CN102646823A - Lithium titanate cathode material and method for preparing same, and battery produced by employing same - Google Patents
Lithium titanate cathode material and method for preparing same, and battery produced by employing same Download PDFInfo
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- CN102646823A CN102646823A CN2012101542732A CN201210154273A CN102646823A CN 102646823 A CN102646823 A CN 102646823A CN 2012101542732 A CN2012101542732 A CN 2012101542732A CN 201210154273 A CN201210154273 A CN 201210154273A CN 102646823 A CN102646823 A CN 102646823A
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- Prior art keywords
- lithium titanate
- anode material
- titanate anode
- lithium
- source
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 94
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 94
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 83
- 238000000034 method Methods 0.000 title abstract description 20
- 239000010406 cathode material Substances 0.000 title abstract description 7
- 229910052735 hafnium Inorganic materials 0.000 claims abstract description 13
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000000126 substance Substances 0.000 claims abstract description 11
- 239000010405 anode material Substances 0.000 claims description 56
- 239000010936 titanium Substances 0.000 claims description 29
- 239000000463 material Substances 0.000 claims description 28
- 239000011575 calcium Substances 0.000 claims description 27
- 238000005245 sintering Methods 0.000 claims description 24
- 239000002245 particle Substances 0.000 claims description 13
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 12
- 229910052791 calcium Inorganic materials 0.000 claims description 12
- 229910052751 metal Inorganic materials 0.000 claims description 9
- 239000002184 metal Substances 0.000 claims description 9
- 238000002360 preparation method Methods 0.000 claims description 9
- 229910052719 titanium Inorganic materials 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 7
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 6
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 6
- 239000001110 calcium chloride Substances 0.000 claims description 6
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 6
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 3
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 3
- 239000000428 dust Substances 0.000 claims description 3
- WOEQEDQNDRKHPV-UHFFFAOYSA-N ethanol;hafnium Chemical compound [Hf].CCO WOEQEDQNDRKHPV-UHFFFAOYSA-N 0.000 claims description 3
- 229910000449 hafnium oxide Inorganic materials 0.000 claims description 3
- WIHZLLGSGQNAGK-UHFFFAOYSA-N hafnium(4+);oxygen(2-) Chemical compound [O-2].[O-2].[Hf+4] WIHZLLGSGQNAGK-UHFFFAOYSA-N 0.000 claims description 3
- 239000000920 calcium hydroxide Substances 0.000 claims description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 2
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 12
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 9
- 229910001416 lithium ion Inorganic materials 0.000 description 9
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 8
- 230000004087 circulation Effects 0.000 description 8
- 239000000203 mixture Substances 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- 210000004027 cell Anatomy 0.000 description 6
- 239000003792 electrolyte Substances 0.000 description 6
- 102220043159 rs587780996 Human genes 0.000 description 5
- 239000000523 sample Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 238000005303 weighing Methods 0.000 description 5
- 230000008901 benefit Effects 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 230000014759 maintenance of location Effects 0.000 description 4
- 229910052596 spinel Inorganic materials 0.000 description 4
- 239000011029 spinel Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- 239000002202 Polyethylene glycol Substances 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 229920001223 polyethylene glycol Polymers 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 229910013553 LiNO Inorganic materials 0.000 description 2
- 229910013870 LiPF 6 Inorganic materials 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 229910010413 TiO 2 Inorganic materials 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000003213 activating effect Effects 0.000 description 2
- 239000005030 aluminium foil Substances 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000010955 niobium Substances 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 2
- QGHDLJAZIIFENW-UHFFFAOYSA-N 4-[1,1,1,3,3,3-hexafluoro-2-(4-hydroxy-3-prop-2-enylphenyl)propan-2-yl]-2-prop-2-enylphenol Chemical group C1=C(CC=C)C(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C(CC=C)=C1 QGHDLJAZIIFENW-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical group [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- -1 and therefore Substances 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- 230000000881 depressing effect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000003574 free electron Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 150000002602 lanthanoids Chemical class 0.000 description 1
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- VSZWPYCFIRKVQL-UHFFFAOYSA-N selanylidenegallium;selenium Chemical compound [Se].[Se]=[Ga].[Se]=[Ga] VSZWPYCFIRKVQL-UHFFFAOYSA-N 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 238000003836 solid-state method Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- JBQYATWDVHIOAR-UHFFFAOYSA-N tellanylidenegermanium Chemical compound [Te]=[Ge] JBQYATWDVHIOAR-UHFFFAOYSA-N 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 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
Abstract
The invention provides a lithium titanate cathode material and a method for preparing the same, and a battery produced by employing the same. The chemical formula of the lithium titanate cathode material is as follows: Li4-xCaxTi5-yHfyO12, wherein x is greater than or equal to 0.01 and less than or equal to 0.05, and y is greater than or equal to 0.001 and less than or equal to 0.01. The lithium titanate cathode material is added with calcium element so that the electric conductivity of the battery is improved; besides, hafnium is added to inhibit grain growth; therefore, the rate capability of the lithium titanate cathode material is improved; and the problems of poor electric conductivity and unsatisfactory electrochemical properties of the lithium titanate cathode material are solved.
Description
Technical field
The present invention relates to lithium ion battery, ultracapacitor field, especially, relate to a kind of lithium titanate anode material and preparation method.In addition, the invention still further relates to a kind of battery that adopts above-mentioned negative material to make.
Background technology
Along with the exhaustion day by day of fossil energy and increasingly sharpening of environmental pollution, the source problem that comes of automobile power receives unprecedented concern.The power supply of mobile electronic device adopts lithium ion battery usually at present, and it is the electric automobile energy supply that this battery can be used as ultracapacitor simultaneously.But it is negative pole for anodal, material with carbon element that existing commercialization lithium ion battery adopts cobalt acid lithium or nickel-cobalt-manganese ternary material usually, if the pairing of this both positive and negative polarity is applied on the electrokinetic cell, will produce very big safety problem.In the continuous charge and discharge process of electrokinetic cell, lithium ion probably forms Li dendrite at carbon material surface, thereby diaphragm causes battery short circuit.A kind of novel lithium ionic cell cathode material lithium titanate becomes the focus of research gradually at present; It has plurality of advantages: (1) embeds at lithium ion that crystal structure can keep the stability of height in the process of deviating from, and makes it have good cycle performance and discharge voltage stably; (2) have higher relatively electrode voltage (1.55V), this makes this electrode material in the electrolytical burning voltage of most liquid interval, to use, thereby has avoided the generation of electrolyte decomposition phenomenon or protective layer; (3) Li
4Ti
5O
12Platform appears in voltage when being charged to spinel structure and rock salt structure two-phase section, utilizes this point, can be used as the indication that charging finishes; (4) Li
4Ti
5O
12Chemical diffusion coefficient at normal temperatures is 2 * 10
-8Cm
2S
-1, than big 1 one magnitude of carbon negative pole material, charge-discharge velocity is very fast.
But lithium ion battery must possess macroion conductivity and electron conduction simultaneously if possess good electrochemical.The spinel structure of lithium titanate is that lithium ion provides good three-dimensional channel, and lithium ion conductivity is quite high; But the electronic conductivity of lithium titanate material is then very poor.Prior art is being improved on the lithium titanate conductivity, adopts two kinds of methods basically: (1) is other element that in lithium titanate anode material, mixes, as; Sodium (Na), magnesium (Mg), zinc (Zn), tantalum (Ta), niobium (Nb), zirconium (Zr), copper (Cu), chromium (Cr), nickel (Ni), manganese (Mn), yttrium (Y) and some thuliums (group of the lanthanides); (2) surface carbon coats.Though above method can solve the problem of lithium titanate material electronic conductance rate variance to a certain extent, its chemical property is still undesirable.
Summary of the invention
The battery that the object of the present invention is to provide this negative material of a kind of lithium titanate anode material and preparation method and employing to make is to solve lithium titanate material electronic conductance rate variance, the unfavorable problem of chemical property.
For realizing above-mentioned purpose, one side of the present invention provides a kind of lithium titanate anode material, and the chemical formula of above-mentioned lithium titanate anode material is: Li
4-xCa
xTi
5-yHf
yO
12, wherein, 0.01≤x≤0.05,0.001≤y≤0.01.
Further, scope 0.015≤x≤0.03 of X, scope 0.0015≤y≤0.005 of Y.
Further, X=0.02, Y=0.002.
Further, the particle diameter of lithium titanate anode material is 1 ~ 5 μ m.
Another aspect of the present invention also provides a kind of preparation method of lithium titanate anode material, may further comprise the steps: with the titanium source, and the lithium source, calcium source and hafnium source obtain first material after mixing; First material is carried out sintering obtain second material; Second material is pulverized, disperseed, obtain lithium titanate anode material.
Further, the calcium source is a kind of or any kind in calcium carbonate, calcium hydroxide, the calcium chloride.
Further, the hafnium source is a kind of or any kind of Hf metal dust, hafnium oxide or ethanol hafnium.
Another aspect of the present invention also provides a kind of battery, and this battery adopts above-mentioned lithium titanate anode material as negative material.
The present invention has following beneficial effect:
The present invention makes lithium titanate anode material have excellent high rate performance, excellent conducting performance through doping calcium, two kinds of elements of hafnium, has the cycle performance excellence; High repeatability and other advantages; And cost of material is cheap, and preparation technology is simple, is fit to industrial-scale production.
Except top described purpose, feature and advantage, the present invention also has other purpose, feature and advantage.To do further detailed explanation to the present invention with reference to figure below.
Description of drawings
The accompanying drawing that constitutes the application's a part is used to provide further understanding of the present invention, and illustrative examples of the present invention and explanation thereof are used to explain the present invention, do not constitute improper qualification of the present invention.In the accompanying drawings:
Fig. 1 is 50 circulation volume resolution charts of preferred embodiment of the present invention product;
Fig. 2 is the high rate performance curve chart of preferred embodiment of the present invention product;
Fig. 3 is the X-ray diffracting spectrum of preferred embodiment of the present invention product;
Fig. 4 is the stereoscan photograph of preferred embodiment of the present invention product;
Fig. 5 is the particle size distribution figure of preferred embodiment of the present invention product.
Embodiment
Below in conjunction with accompanying drawing embodiments of the invention are elaborated, but the multitude of different ways that the present invention can be defined by the claims and cover is implemented.
One aspect of the present invention provides a kind of lithium titanate anode material, adopts calcium constituent (Ca
2+) and hafnium element (Hf) be entrained in simultaneously in the lithium titanate, obtaining chemical formula is Li
4-xCa
xTi
5-yHf
yO
12Chemicals, wherein, 0.01≤x≤0.05,0.001≤y≤0.01.Ca
2+Replace the lithium ion (Li that is positioned at tetrahedron or octahedral voids
+), generate excess electron, make free electron concentration raise, thereby improve the electronic conductivity of lithium titanate.
Hf and titanium (Ti) are positioned at same subgroup, and electron configuration is arranged similar with Ti, and therefore, chemical property is comparatively similar, can occupy the octahedral voids of Ti atom.The purpose that Hf partly replaces Ti mainly is to form defective, suppresses the further growth of crystal grain, obtains monodispersed particle, thereby reduces Li
+With the migration path of electronics, make electrolyte soak into electrode material fully, improve high rate performance.
The scope of X: 0.01≤x≤0.05 wherein; The scope of Y: 0.001≤y≤0.01.If X or Y's is too small, then the concentration of calcium or hafnium is low excessively, the uniformity of calcium and hafnium in the very difficult assurance doping process, and concentration is low excessively simultaneously, can obviously not improve chemical property; X or Y's is excessive, then can influence Li
4Ti
5O
12Original cubic spinel structure, thus Li influenced
4Ti
5O
12Stability of structure in discharge process, and reduce its specific discharge capacity.
When the scope of X is 0.015≤x≤0.03, the scope of Y is 0.0015≤y≤0.005 o'clock, and the battery performance of resulting lithium titanate anode material assembling is excellent, good cycle, and specific discharge capacity is high.
When X is 0.02, Y is 0.002 o'clock, and lithium titanate anode material is Li
3.98Ca
0.02Ti
4.998Hf
0.002O
12The battery of this negative material assembling, specific discharge capacity is the highest, and 500 times circulation back 1C discharge capacity still can reach 150mAh/g, and cycle performance is best.
The particle diameter of lithium titanate anode material is 1 ~ 5 μ m.The particle diameter of lithium titanate anode material is too high or too low, all can influence the chemical property of lithium titanate anode material.
According to molecular formula Li
4-xCa
xTi
5-yHf
yO
12, can calculate the titanium source through this formula of quality=molal weight * molecular weight, lithium source, calcium source, the weight that feeds intake in hafnium source.
Another aspect of the present invention also provides a kind of preparation method of lithium titanate anode material, may further comprise the steps:
Mix: with the titanium source, the lithium source, calcium source and hafnium source obtain first material after mixing.
Sintering: first material is carried out sintering obtain second material.
Pulverize: second material is pulverized, disperseed, obtain lithium titanate anode material.
Detitanium-ore-type (TiO is adopted in the titanium source
2), metatitanic acid (H
2TiO
3), rutile-type (TiO
2), isopropyl titanate Ti{OCH (CH
3)
2}
4In a kind of or any kind.
Lithium carbonate (Li is adopted in the lithium source
2CO
3), lithium hydroxide (LiOH), lithium hydroxide (LiOHH
2O), lithium acetate (CH
3COOLi) a kind of or any kind in.
Calcium carbonate (CaCO is adopted in the calcium source
3), calcium hydroxide (Ca (OH)
2), a kind of or any kind in the calcium chloride (CaCl).
Hf metal dust, hafnium oxide (HfO are adopted in the hafnium source
2), ethanol hafnium Hf (OC
2H
5)
4A kind of or any kind.
Synthetic lithium titanate Li
4-xCa
xTi
5-yHf
yO
12Adopt the operation of conventional high temperature solid-state method or sol-gal process.
Blend step adopts conventional doing to mix or the mode of wet mixing is operated, and charging sequence is: add the titanium source compound earlier, add Li source compound again, add calcium source and hafnium source at last.
Sintering step adopts full-automatic air electricity pushed bat kiln to carry out sintering, and push pedal speed is 10 ~ 50min/ push pedal.Bubbling air in burner hearth, each warm area throughput is 4 ~ 20L/min.Sintering temperature is 650 ~ 900 ℃.Burner hearth has 10 warm areas, and temperature rises gradually.Main warm area temperature is sintering temperature.
Material disperseed after pulverising step adopted conventional crushing operation to sintering.
Another aspect of the present invention also provides a kind of battery, and this battery adopts above-mentioned lithium titanate anode material as negative material.Above-mentioned lithium titanate anode material and metal lithium sheet are formed half-cell; Lithium titanate activating agent, binding agent, conductive black are 91: 5: 4 inputs according to mass ratio; Drip N-methyl pyrrolidone (NMP) solvent, after fully grinding slurry evenly is coated on the aluminium foil, 120 ℃ of following vacuumize 12 hours; Stamp out the electrode slice of required area then, with electrolyte lithium hexafluoro phosphate (LiPF
6) be dissolved in the mixed solution of the ethylene carbonate that volume ratio is 1:1 (EC) and dimethyl carbonate (DMC) and form electrolyte, concentration is 1mol/L, in glove box, accomplishes the assembling of CR2032 button cell.Binding agent is Kynoar (PVDF).
Embodiment
Following examples specimen in use and instrument are commercially available.
The detection of conductivity: respectively with the lithium titanate anode material of embodiment 1 ~ 5.
Embodiment 1: according to molecular formula Li
3.98Ca
0.02Ti
4.998Hf
0.002O
12Stoichiometric proportion, take by weighing 39.91kg Detitanium-ore-type TiO
2, the Li of 14.70kg
2CO
3, the CaCO of 0.20kg
3, the HfO of 0.042kg
2, in the 100L dry mixer, mix; Mix back entering fully automatic electric ejection plate kiln and carry out 750 ℃ of sintering; Sintering adopts the staged temperature schedule, and the temperature settings of different warm areas is (250 ℃ of 1 warm areas, 350 ℃ of 2 warm areas; 450 ℃ of 3 warm areas; 550 ℃ of 4 warm areas, 600 ℃ of 5 warm areas, 6 to 10 warm areas are 750 ℃) push pedal speed is the 20min/ push pedal; Sintering utilizes airslide disintegrating mill to pulverize after accomplishing, and regulates and pulverizes and value parameter, and making and pulverizing air pressure is 0.5MPa, and the feeding frequency is 40Hz, and the grading wheel frequency is 90Hz, obtains grain and is the lithium titanate anode material of D50=1.5 μ m.
Negative material and the metal lithium sheet of embodiment 1 are formed half-cell; Lithium titanate activating agent, PVDF, conductive black are 91: 5 by mass ratio:: 4 add; Drip an amount of nmp solvent, slurry evenly is coated on the aluminium foil 120 ℃ of following vacuumize 12h after fully grinding; Stamp out the electrode slice of required area then, with electrolyte LiPF
6Be dissolved in the mixed solution of EC that volume ratio is 1:1 and DMC and form electrolyte, concentration is 1mol/L, in glove box, accomplishes the assembling of CR2032 button cell.
Process the constant current charge-discharge behavior behind the battery through the lithium titanate anode material in the LAND charge-discharge test appearance test implementation example 1; First discharge specific capacity (0.1C) is 170.1mAh/g; The 6C discharge capacity can reach 145mAh/g; The 20C capacity reaches 130mAh/g, and 500 circulation back 1C discharge capacities still can reach 150mAh/g.
Lithium titanate anode material among the embodiment 1 is placed the piston type compression mold, and depressing to diameter at 20Mpa pressure is 1.5cm, and thickness is the disk of 1cm.Adopt four probe method to measure the resistivity of zones of different on the disk, the resistivity on the same disk is averaged, and mean value is got the conductivity that inverse obtains lithium titanate anode material.The conductivity of lithium titanate anode material is 1.48 * 10 among the embodiment 1
-3Scm
-1
Lithium titanate anode material among the embodiment 1 processed carry out 50 cycle discharge specific capacities tests behind the battery, the result is as shown in Figure 1, and the current density of 1,2 circulation (cyc) is 0.1C among the figure; 3,4cyc is 0.2C, and 5cyc is 0.5C; 6cyc is 0.8C, and 7cyc is 1C, and 8cyc is 2C; 9cyc is 5C, and 10cyc is 10C, and 11cyc all is later the 1C discharge.Can know that from Fig. 1 the lithium titanate capacity is almost undamped in cyclic process.Lithium titanate anode material among the embodiment 1 processed carry out the high rate performance test behind the battery, the result is as shown in Figure 2, and it is very good that the lithium titanate voltage platform keeps.Lithium titanate anode material among the embodiment 1 is carried out X-ray diffraction, and the result is as shown in Figure 3, and the lithium titanate anode material of embodiment 1 is pure spinel structure, visible a small amount of miscellaneous growth that can not influence the lithium titanate crystal.Lithium titanate anode material among the embodiment 1 is carried out electron-microscope scanning, and the result is as shown in Figure 4, and the lithium titanate anode material of the embodiment of the invention 1 is that monodispersed submicron particles is formed.Lithium titanate anode material among the embodiment 1 is carried out particle size distribution test, and the result is as shown in Figure 5, and the lithium titanate anode material particle diameter particle size distribution of the embodiment of the invention 1 is comparatively concentrated, is normal distribution.
Embodiment 2: according to molecular formula Li
3.95Ca
0.05Ti
4.999Hf
0.001O
12Stoichiometric proportion, take by weighing the TiO (OH) of 48.93kg
2, the CH of 13.03kg
3COOLi, the Ca of 3.70kg (OH)
2, the Hf (OC of 0.21kg
2H
5)
4, press the solid-liquid volume ratio and add deionized water at 3: 1, and add the 0.62kg polyethylene glycol, in duplicate rows star power mixer, mix; Carrying out drying under reduced pressure after mixing and remove solvent, pressure is-0.08 ~-0.09MPa; Entering fully automatic electric ejection plate kiln carries out 700 ℃ of sintering after being dried to powder, and push pedal speed is the 25min/ push pedal.Sintering adopts the staged temperature schedule; The temperature settings of different warm areas is (250 ℃ of 1 warm areas, 300 ℃ of 2 warm areas, 400 ℃ of 3 warm areas; 500 ℃ of 4 warm areas; 600 ℃ of 5 warm areas, 6 to 10 warm areas are 700 ℃) sintering carries out pulverising step (revolution rotating speed: 200 rev/mins of rotation rotating speeds: 600 rev/mins), obtain the lithium titanate anode material that suitable particle size is D50=1.5 μ m after accomplishing.
This sample and metal lithium sheet are formed half-cell, accomplish the battery assembling according to the method for embodiment 1.The constant current charge-discharge behavior of the lithium battery through the assembling of the lithium titanate anode material in the LAND charge-discharge test appearance test implementation example 2, first discharge specific capacity (0.1C) be 168mAh/g, 500 circulations afterwards capability retention are 89.8%.
Lithium titanate anode material among the embodiment 2 is carried out conductivity according to the method for embodiment 1 detect, its conductivity is 5.32 * 10
-3Scm
-1
Embodiment 3: according to molecular formula Li
3.97Ca
0.03Ti
4.9985Hf
0.0015O
12Stoichiometric proportion, take by weighing the TiO (OH) of 48.92kg
2, the CH of 13.10kg
3COOLi, the Ca of 0.22kg (OH)
2, the Hf (OC of 0.54kg
2H
5)
4Press the solid-liquid volume ratio and add deionized water at 3: 1, and add the 0.62kg polyethylene glycol, in duplicate rows star power mixer, mix; Carrying out drying under reduced pressure after mixing and remove solvent, pressure is-0.08 ~-0.09MPa; Entering fully automatic electric ejection plate kiln carries out 800 ℃ of sintering after being dried to powder, and push pedal speed is the 15min/ push pedal.Sintering adopts the staged temperature schedule; The temperature settings of different warm areas is (300 ℃ of 1 warm areas, 400 ℃ of 2 warm areas, 500 ℃ of 3 warm areas; 600 ℃ of 4 warm areas; 700 ℃ of 5 warm areas, 6 to 10 warm areas are 800 ℃) sintering carries out pulverising step (revolution rotating speed: 200 rev/mins of rotation rotating speeds: 600 rev/mins), obtain the lithium titanate anode material that suitable particle size is D50=1.5 μ m after accomplishing.
This sample and metal lithium sheet are formed half-cell, accomplish the battery assembling according to the method for embodiment 1.The constant current charge-discharge behavior of the lithium battery through the assembling of the lithium titanate anode material in the LAND charge-discharge test appearance test implementation example 3, first discharge specific capacity (0.1C) be 169.3mAh/g, 500 circulations afterwards capability retention are 90.2%.
Lithium titanate anode material among the embodiment 3 is carried out conductivity according to the method for embodiment 1 detect, its conductivity is 3.65 * 10
-5Scm
-1
Embodiment 4: according to molecular formula Li
3.985Ca
0.015Ti
4.995Hf
0.005O
12Stoichiometric proportion, take by weighing the Ti{OCH (CH of 141.97kg
3)
2}
4, the LiNO of 13.74kg
3, the CaCl of 0.17kg
2, the Hf (OC of 0.18kg
2H
5)
4Press the solid-liquid volume ratio and add deionized water at 3: 1, and add the 0.62kg polyethylene glycol, in duplicate rows star power mixer, mix; Carrying out drying under reduced pressure after mixing and remove solvent, pressure is-0.08 ~-0.09MPa; Entering fully automatic electric ejection plate kiln carries out 900 ℃ of sintering after being dried to powder, and push pedal speed is the 10min/ push pedal.Sintering adopts the staged temperature schedule; The temperature settings of different warm areas is (250 ℃ of 1 warm areas, 300 ℃ of 2 warm areas, 400 ℃ of 3 warm areas; 500 ℃ of 4 warm areas; 600 ℃ of 5 warm areas, 6 to 10 warm areas are 700 ℃) sintering carries out pulverising step (revolution rotating speed: 200 rev/mins of rotation rotating speeds: 600 rev/mins), obtain the lithium titanate anode material that suitable particle size is D50=1.5 μ m after accomplishing.
This sample and metal lithium sheet are formed half-cell, accomplish the battery assembling according to the method for embodiment 1.The constant current charge-discharge behavior of the lithium battery through the assembling of the lithium titanate anode material in the LAND charge-discharge test appearance test implementation example 4.First discharge specific capacity (0.1C) is 171.6mAh/g, and 500 times circulation back capability retention is 89.0%.
Lithium titanate anode material among the embodiment 4 is carried out conductivity according to the method for embodiment 1 detect, its conductivity is 5.85 * 10
-4Scm
-1
Embodiment 5: according to molecular formula Li
3.99Ca
0.01Ti
4.99Hf
0.01O
12Stoichiometric proportion, take by weighing 141.8kg isopropyl titanate Ti{OCH (CH
3)
2}
4, the LiNO of 13.8kg
3, the CaCl of 0.11kg
2, the Hf (OC of 0.359kg
2H
5)
4, add a certain amount of deionized water, form gel, aging 3h.After this in baking oven, carry out 120 ℃ of oven dry, ball milling.After this drop into the fully automatic electric ejection plate kiln and carry out sintering for 650 ℃, push pedal speed is the 24min/ push pedal; Sintering adopts the staged temperature schedule, and the temperature settings of different warm areas is (150 ℃ of 1 warm areas, 200 ℃ of 2 warm areas; 350 ℃ of 3 warm areas, 450 ℃ of 4 warm areas, 550 ℃ of 5 warm areas; 6 to 10 warm areas are 650 ℃), after accomplishing, sintering obtains the lithium titanate anode material of granularity D50=1.8 μ m.
This sample and metal lithium sheet are formed half-cell, accomplish the assembling of CR2032 button cell according to the method for embodiment 1.The constant current charge-discharge behavior of the lithium battery through the assembling of the lithium titanate anode material in the LAND charge-discharge test appearance test implementation example 5, first discharge specific capacity (0.1C) be 170mAh/g, 500 circulations afterwards capability retention are 88.2%.
Lithium titanate anode material among the embodiment 5 is carried out conductivity according to the method for embodiment 1 detect, its conductivity is 2.17 * 10
-4Scm
-1
The above is merely the preferred embodiments of the present invention, is not limited to the present invention, and for a person skilled in the art, the present invention can have various changes and variation.All within spirit of the present invention and principle, any modification of being done, be equal to replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (8)
1. a lithium titanate anode material is characterized in that, the chemical formula of said lithium titanate anode material is: Li
4-xCa
xTi
5-yHf
yO
12, wherein, 0.01≤x≤0.05,0.001≤y≤0.01.
2. lithium titanate anode material according to claim 1 is characterized in that, scope 0.015≤x≤0.03 of said X, scope 0.0015≤y≤0.005 of said Y.
3. lithium titanate anode material according to claim 2 is characterized in that, said X=0.02, said Y=0.002.
4. according to each described lithium titanate anode material among the claim 1-3, it is characterized in that the particle diameter of said lithium titanate anode material is 1 ~ 5 μ m.
5. the preparation method of a lithium titanate anode material is characterized in that, may further comprise the steps:
With the titanium source, the lithium source, calcium source and hafnium source obtain first material after mixing;
First material is carried out sintering obtain second material;
Second material is pulverized, disperseed, obtain each said lithium titanate anode material in the claim 1 ~ 4.
6. preparation method according to claim 5 is characterized in that, said calcium source is a kind of or any kind in calcium carbonate, calcium hydroxide, the calcium chloride.
7. preparation method according to claim 5 is characterized in that, said hafnium source is a kind of or any kind of Hf metal dust, hafnium oxide or ethanol hafnium.
8. a battery is characterized in that, each described lithium titanate anode material is as negative material in the said battery employing claim 1 ~ 4.
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| CN102983319A (en) * | 2012-12-18 | 2013-03-20 | 上海纳米技术及应用国家工程研究中心有限公司 | Modified lithium titanate material and preparation method thereof |
| CN103208650A (en) * | 2013-04-12 | 2013-07-17 | 北京石磊乾坤含氟新材料研究院有限责任公司 | Synthesis method and new application for potassium octafluoro hafnate |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101877407A (en) * | 2009-04-30 | 2010-11-03 | 比亚迪股份有限公司 | Cathode active material, preparation method thereof and battery |
| CN101960655A (en) * | 2008-03-04 | 2011-01-26 | 埃纳德尔公司 | Anode for lithium-ion cell and method of making the same |
| CN102376945A (en) * | 2010-08-20 | 2012-03-14 | 三星Sdi株式会社 | Negative active material, method of preparing same, and rechargeable lithium battery including same |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101960655A (en) * | 2008-03-04 | 2011-01-26 | 埃纳德尔公司 | Anode for lithium-ion cell and method of making the same |
| CN101877407A (en) * | 2009-04-30 | 2010-11-03 | 比亚迪股份有限公司 | Cathode active material, preparation method thereof and battery |
| CN102376945A (en) * | 2010-08-20 | 2012-03-14 | 三星Sdi株式会社 | Negative active material, method of preparing same, and rechargeable lithium battery including same |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102983319A (en) * | 2012-12-18 | 2013-03-20 | 上海纳米技术及应用国家工程研究中心有限公司 | Modified lithium titanate material and preparation method thereof |
| CN103208650A (en) * | 2013-04-12 | 2013-07-17 | 北京石磊乾坤含氟新材料研究院有限责任公司 | Synthesis method and new application for potassium octafluoro hafnate |
| CN103208650B (en) * | 2013-04-12 | 2014-12-31 | 北京石磊乾坤含氟新材料研究院有限责任公司 | Synthesis method and new application for potassium octafluoro hafnate |
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