CN104591111B - A kind of phosphate material, preparation method and use - Google Patents
A kind of phosphate material, preparation method and use Download PDFInfo
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- CN104591111B CN104591111B CN201310533875.3A CN201310533875A CN104591111B CN 104591111 B CN104591111 B CN 104591111B CN 201310533875 A CN201310533875 A CN 201310533875A CN 104591111 B CN104591111 B CN 104591111B
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- phosphate material
- europium
- lithium
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- phosphate
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- 229910019142 PO4 Inorganic materials 0.000 title claims abstract description 81
- 239000000463 material Substances 0.000 title claims abstract description 80
- 239000010452 phosphate Substances 0.000 title claims abstract description 69
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 title claims abstract description 69
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 32
- 229910052693 Europium Inorganic materials 0.000 claims abstract description 29
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000002738 chelating agent Substances 0.000 claims abstract description 21
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims abstract description 18
- 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 16
- 238000000034 method Methods 0.000 claims abstract description 13
- 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
- 239000007789 gas Substances 0.000 claims abstract description 11
- 150000002696 manganese Chemical class 0.000 claims abstract description 11
- 239000000203 mixture Substances 0.000 claims abstract description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 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
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 7
- 239000010405 anode material Substances 0.000 claims abstract description 5
- 239000007864 aqueous solution Substances 0.000 claims abstract description 3
- 238000001914 filtration Methods 0.000 claims abstract 2
- 238000003756 stirring Methods 0.000 claims description 9
- 229910010785 LiFexMn1-xPO4 Inorganic materials 0.000 claims description 8
- 229910010782 LiFexMn1−xPO4 Inorganic materials 0.000 claims description 8
- 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 group OP(O)(=O)CN(CP(O)(O)=O)CP(O)(O)=O YDONNITUKPKTIG-UHFFFAOYSA-N 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
- 229940099596 manganese sulfate Drugs 0.000 claims description 4
- 235000007079 manganese sulphate Nutrition 0.000 claims description 4
- 239000011702 manganese sulphate Substances 0.000 claims description 4
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical group [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 4
- 241000040710 Chela Species 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
- 229920002472 Starch Polymers 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
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 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
- 229910052808 lithium carbonate Inorganic materials 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
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 claims description 2
- 229940120146 EDTMP Drugs 0.000 claims description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 2
- 229920002125 Sokalan® Polymers 0.000 claims description 2
- DLEPCXYNAPUMDZ-UHFFFAOYSA-N butan-2-ylphosphonic acid Chemical class CCC(C)P(O)(O)=O DLEPCXYNAPUMDZ-UHFFFAOYSA-N 0.000 claims description 2
- 229910001940 europium oxide Inorganic materials 0.000 claims description 2
- AEBZCFFCDTZXHP-UHFFFAOYSA-N europium(3+);oxygen(2-) Chemical group [O-2].[O-2].[O-2].[Eu+3].[Eu+3] AEBZCFFCDTZXHP-UHFFFAOYSA-N 0.000 claims description 2
- 229910052698 phosphorus Inorganic materials 0.000 claims description 2
- 239000011574 phosphorus Substances 0.000 claims description 2
- 239000004584 polyacrylic acid Substances 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 125000000185 sucrose group Chemical group 0.000 claims description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims 1
- 238000005660 chlorination reaction Methods 0.000 claims 1
- -1 hydroxy ethylidene Chemical group 0.000 claims 1
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 claims 1
- 150000003009 phosphonic acids Chemical class 0.000 claims 1
- 229910000668 LiMnPO4 Inorganic materials 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 5
- 238000010792 warming Methods 0.000 abstract description 4
- 229910010710 LiFePO Inorganic materials 0.000 abstract description 3
- 238000013019 agitation Methods 0.000 abstract 1
- 239000011572 manganese Substances 0.000 description 13
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical group [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 10
- 239000012071 phase Substances 0.000 description 9
- 239000006104 solid solution Substances 0.000 description 8
- DBVJJBKOTRCVKF-UHFFFAOYSA-N Etidronic acid Chemical compound OP(=O)(O)C(O)(C)P(O)(O)=O DBVJJBKOTRCVKF-UHFFFAOYSA-N 0.000 description 6
- 229910052493 LiFePO4 Inorganic materials 0.000 description 6
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 6
- 229910001416 lithium ion Inorganic materials 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 229910011990 LiFe0.5Mn0.5PO4 Inorganic materials 0.000 description 5
- 238000010438 heat treatment Methods 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
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 239000002253 acid Substances 0.000 description 3
- DUYCTCQXNHFCSJ-UHFFFAOYSA-N dtpmp Chemical compound OP(=O)(O)CN(CP(O)(O)=O)CCN(CP(O)(=O)O)CCN(CP(O)(O)=O)CP(O)(O)=O DUYCTCQXNHFCSJ-UHFFFAOYSA-N 0.000 description 3
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical group [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 3
- 230000010287 polarization Effects 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- 244000248349 Citrus limon Species 0.000 description 2
- 235000005979 Citrus limon Nutrition 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- NNMXSTWQJRPBJZ-UHFFFAOYSA-K europium(iii) chloride Chemical compound Cl[Eu](Cl)Cl NNMXSTWQJRPBJZ-UHFFFAOYSA-K 0.000 description 2
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 229910011861 LiFe0.33Mn0.67PO4 Inorganic materials 0.000 description 1
- 229910001305 LiMPO4 Inorganic materials 0.000 description 1
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 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 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- QSNQXZYQEIKDPU-UHFFFAOYSA-N [Li].[Fe] Chemical compound [Li].[Fe] QSNQXZYQEIKDPU-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000001412 amines Chemical class 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
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 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
- 230000002079 cooperative effect Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 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
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000006467 substitution reaction Methods 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
Landscapes
- Battery Electrode And Active Subsutance (AREA)
Abstract
The present invention discloses a kind of preparation method of phosphate material, the described method comprises the following steps：（1）Molysite, manganese salt, lithium salts, carbon source and europium source are dissolved in the aqueous solution of phosphorated chelating agent, the agitation and filtration at 50~110 DEG C, remove moisture and obtain phosphate material presoma；（2）Phosphate material presoma is moved into high-temperature atmosphere furnace, in argon gas, nitrogen or nitrogen and hydrogen mixture atmosphere, 400 500 DEG C are heated to 5 10 DEG C/min speed, constant temperature calcining 14 hours, it is warming up to 600 750 DEG C at the same rate again, constant temperature calcining is cooled to room temperature after 6 12 hours, obtains phosphate material.Phosphate material prepared by the inventive method has homogeneous phase, can play LiFePO well4And LiMnPO4Cooperative effect, there is more preferable capacity and voltage.The invention also discloses the phosphate material being prepared using methods described and its purposes in anode material of lithium battery.
Description
Technical field
The present invention relates to energy and material technology, more particularly to a kind of phosphate material for anode material for lithium-ion batteries
Material, preparation method and use.
Background technology
Lithium ion battery is the green high-capacity battery of a new generation, have voltage is high, specific energy density is big, have extended cycle life,
The many merits such as self discharge is small, memory-less effect, operating temperature range are wide, are widely used in mobile phone, notebook computer, number
Code-phase machine, video camera, electronic instrument etc., the fields such as instrument, electric automobile, energy-storage battery are cut down in UPS, electronic generation also has light
Application prospect.In recent years, the yield of lithium ion battery is skyrocketed through, and application field constantly expands, it has also become in two Pius XIs
The discipline new high-tech product significant to national economy and people's lives.
At present, lithium ion battery has reached its maturity in the compact battery field of portable type electronic product, and application is just
Progressively to middle Large Copacity, in high-power power type and accumulation energy type field of batteries expand.Positive electrode is studied and performance improvement is
One of core of lithium ion battery development.The ripe positive electrode being used widely in compact battery field, including cobalt
Sour lithium, LiMn2O4 and multi-element composite material etc. can not still meet to require.Because the security of these positive electrodes, environmental protection
Property etc. can not all meet the needs of large-sized power battery.
The phosphate cathode material of olivine structural turns into study hotspot both domestic and external.The material has many advantages,
Such as：Raw material is cheap, aboundresources；Stability Analysis of Structures, security performance are splendid（O in LiMPO4 is combined with P with strong covalent bond, material
Material is difficult that analysis oxygen decomposition reaction occurs during removal lithium embedded）；High-temperature behavior and heat endurance be substantially better than it is known other just
Pole material；Cycle performance is excellent；It is nontoxic, it is real green material.Compared with other traditional positive electrodes, phosphate positive pole
Material has very prominent advantage in terms of cost, high-temperature behavior, security, is expected to turn into power type and accumulation energy type lithium ion
The preferable positive electrode of battery.At present, phosphate cathode material is mainly based on LiFePO4 and lithium manganese phosphate, but phosphoric acid
The voltage platform of iron lithium material only has 3.4V, Gu its energy density is very low, has had a strong impact on that it is applied.And lithium manganese phosphate is led
Electrically poor, capacity is low.
LiFe at presentxMn1-xPO4Subject matter be that electric conductivity is bad, cause voltage and capacity relatively low；LiFexMn1-xPO4
Synthesis be often LiFePO4And LiMnPO4Simple mixtures, cooperative effect is poor, and voltage is low, and capacity is low, high rate performance
Difference.
The content of the invention
There is provided it is an object of the invention to overcome in place of above-mentioned the deficiencies in the prior art a kind of with uniform phase
LiFexMn1-xPO4, LiFePO can be played very well4And LiMnPO4Cooperative effect, there is the phosphate material of higher capacity and voltage
The preparation method of material；Another object of the present invention is to provide a kind of phosphate material being prepared using methods described；This
A further object of invention is in the purposes in the offer phosphate material in anode material of lithium battery.
To achieve the above object, the technical scheme taken of the present invention is：A kind of preparation method of phosphate material, the side
Method comprises the following steps：
（1）Molysite, manganese salt, lithium salts, carbon source and europium source are dissolved in the aqueous solution of phosphorated chelating agent, at 50~110 DEG C
It is sufficiently stirred, filters, removes moisture and produce phosphate material presoma；
（2）Phosphate material presoma is moved into high-temperature atmosphere furnace, in argon gas, nitrogen or nitrogen and hydrogen mixture atmosphere,
400-500 DEG C is heated to 5-10 DEG C/min speed, constant temperature calcining 1-4 hours, then again with 5-10 DEG C/min speed
Rate is warming up to 600-750 DEG C, and constant temperature calcining naturally cools to room temperature after 6-12 hours, obtains phosphate material.
As the preferred embodiment of the preparation method of phosphate material of the present invention, the step（1）In, phosphorous chela
Mixture：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 the phosphorus chelating agent is 40~60wt%.The step（1）In can add or be added without europium source, it is preferable that institute
State step（1）Middle to add by europium source, the addition in europium source can effectively improve the electric conductivity of gained phosphate material, so as to improve material
Material volume capacity, the polarization of material is reduced, improve discharge voltage plateau.The phosphate material being prepared is added behind europium source
LiFexMn1-xPO4（0<x<1）The average voltage of solid solution is higher 0.3V than the 3.4V of LiFePO4 in 3.7V or so, at room temperature
Capacity under 1C electric currents also reaches 156mAh/g, and the actual capacity of general lithium manganese phosphate is absolutely proved in 120mAh/g or so
The addition in europium source causes gained phosphate material LiFexMn1-xPO4（0<x<1）Solid solution has higher electric conductivity, relatively low
Polarization, so as to make it have higher discharge voltage plateau and capacity.
As the preferred embodiment of the preparation method of phosphate material of the present invention, the phosphorated chelating agent is amino
Three methylenephosphonic acids（ATMP）, 1-hydroxy ethylidene-1,1-diphosphonic acid（HEDP）, 2- phosphonobutanes -1,2,4- tricarboxylic acids（PBTCA）, divinyl three
The methylenephosphonic acid of amine five（DTPMP）, ethylene diamine tetra methylene phosphonic acid（EDTMPA）At least one of.
As the preferred embodiment of the preparation method of phosphate material of the present invention, the molysite is ferric nitrate, lemon
At least one of lemon acid iron.
As the preferred embodiment of the preparation method of phosphate material of the present invention, the manganese salt is manganese nitrate, sulphur
At least one of sour manganese.
As the preferred embodiment of the preparation method of phosphate material of the present invention, the lithium salts be lithium hydroxide,
At least one of lithium carbonate, lithium acetate, lithium nitrate, lithium fluoride.
As the preferred embodiment of the preparation method of phosphate material of the present invention, the carbon source is sucrose, poly- second
At least one of glycol, starch, polyacrylic acid, glucose.
As the preferred embodiment of the preparation method of phosphate material of the present invention, the europium source is europium oxide, chlorine
Change at least one of europium, europium nitrate, europium.
As the preferred embodiment of the preparation method of phosphate material of the present invention, the step（2）In high temperature
Atmosphere furnace is at least one of atmosphere protection type pushed bat kiln, vacuum rotary kiln, roller kilns.
There is uniform phase, LiFePO can be played well in addition, the present invention also provides one kind4And LiMnPO4Collaboration effect
, should there is the phosphate material of higher capacity and voltage, the phosphate material is prepared into using any method described above
Arrive, the chemical formula of the phosphate material is LiFexMn1-xPO4, wherein 0<x<1.
The last present invention also provides a kind of purposes of phosphate material described above in anode material of lithium battery.
The preparation method of phosphate material of the present invention, pass through the manganese salt and molysite ionic level in the liquid phase of solubility
It is sintered to form a kind of LiFe of solid solution after well mixedxMn1-xPO4（0<x<1）, solving mixing early stage inequality causes
Can not form homogeneous LiFexMn1-xPO4（0<x<1）.The LiFexMn1-xPO4（0<x<1）Solid solution be not by
LiFePO4And LiMnPO4It is simply mixed, it is a kind of uniform phase, can play both coordinating effects well, make it have
Higher capacity and voltage.The phosphate material LiFe that the method for the invention is preparedxMn1-xPO4（0<x<1）Solid solution
Average voltage is in 3.7V or so, and higher 0.3V than the 3.4V of LiFePO4, the capacity under 1C electric currents also reaches 156mAh/ at room temperature
G, and the actual capacity of general lithium manganese phosphate is in 120mAh/g or so.
Brief description of the drawings
Fig. 1 is a kind of phase structure figure of embodiment of phosphate material of the present invention.
Fig. 2 is a kind of discharge curve of embodiment of phosphate material of the present invention.
Embodiment
To better illustrate the object, technical solutions and advantages of the present invention, below in conjunction with the drawings and specific embodiments pair
The present invention is described further.
Embodiment 1
A kind of embodiment of phosphate material of the present invention, phosphate material described in the present embodiment using following methods prepare and
Into：
（1）HEDP is dissolved in the water, obtains phosphorated chelating agent, gained phosphorated chelating agent HEDP concentration is 40wt%, fully
Stirring adds ferric nitrate, manganese nitrate, Europium chloride, glucose and lithium hydroxide mixing, the phosphorated chelating agent until completely dissolved：
Molysite+manganese salt：Lithium salts：Carbon source：The mol ratio in europium source is 1:1:1:0.02:0.005, and the molysite：The mol ratio of manganese salt is
1:1, and heating stirring removes moisture after 2 hours in 100 DEG C of water-baths simultaneously, produces the LiFe of europium doping0.5Mn0.5PO4Forerunner
Body；
（2）The LiFe that europium is adulterated0.5Mn0.5PO4Presoma move into atmosphere protection type pushed bat kiln in, argon gas, nitrogen or
In nitrogen and hydrogen mixture atmosphere, 400 DEG C are heated to 6 DEG C/min speed, constant temperature calcining 4 hours, then again with same
Speed is warming up to 600 DEG C, and constant temperature calcining naturally cools to room temperature after 12 hours, obtains phosphate material LiFe0.5Mn0.5PO4。
Embodiment 2
A kind of embodiment of phosphate material of the present invention, phosphate material described in the present embodiment using following methods prepare and
Into：
（1）ATMP is dissolved in the water, obtains phosphorated chelating agent, gained phosphorated chelating agent ATMP concentration is 60wt%, fully
Stirring adds ironic citrate, manganese sulfate, europium nitrate and lithium acetate mixing, the phosphorated chelating agent until completely dissolved：Molysite+manganese
Salt：Lithium salts：Carbon source：The mol ratio in europium source is 1:0.8:1:0:0.01, and the molysite：The mol ratio of manganese salt is 1:2, and simultaneously
Heating stirring removes moisture after 4 hours in 50 DEG C of water-baths, produces the LiFe of europium doping0.33Mn0.67PO4Presoma；
（2）The LiFe that europium is adulterated0.33Mn0.67PO4Presoma is moved into high-temperature atmosphere furnace, is mixed in argon gas, nitrogen or nitrogen hydrogen
Close in gas atmosphere, heat to 500 DEG C with 10 DEG C/min speed, constant temperature calcining 1 hour, then heat up at the same rate again
To 700 DEG C, constant temperature calcining naturally cools to room temperature after 6 hours, obtains phosphate material LiFe0.33Mn0.67PO4。
Embodiment 3
A kind of embodiment of phosphate material of the present invention, phosphate material described in the present embodiment using following methods prepare and
Into：
（1）HEDP is dissolved in the water, obtains phosphorated chelating agent, gained phosphorated chelating agent HEDP concentration is 45wt%, fully
Stirring adds ferric nitrate, manganese sulfate, europium nitrate, sucrose and lithium nitrate mixing, the phosphorated chelating agent until completely dissolved：Molysite
+ manganese salt：Lithium salts：Carbon source：The mol ratio in europium source is 1:0.8:1:0.2:0.005, and the molysite：The mol ratio of manganese salt is 2:1,
And heating stirring removes moisture after 2 hours in 110 DEG C of water-baths simultaneously, the LiFe of europium doping is produced0.67Mn0.33PO4Presoma；
（2）The LiFe that europium is adulterated0.67Mn0.33PO4Presoma is moved into high-temperature atmosphere furnace, is mixed in argon gas, nitrogen or nitrogen hydrogen
Close in gas atmosphere, heat to 400 DEG C with 8 DEG C/min speed, constant temperature calcining 3 hours, then heat up at the same rate again
To 750 DEG C, constant temperature calcining naturally cools to room temperature after 8 hours, obtains phosphate material LiFe0.67Mn0.33PO4。
Embodiment 4
A kind of embodiment of phosphate material of the present invention, phosphate material described in the present embodiment using following methods prepare and
Into：
（1）First PBTCA is dissolved in the water, obtains phosphorated chelating agent, gained phosphorated chelating agent PBTCA concentration is 50wt%,
It is sufficiently stirred and adds ferric nitrate, manganese nitrate, Europium chloride, polyethylene glycol and lithium carbonate mixing, the phosphorous chela until completely dissolved
Mixture：Molysite+manganese salt：Lithium salts：Carbon source：The mol ratio in europium source is 1:1.1:1:0.1:0.001, and the molysite：Manganese salt is rubbed
You are than being 1:1, and heating stirring removes moisture after 3 hours in 80 DEG C of water-baths simultaneously, produces the LiFe of europium doping0.5Mn0.5PO4
Presoma；
（2）The LiFe that europium is adulterated0.5Mn0.5PO4Presoma is moved into high-temperature atmosphere furnace, is mixed in argon gas, nitrogen or nitrogen hydrogen
Close in gas atmosphere, heat to 500 DEG C with 5 DEG C/min speed, constant temperature calcining 2 hours, then heat up at the same rate again
To 650 DEG C, constant temperature calcining naturally cools to room temperature after 10 hours, obtains phosphate material LiFe0.5Mn0.5PO4。
Embodiment 5
A kind of embodiment of phosphate material of the present invention, phosphate material described in the present embodiment using following methods prepare and
Into：
（1）First DTPMP is dissolved in the water, obtains phosphorated chelating agent, gained phosphorated chelating agent DTPMP concentration is 55wt%,
It is sufficiently stirred and adds ferric nitrate, manganese sulfate, starch and lithium fluoride mixing, the phosphorated chelating agent until completely dissolved：Molysite+manganese
Salt：Lithium salts：Carbon source：The mol ratio in europium source is 1:0.9:1:0.15:0, and the molysite：The mol ratio of manganese salt is 1:1, and simultaneously
Heating stirring removes moisture after 3 hours in 70 DEG C of water-baths, produces LiFe0.5Mn0.5PO4Presoma；
（2）By LiFe0.5Mn0.5PO4Presoma is moved into high-temperature atmosphere furnace, in argon gas, nitrogen or nitrogen and hydrogen mixture atmosphere
In, 450 DEG C are heated to 7 DEG C/min speed, constant temperature calcining 3 hours, is then warming up to 680 DEG C at the same rate again,
Constant temperature calcining naturally cools to room temperature after 9 hours, obtains phosphate material LiFe0.5Mn0.5PO4。
Phase structure and the discharge curve experiment of 6 phosphate material of the present invention of embodiment
The phase structure of phosphate material of the present invention is detected, as shown in Figure 1.Can by the phase structure figure of accompanying drawing 1
Know, present invention gained phosphate material solid solution belongs to a kind of homogeneous phase, without other any miscellaneous peaks.
The discharge curve of phosphate material of the present invention is detected, as a result as shown in Figure 2.From accompanying drawing 2, this hair
The average voltage of bright gained phosphate material solid solution is in 3.7V or so, and higher 0.3V than the 3.4V of LiFePO4, capacity also reaches
To 156mAh/g, and the actual capacity of general lithium manganese phosphate is in 120mAh/g or so.Thus prove, present invention gained phosphate material
Material solid solution has higher electric conductivity, relatively low polarization, so as to make it have higher discharge voltage plateau and capacity.
Finally, it should be noted that the above embodiments are merely illustrative of the technical solutions of the present invention rather than the present invention is protected
The limitation of scope is protected, although being explained in detail with reference to preferred embodiment to the present invention, one of ordinary skill in the art should
Understand, technical scheme can be modified or equivalent substitution, without departing from the essence of technical solution of the present invention
And scope.
Claims (6)
1. a kind of preparation method of phosphate material, it is characterised in that the described method comprises the following steps：
(1) molysite, manganese salt, lithium salts, carbon source and europium source are dissolved in the aqueous solution of phosphorated chelating agent, at 50~110 DEG C fully
Stirring, filtering, remove moisture and produce phosphate material presoma；
(2) phosphate material presoma is moved into high-temperature atmosphere furnace, in argon gas, nitrogen or nitrogen and hydrogen mixture atmosphere, with 5-
10 DEG C/min speed heats to 400-500 DEG C, constant temperature calcining 1-4 hours, then again with 5-10 DEG C/min speed liter
Temperature arrives 600-750 DEG C, and constant temperature calcining naturally cools to room temperature after 6-12 hours, obtains phosphate material, the phosphate material
Chemical formula be LiFexMn1-xPO4, wherein 0<x<1, the molysite is ironic citrate, and the manganese salt is manganese sulfate, phosphorous chela
Mixture：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 the phosphorus chelating agent is 40~60wt%, and the phosphorated chelating agent is ATMP, hydroxy ethylidene two
Phosphonic acids, 2- phosphonobutanes -1,2, at least one in 4- tricarboxylic acids, diethylene triamine pentamethylene phosphonic, ethylene diamine tetra methylene phosphonic acid
Kind.
2. the preparation method of phosphate material as claimed in claim 1, it is characterised in that the lithium salts is lithium carbonate, acetic acid
At least one of lithium, lithium nitrate, lithium fluoride.
3. the preparation method of phosphate material as claimed in claim 1, it is characterised in that the carbon source is sucrose, poly- second two
At least one of alcohol, starch, polyacrylic acid, glucose.
4. the preparation method of phosphate material as claimed in claim 1, it is characterised in that the europium source is europium oxide, chlorination
At least one of europium, europium nitrate, europium.
5. the preparation method of phosphate material as claimed in claim 1, it is characterised in that described high-temperature atmosphere furnace is atmosphere
At least one of protection formula pushed bat kiln, vacuum rotary kiln, roller kilns.
A kind of 6. purposes of the phosphate material in anode material of lithium battery as claimed in claim 1.
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| 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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| 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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