CN101807696A - Titanium phosphate lithium material used for cathode of lithium ion battery and preparation method thereof - Google Patents
Titanium phosphate lithium material used for cathode of lithium ion battery and preparation method thereof Download PDFInfo
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- CN101807696A CN101807696A CN201010144810A CN201010144810A CN101807696A CN 101807696 A CN101807696 A CN 101807696A CN 201010144810 A CN201010144810 A CN 201010144810A CN 201010144810 A CN201010144810 A CN 201010144810A CN 101807696 A CN101807696 A CN 101807696A
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- titanium phosphate
- titanium
- phosphate lithium
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- 239000000463 material Substances 0.000 title claims abstract description 70
- MKGYHFFYERNDHK-UHFFFAOYSA-K P(=O)([O-])([O-])[O-].[Ti+4].[Li+] Chemical compound P(=O)([O-])([O-])[O-].[Ti+4].[Li+] MKGYHFFYERNDHK-UHFFFAOYSA-K 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 16
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 16
- 238000002156 mixing Methods 0.000 claims abstract description 14
- 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 abstract description 5
- 239000002228 NASICON Substances 0.000 claims abstract description 5
- 239000008103 glucose Substances 0.000 claims abstract description 5
- 238000000498 ball milling Methods 0.000 claims description 17
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 15
- 229910052744 lithium Inorganic materials 0.000 claims description 15
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 14
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 12
- 238000001354 calcination Methods 0.000 claims description 12
- 229910052799 carbon Inorganic materials 0.000 claims description 12
- 150000001875 compounds Chemical class 0.000 claims description 12
- 238000005303 weighing Methods 0.000 claims description 12
- 239000000126 substance Substances 0.000 claims description 10
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 8
- 239000010936 titanium Substances 0.000 claims description 8
- -1 hydrocarbon oxygen compound Chemical class 0.000 claims description 7
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 6
- 229910052698 phosphorus Inorganic materials 0.000 claims description 6
- 239000011574 phosphorus Substances 0.000 claims description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- 239000004215 Carbon black (E152) Substances 0.000 claims description 4
- 229920002472 Starch Polymers 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 4
- 229930195733 hydrocarbon Natural products 0.000 claims description 4
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 4
- SNKMVYBWZDHJHE-UHFFFAOYSA-M lithium;dihydrogen phosphate Chemical compound [Li+].OP(O)([O-])=O SNKMVYBWZDHJHE-UHFFFAOYSA-M 0.000 claims description 4
- 239000008107 starch Substances 0.000 claims description 4
- 235000019698 starch Nutrition 0.000 claims description 4
- 239000004408 titanium dioxide Substances 0.000 claims description 4
- JUWGUJSXVOBPHP-UHFFFAOYSA-B titanium(4+);tetraphosphate Chemical compound [Ti+4].[Ti+4].[Ti+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O JUWGUJSXVOBPHP-UHFFFAOYSA-B 0.000 claims description 3
- 239000004254 Ammonium phosphate Substances 0.000 claims description 2
- 229930006000 Sucrose Natural products 0.000 claims description 2
- 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 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 2
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 2
- 229910000148 ammonium phosphate Inorganic materials 0.000 claims description 2
- 235000019289 ammonium phosphates Nutrition 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 229910000388 diammonium phosphate Inorganic materials 0.000 claims description 2
- 235000019838 diammonium phosphate Nutrition 0.000 claims description 2
- YNQRWVCLAIUHHI-UHFFFAOYSA-L dilithium;oxalate Chemical compound [Li+].[Li+].[O-]C(=O)C([O-])=O YNQRWVCLAIUHHI-UHFFFAOYSA-L 0.000 claims description 2
- 239000007789 gas Substances 0.000 claims description 2
- 150000002430 hydrocarbons Chemical class 0.000 claims description 2
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 2
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 2
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 2
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 2
- 239000002243 precursor Substances 0.000 claims description 2
- 238000003825 pressing Methods 0.000 claims description 2
- 239000005720 sucrose Substances 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims 2
- 239000011261 inert gas Substances 0.000 claims 1
- 229910052757 nitrogen Inorganic materials 0.000 claims 1
- 239000000203 mixture Substances 0.000 abstract description 5
- 229910019142 PO4 Inorganic materials 0.000 abstract 1
- 239000010406 cathode material Substances 0.000 abstract 1
- 238000005253 cladding Methods 0.000 abstract 1
- 239000013078 crystal Substances 0.000 abstract 1
- 238000003801 milling Methods 0.000 abstract 1
- 239000005416 organic matter Substances 0.000 abstract 1
- 239000002994 raw material Substances 0.000 abstract 1
- 229910012465 LiTi Inorganic materials 0.000 description 37
- 238000001228 spectrum Methods 0.000 description 11
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 8
- 238000010583 slow cooling Methods 0.000 description 8
- 238000010792 warming Methods 0.000 description 8
- 238000007599 discharging Methods 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 5
- 229910010413 TiO 2 Inorganic materials 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 229910013870 LiPF 6 Inorganic materials 0.000 description 4
- 239000002270 dispersing agent Substances 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 230000002441 reversible effect Effects 0.000 description 4
- 229910000733 Li alloy Inorganic materials 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000001989 lithium alloy Substances 0.000 description 3
- 239000000523 sample Substances 0.000 description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical class CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 210000004027 cell Anatomy 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000003487 electrochemical reaction Methods 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 1
- 229910015645 LiMn Inorganic materials 0.000 description 1
- 229910018095 Ni-MH Inorganic materials 0.000 description 1
- 229910018477 Ni—MH Inorganic materials 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- OJIJEKBXJYRIBZ-UHFFFAOYSA-N cadmium nickel Chemical compound [Ni].[Cd] OJIJEKBXJYRIBZ-UHFFFAOYSA-N 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000006253 efflorescence Methods 0.000 description 1
- 239000002001 electrolyte material Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- KUJOABUXCGVGIY-UHFFFAOYSA-N lithium zinc Chemical compound [Li].[Zn] KUJOABUXCGVGIY-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 206010037844 rash Diseases 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
Images
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)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention relates to a titanium phosphate lithium material used for the cathode of a lithium ion battery and a preparation method thereof. The crystal structure of the titanium phosphate lithium material is an NASICON structure, and the composition is LixTi2(PO4)3, wherein x is 1 to 1.05. The preparation method of the material comprises the following steps: firstly, evenly mixing lithium-contained, titanium-contained and phosphorus-contained inorganic matter raw materials, and carrying out one-step roasting in an air atmosphere with the temperature of 800 to 1000 DEG C to prepare high-purity titanium phosphate lithium; then mixing the prepared titanium phosphate lithium with organic matter of glucose and the like in a certain proportion; milling and evenly mixing by a planet ball mill; then roasting in an inert atmosphere to obtain the carbon-cladding titanium phosphate lithium material. The preparation method is simple and has low cost, and the obtained titanium phosphate lithium cathode material has high purity, complete structure, high electrical conductivity and good electrochemical properties.
Description
Technical field
The present invention relates to lithium ion battery negative material and preparing technical field, especially a kind of titanium phosphate lithium material that is used for lithium ion battery negative and preparation method thereof.
Background technology
The lasting in short supply of the continuous deterioration of global environment and energy supply is that the 21 century mankind must face the most serious two large problems, and Application and Development new forms of energy and renewable and clean energy resource are very urgent.Lithium rechargeable battery is as novel green battery, and development is quite rapid since nineteen ninety comes out.Compare with secondary cells such as the lead-acid battery of using always, nickel-cadmium cell, Ni-MH batteries, special advantages such as lithium rechargeable battery has the open circuit voltage height, energy density is big, self-discharge rate is low, long service life, pollution-free and security performance are good, range of application more and more widely.
The negative material of lithium ion battery is one of key that guarantees the lithium ion battery premium properties.Present business-like lithium ion battery negative material mainly is a material with carbon element, wherein mainly contains graphite and coke.Carbon negative pole material has advantages such as the reaction of big specific capacity, highly reversible removal lithium embedded, good chemical stability and charge-discharge characteristic.Its shortcoming mainly is low to the lithium current potential, generally between 0～0.2V.Lithium ion battery easily at electrode surface precipitating metal lithium, causes the short circuit of inside battery when adopting material with carbon element as negative pole when overcharging with high power charging-discharging, produces a large amount of heat, makes battery on fire even blast, and has brought serious potential safety hazard thus.For various lithium alloy Li
xM (M=Si, Sn, Ge etc.) material is sayed as lithium ion battery negative material, though Zinc-lithium alloy material can be avoided the Li dendrite growth, improves battery security effectively.But lithium alloy is in the removal lithium embedded course of reaction, and the change in volume of material is bigger, causes electrode material efflorescence gradually in the charge and discharge cycles process, and cycle performance is relatively poor.
The titanium phosphate lithium during as lithium ion battery negative material its theoretical capacity 138.3mAh/g is arranged, this material has cheap, environmental friendliness, Stability Analysis of Structures, chemical compatibility is good, electrochemical reaction platform stable advantages such as (charge and discharge platform about 2.45V), can with the positive electrode LiMn of present broad research
2O
4, LiCoO
2Deng forming the aqueous lithium ion battery, improve the security performance of battery, reduce the battery cost.But LiTi
2(PO
4)
3Also there are some problems in the synthetic and practicability process of negative material:
1, because material electric conductivity low, cause in its charge and discharge process polarization phenomena serious, the chemical property of material is poor.2, LiTi
2(PO
4)
3Material need carry out repeatedly heat treatment and grinding when synthetic, as E.
Deng people (E.
T.
A.Dindune, et.La-dopedLiTi
2(PO
4)
3Ceramics, Solid State Ionics, 2008,179:51-56) with Li
2CO
3, TiO
2And NH
4H
2PO
4Be feedstock production LiTi
2(PO
4)
3During material, passed through four ball millings and three roastings preparation, its preparation technology is comparatively complicated, and cost is quite high.
Summary of the invention
It is good to the invention provides a kind of chemical compatibility, the electrochemical reaction platform stable, and eco-friendly titanium phosphate lithium-material with carbon element, this material can be used for preparing lithium ion battery negative.The present invention also provides the preparation method of above-mentioned titanium phosphate lithium material.
A kind of titanium phosphate lithium material that is used for lithium ion battery negative, the structure of titanium phosphate lithium is the NASICON structure, molecular formula is Li
xTi
2(PO
4)
3, wherein x is 1～1.05.
Consisting of of preferred titanium phosphate lithium material: the content of the titanium phosphate lithium of NASICON structure is 90wt%～100wt%, and the content of carbon is 0-10wt%;
A kind of preparation method who is used for the titanium phosphate lithium material of lithium ion battery negative may further comprise the steps:
1) preparation of former material precursor and mixing: with lithium-containing compound, titanium dioxide and phosphorus-containing compound stoichiometric proportion (1～1.05): 2: 3 ratio weighing in lithium, titanium, phosphorus; Press 5: 1 batch mixings of ball material mass ratio on planetary ball mill with the rotating speed ball milling of 150～300r/min 6～24 hours, obtain the powdery presoma;
2) high-temperature roasting is handled: with the powdery presoma of step 1) gained constant temperature calcining 8～20 hours under 800 ℃～1000 ℃ temperature, natural cooling obtains the titanium phosphate lithium salts of white;
3) secondary ball milling: with step 2) 1: 0.2～0.02 weighing of pressing mass ratio of the titanium phosphate lithium salts of gained and organic substance mixes; On planetary ball mill, obtained the presoma of powdery in 6～24 hours with the rotating speed ball milling of 150～300r/min by 5: 1 batch mixings of ball material mass ratio;
4) after baking: the powdery presoma that secondary ball milling obtains is put into the high temperature furnace that is connected with inert atmosphere, and throughput is 10～60ml/min, and constant temperature calcining is 6～12 hours under 500 ℃～750 ℃ temperature; Treat to obtain titanium phosphate lithium-carbon (LiTi behind the natural cooling
2(PO
4)
3/ C) material;
Said lithium-containing compound can be selected from any in lithium carbonate, lithium hydroxide, lithium oxalate, lithium acetate, lithium dihydrogen phosphate or the lithium nitrate among the present invention, titanium dioxide can be selected from any in rutile, anatase, three kinds of kenels of brockite, and phosphorus-containing compound can be selected from any in lithium dihydrogen phosphate, ammonium dihydrogen phosphate, diammonium hydrogen phosphate or the ammonium phosphate.Said organic substance is hydrocarbon oxygen compound or hydrocarbon, and with glucose, one or more in starch, the sucrose are advisable.
Advantage of the present invention is: this negative material Stability Analysis of Structures, and the removal lithium embedded invertibity is good, the security performance height, charge and discharge platform is stable.
Preparation method of the present invention also has following characteristics:
1) the synthetic titanium phosphate lithium advantages of good crystallization of step high temperature solid-state roasting, the thing phase purity height of material.
2) carbon coating layer of the carbon of organic substance cracking when high temperature formation around titanium phosphate cathode of lithium material granule, the LiTi that can improve
2(PO
4)
3Electron transport ability between particle improves conductivity of electrolyte materials effectively, and the charge-discharge performance of material is greatly improved, and the carbon content in the carbon Combined Processing process is controlled easily simultaneously.
3) this preparation technology is simple, and is easy to control, easily realizes industrialization.
Description of drawings
Fig. 1 is the XRD figure spectrum of embodiment 1～embodiment 4, and wherein a curve is LiTi among the embodiment 1
2(PO
4)
3The XRD figure spectrum of material, the b curve is LiTi among the embodiment 1
2(PO
4)
3The XRD figure spectrum of/C material, the c curve is LiTi among the embodiment 2
2(PO
4)
3The XRD figure spectrum of/C material, the d curve is LiTi among the embodiment 3
2(PO
4)
3The XRD figure spectrum of/C material, the e curve is LiTi among the embodiment 4
2(PO
4)
3The XRD figure spectrum of/C material.
Fig. 2 is LiTi among the embodiment 1
2(PO
4)
3The HRTEM photo of/C material.
Fig. 3 is the first charge-discharge curve under the prepared material 0.1C multiplying power of embodiment 1～embodiment 4, and voltage range 1.5～3.5V, electrolyte are 1mol/L LiPF
6Equal-volume than ethylene carbonate (EC), dimethyl carbonic ether (DMC) solution, probe temperature is 25 ℃ ± 0.5 ℃.Wherein a curve is LiTi among the embodiment 1
2(PO
4)
3The material charging and discharging curve, b, c, d, the e curve is respectively embodiment 1,2, LiTi in 3,4
2(PO
4)
3The charging and discharging curve of/C material.
Fig. 4 is embodiment 1 prepared LiTi
2(PO
4)
3The charging and discharging curve of/C material under 0.1C, 0.5C and 1C multiplying power, voltage range 1.5～3.5V, electrolyte are 1mol/L LiPF
6Equal-volume than ethylene carbonate (EC), dimethyl carbonic ether (DMC) solution, probe temperature is 25 ℃ ± 0.5 ℃.
Fig. 5 is embodiment 1 prepared LiTi
2(PO
4)
3The cycle performance of/C material under 0.1C, 0.5C and 1C multiplying power fills curve, and voltage range 1.5～3.5V, electrolyte are 1mol/L LiPF
6Equal-volume than ethylene carbonate (EC), dimethyl carbonic ether (DMC) solution, probe temperature is 25 ℃ ± 0.5 ℃.
Embodiment
Embodiment 1
With LiH
2PO
4, TiO
2And NH
4H
2PO
4Press Li: Ti: P=1: 2: 3 stoichiometric proportion weighing batch mixing as dispersant, is blended in that the rotating speed ball milling with 300r/min mixed in 12 hours on the planetary ball mill with absolute ethyl alcohol at 5: 1 by ball material mass ratio.Compound 80 ℃ stir down dry back in box type furnace with 5 ℃/min be warming up to 950 ℃ of constant temperature calcinings after 12 hours stove in slow cooling obtain white LiTi to room temperature
2(PO
4)
3Particle, its XRD figure spectrum are seen among Fig. 1 shown in a curve.
With synthetic pure LiTi
2(PO
4)
3Mix with an amount of glucose (by mass ratio 1: 0.1) weighing, on the planetary ball mill with the rotating speed ball milling of 300r/min after 12 hours at N
2Protection down with 5 ℃/min be warming up to 700 ℃ of constant temperature calcinings after 6 hours in the stove slow cooling to room temperature obtain LiTi
2(PO
4)
3/ C target product, its XRD figure spectrum see among Fig. 1 that shown in the b curve, Fig. 2 has provided its HRTEM photo.Record that carbon content is 2.39% in the gained composite material.
LiTi with example 1 gained
2(PO
4)
3And LiTi
2(PO
4)
3/ C material is made electrode as follows.
With organic solvent 1-methyl-2 pyrrolidones (NMP) is solvent, after the electrode material, conductive agent (acetylene black) and the binding agent Kynoar (PVDF) that prepare pressed 75: 15: 10 mixing and stirring of mass ratio, being evenly coated in diameter is on the aluminum foil current collector of 14mm, 75 ℃ of oven dry in drying box, use the tablet press machine compacting then evenly, make electrode slice to be measured.Adopt the button type simulated battery that prepared electrode slice is carried out the battery assembling.Be metal lithium sheet to electrode wherein, barrier film is the Celgard2325 composite membrane, and electrolyte is 1mol/L LiPF
6Equal-volume than ethylene carbonate (EC), dimethyl carbonic ether (DMC) solution, battery pack is contained in the glove box that is full of argon gas and finishes.The battery of being adorned is done the constant current charge-discharge test between 1.5～3.5V voltage range.Fig. 3 has provided the first charge-discharge curve (1C=138mAh/g) of gained battery in the 0.1C multiplying power, and a is LiTi pure in the example 1
2(PO
4)
3Material charging and discharging curve, b are LiTi in the example 1
2(PO
4)
3The charging and discharging curve of/C material.Fig. 4 has provided LiTi in the example 1
2(PO
4)
3The charging and discharging curve of/C material under 0.1C, 0.5C and 1C different multiplying.Fig. 5 has provided LiTi in the example 1
2(PO
4)
3The cycle performance curve of/C material under 0.1C, 0.5C and 1C multiplying power.LiTi in the example 1
2(PO
4)
3The discharge capacity of/C material under 0.1C and 1C multiplying power reached 131mAh/g and 91.3mAh/g.Identical therewith in following examples.
Embodiment 2:
With Li
2CO
3, TiO
2And NH
4H
2PO
4Press Li: Ti: P=1: 2: 3 stoichiometric proportion weighing batch mixing as dispersant, is blended in that the rotating speed ball milling with 300r/min mixed in 12 hours on the planetary ball mill with absolute ethyl alcohol at 5: 1 by ball material mass ratio.Compound 80 ℃ stir down dry back in box type furnace with 5 ℃/min be warming up to 950 ℃ of constant temperature calcinings after 16 hours stove in slow cooling obtain white LiTi to room temperature
2(PO
4)
3Particle.With synthetic pure LiTi
2(PO
4)
3Mix with an amount of glucose (by mass ratio 1: 0.1) weighing, on the planetary ball mill with the rotating speed ball milling of 300r/min after 12 hours at N
2Protection down with 5 ℃/min be warming up to 700 ℃ of constant temperature calcinings after 6 hours in the stove slow cooling to room temperature obtain LiTi
2(PO
4)
3/ C target product, its XRD figure spectrum are seen among Fig. 1 shown in the c curve.Method by embodiment 1 prepares electrode slice, LiTi
2(PO
4)
3/ C material is assembled into behind the battery with the 0.1C rate charge-discharge, and its first charge-discharge curve is seen the c curve among Fig. 3, and the reversible first charge/discharge capacity of mensuration is 127mAh/g.
Embodiment 3:
With LiOH, TiO
2And NH
4H
2PO
4Press Li: Ti: P=1: 2: 3 stoichiometric proportion weighing batch mixing as dispersant, is blended in that the rotating speed ball milling with 300r/min mixed in 12 hours on the planetary ball mill with absolute ethyl alcohol at 5: 1 by ball material mass ratio.Compound 80 ℃ stir down dry back in box type furnace with 5 ℃/min be warming up to 1000 ℃ of constant temperature calcinings after 12 hours stove in slow cooling obtain white LiTi to room temperature
2(PO
4)
3Particle.With synthetic pure LiTi
2(PO
4)
3Mix with an amount of starch (by mass ratio 1: 0.1) weighing, on the planetary ball mill with the rotating speed ball milling of 300r/min after 12 hours at N
2Protection down with 5 ℃/min be warming up to 600 ℃ of constant temperature calcinings after 6 hours in the stove slow cooling to room temperature obtain LiTi
2(PO
4)
3/ C target product, its XRD figure spectrum are seen among Fig. 1 shown in the d curve.Method by embodiment 1 prepares electrode slice, LiTi
2(PO
4)
3/ C material is assembled into behind the battery with the 0.1C rate charge-discharge, and its first charge-discharge curve is seen the d curve among Fig. 3, and the reversible first charge/discharge capacity of mensuration is 124mAh/g.
Embodiment 4:
With Li
2CO
3, TiO
2(NH
4)
2HPO
4Press Li: Ti: P=1: 2: 3 stoichiometric proportion weighing batch mixing as dispersant, is blended in that the rotating speed ball milling with 300r/min mixed in 12 hours on the planetary ball mill with absolute ethyl alcohol at 5: 1 by ball material mass ratio.Compound 80 ℃ stir down dry back in box type furnace with 5 ℃/min be warming up to 950 ℃ of constant temperature calcinings after 16 hours stove in slow cooling obtain white LiTi to room temperature
2(PO
4)
3Particle.With synthetic pure LiTi
2(PO
4)
3Mix with an amount of starch (by mass ratio 1: 0.1) weighing, on the planetary ball mill with the rotating speed ball milling of 300r/min after 12 hours at N
2Protection down with 5 ℃/min be warming up to 500 ℃ of constant temperature calcinings after 6 hours in the stove slow cooling to room temperature obtain LiTi
2(PO
4)
3/ C target product, its XRD figure spectrum are seen among Fig. 1 shown in the e curve.Method by embodiment 1 prepares electrode slice, LiTi
2(PO
4)
3/ C material is assembled into behind the battery with the 0.1C rate charge-discharge, and its first charge-discharge curve is seen the e curve among Fig. 3, and the reversible first charge/discharge capacity of mensuration is 113.3mAh/g.
Claims (9)
1. titanium phosphate lithium material that is used for lithium ion battery negative, it is characterized in that: the structure of titanium phosphate lithium is the NASICON structure, molecular formula is Li
xTi
2(PO
4)
3, wherein x is 1～1.05.
2. titanium phosphate lithium material according to claim 1 is characterized in that: the consisting of of described titanium phosphate lithium material: the content of the titanium phosphate lithium of NASICON structure is 90wt%～100wt%, and the content of carbon is 0-10wt%.
3. the preparation method of titanium phosphate lithium material according to claim 1 is characterized in that: may further comprise the steps:
1) preparation of former material precursor and mixing: with lithium-containing compound, titanium dioxide and phosphorus-containing compound stoichiometric proportion 1～1.05: 2: 3 ratio weighing in lithium, titanium, phosphorus; Press 5: 1 batch mixings of ball material mass ratio on planetary ball mill with the rotating speed ball milling of 150～300r/min 6～24 hours;
2) high-temperature roasting is handled: with the powdery presoma of step 1) gained constant temperature calcining 8～20 hours under 800 ℃～1000 ℃ temperature, natural cooling obtains the titanium phosphate lithium salts of white;
3) secondary ball milling: with step 2) 1: 0.2～0.02 weighing of pressing mass ratio of the titanium phosphate lithium salts of gained and organic substance mixes; On planetary ball mill, obtained the presoma of powdery in 6～24 hours with the rotating speed ball milling of 150～300r/min by 5: 1 batch mixings of ball material mass ratio;
4) after baking: the powdery presoma that secondary ball milling obtains is put into the high temperature furnace that is connected with inert atmosphere, and throughput is 10～60ml/min, and constant temperature calcining is 6～12 hours under 500 ℃～750 ℃ temperature; Treat to obtain titanium phosphate lithium-material with carbon element behind the natural cooling.
4. preparation method according to claim 3 is characterized in that: described lithium-containing compound is any in lithium carbonate, lithium hydroxide, lithium oxalate, lithium acetate, lithium dihydrogen phosphate or the lithium nitrate.
5. preparation method according to claim 3 is characterized in that: described titanium dioxide is any in rutile, anatase, three kinds of kenels of brockite.
6. preparation method according to claim 3 is characterized in that: described phosphorus-containing compound is any in lithium dihydrogen phosphate, ammonium dihydrogen phosphate, diammonium hydrogen phosphate or the ammonium phosphate.
7. preparation method according to claim 3 is characterized in that: described organic substance is hydrocarbon oxygen compound or hydrocarbon.
8. preparation method according to claim 7 is characterized in that: described organic substance is one or more in glucose, starch, the sucrose.
9. preparation method according to claim 3 is characterized in that: described inert gas is nitrogen or argon gas.
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