CN114348982A - Ferrous manganous phosphate, ferrous manganous lithium phosphate, preparation methods thereof, lithium ion battery and electric equipment - Google Patents
Ferrous manganous phosphate, ferrous manganous lithium phosphate, preparation methods thereof, lithium ion battery and electric equipment Download PDFInfo
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- CN114348982A CN114348982A CN202210021266.9A CN202210021266A CN114348982A CN 114348982 A CN114348982 A CN 114348982A CN 202210021266 A CN202210021266 A CN 202210021266A CN 114348982 A CN114348982 A CN 114348982A
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- 229910019142 PO4 Inorganic materials 0.000 title claims abstract description 51
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 title claims abstract description 44
- 239000010452 phosphate Substances 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 title claims abstract description 17
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 16
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 16
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 title claims description 15
- 229910001386 lithium phosphate Inorganic materials 0.000 title claims description 14
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 74
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 52
- 239000011572 manganese Substances 0.000 claims abstract description 47
- 239000002002 slurry Substances 0.000 claims abstract description 44
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 42
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 37
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 33
- 230000032683 aging Effects 0.000 claims abstract description 33
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 33
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 32
- 238000001035 drying Methods 0.000 claims abstract description 31
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 27
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 27
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 26
- 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 claims abstract description 25
- 229910052742 iron Inorganic materials 0.000 claims abstract description 23
- 238000000227 grinding Methods 0.000 claims abstract description 19
- 239000002994 raw material Substances 0.000 claims abstract description 19
- 229910000616 Ferromanganese Inorganic materials 0.000 claims abstract description 17
- JEBAUTBPSKCVJM-UHFFFAOYSA-N [P].[Mn].[Fe] Chemical compound [P].[Mn].[Fe] JEBAUTBPSKCVJM-UHFFFAOYSA-N 0.000 claims abstract description 17
- DALUDRGQOYMVLD-UHFFFAOYSA-N iron manganese Chemical compound [Mn].[Fe] DALUDRGQOYMVLD-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000000843 powder Substances 0.000 claims abstract description 17
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 claims abstract description 16
- 238000002156 mixing Methods 0.000 claims abstract description 15
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910000398 iron phosphate Inorganic materials 0.000 claims abstract description 14
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 14
- 239000011574 phosphorus Substances 0.000 claims abstract description 14
- KWCHQJSISLQWHH-UHFFFAOYSA-N phosphoric acid;trihydrate Chemical compound O.O.O.OP(O)(O)=O KWCHQJSISLQWHH-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000007865 diluting Methods 0.000 claims abstract description 9
- 239000002904 solvent Substances 0.000 claims abstract description 7
- 239000007788 liquid Substances 0.000 claims abstract description 5
- 238000000926 separation method Methods 0.000 claims abstract description 4
- 239000000463 material Substances 0.000 claims description 27
- 238000000034 method Methods 0.000 claims description 24
- 239000002245 particle Substances 0.000 claims description 20
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 14
- 239000008103 glucose Substances 0.000 claims description 14
- CPSYWNLKRDURMG-UHFFFAOYSA-L hydron;manganese(2+);phosphate Chemical compound [Mn+2].OP([O-])([O-])=O CPSYWNLKRDURMG-UHFFFAOYSA-L 0.000 claims description 11
- 229940093474 manganese carbonate Drugs 0.000 claims description 11
- 235000006748 manganese carbonate Nutrition 0.000 claims description 11
- 239000011656 manganese carbonate Substances 0.000 claims description 11
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 claims description 11
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 claims description 11
- 239000007787 solid Substances 0.000 claims description 11
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 10
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- 239000002244 precipitate Substances 0.000 claims description 9
- QSNQXZYQEIKDPU-UHFFFAOYSA-N [Li].[Fe] Chemical compound [Li].[Fe] QSNQXZYQEIKDPU-UHFFFAOYSA-N 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 4
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 4
- PPNAOCWZXJOHFK-UHFFFAOYSA-N manganese(2+);oxygen(2-) Chemical compound [O-2].[Mn+2] PPNAOCWZXJOHFK-UHFFFAOYSA-N 0.000 claims description 4
- VASIZKWUTCETSD-UHFFFAOYSA-N manganese(II) oxide Inorganic materials [Mn]=O VASIZKWUTCETSD-UHFFFAOYSA-N 0.000 claims description 4
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 4
- 239000013618 particulate matter Substances 0.000 claims description 3
- 238000010298 pulverizing process Methods 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims 1
- AWKHTBXFNVGFRX-UHFFFAOYSA-K iron(2+);manganese(2+);phosphate Chemical compound [Mn+2].[Fe+2].[O-]P([O-])([O-])=O AWKHTBXFNVGFRX-UHFFFAOYSA-K 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 37
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 20
- 239000000047 product Substances 0.000 description 15
- CURXSYBGPUHYTE-UHFFFAOYSA-K [OH-].[OH-].[OH-].[Fe+3].OP(O)(O)=O Chemical compound [OH-].[OH-].[OH-].[Fe+3].OP(O)(O)=O CURXSYBGPUHYTE-UHFFFAOYSA-K 0.000 description 12
- 238000007873 sieving Methods 0.000 description 12
- 238000004090 dissolution Methods 0.000 description 10
- 229910052757 nitrogen Inorganic materials 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 8
- 239000004576 sand Substances 0.000 description 7
- 238000001694 spray drying Methods 0.000 description 7
- 238000010790 dilution Methods 0.000 description 6
- 239000012895 dilution Substances 0.000 description 6
- 229910015835 LiMn0.65Fe0.35PO4 Inorganic materials 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000005955 Ferric phosphate Substances 0.000 description 3
- 229940032958 ferric phosphate Drugs 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 229910000399 iron(III) phosphate Inorganic materials 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- 238000010532 solid phase synthesis reaction Methods 0.000 description 3
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 239000007790 solid phase Substances 0.000 description 2
- 229910015855 LiMn0.7Fe0.3PO4 Inorganic materials 0.000 description 1
- 229910015944 LiMn0.8Fe0.2PO4 Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 229960005070 ascorbic acid Drugs 0.000 description 1
- 235000010323 ascorbic acid Nutrition 0.000 description 1
- 239000011668 ascorbic acid Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000007323 disproportionation reaction Methods 0.000 description 1
- PQVSTLUFSYVLTO-UHFFFAOYSA-N ethyl n-ethoxycarbonylcarbamate Chemical compound CCOC(=O)NC(=O)OCC PQVSTLUFSYVLTO-UHFFFAOYSA-N 0.000 description 1
- 229940116007 ferrous phosphate Drugs 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 229910000155 iron(II) phosphate Inorganic materials 0.000 description 1
- SDEKDNPYZOERBP-UHFFFAOYSA-H iron(ii) phosphate Chemical compound [Fe+2].[Fe+2].[Fe+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O SDEKDNPYZOERBP-UHFFFAOYSA-H 0.000 description 1
- GLXDVVHUTZTUQK-UHFFFAOYSA-M lithium hydroxide monohydrate Substances [Li+].O.[OH-] GLXDVVHUTZTUQK-UHFFFAOYSA-M 0.000 description 1
- 229940040692 lithium hydroxide monohydrate Drugs 0.000 description 1
- -1 manganese iron phosphate trihydrate Chemical compound 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
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Abstract
The application provides ferromanganese phosphate, lithium ferromanganese phosphate, a preparation method thereof, a lithium ion battery and electric equipment. The preparation method of the ferrous manganous phosphate comprises the following steps: mixing raw materials including iron powder, a manganese source and phosphoric acid, and carrying out solid-liquid separation to obtain a manganese-iron-phosphorus solution; diluting the ferromanganese phosphate solution with water, and then aging in an inert atmosphere to obtain the ferric manganous phosphate trihydrate. The ferrous manganous phosphate is prepared by the preparation method. The raw material of the lithium manganese iron phosphate comprises manganese iron phosphate. The preparation method of the lithium manganese iron phosphate comprises the following steps: mixing raw materials including manganous iron phosphate, a lithium source, a phosphorus source, a carbon source and a solvent to obtain slurry; and grinding and drying the slurry to obtain powder, and roasting to obtain the carbon-coated lithium manganese iron phosphate. The raw material of the lithium ion battery comprises lithium manganous phosphate. An electric device comprising a lithium ion battery. According to the preparation method of the manganous iron phosphate, the manganese and the iron are mixed at the atomic level, and the prepared manganous iron phosphate has excellent electrochemical performance.
Description
Technical Field
The application relates to the field of materials, in particular to ferromanganese phosphate, lithium ferromanganese phosphate, a preparation method of the ferromanganese phosphate, a lithium ion battery and electric equipment.
Background
The lithium ferrous manganese phosphate as the next generation material of lithium ferrous phosphate has the advantages of high voltage platform, large energy density and the like. Particularly, the ternary battery is compounded with ternary materials, the energy density is ensured, and meanwhile, the safety performance of the ternary battery is greatly improved, so that the ternary battery is a hot spot of current research and development in China.
At present, the synthesis method of the ferromanganese phosphate is many and basically similar to the synthesis of the lithium iron phosphate. The pure solid phase method comprises the steps of directly sintering raw materials such as a phosphorus source, an iron source, a manganese source, a lithium source and the like to obtain the manganous iron lithium phosphate, or synthesizing manganese phosphate as the manganese source and part of the phosphorus source, mixing the manganese phosphate, the iron source and the lithium source, and sintering to obtain the manganous iron lithium phosphate. The method has the disadvantages that uniform mixing of manganese and iron on an atomic layer can not be realized, and the prepared manganous iron phosphate has poor charging constant voltage section and rate discharge performance; and the trivalent manganese is easy to generate disproportionation reaction in the solution to generate bivalent manganese and tetravalent manganese, and the purity of the product is not high.
Some lithium iron manganous phosphate is prepared by a hydrothermal method, but the use amount of lithium is 3 times of the theoretical value, so the cost is high. Meanwhile, the equipment is high-temperature and high-pressure equipment, so that the equipment investment is high, and the total cost is much higher than that of a solid phase method.
Disclosure of Invention
The present application aims to provide ferromanganese phosphate, lithium ferromanganese phosphate, and methods for preparing the same, a lithium ion battery, and an electric device, so as to solve the above problems.
In order to achieve the purpose, the following technical scheme is adopted in the application:
a preparation method of manganous iron phosphate comprises the following steps:
mixing raw materials including iron powder, a manganese source and phosphoric acid, and carrying out solid-liquid separation to obtain a manganese-iron-phosphorus solution;
and diluting the manganese-iron-phosphorus solution with water, and then aging in an inert atmosphere to obtain ferric manganous phosphate trihydrate.
Preferably, the manganese source comprises one or more of manganese carbonate, manganous phosphate and manganous oxide;
preferably, the manganese source is manganese carbonate;
preferably, the molar mass of the phosphoric acid is 2 to 10 times the sum of the molar masses of Fe in the iron powder and Mn in the manganese source;
preferably, the mass ratio of the ferromanganese solution to the water is 1: (2-3);
preferably, the temperature of the aging is 80 to 95 ℃.
Preferably, the aging process further comprises washing, drying and crushing the precipitate;
preferably, the temperature of the drying is less than or equal to 110 ℃;
preferably, the temperature of the drying is 80-110 ℃;
preferably, the particle size D50 of the crushed material is 5-30 μm.
The application also provides ferrous manganous phosphate prepared by the preparation method.
The application also provides lithium manganous phosphate, and the raw material of the lithium manganous phosphate comprises the ferric manganous phosphate.
The application also provides a preparation method of the lithium iron manganous phosphate, which comprises the following steps:
mixing raw materials including the manganous iron phosphate, a lithium source, a phosphorus source, a carbon source and a solvent to obtain slurry;
and grinding and drying the slurry to obtain powder, and roasting the powder to obtain the carbon-coated lithium manganese iron phosphate.
Preferably, the carbon source comprises glucose;
preferably, the lithium source comprises one or more of lithium carbonate, lithium hydroxide, lithium phosphate;
preferably, the phosphorus source comprises one or more of phosphoric acid, ammonium dihydrogen phosphate, lithium phosphate;
preferably, the phosphorus source and the lithium source are both lithium phosphate, and the mass ratio of the ferrous manganese phosphate to the lithium carbonate to the glucose is 100: (28.2-29.4): (10.0-12.1);
preferably, the solid content of the slurry is 20% to 50%;
preferably, the solvent comprises one or more of water, methanol, ethanol.
Preferably, after said grinding, the particles in said slurry have a particle size D50 in the range of 0.25 to 0.5 μm;
preferably, the water content of the powder is less than or equal to 2 wt%;
preferably, the roasting temperature is 650-750 ℃, and the time is 4-12 h;
preferably, the roasting further comprises crushing;
preferably, the particle size D50 of the crushed material is 0.5-1.5 μm.
The application also provides a lithium ion battery, and the raw material of the lithium ion battery comprises the lithium manganous phosphate.
The application also provides an electric equipment, including lithium ion battery.
Compared with the prior art, the beneficial effect of this application includes:
according to the preparation method of the manganous iron phosphate, iron powder and a manganese source are dissolved by using phosphoric acid, then the iron powder and the manganese source are diluted by water and aged in an inert atmosphere, and the manganous iron phosphate trihydrate is obtained by a liquid phase precipitation method under the condition that a reducing agent is not used, so that the atomic-level mixing of manganese and iron is realized.
The manganous iron phosphate provided by the application takes the obtained manganous iron phosphate trihydrate as a precursor, the constant voltage section has a low proportion, the 0.5C constant voltage section is less than 10%, the charge and discharge performance is excellent, and the specific capacity can reach 150 mAh/g.
The preparation method of the lithium ferrous manganese phosphate provided by the application is simple in process, and the obtained lithium ferrous manganese phosphate has excellent electric performance.
The lithium ion battery and the electric equipment provided by the application have excellent electrical properties.
Drawings
To more clearly illustrate the technical solutions of the embodiments of the present application, the drawings that are required to be used in the embodiments are briefly described below, and it should be understood that the following drawings only illustrate some embodiments of the present application and therefore should not be considered as limiting the scope of the present application.
FIG. 1 is an SEM photograph of ferromanganese phosphate trihydrate prepared in example 1;
fig. 2 is an SEM image of carbon-coated lithium manganous phosphate prepared in example 1;
FIG. 3 is an XRD spectrum of manganous iron phosphate trihydrate prepared in example 1.
Detailed Description
The terms as used herein:
"prepared from … …" is synonymous with "comprising". The terms "comprises," "comprising," "includes," "including," "has," "having," "contains," "containing," or any other variation thereof, as used herein, are intended to cover a non-exclusive inclusion. For example, a composition, process, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, process, method, article, or apparatus.
The conjunction "consisting of … …" excludes any unspecified elements, steps or components. If used in a claim, the phrase is intended to claim as closed, meaning that it does not contain materials other than those described, except for the conventional impurities associated therewith. When the phrase "consisting of … …" appears in a clause of the subject matter of the claims rather than immediately after the subject matter, it defines only the elements described in the clause; other elements are not excluded from the claims as a whole.
When an amount, concentration, or other value or parameter is expressed as a range, preferred range, or as a range of upper preferable values and lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. For example, when the range "1 ~ 5" is disclosed, the ranges described should be construed to include the ranges "1 ~ 4", "1 ~ 3", "1 ~ 2 and 4 ~ 5", "1 ~ 3 and 5", and the like. When a range of values is described herein, unless otherwise stated, the range is intended to include the endpoints thereof and all integers and fractions within the range.
In these examples, the parts and percentages are by mass unless otherwise indicated.
"part by mass" means a basic unit of measure indicating a mass ratio of a plurality of components, and 1 part may represent any unit mass, for example, 1g or 2.689 g. If we say that the part by mass of the component A is a part by mass and the part by mass of the component B is B part by mass, the ratio of the part by mass of the component A to the part by mass of the component B is a: b. alternatively, the mass of the A component is aK and the mass of the B component is bK (K is an arbitrary number, and represents a multiple factor). It is unmistakable that, unlike the parts by mass, the sum of the parts by mass of all the components is not limited to 100 parts.
"and/or" is used to indicate that one or both of the illustrated conditions may occur, e.g., a and/or B includes (a and B) and (a or B).
A preparation method of manganous iron phosphate comprises the following steps:
mixing raw materials including iron powder, a manganese source and phosphoric acid, and carrying out solid-liquid separation to obtain a manganese-iron-phosphorus solution;
and diluting the manganese-iron-phosphorus solution with water, and then aging in an inert atmosphere to obtain ferric manganous phosphate trihydrate.
The molecular formula of the obtained ferric manganous phosphate trihydrate is MnaFebPO4·3H2O, wherein a + b is 1. It should be noted that, when the manganese content is greater than or equal to 0.6, the rate charging and discharging capacity (or electrical property) of the lithium iron manganous phosphate synthesized by the preparation method provided by the application is much better (more obvious) than the performance of the lithium iron manganous phosphate prepared by the traditional method.
In an alternative embodiment, the manganese source comprises one or more of manganese carbonate, manganous phosphate, and manganous oxide;
in an alternative embodiment, the manganese source is manganese carbonate;
in an alternative embodiment, the molar mass of the phosphoric acid is 2 to 10 times the sum of the molar masses of Fe in the iron powder and Mn in the manganese source;
in an alternative embodiment, the mass ratio of the ferromanganese solution to the water is 1: (2-3);
the purpose of dilution with water is to control the pH of the aged solution of ferromanganese, iron and phosphorus, generally between 0.5 and 2 (preferably between 1 and 1.5); if water is not added or is added little, the pH value of the solution is too low, precipitates cannot be obtained after aging, or the yield is low; excessive water is added, so that the water is easy to dilute excessively, the aging is not facilitated, the utilization rate of equipment is low, and the cost is high.
In an alternative embodiment, the temperature of aging is from 80 to 95 ℃.
Iron powder and manganese carbonate are used as basic raw materials, but sulfate used in the traditional process is not used, firstly, only gas is generated in the reaction process, other impurity ions are not introduced, and the product purity is high; secondly, the washing liquid can be used repeatedly, and compared with the traditional process method, the problems of repeated washing and waste water discharge in the later period are solved. And thirdly, because the iron powder is used as a reaction raw material, the divalent iron and the divalent manganese are not easy to oxidize in the process, and the addition of reducing agents such as ascorbic acid and the like is omitted.
Optionally, the molar mass of the phosphoric acid may be any value between 2 times, 3 times, 4 times, 5 times, 6 times, 7 times, 8 times, 9 times, 10 times, or 2-10 times of the sum of the molar masses of Fe in the iron powder and Mn in the manganese source; the mass ratio of the ferromanganese solution to the water may be 1: 2. 1: 2.5, 1: 3 or 1: (2-3) any value therebetween; the temperature of the aging can be any value between 80 ℃, 85 ℃, 90 ℃, 95 ℃ or 80-95 ℃.
In an alternative embodiment, the aging further comprises washing, drying and pulverizing the precipitate;
in an alternative embodiment, the temperature of the drying is less than or equal to 110 ℃;
in an alternative embodiment, the temperature of the drying is 80-110 ℃;
in an alternative embodiment, the particle size D50 of the comminuted material is between 5 and 30 μm.
Optionally, the drying temperature may be any value between 80 ℃, 90 ℃, 100 ℃, 110 ℃ or 80-110 ℃; the particle diameter D50 of the crushed material can be any value of 5 μm, 10 μm, 15 μm, 20 μm, 25 μm, 30 μm or 5-30 μm.
The application also provides ferrous manganous phosphate prepared by the preparation method.
The application also provides lithium manganous phosphate, and the raw material of the lithium manganous phosphate comprises the ferric manganous phosphate.
The molecular formula of the lithium manganese iron phosphate is LiMnaFebPO4Wherein a + b is 1.
The application also provides a preparation method of the lithium iron manganous phosphate, which comprises the following steps:
mixing raw materials including the manganous iron phosphate, a lithium source, a phosphorus source, a carbon source and a solvent to obtain slurry;
and grinding and drying the slurry to obtain powder, and roasting the powder to obtain the carbon-coated lithium manganese iron phosphate.
In an alternative embodiment, the carbon source comprises glucose;
in an alternative embodiment, the lithium source comprises one or more of lithium carbonate, lithium hydroxide, lithium phosphate;
in an alternative embodiment, the phosphorus source comprises one or more of phosphoric acid, ammonium dihydrogen phosphate, lithium phosphate;
in an optional embodiment, the phosphorus source and the lithium source are both lithium phosphate, and the mass ratio of the ferrous manganese phosphate, the lithium carbonate and the glucose is 100: (28.2-29.4):
(10.0-12.1)；
in an alternative embodiment, the slurry has a solids content of 20% to 50%;
in an alternative embodiment, the solvent comprises one or more of water, methanol, ethanol.
Optionally, the mass ratio of the ferrous manganous phosphate to the lithium carbonate to the glucose may be 100: 28.2: 10.0, 100: 28.2: 12.1, 100:29.4: 10.0, 100:29.4: 12.1, 100: 29.0: 10.0, 100: 29.0: 12.1 or 100: (28.2-29.4): (10.0-12.1); the solids content of the slurry may be 20%, 30%, 40%, 50% or any value between 20% and 50%.
In an alternative embodiment, the particulate matter in the slurry has a particle size D50 of 0.25 to 0.5 μm after the milling;
optionally, the particle size D50 of the particulate matter in the slurry may be any value between 0.25 μm, 0.3 μm, 0.35 μm, 0.4 μm, 0.45 μm, 0.5 μm, or 0.25-0.5 μm;
in an alternative embodiment, the moisture content of the powder is less than or equal to 2 wt%;
in an alternative embodiment, the roasting temperature is 650-750 ℃ and the time is 4-12 h;
optionally, the baking temperature may be any value between 650 ℃, 660 ℃, 670 ℃, 680 ℃, 690 ℃, 700 ℃, 710 ℃, 720 ℃, 730 ℃, 740 ℃, 750 ℃ or 650 and 750 ℃, and the time may be any value between 4h, 6h, 8h, 10h, 12h or 4-12 h;
in an alternative embodiment, the firing further comprises pulverizing;
in an alternative embodiment, the particle size D50 of the comminuted material is between 0.5 and 1.5 μm.
Optionally, the particle size D50 of the crushed material may be any value between 0.5 μm, 0.6 μm, 0.7 μm, 0.8 μm, 0.9 μm, 1.0 μm, 1.1 μm, 1.2 μm, 1.3 μm, 1.4 μm, 1.5 μm or 0.5-1.5 μm.
The application also provides a lithium ion battery, and the raw material of the lithium ion battery comprises the lithium manganous phosphate.
The application also provides an electric equipment, including lithium ion battery.
Embodiments of the present application will be described in detail below with reference to specific examples, but those skilled in the art will appreciate that the following examples are only illustrative of the present application and should not be construed as limiting the scope of the present application. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
Example 1
This embodiment provides a three-waterManganous iron (Mn) orthophosphate0.65Fe0.35)3(PO4)2·3H2The preparation method of the compound comprises the following steps:
acid dissolution: reducing iron powder and manganese carbonate according to a molar ratio of Fe: mn is 0.35:0.65, wherein the molar mass of the phosphoric acid in the phosphoric acid solution is 2 times of the total molar mass of Fe and Mn. And after the dissolution is finished, filtering to remove insoluble substances to obtain a clear manganese iron phosphorus solution.
Diluting: according to the mass ratio of the manganese iron phosphorus solution to water of 1: 2, adding water for dilution, and transferring the diluted solution into an aging tank;
aging under inert atmosphere: introducing nitrogen into the aging tank, and aging at 95 ℃ to generate sheet manganous iron phosphate trihydrate;
drying under inert atmosphere: washing the precipitate for three times, and drying in an oven filled with nitrogen at 110 ℃;
crushing: grinding the dried material by using a mechanical mill until the granularity D50 is 5-30 mu m, and sieving to obtain a finished product.
The SEM image of the resulting manganous iron phosphate trihydrate is shown in FIG. 1.
The composition of the resulting manganous iron phosphate trihydrate is shown in table 1 below:
TABLE 1 composition of manganous iron phosphate trihydrate
As can be seen from Table 1, the obtained manganous-iron phosphate trihydrate has high purity and few impurity ions.
This example also provides a lithium iron manganese phosphate LiMn0.65Fe0.35PO4The preparation method comprises the following steps:
manganese ferric phosphate trihydrate, lithium phosphate and glucose are mixed according to the mass ratio: 100:28.86:10.0 and water are mixed into uniform slurry, and the solid content of the slurry is controlled at 30 percent;
grinding the slurry using a sand mill to a particle size D50 of 0.25 μm to 0.5 μm;
drying the slurry into powder by spray drying, wherein the water content is controlled to be below 2%;
roasting at 720 ℃ for 10 hours in an inert atmosphere to obtain carbon-coated lithium manganese iron phosphate;
and (3) crushing the roasted material until the granularity D50 is 0.5-1.5 mu m, and sieving to obtain the finished product of carbon-coated lithium manganese iron phosphate.
An SEM image of the obtained carbon-coated lithium manganese iron phosphate is shown in fig. 2.
The XRD pattern of the obtained manganous iron phosphate trihydrate is shown in figure 3.
Example 2
This example provides an iron manganous phosphate trihydrate (Mn)0.65Fe0.35)3(PO4)2·3H2The preparation method of the compound comprises the following steps:
acid dissolution: reducing iron powder and manganous oxide according to the molar ratio of Fe: mn is added to the phosphoric acid solution at a ratio of 0.2:0.8, wherein the molar mass of the phosphoric acid in the phosphoric acid solution is 3 times of the total molar mass of Fe and Mn. And after the dissolution is finished, filtering to remove insoluble substances to obtain a clear manganese iron phosphorus solution.
Diluting: according to the mass ratio of the manganese iron phosphorus solution to water of 1: 2.5 adding water for dilution, and transferring the diluted solution into an aging tank;
aging under inert atmosphere: introducing nitrogen into the aging tank, and aging at 90 ℃ to generate sheet manganous iron phosphate trihydrate;
drying under inert atmosphere: washing the precipitate for three times, and drying in an oven filled with nitrogen at 80 ℃;
crushing: grinding the dried material by using a mechanical mill until the granularity D50 is 5-30 mu m, and sieving to obtain a finished product.
This example also provides a lithium iron manganese phosphate LiMn0.8Fe0.2PO4The preparation method comprises the following steps:
manganese ferric phosphate trihydrate, lithium phosphate and glucose are mixed according to the mass ratio: 100:29.4:11.0 and water are mixed into uniform slurry, and the solid content of the slurry is controlled to be 35 percent;
grinding the slurry using a sand mill to a particle size D50 of 0.25 μm to 0.5 μm;
drying the slurry into powder by spray drying, wherein the water content is controlled to be below 2%;
roasting at 650 ℃ for 12 hours in an inert atmosphere to obtain carbon-coated lithium manganese iron phosphate;
and (3) crushing the roasted material until the granularity D50 is 0.5-1.5 mu m, and sieving to obtain the finished product of carbon-coated lithium manganese iron phosphate.
Example 3
This example provides an iron manganous phosphate trihydrate (Mn)0.65Fe0.35)3(PO4)2·3H2The preparation method of the compound comprises the following steps:
acid dissolution: reducing iron powder and manganous phosphate according to a molar ratio of Fe: mn is added to the phosphoric acid solution at a ratio of 0.3:0.7, wherein the molar mass of the phosphoric acid in the phosphoric acid solution is 5 times of the total molar mass of Fe and Mn. And after the dissolution is finished, filtering to remove insoluble substances to obtain a clear manganese iron phosphorus solution.
Diluting: according to the mass ratio of the manganese iron phosphorus solution to water of 1: 3 adding water for dilution, and transferring the diluted solution into an aging tank;
aging under inert atmosphere: introducing nitrogen into the aging tank, and aging at 85 ℃ to generate sheet manganous iron phosphate trihydrate;
drying under inert atmosphere: washing the precipitate for three times, and drying in an oven filled with nitrogen at 90 ℃;
crushing: grinding the dried material by using a mechanical mill until the granularity D50 is 5-30 mu m, and sieving to obtain a finished product.
This example also provides a lithium iron manganese phosphate LiMn0.7Fe0.3PO4The preparation method comprises the following steps:
manganese ferric phosphate trihydrate, lithium phosphate and glucose are mixed according to the mass ratio: 100:29.4:12 and water are mixed into uniform slurry, and the solid content of the slurry is controlled to be 20 percent;
grinding the slurry using a sand mill to a particle size D50 of 0.25 μm to 0.5 μm;
drying the slurry into powder by spray drying, wherein the water content is controlled to be below 2%;
roasting for 6 hours at 700 ℃ in an inert atmosphere to obtain carbon-coated lithium manganese iron phosphate;
and (3) crushing the roasted material until the granularity D50 is 0.5-1.5 mu m, and sieving to obtain the finished product of carbon-coated lithium manganese iron phosphate.
Example 4
This example provides an iron manganous phosphate trihydrate (Mn)0.65Fe0.35)3(PO4)2·3H2The preparation method of the compound comprises the following steps:
acid dissolution: reducing iron powder and manganese carbonate according to a molar ratio of Fe: mn is 0.35:0.65, wherein the molar mass of the phosphoric acid in the phosphoric acid solution is 2 times of the total molar mass of Fe and Mn. And after the dissolution is finished, filtering to remove insoluble substances to obtain a clear manganese iron phosphorus solution.
Diluting: according to the mass ratio of the manganese iron phosphorus solution to water of 1: 2, adding water for dilution, and transferring the diluted solution into an aging tank;
aging under inert atmosphere: introducing nitrogen into the aging tank, and aging at 95 ℃ to generate sheet manganous iron phosphate trihydrate;
drying under inert atmosphere: washing the precipitate for three times, and drying in an oven filled with nitrogen at 110 ℃;
crushing: grinding the dried material by using a mechanical mill until the granularity D50 is 5-30 mu m, and sieving to obtain a finished product.
This example also provides a lithium iron manganese phosphate LiMn0.65Fe0.35PO4The preparation method comprises the following steps:
ferric manganous phosphate trihydrate, lithium hydroxide monohydrate and phosphoric acid (wt 85%), glucose are mixed according to the mass ratio: 100:31.3:28.1:10.0 water are mixed into uniform slurry, and the solid content of the slurry is controlled to be 30 percent;
grinding the slurry using a sand mill to a particle size D50 of 0.25 μm to 0.5 μm;
drying the slurry into powder by spray drying, wherein the water content is controlled to be below 2%;
roasting at 720 ℃ for 10 hours in an inert atmosphere to obtain carbon-coated lithium manganese iron phosphate;
and (3) crushing the roasted material until the granularity D50 is 0.5-1.5 mu m, and sieving to obtain the finished product of carbon-coated lithium manganese iron phosphate.
Example 5
This example provides an iron manganous phosphate trihydrate (Mn)0.65Fe0.35)3(PO4)2·3H2The preparation method of the compound comprises the following steps:
acid dissolution: reducing iron powder and manganese carbonate according to a molar ratio of Fe: mn is 0.35:0.65, wherein the molar mass of the phosphoric acid in the phosphoric acid solution is 2 times of the total molar mass of Fe and Mn. And after the dissolution is finished, filtering to remove insoluble substances to obtain a clear manganese iron phosphorus solution.
Diluting: according to the mass ratio of the manganese iron phosphorus solution to water of 1: 2, adding water for dilution, and transferring the diluted solution into an aging tank;
aging under inert atmosphere: introducing nitrogen into the aging tank, and aging at 95 ℃ to generate sheet manganous iron phosphate trihydrate;
drying under inert atmosphere: washing the precipitate for three times, and drying in an oven filled with nitrogen at 110 ℃;
crushing: grinding the dried material by using a mechanical mill until the granularity D50 is 5-30 mu m, and sieving to obtain a finished product.
This example also provides a lithium iron manganese phosphate LiMn0.65Fe0.35PO4The preparation method comprises the following steps:
manganese iron phosphate trihydrate, lithium carbonate and ammonium dihydrogen phosphate, wherein glucose is prepared according to the mass ratio: mixing water with the weight ratio of 100:27.6:28.0:10.0 to form uniform slurry, wherein the solid content of the slurry is controlled to be 30%;
grinding the slurry using a sand mill to a particle size D50 of 0.25 μm to 0.5 μm;
drying the slurry into powder by spray drying, wherein the water content is controlled to be below 2%;
roasting at 720 ℃ for 10 hours in an inert atmosphere to obtain carbon-coated lithium manganese iron phosphate;
and (3) crushing the roasted material until the granularity D50 is 0.5-1.5 mu m, and sieving to obtain the finished product of carbon-coated lithium manganese iron phosphate.
Comparative example 1
Iron phosphate, manganese carbonate, phosphoric acid (wt 85%), lithium carbonate and glucose in a mass ratio of: 100:141:142:71:41 and water are mixed into uniform slurry, and the solid content of the slurry is controlled at 30 percent;
grinding the slurry to a particle size D50 of 0.25-0.5um by using a sand mill;
drying the slurry into powder by spray drying, wherein the water content is controlled to be below 2%;
roasting at 720 ℃ for 10 hours in an inert atmosphere to obtain carbon-coated lithium manganese iron phosphate;
crushing the roasted material until the granularity D50 is 0.5-1.5um, and sieving to obtain the finished product of carbon-coated lithium ferrous manganese phosphate LiMn0.65Fe0.35PO4。
Comparative example 2
Iron phosphate, manganese phosphate, lithium carbonate and glucose are mixed according to the mass ratio: 100:184:71:48 and water are mixed into uniform slurry, and the solid content of the slurry is controlled to be 30 percent;
grinding the slurry to a particle size D50 of 0.25-0.5um by using a sand mill;
drying the slurry into powder by spray drying, wherein the water content is controlled to be below 2%;
roasting at 720 ℃ for 10 hours in an inert atmosphere to obtain carbon-coated lithium manganese iron phosphate;
crushing the roasted material until the granularity D50 is 0.5-1.5um, and sieving to obtain the finished product of carbon-coated lithium ferrous manganese phosphate LiMn0.65Fe0.35PO4。
The 0.5C charge and discharge properties of the lithium iron manganous phosphate obtained in the examples and comparative examples were tested, and the results are shown in table 2 below:
TABLE 20.5C Charge and discharge Properties
| Synthetic schemes | 0.5C charging constant voltage segment ratio | 0.5C specific discharge capacity (mAh/g) |
| Example 1 | 11.10％ | 150 |
| Comparative example 1 | 20.85％ | 144 |
| Comparative example 2 | 15.82％ | 137 |
As can be seen from table 2 above, in example 1, the liquid-phase precipitation method is used to preferentially prepare ferric manganous phosphate trihydrate with an atomic layer surface uniformly mixed, and then the lithium source and the phosphorus source are supplemented to serve as precursors to prepare the ferric manganous phosphate lithium with excellent electrochemical performance, compared with the traditional solid-phase sintering methods of comparative example 1 and comparative example 2, the 0.5C charging constant-voltage section occupation ratio is smaller, which indicates that the polarization of the obtained material is smaller; the specific capacity of the obtained ferromanganese phosphate is 150mAh/g and is one level of the lithium iron phosphate, and the specific capacity of the material prepared by the comparative example process is 135-145 mAh/g. Therefore, the material prepared by the method provided by the application has obviously better performance than the traditional process. The reason is that the iron source and the manganese source are independently added in the current solid-phase synthesis of the lithium iron manganous phosphate, the uniform mixing of the iron and the manganese can be achieved by subsequent grinding and high-temperature solid-phase diffusion, the uniform mixing of the iron and the manganese can not be achieved on the atomic level, and the uniform mixing of the iron and the manganese is achieved on the atomic level by adopting a liquid-phase precipitation method.
Finally, it should be noted that: the above embodiments are only used for illustrating the technical solutions of the present application, and not for limiting the same; although the present application has been described in detail with reference to the foregoing embodiments, it should be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present application.
Moreover, those skilled in the art will appreciate that while some embodiments herein include some features included in other embodiments, rather than other features, combinations of features of different embodiments are meant to be within the scope of the application and form different embodiments. For example, in the claims above, any of the claimed embodiments may be used in any combination. The information disclosed in this background section is only for enhancement of understanding of the general background of the application and should not be taken as an acknowledgement or any form of suggestion that this information forms the prior art already known to a person skilled in the art.
Claims (10)
1. A preparation method of ferromanganese phosphate is characterized by comprising the following steps:
mixing raw materials including iron powder, a manganese source and phosphoric acid, and carrying out solid-liquid separation to obtain a manganese-iron-phosphorus solution;
and diluting the manganese-iron-phosphorus solution with water, and then aging in an inert atmosphere to obtain ferric manganous phosphate trihydrate.
2. The method of claim 1, wherein the manganese source comprises one or more of manganese carbonate, manganous phosphate, and manganous oxide;
preferably, the manganese source is manganese carbonate;
preferably, the molar mass of the phosphoric acid is 2 to 10 times the sum of the molar masses of Fe in the iron powder and Mn in the manganese source;
preferably, the mass ratio of the ferromanganese solution to the water is 1: (2-3);
preferably, the temperature of the aging is 80 to 95 ℃.
3. The method according to claim 1 or 2, wherein the aging further comprises washing, drying and pulverizing the precipitate;
preferably, the temperature of the drying is less than or equal to 110 ℃;
preferably, the temperature of the drying is 80-110 ℃;
preferably, the particle size D50 of the crushed material is 5-30 μm.
4. An iron manganous phosphate prepared by the method of any one of claims 1 to 3.
5. A lithium manganous phosphate characterized in that a raw material thereof comprises the iron manganous phosphate according to claim 4.
6. The method for preparing lithium iron manganous phosphate according to claim 5, comprising the following steps:
mixing raw materials including the manganous iron phosphate, a lithium source, a phosphorus source, a carbon source and a solvent to obtain slurry;
and grinding and drying the slurry to obtain powder, and roasting the powder to obtain the carbon-coated lithium manganese iron phosphate.
7. The method according to claim 6, wherein the carbon source comprises glucose;
preferably, the lithium source comprises one or more of lithium carbonate, lithium hydroxide, lithium phosphate;
preferably, the phosphorus source comprises one or more of phosphoric acid, ammonium dihydrogen phosphate, lithium phosphate;
preferably, the phosphorus source and the lithium source are both lithium phosphate, and the mass ratio of the ferrous manganese phosphate to the lithium carbonate to the glucose is 100: (28.2-29.4): (10.0-12.1);
preferably, the solid content of the slurry is 20% to 50%;
preferably, the solvent comprises one or more of water, methanol, ethanol.
8. The production method according to claim 6 or 7, wherein the particle diameter D50 of the particulate matter in the slurry after the grinding is 0.25 to 0.5 μm;
preferably, the water content of the powder is less than or equal to 2 wt%;
preferably, the roasting temperature is 650-750 ℃, and the time is 4-12 h;
preferably, the roasting further comprises crushing;
preferably, the particle size D50 of the crushed material is 0.5-1.5 μm.
9. A lithium ion battery characterized in that its raw material comprises the lithium manganous phosphate according to claim 5.
10. An electric device comprising the lithium ion battery of claim 9.
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