CN104591111A - A phosphate material, a preparing method thereof and uses of the material - Google Patents
A phosphate material, a preparing method thereof and uses of the material Download PDFInfo
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- CN104591111A CN104591111A CN201310533875.3A CN201310533875A CN104591111A CN 104591111 A CN104591111 A CN 104591111A CN 201310533875 A CN201310533875 A CN 201310533875A CN 104591111 A CN104591111 A CN 104591111A
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- China
- Prior art keywords
- phosphate material
- preparation
- europium
- lithium
- phosphate
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- 239000000463 material Substances 0.000 title claims abstract description 80
- 229910019142 PO4 Inorganic materials 0.000 title claims abstract description 75
- 239000010452 phosphate Substances 0.000 title claims abstract description 75
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 title claims abstract description 75
- 238000000034 method Methods 0.000 title claims abstract description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 30
- 229910052693 Europium Inorganic materials 0.000 claims abstract description 27
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000002738 chelating agent Substances 0.000 claims abstract description 22
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000001354 calcination Methods 0.000 claims abstract description 16
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 15
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 12
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 12
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 12
- 150000002696 manganese Chemical class 0.000 claims abstract description 11
- 229910052786 argon Inorganic materials 0.000 claims abstract description 8
- 239000001257 hydrogen Substances 0.000 claims abstract description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 8
- 238000003756 stirring Methods 0.000 claims abstract description 8
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000007864 aqueous solution Substances 0.000 claims abstract description 3
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 3
- 239000011574 phosphorus Substances 0.000 claims abstract description 3
- 238000002360 preparation method Methods 0.000 claims description 22
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 17
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 8
- DBVJJBKOTRCVKF-UHFFFAOYSA-N Etidronic acid Chemical compound OP(=O)(O)C(O)(C)P(O)(O)=O DBVJJBKOTRCVKF-UHFFFAOYSA-N 0.000 claims description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 7
- 239000007789 gas Substances 0.000 claims description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 claims description 6
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 claims description 6
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 6
- YDONNITUKPKTIG-UHFFFAOYSA-N [Nitrilotris(methylene)]trisphosphonic acid Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CP(O)(O)=O YDONNITUKPKTIG-UHFFFAOYSA-N 0.000 claims description 5
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 5
- 229910002651 NO3 Inorganic materials 0.000 claims description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 4
- 239000010405 anode material Substances 0.000 claims description 4
- GAGGCOKRLXYWIV-UHFFFAOYSA-N europium(3+);trinitrate Chemical compound [Eu+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GAGGCOKRLXYWIV-UHFFFAOYSA-N 0.000 claims description 4
- NNMXSTWQJRPBJZ-UHFFFAOYSA-K europium(iii) chloride Chemical compound Cl[Eu](Cl)Cl NNMXSTWQJRPBJZ-UHFFFAOYSA-K 0.000 claims description 4
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 claims description 3
- 229940120146 EDTMP Drugs 0.000 claims description 3
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 3
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 3
- 229920002472 Starch Polymers 0.000 claims description 3
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 3
- 229930006000 Sucrose Natural products 0.000 claims description 3
- NFDRPXJGHKJRLJ-UHFFFAOYSA-N edtmp Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CCN(CP(O)(O)=O)CP(O)(O)=O NFDRPXJGHKJRLJ-UHFFFAOYSA-N 0.000 claims description 3
- 239000008103 glucose Substances 0.000 claims description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 3
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 3
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 3
- -1 polyoxyethylene Polymers 0.000 claims description 3
- 239000008107 starch Substances 0.000 claims description 3
- 235000019698 starch Nutrition 0.000 claims description 3
- 239000005720 sucrose Substances 0.000 claims description 3
- 229920002125 Sokalan® Polymers 0.000 claims description 2
- AEBZCFFCDTZXHP-UHFFFAOYSA-N europium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Eu+3].[Eu+3] AEBZCFFCDTZXHP-UHFFFAOYSA-N 0.000 claims description 2
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 claims description 2
- 239000004584 polyacrylic acid Substances 0.000 claims description 2
- 239000003352 sequestering agent Substances 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 6
- 239000010406 cathode material Substances 0.000 abstract description 4
- 230000002195 synergetic effect Effects 0.000 abstract description 2
- 238000010438 heat treatment Methods 0.000 abstract 3
- 239000002243 precursor Substances 0.000 abstract 2
- 229910052493 LiFePO4 Inorganic materials 0.000 abstract 1
- 229910000668 LiMnPO4 Inorganic materials 0.000 abstract 1
- 238000001816 cooling Methods 0.000 abstract 1
- 238000001914 filtration Methods 0.000 abstract 1
- 150000002505 iron Chemical class 0.000 abstract 1
- 239000012071 phase Substances 0.000 description 9
- 238000002156 mixing Methods 0.000 description 8
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 6
- 229910001416 lithium ion Inorganic materials 0.000 description 6
- 239000007774 positive electrode material Substances 0.000 description 6
- 229910011990 LiFe0.5Mn0.5PO4 Inorganic materials 0.000 description 5
- ILXAVRFGLBYNEJ-UHFFFAOYSA-K lithium;manganese(2+);phosphate Chemical compound [Li+].[Mn+2].[O-]P([O-])([O-])=O ILXAVRFGLBYNEJ-UHFFFAOYSA-K 0.000 description 5
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 4
- 230000010287 polarization Effects 0.000 description 3
- 238000009825 accumulation Methods 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 229910011861 LiFe0.33Mn0.67PO4 Inorganic materials 0.000 description 1
- 229910010710 LiFePO Inorganic materials 0.000 description 1
- 229910001305 LiMPO4 Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 230000035800 maturation Effects 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
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003786 synthesis reaction 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
Abstract
A preparing method of a phosphate material is disclosed. The method includes following steps of: (1) dissolving an iron salt, a manganese salt, a lithium salt, a carbon source and a europium source into an aqueous solution of a phosphorus-containing chelating agent, stirring and filtering at 50-110 DEG C, and removing water to obtain a phosphate material precursor; and (2) transferring the phosphate material precursor into a high-temperature atmosphere furnace, heating to 400-500 DEG C at a heating speed of 5-10 DEG C/min in argon, nitrogen or a nitrogen-hydrogen mixed atmosphere, calcinating at the constant temperature for 1-4 h, heating to 600-750 DEG C at the same speed, calcinating at the constant temperature for 6-12 h, and cooling to room temperature to obtain the phosphate material. The phosphate material prepared by the method has a homogeneous phase, exerts synergistic effects of LiFePO4 and LiMnPO4 well, and has good capacity and voltage. The invention also discloses the phosphate material prepared by the method and uses of the phosphate material in lithium battery cathode materials.
Description
Technical field
The present invention relates to energy and material technology, particularly relate to a kind of phosphate material for anode material for lithium-ion batteries, Preparation Method And The Use.
Background technology
Lithium ion battery is the green high-capacity battery of a new generation, there is the many merits such as voltage is high, specific energy density large, have extended cycle life, self-discharge is little, memory-less effect, operating temperature range are wide, be widely used in mobile telephone, notebook computer, digital camera, Kamera, electronic instrument etc., cut down the fields such as instrument, electromobile, energy-storage battery in UPS, electronic generation also there is bright application prospect.In recent years, the output of lithium ion battery rapidly increases, and Application Areas constantly expands, and has become in 21st century national economy and the significant new high-tech product of people's lives.
At present, lithium ion battery reaches its maturity in the compact battery field of portable type electronic product, range of application just progressively to middle Large Copacity, in high-power power type and accumulation energy type field of batteries expand.Positive electrode material research and improvement in performance are one of cores of lithium ion battery development.The positive electrode material of the maturation of being used widely in compact battery field, comprises cobalt acid lithium, lithium manganate and multi-element composite material etc. and still can not meet the demands.This is because the security of these positive electrode materials, the feature of environmental protection etc. all can not meet the demand of large-sized power battery.
The phosphate cathode material of olivine structural has become study hotspot both domestic and external.This material has many advantages, such as: cheaper starting materials, and aboundresources; Stability Analysis of Structures, safety performance splendid (O and the P in LiMPO4 combines with strong covalent bond, and material is difficult to analyse oxygen decomposition reaction in removal lithium embedded process); High-temperature behavior and thermostability are obviously better than other known positive electrode materials; Cycle performance is excellent; Nontoxic, be real green material.Compared with other traditional positive electrode materials, phosphate cathode material has very outstanding advantage in cost, high-temperature behavior, security, is expected to become power type and the desirable positive electrode material of accumulation energy type lithium ion battery.At present, phosphate cathode material is mainly based on iron lithium phosphate and lithium manganese phosphate, but the voltage platform of LiFePO 4 material only has 3.4V, Gu its energy density is very low, has had a strong impact on its application.And the poorly conductive of lithium manganese phosphate, capacity is low.
Current LiFe
xmn
1-xpO
4subject matter be that electroconductibility is bad, cause voltage and capacity lower; LiFe
xmn
1-xpO
4synthesis be often LiFePO
4and LiMnPO
4simple mixtures, synergistic effect is poor, and voltage is low, and capacity is low, and high rate performance is poor.
Summary of the invention
The object of the invention is to overcome above-mentioned the deficiencies in the prior art part and a kind of LiFe with uniform phase is provided
xmn
1-xpO
4, LiFePO can be played very well
4and LiMnPO
4synergistic effect, there is the preparation method of the phosphate material of higher capacity and voltage; Another object of the present invention is to provide a kind of phosphate material adopting described method to prepare; Another object of the present invention is to provide the purposes of described phosphate material in anode material of lithium battery.
For achieving the above object, the technical scheme that the present invention takes is: a kind of preparation method of phosphate material, said method comprising the steps of:
(1) be dissolved in the aqueous solution of phosphorated chelating agent by molysite, manganese salt, lithium salts, carbon source and europium source, fully stir at 50 ~ 110 DEG C, filter, namely removing moisture obtain phosphate material presoma;
(2) phosphate material presoma is moved in high-temperature atmosphere furnace, in argon gas, nitrogen or nitrogen and hydrogen mixture atmosphere, 400-500 DEG C is heated to the speed of 5-10 DEG C/min, constant temperature calcining 1-4 hour, and then with the ramp of 5-10 DEG C/min to 600-750 DEG C, naturally cool to room temperature after constant temperature calcining 6-12 hour, obtain phosphate material.
As the preferred implementation of the preparation method of phosphate material of the present invention, in described step (1), phosphorated chelating agent: molysite+manganese salt: lithium salts: carbon source: the mol ratio in europium source is 1:0.8 ~ 1.1:0.95 ~ 1.05:0.0 ~ 0.2:0 ~ 0.01, the concentration of described phosphorus sequestrant is 40 ~ 60wt%.Can add in described step (1) or not add europium source, preferably, adding in described step (1) by europium source, europium source add the electroconductibility that effectively can improve gained phosphate material, thus improve material volume capacity, reduce the polarization of material, improve discharge voltage plateau.The phosphate material LiFe prepared after adding europium source
xmn
1-xpO
4(0<x<1) average voltage of sosoloid is at about 3.7V, than the 3.4V height 0.3V of iron lithium phosphate, capacity under room temperature under 1C electric current also reaches 156mAh/g, and the actual capacity of general lithium manganese phosphate is at about 120mAh/g, absolutely prove that adding of europium source makes gained phosphate material LiFe
xmn
1-xpO
4(0<x<1) sosoloid has higher electroconductibility, lower polarization, thus makes it have higher discharge voltage plateau and capacity.
As the preferred implementation of the preparation method of phosphate material of the present invention, described phosphorated chelating agent is Amino Trimethylene Phosphonic Acid (ATMP), 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid (HEDP), 2-phosphonobutane-1, at least one in 2,4-tricarboxylic acid (PBTCA), diethylene triamine pentamethylene phosphonic (DTPMP), ethylene diamine tetra methylene phosphonic acid (EDTMPA).
As the preferred implementation of the preparation method of phosphate material of the present invention, described molysite is at least one in iron nitrate, ironic citrate.
As the preferred implementation of the preparation method of phosphate material of the present invention, described manganese salt is at least one in manganous nitrate, manganous sulfate.
As the preferred implementation of the preparation method of phosphate material of the present invention, described lithium salts is at least one in lithium hydroxide, Quilonum Retard, Lithium Acetate, lithium nitrate, lithium fluoride.
As the preferred implementation of the preparation method of phosphate material of the present invention, described carbon source is at least one in sucrose, polyoxyethylene glycol, starch, polyacrylic acid, glucose.
As the preferred implementation of the preparation method of phosphate material of the present invention, described europium source is at least one in europium sesquioxide, Europium trichloride, europium nitrate, europium.
As the preferred implementation of the preparation method of phosphate material of the present invention, the high-temperature atmosphere furnace in described step (2) is at least one in atmosphere protection type pushed bat kiln, vacuum rotary kiln, roller kiln.
In addition, the present invention also provides one to have uniform phase, well can play LiFePO
4and LiMnPO
4synergistic effect, there is the phosphate material of higher capacity and voltage, described phosphate material adopts any one method described above to prepare, and the chemical formula of described phosphate material is LiFe
xmn
1-xpO
4, wherein 0<x<1.
Last the present invention also provides the purposes of a kind of phosphate material described above in anode material of lithium battery.
The preparation method of phosphate material of the present invention, by the manganese salt of solubility and molysite in the liquid phase ionic level carry out after mixing sintering the LiFe forming a kind of solid solution
xmn
1-xpO
4(0<x<1) the uneven LiFe that can not form homogeneous phase caused of mixing in early stage, is solved
xmn
1-xpO
4(0<x<1).Described LiFe
xmn
1-xpO
4(0<x<1) sosoloid is not by LiFePO
4and LiMnPO
4simple mixing, it is a kind of uniform phase, well can play both coordinating effects, make it have higher capacity and voltage.The phosphate material LiFe that the method for the invention prepares
xmn
1-xpO
4(0<x<1) average voltage of sosoloid is at about 3.7V, than the 3.4V height 0.3V of iron lithium phosphate, capacity under room temperature under 1C electric current also reaches 156mAh/g, and the actual capacity of general lithium manganese phosphate is at about 120mAh/g.
Accompanying drawing explanation
Fig. 1 is the phase structure figure of a kind of embodiment of phosphate material of the present invention.
Fig. 2 is the discharge curve of a kind of embodiment of phosphate material of the present invention.
Embodiment
For better the object, technical solutions and advantages of the present invention being described, below in conjunction with the drawings and specific embodiments, the invention will be further described.
Embodiment 1
A kind of embodiment of phosphate material of the present invention, phosphate material described in the present embodiment adopts following methods to be prepared from:
(1) HEDP is dissolved in the water, obtain phosphorated chelating agent, the concentration of gained phosphorated chelating agent HEDP is 40wt%, abundant stirring adds the mixing of iron nitrate, manganous nitrate, Europium trichloride, glucose and lithium hydroxide until completely dissolved, described phosphorated chelating agent: molysite+manganese salt: lithium salts: carbon source: the mol ratio in europium source is 1:1:1:0.02:0.005, and described molysite: the mol ratio of manganese salt is 1:1, and simultaneously in 100 DEG C of water-baths heated and stirred remove moisture after 2 hours, obtain the LiFe of europium doping
0.5mn
0.5pO
4presoma;
(2) by the LiFe of europium doping
0.5mn
0.5pO
4presoma moves in atmosphere protection type pushed bat kiln; in argon gas, nitrogen or nitrogen and hydrogen mixture atmosphere; 400 DEG C are heated to the speed of 6 DEG C/min; constant temperature calcining 4 hours; and then with same ramp to 600 DEG C; constant temperature calcining naturally cooled to room temperature after 12 hours, obtained phosphate material LiFe
0.5mn
0.5pO
4.
Embodiment 2
A kind of embodiment of phosphate material of the present invention, phosphate material described in the present embodiment adopts following methods to be prepared from:
(1) ATMP is dissolved in the water, obtain phosphorated chelating agent, the concentration of gained phosphorated chelating agent ATMP is 60wt%, abundant stirring adds the mixing of ironic citrate, manganous sulfate, europium nitrate and Lithium Acetate until completely dissolved, described phosphorated chelating agent: molysite+manganese salt: lithium salts: carbon source: the mol ratio in europium source is 1:0.8:1:0:0.01, and described molysite: the mol ratio of manganese salt is 1:2, and simultaneously in 50 DEG C of water-baths heated and stirred remove moisture after 4 hours, obtain the LiFe of europium doping
0.33mn
0.67pO
4presoma;
(2) by the LiFe of europium doping
0.33mn
0.67pO
4presoma moves in high-temperature atmosphere furnace, in argon gas, nitrogen or nitrogen and hydrogen mixture atmosphere, heats to 500 DEG C with 10 DEG C/min speed, constant temperature calcining 1 hour, and then with same ramp to 700 DEG C, constant temperature calcining naturally cooled to room temperature after 6 hours, obtained phosphate material LiFe
0.33mn
0.67pO
4.
Embodiment 3
A kind of embodiment of phosphate material of the present invention, phosphate material described in the present embodiment adopts following methods to be prepared from:
(1) HEDP is dissolved in the water, obtain phosphorated chelating agent, the concentration of gained phosphorated chelating agent HEDP is 45wt%, abundant stirring adds the mixing of iron nitrate, manganous sulfate, europium nitrate, sucrose and lithium nitrate until completely dissolved, described phosphorated chelating agent: molysite+manganese salt: lithium salts: carbon source: the mol ratio in europium source is 1:0.8:1:0.2:0.005, and described molysite: the mol ratio of manganese salt is 2:1, and simultaneously in 110 DEG C of water-baths heated and stirred remove moisture after 2 hours, obtain the LiFe of europium doping
0.67mn
0.33pO
4presoma;
(2) by the LiFe of europium doping
0.67mn
0.33pO
4presoma moves in high-temperature atmosphere furnace, in argon gas, nitrogen or nitrogen and hydrogen mixture atmosphere, heats to 400 DEG C with 8 DEG C/min speed, constant temperature calcining 3 hours, and then with same ramp to 750 DEG C, constant temperature calcining naturally cooled to room temperature after 8 hours, obtained phosphate material LiFe
0.67mn
0.33pO
4.
Embodiment 4
A kind of embodiment of phosphate material of the present invention, phosphate material described in the present embodiment adopts following methods to be prepared from:
(1) first PBTCA is dissolved in the water, obtain phosphorated chelating agent, the concentration of gained phosphorated chelating agent PBTCA is 50wt%, abundant stirring adds the mixing of iron nitrate, manganous nitrate, Europium trichloride, polyoxyethylene glycol and Quilonum Retard until completely dissolved, described phosphorated chelating agent: molysite+manganese salt: lithium salts: carbon source: the mol ratio in europium source is 1:1.1:1:0.1:0.001, and described molysite: the mol ratio of manganese salt is 1:1, and simultaneously in 80 DEG C of water-baths heated and stirred remove moisture after 3 hours, obtain the LiFe of europium doping
0.5mn
0.5pO
4presoma;
(2) by the LiFe of europium doping
0.5mn
0.5pO
4presoma moves in high-temperature atmosphere furnace, in argon gas, nitrogen or nitrogen and hydrogen mixture atmosphere, heats to 500 DEG C with 5 DEG C/min speed, constant temperature calcining 2 hours, and then with same ramp to 650 DEG C, constant temperature calcining naturally cooled to room temperature after 10 hours, obtained phosphate material LiFe
0.5mn
0.5pO
4.
Embodiment 5
A kind of embodiment of phosphate material of the present invention, phosphate material described in the present embodiment adopts following methods to be prepared from:
(1) first DTPMP is dissolved in the water, obtain phosphorated chelating agent, the concentration of gained phosphorated chelating agent DTPMP is 55wt%, abundant stirring adds the mixing of iron nitrate, manganous sulfate, starch and lithium fluoride until completely dissolved, described phosphorated chelating agent: molysite+manganese salt: lithium salts: carbon source: the mol ratio in europium source is 1:0.9:1:0.15:0, and described molysite: the mol ratio of manganese salt is 1:1, and simultaneously in 70 DEG C of water-baths heated and stirred remove moisture after 3 hours, obtain LiFe
0.5mn
0.5pO
4presoma;
(2) by LiFe
0.5mn
0.5pO
4presoma moves in high-temperature atmosphere furnace, in argon gas, nitrogen or nitrogen and hydrogen mixture atmosphere, heats to 450 DEG C with 7 DEG C/min speed, constant temperature calcining 3 hours, and then with same ramp to 680 DEG C, constant temperature calcining naturally cooled to room temperature after 9 hours, obtained phosphate material LiFe
0.5mn
0.5pO
4.
The phase structure of embodiment 6 phosphate material of the present invention and discharge curve test
Detect the phase structure of phosphate material of the present invention, as shown in Figure 1.From the phase structure figure of accompanying drawing 1, gained phosphate material sosoloid of the present invention belongs to a kind of homogeneous phase, does not have other any assorted peaks.
Detect the discharge curve of phosphate material of the present invention, result as shown in Figure 2.From accompanying drawing 2, the average voltage of gained phosphate material sosoloid of the present invention is at about 3.7V, and than the 3.4V height 0.3V of iron lithium phosphate, capacity also reaches 156mAh/g, and the actual capacity of general lithium manganese phosphate is at about 120mAh/g.Prove thus, gained phosphate material sosoloid of the present invention has higher electroconductibility, lower polarization, thus makes it have higher discharge voltage plateau and capacity.
Finally to should be noted that; above embodiment is only in order to illustrate technical scheme of the present invention but not limiting the scope of the invention; although be explained in detail the present invention with reference to preferred embodiment; those of ordinary skill in the art is to be understood that; can modify to technical scheme of the present invention or equivalent replacement, and not depart from essence and the scope of technical solution of the present invention.
Claims (11)
1. a preparation method for phosphate material, is characterized in that, said method comprising the steps of:
(1) be dissolved in the aqueous solution of phosphorated chelating agent by molysite, manganese salt, lithium salts, carbon source and europium source, fully stir at 50 ~ 110 DEG C, filter, namely removing moisture obtain phosphate material presoma;
(2) phosphate material presoma is moved in high-temperature atmosphere furnace, in argon gas, nitrogen or nitrogen and hydrogen mixture atmosphere, 400-500 DEG C is heated to the speed of 5-10 DEG C/min, constant temperature calcining 1-4 hour, and then with the ramp of 5-10 DEG C/min to 600-750 DEG C, naturally cool to room temperature after constant temperature calcining 6-12 hour, obtain phosphate material.
2. the preparation method of phosphate material as claimed in claim 1, it is characterized in that, in described step (1), phosphorated chelating agent: molysite+manganese salt: lithium salts: carbon source: the mol ratio in europium source is 1:0.8 ~ 1.1:0.95 ~ 1.05:0.0 ~ 0.2:0 ~ 0.01, the concentration of described phosphorus sequestrant is 40 ~ 60wt%.
3. the preparation method of phosphate material as claimed in claim 1 or 2, it is characterized in that, described phosphorated chelating agent is at least one in Amino Trimethylene Phosphonic Acid, 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid, 2-phosphonobutane-1,2,4-tricarboxylic acid, diethylene triamine pentamethylene phosphonic, ethylene diamine tetra methylene phosphonic acid.
4. the preparation method of phosphate material as claimed in claim 1 or 2, it is characterized in that, described molysite is at least one in iron nitrate, ironic citrate.
5. the preparation method of phosphate material as claimed in claim 1 or 2, it is characterized in that, described manganese salt is at least one in manganous nitrate, manganous sulfate.
6. the preparation method of phosphate material as claimed in claim 1 or 2, it is characterized in that, described lithium salts is at least one in lithium hydroxide, Quilonum Retard, Lithium Acetate, lithium nitrate, lithium fluoride.
7. the preparation method of phosphate material as claimed in claim 1 or 2, it is characterized in that, described carbon source is at least one in sucrose, polyoxyethylene glycol, starch, polyacrylic acid, glucose.
8. the preparation method of phosphate material as claimed in claim 1 or 2, it is characterized in that, described europium source is at least one in europium sesquioxide, Europium trichloride, europium nitrate, europium.
9. the preparation method of phosphate material as claimed in claim 1 or 2, it is characterized in that, the high-temperature atmosphere furnace in described step (2) is at least one in atmosphere protection type pushed bat kiln, vacuum rotary kiln, roller kiln.
10. adopt as arbitrary in claim 1-9 as described in the phosphate material for preparing of method, it is characterized in that, the chemical formula of described phosphate material is LiFe
xmn
1-xpO
4, wherein 0<x<1.
11. 1 kinds of phosphate material purposes in anode material of lithium battery as claimed in claim 10.
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|---|---|---|---|---|
| CN106505186A (en) * | 2016-11-28 | 2017-03-15 | 湖南大学 | A kind of lithium iron phosphate positive material of in-stiu coating graphene film and preparation method thereof |
| CN109399730A (en) * | 2018-10-19 | 2019-03-01 | 百杰瑞(荆门)新材料有限公司 | A method of nickel-cobalt-manganese ternary presoma is prepared using organic phosphonate complexing agent |
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| CN101962180A (en) * | 2010-10-22 | 2011-02-02 | 深圳市科拓新能源材料有限公司 | Preparation method of lithium iron phosphate |
| CN102709553A (en) * | 2012-05-28 | 2012-10-03 | 深圳市贝特瑞新能源材料股份有限公司 | Positive electrode material and synthetic method thereof |
| CN102956887A (en) * | 2012-11-14 | 2013-03-06 | 佛山市德方纳米科技有限公司 | Preparation method of nano-grade lithium manganese phosphate anode material |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101962180A (en) * | 2010-10-22 | 2011-02-02 | 深圳市科拓新能源材料有限公司 | Preparation method of lithium iron phosphate |
| CN102709553A (en) * | 2012-05-28 | 2012-10-03 | 深圳市贝特瑞新能源材料股份有限公司 | Positive electrode material and synthetic method thereof |
| CN102956887A (en) * | 2012-11-14 | 2013-03-06 | 佛山市德方纳米科技有限公司 | Preparation method of nano-grade lithium manganese phosphate anode material |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106505186A (en) * | 2016-11-28 | 2017-03-15 | 湖南大学 | A kind of lithium iron phosphate positive material of in-stiu coating graphene film and preparation method thereof |
| CN106505186B (en) * | 2016-11-28 | 2019-04-05 | 湖南大学 | A kind of lithium iron phosphate positive material and preparation method thereof of in-stiu coating graphene film |
| CN109399730A (en) * | 2018-10-19 | 2019-03-01 | 百杰瑞(荆门)新材料有限公司 | A method of nickel-cobalt-manganese ternary presoma is prepared using organic phosphonate complexing agent |
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