CN102306789B - 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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- CN102306789B CN102306789B CN2011102283355A CN201110228335A CN102306789B CN 102306789 B CN102306789 B CN 102306789B CN 2011102283355 A CN2011102283355 A CN 2011102283355A CN 201110228335 A CN201110228335 A CN 201110228335A CN 102306789 B CN102306789 B CN 102306789B
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- 239000002131 composite material Substances 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 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 25
- 238000000034 method Methods 0.000 claims abstract description 7
- 239000010936 titanium Substances 0.000 claims description 63
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 21
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 14
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 14
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- 239000000126 substance Substances 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 11
- 229910052719 titanium Inorganic materials 0.000 claims description 11
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 10
- 229910052744 lithium Inorganic materials 0.000 claims description 8
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 8
- 238000013019 agitation Methods 0.000 claims description 7
- 238000001354 calcination Methods 0.000 claims description 7
- 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 4
- 239000008139 complexing agent Substances 0.000 claims description 3
- 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
- 230000008020 evaporation Effects 0.000 claims description 2
- 238000001704 evaporation Methods 0.000 claims description 2
- 239000011975 tartaric acid Substances 0.000 claims description 2
- 235000002906 tartaric acid Nutrition 0.000 claims description 2
- 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
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims 3
- 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
- 229910052720 vanadium Inorganic materials 0.000 claims 2
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims 2
- 229910021541 Vanadium(III) oxide Inorganic materials 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
- 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
- 230000003647 oxidation Effects 0.000 claims 1
- 238000007254 oxidation reaction Methods 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
- 239000000243 solution Substances 0.000 description 30
- BJFIDCADFRDPIO-DZCXQCEKSA-N (2S)-N-[(2S)-6-amino-1-[(2-amino-2-oxoethyl)amino]-1-oxohexan-2-yl]-1-[[(4R,7S,10S,13S,16S,19R)-19-amino-7-(2-amino-2-oxoethyl)-10-(3-amino-3-oxopropyl)-16-[(4-hydroxyphenyl)methyl]-6,9,12,15,18-pentaoxo-13-(phenylmethyl)-1,2-dithia-5,8,11,14,17-pentazacycloeicos-4-yl]-oxomethyl]-2-pyrrolidinecarboxamide Chemical compound NCCCC[C@@H](C(=O)NCC(N)=O)NC(=O)[C@@H]1CCCN1C(=O)[C@H]1NC(=O)[C@H](CC(N)=O)NC(=O)[C@H](CCC(N)=O)NC(=O)[C@H](CC=2C=CC=CC=2)NC(=O)[C@H](CC=2C=CC(O)=CC=2)NC(=O)[C@@H](N)CSSC1 BJFIDCADFRDPIO-DZCXQCEKSA-N 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000000694 effects Effects 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
- 238000013459 approach Methods 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
- 238000005516 engineering process Methods 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
- 238000012360 testing method Methods 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
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
Due to the needs of electronics and 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 more and more higher to the requirement of its security performance.Commercial lithium ion battery negative material is mainly material with carbon element now, 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 to developing, a kind of security performance is good, the lithium ion battery negative material of multiplying power and cycle performance excellence, to meet the needs of some new industries development, as 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 scientific and technological development, single spinel-type Li
4Ti
5O
12Chemical property particularly its multiplying power and cycle performance or not ideal enough.
Summary of the invention
In order to address the above problem, one of purpose of the present 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 purpose of the present invention is to provide described 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 as follows:
A kind of Li
4Ti
5O
12/ Li
3V
2(PO
4)
3The preparation method of composite material, is characterized in that, this Li
4Ti
5O
12/ Li
3V
2(PO
4)
3Composite material comprises the following material calculated by mass parts:
Spinel-type Li
4Ti
5O
1298～99.5 parts
Monocline Li
3V
2(PO
4)
30.5～2 parts;
Prepare described Li
4Ti
5O
12/ Li
3V
2(PO
4)
3The method of composite material comprises and is prepared as follows step:
Steps A, preparation monocline Li
3V
2(PO
4)
3
A, vanadium source and oxalic acid are dissolved in to deionized water, stir 0.5～1.5h and form the solution I, wherein according to amount of substance, calculate n
V︰ n
Oxalic acid=1 ︰ 1.5～2;
B, first lithium source and phosphoric acid root are added in the solution I, then use the volume of deionized water regulator solution I, stir 0.5～1.5h and form the solution II, wherein calculate according to amount of substance,
The deionized water of described regulator solution I volume is 1.5～3.5 times of deionized water used in step a;
C, complexing agent is dissolved in to deionized water under ultrasonic dispersion condition, obtains the solution III;
D, in 60～80 ℃ of water-baths, in the situation that vigorous stirring slowly is added drop-wise to the solution III in the solution II, obtain the solution IV;
E, by gained solution IV in steps d prior in 60～80 ℃ of water-baths, reacting 3～5h, then under 70～90 ℃, moisture evaporation 1～3h is obtained to gel;
F, gained gel dry 10～18h in the baking oven of 80～120 ℃ obtains xerogel;
G, the gained xerogel is ground to 8～15min, at N
2Protect lower 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 to absolute ethyl alcohol under magnetic agitation, obtains the solution V; Wherein, calculate V according to volume ratio
The titanium source: V
Absolute ethyl alcohol=1:4～10;
Step C, by Li Yuan ﹑ monocline Li
3V
2(PO
4)
3, deionized water and acrylic acid is distributed in absolute ethyl alcohol in the mode of ultrasonic dispersion, obtains the mixture VI, wherein according to amount of substance, calculates n
Ti: n
Li=1:0.8～0.88,
n
Ti︰ n
Acrylic acid=1:0.5～2;
Step D, the mixture VI of gained in step C is transferred in reactor, stirred 0.5～2h and obtain the suspension VII;
Step e, the solution V is transferred in dropping funel, under vigorous stirring, the solution V slowly is added drop-wise in the suspension VII, until stir, form gel;
Step F, gained gel in step e is placed in to the dry 12～20h of baking oven of 100～120 ℃, obtains xerogel;
Step G, xerogel is ground to 8～15min be placed on the N of 450～600 ℃
2Pre-burning 5～8h in air-flow, obtain the pre-burning thing;
Step H, the pre-burning thing is ground to 10～20min, compressing tablet, be placed in the N of 750～850 ℃
2Calcine 12～20h in air-flow, obtain calcined material;
Step I, calcined material is cooled to room temperature, grinds 10～20min and obtain described Li
4Ti
5O
12/ Li
3V
2(PO
4)
3Composite material.
Preferably, described lithium source is lithium hydroxide (LiOHH
2O) ﹑ lithium nitrate (LiNO
3), lithium acetate (CH
3COOLi2H
2The mixture of one or several O).
Preferably, described vanadium source is vanadic oxide (V
2O
5), ammonium metavanadate (NH
4VO
3) in a kind of or mixture of two kinds.
Preferably, described phosphoric acid root is phosphoric acid (H
3PO
4), ammonium dihydrogen phosphate (NH
4H
2PO
4) in a kind of or mixture of two kinds
Preferably, described titanium source is tetra-n-butyl titanate or (four) isopropyl titanate.
Preferably, described complexing agent is one or several the mixture in Ning Meng Suan ﹑ Gan An Suan ﹑ tartaric acid etc.
The present invention uses the original position liquid phase method by monocline Li
3V
2(PO
4)
3Be called for short LVP, be coated on spinel-type Li
4Ti
5O
12Upper, monocline LVP can be not only Li
4Ti
5O
12Provide mechanical support, and monocline LVP itself is again the de-good material of embedding of lithium ion; Simultaneously, monocline LVP is at spinelle Li
4Ti
5O
12Can play the effect of bridge between particle, to reduce intergranular impedance, little impedance is conducive to the performance of material electrochemical performance.
Monocline LVP is by octahedra VO
6With tetrahedron PO
4Be linked to be and have three-dimensional frame structure by shared oxygen atom, the three-dimensional frame structure of this opening is conducive to the diffusion of lithium ion.In this material due to 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, in monocline LVP, can continue the embedding lithium, the chemical composition of embedding lithium state can approximate representation be Li fully
5V
2(PO
4)
3, the V in 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 occur corresponding the de-embedding of lithium ion of 0.5 unit respectively.In experiment, specific capacity can approach theoretical value.
Use method of the present invention, to Li
4Ti
5O
12Carry out finishing, it is high that the gained composite material has a specific discharge capacity, the characteristics of multiplying power and good cycle.Composite material is exactly a kind of multiphase solid material that the combinations of substances by two kinds or two or more physics and chemistry different in kinds forms.In composite material, each component keeps relative independence, 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 between component the produced combination property that acts synergistically.Composite material has made up the shortcoming of homogenous material on the basis of performance component advantage, therefore has the potential of very excellent developing material.Illustrate that this liquid phase in-situ compositing is a kind of effective ways that prepare high-performance composite titanic acid lithium material, illustrate that monocline LVP is a kind of good coating Li simultaneously
4Ti
5O
12Material.In a word, the present invention and the Li coated prepared by 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 there is the characteristic of safety, environmental protection.
Embodiment
Embodiment 1
A kind of Li
4Ti
5O
12/ Li
3V
2(PO
4)
3Composite material, comprise 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, by vanadic oxide (V
2O
5) and oxalic acid be dissolved in the 200ml deionized water, stir 1h and form the solution I, wherein according to amount of substance, calculate n
V︰ n
Oxalic acid=2 ︰ 3;
B, first by lithium hydroxide (LiOHH
2O) and phosphoric acid (H
3PO
4) add in the solution I, then with the 500ml deionized water, regulate the volume of mixed solution I, stir 1h and form the solution II, wherein according to amount of substance, calculate,
C, the 1.8g citric acid is dissolved under ultrasonic dispersion condition to the 75ml deionized water, obtains the solution III;
D, in 70 ℃ of water-baths, in the situation that vigorous stirring slowly is added drop-wise to the solution III in the solution II, obtain the solution IV;
E, by gained solution IV in steps d prior in 70 ℃ of water-baths, reacting 4h, then in 80 ℃ of lower transpiring moisture 2h, obtain gel;
F, gained gel dry 10h in the baking oven of 120 ℃ obtains xerogel;
G, the gained xerogel is ground to 10min, at N
2Protect lower 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 to absolute ethyl alcohol under magnetic agitation, obtains the solution V; Wherein, calculate V according to volume ratio
The titanium source: V
Absolute ethyl alcohol=1:5;
Step C, by spinel-type Li
4Ti
5O
12﹑ monocline LVP, deionized water and acrylic acid are distributed in absolute ethyl alcohol in the mode of ultrasonic dispersion, obtain the mixture VI, wherein according to amount of substance, calculate n
Li: n
Ti=0.84,
n
Acrylic acid︰ n
Ti=0.5;
Step D, the mixture VI of gained in step C is transferred in reactor, stirred 1h and obtain the suspension VII;
Step e, the solution V is transferred in dropping funel, under vigorous stirring, the solution V slowly is added drop-wise in the suspension VII, until stir, form gel;
Step F, gained gel in step e is placed in to the dry 16h of baking oven of 120 ℃, obtains xerogel;
Step G, xerogel is ground to the N that 10min is placed on 500 ℃
2Pre-burning 6h in air-flow, obtain the pre-burning thing;
Step H, the pre-burning thing is ground to 15min, compressing tablet, be placed in the N of 800 ℃
2Calcine 18h in air-flow, obtain calcined material;
Step I, calcined material is cooled to room temperature, grinds 15min and obtain described 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, comprise 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, by ammonium metavanadate (NH
4VO
3) and oxalic acid be dissolved in the 200ml deionized water, stir 1h and form the solution I, wherein according to amount of substance, calculate n
V︰ n
Oxalic acid=2 ︰ 3;
B, first by lithium nitrate (LiNO
3) and ammonium dihydrogen phosphate (NH
4H
2PO
4) add in the solution I, then use the volume of 500ml deionized water regulator solution I, stir 1h and form the solution II, wherein according to amount of substance, calculate,
C, the 2.7g glycine is dissolved under ultrasonic dispersion condition to the 75ml deionized water, obtains the solution III;
D, in 70 ℃ of water-baths, in the situation that vigorous stirring slowly is added drop-wise to the solution III in the solution II, obtain the solution IV;
E, by gained solution IV in steps d prior in 70 ℃ of water-baths, reacting 5h, then under 80 ℃, steam method moisture 2h and obtain gel;
F, gained gel dry 18h in the baking oven of 120 ℃ obtains xerogel;
G, the gained xerogel is ground to 10min, at N
2Protect lower 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 to absolute ethyl alcohol under magnetic agitation, obtains the solution V; Wherein, calculate V according to volume ratio
The titanium source: V
Absolute ethyl alcohol=1:5;
Step C, by spinel-type Li
4Ti
5O
12﹑ monocline LVP, deionized water and acrylic acid are distributed in absolute ethyl alcohol in the mode of ultrasonic dispersion, obtain the mixture VI, wherein according to amount of substance, calculate n
Li: n
Ti=0.84,
n
Acrylic acid︰ n
Ti=0.7;
Step D, the mixture VI of gained in step C is transferred in reactor, stirred 1h and obtain the suspension VII;
Step e, the solution V is transferred in dropping funel, under vigorous stirring, the solution V slowly is added drop-wise in the suspension VII, until stir, form gel;
Step F, gained gel in step e is placed in to the dry 16h of baking oven of 120 ℃, obtains xerogel;
Step G, xerogel is ground to the N that 10min is placed on 500 ℃
2Pre-burning 6h in air-flow, obtain the pre-burning thing;
Step H, the pre-burning thing is ground to 15min, compressing tablet, be placed in the N of 800 ℃
2Calcine 20h in air-flow, obtain calcined material;
Step I, calcined material is cooled to room temperature, grinds 15min and obtain described 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, comprise 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, by vanadic oxide (V
2O
5) and oxalic acid be dissolved in the 150ml deionized water, stir 1h and form the solution I, wherein according to amount of substance, calculate n
V︰ n
Oxalic acid=2 ︰ 3.5;
B, first by lithium acetate (CH
3COOLi2H
2O) and phosphoric acid (H
3PO
4) add in the solution I, then use the volume of 300ml deionized water regulator solution I, stir 1h and form the solution II, wherein according to amount of substance, calculate,
C, the 3.6g glycine is dissolved under ultrasonic dispersion condition to the 100ml deionized water, obtains the solution III;
D, in 70 ℃ of water-baths, in the situation that vigorous stirring slowly is added drop-wise to the solution III in the solution II, obtain the solution IV;
E, by gained solution IV in steps d prior in 70 ℃ of water-baths, reacting 4h, then in 90 ℃ of lower transpiring moisture 1h, obtain gel;
F, gained gel dry 16h in the baking oven of 120 ℃ obtains xerogel;
G, the gained xerogel is ground to 10min, at N
2Protect lower 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 to absolute ethyl alcohol under magnetic agitation, obtains the solution V; Wherein, calculate V according to volume ratio
The titanium source: V
Absolute ethyl alcohol=1:7;
Step C, by spinel-type Li
4Ti
5O
12﹑ monocline LVP, deionized water and acrylic acid are distributed in absolute ethyl alcohol in the mode of ultrasonic dispersion, obtain the mixture VI, wherein according to amount of substance, calculate n
Li: n
Ti=0.86,
n
Acrylic acid︰ n
Ti=2;
Step D, the mixture VI of gained in step C is transferred in reactor, stirred 1h and obtain the suspension VII;
Step e, the solution V is transferred in dropping funel, under vigorous stirring, the solution V slowly is added drop-wise in the suspension VII, until stir, form gel;
Step F, gained gel in step e is placed in to the dry 20h of baking oven of 100 ℃, obtains xerogel;
Step G, xerogel is ground to the N that 10min is placed on 500 ℃
2Pre-burning 6h in air-flow, obtain the pre-burning thing;
Step H, the pre-burning thing is ground to 15min, compressing tablet, be placed in the N of 800 ℃
2Calcine 16h in air-flow, obtain calcined material;
Step I, calcined material is cooled to room temperature, grinds 15min and obtain described 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, comprise 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, by vanadic oxide (V
2O
5), ammonium metavanadate (NH
4VO
3) and oxalic acid be dissolved in the 200ml deionized water, stir 1h and form the solution I, wherein according to amount of substance, calculate n
V︰ n
Oxalic acid=2 ︰ 3;
B, first by lithium hydroxide (LiOHH
2O), lithium acetate (CH
3COOLi2H
2O) and phosphoric acid (H
3PO
4) add in the solution I, then with the 200ml deionized water, regulate the volume of mixed solution I, stir and within 0.5 hour, form the solution II, wherein according to amount of substance, calculate,
C, 1.5g citric acid, 1.5g glycine are dissolved in to the 80ml deionized water under ultrasonic dispersion condition, obtain the solution III;
D, in 60 ℃ of water-baths, in the situation that vigorous stirring slowly is added drop-wise to the solution III in the solution II, obtain the solution IV;
E, by gained solution IV in steps d prior in 60 ℃ of water-baths, reacting 5h, then in 80 ℃ of lower transpiring moisture 3h, obtain gel;
F, gained gel dry 12h in the baking oven of 120 ℃ obtains xerogel;
G, the gained xerogel is ground to 8min, at N
2Protect lower 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 to absolute ethyl alcohol under magnetic agitation, obtains the solution V; Wherein, calculate V according to volume ratio
The titanium source: V
Absolute ethyl alcohol=1:6;
Step C, by spinel-type Li
4Ti
5O
12﹑ monocline LVP, deionized water and acrylic acid are distributed in absolute ethyl alcohol in the mode of ultrasonic dispersion, obtain the mixture VI, wherein according to amount of substance, calculate n
Li: n
Ti=0.88,
n
Acrylic acid︰ n
Ti=1;
Step D, the mixture VI of gained in step C is transferred in reactor, stirred 0.5h and obtain the suspension VII;
Step e, the solution V is transferred in dropping funel, under vigorous stirring, the solution V slowly is added drop-wise in the suspension VI, until stir, form gel;
Step F, gained gel in step e is placed in to the dry 16h of baking oven of 120 ℃, obtains xerogel;
Step G, xerogel is ground to the N that 8min is placed on 450 ℃
2Pre-burning 5h in air-flow, obtain the pre-burning thing;
Step H, the pre-burning thing is ground to 10min, compressing tablet, be placed in the N of 750 ℃
2Calcine 18h in air-flow, obtain calcined material;
Step I, calcined material is cooled to room temperature, grinds 10min and obtain described 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, comprise 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, by vanadic oxide (V
2O
5) and oxalic acid be dissolved in the 150ml deionized water, stir 1h and form the solution I, wherein according to amount of substance, calculate n
V︰ n
Oxalic acid=2 ︰ 3;
B, first by 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, then use the volume of 300ml deionized water regulator solution I, stir 1.5h and form the solution II, wherein according to amount of substance, calculate,
C, 1g citric acid, 1g Gan An Suan ﹑ 1g Jiu Shi Suan ﹑ are dissolved in to the 75ml deionized water under ultrasonic dispersion condition, obtain the solution III;
D, in 80 ℃ of water-baths, in the situation that vigorous stirring slowly is added drop-wise to the solution III in the solution II, obtain the solution IV;
E, by gained solution IV in steps d prior in 80 ℃ of water-baths, reacting 4h, then in 90 ℃ of lower transpiring moisture 1.5h, obtain gel;
F, gained gel dry 10h in the baking oven of 120 ℃ obtains xerogel;
G, the gained xerogel is ground to 15min, at N
2Protect lower 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 to absolute ethyl alcohol under magnetic agitation, obtains the solution V; Wherein, calculate V according to volume ratio
The titanium source: V
Absolute ethyl alcohol=1:10;
Step C, by spinel-type Li
4Ti
5O
12﹑ monocline LVP, deionized water and acrylic acid are distributed in absolute ethyl alcohol in the mode of ultrasonic dispersion, obtain the mixture VI, wherein according to amount of substance, calculate n
Li: n
Ti=0.82,
n
Acrylic acid︰ n
Ti=1.5;
Step D, the mixture VI of gained in step C is transferred in reactor, stirred 1h and obtain the suspension VII;
Step e, the solution V is transferred in dropping funel, under vigorous stirring, the solution V slowly is added drop-wise in the suspension VII, until stir, form gel;
Step F, gained gel in step e is placed in to the dry 16h of baking oven of 120 ℃, obtains xerogel;
Step G, xerogel is ground to the N that 15min is placed on 600 ℃
2Pre-burning 5h in air-flow, obtain the pre-burning thing;
Step H, the pre-burning thing is ground to 20min, compressing tablet, be placed in the N of 850 ℃
2In air-flow, calcining is 18 hours, obtains calcined material;
Step I, calcined material is cooled to room temperature, grinds 20min and obtain described Li
4Ti
5O
12/ Li
3V
2(PO
4)
3Composite material.
Above-described embodiment, be preferred embodiment of the present invention, not is used for limiting the scope of the present invention, and the equivalence of being done with the described feature of the claims in the present invention and principle therefore all changes or modifies, within all should being included in the claims in the present invention scope.
Test the present invention and the Li coated
4Ti
5O
12Initial charge specific capacity under different multiplying; The results are shown in Table 1,
Table 1
Test the present invention and the Li coated
4Ti
5O
12Under 0.5C, the charge ratio capability retention of 30 times relatively, the results are shown in Table 2;
Table 2
Carry out as can be seen from Table 1 and Table 2 Li of the present invention
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 lower 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 charger holdup be 91%; Therefore, the prepared lithium titanate composite material of the present invention has excellent multiplying power and cycle performance.
Claims (6)
1. a Li
4Ti
5O
12/ Li
3V
2(PO
4)
3The preparation method of composite material, is characterized in that, this Li
4Ti
5O
12/ Li
3V
2(PO
4)
3Composite material comprises the following material calculated by mass parts:
Spinel-type Li
4Ti
5O
1298～99.5 parts
Monocline Li
3V
2(PO
4)
30.5～2 parts;
Prepare described Li
4Ti
5O
12/ Li
3V
2(PO
4)
3The method of composite material comprises and is prepared as follows step:
Steps A, preparation monocline Li
3V
2(PO
4)
3
A, vanadium source and oxalic acid are dissolved in to deionized water, stir 0.5～1.5h and form the solution I, wherein according to amount of substance, calculate n
V︰ n
Oxalic acid=1 ︰ 1.5～2;
B, first lithium source and phosphoric acid root are added in the solution I, then use the volume of deionized water regulator solution I, stir 0.5～1.5h and form the solution II, wherein calculate according to amount of substance,
The deionized water of described regulator solution I volume is 1～3.5 times of deionized water used in step a;
C, complexing agent is dissolved in to deionized water under ultrasonic dispersion condition, obtains the solution III;
D, in 60～80 ℃ of water-baths, in the situation that vigorous stirring slowly is added drop-wise to the solution III in the solution II, obtain the solution IV;
E, by gained solution IV in steps d prior in 60～80 ℃ of water-baths, reacting 3～5h, then under 70～90 ℃, moisture evaporation 1～3h is obtained to gel;
F, gained gel dry 10～18h in the baking oven of 80～120 ℃ obtains xerogel;
G, the gained xerogel is ground to 8～15min, at N
2Protect lower 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 to absolute ethyl alcohol under magnetic agitation, obtains the solution V; Wherein, calculate V according to volume ratio
The titanium source: V
Absolute ethyl alcohol=1:4～10;
Step C, by Li Yuan ﹑ monocline Li
3V
2(PO
4)
3, deionized water and acrylic acid is distributed in absolute ethyl alcohol in the mode of ultrasonic dispersion, obtains the mixture VI, wherein according to amount of substance, calculates n
Ti: n
Li=1:0.8～0.88,
n
Ti︰ n
Acrylic acid=1:0.5～2;
Step D, the mixture VI of gained in step C is transferred in reactor, stirred 0.5～2h and obtain the suspension VII;
Step e, the solution V is transferred in dropping funel, under vigorous stirring, the solution V slowly is added drop-wise in the suspension VII, until stir, form gel;
Step F, gained gel in step e is placed in to the dry 12～20h of baking oven of 100～120 ℃, obtains xerogel;
Step G, xerogel is ground to 8～15min be placed on the N of 450～600 ℃
2Pre-burning 5～8h in air-flow, obtain the pre-burning thing;
Step H, the pre-burning thing is ground to 10～20min, compressing tablet, be placed in the N of 750～850 ℃
2Calcine 12～20h in air-flow, obtain calcined material;
Step I, calcined material is cooled to room temperature, grinds 10～20min and obtain described Li
4Ti
5O
12/ Li
3V
2(PO
4)
3Composite material.
2. Li according to claim 1
4Ti
5O
12/ Li
3V
2(PO
4)
3The preparation method of composite material, is characterized in that, described lithium source is one or several the mixture in Qing oxidation Li ﹑ lithium nitrate, lithium acetate.
3. Li according to claim 2
4Ti
5O
12/ Li
3V
2(PO
4)
3The preparation method of composite material, is characterized in that, the mixture that described vanadium source is a kind of in vanadic oxide, ammonium metavanadate or two kinds.
4. Li according to claim 1
4Ti
5O
12/ Li
3V
2(PO
4)
3The preparation method of composite material, is characterized in that, the mixture that described phosphoric acid root is a kind of in phosphoric acid, ammonium dihydrogen phosphate or two kinds.
5. Li according to claim 1
4Ti
5O
12/ Li
3V
2(PO
4)
3The preparation method of composite material, is characterized in that, described titanium source is tetra-n-butyl titanate or (four) isopropyl titanate.
6. Li according to claim 1
4Ti
5O
12/ Li
3V
2(PO
4)
3The preparation method of composite material, is characterized in that, described complexing agent is one or several the mixture in Ning Meng Suan ﹑ Gan An Suan ﹑ tartaric acid.
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| 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 |
| 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 |
| 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 |
| CN110137482B (en) * | 2019-06-17 | 2021-02-19 | 桑顿新能源科技(长沙)有限公司 | Carbon-coated negative electrode material, 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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| 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 |
| CN101764209A (en) * | 2010-01-04 | 2010-06-30 | 苏州星恒电源有限公司 | Lithium titanate composite electrode material with surface coating layer |
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