CN109748255B - 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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- CN109748255B CN109748255B CN201811542451.2A CN201811542451A CN109748255B CN 109748255 B CN109748255 B CN 109748255B CN 201811542451 A CN201811542451 A CN 201811542451A CN 109748255 B CN109748255 B CN 109748255B
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- 229910019142 PO4 Inorganic materials 0.000 title claims abstract description 21
- 238000000034 method Methods 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 18
- 239000010452 phosphate Substances 0.000 title claims abstract description 18
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 8
- 239000010405 anode material Substances 0.000 title abstract description 8
- 229920000447 polyanionic polymer Polymers 0.000 title abstract description 7
- 239000002904 solvent Substances 0.000 claims abstract description 25
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims abstract description 24
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 18
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims abstract description 18
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000004094 surface-active agent Substances 0.000 claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 229910012265 LiPO2F2 Inorganic materials 0.000 claims abstract description 3
- 229910001386 lithium phosphate Inorganic materials 0.000 claims abstract description 3
- 239000000203 mixture Substances 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
- 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
- 235000010482 polyoxyethylene sorbitan monooleate Nutrition 0.000 claims description 7
- 229920000053 polysorbate 80 Polymers 0.000 claims description 7
- 239000010406 cathode material Substances 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 6
- 238000001694 spray drying Methods 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 4
- 239000002243 precursor Substances 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 4
- 238000005204 segregation Methods 0.000 abstract description 4
- 239000006185 dispersion Substances 0.000 abstract description 3
- 229910052744 lithium Inorganic materials 0.000 abstract description 3
- 238000005063 solubilization Methods 0.000 abstract description 3
- 230000007928 solubilization Effects 0.000 abstract description 3
- 150000001875 compounds Chemical class 0.000 abstract description 2
- 239000007774 positive electrode material Substances 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 2
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 2
- DVATZODUVBMYHN-UHFFFAOYSA-K lithium;iron(2+);manganese(2+);phosphate Chemical compound [Li+].[Mn+2].[Fe+2].[O-]P([O-])([O-])=O DVATZODUVBMYHN-UHFFFAOYSA-K 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000007790 solid phase Substances 0.000 description 2
- 238000010532 solid phase synthesis reaction Methods 0.000 description 2
- 229910015645 LiMn Inorganic materials 0.000 description 1
- 229910012258 LiPO Inorganic materials 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 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
- 238000004458 analytical method Methods 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
- 238000005516 engineering process Methods 0.000 description 1
- VEPSWGHMGZQCIN-UHFFFAOYSA-H ferric oxalate Chemical compound [Fe+3].[Fe+3].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O VEPSWGHMGZQCIN-UHFFFAOYSA-H 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 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
- 238000005245 sintering Methods 0.000 description 1
- 238000003980 solgel 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
Abstract
The invention discloses a solution for synthesizing polyanion phosphate anode material by a semi-wet method, which comprises the following components in percentage by massThe following components: 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 an inorganic new energy material, and particularly relates to a solution for synthesizing a polyanionic phosphate anode material by a semi-wet method.
Background
Polyanion phosphate positive electrode materials represented by lithium iron phosphate have good cycle stability because of having a stable anion structure, and most of the polyanion positive electrode materials on the market at present have a phosphate structure, such as lithium iron phosphate, lithium manganese phosphate, lithium vanadium phosphate, lithium iron manganese phosphate and the like.
The methods suitable for the industrial production of the polyanionic phosphate positive electrode materials are mainly solid-phase production processes, but the solid-phase method has a series of problems of poor batch consistency, unstable quality and the like in essence, and the preparation methods of the polyanionic phosphate positive electrode materials, such as wet chemical methods of a hydrothermal method, a sol-gel method and the like, are relatively suitable for the preparation of small-batch samples although the consistency is good, so in order to solve the problem of poor consistency caused by the solid-phase method, semi-wet method synthesis polyanionic phosphate positive electrode materials represented by spray drying are developed in the industry successively.
The method mainly represents a process that transition metal oxide (or other types of transition metal salt) is mixed with a solution containing lithium and phosphate, and then high-temperature spray drying is carried out, so that the quality consistency of the obtained product is better than that of the traditional solid-phase production process, but the method has the main problems that the solution system is easy to cause raw material concentration segregation in the drying process to cause quality fluctuation, and on the other hand, in order to realize material modification, some modifying ions are often added into the solution, but the modifying ions usually exist in the form of insoluble components, so that the mixing uniformity degree of the product precursor is reduced.
Disclosure of Invention
The invention provides a solution for synthesizing a polyanion phosphate anode material by a semi-wet method for solving the technical problems in the known technology, can effectively solve the problem of raw material concentration segregation in the spray drying process of a precursor of the polyanion phosphate anode material, and has good solubilization and dispersion effects on insoluble components of the solution used for modifying the material.
In order to solve the technical problems, the invention adopts the technical scheme that: a solution for synthesizing polyanionic phosphate cathode material by a semi-wet method comprises the following components in percentage by mass:
solute 5.5-10%
80 to 92 percent of solvent
2.5 to 10 percent of solubilizer
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 soluteIs Li3PO4、LiPO2F2、LiPOF3One kind of (1).
The surfactant is formed by mixing tween-80 and span-60 according to a volume ratio of tween-80/span-60 of 2-15.
The invention has the beneficial effects that: 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 of the solution used for modifying the material.
Detailed Description
In order to further understand the contents, features and effects of the present invention, the following examples are illustrated and described in detail as follows:
example 1
A solution for semi-wet synthesizing polyanionic phosphate as positive electrode material contains Li as solute component3PO4The mass percent is 6%, and the solvent components are ethanol: n-butanol: isopropyl alcohol: butanediol: water-8%: 6%: 3%: 7%: 76 percent of solvent, 90.5 percent of total mass percent of solvent, and the solubilizer is surfactant with the volume ratio of tween-80/span-60 ═ 5, and the total mass percent of the solubilizer is 3.5 percent.
Example 2
A solution for semi-wet synthesis of polyanionic phosphate as positive electrode material contains LiPO as solute component2F2The mass percent is 7%, and the solvent components are ethanol: n-butanol: isopropyl alcohol: butanediol: 15% of water: 7%: 4%: 6%: 68 percent of solvent, 88 percent of solubilizer in total mass percent, wherein the solubilizer is surfactant with the volume ratio of tween-80/span-60 ═ 8, and the solubilizer is 5 percent in total mass percent.
Example 3
A solution for semi-wet synthesis of polyanionic phosphate positive electrode material contains LiPOF as solute component3The mass percent is 8%, and the solvent components are ethanol: n-butanol: isopropyl alcohol: butanediol: water is 9%: 8%: 4%: 6%: 73 percent of the total mass percent of the solvent, 85 percent of the solubilizer which is a surfactant with the volume ratio of tween-80/span-60 ═ 15, and the total mass of the solubilizerThe amount percentage is 7%.
Comparative example 1
Preparing LiH with the mass percentage of 15%2PO4Solutions of
The LiMn is prepared by ball milling, mixing, spray drying and sintering the iron oxalate and the manganese acetate respectively in the examples 1, 2 and 3 and the comparative example 10.5Fe0.5PO4material/C, 10 batches were prepared and submitted to consistency analysis with the following performance comparisons:
| examples of such applications are | Example 1 | Example 2 | Example 3 | Comparative example 1 |
| First batch | 165 | 160 | 155 | 148 |
| Second batch | 164 | 159 | 156 | 152 |
| Third batch | 163 | 162 | 154 | 155 |
| Fourth batch | 165 | 161 | 155 | 142 |
| Fifth batch | 164 | 162 | 155 | 151 |
| Sixth batch of | 166 | 159 | 155 | 140 |
| Seventh batch of | 166 | 160 | 156 | 153 |
| Eighth batch | 163 | 162 | 154 | 151 |
| Ninth batch (C) | 165 | 161 | 155 | 140 |
| The tenth batch | 165 | 162 | 155 | 153 |
| Mean value of | 164.6 | 160.8 | 155 | 148.5 |
| Standard deviation of | 1.0198 | 1.1662 | 0.6324 | 5.4268 |
| Variance (variance) | 1.04 | 1.36 | 0.40 | 29.45 |
Therefore, the lithium iron manganese phosphate sample prepared by the solution prepared by the invention is better than the sample prepared by the lithium dihydrogen phosphate solution in performance and volume batch consistency
The above-mentioned embodiments are only for illustrating the technical ideas and features of the present invention, and the purpose thereof is to enable those skilled in the art to understand the contents of the present invention and to carry out the same, and the present invention shall not be limited to the embodiments, i.e. the equivalent changes or modifications made within the spirit of the present invention shall fall within the scope of the present invention.
Claims (1)
1. The solution for synthesizing the polyanionic phosphate cathode material by the semi-wet method is characterized by comprising the following components in percentage by mass:
solute 5.5-10%
80 to 92 percent of solvent
2.5 to 10 percent of solubilizer
The solute is Li3PO4、LiPO2F2、LiPOF3One of (1); 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, and the surfactant is formed by mixing tween-80 and span-60 according to a volume ratio of tween-80/span-60 of 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 |
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- 2018-12-17 CN CN201811542451.2A patent/CN109748255B/en active Active
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| 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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