CN104733698B - A kind of method preparing Vanadium sesquioxide cladding lithium titanate anode material - Google Patents
A kind of method preparing Vanadium sesquioxide cladding lithium titanate anode material Download PDFInfo
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- CN104733698B CN104733698B CN201510125772.2A CN201510125772A CN104733698B CN 104733698 B CN104733698 B CN 104733698B CN 201510125772 A CN201510125772 A CN 201510125772A CN 104733698 B CN104733698 B CN 104733698B
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- lithium titanate
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Abstract
The present invention relates to technical field of lithium-ion battery, particularly a kind of method preparing Vanadium sesquioxide cladding lithium titanate anode material.It is dissolved in Quilonorm (SKB) and Polyvinylpyrrolidone PVP in 500mL distilled water, adds nano titanium oxide, magnetic agitation 1h obtains slurry, be spray-dried and obtain lithium titanate precursor；Presoma is heat-treated to reaction in air atmosphere and completes, and obtains pure lithium titanate anode material；It is dissolved in ammonium metavanadate and glycine in distilled water, add pure lithium titanate anode material, magnetic agitation 1h, after solvent evaporated, vacuum drying obtains Vanadium sesquioxide cladding lithium titanate precursor；Presoma is heat-treated to reaction in argon gas atmosphere and completes, and obtains target product Vanadium sesquioxide cladding lithium titanate anode material.
Description
Technical field
The present invention relates to technical field of lithium-ion battery, particularly one kind prepare Vanadium sesquioxide cladding lithium titanate bearing
The method of pole material.
Background technology
The lithium ion battery negative material of commercialization adopts various embedding lithium material with carbon elements mostly, has the drawback that：With electrolysis
Liquid reacts formation surface passivated membrane, leads to electrolyte consumption and initial coulomb efficiency low；Separate out Li dendrite, make battery short
Road, brings serious potential safety hazard.Spinel type lithium titanate (Li4Ti5O12) as a kind of new lithium ion battery negative material
Material has obvious advantage：Zero strain, cycle performance is excellent；Higher oxidation-reduction potential (1.5VvsLi), not with conventional electricity
Solution liquid reacts, and safety is good；Environmental friendliness, easily prepares, and cost is low.But Li4Ti5O12Electrical conductivity low, lead to it
High rate capability is poor, and this greatly constrains it and promotes and application, the field especially attracted attention in this whole world of electrokinetic cell, material
High magnification operating characteristic be determine its can large-scale commercial application one of key factor, therefore improve Li4Ti5O12Height
High rate performance becomes one of core topic of current researchers' concern.Such material is furtherd investigate and is actively pushed forward it
Industrialization pace, is to solve electric vehicles long-life, the key of the lithium ion battery of safety, the quick industry of such material
Change and not only there is very big economic benefit, also there is the war trip meaning in abyss, be conducive to the sustainable of China or even global economy
Development.
Content of the invention
In order to improve Li4Ti5O12Electron conduction difference problem, the present invention proposes one kind and prepares Vanadium sesquioxide cladding titanium
The method of sour lithium titanate cathode material, to improve the specific capacity under the conditions of its high magnification.
Technical scheme：
1) stirring mixing：Weigh a certain amount of Quilonorm (SKB) and Polyvinylpyrrolidone (PVP), be dissolved in 500mL distilled water；
Add a certain amount of nano titanium oxide, magnetic agitation 1h obtains slurry.
2) it is spray-dried：By step 1) described slurry is spray-dried at 110 DEG C and obtains lithium titanate precursor.
3) Pintsch process：By step 2) described lithium titanate precursor is heat-treated to reaction in air atmosphere and completes, and obtains pure
Lithium titanate anode material；Wherein, described heat treatment is roasting 8h at 750 DEG C.
4) Vanadium sesquioxide cladding lithium titanate precursor preparation：Weigh a certain amount of ammonium metavanadate and glycine, be dissolved in
In 500mL distilled water；Add step 3) described pure lithium titanate anode material, magnetic agitation 1h；After solvent evaporated at 100 DEG C, 80
At DEG C, vacuum drying 1h obtains Vanadium sesquioxide cladding lithium titanate precursor.
5) high-temperature process：By step 4) described Vanadium sesquioxide cladding lithium titanate precursor is heat-treated in argon gas atmosphere
Reaction completes, and obtains target product Vanadium sesquioxide cladding lithium titanate anode material；Wherein, described heat treatment is roasting at 600 DEG C
Burn 6h.
The invention has the beneficial effects as follows：
In lithium titanate Surface coating Vanadium sesquioxide, improve Li4Ti5O12Electron conduction, thus reach acquisition tool
There is the purpose of this composite of high rate capability.
The Vanadium sesquioxide cladding lithium titanate anode material of present invention preparation is pure phase, and crystal grain distribution uniformly, has high power
Rate performance and good cycle performance.When wherein Vanadium sesquioxide covering amount is 2%, the discharge capacity under 0.2C, 10C is respectively
For 173mAhg-1、154mAhg-1；After experiencing the circulation of 200 times under 10C, its discharge capacity is left 96.8%.
Brief description
Fig. 1 is embodiment 1, the X x ray diffration pattern x of embodiment 2, embodiment 3 and embodiment 4 sample.In FIG, horizontal seat
Be designated as 2 θ/°, θ be the angle of diffraction.
Fig. 2 is embodiment 3 transmission electron microscope figure.
Fig. 3 is embodiment 1, embodiment 2, the embodiment 3 and embodiment 4 sample cycle performance under different multiplying.In Fig. 3
In, abscissa is cycle-index, and vertical coordinate is specific capacity/mAhg-1, charge-discharge magnification is respectively 0.2C, and (corresponding circulation is secondary
Number is 0 10 times), 0.5C (corresponding cycle-index be 11 20 times), 1C (corresponding cycle-index is 21 30 times),
2C (corresponding cycle-index be 31 40 times), 5C (corresponding cycle-index is 41 50 times), (corresponding follows 10C
Ring number of times is 51 60 times).
Fig. 4 is the cycle performance under 10C for the negative material of embodiment 3.In the diagram, abscissa is cycle-index, indulges and sits
It is designated as specific capacity/mAhg-1.
Specific embodiment
The present invention prepares the method that Vanadium sesquioxide coats lithium titanate anode material, specifically implements as follows：
1) stirring mixing：Weigh a certain amount of Quilonorm (SKB) and Polyvinylpyrrolidone PVP (molecular weight 40000 (avg)), molten
In 500mL distilled water；Add a certain amount of nano titanium oxide, magnetic agitation 1h obtains slurry.
2) it is spray-dried：By step 1) described slurry is spray-dried at 110 DEG C and obtains lithium titanate precursor.
3) Pintsch process：By step 2) described lithium titanate precursor is heat-treated to reaction in air atmosphere and completes, and obtains pure
Lithium titanate anode material；Wherein, described heat treatment is roasting 8h at 750 DEG C.
4) Vanadium sesquioxide cladding lithium titanate precursor preparation：Weigh a certain amount of ammonium metavanadate and glycine, be dissolved in
In 500mL distilled water；Add step 3) described pure lithium titanate anode material, magnetic agitation 1h；After solvent evaporated at 100 DEG C, 80
At DEG C, vacuum drying 1h obtains Vanadium sesquioxide cladding lithium titanate precursor.
5) high-temperature process：By step 4) described Vanadium sesquioxide cladding lithium titanate precursor is heat-treated in argon gas atmosphere
Reaction completes, and obtains target product Vanadium sesquioxide cladding lithium titanate anode material；Wherein, described heat treatment is roasting at 600 DEG C
Burn 6h.
Embodiment 1
Li4Ti5O12The preparation of negative material
Weigh 0.06mol Quilonorm (SKB) and 1.5g Polyvinylpyrrolidone (PVP), be dissolved in 500mL distilled water；Add
0.075mol nano titanium oxide, magnetic agitation 1h obtains slurry；Slurry is spray-dried at 110 DEG C and obtains lithium titanate forerunner
Body；By lithium titanate precursor, in air atmosphere, roasting 8h at 750 DEG C obtains pure lithium titanate anode material.X x ray diffration pattern x
See Fig. 1.
Embodiment 2
1% Vanadium sesquioxide cladding Li4Ti5O12The preparation of negative material
Weigh 0.06mol Quilonorm (SKB) and 1.5g Polyvinylpyrrolidone (PVP), be dissolved in 500mL distilled water；Add
0.075mol nano titanium oxide, magnetic agitation 1h obtains slurry；Slurry is spray-dried at 110 DEG C and obtains lithium titanate forerunner
Body；By lithium titanate precursor, in air atmosphere, roasting 8h at 750 DEG C obtains pure lithium titanate anode material；Weigh the inclined vanadium of 0.109g
Sour ammonium and 0.01mol glycine, are dissolved in 500mL distilled water；Add pure lithium titanate anode material, magnetic agitation 1h；At 100 DEG C
After solvent evaporated, at 80 DEG C, vacuum drying 1h obtains Vanadium sesquioxide cladding lithium titanate precursor；Vanadium sesquioxide is coated titanium
Sour lithium presoma roasting 6h at 600 DEG C in argon gas atmosphere obtains Vanadium sesquioxide cladding lithium titanate anode material.X ray
Diffraction pattern is shown in Fig. 1.
Embodiment 3
2% Vanadium sesquioxide cladding Li4Ti5O12The preparation of negative material
Weigh 0.06mol Quilonorm (SKB) and 1.5g Polyvinylpyrrolidone (PVP), be dissolved in 500mL distilled water；Add
0.075mol nano titanium oxide, magnetic agitation 1h obtains slurry；Slurry is spray-dried at 110 DEG C and obtains lithium titanate forerunner
Body；By lithium titanate precursor, in air atmosphere, roasting 8h at 750 DEG C obtains pure lithium titanate anode material；Weigh the inclined vanadium of 0.220g
Sour ammonium and 0.01mol glycine, are dissolved in 500mL distilled water；Add pure lithium titanate anode material, magnetic agitation 1h；At 100 DEG C
After solvent evaporated, at 80 DEG C, vacuum drying 1h obtains Vanadium sesquioxide cladding lithium titanate precursor；Vanadium sesquioxide is coated titanium
Sour lithium presoma roasting 6h at 600 DEG C in argon gas atmosphere obtains Vanadium sesquioxide cladding lithium titanate anode material.X ray
Diffraction pattern is shown in Fig. 1, and projection electron microscope figure is shown in Fig. 2.
Embodiment 4
3% Vanadium sesquioxide cladding Li4Ti5O12The preparation of negative material
Weigh 0.06mol Quilonorm (SKB) and 1.5g Polyvinylpyrrolidone (PVP), be dissolved in 500mL distilled water；Add
0.075mol nano titanium oxide, magnetic agitation 1h obtains slurry；Slurry is spray-dried at 110 DEG C and obtains lithium titanate forerunner
Body；By lithium titanate precursor, in air atmosphere, roasting 8h at 750 DEG C obtains pure lithium titanate anode material；Weigh the inclined vanadium of 0.333g
Sour ammonium and 0.01mol glycine, are dissolved in 500mL distilled water；Add pure lithium titanate anode material, magnetic agitation 1h；At 100 DEG C
After solvent evaporated, at 80 DEG C, vacuum drying 1h obtains Vanadium sesquioxide cladding lithium titanate precursor；Vanadium sesquioxide is coated titanium
Sour lithium presoma roasting 6h at 600 DEG C in argon gas atmosphere obtains Vanadium sesquioxide cladding lithium titanate anode material.X ray
Diffraction pattern is shown in Fig. 1.
It is consistent with document report with the diffraction maximum of embodiment 4 gained sample by Fig. 1 embodiment 1, embodiment 2, embodiment 3,
Show not interfering with Li in Vanadium sesquioxide cladding4Ti5O12Phase.
As seen from Figure 2, lithium titanate Surface coating 4nm thickness Vanadium sesquioxide in embodiment 3 gained sample.
The composite negative pole material of present invention preparation can prepare negative electrode for lithium ion battery using coating method.Its concrete operations is
By active component (Li4Ti5O12), conductive agent Super-Pcarbon, binding agent LA132 press 85:10:5 mass ratio mixing, so
After be evenly coated on aluminium foil, through 100 DEG C vacuum drying after obtain negative plate.
Electrochemical property test：
Negative pole (negative pole preparation method is as above), lithium metal are made for active component with the material that above-described embodiment prepares
For positive pole, Celgard2400 is barrier film, 1mol/LLiPF6EC/DEC/DMC (volume ratio be 1:1:1) solution is electrolyte.
It is assembled into CR2032 button cell, constant current charge-discharge performance test is carried out on battery test system.Charge voltage range be 1～
3V.Cycle performance figure see Fig. 3,4.
Fig. 3 be according to embodiment 1, embodiment 2, embodiment 3 and embodiment 4 be obtained sample 0.2C, 0.5C, 1C, 2C,
Cycle performance under 5C, 10C.From figure 3, it can be seen that increasing with Vanadium sesquioxide covering amount, Li4Ti5O12In each charge and discharge
Discharge capacity under electric multiplying power first increases and reduces afterwards, and wherein Vanadium sesquioxide covering amount is to have best electrochemistry when 2%
Can, in Li4Ti5O12/ C is respectively 173mAh/g, 154mAh/g in the discharge capacity of 0.2C, 10C.
Fig. 4 is obtained circulation under 10C for the sample for embodiment 3.It can be seen that after the experience circulation of 100 times, its electric discharge is held
Amount is left 96.8%, shows that Vanadium sesquioxide cladding lithium titanate has preferable cycle performance under 10C.
Claims (6)
1. a kind of prepare Vanadium sesquioxide coat lithium titanate anode material method it is characterised in that：The concrete step of methods described
Suddenly it is,
1) stirring mixing
Quilonorm (SKB) and Polyvinylpyrrolidone PVP are dissolved in 500mL distilled water, add nano titanium oxide, magnetic agitation 1h
Obtain slurry；
2) it is spray-dried
By step 1) gained slurry spraying be dried to obtain lithium titanate precursor；
3) Pintsch process
By step 2) gained lithium titanate precursor is heat-treated to reaction in air atmosphere and completes, and obtains pure lithium titanate anode material；
4) Vanadium sesquioxide cladding lithium titanate precursor preparation
Ammonium metavanadate and glycine are dissolved in 500mL distilled water, add step 3) the pure lithium titanate anode material of gained, magnetic force stirs
Mix 1h, vacuum drying after solvent evaporated obtains Vanadium sesquioxide cladding lithium titanate precursor；
5) high-temperature process
By step 4) gained Vanadium sesquioxide cladding lithium titanate precursor is heat-treated to reaction in argon gas atmosphere and completes, and obtains target
Product Vanadium sesquioxide coats lithium titanate anode material.
2. prepare as claimed in claim 1 Vanadium sesquioxide coat lithium titanate anode material method it is characterised in that：Step
2) be spray-dried described in is to be spray-dried at 110 DEG C.
3. prepare as claimed in claim 1 Vanadium sesquioxide coat lithium titanate anode material method it is characterised in that：Step
3) heat treatment described in is roasting 8h at 750 DEG C.
4. prepare as claimed in claim 1 Vanadium sesquioxide coat lithium titanate anode material method it is characterised in that：Step
4) solvent evaporated described in is solvent evaporated at 100 DEG C.
5. prepare as claimed in claim 1 Vanadium sesquioxide coat lithium titanate anode material method it is characterised in that：Step
4) vacuum drying described in is vacuum dried 1h at being 80 DEG C.
6. prepare as claimed in claim 1 Vanadium sesquioxide coat lithium titanate anode material method it is characterised in that：Step
5) heat treatment described in is roasting 6h at 600 DEG C.
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| CN107808953B (en) * | 2017-10-17 | 2020-05-22 | 合肥国轩高科动力能源有限公司 | Preparation method of lithium titanate negative electrode material with low moisture absorption and less gas generation |
| CN108574097B (en) * | 2018-05-16 | 2020-08-11 | 合肥工业大学 | Lithium ion battery cathode material |
| CN112125340B (en) * | 2020-09-18 | 2022-05-17 | 厦门厦钨新能源材料股份有限公司 | Lithium manganate and preparation method and application thereof |
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| 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 |
| KR101108189B1 (en) * | 2010-06-11 | 2012-01-31 | 삼성에스디아이 주식회사 | Negative active material, and electrode and lithium battery containing the material |
| CN102299313A (en) * | 2011-08-10 | 2011-12-28 | 东莞市迈科科技有限公司 | Preparation method of spinel-type lithium titanate |
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