CN100390052C - Method for synthesizing spheroidal lithium phosphate - Google Patents
Method for synthesizing spheroidal lithium phosphate Download PDFInfo
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- CN100390052C CN100390052C CNB2006100113787A CN200610011378A CN100390052C CN 100390052 C CN100390052 C CN 100390052C CN B2006100113787 A CNB2006100113787 A CN B2006100113787A CN 200610011378 A CN200610011378 A CN 200610011378A CN 100390052 C CN100390052 C CN 100390052C
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- phosphoric acid
- lithium
- transition metal
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- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 title claims description 8
- 238000000034 method Methods 0.000 title abstract description 11
- 230000002194 synthesizing effect Effects 0.000 title description 5
- 229910001386 lithium phosphate Inorganic materials 0.000 title description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 18
- 150000001875 compounds Chemical class 0.000 claims abstract description 12
- 239000010452 phosphate Substances 0.000 claims abstract description 11
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 10
- 229910052751 metal Inorganic materials 0.000 claims abstract description 10
- 239000002184 metal Substances 0.000 claims abstract description 10
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 9
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 9
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 9
- -1 phosphate radical ions Chemical class 0.000 claims abstract description 9
- 150000003839 salts Chemical class 0.000 claims abstract description 9
- 229910001428 transition metal ion Inorganic materials 0.000 claims abstract description 9
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 7
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 26
- 238000001816 cooling Methods 0.000 claims description 24
- 238000002360 preparation method Methods 0.000 claims description 18
- 238000000197 pyrolysis Methods 0.000 claims description 18
- 238000005245 sintering Methods 0.000 claims description 18
- 238000001035 drying Methods 0.000 claims description 13
- 229910052757 nitrogen Inorganic materials 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 229910019142 PO4 Inorganic materials 0.000 claims description 10
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 9
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 9
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 9
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 8
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 claims description 8
- 230000004927 fusion Effects 0.000 claims description 7
- 239000004254 Ammonium phosphate Substances 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- 229910000148 ammonium phosphate Inorganic materials 0.000 claims description 6
- 235000019289 ammonium phosphates Nutrition 0.000 claims description 6
- 239000006229 carbon black Substances 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 6
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 5
- 239000000654 additive Substances 0.000 claims description 5
- 230000000996 additive effect Effects 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical group [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Chemical compound [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 claims description 4
- 150000003016 phosphoric acids Chemical class 0.000 claims description 4
- 229910052723 transition metal Inorganic materials 0.000 claims description 4
- 150000003624 transition metals Chemical class 0.000 claims description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 3
- 229910013275 LiMPO Inorganic materials 0.000 claims description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 3
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 3
- 150000001722 carbon compounds Chemical class 0.000 claims description 3
- 229910052744 lithium Inorganic materials 0.000 claims description 3
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 3
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 229910052728 basic metal Inorganic materials 0.000 claims description 2
- 150000003818 basic metals Chemical group 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 229940116007 ferrous phosphate Drugs 0.000 claims description 2
- 229910002804 graphite Inorganic materials 0.000 claims description 2
- 239000010439 graphite Substances 0.000 claims description 2
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims description 2
- 150000002500 ions Chemical class 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 229910000398 iron phosphate Inorganic materials 0.000 claims description 2
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical group [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 claims description 2
- 229910000155 iron(II) phosphate Inorganic materials 0.000 claims description 2
- SDEKDNPYZOERBP-UHFFFAOYSA-H iron(ii) phosphate Chemical group [Fe+2].[Fe+2].[Fe+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O SDEKDNPYZOERBP-UHFFFAOYSA-H 0.000 claims description 2
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 238000002844 melting Methods 0.000 claims description 2
- 230000008018 melting Effects 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000000047 product Substances 0.000 abstract description 33
- 239000013067 intermediate product Substances 0.000 abstract description 12
- 239000000203 mixture Substances 0.000 abstract description 9
- 239000008187 granular material Substances 0.000 abstract 3
- 239000002131 composite material Substances 0.000 abstract 1
- 229910000319 transition metal phosphate Inorganic materials 0.000 abstract 1
- 239000002245 particle Substances 0.000 description 13
- 206010013786 Dry skin Diseases 0.000 description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 11
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 11
- 239000008367 deionised water Substances 0.000 description 11
- 229910021641 deionized water Inorganic materials 0.000 description 11
- 239000010450 olivine Substances 0.000 description 11
- 229910052609 olivine Inorganic materials 0.000 description 11
- 238000007789 sealing Methods 0.000 description 11
- 238000005406 washing Methods 0.000 description 11
- 238000002156 mixing Methods 0.000 description 4
- 101100513612 Microdochium nivale MnCO gene Proteins 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 2
- 229910010710 LiFePO Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 238000010532 solid phase synthesis reaction Methods 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 229910001508 alkali metal halide Inorganic materials 0.000 description 1
- 150000008045 alkali metal halides Chemical class 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000002482 conductive additive Substances 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000009791 electrochemical migration reaction Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- AWKHTBXFNVGFRX-UHFFFAOYSA-K iron(2+);manganese(2+);phosphate Chemical compound [Mn+2].[Fe+2].[O-]P([O-])([O-])=O AWKHTBXFNVGFRX-UHFFFAOYSA-K 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 238000010671 solid-state reaction Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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Abstract
The present invention provides a method for preparing spherical or spheroid phosphoric acid metal lithium salt. The method has the steps that a compound containing one or a plurality of kinds of lithium ions, transition metal ions and phosphate radical ions can be mixed and milled, and then the mixture is pyrolyzed in inert atmosphere; the pyrolyzed intermediate product is mixed with a certain amount of alkali metal molten salt, and then is sintered at high temperature; after the sintered primary product is washed, filtered and dried, the obtained phosphoric acid metal lithium salt is a spherical or spheroid granule of which the diameter is from 1 to 5 mu m, and the size of the granule can be effectively controlled according to composite conditions. When the method is adopted, the product can be quickly compounded, sintered time is short, and the energy source consumption is little. The spherical or spheroid phosphoric acid metal lithium salt has the advantages of uniform granule, small specific surface area, good processing performance, large tap density, and high volumetric specific energy density and safety, and is widely used for the fields of electrical tools, electric bicycles, electric automobiles, etc.
Description
Technical field
The present invention relates to the lithium ion battery field, relate in particular to a kind of preparation method of spherical phosphate metal lithium salts electrode materials.
Technical background
As a kind of novel cathode material for lithium ion battery, LiMPO
4Homologue is LiFePO particularly
4Extensive concern and further investigation (J.B.Goodenough, J.Electrochem.Soc.144 (1997) 1184 for A.K.Padhi, K.S.Nanjundaswarmyy) have been obtained.LiFePO
4Theoretical capacity with 170mAh/g, actual capacity can surpass 160mAh/g, than commercial LiCoO
2Want high, the about 3.4V of discharge platform compares LiCoO
2Low slightly.But its raw material sources is extensive, and is with low cost, safe, environmentally friendly, is particularly suitable for various high-power electric appliances with power cells such as battery and automobiles.Shortcoming is that electronic conductivity is lower by (～10
-8S/cm), heavy-current discharge performance is very poor under the normal temperature.By adding easy conductive thing such as carbon black, copper powder, the high temperature pyrolysis carbon coated is carried out metal ion mixing, and synthesis of nano particle etc. has been alleviated the influence of low conductivity greatly.But because its real density is lower, particularly add a certain amount of conductive agent such as carbon black after, actual density is lower, is difficult to reach application requiring.If the LiFePO of synthesizing spherical
4Product, its tap density will be greatly enhanced so, and specific surface area descends simultaneously, and safety performance is better, and processing characteristics is also very good.People such as Ying Jierong adopt synthesizing spherical presoma ferrous ammonium phosphate, obtain spheric iron lithium phosphate (CN200510002012.9 with sintering again, the preparation method of high-density spherical ferric lithium phosphate and iron manganese phosphate for lithium), this method adopts aqueous phase precipitation to obtain presoma, its complicated operation, condition are difficult to control.Bewlay, people such as S.L adopt spray-dired method to obtain spheric LiFePO
4(Bewlay, S.L et al Conductivityimprovements to spray-produced LiFePO
4By addition of a carbon source, Materials Letters, 58 (11) 1788-1791), but in the process of spraying,, be difficult to obtain single peridotites phase because high temperature unavoidably produces ferric iron impurity.If can adopt conventional solid phase method synthesizing spherical, monophasic phosphate metal lithium salts, will have great application prospect so, yet this respect does not but have relevant report.
Summary of the invention
The preparation method who the purpose of this invention is to provide a kind of spherical phosphate metal lithium salts.This method is to add a certain amount of alkali metal fusion salt in the solid phase method building-up process of routine, obtains the spheric product mutually by producing high-temperature fusion.Sphere of the present invention and spheroidal lithium phosphate LiMPO
4The preparation method, its step is as follows:
(1) one or more the compound that will contain lithium ion, transition metal ion M and phosphate anion is ground, and carries out pyrolysis in the inert atmosphere stove;
(2) intermediate after the pyrolysis adds alkali metal fusion salt and mixes the back sintering, and wherein the molar ratio of melting salt and intermediate (in the transition metal total amount) is 0.1-10;
(3) cooling washes the synthetic head product with water, filters then, and drying is ground, and obtains finished product.
Wherein, the mol ratio of Li: M: P is 0.97～1.2: 0.95～1.05 usually in step (1): 0.95～1.05, and pyrolysis temperature is 200-600 ℃, the treatment time is 1-30 hour.Above-mentioned transition metal ion M be selected from Fe, Mn, Co, Ni, Cu, Zn ionic one or more, the preferred divalent ion of these metals.
Above-mentioned preparation phosphate metal lithium salts the compound that contains transition metal ion be selected from carbonate, vitriol, phosphoric acid salt, acetate, oxalate, muriate, oxide compound, sulfide, the fluorochemical of transition metal, be preferably carbonate, acetate, oxalate and oxide compound; The compound that contains lithium ion is selected from Quilonum Retard, Trilithium phosphate, Lithium Sulphate, lithium acetate, monometallic, phosphoric acid hydrogen two lithiums, lithium fluoride, lithium chloride, lithium hydroxide, is preferably Quilonum Retard, monometallic and lithium hydroxide; The compound that contains phosphate anion is selected from phosphoric acid, primary ammonium phosphate, Secondary ammonium phosphate, ammonium phosphate, Trilithium phosphate, monometallic, phosphoric acid hydrogen two lithiums, tertiary iron phosphate, ferrous phosphate, ferrous ammonium phosphate, is preferably primary ammonium phosphate, Secondary ammonium phosphate, monometallic and ferrous ammonium phosphate.
Step (1) can further be added the simple substance of carbon or can be produced carbon compound as additive when pyrolysis, such additive comprises that graphite, carbon black and other can produce carbon compound, these materials can be used as conductive additive on the one hand, improve the conductivity of material, can serve as reductive agent on the other hand, guarantee that transition metal ion is a divalence in the finished product.Additive is preferably carbon black and other carbonaceous organic material, as sugar, citric acid.
Usually, the used rare gas element of above-mentioned steps (1) is nitrogen or argon gas.
In step (2), alkali metal fusion salt is selected from basic metal Li, Na, one or more of the carbonate of K, vitriol, phosphoric acid salt, fluorochemical, muriate, bromide, iodide, sulfide, oxyhydroxide, it is medium and don't produce the alkali metal halide of oxidizing atmosphere to be preferably decomposition temperature.Sintering temperature is 500-900 ℃, and the time is 0.5～30 hour.
Owing to added alkali metal fusion salt, when high temperature sintering, produce liquid phase, ionic migration when helping solid state reaction, thus accelerate crystallization velocity, shorten generated time.Simultaneously the liquid phase that produces during high temperature under the effect of its surface compressed tensile, impels particle to become sphere or class sphere.
Adopt method of the present invention to prepare spherical phosphate metal lithium salts, simple to operate, sintering time is short, and energy waste is few, and cost is lower.The product particle of preparation is spherical in shape or class is spherical, and crystal property is good, the specific storage height, and tap density is big, energy density per unit volume metric density height, cycle performance is good, and safety performance is good, is particularly suitable for power cell.
Description of drawings
Fig. 1 is the X-ray diffractogram by the prepared LiFePO 4 of embodiment 1.
Fig. 2 is the field emission scanning electron microscope figure by the prepared LiFePO 4 of embodiment 1.
Fig. 3 is the field emission scanning electron microscope figure by the prepared LiFePO 4 of embodiment 2.
Fig. 4 is the cyclic voltammetry curve figure by the prepared LiFePO 4 of embodiment 1.
Fig. 5 is the cycle diagram by the prepared LiFePO 4 of embodiment 1.
For clearer explanation the present invention, enumerate following example, but the present invention is not had any restriction.
Embodiment 1
With Li
2CO
3, FeC
2O
42H
2O, NH
4H
2PO
4Mixed in 0.55: 1: 1 in molar ratio, adding during mixing with the lithium ion mol ratio is 5% sugar, in the sealing tube furnace of nitrogen protection in 400 ℃ of pyrolysis 5 hours.After the cooling KCl of intermediate product with 2 times of mol ratios mixed, again 760 ℃ of sintering 3 hours, naturally cooling, the head product deionized water wash is used washing with alcohol again, filters and 100 ℃ of dryings of vacuum, obtains the LiFePO 4 particulate product.
The LiFePO 4 product of gained is an olivine structural, tap density 1.52gcm
-3Adopt Cu target K α radiation, λ=0.15406nm obtains the X-ray diffraction pattern of this product, as shown in Figure 1.Can see that by field emission scanning electron microscope this LiFePO 4 particle is sphere or class sphere, diameter is 2-4 μ m, as shown in Figure 2.This product cyclic voltammetry curve as shown in Figure 4, the numeral among the figure shows scanning times, is respectively 1,2,20, voltage range 2.8-4.0V, scanning speed 0.1mVs
-1, 25 ℃ of temperature.Its cycle diagram as shown in Figure 5, electric current is 0.5mAcm
-2, voltage range 2.8-4.0V, loading capacity is 130.3mAhg first
-1, circulating, capacity is 137.2mAhg after 40 times
-1
Embodiment 2
With Li
2CO
3, FeC
2O
42H
2O, (NH
4)
2HPO
4Mixed in 0.51: 1: 1 in molar ratio, adding and lithium ion mol ratio are 5% citric acid during mixing, in 300 ℃ of pyrolysis 12 hours, lead to nitrogen protection in the tube furnace of sealing.After the cooling KCl of intermediate product with 4 times of mol ratios mixed, again 760 ℃ of sintering 10 hours, naturally cooling, the head product deionized water wash is used washing with alcohol again, filters and 100 ℃ of dryings of vacuum.As shown in Figure 3, the product of gained is an olivine structural, and particle is spherical, and diameter is 5-6 μ m, tap density 1.64gcm
-3, loading capacity is 121.3mAhg first
-1
Embodiment 3
With LiOHH
2O, NH
4FePO
4Mixed in 1.2: 1 in molar ratio, and in the tube furnace of sealing,, led to nitrogen protection in 350 ℃ of pyrolysis 24 hours.After the cooling with the K of intermediate product and 1 times of mol ratio
2CO
3Mix, again 900 ℃ of sintering 0.5 hour, naturally cooling, the head product deionized water wash is used washing with alcohol again, filters also 100 ℃ of dryings of vacuum.The product of gained is an olivine structural, and particle is the class sphere, and diameter is 5-7 μ m, and tap density is 1.54gcm
-3, loading capacity is 120.6mAhg first
-1
Embodiment 4
With 1mol Li
3PO
4With 1mol Fe
3(PO
4)
28H
2O mixes, and does 200 ℃ of pyrolysis 30 hours in the tube furnace of sealing, logical nitrogen protection.After the cooling KI of intermediate product with 0.2 times of mol ratio mixed, again 700 ℃ of sintering 20 hours, naturally cooling, the head product deionized water wash is used washing with alcohol again, filters and 120 ℃ of dryings of vacuum.The product of gained is an olivine structural, and particle is the class sphere, diameter 2-5 μ m, and tap density is 1.45gcm
-3
Embodiment 5
With 1mol LiH
2PO
4With 0.5mol Fe
2O
3Mix, adding and lithium ion mol ratio are 50% carbon black during mixing, handle logical nitrogen protection 1 hour in 600 ℃ in the tube furnace of sealing.After the cooling intermediate product is mixed with the LiCl of 1.4 times of mol ratios and the LiF of 0.6 mol ratio, again 550 ℃ of sintering 30 hours, naturally cooling, the head product deionized water wash is used washing with alcohol again, filters and 120 ℃ of dryings of vacuum.The product of gained is an olivine structural, and particle is the class sphere, diameter 1-2 μ m, and tap density is 1.23gcm
-3
Embodiment 6
With 0.99mol LiAc2H
2O, 0.5mol FeS and 0.5mol MnAc
22H
2O, 1mol (NH
4)
3PO
4Mix, in the tube furnace of sealing,, lead to nitrogen protection in 400 ℃ of pyrolysis 9 hours.After the cooling NaI of intermediate product with 0.5 times of mol ratio mixed, again 700 ℃ of sintering 20 hours, naturally cooling, the head product deionized water wash is used washing with alcohol again, filters and 120 ℃ of dryings of vacuum.The product of gained is an olivine structural, and particle is the class sphere, diameter 2-5 μ m, and tap density is 1.40gcm
-3
Embodiment 7
With 1mol LiH
2PO
4, 0.4mol FeC
2O
42H
2O and 0.6mol MnCO
3Mix, in the tube furnace of sealing,, lead to nitrogen protection in 450 ℃ of pyrolysis 10 hours.After the cooling with intermediate product with and 6 times KOH mixes, again 50 ℃ of sintering 30 hours, naturally cooling, the head product deionized water wash is used washing with alcohol again, filtration is 120 ℃ of dryings of vacuum also.The product of gained is an olivine structural, and particle is the class sphere, and diameter is 3-4 μ m, and tap density is 1.42gcm
-3
Embodiment 8
With 1.1mol Li
2CO
3, 0.85mol FeC
2O
42H
2O, 0.1molCuAc
22H
2O, 0.05mol ZnCO
3, 1mol (NH
4)
2HPO
4Mix, in the tube furnace of sealing,, lead to nitrogen protection in 350 ℃ of pyrolysis 6 hours.After the cooling with the Li of intermediate product and 1 times of mol ratio
2SO
4Li with 2 times of mol ratios
3PO
4Mix, again 870 ℃ of sintering 2 hours, naturally cooling, the head product deionized water wash is used washing with alcohol again, filters also 120 ℃ of dryings of vacuum.The product of gained is an olivine structural, and particle is the class sphere, diameter 3-5 μ m, and tap density is 1.52gcm
-3
Embodiment 9
With 1.2mol LiCl, 0.5mol FeCl
2With 0.25mol MnCO
3And 0.25molCoCO
3, 1mol NH
4H
2PO
4Mix, in the tube furnace of sealing,, lead to nitrogen protection in 500 ℃ of pyrolysis 5 hours.After the cooling LiF of intermediate product with 4 times of mol ratios mixed, again 850 ℃ of sintering 12 hours, naturally cooling, the head product deionized water wash is used washing with alcohol again, filters and 100 ℃ of dryings of vacuum.The product of gained is an olivine structural, and particle is the class sphere, diameter 5-15 μ m, and tap density is 1.92gcm
-3
With LiH
2PO
4, MnCO
3Mixed in 1: 1 in molar ratio, and in the tube furnace of sealing,, led to nitrogen protection in 550 ℃ of pyrolysis 12 hours.After the cooling with the K of intermediate product and 0.55 times of mol ratio
2The KF of S and 0.45 times of mol ratio mixes, again 650 ℃ of sintering 15 hours, and naturally cooling, the head product deionized water wash is used washing with alcohol again, filters also 120 ℃ of dryings of vacuum.The product of gained is an olivine structural, and particle is the class sphere, and diameter is 2-4 μ m, and tap density is 1.37gcm
-3
Embodiment 11
With 1mol LiH
2PO
4, 0.2mol NiO and 0.8mol CoC
2O
4Mix, in the tube furnace of sealing,, lead to nitrogen protection in 300 ℃ of pyrolysis 12 hours.After the cooling intermediate product is mixed with 8 times of mol ratio KF, again 880 ℃ of sintering 24 hours, naturally cooling, the head product deionized water wash is used washing with alcohol again, filters and 120 ℃ of dryings of vacuum.The product of gained is an olivine structural, and particle is the class sphere, and diameter is 3-6 μ m, and tap density is 1.47gcm
-3
Claims (12)
1. spherical phosphate metal lithium salts LiMPO
4The preparation method, comprise the steps:
(1) one or more the compound that will contain lithium ion, transition metal ion M and phosphate anion is ground, in the inert atmosphere stove 200-600 ℃ pyrolysis 1-30 hour;
(2) intermediate after the pyrolysis adds alkali metal fusion salt and mixes the back sintering, and wherein the molar ratio of melting salt and transition metal total amount is 0.1-10;
(3) cooling washes the synthetic head product with water, filters then, and drying is ground, and obtains finished product.
2. preparation method as claimed in claim 1 is characterized in that, the mol ratio of Li: M: P is 0.97～1.2: 0.95～1.05 in the described step (1): 0.95～1.05.
3. preparation method as claimed in claim 1 is characterized in that, described transition metal ion M be selected from Fe, Mn, Co, Ni, Cu, Zn ionic one or more.
4. preparation method as claimed in claim 1 is characterized in that, described transition metal ion is a divalent ion.
5. preparation method as claimed in claim 1 is characterized in that, the described compound that contains lithium ion is selected from: Quilonum Retard, Trilithium phosphate, Lithium Sulphate, lithium acetate, monometallic, phosphoric acid hydrogen two lithiums, lithium fluoride, lithium chloride, lithium hydroxide.
6. preparation method as claimed in claim 1 is characterized in that, the described compound that contains transition metal ion is selected from carbonate, vitriol, phosphoric acid salt, acetate, oxalate, muriate, oxide compound, sulfide, the fluorochemical of transition metal.
7. preparation method as claimed in claim 1, it is characterized in that the described compound that contains phosphate anion is selected from: phosphoric acid, primary ammonium phosphate, Secondary ammonium phosphate, ammonium phosphate, Trilithium phosphate, monometallic, phosphoric acid hydrogen two lithiums, tertiary iron phosphate, ferrous phosphate, ferrous ammonium phosphate.
8. preparation method as claimed in claim 1 is characterized in that, described step (1) is further added carbon simple substance or can be produced carbon compound as additive when pyrolysis.
9. preparation method as claimed in claim 8 is characterized in that, described additive is selected from: graphite, carbon black, sugar, citric acid.
10. preparation method as claimed in claim 1 is characterized in that, the used rare gas element of described step (1) is nitrogen or argon gas.
11. preparation method as claimed in claim 1, it is characterized in that, described alkali metal fusion salt is selected from basic metal Li, Na, one or more of the carbonate of K, vitriol, phosphoric acid salt, fluorochemical, muriate, bromide, iodide, sulfide, oxyhydroxide.
12. preparation method as claimed in claim 1 is characterized in that, the sintering temperature of described step (2) is 500-900 ℃, and the time is 0.5～30 hour.
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| CN114249311B (en) | 2021-11-26 | 2023-03-07 | 广东邦普循环科技有限公司 | Preparation method of porous sodium ion battery positive electrode material sodium iron phosphate |
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