CN102437332A - Preparation method of manganese and barium activated lithium iron phosphate as cathode material - Google Patents
Preparation method of manganese and barium activated lithium iron phosphate as cathode material Download PDFInfo
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- CN102437332A CN102437332A CN2011103359417A CN201110335941A CN102437332A CN 102437332 A CN102437332 A CN 102437332A CN 2011103359417 A CN2011103359417 A CN 2011103359417A CN 201110335941 A CN201110335941 A CN 201110335941A CN 102437332 A CN102437332 A CN 102437332A
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- barium
- manganese
- lithium
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- 229910052788 barium Inorganic materials 0.000 title claims abstract description 40
- 239000011572 manganese Substances 0.000 title claims abstract description 39
- 229910052748 manganese Inorganic materials 0.000 title claims abstract description 32
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims 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 36
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 31
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 27
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 25
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052742 iron Inorganic materials 0.000 claims abstract description 11
- 238000000875 high-speed ball milling Methods 0.000 claims abstract description 9
- 239000002994 raw material Substances 0.000 claims abstract description 9
- 239000000463 material Substances 0.000 claims description 39
- 230000004913 activation Effects 0.000 claims description 24
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 claims description 22
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 16
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 10
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 10
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 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 8
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 238000003837 high-temperature calcination Methods 0.000 claims description 7
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 7
- IWOUKMZUPDVPGQ-UHFFFAOYSA-N barium nitrate Chemical compound [Ba+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O IWOUKMZUPDVPGQ-UHFFFAOYSA-N 0.000 claims description 6
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 5
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 4
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 4
- 229910000388 diammonium phosphate Inorganic materials 0.000 claims description 4
- 235000019838 diammonium phosphate Nutrition 0.000 claims description 4
- 229940062993 ferrous oxalate Drugs 0.000 claims description 4
- OWZIYWAUNZMLRT-UHFFFAOYSA-L iron(2+);oxalate Chemical compound [Fe+2].[O-]C(=O)C([O-])=O OWZIYWAUNZMLRT-UHFFFAOYSA-L 0.000 claims description 4
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 3
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 claims description 3
- 229910001626 barium chloride Inorganic materials 0.000 claims description 3
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 claims description 3
- 229910001863 barium hydroxide Inorganic materials 0.000 claims description 3
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Inorganic materials [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 claims description 3
- CJDPJFRMHVXWPT-UHFFFAOYSA-N barium sulfide Chemical compound [S-2].[Ba+2] CJDPJFRMHVXWPT-UHFFFAOYSA-N 0.000 claims description 3
- CSSYLTMKCUORDA-UHFFFAOYSA-N barium(2+);oxygen(2-) Chemical compound [O-2].[Ba+2] CSSYLTMKCUORDA-UHFFFAOYSA-N 0.000 claims description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims description 3
- SNKMVYBWZDHJHE-UHFFFAOYSA-M lithium;dihydrogen phosphate Chemical compound [Li+].OP(O)([O-])=O SNKMVYBWZDHJHE-UHFFFAOYSA-M 0.000 claims description 3
- IPJKJLXEVHOKSE-UHFFFAOYSA-L manganese dihydroxide Chemical compound [OH-].[OH-].[Mn+2] IPJKJLXEVHOKSE-UHFFFAOYSA-L 0.000 claims description 3
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 3
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 17
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 16
- 239000002245 particle Substances 0.000 abstract description 12
- 238000002156 mixing Methods 0.000 abstract description 11
- 238000009792 diffusion process Methods 0.000 abstract description 8
- 239000013078 crystal Substances 0.000 abstract description 6
- 229910019142 PO4 Inorganic materials 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
- 238000001354 calcination Methods 0.000 abstract description 3
- 238000001035 drying Methods 0.000 abstract 2
- 239000002243 precursor Substances 0.000 abstract 2
- 229910052493 LiFePO4 Inorganic materials 0.000 abstract 1
- 230000002238 attenuated effect Effects 0.000 abstract 1
- 125000004122 cyclic group Chemical group 0.000 abstract 1
- 239000012299 nitrogen atmosphere Substances 0.000 abstract 1
- 238000000034 method Methods 0.000 description 11
- 239000000126 substance Substances 0.000 description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 8
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 description 8
- 229910052799 carbon Inorganic materials 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 239000010405 anode material Substances 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 5
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 5
- 239000002001 electrolyte material Substances 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
- 239000008151 electrolyte solution Substances 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 229910001425 magnesium ion Inorganic materials 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000013459 approach Methods 0.000 description 2
- 229910001422 barium ion Inorganic materials 0.000 description 2
- YSZKOFNTXPLTCU-UHFFFAOYSA-N barium lithium Chemical group [Li].[Ba] YSZKOFNTXPLTCU-UHFFFAOYSA-N 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000002019 doping agent Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000003350 kerosene Substances 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
- 159000000009 barium salts Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit 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
- 239000002131 composite material Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 229940032958 ferric phosphate Drugs 0.000 description 1
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 description 1
- 229910000399 iron(III) phosphate Inorganic materials 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 239000011656 manganese carbonate Substances 0.000 description 1
- 235000006748 manganese carbonate Nutrition 0.000 description 1
- 229910000016 manganese(II) carbonate Inorganic materials 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
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 230000008569 process 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a preparation method of manganese and barium activated lithium iron phosphate as a cathode material. The preparation method comprises the steps of: mixing raw materials including a lithium source, a manganese source, a barium source, an iron source and a phosphate source according to the proportion of 1mol:(0.00002-0.00005)mol:(0.0003-0.003)mol:1mol:1mol; then, performing high-speed ball milling at the rotation speed of 200r/minm for 20h in an absolute ethyl alcohol medium; drying at 105-120 DEG C to obtain a precursor; placing the precursor obtained through drying in a high-temperature furnace; and calcinating for 24h at the high temperature of 500-750 DEG C in a common pure nitrogen atmosphere to obtain the manganese and barium activated lithium iron phosphate as the cathode material. Because a small amount of substitutive manganese and barium are doped, the shape and the particle size of a product are favorably controlled to obtain a stable lithium iron phosphate compound, of which the crystal lattice is activated, the lithium ion diffusion coefficient is increased, and the initial discharge capacity of the obtained cathode material reaches 160.52mAh/g; a charge-discharge platform of the cathode material is about 3.5V relative to a lithium electrode potential, the initial discharge capacity exceeds 168mAh/g, and the capacity is attenuated by about 1.2% after 100 times of charge-discharge cycles; and compared with a control embodiment, namely undoped LiFePO4, the cathode material is greatly improved in specific capacity and cyclic stability.
Description
Technical field
Manganese of the present invention, barium activation lithium iron phosphate positive material preparation method belong 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 of 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, nanometerizations and have improved high rate performance, and basic idea improves conductivity exactly and shortens ion, electric transmission path.Doping is one type of important material modification method.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 one 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 the influence of people's carbon to material electrochemical performance.Shi Zhicong etc. " adopt solid phase reaction to combine 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, spherical for class, particle is little, and particle size distribution is all colluded.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 N-type semiconductor N, has increased the conductivity of material.The identical ^ of Liu adopts that improved solid phase method has prepared that particle is fine, the uniform LiFePO4 of particle size distribution and Li0,98Mn, and the o.o2LiFePO4 compound, mixing helps controlling the 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 rate charge-discharge performance of iron position doping can improvement 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.Chosen ionic radius near 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 the 4-6 one 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 particle tiny and uniform nanoscale positive electrode 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 help 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 through 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.Said 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.
Through 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.
Confirm it is 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 can conductivity be improved through 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 manganese, barium activation lithium iron phosphate positive material preparation method that a kind of manganese, barium activation improve its performance at present.
The present invention can improve, improve the lithium ion anode material performance in view of the doping approach, has been a kind of feasible mode of generally acknowledging.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 a 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.With equal ability such as oxygen, nitrogen, sulphur chemical combination, the deepening owing to be prone to oxidated, 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 a 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 through barium make an experiment, 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.
Manganese of the present invention, barium activation lithium iron phosphate positive material, it is characterized in that: its chemical composition or chemical general formula can be expressed as: LiMnxBayFePO
4, x=0.00002-0.00005, y=0.0003-0.003; Wherein the mol of Li, Mn, Ba, Fe, P ratio is: 1mol Li: 0.00002-0.00005mol Mn: 0.0003-0.003mol Ba: 1mol Fe: 1mol P.
Manganese of the present invention, barium activation lithium iron phosphate positive material preparation method is characterized in that: the raw material in its lithium source, source of iron, phosphoric acid root, manganese source, barium source, according to 1mol Li: 0.00002-0.00005mol Mn: 0.0003-0.003mol Ba: 1mol Fe: after the 1mol P mixed; In ethanol medium; Rotating speed 200-800r/mimn high speed ball milling 15-20h with 105-120 ℃ of oven dry, obtains presoma; The presoma that oven dry is obtained places in the high temperature furnace; In blanket of nitrogen,, promptly get manganese of the present invention, barium activation lithium iron phosphate positive material through 500-750 ℃ of high-temperature calcination 16-24h.Its lithium source is one of lithium carbonate, lithium hydroxide or lithium dihydrogen phosphate; Source of iron is a ferrous oxalate; The phosphoric acid root is one of ammonium dihydrogen phosphate or diammonium hydrogen phosphate; The manganese source is one of the inferior manganese of carbonic acid, manganous hydroxide, manganese dioxide, 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: manganese of the present invention, barium activation lithium iron phosphate positive material preparation method; The gained material is perhaps because a small amount of manganese, barium of replacing that mixes; Help controlling the pattern and the particle diameter of product, obtain stable LiFePO4 compound, manganese, barium ions occupy the replacement lithium ion; Its lattice has obtained activation, has improved the lithium ion diffusion coefficient; Dopant ion though mixing, barium lithium position can improve conductivity of electrolyte materials, owing to 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.Product unit cell volume after manganese mixes all has minimizing, and electronic conductivity improves than the electronic conductivity of LiFePO4, and its impedance in electrolyte solution is significantly reduced, and chemical property also obviously improves; Its first discharge capacity reach 160.52mAh/g; The relative lithium electrode current potential of its charge and discharge platform is about 3.5V, and initial discharge capacity surpasses 168mAh/g, and capacity decays about 1.2% 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.
Embodiment
Below in conjunction with embodiment the present invention is described further, but execution mode of the present invention is not limited thereto.
Below adopt the calcination method synthetic method,, be illustrated manganese of the present invention, barium activation lithium iron phosphate positive material preparation method.
Manganese of the present invention, barium activation lithium iron phosphate positive material preparation method; 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., and the phosphoric acid root can be used: ammonium dihydrogen phosphate or diammonium hydrogen phosphate etc., manganese source are the inferior manganese MnCO3 of carbonic acid;, manganous hydroxide Mn (OH) 2, manganese dioxide MnO2 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%), manganese dioxide (99.8%), brium carbonate (BaCO3) (99.8%), ferrous oxalate (FeC204.2H2O) (99.06%), diammonium hydrogen phosphate (NH4H2PO4) (98%) is a raw material; According to 1mol Li: 0.00002-0.00005mol Mn: 0.0003-0.003mol Ba: 1mol Fe: after the 1mol P mixed, in ethanol medium, rotating speed 200-800r/mimn 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 blanket of nitrogen; Through 500-750 ℃ of high-temperature calcination 16-24h, promptly get manganese of the present invention, barium activation lithium iron phosphate positive material.
Embodiment 1
Li2CO3 (99.73%); MnO2 (99.8%), BaCO3 (99.8%), FeC2O4.2H2O (99.06%); NH4H2PO4 (98%) raw material; According to 1mol Li: 0.00002molMn: 0.0003mol Ba: 1mol Fe: after the 1mol P mixed, in absolute ethyl alcohol (AR) medium, high speed ball milling 20h (rotating speed 200r/mimn).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.Promptly get manganese of the present invention, barium activation lithium iron phosphate positive material.
Embodiment 2
Li2CO3 (99.73%); MnO2 (99.8%), BaCO3 (99.8%), FeC2O4.2H2O (99.06%); NH4H2PO4 (98%) raw material; According to 1mol Li: 0.00004mol Mn: 0.001mol Ba: 1mol Fe: after the 1mol P mixed, in absolute ethyl alcohol (AR) medium, high speed ball milling 20h (rotating speed 200r/mimn).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.Promptly get manganese of the present invention, barium activation lithium iron phosphate positive material.
Embodiment 3
Li2CO3 (99.73%); MnO2 (99.8%), BaCO3 (99.8%), FeC2O4.2H2O (99.06%); NH4H2PO4 (98%) raw material; According to 1mol Li: 0.00005mol Mn: 0.003mol Ba: 1mol Fe: after the 1mol P mixed, in absolute ethyl alcohol (AR) medium, high speed ball milling 20h (rotating speed 200r/mimn).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.Promptly get manganese of the present invention, barium activation lithium iron phosphate positive material.
Embodiment 4 (not mixing contrast)
With Li2CO3 (99.73%), FeC2O4.2H2O (99.06%), NH4H2PO4 (98%) raw material, according to 1molLi: 1mol Fe: after the 1mol P mixed, in absolute ethyl alcohol (AR) medium, high speed ball milling 20h (rotating speed 200r/mimn.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.Promptly get lithium ion anode material.
Adopt the testing equipment of prior art and the method for testing of prior art,, carry out test result with the control Example of not mixing 4 and be manganese, the barium activation lithium iron phosphate positive material of above embodiment 1-3:
The manganese of embodiment of the invention 1-3, barium activation lithium iron phosphate positive material, discharge capacity reaches more than the 155.52mAh/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 164mAh/g, and capacity decays about 3.0% approximately after 100 charge and discharge cycles.
Barium activation lithium iron phosphate positive material preparation method of the present invention, the back of mixing is assorted, the raising of gained material specific capacity and cyclical stability; Perhaps this be because a small amount of manganese, barium of replacing that mixes; Help controlling the 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; Dopant ion though mixing, barium lithium position can improve conductivity of electrolyte materials, owing to 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 rate charge-discharge performance of iron position doping can improvement LiFePO4 improves cycle performance.Product unit cell volume after manganese mixes all has minimizing, and electronic conductivity improves than the electronic conductivity of LiFePO4, and its impedance in electrolyte solution is significantly reduced, and chemical property also obviously improves; Its first discharge capacity reach 155.52mAh/g; The relative lithium electrode current potential of its charge and discharge platform is about 3.5V, and initial discharge capacity surpasses 164mAh/g, and capacity decays about 3.0% 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.Be to replace manganese, barium on a small quantity owing to mix, help controlling the pattern and the particle diameter of product, obtain stable LiFePO4 compound, its lattice has obtained activation, has improved the result of lithium ion diffusion coefficient.
Claims (2)
1. a manganese, barium activation lithium iron phosphate positive material preparation method is characterized in that: the raw material in its lithium source, source of iron, phosphoric acid root, manganese source, barium source, according to 1mol Li: 0.00002-0.00005mol Mn: 0.0003-0.003mol Ba: 1mol Fe: after the 1mol P mixed; In ethanol medium; Rotating speed 200-800r/mimn high speed ball milling 15-20h with 105-120 ℃ of oven dry, obtains presoma; The presoma that oven dry is obtained places in the high temperature furnace; In blanket of nitrogen,, promptly get manganese, barium activation lithium iron phosphate positive material through 500-750 ℃ of high-temperature calcination 16-24h.
2. manganese according to claim 1, barium activation lithium iron phosphate positive material preparation method; It is characterized in that: its lithium source is one of lithium carbonate, lithium hydroxide, lithium dihydrogen phosphate; Source of iron is a ferrous oxalate; The phosphoric acid root is one of ammonium dihydrogen phosphate, diammonium hydrogen phosphate, and the manganese source is one of the inferior manganese of carbonic acid, manganous hydroxide, manganese dioxide, and the barium source is one of brium carbonate, barium hydroxide, barium chloride, barium nitrate, barium monoxide, barium sulphide.
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| JP2006048991A (en) * | 2004-08-02 | 2006-02-16 | Sumitomo Osaka Cement Co Ltd | Positive electrode active material for lithium battery, its manufacturing method, and lithium battery |
| CN101393982A (en) * | 2008-10-28 | 2009-03-25 | 南京海泰纳米材料有限公司 | Method for producing carbon coated nano stage lithium iron phosphate by precipitation |
| CN101582498A (en) * | 2009-06-18 | 2009-11-18 | 东北师范大学 | Method for preparing nanometer ferrous phosphate lithium /carbon composite material |
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| CN101393982A (en) * | 2008-10-28 | 2009-03-25 | 南京海泰纳米材料有限公司 | Method for producing carbon coated nano stage lithium iron phosphate by precipitation |
| CN101582498A (en) * | 2009-06-18 | 2009-11-18 | 东北师范大学 | Method for preparing nanometer ferrous phosphate lithium /carbon composite material |
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