CN102306789A - Li4Ti5O12/Li3V2(PO4)3 composite material and preparation method thereof - Google Patents
Li4Ti5O12/Li3V2(PO4)3 composite material and preparation method thereof Download PDFInfo
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- CN102306789A CN102306789A CN201110228335A CN201110228335A CN102306789A CN 102306789 A CN102306789 A CN 102306789A CN 201110228335 A CN201110228335 A CN 201110228335A CN 201110228335 A CN201110228335 A CN 201110228335A CN 102306789 A CN102306789 A CN 102306789A
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- 239000002131 composite material Substances 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 229910002986 Li4Ti5O12 Inorganic materials 0.000 title abstract 4
- 229910001367 Li3V2(PO4)3 Inorganic materials 0.000 title abstract 3
- 239000000463 material Substances 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 6
- 239000010936 titanium Substances 0.000 claims description 37
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 11
- 229910052744 lithium Inorganic materials 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 7
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 claims description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 4
- 239000008139 complexing agent Substances 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 239000004471 Glycine Substances 0.000 claims description 2
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 2
- 239000011975 tartaric acid Substances 0.000 claims description 2
- 235000002906 tartaric acid Nutrition 0.000 claims 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 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims 8
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims 6
- 239000008367 deionised water Substances 0.000 claims 6
- 229910021641 deionized water Inorganic materials 0.000 claims 6
- 238000003756 stirring Methods 0.000 claims 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims 2
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims 2
- 235000006408 oxalic acid Nutrition 0.000 claims 2
- 239000000725 suspension Substances 0.000 claims 2
- 238000001132 ultrasonic dispersion Methods 0.000 claims 2
- 229910052720 vanadium Inorganic materials 0.000 claims 2
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims 2
- 229910001868 water Inorganic materials 0.000 claims 2
- 229910021541 Vanadium(III) oxide Inorganic materials 0.000 claims 1
- 238000013019 agitation Methods 0.000 claims 1
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims 1
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims 1
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims 1
- 238000001354 calcination Methods 0.000 claims 1
- 229910052742 iron Inorganic materials 0.000 claims 1
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims 1
- 235000019837 monoammonium phosphate Nutrition 0.000 claims 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 12
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 12
- 229910052596 spinel Inorganic materials 0.000 abstract description 2
- 239000011029 spinel Substances 0.000 abstract description 2
- 230000005518 electrochemistry Effects 0.000 abstract 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- YWJVFBOUPMWANA-UHFFFAOYSA-H [Li+].[V+5].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O Chemical compound [Li+].[V+5].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O YWJVFBOUPMWANA-UHFFFAOYSA-H 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Inorganic Compounds Of Heavy Metals (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention relates to the technical field of lithium ion battery materials, in particular to a Li4Ti5O12/Li3V2(PO4)3 composite material and a preparation method thereof. In the invention, monoclinic Li3V2(PO4)3 is coated on spinel type Li4Ti5O12, can be used for providing mechanical support for the Li4Ti5O12 and is a good lithium ion removing material. The material prepared by the method has high multiplying power and high cycle performance; and the material and the preparation method have the characteristics of environment friendliness, are safe and can be used for preparing materials with high electrochemistry properties.
Description
Technical field
The present invention relates to the preparation method of lithium ion battery electrode material, particularly relate to a kind of Li
4Ti
5O
12/ Li
3V
2(PO
4)
3Composite material and preparation method thereof.
Background technology
Because the needs of the electronics and the information industry development, lithium ion battery has obtained develop rapidly in the more than ten years in the past.Along with a lot of industries of expanding economy to the demand of lithium ion battery still increasing, also increasingly high to the requirement of its security performance.Commercial now lithium ion battery negative material mainly is a material with carbon element, but there is potential safety hazard in material with carbon element, and the material with carbon element high rate performance is poor simultaneously.So the researcher has done a large amount of work, and a kind of security performance is good in the hope of developing, multiplying power and the excellent lithium ion battery negative material of cycle performance, to satisfy the needs of some new industries development, like the electric motor car industry.Spinel-type Li
4Ti
5O
12Because of its have zero strain structure, security performance is good, charge and discharge platform is steady etc., and advantage becomes a kind of very promising lithium ion battery negative material.But along with development of science and technology, single spinel-type Li
4Ti
5O
12Chemical property particularly its multiplying power and cycle performance still are not ideal enough.
Summary of the invention
In order to address the above problem, one of the object of the invention has been to provide a kind of multiplying power of excellence and the Li of cycle performance
4Ti
5O
12/ Li
3V
2(PO
4)
3Composite material;
Two of the object of the invention is to provide said Li
4Ti
5O
12/ Li
3V
2(PO
4)
3The preparation method of composite material.
To achieve these goals, technical scheme of the present invention is following:
A kind of Li
4Ti
5O
12/ Li
3V
2(PO
4)
3Composite material comprises the following material that calculates by mass parts:
Spinel-type Li
4Ti
5O
1298～99.5 parts
Monocline Li
3V
2(PO
4)
30.5～2 parts;
Prepare said Li
4Ti
5O
12/ Li
3V
2(PO
4)
3The method of composite material comprises being prepared as follows step:
Steps A, preparation monocline Li
3V
2(PO
4)
3
A, vanadium source and oxalic acid are dissolved in deionized water, stir 0.5～1.5h and form solution I, wherein calculate n according to amount of substance
V: n
Oxalic acid=1: 1.5～2;
B, elder generation add lithium source and phosphoric acid root in the solution I, use the volume of deionized water regulator solution I then, stir 0.5～1.5h and form solution II, wherein calculate n according to amount of substance
PO4-: n
Li+=1: 1～1.03, the deionized water of said regulator solution I volume is 1.5～3.5 times of used deionized water among the step a;
C, complexing agent is dissolved in deionized water under ultrasonic dispersion condition, obtains solution III;
D, in 60～80 ℃ of water-baths, under the situation of vigorous stirring, solution III slowly is added drop-wise in the solution II, obtain solution IV;
E, with gained solution IV in the steps d prior to reacting 3～5h in 60～80 ℃ of water-baths, under 70～90 ℃, water evaporates 1～3h is obtained gel then;
F, gained gel dry 10～18h in 80～120 ℃ baking oven obtains xerogel;
G, the gained xerogel is ground 8～15min, at N
2Protect following 350～450 ℃ of pre-burning 3～5h, grind 20～25min, compressing tablet, 700～850 ℃ of calcining 6～8h obtain monocline Li
3V
2(PO
4)
3
Step B, the titanium source is dissolved in absolute ethyl alcohol under magnetic agitation, obtains solution V; Wherein, calculate V according to volume ratio
Source of iron: V
Absolute ethyl alcohol=1: 4～10;
Step C, with lithium source, monocline Li
3V
2(PO
4)
3, deionized water and acrylic acid is distributed in the absolute ethyl alcohol with the mode of ultrasonic dispersion, obtains mixture VI, wherein calculates n according to amount of substance
Ti: n
Li=1: 0.8～0.88, n
Ti: n
H2O=1: 1.5～3.5, n
Ti: n
Acrylic acid=1: 0.5～2;
Step D, the mixture VI of gained among the step C is transferred in the reactor, stir 0.5～2h and obtain suspension VII;
Step e, solution V is transferred in the dropping funel, under the vigorous stirring solution V slowly is added drop-wise among the suspension VII, form gel until stirring;
Step F, gained gel in the step e is placed 100～120 ℃ the dry 12～20h of baking oven, obtain xerogel;
Step G, xerogel is ground the N that 8～15min is placed on 450～600 ℃
2Pre-burning 5～8h in the air-flow obtains the pre-burning thing;
Step H, the pre-burning thing is ground 10～20min, compressing tablet, place 750～850 ℃ N
2Calcine 12～20h in the air-flow, obtain calcine;
Step I, calcine is cooled to room temperature, grinds 10～20min and obtain said Li
4Ti
5O
12/ Li
3V
2(PO
4)
3Composite material.
Preferably, said lithium source is lithium hydroxide (LiOHH
2O), lithium nitrate (LiNO
3), lithium acetate (CH
3COOLi2H
2The mixture of one or several O).
Preferably, said vanadium source is vanadic oxide (V
2O
5), ammonium metavanadate (NH
4VO
3) in a kind of or two kinds mixture.
Preferably, said phosphoric acid root is phosphoric acid (H
3PO
4), ammonium dihydrogen phosphate (NH
4H
2PO
4) in a kind of or two kinds mixture
Preferably, said titanium source is tetra-n-butyl titanate or (four) isopropyl titanate.
Preferably, said complexing agent is one or several the mixture in citric acid, glycine, the tartaric acid etc.
The present invention with the original position liquid phase method with monocline Li
3V
2(PO
4)
3Be called for short LVP, be coated on spinel-type Li
4Ti
5O
12On, monocline LVP not only can be Li
4Ti
5O
12Mechanical support is provided, and monocline LVP itself is that lithium ion takes off the good material of embedding again; Simultaneously, monocline LVP is at spinelle Li
4Ti
5O
12Can play the effect of bridge between particle, to reduce intergranular impedance, little impedance helps the performance of material electrochemical performance.
Monocline LVP is by octahedra VO
6With tetrahedron PO
4Be linked to be through shared oxygen atom and have three-dimensional frame structure, the three-dimensional frame structure of this opening helps the diffusion of lithium ion.In this material because PO
4Tetrahedron has played firm effect to whole frame structure, so the structure of this material is still very stable after three lithium ions are deviate from fully.In addition, can continue the embedding lithium among the monocline LVP, the chemical composition of embedding lithium attitude can approximate representation be Li fully
5V
2(PO
4)
3, the V among the LVP
3+Be reduced into V
2+In this embedding lithium process, 1.98,1.86,1.73 and 1.70V (vs Li/Li
+) locate electrochemical reaction can take place, the lithium ion of corresponding respectively 0.5 unit takes off embedding.Specific capacity can be near theoretical value in the experiment.
Use method of the present invention, to Li
4Ti
5O
12Carry out finishing, the gained composite material has the specific discharge capacity height, the characteristics of multiplying power and good cycle.Composite material is exactly a kind of multiphase solid material that is formed by two kinds or the two or more physics combinations of substances different with chemical property.Each component keeps relative independence in the composite material, but its character is not the simple addition of each component property, but on the basis of some characteristic that keeps each component material, has the combination property that acts synergistically and produced between component.Composite material has remedied the shortcoming of homogenous material on the basis of performance component advantage, therefore have the potential of very excellent developing material.Explain that this liquid phase in-situ compositing is a kind of effective ways that prepare high-performance composite titanic acid lithium material, explain that simultaneously monocline LVP is a kind of good coating Li
4Ti
5O
12Material.In a word, the present invention and the Li that coats for preparing with sol-gel process
4Ti
5O
12Compare the Li that monocline LVP coats
4Ti
5O
12Composite material, not only show excellent multiplying power and cycle performance, and have the characteristic of safety, environmental protection.
Embodiment
Embodiment 1
A kind of Li
4Ti
5O
12/ Li
3V
2(PO
4)
3Composite material comprises 99 parts of the spinel type lithium titanates, 1 part of the monocline lithium phosphate vanadium that calculate by mass parts.
Li
4Ti
5O
12/ Li
3V
2(PO
4)
3The preparation method of composite material comprises following concrete steps:
Steps A, preparation monocline Li
3V
2(PO
4)
3
A, with vanadic oxide (V
2O
5) and oxalic acid be dissolved in the 200ml deionized water, stir 1h and form solution I, wherein calculate n according to amount of substance
V: n
Oxalic acid=2: 3;
B, elder generation are with lithium hydroxide (LiOHH
2O) and phosphoric acid (H
3PO
4) add in the solution I, regulate the volume of mixed solution I then with the 500ml deionized water, stir 1h and form solution II, wherein calculate n according to amount of substance
PO4-: n
Li+=1: 1;
C, the 1.8g citric acid is dissolved in the 75ml deionized water under ultrasonic dispersion condition, obtains solution III;
D, in 70 ℃ of water-baths, under the situation of vigorous stirring, solution III slowly is added drop-wise in the solution II, obtain solution IV;
E, with gained solution IV in the steps d prior to reacting 4h in 70 ℃ of water-baths, obtain gel in 80 ℃ of following transpiring moisture 2h then;
F, gained gel dry 10h in 120 ℃ baking oven obtains xerogel;
G, the gained xerogel is ground 10min, at N
2Protect following 350 ℃ of pre-burning 4h, grind 20min, compressing tablet, 700 ℃ of calcining 8h obtain monocline Li
3V
2(PO
4)
3(monocline LVP);
Step B, tetra-n-butyl titanate is dissolved in absolute ethyl alcohol under magnetic agitation, obtains solution V; Wherein, calculate V according to volume ratio
The titanium source: V
Absolute ethyl alcohol=1: 5;
Step C, with spinel-type Li
4Ti
5O
12, monocline LVP, deionized water and acrylic acid is distributed in the absolute ethyl alcohol with the mode of ultrasonic dispersion, obtains mixture VI, wherein calculates n according to amount of substance
Li: n
Ti=0.84, n
H2O: n
Ti=2.0, n
Acrylic acid: n
Ti=0.5;
Step D, the mixture VI of gained among the step C is transferred in the reactor, stir 1h and obtain suspension VII;
Step e, solution V is transferred in the dropping funel, under the vigorous stirring solution V slowly is added drop-wise among the suspension VII, form gel until stirring;
Step F, gained gel in the step e is placed 120 ℃ the dry 16h of baking oven, obtain xerogel;
Step G, xerogel is ground the N that 10min is placed on 500 ℃
2Pre-burning 6h in the air-flow obtains the pre-burning thing;
Step H, the pre-burning thing is ground 15min, compressing tablet, place 800 ℃ N
2Calcine 18h in the air-flow, obtain calcine;
Step I, calcine is cooled to room temperature, grinds 15min and obtain said Li
4Ti
5O
12/ Li
3V
2(PO
4)
3Composite material.
Embodiment 2
A kind of Li
4Ti
5O
12/ Li
3V
2(PO
4)
3Composite material comprises 99 parts of the spinel type lithium titanates, 1 part of the monocline lithium phosphate vanadium that calculate by mass parts.
Li
4Ti
5O
12/ Li
3V
2(PO
4)
3The preparation method of composite material comprises following concrete steps:
Steps A, preparation monocline Li
3V
2(PO
4)
3
A, with ammonium metavanadate (NH
4VO
3) and oxalic acid be dissolved in the 200ml deionized water, stir 1h and form solution I, wherein calculate n according to amount of substance
V: n
Oxalic acid=2: 3;
B, elder generation are with lithium nitrate (LiNO
3) and ammonium dihydrogen phosphate (NH
4H
2PO
4) add in the solution I, use the volume of 500ml deionized water regulator solution I then, stir 1h and form solution II, wherein calculate n according to amount of substance
PO4-: n
Li+=1: 1.03;
C, the 2.7g glycine is dissolved in the 75ml deionized water under ultrasonic dispersion condition, obtains solution III;
D, in 70 ℃ of water-baths, under the situation of vigorous stirring, solution III slowly is added drop-wise in the solution II, obtain solution IV;
E, with gained solution IV in the steps d prior to reacting 5h in 70 ℃ of water-baths, obtain gel in 80 ℃ of following steaming method moisture 2h then;
F, gained gel dry 18h in 120 ℃ baking oven obtains xerogel;
G, the gained xerogel is ground 10min, at N
2Protect following 350 ℃ of pre-burning 4h, grind 20min, compressing tablet, 700 ℃ of calcining 8h obtain monocline Li
3V
2(PO
4)
3(monocline LVP);
Step B, (four) isopropyl titanate is dissolved in absolute ethyl alcohol under magnetic agitation, obtains solution V; Wherein, calculate V according to volume ratio
The titanium source: V
Absolute ethyl alcohol=1: 5;
Step C, with spinel-type Li
4Ti
5O
12, monocline LVP, deionized water and acrylic acid is distributed in the absolute ethyl alcohol with the mode of ultrasonic dispersion, obtains mixture VI, wherein calculates n according to amount of substance
Li: n
Ti=0.84, n
H2O: n
Ti=2.5, n
Acrylic acid: n
Ti=0.7;
Step D, the mixture VI of gained among the step C is transferred in the reactor, stir 1h and obtain suspension VII;
Step e, solution V is transferred in the dropping funel, under the vigorous stirring solution V slowly is added drop-wise among the suspension VII, form gel until stirring;
Step F, gained gel in the step e is placed 120 ℃ the dry 16h of baking oven, obtain xerogel;
Step G, xerogel is ground the N that 10min is placed on 500 ℃
2Pre-burning 6h in the air-flow obtains the pre-burning thing;
Step H, the pre-burning thing is ground 15min, compressing tablet, place 800 ℃ N
2Calcine 20h in the air-flow, obtain calcine;
Step I, calcine is cooled to room temperature, grinds 15min and obtain said Li
4Ti
5O
12/ Li
3V
2(PO
4)
3Composite material.
Embodiment 3
A kind of Li
4Ti
5O
12/ Li
3V
2(PO
4)
3Composite material comprises 99.5 parts of the spinel type lithium titanates, 0.5 part of the monocline lithium phosphate vanadium that calculate by mass parts.
Li
4Ti
5O
12/ Li
3V
2(PO
4)
3The preparation method of composite material comprises following concrete steps:
Steps A, preparation monocline Li
3V
2(PO
4)
3
A, with vanadic oxide (V
2O
5) and oxalic acid be dissolved in the 150ml deionized water, stir 1h and form solution I, wherein calculate n according to amount of substance
V: n
Oxalic acid=2: 3.5;
B, elder generation are with lithium acetate (CH
3COOLi2H
2O) and phosphoric acid (H
3PO
4) add in the solution I, use the volume of 300ml deionized water regulator solution I then, stir 1h and form solution II, wherein calculate n according to amount of substance
PO4-: n
Li+=1: 1;
C, the 3.6g glycine is dissolved in the 100ml deionized water under ultrasonic dispersion condition, obtains solution III;
D, in 70 ℃ of water-baths, under the situation of vigorous stirring, solution III slowly is added drop-wise in the solution II, obtain solution IV;
E, with gained solution IV in the steps d prior to reacting 4h in 70 ℃ of water-baths, obtain gel in 90 ℃ of following transpiring moisture 1h then;
F, gained gel dry 16h in 120 ℃ baking oven obtains xerogel;
G, the gained xerogel is ground 10min, at N
2Protect following 350 ℃ of pre-burning 4h, grind 20min, compressing tablet, 750 ℃ of calcining 8h obtain monocline Li
3V
2(PO
4)
3(monocline LVP);
Step B, tetra-n-butyl titanate is dissolved in absolute ethyl alcohol under magnetic agitation, obtains solution V; Wherein, calculate V according to volume ratio
The titanium source: V
Absolute ethyl alcohol=1: 7;
Step C, with spinel-type Li
4Ti
5O
12, monocline LVP, deionized water and acrylic acid is distributed in the absolute ethyl alcohol with the mode of ultrasonic dispersion, obtains mixture VI, wherein calculates n according to amount of substance
Li: n
Ti=0.86, n
H2O: n
Ti=3.0, n
Acrylic acid: n
Ti=2;
Step D, the mixture VI of gained among the step C is transferred in the reactor, stir 1h and obtain suspension VII;
Step e, solution V is transferred in the dropping funel, under the vigorous stirring solution V slowly is added drop-wise among the suspension VII, form gel until stirring;
Step F, gained gel in the step e is placed 100 ℃ the dry 20h of baking oven, obtain xerogel;
Step G, xerogel is ground the N that 10min is placed on 500 ℃
2Pre-burning 6h in the air-flow obtains the pre-burning thing;
Step H, the pre-burning thing is ground 15min, compressing tablet, place 800 ℃ N
2Calcine 16h in the air-flow, obtain calcine;
Step I, calcine is cooled to room temperature, grinds 15min and obtain said Li
4Ti
5O
12/ Li
3V
2(PO
4)
3Composite material.
Embodiment 4
A kind of Li
3V
2(PO
4)
3/ Li
4Ti
5O
12Composite material comprises 98 parts of the spinel type lithium titanates, 2 parts of the monocline lithium phosphate vanadium that calculate by mass parts.
Li
4Ti
5O
12/ Li
3V
2(PO
4)
3The preparation method of composite material comprises following concrete steps:
Steps A, preparation monocline Li
3V
2(PO
4)
3
A, with vanadic oxide (V
2O
5), ammonium metavanadate (NH
4VO
3) and oxalic acid be dissolved in the 200ml deionized water, stir 1h and form solution I, wherein calculate n according to amount of substance
V: n
Oxalic acid=2: 3;
B, elder generation are with lithium hydroxide (LiOHH
2O), lithium acetate (CH
3COOLi2H
2O) and phosphoric acid (H
3PO
4) add in the solution I, regulate the volume of mixed solution I then with the 200ml deionized water, stir and formed solution II in 0.5 hour, wherein calculate n according to amount of substance
PO4-: n
Li+=1: 1.03;
C, 1.5g citric acid, 1.5g glycine are dissolved in the 80ml deionized water under ultrasonic dispersion condition, obtain solution III;
D, in 60 ℃ of water-baths, under the situation of vigorous stirring, solution III slowly is added drop-wise in the solution II, obtain solution IV;
E, with gained solution IV in the steps d prior to reacting 5h in 60 ℃ of water-baths, obtain gel in 80 ℃ of following transpiring moisture 3h then;
F, gained gel dry 12h in 120 ℃ baking oven obtains xerogel;
G, the gained xerogel is ground 8min, at N
2Protect following 450 ℃ of pre-burning 3h, grind 25min, compressing tablet, 750 ℃ of calcining 6h obtain monocline Li
3V
2(PO
4)
3(monocline LVP);
Step B, tetra-n-butyl titanate is dissolved in absolute ethyl alcohol under magnetic agitation, obtains solution V; Wherein, calculate V according to volume ratio
The titanium source: V
Absolute ethyl alcohol=1: 6;
Step C, with spinel-type Li
4Ti
5O
12, monocline LVP, deionized water and acrylic acid is distributed in the absolute ethyl alcohol with the mode of ultrasonic dispersion, obtains mixture VI, wherein calculates n according to amount of substance
Li: n
Ti=0.88, n
H2O: n
Ti=2.0, n
Acrylic acid: n
Ti=1;
Step D, the mixture VI of gained among the step C is transferred in the reactor, stir 0.5h and obtain suspension VII;
Step e, solution V is transferred in the dropping funel, under the vigorous stirring solution V slowly is added drop-wise among the suspension VI, form gel until stirring;
Step F, gained gel in the step e is placed 120 ℃ the dry 16h of baking oven, obtain xerogel;
Step G, xerogel is ground the N that 8min is placed on 450 ℃
2Pre-burning 5h in the air-flow obtains the pre-burning thing;
Step H, the pre-burning thing is ground 10min, compressing tablet, place 750 ℃ N
2Calcine 18h in the air-flow, obtain calcine;
Step I, calcine is cooled to room temperature, grinds 10min and obtain said Li
4Ti
5O
12/ Li
3V
2(PO
4)
3Composite material.
Embodiment 5
A kind of Li
4Ti
5O
12/ Li
3V
2(PO
4)
3Composite material comprises 99.5 parts of the spinel type lithium titanates, 0.5 part of the monocline lithium phosphate vanadium that calculate by mass parts.
Li
4Ti
5O
12/ Li
3V
2(PO
4)
3The preparation method of composite material comprises following concrete steps:
Steps A, preparation monocline Li
3V
2(PO
4)
3
A, with vanadic oxide (V
2O
5) and oxalic acid be dissolved in the 150ml deionized water, stir 1h and form solution I, wherein calculate n according to amount of substance
V: n
Oxalic acid=2: 3;
B, elder generation are with lithium hydroxide (LiOHH
2O), lithium nitrate (LiNO
3), lithium acetate (CH
3COOLi2H
2O) and phosphoric acid (H
3PO
4), ammonium dihydrogen phosphate (NH
4H
2PO
4) add in the solution I, use the volume of 300ml deionized water regulator solution I then, stir 1.5h and form solution II, wherein calculate n according to amount of substance
PO4-: n
Li+=1: 1.03;
C, with 1g citric acid, 1g glycine, 1g tartaric acid, under ultrasonic dispersion condition, be dissolved in the 75ml deionized water, obtain solution III;
D, in 80 ℃ of water-baths, under the situation of vigorous stirring, solution III slowly is added drop-wise in the solution II, obtain solution IV;
E, with gained solution IV in the steps d prior to reacting 4h in 80 ℃ of water-baths, obtain gel in 90 ℃ of following transpiring moisture 1.5h then;
F, gained gel dry 10h in 120 ℃ baking oven obtains xerogel;
G, the gained xerogel is ground 15min, at N
2Protect following 450 ℃ of pre-burning 5h, grind 25min, compressing tablet, 850 ℃ of calcining 8h obtain monocline Li
3V
2(PO
4)
3(monocline LVP);
Step B, (four) isopropyl titanate is dissolved in absolute ethyl alcohol under magnetic agitation, obtains solution V; Wherein, calculate V according to volume ratio
The titanium source: V
Absolute ethyl alcohol=1: 10;
Step C, with spinel-type Li
4Ti
5O
12, monocline LVP, deionized water and acrylic acid is distributed in the absolute ethyl alcohol with the mode of ultrasonic dispersion, obtains mixture VI, wherein calculates n according to amount of substance
Li: n
Ti=0.82, n
H2O: n
Ti=3.0, n
Acrylic acid: n
Ti=1.5;
Step D, the mixture VI of gained among the step C is transferred in the reactor, stir 1h and obtain suspension VII;
Step e, solution V is transferred in the dropping funel, under the vigorous stirring solution V slowly is added drop-wise among the suspension VII, form gel until stirring;
Step F, gained gel in the step e is placed 120 ℃ the dry 16h of baking oven, obtain xerogel;
Step G, xerogel is ground the N that 15min is placed on 600 ℃
2Pre-burning 5h in the air-flow obtains the pre-burning thing;
Step H, the pre-burning thing is ground 20min, compressing tablet, place 850 ℃ N
2Calcining is 18 hours in the air-flow, obtains calcine;
Step I, calcine is cooled to room temperature, grinds 20min and obtain said Li
4Ti
5O
12/ Li
3V
2(PO
4)
3Composite material.
The foregoing description is preferred embodiment of the present invention, is not to be used for limiting practical range of the present invention, so all equivalences of being done with described characteristic of claim of the present invention and principle change or modify, all should be included within the claim scope of the present invention.
Test the present invention and the Li that coats
4Ti
5O
12Initial charge specific capacity under different multiplying; The result sees table 1,
Table 1
Test the present invention and the Li that coats
4Ti
5O
1230 times charge ratio capability retention compares under 0.5C, and the result sees table 2;
Table 2
Can find out Li of the present invention from table 1 and table 2
4Ti
5O
12/ Li
3V
2(PO
4)
3The initial charge specific capacity of composite material under 5C is 149.3mAh g
-1, and do not coat Li
3V
2(PO
4)
3Li
4Ti
5O
12The initial charge specific capacity 89.1mAh g is only arranged
-10.5C following Li of the present invention
4Ti
5O
12/ Li
3V
2(PO
4)
330 charge ratio capacity of composite material are decayed hardly, and do not coat Li
3V
2(PO
4)
3Li
4Ti
5O
12The charging conservation rate be 91%; Therefore, the prepared lithium titanate composite material of the present invention has excellent multiplying power and cycle performance.
Claims (7)
1. Li
4Ti
5O
12/ Li
3V
2(PO
4)
3Composite material is characterized in that, comprises the following material that calculates by mass parts:
The brilliant Li of point
4Ti
5O
1298～99.5 parts
Monocline Li
3V
2(PO
4)
30.5～2 parts.
2. prepare Li described in the claim 1
4Ti
5O
12/ Li
3V
2(PO
4)
3The method of composite material is characterized in that, comprises being prepared as follows step:
Steps A, preparation monocline Li
3V
2(PO
4)
3
A, vanadium source and oxalic acid are dissolved in deionized water, stir 0.5～1.5h and form solution I, wherein calculate n according to amount of substance
V: n
Oxalic acid=1: 1.5～2;
B, elder generation add lithium source and phosphoric acid root in the solution I, use the volume of deionized water regulator solution I then, stir 0.5～1.5h and form solution II, wherein calculate n according to amount of substance
PO4-: n
Li+=1: 1～1.03, the deionized water of said regulator solution I volume is 1～3.5 times of used deionized water among the step a;
C, complexing agent is dissolved in deionized water under ultrasonic dispersion condition, obtains solution III;
D, in 60～80 ℃ of water-baths, under the situation of vigorous stirring, solution III slowly is added drop-wise in the solution II, obtain solution IV;
E, with gained solution IV in the steps d prior to reacting 3～5h in 60～80 ℃ of water-baths, under 70～90 ℃, water evaporates 1～3h is obtained gel then;
F, gained gel dry 10～18h in 80～120 ℃ baking oven obtains xerogel;
G, the gained xerogel is ground 8～15min, at N
2Protect following 350～450 ℃ of pre-burning 3～5h, grind 20～25min, compressing tablet, 700～850 ℃ of calcining 6～8h obtain monocline Li
3V
2(PO
4)
3
Step B, the titanium source is dissolved in absolute ethyl alcohol under magnetic agitation, obtains solution V; Wherein, calculate V according to volume ratio
Source of iron: V
Absolute ethyl alcohol=1: 4～10;
Step C, with lithium source, monocline Li
3V
2(PO
4)
3, deionized water and acrylic acid is distributed in the absolute ethyl alcohol with the mode of ultrasonic dispersion, obtains mixture VI, wherein calculates n according to amount of substance
Ti: n
Li=1: 0.8～0.88, n
Ti: n
H2O=1: 1.5～3.5, n
Ti: n
Acrylic acid=1: 0.5～2;
Step D, the mixture VI of gained among the step C is transferred in the reactor, stir 0.5～2h and obtain suspension VII;
Step e, solution V is transferred in the dropping funel, under the vigorous stirring solution V slowly is added drop-wise among the suspension VII, form gel until stirring;
Step F, gained gel in the step e is placed 100～120 ℃ the dry 12～20h of baking oven, obtain xerogel;
Step G, xerogel is ground the N that 8～15min is placed on 450～600 ℃
2Pre-burning 5～8h in the air-flow obtains the pre-burning thing;
Step H, the pre-burning thing is ground 10～20min, compressing tablet, place 750～850 ℃ N
2Calcine 12～20h in the air-flow, obtain calcine;
Step I, calcine is cooled to room temperature, grinds 10～20min and obtain said Li
4Ti
5O
12/ Li
3V
2(PO
4)
3Composite material.
3. according to the said Li of claim 2
4Ti
5O
12/ Li
3V
2(PO
4)
3The preparation method of composite material is characterized in that, said lithium source is one or several the mixture in lithium hydroxide, lithium nitrate, the lithium acetate.
4. according to the said Li of claim 3
4Ti
5O
12/ Li
3V
2(PO
4)
3The preparation method of composite material is characterized in that, said vanadium source is the mixture of a kind of in vanadic oxide, the ammonium metavanadate or two kinds.
5. according to the said Li of claim 2
4Ti
5O
12/ Li
3V
2(PO
4)
3The preparation method of composite material is characterized in that, said phosphoric acid root is the mixture of a kind of in phosphoric acid, the ammonium dihydrogen phosphate or two kinds
6. according to the said Li of claim 2
4Ti
5O
12/ Li
3V
2(PO
4)
3The preparation method of composite material is characterized in that, said titanium source is tetra-n-butyl titanate or (four) isopropyl titanate.
7. according to the said Li of claim 2
4Ti
5O
12/ Li
3V
2(PO
4)
3The preparation method of composite material is characterized in that, said complexing agent is one or several the mixture in citric acid, glycine, the tartaric acid.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103066266A (en) * | 2012-11-28 | 2013-04-24 | 上海锦众信息科技有限公司 | Method for preparing magnesium-doped lithium-vanadium-titanium composite material |
| CN104779364A (en) * | 2015-03-31 | 2015-07-15 | 中新能科技发展有限公司 | Anode of lithium ion battery, preparation method of anode and lithium ion battery |
| CN106602005A (en) * | 2016-05-11 | 2017-04-26 | 北京纳米能源与系统研究所 | Preparation method of V2(PO4)O/C material, negative electrode of lithium ion battery, prepared from V2(PO4)O/C material prepared thereby and method for preparing negative electrode |
| CN110085810A (en) * | 2018-01-25 | 2019-08-02 | 天津国安盟固利新材料科技股份有限公司 | A kind of preparation method and application of coating modification lithium cobaltate cathode material |
| CN110137482A (en) * | 2019-06-17 | 2019-08-16 | 桑顿新能源科技(长沙)有限公司 | Carbon coating negative electrode material and preparation method thereof and battery |
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| CN101734640A (en) * | 2009-12-29 | 2010-06-16 | 上海交通大学 | Preparation method of lithium ion battery anode material vanadium-lithium phosphate |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103066266A (en) * | 2012-11-28 | 2013-04-24 | 上海锦众信息科技有限公司 | Method for preparing magnesium-doped lithium-vanadium-titanium composite material |
| CN104779364A (en) * | 2015-03-31 | 2015-07-15 | 中新能科技发展有限公司 | Anode of lithium ion battery, preparation method of anode and lithium ion battery |
| CN106602005A (en) * | 2016-05-11 | 2017-04-26 | 北京纳米能源与系统研究所 | Preparation method of V2(PO4)O/C material, negative electrode of lithium ion battery, prepared from V2(PO4)O/C material prepared thereby and method for preparing negative electrode |
| CN106602005B (en) * | 2016-05-11 | 2019-04-26 | 北京纳米能源与系统研究所 | V2(PO4) O/C material preparation method, the cathode and method of lithium ion battery is made |
| CN110085810A (en) * | 2018-01-25 | 2019-08-02 | 天津国安盟固利新材料科技股份有限公司 | A kind of preparation method and application of coating modification lithium cobaltate cathode material |
| CN110085810B (en) * | 2018-01-25 | 2022-06-10 | 天津国安盟固利新材料科技股份有限公司 | Preparation method and application of coated modified lithium cobaltate positive electrode material |
| CN110137482A (en) * | 2019-06-17 | 2019-08-16 | 桑顿新能源科技(长沙)有限公司 | Carbon coating negative electrode material and preparation method thereof and battery |
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