CN102347486B - Method for preparing barium-activated lithium iron phosphate cathode material - Google Patents
Method for preparing barium-activated lithium iron phosphate cathode material Download PDFInfo
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- 229910052788 barium Inorganic materials 0.000 title claims abstract description 46
- 238000000034 method Methods 0.000 title abstract description 14
- 239000010406 cathode material Substances 0.000 title abstract 6
- -1 barium-activated lithium iron phosphate Chemical class 0.000 title abstract 4
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims abstract description 42
- 239000000463 material Substances 0.000 claims abstract description 38
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 32
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 29
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 28
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000002994 raw material Substances 0.000 claims abstract description 9
- 238000000875 high-speed ball milling Methods 0.000 claims abstract description 8
- 239000012299 nitrogen atmosphere Substances 0.000 claims abstract description 4
- 230000004913 activation Effects 0.000 claims description 23
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 claims description 23
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 10
- 229910052742 iron Inorganic materials 0.000 claims description 10
- 238000002360 preparation method Methods 0.000 claims description 10
- 238000003837 high-temperature calcination Methods 0.000 claims description 6
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 5
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 15
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 14
- 239000002245 particle Substances 0.000 abstract description 11
- 238000002156 mixing Methods 0.000 abstract description 10
- 239000000126 substance Substances 0.000 abstract description 9
- 229910019142 PO4 Inorganic materials 0.000 abstract description 6
- 239000013078 crystal Substances 0.000 abstract description 6
- 150000001875 compounds Chemical class 0.000 abstract description 5
- 238000009792 diffusion process Methods 0.000 abstract description 5
- 239000010452 phosphate Substances 0.000 abstract description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 abstract description 5
- 229910001422 barium ion Inorganic materials 0.000 abstract description 3
- 238000001354 calcination Methods 0.000 abstract description 3
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 abstract description 3
- 229910000399 iron(III) phosphate Inorganic materials 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 239000002243 precursor Substances 0.000 abstract 2
- 229910052493 LiFePO4 Inorganic materials 0.000 abstract 1
- 230000002238 attenuated effect Effects 0.000 abstract 1
- 238000001035 drying Methods 0.000 abstract 1
- 239000000203 mixture Substances 0.000 description 10
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 8
- 239000010405 anode material Substances 0.000 description 8
- 229910052799 carbon Inorganic materials 0.000 description 8
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 7
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 description 6
- IWOUKMZUPDVPGQ-UHFFFAOYSA-N barium nitrate Chemical compound [Ba+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O IWOUKMZUPDVPGQ-UHFFFAOYSA-N 0.000 description 6
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 5
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 5
- 229910000388 diammonium phosphate Inorganic materials 0.000 description 5
- 235000019838 diammonium phosphate Nutrition 0.000 description 5
- 229940062993 ferrous oxalate Drugs 0.000 description 5
- OWZIYWAUNZMLRT-UHFFFAOYSA-L iron(2+);oxalate Chemical compound [Fe+2].[O-]C(=O)C([O-])=O OWZIYWAUNZMLRT-UHFFFAOYSA-L 0.000 description 5
- 229910052808 lithium carbonate Inorganic materials 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 4
- 229910021645 metal ion Inorganic materials 0.000 description 4
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 3
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 description 3
- 238000013459 approach Methods 0.000 description 3
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 description 3
- 229910001626 barium chloride Inorganic materials 0.000 description 3
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 description 3
- 229910001863 barium hydroxide Inorganic materials 0.000 description 3
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Inorganic materials [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 3
- CJDPJFRMHVXWPT-UHFFFAOYSA-N barium sulfide Chemical compound [S-2].[Ba+2] CJDPJFRMHVXWPT-UHFFFAOYSA-N 0.000 description 3
- CSSYLTMKCUORDA-UHFFFAOYSA-N barium(2+);oxygen(2-) Chemical compound [O-2].[Ba+2] CSSYLTMKCUORDA-UHFFFAOYSA-N 0.000 description 3
- SNKMVYBWZDHJHE-UHFFFAOYSA-M lithium;dihydrogen phosphate Chemical compound [Li+].OP(O)([O-])=O SNKMVYBWZDHJHE-UHFFFAOYSA-M 0.000 description 3
- 229910001425 magnesium ion Inorganic materials 0.000 description 3
- 229910052748 manganese Inorganic materials 0.000 description 3
- 239000011572 manganese Substances 0.000 description 3
- 235000019837 monoammonium phosphate Nutrition 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 2
- 159000000009 barium salts Chemical class 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000002001 electrolyte material Substances 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 239000003350 kerosene Substances 0.000 description 2
- 229910003002 lithium salt Inorganic materials 0.000 description 2
- 159000000002 lithium salts Chemical class 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000003746 solid phase reaction Methods 0.000 description 2
- 239000005955 Ferric phosphate Substances 0.000 description 1
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 1
- 229910000901 LiFePO4/C Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229940032958 ferric phosphate Drugs 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000010450 olivine Substances 0.000 description 1
- 229910052609 olivine Inorganic materials 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
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
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- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention relates to a method for preparing a barium-activated lithium iron phosphate cathode material. The method is characterized by comprising the steps of: mixing raw materials of a lithium source, a ferrum source, a phosphate source and a barium source according to the proportion of Li:Ba:Fe:P of 1mol:(0.0003mol):1mol:1mol, performing high-speed ball-milling (at the rotating speed of 200r/min) on the mixed raw materials in an absolute ethyl alcohol (AR) medium and drying at 105-120 DEG C to obtain a precursor; and placing the dried precursor in a high-temperature furnace and calcining for 24h at a high temperature of 500-750DEG C in an ordinary pure nitrogen atmosphere to obtain the barium-activated lithium iron phosphate cathode material. The chemical general formula of the material can be represented as Li Ba FePO4. As a bit of substituent barium is doped, the appearance and the particle size of the product are favorably controlled, and a stable lithium iron phosphate compound is obtained. Barium ions replace lithium ions in an occupation manner, the crystal lattice of the compound is activated, the diffusion coefficient of the lithium ions is increased, and the first discharge capacity of the cathode material reaches 145.52mAh/g. The potential of a charge-discharge platform of the cathode material is about 3.5V compared with that of a lithium electrode, the initial discharge capacity exceeds 162mAh/g, and the capacity is attenuated by about 3.2% after 100 times of charge-discharge circles. Compared with the undoped LiFePO4 contrast embodiment, the cathode material has greatly increased specific capacity and cyclical stability. As the price of barium is more than 100 times lower than the price of lithium, the production cost can be reduced by more than 10 times.
Description
Technical field
Barium activation lithium iron phosphate positive material preparation method of the present invention belongs to a kind of anode material of lithium battery preparation method, particularly a kind of ferric phosphate lithium cell method for preparing anode material.
Background technology
At present, the research present situation of LiFePO4 doping vario-property: LiFePO4 LiFePO4 is because it is nontoxic, environmentally friendly, safe, abundant, high, the stable cycle performance, cheap of specific capacity in raw material source, steady discharge platform with theoretical capacity 3.5V of 170mAh/g, LiFePO 4 material has high energy density, cheap price, excellent security, is specially adapted to electrokinetic cell.But its resistivity is bigger.Because LiFePO4, under the normal temperature, the dynamics of LiFePO4 is bad, the high rate performance extreme difference, domestic and international research persons have used such as methods such as coating, doping, nanometers and have improved high rate performance, and basic idea improves conductivity exactly and shortens ion, electric transmission path.Doping is the important material modification method of a class.2002, reported first lithium position doping vario-properties such as Massachusetts science and engineering Chiang professor Yet-Ming can improve the LiFePO4 electronic conductivity greatly.They carry out the doping of high volence metal ion (Mg2+, Al3+, Ti4+, Zr4+, Nb5+ and W6+) solid solution in the lithium position, electronic conductivity has improved 8 orders of magnitude.Sample through above-mentioned doping has better electrochemical performance, and particularly high-rate performance discharges under the electric current of 21.5C (3225mA/g), still can obtain the capacity of 60mAh/g.Doping carbon: carbon has good electric conductivity and lower mass density, adds a spot of carbon of people, can improve the electric conductivity of material on the one hand, can reduce the particle diameter yardstick of material on the other hand.Xxx has studied different phase and has mixed people's carbon to the influence of material electrochemical performance.Shi Zhicong etc. " adopt solid phase reaction in conjunction with the high speed ball-milling method, synthetic positive electrode LiFePO4, experiment shows: LiFePO4 has the discharge voltage plateau of 3.4V, and discharge capacity only decays 9.5% after reaching 147mAh/g charge and discharge cycles 100 times first.LiFePO4/C composite material behind the carbon dope, the granule-morphology rule is the class sphere, and particle is little, and particle diameter distributes and all colludes.Carbon is scattered between the crystal grain, has strengthened the electrical conductance between the particle.LiFePO4 specific discharge capacity and cycle performance behind the carbon dope all significantly improve.Mix in the lithium position: the LiFePO4 crushed grain is assorted to be a kind of important method of improving chemical property.Mix and can improve the conductivity of LiFePO4 in the lithium position.Tan Xianyan etc. " " adopt the calcination method synthesizing lithium ionic cell positive pole material lithium iron phosphate, mix a spot of Mg2+ and have significantly improved conductivity of electrolyte materials, have improved the chemical property of LiFePO4.After the doping, LiFePO4 discharge capacity first reaches 135.52mAh/g; Unadulterated LiFePO4 discharge capacity first has only 116.25mAh/g.Conductivity after the doping has obtained certain raising.This is because doping little metal ion replaces the Li+ position, constitutes the p-type semiconductor, has increased the conductivity of material.The identical ^ of Liu adopts improved solid phase method to prepare LiFePO4 and the Li0 that particle is fine, particle diameter is evenly distributed, 98Mn, and the o.o2LiFePO4 compound, mixing is conducive to control pattern and the particle diameter of product on a small quantity, obtains stable LiFePO4 compound.Because Mn2+ octahedral coordination radius, can think that magnesium ion occupies the replacement lithium ion less than Fe2+.The result shows: the relative lithium electrode current potential of the charge and discharge platform of lithium ion is about 3.5V in the material, and initial discharge capacity surpasses 160mAh/g, and capacity only decays 5.5% after 50 charge and discharge cycles, shows that this method has improved specific energy and cyclical stability.The iron position is assorted disastrously: can improve conductivity of electrolyte materials though mix in the lithium position, because foreign atom can hinder the diffusion of lithium ion in the one dimension passage, thereby be unfavorable for improving the high-rate charge-discharge capability of material.And the doping of iron position can improve the rate charge-discharge performance of LiFePO4, improves cycle performance.^ such as Liu Fangling adopt parcel carbon to improve its surface electronic conductivity, and doped metal ion is to improve its body electronic conductivity.Having chosen ionic radius approaches and 4 different metal ion species Ca3+ of valence state, Ti5+, Ta5+, mix in the Fe position of MO6+, sample unit cell volume after the doping all has minimizing, electronic conductivity has improved 4-6 the order of magnitude than the electronic conductivity of LiFePO4, and its impedance in electrolyte solution is significantly reduced, and chemical property also obviously improves.^ such as Hu Huanyu adopt the synthetic tiny and uniform nanoscale positive electrode of the particle LiFePO4 of high-temperature solid phase reaction method, have good capacity cycle performance, but its high rate capability are poor.Mix a spot of manganese and can reduce the polarization of material, improve the high rate capability of material.This mainly is because the doping of manganese has increased the unit cell volume of LiFePO4, more be conducive to deviating from of lithium, the doping of manganese has caused sintering process to produce crystal structure defects in addition, has improved the electron conduction of material, thereby has made the high-rate charge-discharge capability of material make moderate progress.The phosphate potential crushed grain is assorted: P site doped is feasible in theory, but the doping of carrying out phosphate potential is separately seldom arranged.^ such as Zhang Yurong have studied olivine structural Li2+2xTi2-xCu2x (NbO) 2, and having obtained conductivity by Ti and Cu replacement P is that 1.26 * 10-6S/cm-adds, and initial discharge capacity is the positive electrode of 805.8mAh/g.Such material has higher conductivity, but owing to Fe is all replaced by Ti and Cu, ' guiding discharge voltage is lower, and cycle performance is poor.Though phosphate potential is feasible in theory, study less relatively.
By retrieval, put down in writing 1043 of relevant lithium battery applications for a patent for invention, 2181 of lithium ion battery applications for a patent for invention at present, wherein having a great deal of is relevant method of mixing.
Be confirmed to be the lithium position in theory, or the iron position, or phosphate potential obtains mixing and role, and relevant authoritative experts still have different separately brilliant idea, also constantly studying, exploring.
Present more consistent viewpoint is, LiFePO4 has that fail safe is good, pollution-free, stable cycle performance, specific capacity is high and advantage such as cheap, but also has poorly conductive and the lower shortcoming of tap density.Poorly conductive is to influence the biggest factor that LiFePO4 is used, and conductivity can be improved by mixing, and high-rate charge-discharge capability also improves, and has suppressed the effect of capacity attenuation to a certain extent.The doping approach can improve, improve the lithium ion anode material performance, has been a kind of feasible mode of generally acknowledging.
Summary of the invention
The objective of the invention is to: based on the structural limitations of the lithium iron phosphate positive material (LiFePO4) of prior art, there are its poorly conductive and the low deficiency of lithium ion diffusion coefficient, propose the barium activation lithium iron phosphate positive material preparation method that a kind of barium activation improves its performance.
The present invention has been a kind of feasible mode of generally acknowledging in view of the doping approach can improve, improve the lithium ion anode material performance.According to the chemical property of barium/lithium, electric property, crystal structure characteristic is the characteristics of akin element:
Barium is element the most active in the alkaline-earth metal, because it is very active, and oxidized easily, should be kept in kerosene and the atoleine.
5.212 electron-volts of ionization energy, the first ionization energy 502.9kJ/mol;
Crystal structure: structure cell is body centred cubic cell, and each structure cell contains 2 metallic atoms;
Cell parameter: a=502.8pm; B=502.8pm; C=502.8pm; α=90 °; β=90 °; γ=90 °.
Lithium, metallic element can react with a large amount of inorganic reagents and organic reagent.All can chemical combination with oxygen, nitrogen, sulphur etc., because easily oxidated and deepening, and density is littler than kerosene, so should deposit in the atoleine.
5.392 electron-volts of ionization energy, the first ionization energy 520.2kJ/mol;
Crystal structure: structure cell is body centred cubic cell, and each structure cell contains 2 metallic atoms;
Cell parameter: a=351pm; B=351pm; C=351pm; α=90 °; β=90 °; γ=90 °.
Think that barium should be to be easy to the doping effect of lithium position most.The present invention be mix by barium test, in the situation of mixing with barium, can add 1-2 other element again, constitute 2 yuan or 3 yuan of doping, with obtained performance anode material of lithium battery preferably.
Barium activation lithium iron phosphate positive material of the present invention is to mix by barium to test, explore, and searching, obtained performance be anode material of lithium battery preferably.Barium activation lithium iron phosphate positive material of the present invention is characterized in that: the barium elemental composition is arranged in the LiFePO4.In preferred its LiFePO4, the barium element that contains 0.0003-0.005 mol in the 1mol LiFePO4 is good; Represent Li with the mol ratio: the mol ratio of Ba: Fe: P is: 1: 0.0003: 1: 1.Its preferred chemical composition can be expressed as with chemical general formula: Li Bay FePO4, y=0.0003; The mol ratio of Li wherein, Ba, Fe, P is: 1mol Li: 0.0003mol Ba: 1mol Fe: 1mol P.
Barium of the present invention activation lithium iron phosphate positive material in the situation of mixing with barium, can add 1-2 other element again, constitutes 2 yuan or 3 yuan of doping, with obtained performance anode material of lithium battery preferably.
Barium activation lithium iron phosphate positive material preparation method of the present invention, its lithium source can be used: lithium salts such as lithium carbonate, lithium hydroxide or lithium dihydrogen phosphate, source of iron can be used: ferrous oxalate etc., the phosphoric acid root can be used: ammonium dihydrogen phosphate or diammonium hydrogen phosphate etc., the barium source can be used: barium salts such as brium carbonate, barium hydroxide, barium chloride, barium nitrate, barium monoxide, barium sulphide.
Select for use: lithium carbonate (Li2CO3) (99.73%), brium carbonate (BaCO3) (99.8%), ferrous oxalate (FeC2O4.2H2O) (99.06%), diammonium hydrogen phosphate (NH4H2PO4) (98%) is raw material; According to 1mol Li: 0.0003mol Ba: 1mol Fe: after 1mol P ratio is mixed, in absolute ethyl alcohol (AR) medium, high speed ball milling 20h (rotating speed 200r/min.After the oven dry, presoma is through 500-750 ℃, high-temperature calcination 24h.Namely get barium activation lithium iron phosphate positive material of the present invention.
Barium activation lithium iron phosphate positive material preparation method of the present invention, it is characterized in that: the raw material in its lithium source, source of iron, phosphoric acid root, barium source, according to 1mol Li: 0.0003mol Ba: 1mol Fe: after 1mol P ratio is mixed, in ethanol medium, rotating speed 200-800r/min high speed ball milling 15-20h, with 105-120 ℃ of oven dry, obtain presoma, the presoma that oven dry is obtained places in the high temperature furnace, in nitrogen atmosphere, through 500-750 ℃ of high-temperature calcination 16-24h, namely get barium activation lithium iron phosphate positive material of the present invention; Its chemical composition is: Li Bay Fe PO4, y=0.0003; Wherein the mol of Li, Ba, Fe, P ratio is: 1molLi: 0.0003mol Ba: 1mol Fe: 1mol P.Its lithium source is one of lithium carbonate, lithium hydroxide or lithium dihydrogen phosphate, and source of iron is ferrous oxalate, and the phosphoric acid root is one of ammonium dihydrogen phosphate or diammonium hydrogen phosphate, and the barium source is one of brium carbonate, barium hydroxide, barium chloride, barium nitrate, barium monoxide, barium sulphide.
The present invention's beneficial effect compared with prior art:
Barium activation lithium iron phosphate positive material preparation method of the present invention, material perhaps because a small amount of barium that replaces that mixes, be conducive to control pattern and the particle diameter of product, obtain stable LiFePO4 compound, barium ions occupies the replacement lithium ion, its lattice has obtained activation, has improved the lithium ion diffusion coefficient, its first discharge capacity reach 145.52mAh/g; The relative lithium electrode current potential of its charge and discharge platform is about 3.5V, and initial discharge capacity surpasses 162mAh/g, and capacity decays about 3.2% approximately after 100 charge and discharge cycles; Specific capacity and cyclical stability and unadulterated LiFePO4 discharge capacity first have only 116.25mAh/g to compare, and are greatly improved.Because the price of barium is lower more than hundred times than lithium price, production cost can fall more than ten times.
Embodiment
The invention will be further described below in conjunction with embodiment, but embodiments of the present invention are not limited thereto.
Below adopt the calcination method synthetic method, to barium activation lithium iron phosphate positive material preparation method of the present invention, be illustrated.
Barium activation lithium iron phosphate positive material preparation method of the present invention, its lithium source can be used: lithium salts such as lithium carbonate, lithium hydroxide or lithium dihydrogen phosphate, source of iron can be used: ferrous oxalate etc., the phosphoric acid root can be used: ammonium dihydrogen phosphate or diammonium hydrogen phosphate etc., the barium source can be used: barium salts such as brium carbonate, barium hydroxide, barium chloride, barium nitrate, barium monoxide, barium sulphide.Select for use: lithium carbonate (Li2CO3) (99.73%), brium carbonate (BaCO3) (99.8%), ferrous oxalate (FeC2O4.2H2O) (99.06%), diammonium hydrogen phosphate (NH4H2PO4) (98%) is raw material; According to 1molLi: 0.0003mol Ba: 1mol Fe: after 1mol P ratio is mixed, in ethanol medium, rotating speed 200-800r/min high speed ball milling 20h, with 105-120 ℃ of oven dry, obtain presoma, the presoma that oven dry is obtained places in the high temperature furnace, in nitrogen atmosphere, through 500-750 ℃ of high-temperature calcination 16-24h, namely get barium activation lithium iron phosphate positive material of the present invention.
Embodiment 1
With Li2CO3 (99.73%), BaCO3 (99.8%), FeC2O4.2H2O (99.06%), NH4H2PO4 (98%) raw material, according to 1mol Li: 0.0003mol Ba: 1mol Fe: after 1mol P ratio is mixed, in absolute ethyl alcohol (AR) medium, high speed ball milling 20h (rotating speed 200r/min).After the 105-120 ℃ of oven dry, obtain presoma, the presoma that oven dry is obtained places in the high temperature furnace, in common purity nitrogen (＞99.5%) atmosphere, and through 500-750 ℃, high-temperature calcination 24h.Namely get barium activation lithium iron phosphate positive material of the present invention.
Embodiment 2 (not mixing contrast)
With Li2CO3 (99.73%), FeC2O4.2H2O (99.06%), NH4H2PO4 (98%) raw material, according to 1molLi: 1mol Fe: after 1mol P ratio is mixed, in absolute ethyl alcohol (AR) medium, high speed ball milling 20h (rotating speed 200r/min).After the 105-120 ℃ of oven dry, obtain presoma, the presoma that oven dry is obtained places in the high temperature furnace, in common purity nitrogen (＞99.5%) atmosphere, and through 500-750 ℃, high-temperature calcination 24h.Namely get lithium ion anode material.
Adopt the testing equipment of prior art and the method for testing of prior art, to the barium activation lithium iron phosphate positive material of above embodiment 1, carry out test result with the comparative examples 2 of not mixing and be:
The barium activation lithium iron phosphate positive material of the embodiment of the invention 1, discharge capacity reaches more than the 145.52mAh/g first; Unadulterated LiFePO4 discharge capacity first has only in the 116.25mAh/g.
The barium activation lithium iron phosphate positive material of embodiment of the invention 1-3, the relative lithium electrode current potential of its charge and discharge platform is about 3.5V, and initial discharge capacity surpasses 162mAh/g, and capacity decays about 3.2% approximately after 100 charge and discharge cycles.
Barium activation lithium iron phosphate positive material of the present invention, assorted after mixing, the raising of specific capacity and cyclical stability, perhaps, this is because a small amount of barium that replaces that mixes, be conducive to control pattern and the particle diameter of product, obtain stable LiFePO4 compound, barium ions occupies the replacement lithium ion, its lattice has obtained activation, has improved the result of lithium ion diffusion coefficient.
Claims (1)
1. a barium activates the lithium iron phosphate positive material preparation method, it is characterized in that: the raw material in its lithium source, source of iron, phosphoric acid root, barium source, according to 1mol Li: 0.0003mol Ba: 1mol Fe: after 1mol P ratio is mixed, in ethanol medium, rotating speed 200-800r/min high speed ball milling 15-20h, with 105-120 ℃ of oven dry, obtain presoma, the presoma that oven dry is obtained places in the high temperature furnace, in nitrogen atmosphere, through 500-750 ℃ of high-temperature calcination 16-24h, namely get barium activation lithium iron phosphate positive material.
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| CN102689888A (en) * | 2012-05-18 | 2012-09-26 | 张健 | Method for preparing niobium-doped barium ferric phosphate |
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| CN102674295A (en) * | 2012-05-28 | 2012-09-19 | 何丽萍 | Preparation method of magnesium doped iron barium phosphate |
| CN102674305A (en) * | 2012-05-28 | 2012-09-19 | 韦谷林 | Preparation method of lanthanum-doped barium iron phosphate |
| CN102674302A (en) * | 2012-05-28 | 2012-09-19 | 严积芳 | Method for preparing zirconium doped barium iron phosphate |
| CN102674311A (en) * | 2012-06-06 | 2012-09-19 | 陶荣芝 | Preparation method of gadolinium doped iron phosphate barium |
| CN102862968A (en) * | 2012-06-06 | 2013-01-09 | 陶荣燕 | Preparation method of holmium-mingled barium iron phosphate |
| CN102689892A (en) * | 2012-06-06 | 2012-09-26 | 韦丽梅 | Preparation method of samarium-doped iron phosphate barium |
| CN110456118A (en) * | 2019-08-13 | 2019-11-15 | 大同新成新材料股份有限公司 | A kind of preparation method for adsorbing fused salt mixt carbon felt electrode |
| CN114068918A (en) * | 2020-08-06 | 2022-02-18 | 比亚迪股份有限公司 | Lithium iron phosphate positive active material, preparation method thereof and battery |
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