CN102185136B - Preparation method of lithium ion battery cathode material nano lithium iron phosphate - Google Patents
Preparation method of lithium ion battery cathode material nano lithium iron phosphate Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 24
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 title abstract 5
- 239000010406 cathode material Substances 0.000 title abstract 2
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 claims abstract description 58
- 239000000463 material Substances 0.000 claims abstract description 44
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 38
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 37
- 238000000034 method Methods 0.000 claims abstract description 34
- 239000002002 slurry Substances 0.000 claims abstract description 26
- 239000000843 powder Substances 0.000 claims abstract description 23
- 238000001694 spray drying Methods 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000010438 heat treatment Methods 0.000 claims abstract description 11
- 238000002156 mixing Methods 0.000 claims abstract description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 10
- 150000001875 compounds Chemical class 0.000 claims abstract description 10
- 239000002270 dispersing agent Substances 0.000 claims abstract description 9
- 239000011261 inert gas Substances 0.000 claims abstract description 3
- 239000005955 Ferric phosphate Substances 0.000 claims description 54
- 229940032958 ferric phosphate Drugs 0.000 claims description 54
- 229910000399 iron(III) phosphate Inorganic materials 0.000 claims description 54
- 229940116007 ferrous phosphate Drugs 0.000 claims description 30
- 229910000155 iron(II) phosphate Inorganic materials 0.000 claims description 30
- SDEKDNPYZOERBP-UHFFFAOYSA-H iron(ii) phosphate Chemical compound [Fe+2].[Fe+2].[Fe+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O SDEKDNPYZOERBP-UHFFFAOYSA-H 0.000 claims description 30
- 239000002245 particle Substances 0.000 claims description 25
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 21
- 239000010405 anode material Substances 0.000 claims description 19
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 14
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 13
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 13
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 12
- 238000007599 discharging Methods 0.000 claims description 11
- 208000005156 Dehydration Diseases 0.000 claims description 7
- 230000018044 dehydration Effects 0.000 claims description 7
- 238000006297 dehydration reaction Methods 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 7
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 6
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-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
- 229930006000 Sucrose Natural products 0.000 claims description 5
- 229920000136 polysorbate Polymers 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
- RCEAADKTGXTDOA-UHFFFAOYSA-N OS(O)(=O)=O.CCCCCCCCCCCC[Na] Chemical group OS(O)(=O)=O.CCCCCCCCCCCC[Na] RCEAADKTGXTDOA-UHFFFAOYSA-N 0.000 claims description 4
- 239000002202 Polyethylene glycol Substances 0.000 claims description 4
- -1 Sucrose Fatty Acid Ester Chemical class 0.000 claims description 4
- 238000002425 crystallisation Methods 0.000 claims description 4
- 230000008025 crystallization Effects 0.000 claims description 4
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 4
- YNQRWVCLAIUHHI-UHFFFAOYSA-L dilithium;oxalate Chemical compound [Li+].[Li+].[O-]C(=O)C([O-])=O YNQRWVCLAIUHHI-UHFFFAOYSA-L 0.000 claims description 4
- 239000000194 fatty acid Substances 0.000 claims description 4
- 229930195729 fatty acid Natural products 0.000 claims description 4
- 239000008103 glucose Substances 0.000 claims description 4
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- 229920001223 polyethylene glycol Polymers 0.000 claims description 4
- ZZZCUOFIHGPKAK-UHFFFAOYSA-N D-erythro-ascorbic acid Natural products OCC1OC(=O)C(O)=C1O ZZZCUOFIHGPKAK-UHFFFAOYSA-N 0.000 claims description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 3
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 3
- 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 3
- 229930003268 Vitamin C Natural products 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 3
- 229950008882 polysorbate Drugs 0.000 claims description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 3
- 238000012545 processing Methods 0.000 claims description 3
- 235000019154 vitamin C Nutrition 0.000 claims description 3
- 239000011718 vitamin C Substances 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- CDOUZKKFHVEKRI-UHFFFAOYSA-N 3-bromo-n-[(prop-2-enoylamino)methyl]propanamide Chemical compound BrCCC(=O)NCNC(=O)C=C CDOUZKKFHVEKRI-UHFFFAOYSA-N 0.000 claims description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical class CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 2
- IPBYARKNCJJHKZ-UHFFFAOYSA-L [Fe+2].O.[PH2](=O)[O-].[PH2](=O)[O-] Chemical compound [Fe+2].O.[PH2](=O)[O-].[PH2](=O)[O-] IPBYARKNCJJHKZ-UHFFFAOYSA-L 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 125000001931 aliphatic group Chemical group 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 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 2
- 239000001913 cellulose Chemical class 0.000 claims description 2
- 229920002678 cellulose Chemical class 0.000 claims description 2
- 235000019329 dioctyl sodium sulphosuccinate Nutrition 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- 150000004665 fatty acids Chemical class 0.000 claims description 2
- PHNWGDTYCJFUGZ-UHFFFAOYSA-N hexyl dihydrogen phosphate Chemical compound CCCCCCOP(O)(O)=O PHNWGDTYCJFUGZ-UHFFFAOYSA-N 0.000 claims description 2
- 150000002505 iron Chemical class 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 239000007800 oxidant agent Substances 0.000 claims description 2
- 230000001590 oxidative effect Effects 0.000 claims description 2
- 229920002401 polyacrylamide Polymers 0.000 claims description 2
- 229920000570 polyether Polymers 0.000 claims description 2
- 239000012266 salt solution Substances 0.000 claims description 2
- 238000009938 salting Methods 0.000 claims description 2
- 239000000203 mixture Substances 0.000 abstract description 5
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 3
- 229910000398 iron phosphate Inorganic materials 0.000 abstract 4
- 238000003756 stirring Methods 0.000 abstract 1
- 238000005303 weighing Methods 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 230000004087 circulation Effects 0.000 description 10
- 239000002994 raw material Substances 0.000 description 9
- 238000000498 ball milling Methods 0.000 description 8
- 239000007789 gas Substances 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 8
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 230000002572 peristaltic effect Effects 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 description 4
- 238000005245 sintering Methods 0.000 description 4
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 229910003002 lithium salt Inorganic materials 0.000 description 3
- 159000000002 lithium salts Chemical class 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 238000003836 solid-state method Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000006245 Carbon black Super-P Substances 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 239000005030 aluminium foil Substances 0.000 description 2
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 2
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 235000019837 monoammonium phosphate Nutrition 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 229910052493 LiFePO4 Inorganic materials 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000000875 high-speed ball milling Methods 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- PVFSDGKDKFSOTB-UHFFFAOYSA-K iron(3+);triacetate Chemical compound [Fe+3].CC([O-])=O.CC([O-])=O.CC([O-])=O PVFSDGKDKFSOTB-UHFFFAOYSA-K 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910000402 monopotassium phosphate Inorganic materials 0.000 description 1
- 235000019796 monopotassium phosphate Nutrition 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 description 1
- 125000004437 phosphorous atom Chemical group 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 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 preparation method of a lithium ion battery cathode material nano lithium iron phosphate which belongs to the technical field of nano lithium iron phosphate preparation. The method comprises the following steps: preparing hydrous nano iron phosphate by a rotating packed bed method; roasting and dehydrating the hydrous nano iron phosphate to obtain anhydrous nano iron phosphate powder; weighing lithium source compound, carbon source compound and anhydrous nano iron phosphate according to a stoichiometric ratio, adding pure water and a dispersant, mixing and stirring the mixture uniformly, preparing a slurry, performing spray drying of the prepared slurry, performing heat treatment of the obtained powder with the protection of inert gas to obtain the nano lithium iron phosphate material. The nano lithium iron phosphate material prepared by the invention has uniform components and good batch stability, has specific discharge capacity at 1C rate of more than 130 mAh/g and specific discharge capacity at 5C rate of more than 110 mAh/g at room temperature, and has great application value in the power-type lithium ion battery field. The method is applicable to large-scale production, and has low cost.
Description
Technical field
The invention belongs to the nano-lithium iron phosphate preparing technical field, particularly a kind of preparation method of anode material for lithium-ion batteries nano-lithium iron phosphate.
Background technology
LiFePO 4 (LiFePO
4) be a kind of lithium ion battery novel anode material grown up in recent years.Have raw material sources abundant, preparation cost is low, and specific capacity is high, good cycle, the advantage such as environmental pollution is little.At present, power type of new generation or accumulation energy type lithium ion battery have been widely used in.
But it is Shortcomings part still at aspects such as high rate during charging-discharging, cryogenic property, volumetric specific energys, these problems have had a strong impact on performance, the operating characteristics that has also affected battery and the scopes of application such as the energy density, power density of battery, the too high large-scale promotion application that also affects battery pack of the battery manufacture cost that the material consistency problem causes.Therefore, must fundamentally solve the bottleneck problem that material exists, from aspects such as material synthesis techniques, promote the intrinsic performance of ferrousphosphate lithium material.
At present, on market, most of LiFePO4 producer directly adopts high temperature solid-state method to prepare ferrousphosphate lithium material.Although the high temperature solid-state method synthesis process is simple, but reactant is difficult for mixing, reaction time is long, and need repeatedly sintering, synthetic product granularity major part is micron order, and skewness, often contains impurity, pattern is irregular, and the chemical property of different batches material differs greatly.This is because solid phase method is difficult to control accurately lithium, iron, phosphorus ratio, and product purity, crystallization shape, granularity control also have great difficulty, product less stable in batches, and whole production process flow process is long, and energy consumption is larger.Existing studies have shown that the high rate performance of nano-lithium iron phosphate compares all and improve with the micron order LiFePO 4 with cryogenic property; but how to prepare a well behaved nanometer ferrousphosphate lithium material difficult problem really; find advanced technology, process stabilizing, practicality simple to operate and technology path that can large-scale production; simultaneously; also to consider manufacturing cost, the economy of the aspects such as energy consumption and environmental protection and social influence.
Summary of the invention
The preparation method who the purpose of this invention is to provide a kind of anode material for lithium-ion batteries nano-lithium iron phosphate is characterized in that the method carries out according to the following steps:
(1) utilize the RPB method to prepare nano hydrated ferric phosphate;
(2) the nano hydrated ferric phosphate prepared by step (1), 400～600 ℃ of lower roasting dehydrations 4～12 hours, obtains the waterless nano ferric phosphate powder body;
(3) according to mol ratio Li: C: Fe=(1～1.05): (1～1.2): 1 takes the waterless nano ferric phosphate of preparation in nanometer Li source compound, carbon-source cpd and step (2), add pure water and dispersant, be uniformly mixed, obtain the slurry that solid content is 20～50%, in slurry, the granularity of SS is 20～60nm;
(4) slurry step (3) made carries out spray drying, the presoma powder that obtains mixing;
(5) powder step (4) obtained 500～850 ℃ of heat treatments 2～14 hours, obtains nanometer ferrousphosphate lithium material under inert gas shielding.
Described nano hydrated ferric phosphate granularity is 20～60nm.
Described nanometer Li source compound granularity is 20～60nm.
Described nanometer Li source compound is a kind of in lithium carbonate, lithium hydroxide, lithium nitrate, lithium acetate and lithium oxalate.
In step (3), described carbon-source cpd is one or more in sucrose, glucose, citric acid, pentaerythrite, vitamin C, polyethylene glycol and polyethers.
In step (3), described dispersant is lauryl sodium sulfate, dodecyl sodium sulfate, dioctyl sodium sulfosuccinate (A Luosuo-OT), any one in Sucrose Fatty Acid Ester, aliphatic acid sorb smooth (Span), polysorbate (Tween), polyoxyethylene, polyvinyl alcohol, triethyl group hexyl phosphoric acid, methyl anyl alcohol, cellulose derivative, polyacrylamide, fatty acid polyethylene glycol ester.
Carbon content in described nanometer ferrousphosphate lithium material is 0.5～5%.
Gained nanometer ferrousphosphate lithium material granularity is greatly between 40～160nm.
The invention provides a kind of method that spray drying-carbothermic method prepares nanometer ferrousphosphate lithium material; at first from the presoma ferric phosphate of synthesizing lithium ferrous phosphate, start with; select novel RPB to prepare nano ferric phosphate; and select nano lithium carbonate and other nanoscale lithium salts; subsequently; adopt ball milling mixing and spray drying technology to prepare mixed uniformly precursor material; finally under atmosphere protection, with lower temperature heat treatment, obtain narrower particle size distribution, the nanometer ferrous phosphate lithium material that free-running property is good.
Beneficial effect of the present invention is:
(1) make raw material with cheap ferric phosphate, do not use expensive ferrous iron, not only reduced production cost, and avoided the easy oxidation of ferrous iron to generate the impurity that is difficult to remove and cause product impure;
(2) using ferric phosphate as source of iron and phosphorus source, iron, phosphorus atoms distribute very evenly and ratio is fixed;
(3) adopt the high speed ball milling, add dispersant that nano ferric phosphate and nanometer lithium source material and carbon source material are fully mixed simultaneously, the evolving path of lithium ion in the nano ferric phosphate particle is short, utilizes and improves material conductivity and high rate performance; Micron order material before comparing mixes, and Ball-milling Time shortens greatly, and rotational speed of ball-mill reduces, and from the production angle, considers, has saved energy consumption, has improved production efficiency.
(4) adopt RPB to prepare the method for the lithium source materials such as nano ferric phosphate and nano lithium carbonate, technique is simple, is easy to control, and fast, efficiency is high in reaction, and the product quality consistency is high, stable performance, and preparation cost is low, is beneficial to large-scale production.
(5) adopt the high temperature solid-state method production technology of a step sintering simple, the cycle is short; Because various precursor material are nanometer scale, therefore, sintering temperature descends, and sintering time shortens, and has further reduced power consumption, emission-free pollution, the applicable large batch of suitability for industrialized production of waiting in whole technical process;
(6) adopt spray-dired method, the wink-dry slurry, avoid segregation in the composition dry run, and the products obtained therefrom composition is even, in batches good stability;
(7) at nano ferric phosphate preparation and precursor material ball milling mix stages all than the even carbon dope that is easier to realize metal ion mixing and granule interior, to material modification and improve conductivity and be highly profitable;
(8) synthetic nanometer ferrousphosphate lithium material has good chemical property as anode material for lithium-ion batteries, at room temperature 1C multiplying power discharging specific capacity is greater than 130mAh/g, 5C multiplying power discharging specific capacity is greater than 110mAh/g, and cyclicity is good, be applicable to the power anode material for lithium-ion batteries.
The accompanying drawing explanation
Fig. 1 is the cycle performance curve (1C six circulations, 5C ten circulations, 10C ten circulations, 15C bis-ten circulations, 5C five circulations) of the prepared nano-lithium iron phosphate of embodiment mono-under different multiplying;
Fig. 2 is the transmission electron microscope photo of the prepared nano-lithium iron phosphate of embodiment bis-.
Embodiment
Below in conjunction with embodiment, technical scheme of the present invention is described further, following examples do not produce restriction to the present invention.
The present invention's nanometer Li source compound used is lithium carbonate, lithium hydroxide, lithium nitrate, a kind of in lithium acetate and lithium oxalate, commercially available, wherein nano lithium carbonate also can utilize the self-control of RPB method, utilize the RPB method to prepare nano lithium carbonate, technique is as follows: first water-soluble lithium salts or lithium hydroxide are dissolved in water to obtain to lithium source solution, and in the solution of lithium source, add water soluble dispersing agent to form mixed solution, start RPB, make its rotation, then with measuring pump, by charging aperture and liquid distribution trough, this mixed solution is sprayed, be distributed on the porous aggregate of RPB annular fill area, pass into CO simultaneously
2perhaps the water soluble carbonate saline solution makes water-soluble lithium salts or lithium hydroxide solution and CO under centrifugal action
2gas or water soluble carbonate saline solution fully mix fast, the nano lithium carbonate particle that reactive crystallization generates is discharged by the discharging opening of RPB with mixed liquor, after filtration, washing, drying process obtain nano-scale lithium carbonate after processing, the nano-scale lithium carbonate granularity of preparation is greatly between 10～100nm.The present invention's nanometer Li source compound granularity used is 20～60nm.
Utilize the RPB method to prepare nano hydrated ferric phosphate, with reference to the applicant's patent " a kind of preparation method of nano ferric phosphate " (application number: 200910235404.8), technique is as follows: by phosphoric acid or soluble phosphoric acid salting liquid both one of, one of water-soluble divalent iron salt and oxidant or water-soluble trivalent ferric salt solution, the mixed solution and the alkaline aqueous solution that with water soluble dispersing agent, form are input in the RPB layer, regulate the rotating speed of RPB, control the pH value of reaction system between 1.6-6.0 with aqueous slkali, the nano ferric phosphate particle that reactive crystallization generates is discharged by the discharging opening of RPB with mixed liquor, after filtration, washing, drying process obtains nanoscale hypophosphite monohydrate iron after processing, the nano hydrated ferric phosphate granularity of preparation is greatly between 10～100nm.The present invention's nano hydrated ferric phosphate granularity used is 20～60nm.
Embodiment mono-:
Prepare the anode material for lithium-ion batteries nano-lithium iron phosphate, carry out according to the following steps:
(1) take lithium hydroxide and sodium carbonate as raw material, utilize the RPB method to prepare nano lithium carbonate, the particle mean size of gained lithium carbonate is 60nm;
(2) take ferric nitrate, phosphoric acid and ammoniacal liquor as raw material, utilize the RPB method to prepare nano hydrated ferric phosphate, specifically can with reference to the applicant's patent " a kind of preparation method of nano ferric phosphate ", (application number: 200910235404.8), the nano hydrated ferric phosphate particle mean size of gained be 40nm;
(3) get nano hydrated ferric phosphate FePO prepared by 620g step (2)
42H
2O, the heating rate with 4 ℃/min in air atmosphere is raised to 550 ℃ of roasting 6hr dehydrations, obtains waterless nano ferric phosphate powder;
(4) take 110g sucrose, 500g waterless nano ferric phosphate and 125g nano lithium carbonate (mol ratio Li: C: Fe=1.02: 1.16: 1), add 3000ml water, the 20mg dodecyl sodium sulfate, ball milling mixing 2hr in basket ball mill, rotational speed of ball-mill 600rpm, form the slurry that uniform solid content is 20%, in slurry, the particle mean size of SS is 50nm;
(5) pneumatic spray drying device drying for slurry step (4) made, adopt and the fluidized drying mode, atomising device adopts the double-current method nozzle, Control Nozzle gas flow and pressure and and the peristaltic pump charging rate, make inlet temperature remain on 200 ℃, outlet temperature is 120 ℃, and outlet air separates emptying through the one-level whirlpool, obtains the presoma powder mixed after spray drying;
(6) powder step (5) obtained at 600 ℃ of heat treatment 10hr, obtains nanometer ferrousphosphate lithium material under the high pure nitrogen protection.
Record the weight content of carbon in ferrousphosphate lithium material and be about 4.0%.Gained nanometer ferrousphosphate lithium material particle mean size is 100nm.
Nanometer ferrousphosphate lithium material, Super-P conductive carbon black, PVDF binding agent are mixed in mass ratio at 8: 1: 1, the NMP of take makes uniform slurry as solvent, then by its blade coating on the aluminium foil of 20 micron thick, obtain anode pole piece after 120 ℃ of vacuumize, take the lithium paper tinsel as to electrode, fill to obtain experimental cell in being full of the glove box of argon gas, carry out charge-discharge test with constant current, charging/discharging voltage is 2.5-4.2V, it is 135mAh/g that room temperature records average specific discharge capacity under the 1C multiplying power, average specific discharge capacity 113mAh/g under the 5C multiplying power.The cycle performance curve of prepared nano-lithium iron phosphate under different multiplying be (six circulations of 1C, ten circulations of 5C, ten circulations of 10C, 20 circulations of 15C, five circulations of 5C) as shown in Figure 1.
Embodiment bis-:
Prepare the anode material for lithium-ion batteries nano-lithium iron phosphate, carry out according to the following steps:
(1) take ferric acetate, phosphoric acid and potassium hydroxide as raw material, utilize the RPB method to prepare nano hydrated ferric phosphate, specifically can with reference to the applicant's patent " a kind of preparation method of nano ferric phosphate ", (application number: 200910235404.8), the nano hydrated ferric phosphate particle mean size of gained be 20nm;
(2) get nano hydrated ferric phosphate FePO prepared by 620g step (1)
42H
2O, in air atmosphere, 400 ℃ of roasting 12hr dehydrations, obtain waterless nano ferric phosphate powder;
(3) take the lithium hydroxide that 120g glucose, 500g waterless nano ferric phosphate and 145g particle mean size are 20nm (mol ratio Li: C: Fe=1.04: 1.2: 1), add 2000ml water, the 80mg polyvinyl alcohol, ball milling mixing 3hr in basket ball mill, rotational speed of ball-mill 800rpm, form the slurry that uniform solid content is 30%, in slurry, the particle mean size of SS is 20nm;
(4) pneumatic spray drying device drying for slurry step (3) made, adopt and the fluidized drying mode, atomising device adopts the double-current method nozzle, Control Nozzle gas flow and pressure and and the peristaltic pump charging rate, make inlet temperature remain on 250 ℃, outlet temperature is 150 ℃, and outlet air separates emptying through the one-level whirlpool, obtains the presoma powder mixed after spray drying;
(5) powder step (4) obtained at 550 ℃ of heat treatment 12hr, obtains nanometer ferrousphosphate lithium material under the high pure nitrogen protection.
Record the weight content of carbon in nanometer ferrousphosphate lithium material and be about 5.0%.Gained nanometer ferrousphosphate lithium material particle mean size is 60nm.The transmission electron microscope photo of prepared nano-lithium iron phosphate as shown in Figure 2.
Carry out the charge-discharge performance test with embodiment mono-: carry out charge-discharge test with constant current, charging/discharging voltage is 2.5-4.2V, and it is 138mAh/g that room temperature records average specific discharge capacity under the 1C multiplying power, average specific discharge capacity 128mAh/g under the 5C multiplying power.
Embodiment tri-:
Prepare the anode material for lithium-ion batteries nano-lithium iron phosphate, carry out according to the following steps:
(1) take iron chloride, ammonium dihydrogen phosphate and ammoniacal liquor as raw material, utilize the RPB method to prepare nano hydrated ferric phosphate, specifically can with reference to the applicant's patent " a kind of preparation method of nano ferric phosphate ", (application number: 200910235404.8), the nano hydrated ferric phosphate particle mean size of gained be 50nm;
(2) get nano hydrated ferric phosphate FePO prepared by 620g step (1)
42H
2O, in air atmosphere, 450 ℃ of roasting 10hr dehydrations, obtain waterless nano ferric phosphate powder;
(3) take the nanometer lithium acetate that 100g pentaerythrite, 500g waterless nano ferric phosphate and 350g particle mean size are 60nm (Li: C: Fe=1.04: 1.11: 1), add 1000ml water, add the 40mg lauryl sodium sulfate, ball milling mixing 5hr in basket ball mill, rotational speed of ball-mill 1200rpm, form the slurry that uniform solid content is 50%, in slurry, the particle mean size of SS is 60nm;
(4) pneumatic spray drying device drying for slurry step (3) made, adopt and the fluidized drying mode, atomising device adopts the double-current method nozzle, Control Nozzle gas flow and pressure and and the peristaltic pump charging rate, make inlet temperature remain on 300 ℃, outlet temperature is 110 ℃, and outlet air separates emptying through the one-level whirlpool, obtains the presoma powder mixed after spray drying;
(5) powder step (4) obtained at 650 ℃ of heat treatment 8hr, obtains nanometer ferrousphosphate lithium material under the high pure nitrogen protection.
The weight content that records carbon in ferrousphosphate lithium material is 3.2%.Gained nanometer ferrousphosphate lithium material particle mean size is 80nm.
Carry out the charge-discharge performance test with embodiment mono-: carry out charge-discharge test with constant current, charging/discharging voltage is 2.5-4.2V, and it is 145mAh/g that room temperature records average specific discharge capacity under the 1C multiplying power, average specific discharge capacity 124mAh/g under the 5C multiplying power.
Embodiment tetra-:
Prepare the anode material for lithium-ion batteries nano-lithium iron phosphate, carry out according to the following steps:
(1) take ferric nitrate, ammonium dihydrogen phosphate and ammoniacal liquor as raw material, utilize the RPB method to prepare nano hydrated ferric phosphate, specifically can with reference to the applicant's patent " a kind of preparation method of nano ferric phosphate ", (application number: 200910235404.8), the nano hydrated ferric phosphate particle mean size of gained be 30nm;
(2) get nano hydrated ferric phosphate FePO prepared by 620g step (1)
42H
2O, in air atmosphere, 600 ℃ of roasting 4hr dehydrations, obtain waterless nano ferric phosphate powder;
(3) take the nanometer lithium oxalate that 100g vitamin C, 500g waterless nano ferric phosphate and 170g particle mean size are 30nm (Li: C: Fe=1.01: 1.03: 1), add 1200ml water, the 60mg polysorbate, ball milling mixing 4hr in basket ball mill, rotational speed of ball-mill 1000rpm, form the slurry that uniform solid content is 40%, in slurry, the particle mean size of SS is 30nm;
(4) pneumatic spray drying device drying for slurry step (3) made, adopt and the fluidized drying mode, atomising device adopts the double-current method nozzle, Control Nozzle gas flow and pressure and and the peristaltic pump charging rate, make inlet temperature remain on 300 ℃, outlet temperature is 100 ℃, and outlet air separates emptying through the one-level whirlpool, obtains the presoma powder mixed after spray drying;
(5) powder step (4) obtained at 850 ℃ of heat treatment 2hr, obtains nanometer ferrousphosphate lithium material under the high pure nitrogen protection.
The weight content that records carbon in ferrousphosphate lithium material is 0.5%.Gained nanometer ferrousphosphate lithium material particle mean size is 40nm.
Carry out the charge-discharge performance test with embodiment mono-: carry out charge-discharge test with constant current, charging/discharging voltage is 2.5-4.2V, and it is 140mAh/g that room temperature records average specific discharge capacity under the 0.1C multiplying power, average specific discharge capacity 115mAh/g under the 5C multiplying power.
Embodiment five:
Prepare the anode material for lithium-ion batteries nano-lithium iron phosphate, carry out according to the following steps:
(1) take ferric nitrate, potassium dihydrogen phosphate and ammoniacal liquor as raw material, utilize the RPB method to prepare nano hydrated ferric phosphate, specifically can with reference to the applicant's patent " a kind of preparation method of nano ferric phosphate ", (application number: 200910235404.8), the nano hydrated ferric phosphate particle mean size of gained be 30nm;
(2) get nano hydrated ferric phosphate FePO prepared by 620g step (2)
42H
2O, the heating rate with 4 ℃/min in air atmosphere is raised to 500 ℃ of roasting 8hr dehydrations, obtains waterless nano ferric phosphate powder;
(3) take the nano lithium carbonate that 120g glucose, 500g waterless nano ferric phosphate and 125g particle mean size are 40nm (Li: C: Fe=1.02: 1.21: 1), add 2500ml water, the 40mg lauryl sodium sulfate, ball milling mixing 1hr in basket ball mill, rotational speed of ball-mill 400rpm, form the slurry that uniform solid content is 25%, in slurry, the particle mean size of SS is 40nm;
(4) pneumatic spray drying device drying for slurry step (3) made, adopt and the fluidized drying mode, atomising device adopts the double-current method nozzle, Control Nozzle gas flow and pressure and and the peristaltic pump charging rate, make inlet temperature remain on 250 ℃, outlet temperature is 100 ℃, and outlet air separates emptying through the one-level whirlpool, obtains the presoma powder mixed after spray drying;
(5) powder step (4) obtained at 500 ℃ of heat treatment 14hr, obtains nanometer ferrousphosphate lithium material under the high pure nitrogen protection.
The weight content that records carbon in ferrousphosphate lithium material is 2.0%.Gained nanometer ferrousphosphate lithium material particle mean size is 70nm.
Nanometer ferrousphosphate lithium material, Super-P conductive carbon black, PVDF binding agent are mixed in mass ratio at 8: 1: 1, the NMP of take makes uniform slurry as solvent, then by its blade coating on the aluminium foil of 20 micron thick, obtain anode pole piece after 120 ℃ of vacuumize, take the lithium paper tinsel as to electrode, fill to obtain experimental cell in being full of the glove box of argon gas, carry out charge-discharge test with constant current, charging/discharging voltage is 2.5-4.2V, it is 136mAh/g that room temperature records average specific discharge capacity under the 0.1C multiplying power, average specific discharge capacity 110mAh/g under the 5C multiplying power.
Each embodiment is raw materials used, technique and product performance as shown in table 1.
Claims (8)
1. the preparation method of an anode material for lithium-ion batteries nano-lithium iron phosphate is characterized in that the method carries out according to the following steps:
(1) utilize the RPB method to prepare nano hydrated ferric phosphate; By phosphoric acid or soluble phosphoric acid salting liquid both one of, water-soluble divalent iron salt and one of oxidant or water-soluble trivalent ferric salt solution, the mixed solution and the alkaline aqueous solution that form with water soluble dispersing agent be input in the RPB layer, regulate the rotating speed of RPB, control the pH value of reaction system between 1.6-6.0 with aqueous slkali, the nano ferric phosphate particle that reactive crystallization generates is discharged by the discharging opening of RPB with mixed liquor, after filtration, washing, drying process obtain nanoscale hypophosphite monohydrate iron after processing;
(2) the nano hydrated ferric phosphate prepared by step (1), 400～600 ℃ of lower roasting dehydrations 4～12 hours, obtains the waterless nano ferric phosphate powder body;
(3) according to mol ratio Li: C: Fe=(1～1.05): (1～1.2): 1 takes the waterless nano ferric phosphate of preparation in nanometer Li source compound, carbon-source cpd and step (2), add pure water and dispersant, be uniformly mixed, obtain the slurry that solid content is 20～50%, in slurry, the granularity of SS is 20～60nm;
(4) slurry step (3) made carries out spray drying, the presoma powder that obtains mixing;
(5) powder step (4) obtained 500～850 ℃ of heat treatments 2～14 hours, obtains nanometer ferrousphosphate lithium material under inert gas shielding.
2. the preparation method of a kind of anode material for lithium-ion batteries nano-lithium iron phosphate according to claim 1, is characterized in that described nano hydrated ferric phosphate granularity is 20～60nm.
3. the preparation method of a kind of anode material for lithium-ion batteries nano-lithium iron phosphate according to claim 1, is characterized in that described nanometer Li source compound granularity is 20～60nm.
4. according to the preparation method of the described a kind of anode material for lithium-ion batteries nano-lithium iron phosphate of claim 1 or 3, it is characterized in that described nanometer Li source compound is a kind of in lithium carbonate, lithium hydroxide, lithium nitrate, lithium acetate and lithium oxalate.
5. the preparation method of a kind of anode material for lithium-ion batteries nano-lithium iron phosphate according to claim 1, it is characterized in that, in step (3), described carbon-source cpd is one or more in sucrose, glucose, citric acid, pentaerythrite, vitamin C, polyethylene glycol and polyethers.
6. the preparation method of a kind of anode material for lithium-ion batteries nano-lithium iron phosphate according to claim 1, it is characterized in that in step (3), described dispersant is lauryl sodium sulfate, dodecyl sodium sulfate, dioctyl sodium sulfosuccinate (A Luosuo-OT), any one in Sucrose Fatty Acid Ester, aliphatic acid sorb smooth (Span), polysorbate (Tween), polyoxyethylene, polyvinyl alcohol, triethyl group hexyl phosphoric acid, methyl anyl alcohol, cellulose derivative, polyacrylamide, fatty acid polyethylene glycol ester.
7. the preparation method of a kind of anode material for lithium-ion batteries nano-lithium iron phosphate according to claim 1, is characterized in that the carbon content in described nanometer ferrousphosphate lithium material is 0.5～5%.
8. the preparation method of a kind of anode material for lithium-ion batteries nano-lithium iron phosphate according to claim 1, is characterized in that gained nanometer ferrousphosphate lithium material granularity is between 40～160nm.
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| CN103258995A (en) * | 2013-06-06 | 2013-08-21 | 郑州瑞普生物工程有限公司 | Preparation method of lithium iron phosphate material |
| CN104300119B (en) * | 2013-07-17 | 2019-05-24 | 东莞东阳光科研发有限公司 | A kind of preparation method of lithium iron phosphate positive material |
| CN108336352A (en) * | 2017-12-29 | 2018-07-27 | 贵州唯特高新能源科技有限公司 | A kind of preparation method of high conductivity high vibration high density lithium iron phosphate |
| CN108288698A (en) * | 2018-01-24 | 2018-07-17 | 杭州金马新能源科技有限公司 | A kind of preparation method of lithium iron phosphate positive material |
| CN113769633B (en) * | 2021-08-27 | 2024-05-03 | 合肥国轩高科动力能源有限公司 | Slurry mixing method for lithium ion battery |
| CN115072693B (en) * | 2022-06-29 | 2023-11-24 | 蜂巢能源科技股份有限公司 | Lithium iron phosphate positive electrode material, preparation method thereof and lithium ion battery |
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