gas such as helium, argon gas, carbon dioxide to nitrogen gas generation similar experimental result.
Above-described embodiment of the present invention, do not form the restriction to protection range of the present invention.Any modification of doing within the spirit and principles in the present invention, be equal to and replace and improvement etc., within all should being included in claim protection range of the present invention.
Claims (4)
1. the preparation method of a lithium iron phosphate positive material is characterized in that comprising the following steps:
1) according to mol ratio Li: Fe: P: C=1.02: 1: 1: 0.2～0.5 takes lithium source, ferrous oxalate, ammonium dihydrogen phosphate, organic carbon source, take alcohol or acetone as dispersant, carries out the ball milling dispersion treatment, then carries out vacuum drying treatment and obtain presoma;
2) described presoma is placed under 550 ℃ of conditions of tube furnace, carries out pre-burning under nitrogen protection, 5 ℃/minute of heating rates, temperature retention time 5 hours, the naturally cooling room temperature of being down to, carry out coarse crushing to Preburning material;
3) will be placed in tube furnace through the Preburning material of coarse crushing and carry out double sintering, the heating rate with 5 ℃/minute under inert gas shielding rises to 700-750 ℃, insulation 8-15 hour; In temperature-rise period, the inert gas inlet pressure is 0.15MPa, and flow is 0.1L/min; After temperature reaches design temperature, introduce carbon-source gas and silicon source gas and carry out the vapour deposition coating, carbon-source gas inlet pressure 0.1～0.2MPa in vapor deposition processes, flow is 0.04～0.12L/min; Silicon source gas inlet pressure 0.1～0.2MPa, flow are 0.04～0.12L/min; Regulate simultaneously inert gas inlet pressure 0.1～0.2MPa, flow is 0.04～0.12L/min; After vapour deposition time 30min-240min, close carbon-source gas and silicon source gas air inlet, keep inert gas inlet pressure 0.15MPa, flow is 0.1L/min; Complete remaining sintering process under this inert atmosphere, and naturally cool to room temperature, namely obtain having surface C/lithium iron phosphate positive material of SiC coating layer.
2. preparation method according to claim 1, is characterized in that: step 1) described in the lithium source be the combination of a kind of in lithium carbonate, lithium hydroxide, lithium acetate, lithium fluoride or at least two kinds; Described organic carbon source is the combination of a kind of in glucose, sucrose, phenolic resins, epoxy resin or polyethylene or at least two kinds.
3. preparation method according to claim 1, is characterized in that: step 3) described in carbon-source gas be the combination of a kind of in methane, ethane, ethene, acetylene, benzene, toluene or at least two kinds; Described silicon source gas be monosilane, disilane, a kind of or combination of at least two kinds in silicon tetrafluoride.
4. preparation method according to claim 1, is characterized in that: step 3) described in inert gas be the mist of a kind of in helium, nitrogen and argon gas or at least two kinds.
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