CN109748255A - Solution for synthesizing polyanion phosphate anode material by semi-wet method - Google Patents
Solution for synthesizing polyanion phosphate anode material by semi-wet method Download PDFInfo
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- CN109748255A CN109748255A CN201811542451.2A CN201811542451A CN109748255A CN 109748255 A CN109748255 A CN 109748255A CN 201811542451 A CN201811542451 A CN 201811542451A CN 109748255 A CN109748255 A CN 109748255A
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- solution
- solute
- solubilizer
- polyanion
- solvent
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- 238000000034 method Methods 0.000 title claims abstract description 24
- 229910019142 PO4 Inorganic materials 0.000 title claims abstract description 19
- 239000010452 phosphate Substances 0.000 title claims abstract description 18
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 title claims abstract description 17
- 229920000447 polyanionic polymer Polymers 0.000 title claims description 16
- 230000002194 synthesizing effect Effects 0.000 title abstract description 3
- 239000010405 anode material Substances 0.000 title abstract 3
- 239000002904 solvent Substances 0.000 claims abstract description 24
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims abstract description 19
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims abstract description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 17
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000004094 surface-active agent Substances 0.000 claims abstract description 8
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 6
- 239000000203 mixture Substances 0.000 claims abstract description 6
- 229910012265 LiPO2F2 Inorganic materials 0.000 claims abstract description 4
- 229910001386 lithium phosphate Inorganic materials 0.000 claims abstract description 4
- 150000001875 compounds Chemical class 0.000 claims abstract description 3
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical group [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 claims abstract description 3
- 239000010406 cathode material Substances 0.000 claims description 14
- 230000015572 biosynthetic process Effects 0.000 claims description 9
- 238000003786 synthesis reaction Methods 0.000 claims description 9
- HVUMOYIDDBPOLL-XWVZOOPGSA-N Sorbitan monostearate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O HVUMOYIDDBPOLL-XWVZOOPGSA-N 0.000 claims description 7
- 235000019441 ethanol Nutrition 0.000 claims description 7
- 235000010482 polyoxyethylene sorbitan monooleate Nutrition 0.000 claims description 7
- 229920000053 polysorbate 80 Polymers 0.000 claims description 7
- 125000005909 ethyl alcohol group Chemical group 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 9
- 238000001694 spray drying Methods 0.000 abstract description 5
- 238000002156 mixing Methods 0.000 abstract description 3
- 238000005204 segregation Methods 0.000 abstract description 3
- 239000006185 dispersion Substances 0.000 abstract description 2
- 230000000694 effects Effects 0.000 abstract description 2
- 239000002243 precursor Substances 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract 1
- 230000007928 solubilization Effects 0.000 abstract 1
- 238000005063 solubilization Methods 0.000 abstract 1
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910052493 LiFePO4 Inorganic materials 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- AWKHTBXFNVGFRX-UHFFFAOYSA-K iron(2+);manganese(2+);phosphate Chemical compound [Mn+2].[Fe+2].[O-]P([O-])([O-])=O AWKHTBXFNVGFRX-UHFFFAOYSA-K 0.000 description 2
- 239000007790 solid phase Substances 0.000 description 2
- 238000010532 solid phase synthesis reaction Methods 0.000 description 2
- 229910016096 LiMn0.5Fe0.5PO4 Inorganic materials 0.000 description 1
- ZVKRVGZVXQYLPZ-UHFFFAOYSA-N [Li].[V].P(O)(O)(O)=O Chemical compound [Li].[V].P(O)(O)(O)=O ZVKRVGZVXQYLPZ-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000001450 anions Chemical group 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 229940062993 ferrous oxalate Drugs 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- OWZIYWAUNZMLRT-UHFFFAOYSA-L iron(2+);oxalate Chemical compound [Fe+2].[O-]C(=O)C([O-])=O OWZIYWAUNZMLRT-UHFFFAOYSA-L 0.000 description 1
- SNKMVYBWZDHJHE-UHFFFAOYSA-M lithium;dihydrogen phosphate Chemical compound [Li+].OP(O)([O-])=O SNKMVYBWZDHJHE-UHFFFAOYSA-M 0.000 description 1
- ILXAVRFGLBYNEJ-UHFFFAOYSA-K lithium;manganese(2+);phosphate Chemical compound [Li+].[Mn+2].[O-]P([O-])([O-])=O ILXAVRFGLBYNEJ-UHFFFAOYSA-K 0.000 description 1
- 229940071125 manganese acetate Drugs 0.000 description 1
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 1
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- -1 transition metal salt Chemical class 0.000 description 1
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- Battery Electrode And Active Subsutance (AREA)
- Secondary Cells (AREA)
Abstract
The invention discloses a solution for synthesizing a polyanionic phosphate anode material by a semi-wet method, which comprises the following components in percentage by mass: 5.5-10% of solute, 80-92% of solvent and 2.5-10% of solubilizer, wherein the solute is a compound containing Li and P elements; the solvent is a mixture of ethanol, n-butanol, isopropanol, butanediol and water, and the mixing proportion is ethanol: n-butanol: isopropyl alcohol: butanediol: 5% -15% of water: 5% -8%: 2% -4%: 5% -9%: 64% -83%; the solubilizer is a surfactant. The solute is Li3PO4、LiPO2F2、LiPOF3One kind of (1). The method can effectively solve the problem of raw material concentration segregation in the process of spray drying the precursor of the polyanionic phosphate anode material, and has good solubilization and dispersion effects on insoluble components in the solution used for modifying the material.
Description
Technical field
The invention belongs to inorganic new energy materials, are synthesizing polyanion phosphate just for half wet process more particularly to one kind
The solution of pole material.
Background technique
Using LiFePO4 as the polyanion phosphate cathode material of representative, because it is with stable anion structure, because
This is with good cyclical stability, and polyanion positive electrode on the market is mostly phosphate structure at present, as LiFePO4,
Lithium manganese phosphate, phosphoric acid vanadium lithium, iron manganese phosphate for lithium etc..
The above polyanion phosphate cathode material, being suitble to the method for its industrialization production is mainly solid phase production work
Skill, but a series of problems, such as solid phase method essentially has batch consistency poor from it, and quality is unstable, preparation method
Such as hydro-thermal method, sol-gal process wet chemical method are relatively more suitable for the sample system of small lot although consistency is fine
It is standby, therefore in order to improve the problem of solid phase method bring consistency difference, industrial circle is developed in succession to be spray-dried as representative
Half wet process synthesizes polyanion phosphate cathode material.
Its main representative technique is exactly by transition metal oxide (or other kinds of transition metal salt) and containing lithium, phosphoric acid
The solution of root mixes, then carries out high temperature spray-drying, and it is raw that its quality consistency of the product obtained in this way is better than traditional solid phase
Production. art, but main problem existing for this method is, and solution system be easy to cause material concentration to be segregated in the drying process, causes
Quality fluctuation, still further aspect also tend to that some modified ions are added in the solution to realize the modification of material, but it is modified from
Son usually exists in the form of insoluble component, so that the mixing uniformity of product precursor declines.
Summary of the invention
The present invention is to solve technical problem present in well-known technique and provide a kind of for half wet process synthesis polyanion
The solution of phosphate cathode material can effectively solve the original in polyanion phosphate cathode material presoma spray-drying process
Expect concentration segregation problems, do not dissolve component simultaneously for solution used in material modification, there is good solubilising and dispersion to make
With.
In order to solve the above-mentioned technical problem, the technical solution adopted by the present invention is that: one kind for the poly- yin of half wet process synthesis from
The solution of sub- phosphate cathode material, by mass percentage, including following components:
Solute 5.5%-10%
Solvent 80-92%
Solubilizer 2.5%-10%
The solute is the compound containing Li and P element simultaneously；Solvent be ethyl alcohol, n-butanol, isopropanol, butanediol and
The mixture of water, by mass percentage, mixed proportion are ethyl alcohol: n-butanol: isopropanol: butanediol: water=5%-15%:
5%-8%:2%-4%:5%-9%:64%-83%；The solubilizer is surfactant.
The solute is Li3PO4、LiPO2F2、LiPOF3One of.
The surfactant is that Tween-80 and Span -60 are mixed according to volume ratio Tween-80/Span -60=2~15.
The beneficial effects of the present invention are: polyanion phosphate cathode material presoma spray-drying process can be solved effectively
In material concentration segregation problems, simultaneously for solution used in material modification do not dissolve component, have it is good solubilising and
Peptizaiton.
Specific embodiment
In order to further understand the content, features and effects of the present invention, the following examples are hereby given, and it is described in detail
It is as follows:
Embodiment 1
A kind of solution for half wet process synthesis polyanion phosphate cathode material, solute component Li3PO4Quality hundred
It is divided into 6%, solvent composition is ethyl alcohol: n-butanol: isopropanol: butanediol: water=8%:6%:3%:7%:76%, the total matter of solvent
Percentage 90.5% is measured, solubilizer is volume ratio Tween-80/Span -60=5 surfactant, the gross mass hundred of solubilizer
Divide ratio 3.5%.
Embodiment 2
A kind of solution for half wet process synthesis polyanion phosphate cathode material, solute component LiPO2F2Quality hundred
Be divided into 7%, solvent composition is ethyl alcohol: n-butanol: isopropanol: butanediol: water=15%:7%:4%:6%:68%, solvent are total
Mass percent 88%, solubilizer are volume ratio Tween-80/Span -60=8 surfactant, the gross mass hundred of solubilizer
Divide ratio 5%.
Embodiment 3
A kind of solution for half wet process synthesis polyanion phosphate cathode material, solute component LiPOF3Quality hundred
It is divided into 8%, solvent composition is ethyl alcohol: n-butanol: isopropanol: butanediol: water=9%:8%:4%:6%:73%, the total matter of solvent
Percentage 85% is measured, solubilizer is volume ratio Tween-80/Span -60=15 surfactant, the gross mass percentage of solubilizer
Than 7%.
Comparative example 1
Prepare the LiH that mass percent is 15%2PO4Solution
Embodiment 1,2,3 and comparative example 1 are burnt with after ferrous oxalate, the spray drying of manganese acetate ball milling mixing respectively
Knot prepares LiMn0.5Fe0.5PO4/ C-material carries out consistency analysis after preparing 10 batches, and performance comparison is as shown in the table:
| Citing | Embodiment 1 | Embodiment 2 | Embodiment 3 | Comparative example 1 |
| First | 165 | 160 | 155 | 148 |
| Second batch | 164 | 159 | 156 | 152 |
| Third batch | 163 | 162 | 154 | 155 |
| 4th batch | 165 | 161 | 155 | 142 |
| 5th batch | 164 | 162 | 155 | 151 |
| 6th batch | 166 | 159 | 155 | 140 |
| 7th batch | 166 | 160 | 156 | 153 |
| 8th batch | 163 | 162 | 154 | 151 |
| 9th batch | 165 | 161 | 155 | 140 |
| Tenth batch | 165 | 162 | 155 | 153 |
| Average value | 164.6 | 160.8 | 155 | 148.5 |
| Standard deviation | 1.0198 | 1.1662 | 0.6324 | 5.4268 |
| Variance | 1.04 | 1.36 | 0.40 | 29.45 |
As it can be seen that the iron manganese phosphate for lithium sample prepared using the solution that the present invention prepares, in performance and capacity batch one
All it is better than the sample that lithium dihydrogen phosphate solution prepares in cause property
Embodiment described above is merely to illustrate technical idea and feature of the invention, in the art its object is to make
Technical staff it will be appreciated that the contents of the present invention and implement accordingly, patent model of the invention only cannot be limited with the present embodiment
It encloses, i.e., same changes or modifications made by all disclosed spirit are still fallen in the scope of the patents of the invention.
Claims (3)
1. a kind of solution for half wet process synthesis polyanion phosphate cathode material, which is characterized in that by mass percentage,
Including following components:
Solute 5.5%-10%
Solvent 80-92%
Solubilizer 2.5%-10%
The solute is the compound containing Li and P element simultaneously；Solvent is ethyl alcohol, n-butanol, isopropanol, butanediol and water
Mixture, by mass percentage, mixed proportion are ethyl alcohol: n-butanol: isopropanol: butanediol: water=5%-15%:5%-
8%:2%-4%:5%-9%:64%-83%；The solubilizer is surfactant.
2. the solution for half wet process synthesis polyanion phosphate cathode material according to claim 1, which is characterized in that
The solute is Li3PO4、LiPO2F2、LiPOF3One of.
3. the solution for half wet process synthesis polyanion phosphate cathode material according to claim 1, which is characterized in that
The surfactant is that Tween-80 and Span -60 are mixed according to volume ratio Tween-80/Span -60=2~15.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101913588A (en) * | 2010-07-08 | 2010-12-15 | 中国科学院宁波材料技术与工程研究所 | Method for preparing lithium iron phosphate nano material |
| CN102315444A (en) * | 2010-07-08 | 2012-01-11 | 中国科学院宁波材料技术与工程研究所 | Nano-modified polyanionic cathode active material, preparation method thereof, and lithium ion secondary battery |
| CN103413943A (en) * | 2013-08-14 | 2013-11-27 | 宁波奈克斯特新材料科技有限公司 | Lithium manganese phosphate positive electrode material and preparation method thereof |
-
2018
- 2018-12-17 CN CN201811542451.2A patent/CN109748255B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101913588A (en) * | 2010-07-08 | 2010-12-15 | 中国科学院宁波材料技术与工程研究所 | Method for preparing lithium iron phosphate nano material |
| CN102315444A (en) * | 2010-07-08 | 2012-01-11 | 中国科学院宁波材料技术与工程研究所 | Nano-modified polyanionic cathode active material, preparation method thereof, and lithium ion secondary battery |
| CN103413943A (en) * | 2013-08-14 | 2013-11-27 | 宁波奈克斯特新材料科技有限公司 | Lithium manganese phosphate positive electrode material and preparation method thereof |
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