CN102945960A - Template induction method for preparing lithium iron phosphate nano particles - Google Patents
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- CN102945960A CN102945960A CN2012104792566A CN201210479256A CN102945960A CN 102945960 A CN102945960 A CN 102945960A CN 2012104792566 A CN2012104792566 A CN 2012104792566A CN 201210479256 A CN201210479256 A CN 201210479256A CN 102945960 A CN102945960 A CN 102945960A
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Abstract
The invention discloses a template induction method for preparing lithium iron phosphate nano particles. The method comprises the steps of preprocessing silicon wafers to obtain hydroxylation silicon substrates; preparing 3-aminopropyl-trimethoxy silane (APTMS) membrane templates; subjecting the APTMS membrane template surfaces to amino in situ phosphorylation; and preparing the lithium iron phosphate nano particles. According to the template induction method for preparing lithium iron phosphate nano particles, the prepared lithium iron phosphate nano particles are high in purity and uniform in particle diameter. The method has the advantages of being abundant in material source, low in preparation process energy consumption, small in prepared nano particle size, non-toxic and the like.
Description
Technical field
The present invention relates to the method that a kind of masterplate revulsion prepares the LiFePO 4 nano particle, belong to the battery material field.
Background technology
Along with becoming increasingly conspicuous of the energy and environmental problem, clean energy resource receives much attention, and this has higher requirement to secondary power supply.Lithium ion battery is widely used in various portable type electronic products and communication tool as a kind of high performance secondary green battery.Olivine-type anode material for lithium-ion batteries LiFePO
4Have that raw material resources are abundant, inexpensive, nontoxic, the advantage such as environmental friendliness, theoretical capacity are high, thermal stability and good cycle, be the first-selected positive electrode of lithium ion battery.
But the diffusion velocity of lithium ion in this electrode material is slow, LiFePO
4Poor electric conductivity, the utilance of material is low, the rate charge-discharge poor performance of electrode has restricted the output of the large multiplying power of ferrousphosphate lithium material.At LiFePO
4Charge and discharge process in since crystal in PO
4 3-Limited Li
+Mobile space so that Li
+Embedding in material, the process of taking off only have two-dimentional mobility, so LiFePO
4Electronics, ionic conductivity all lower, under the condition of heavy-current discharge, have larger capacitance loss.For Li
+At LiFePO
4In embedding, off line reason, A. S. Andersson has proposed two kinds of possible charging and recharging model-radiation models (Radial Model) and mosaic model (Mosaic Model).Most of scientific research personnel think that two kinds of models exist simultaneously.From Li
+Embedding off line reason set out, at present to LiFePO
4Research work mainly launch from two aspects: on the one hand, control grain growth by different approaches, prepare uniform particle diameter, tiny material, the ionic conduction performance of strengthening material; On the other hand, on the basis of Optimization Technology, improve simultaneously electronics, the ionic conductivity of material by means such as crystalline phase doping, amorphous phase doping.
Therefore, LiFePO
4The nanometer of material makes its particle size reduce to a great extent, shortens the evolving path of lithium ion, improves LiFePO
4The chemical property of electrode.By the LiFePO 4 of preparation nano-scale, reducing its particle agglomeration is to improve the whole chemical property of LIB, improves one of effective ways of the large high rate performance of ferrousphosphate lithium material.
Recent domestic has been reported in a large number about distinct methods and has been synthesized, improved LiFePO
4Material.The less 1-100 μ m that is distributed in of particle size that sol-gel process and emulsification seasoning are synthetic, but because calcination process makes particle agglomeration or sintering degree larger, increased lithium ion in intragranular diffusion length, the conductivity of material and large multiplying power output performance do not have substantial improvement; Hydro thermal method is with FeSO
4, H
3PO
4, LiOH synthesizes granularity at the LiFePO of 50-100nm for 1:1:3 in molar ratio
4Particle, its size can drop to 50nm after adding surfactant softex kw (CTAB), but hydro thermal method needs high temperature high voltage resistant equipment, and the industrialization difficulty is larger.
Summary of the invention
Technical problem to be solved by this invention is to provide for above-mentioned prior art the method for the standby LiFePO 4 nano particle of a kind of template-mediated legal system, and dimensional controllability is high, prepared LiFePO 4 nano particle diameter homogeneous, and size is little.
The present invention solves the problems of the technologies described above the technical scheme that adopts:
The method of the standby LiFePO 4 nano particle of template-mediated legal system, it may further comprise the steps:
1) preliminary treatment of silicon chip: with silicon chip successively Ultrasonic Cleaning 5 ~ 15min in acetone, ultra-pure water, then put into Piranha solution and soak 30-60min in 60 ~ 100 ℃, take out silicon chip and wash with ultra-pure water, dry up with nitrogen again and obtain hydroxylated silicon-based substrates;
2) preparation of 3-aminopropyl-trimethoxy silane (APTMS) thin-film template: the ethanolic solution that the hydroxylated silicon-based substrates that step 1) is obtained is put into APTMS soaked 1-2 hour, successively with ethanol, ultra-pure water flushing, dry up with nitrogen again and obtain the APTMS self-assembled film after the taking-up;
3) the APTMS self-assembled film that APTMS self-assembled film surface amino groups original position phosphorylation: with step 2) obtains immerses and contains phosphorous oxychloride and 2,3, in the acetonitrile solution of 5-trimethylpyridine, room temperature reaction 20-90 minute, taking-up is washed with ultra-pure water, dries up the APTMS self-assembled film that obtains phosphorylation with nitrogen;
4) preparation of LiFePO 4 nano particle: the APTMS self-assembled film of the phosphorylation that step 3) is obtained immersed in the ultra-pure water solution that contains ferrous salt, phosphate, lithium salts reaction 5 minutes-60 minutes, then take out with the ultra-pure water flushing, nitrogen dries up and makes the LiFePO 4 nano particle.
Press such scheme, described silicon chip is the bulk of (1 ~ 2) cm * (1 ~ 2) cm * 0.5mm.
Press such scheme, the volume ratio of the concentrated sulfuric acid and hydrogen peroxide is 4:1 in the described Piranha solution.
Press such scheme, the APTMS volumetric concentration is 0.1%-2% in the ethanolic solution of described APTMS.
Press such scheme, the mol ratio of phosphorous oxychloride and 2,3,5-trimethylpyridine is 1:1 in the described acetonitrile solution of described step 3), and the triclosan oxidation phosphorus concentration is 0.05-0.8mol/L.
Press such scheme, the mol ratio of ferrous salt, phosphate, lithium salts is 1 ~ 2:1 ~ 2:3 ~ 6 in the solution of ultra-pure water described in the step 4), and ferrous salt concentration is 0.001-0.1mol/L.
Press such scheme, the described ferrous salt of described step 4), phosphate, lithium salts are respectively ferrous sulfate heptahydrate, diammonium hydrogen phosphate, Lithium hydroxide monohydrate.
Press such scheme, it is 20 ~ 50 ℃ that the APTMS self-assembled film immersion of the phosphorylation described in the step 4) contains the temperature of reacting in the ultra-pure water aqueous solution of ferrous salt, phosphate, lithium salts.
Compared with prior art, beneficial effect of the present invention is:
1) compares with traditional preparation method, the prepared LiFePO 4 nano-particles size controllability of the present invention is high, the AFM 3 dimensional drawing as a result scale ratio of the LiFePO 4 nano particle that makes of indicating template revulsion is more even, the degree of crystallization of particle and reunite less; Uniform particle diameter, size is little, detects to such an extent that average grain diameter is 10nm through AFM;
2) the present invention adopts the template-mediated method, its principle is to utilize chemisorbed or the chemical reaction of solid-liquid interface, form chemical bond by surface of solids adsorption activity material and connect, tend to the ordered molecular film that molecular recognition is high closely, prepare resulting LiFePO 4 nano particle product purity high;
3) preparation method's reaction temperature of the present invention is no more than 100 ℃, need not roasting and mechanical treatment, reaction temperature and, energy consumption is little;
4) raw material sources are abundant: preparation LiFePO
4The raw material of nano particle is basic industrial chemicals, is easy to obtain;
5) LiFePO of preparation
4The nano particle good combination property, Stability Analysis of Structures, security performance are good, nontoxic, non-secondary pollution.
Description of drawings
Fig. 1 is the contact angle figure of the hydroxylated silicon-based substrates for preparing of the embodiment of the invention 1;
Fig. 2 is the contact angle figure of the APTMS self-assembled film for preparing of the embodiment of the invention 1;
Fig. 3 is the APTMS self-assembled film infrared spectrogram that the embodiment of the invention 1 prepares;
Fig. 4 is the APTMS self-assembled film AFM figure that the embodiment of the invention 1 prepares;
Fig. 5 is the surface contact angle figure of the APTMS self-assembled film of the phosphorylation for preparing of the embodiment of the invention 2;
Fig. 6 is the infrared spectrogram of the APTMS self-assembled film of the phosphorylation for preparing of the embodiment of the invention 2;
Fig. 7 is the atomic force microscope figure of the APTMS self-assembled film of the phosphorylation for preparing of the embodiment of the invention 2;
Fig. 8 is the atomic force microscope figure of the lithium iron phosphate nano particle of the embodiment of the invention 3 preparations;
Fig. 9 is the atomic force microscope 3 dimensional drawing of the lithium iron phosphate nano particle of the embodiment of the invention 4 preparations;
Figure 10 is the xps energy spectrum figure of the lithium iron phosphate nano particle of the embodiment of the invention 4 preparations.
Embodiment
In order to understand better the present invention, further illustrate content of the present invention below in conjunction with embodiment, but the present invention not only is confined to the following examples.
Used 3-aminopropyl-trimethoxy silane (APTMS) is that Sigma aldrich company produces among the following embodiment, acetone is the huge chemical reagent factory production of Tianjin Dongli District, hydrogen peroxide is Tianjin Da Mao chemical reagent factory production, the concentrated sulfuric acid is produced for east, Kaifeng chemical reagent work of large chemical industry Co., Ltd, 2,3,5-trimethylpyridine, phosphorous oxychloride, acetonitrile, ferrous sulfate heptahydrate, lithium hydroxide, diammonium hydrogen phosphate are that Chemical Reagent Co., Ltd., Sinopharm Group produces.It is pure that above medicine is analysis.Ultrapure resistivity of water used in the experiment is not less than 18 MWcm.
Described in the following embodiment in the Piranha solution volume ratio of the concentrated sulfuric acid and hydrogen peroxide be 4:1.
The preliminary treatment of silicon chip: bulk silicon priority Ultrasonic Cleaning 5min in acetone, ultra-pure water that will cut into 1cm * 1cm * 0.5mm, then put into Piranha solution and soak 30min in 60 ℃, take out silicon chip and wash with ultra-pure water, dry up with nitrogen again and obtain hydroxylated silicon-based substrates;
The preparation of 3-aminopropyl-trimethoxy silane (APTMS) thin-film template: will soak through the ethanolic solution that the hydroxylated silicon-based substrates that above-mentioned steps obtains is put into volumetric concentration 0.2%APTMS and carry out self assembly in 1 hour, successively with ethanol, ultra-pure water flushing, dry up with nitrogen again and obtain the APTMS self-assembled film after the taking-up;
Accompanying drawing 1 is the contact angle figure of the hydroxylated silicon-based substrates for preparing of embodiment 1, and water droplet is drawout almost completely, and contact angle is very little.
Accompanying drawing 2 is contact angle figure of the APTMS self-assembled film for preparing of embodiment 1, and contact angle increases, and hydrophobicity obviously strengthens.
Accompanying drawing 3 is APTMS self-assembled film infrared spectrograms that embodiment 1 prepares, 1617 cm
-1Belong to the interior flexural vibrations absworption peak of N=H, 1107 cm
-1Be the characteristic absorption peak of C-N, 817 cm
-1Be the outside sweep vibration of N-H, 740 cm
-1Belong to the characteristic absorption peak of Si-C, position and the bibliographical information of each diffraction maximum are basically identical, show that APTMS successfully is assembled into hydroxylated silicon-based substrates surface.
Accompanying drawing 4 is APTMS self-assembled film AFM figure of embodiment 1 preparation, and the surface that can find out the APTMS self-assembled film is even compact very.
1) preliminary treatment of silicon chip: silicon chip priority Ultrasonic Cleaning 15min in acetone, ultra-pure water that will cut into 2cm * 2cm * 0.5mm, then put into Piranha solution and soak 60min in 100 ℃, take out silicon chip and wash with ultra-pure water, dry up with nitrogen again and obtain hydroxylated silicon-based substrates;
2) preparation of 3-aminopropyl-trimethoxy silane (APTMS) thin-film template: the hydroxylated silicon-based substrates that step 1) obtains is put into the 2%(volume fraction) ethanolic solution of APTMS soaks and carried out self assembly in 1-2 hour, successively with ethanol, ultra-pure water flushing, dry up with nitrogen again and obtain the APTMS self-assembled film after the taking-up;
3) the APTMS self-assembled film that APTMS self-assembled film surface amino groups original position phosphorylation: with step 2) obtains immerses and contains phosphorous oxychloride, 2,3, in the acetonitrile solution of 5-trimethylpyridine, wherein the mol ratio of phosphorous oxychloride and 2,3,5-trimethylpyridine is 1:1, the triclosan oxidation phosphorus concentration is: 0.1mol/L, behind the room temperature reaction 90 minutes, take out with the ultra-pure water flushing, dry up the APTMS self-assembled film that obtains phosphorylation with nitrogen;
Accompanying drawing 5 is surface contact angle figure of APTMS self-assembled film of the phosphorylation of embodiment 2 preparation, film surface-NH
2Group is gradually by-PO (OH)
2After group replaced, hydrophily strengthened, and drop is wetting film surface preferably.
Accompanying drawing 6 is infrared spectrograms of APTMS self-assembled film of the phosphorylation of embodiment 2 preparation, 1260cm
-1Belong to the stretching vibration of P=O; 1048cm
-1Belong to the antisymmetric stretching vibration of P-O; 950cm
-1, 653cm
-1Belong to the symmetrical stretching vibration of P-O; 577 cm
-1Be the flexural vibrations of O=P-O antisymmetry; 546cm
-1Be the vibration of O=P-O symmetric curvature; APTMS self-assembled film surface-NH
2Group is all by-PO (OH)
2Group replaces.
Accompanying drawing 7 is AFM figure of APTMS self-assembled film of the phosphorylation of embodiment 2 preparation, and roughness further reduces, the surface more even compact that becomes.
Embodiment 3
The method of the standby LiFePO 4 nano particle of template-mediated legal system, it may further comprise the steps:
1) preliminary treatment of silicon chip: be the silicon chip Ultrasonic Cleaning 10min in acetone, ultra-pure water successively of 1cm * 1cm * 0.5mm with size, then put into Piranha solution and soak 45min in 80 ℃, take out silicon chip and wash with ultra-pure water, dry up with nitrogen again and obtain hydroxylated silicon-based substrates;
2) preparation of 3-aminopropyl-trimethoxy silane (APTMS) thin-film template: the hydroxylated silicon-based substrates that step 1) obtains is put into the 0.5%(volume fraction) ethanolic solution of APTMS soaks and carried out self assembly in 1.5 hours, successively with ethanol, ultra-pure water flushing, dry up with nitrogen again and obtain the APTMS self-assembled film after the taking-up;
3) the APTMS self-assembled film that APTMS self-assembled film surface amino groups original position phosphorylation: with step 2) obtains immerses and contains phosphorous oxychloride and 2,3, in the acetonitrile solution of 5-trimethylpyridine, wherein the mol ratio of phosphorous oxychloride and 2,3,5-trimethylpyridine is 1:1, the triclosan oxidation phosphorus concentration is: 0.8mol/L, room temperature reaction 60 minutes takes out with the ultra-pure water flushing, dries up the APTMS self-assembled film that obtains phosphorylation with nitrogen;
4) preparation of LiFePO 4 nano particle: the APTMS self-assembled film of the phosphorylation that step 3) is obtained immerses and contains in the ultra-pure water aqueous solution of ferrous sulfate heptahydrate, diammonium hydrogen phosphate, Lithium hydroxide monohydrate, the mol ratio of ferrous sulfate heptahydrate, diammonium hydrogen phosphate, Lithium hydroxide monohydrate is 1:1:3 in the aqueous solution, ferrous sulfate heptahydrate concentration is 0.003mol/L, 35 ℃ of lower reactions 5 minutes, then take out with the ultra-pure water flushing, nitrogen dries up and makes the LiFePO 4 nano particle.
Accompanying drawing 8 is AFM plane graphs of the lithium iron phosphate nano particle of embodiment 3 preparations, and sweep limits is 2 um * 2um, and the lithium iron phosphate nano particle is evenly distributed in substrate surface, and coverage is large, and its average grain diameter is about 10 ± 1nm, and mean roughness is 1.127nm.
Embodiment 4
The method of the standby LiFePO 4 nano particle of template-mediated legal system, it may further comprise the steps:
1) preliminary treatment of silicon chip: be the silicon chip Ultrasonic Cleaning 15min in acetone, ultra-pure water successively of 2cm * 2cm * 0.5mm with size, then put into Piranha solution and soak 30min in 80 ℃, take out silicon chip and wash with ultra-pure water, dry up with nitrogen again and obtain hydroxylated silicon-based substrates;
2) preparation of 3-aminopropyl-trimethoxy silane (APTMS) thin-film template: the hydroxylated silicon-based substrates that step 1) obtains is put into the 0.2%(volume fraction) ethanolic solution of APTMS soaks and carried out self assembly in 1 hour, successively with ethanol, ultra-pure water flushing, dry up with nitrogen again and obtain the APTMS self-assembled film after the taking-up;
3) the APTMS self-assembled film that APTMS self-assembled film surface amino groups original position phosphorylation: with step 2) obtains immerses and contains phosphorous oxychloride and 2,3, in the acetonitrile solution of 5-trimethylpyridine, wherein the mol ratio of phosphorous oxychloride and 2,3,5-trimethylpyridine is 1:1, the triclosan oxidation phosphorus concentration is 0.6mol/L, room temperature reaction 90 minutes takes out with the ultra-pure water flushing, dries up the APTMS self-assembled film that obtains phosphorylation with nitrogen;
4) preparation of LiFePO 4 nano particle: the APTMS self-assembled film of the phosphorylation that step 3) is obtained immerses and contains in the ultra-pure water aqueous solution of ferrous sulfate heptahydrate, diammonium hydrogen phosphate, Lithium hydroxide monohydrate, the mol ratio of ferrous sulfate heptahydrate, diammonium hydrogen phosphate, Lithium hydroxide monohydrate is 1:1:3 in the aqueous solution, ferrous sulfate heptahydrate concentration is 0.01mol/L, 45 ℃ of lower reactions 60 minutes, then take out with the ultra-pure water flushing, nitrogen dries up and makes the LiFePO 4 nano particle.
Accompanying drawing 9 is AFM 3 dimensional drawings of the lithium iron phosphate nano particle of embodiment 4 preparations, can observe local particle and agglomeration occur, forms " island " formula structure, but most of particle is not reunited.
Accompanying drawing 10 is XPS spectrum figure of the lithium iron phosphate nano particle of embodiment 4 preparations.A among Figure 10, b, c, C1s among the d, O1s, P2p, Fe2p(Fe2p
1/2And Fe2p
3/2) respectively corresponding combination can be 284.6eV, 531.44eV, 133.31eV, 725.80eV, 711.80eV.Li1s peak and Fe3p peak are overlapping serious near 55.72eV among Figure 10 e, the existence that can't draw intuitively Li1s peak and elemental lithium.
Table 1 is the lithium iron phosphate nano particle samples XPS analysis initial data of the embodiment of the invention 4 preparations.
Table 2 is lithium iron phosphate nano particle samples XPS analysis initial data of the embodiment of the invention 4 preparations.
In conjunction with d, e figure and table 1 among Figure 10, if without elemental lithium, then XPS detects the Fe2p obtain and the molar content of Fe3p should equate.The molar content that shows Fe2p that above-mentioned hypothesis obtains and Fe3p in testing result such as the table 1 be respectively 3.81% and 4.66%(4.66% 3.81%), obviously, the peak among Figure 10 d is the overlap peak of Li1s and Fe3p, has indirectly proved the existence of elemental lithium.Therefore carry out swarming among Figure 10 e, each element molar content of utilizing known Fe molar content (Fe2p calculates) the Fe3p peak to be separated with the match of Li1s peak after the correction that (first the Fe3p peak is separated from overlap peak, a remaining peak that then obtains is the Li1s peak) out obtain sees Table 2.The Fe3p that match obtains and Li1s are in conjunction with being respectively 55.95eV and 54.47eV.
Table 1 lithium iron phosphate nano particle XPS detects initial data
Table 2 lithium iron phosphate nano particle XPS detects the swarming correction data
Claims (8)
1. the template-mediated legal system is characterized in that for the method for LiFePO 4 nano particle it may further comprise the steps:
1) preliminary treatment of silicon chip: with silicon chip successively Ultrasonic Cleaning 5 ~ 15min in acetone, ultra-pure water, then put into Piranha solution and soak 30-60min in 60 ~ 100 ℃, take out silicon chip and wash with ultra-pure water, dry up with nitrogen again and obtain hydroxylated silicon-based substrates;
2) preparation of APTMS thin-film template: the ethanolic solution that the hydroxylated silicon-based substrates that step 1) is obtained is put into APTMS soaked 1-2 hour, successively with ethanol, ultra-pure water flushing, dried up with nitrogen and obtained the APTMS self-assembled film after the taking-up;
3) the APTMS self-assembled film that APTMS self-assembled film surface amino groups original position phosphorylation: with step 2) obtains immerses and contains phosphorous oxychloride and 2,3, in the acetonitrile solution of 5-trimethylpyridine, room temperature reaction 20-90 minute, taking-up is washed with ultra-pure water, dries up the APTMS self-assembled film that obtains phosphorylation with nitrogen;
4) preparation of LiFePO 4 nano particle: the APTMS self-assembled film of the phosphorylation that step 3) is obtained immersed in the ultra-pure water solution that contains ferrous salt, phosphate, lithium salts reaction 5 minutes-60 minutes, then take out with the ultra-pure water flushing, nitrogen dries up and makes the LiFePO 4 nano particle.
2. the method for the standby LiFePO 4 nano particle of template-mediated legal system according to claim 1 is characterized in that the described silicon chip of step 1) is the bulk of (1 ~ 2) cm * (1 ~ 2) cm * 0.5mm.
3. the method for the standby LiFePO 4 nano particle of template-mediated legal system according to claim 1 is characterized in that the volume ratio of the concentrated sulfuric acid and hydrogen peroxide is 4:1 in the described Piranha solution of step 1).
4. the method for the standby LiFePO 4 nano particle of template-mediated legal system according to claim 1 is characterized in that step 2) the APTMS volumetric concentration is 0.1%-2% in the ethanolic solution of described APTMS.
5. template-mediated legal system according to claim 1 is for the method for LiFePO 4 nano particle, it is characterized in that in the described step 3) phosphorous oxychloride and 2 in the acetonitrile solution, the mol ratio of 3,5-trimethylpyridine is 1:1, and the triclosan oxidation phosphorus concentration is 0.05-0.8mol/L.
6. template-mediated legal system according to claim 1 is for the method for LiFePO 4 nano particle, the mol ratio that it is characterized in that ferrous salt, phosphate, lithium salts in the described ultra-pure water aqueous solution is 1 ~ 2:1 ~ 2:3 ~ 6, and ferrous salt concentration is 0.001-0.1mol/L.
7. the method for the standby LiFePO 4 nano particle of template-mediated legal system according to claim 1, the APTMS self-assembled film that it is characterized in that the phosphorylation described in the step 4) immerse that to contain the temperature of reacting in the ultra-pure water aqueous solution of ferrous salt, phosphate, lithium salts be 20 ~ 50 ℃.
8. according to claim 1, the method for the standby LiFePO 4 nano particle of 6 or 7 described template-mediated legal systems, it is characterized in that institute's ferrous salt, phosphate, lithium salts are respectively ferrous sulfate heptahydrate, diammonium hydrogen phosphate, Lithium hydroxide monohydrate.
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| CN104317163A (en) * | 2014-11-14 | 2015-01-28 | 无锡英普林纳米科技有限公司 | Modification method for resisting adhesion on surface of silicon dioxide template |
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