CN111063870B - Nanomaterial and preparation method thereof, electrode and secondary battery - Google Patents
Nanomaterial and preparation method thereof, electrode and secondary battery Download PDFInfo
- Publication number
- CN111063870B CN111063870B CN201911182109.0A CN201911182109A CN111063870B CN 111063870 B CN111063870 B CN 111063870B CN 201911182109 A CN201911182109 A CN 201911182109A CN 111063870 B CN111063870 B CN 111063870B
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- nitrogen
- pyrophosphate
- precursor
- doped carbon
- coated
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- 238000002360 preparation method Methods 0.000 title claims abstract description 34
- 239000002086 nanomaterial Substances 0.000 title claims abstract description 29
- 239000000463 material Substances 0.000 claims abstract description 76
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 66
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 63
- 239000002243 precursor Substances 0.000 claims abstract description 63
- XPPKVPWEQAFLFU-UHFFFAOYSA-J diphosphate(4-) Chemical compound [O-]P([O-])(=O)OP([O-])([O-])=O XPPKVPWEQAFLFU-UHFFFAOYSA-J 0.000 claims abstract description 57
- 235000011180 diphosphates Nutrition 0.000 claims abstract description 57
- 229910052751 metal Inorganic materials 0.000 claims abstract description 35
- 239000002184 metal Substances 0.000 claims abstract description 35
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 35
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000011574 phosphorus Substances 0.000 claims abstract description 34
- 239000011259 mixed solution Substances 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 25
- 238000010438 heat treatment Methods 0.000 claims abstract description 17
- 239000012298 atmosphere Substances 0.000 claims abstract description 15
- 239000002904 solvent Substances 0.000 claims abstract description 13
- 238000001354 calcination Methods 0.000 claims abstract description 12
- 239000011261 inert gas Substances 0.000 claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims description 32
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 24
- IMQLKJBTEOYOSI-GPIVLXJGSA-N Inositol-hexakisphosphate Chemical group OP(O)(=O)O[C@H]1[C@H](OP(O)(O)=O)[C@@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@@H]1OP(O)(O)=O IMQLKJBTEOYOSI-GPIVLXJGSA-N 0.000 claims description 15
- IMQLKJBTEOYOSI-UHFFFAOYSA-N Phytic acid Natural products OP(O)(=O)OC1C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C1OP(O)(O)=O IMQLKJBTEOYOSI-UHFFFAOYSA-N 0.000 claims description 15
- 235000002949 phytic acid Nutrition 0.000 claims description 15
- 239000000467 phytic acid Substances 0.000 claims description 15
- 229940068041 phytic acid Drugs 0.000 claims description 15
- 229920000877 Melamine resin Polymers 0.000 claims description 12
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical group NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 12
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 10
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical group C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 claims description 9
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- 239000000126 substance Substances 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 30
- 230000015572 biosynthetic process Effects 0.000 abstract description 23
- 238000003786 synthesis reaction Methods 0.000 abstract description 21
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- -1 nitrogen-containing organic compound Chemical class 0.000 abstract description 15
- 239000011258 core-shell material Substances 0.000 abstract description 11
- 239000002994 raw material Substances 0.000 abstract description 11
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 abstract description 10
- 238000010298 pulverizing process Methods 0.000 abstract description 8
- 229910001415 sodium ion Inorganic materials 0.000 description 26
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- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 16
- 239000005416 organic matter Substances 0.000 description 16
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- GEZAUFNYMZVOFV-UHFFFAOYSA-J 2-[(2-oxo-1,3,2$l^{5},4$l^{2}-dioxaphosphastannetan-2-yl)oxy]-1,3,2$l^{5},4$l^{2}-dioxaphosphastannetane 2-oxide Chemical compound [Sn+2].[Sn+2].[O-]P([O-])(=O)OP([O-])([O-])=O GEZAUFNYMZVOFV-UHFFFAOYSA-J 0.000 description 12
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- 239000011591 potassium Substances 0.000 description 7
- 238000010992 reflux Methods 0.000 description 7
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- BAZAXWOYCMUHIX-UHFFFAOYSA-M sodium perchlorate Chemical compound [Na+].[O-]Cl(=O)(=O)=O BAZAXWOYCMUHIX-UHFFFAOYSA-M 0.000 description 6
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- 159000000000 sodium salts Chemical class 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 235000012431 wafers Nutrition 0.000 description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 5
- 239000011230 binding agent Substances 0.000 description 5
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- 239000002244 precipitate Substances 0.000 description 5
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- 238000012360 testing method Methods 0.000 description 5
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 4
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- 238000005520 cutting process Methods 0.000 description 4
- 150000004683 dihydrates Chemical class 0.000 description 4
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- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
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- 238000005406 washing Methods 0.000 description 4
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 239000012300 argon atmosphere Substances 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
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- 231100000252 nontoxic Toxicity 0.000 description 3
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- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 3
- 238000004626 scanning electron microscopy Methods 0.000 description 3
- 239000002210 silicon-based material Substances 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- VKFFEYLSKIYTSJ-UHFFFAOYSA-N tetraazanium;phosphonato phosphate Chemical compound [NH4+].[NH4+].[NH4+].[NH4+].[O-]P([O-])(=O)OP([O-])([O-])=O VKFFEYLSKIYTSJ-UHFFFAOYSA-N 0.000 description 3
- 238000004627 transmission electron microscopy Methods 0.000 description 3
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 2
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- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 2
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- 150000001450 anions Chemical class 0.000 description 2
- RCUAPGYXYWSYKO-UHFFFAOYSA-J barium(2+);phosphonato phosphate Chemical compound [Ba+2].[Ba+2].[O-]P([O-])(=O)OP([O-])([O-])=O RCUAPGYXYWSYKO-UHFFFAOYSA-J 0.000 description 2
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- YACKEPLHDIMKIO-UHFFFAOYSA-N methylphosphonic acid Chemical compound CP(O)(O)=O YACKEPLHDIMKIO-UHFFFAOYSA-N 0.000 description 2
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- 229910052760 oxygen Inorganic materials 0.000 description 2
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- 125000004437 phosphorous atom Chemical group 0.000 description 2
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- HHVIBTZHLRERCL-UHFFFAOYSA-N sulfonyldimethane Chemical compound CS(C)(=O)=O HHVIBTZHLRERCL-UHFFFAOYSA-N 0.000 description 2
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- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229910021580 Cobalt(II) chloride Inorganic materials 0.000 description 1
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
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- DBVJJBKOTRCVKF-UHFFFAOYSA-N Etidronic acid Chemical compound OP(=O)(O)C(O)(C)P(O)(O)=O DBVJJBKOTRCVKF-UHFFFAOYSA-N 0.000 description 1
- 206010024769 Local reaction Diseases 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
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- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 1
- 229930006000 Sucrose Natural products 0.000 description 1
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- 238000002441 X-ray diffraction Methods 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 1
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- 125000004429 atom Chemical group 0.000 description 1
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- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
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- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
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- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- JECJVZVHLPZRNM-UHFFFAOYSA-J cobalt(2+);phosphonato phosphate Chemical compound [Co+2].[Co+2].[O-]P([O-])(=O)OP([O-])([O-])=O JECJVZVHLPZRNM-UHFFFAOYSA-J 0.000 description 1
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- MJRKFYKONYYOJX-UHFFFAOYSA-J phosphonato phosphate;tin(4+) Chemical group [Sn+4].[O-]P([O-])(=O)OP([O-])([O-])=O MJRKFYKONYYOJX-UHFFFAOYSA-J 0.000 description 1
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- 235000011152 sodium sulphate Nutrition 0.000 description 1
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- YLKTWKVVQDCJFL-UHFFFAOYSA-N sodium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Na+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F YLKTWKVVQDCJFL-UHFFFAOYSA-N 0.000 description 1
- XGPOMXSYOKFBHS-UHFFFAOYSA-M sodium;trifluoromethanesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C(F)(F)F XGPOMXSYOKFBHS-UHFFFAOYSA-M 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
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- 239000013589 supplement Substances 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- AXZWODMDQAVCJE-UHFFFAOYSA-L tin(II) chloride (anhydrous) Chemical compound [Cl-].[Cl-].[Sn+2] AXZWODMDQAVCJE-UHFFFAOYSA-L 0.000 description 1
- 229910000375 tin(II) sulfate Inorganic materials 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
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Abstract
本发明属于电池技术领域，尤其涉及一种纳米材料及其制备方法、电极和二次电池。本发明提供的制备方法，包括：将金属前驱体、磷源和含氮有机物溶解在溶剂中，制备混合液；将混合液进行加热反应，制备前驱体；将前驱体在惰性气体气氛下进行煅烧处理，制备氮掺杂碳包覆的焦磷酸盐材料。采用含氮有机物作为合成氮掺杂碳包覆材料的原料，在引入氮源的同时也引入了合成所需的碳源，促进合成具有核壳结构的氮掺杂碳包覆的焦磷酸盐材料，解决了现有锡基负极材料在充放电过程中由于严重的体积膨胀及粉化导致的循环稳定性差、倍率性能低、库伦效率低的问题。
The invention belongs to the technical field of batteries, and particularly relates to a nanomaterial and a preparation method thereof, an electrode and a secondary battery. The preparation method provided by the present invention includes: dissolving a metal precursor, a phosphorus source and a nitrogen-containing organic compound in a solvent to prepare a mixed solution; heating the mixed solution to prepare a precursor; and calcining the precursor in an inert gas atmosphere treatment to prepare a nitrogen-doped carbon-coated pyrophosphate material. Nitrogen-containing organic compounds are used as raw materials for the synthesis of nitrogen-doped carbon-coated materials, and the carbon source required for the synthesis is also introduced while the nitrogen source is introduced, which promotes the synthesis of nitrogen-doped carbon-coated pyrophosphate materials with a core-shell structure. It solves the problems of poor cycle stability, low rate performance and low Coulomb efficiency caused by severe volume expansion and pulverization of the existing tin-based negative electrode material during the charge and discharge process.
Description
Technical Field
The invention belongs to the technical field of batteries, and particularly relates to a nano material, a preparation method thereof, an electrode and a secondary battery.
Background
Because the lithium ion battery is widely applied to the fields of smart phones, electric automobiles and the like, the demand of lithium is rapidly increased year by year, and the storage capacity of lithium resources is limited and is not uniformly distributed, so that the cost is gradually increased, and the requirements of people on low cost and high capacity of energy storage devices are difficult to meet. Sodium, potassium and lithium are elements of the same main group, have similar physical and chemical properties, and store elementsThe quantity is abundant, the cost is low, and the working mechanism is similar to that of the lithium ion battery, so that the development of a novel secondary ion battery based on sodium ions, potassium ions and the like is widely concerned and becomes a potential novel energy storage device for replacing the lithium ion battery. However, sodium and potassium ion batteries, although having many advantages, have some problems, such as the radius of sodium and potassium ions (Na)+：
K+：
) Radius of lithium ion
Is much larger, which results in slow kinetic performance of sodium and potassium ions in the electrolytic material. In recent years, research shows that the selection of a proper negative electrode material can improve the electrochemical properties such as the cycle stability, the rate capability, the specific capacity and the like of a novel secondary ion battery such as sodium and potassium ions, and therefore, the screening of the proper negative electrode material has an important significance for solving the problem of slow dynamic performance of the sodium and potassium ion battery.
The traditional negative electrode material of the sodium ion secondary battery mainly comprises a carbon material, a silicon material, a phosphorus material, a metal oxide, a sulfide, a tin-based negative electrode material and the like, wherein a low-voltage platform of the carbon material easily causes the formation of sodium dendrite and causes serious safety problems, and the theoretical capacity of the negative electrode material is low, so that the negative electrode material cannot meet the requirements of high energy density and power density; although the capacities of the silicon material and the phosphorus material are high, the conductivities of the silicon material and the phosphorus material are poor, so that the rate performance is poor; although metal oxides, sulfides, phosphides, tin-based negative electrode materials and the like have high capacity and good conductivity, the problems of dissolution and volume expansion of intermediates exist in the charging and discharging process, and electrode pulverization phenomena are easily caused, so that the problems of poor cycle performance, low rate performance, low coulombic efficiency and the like are caused.
In the prior art, various attempts have been made to improve the volume expansion and the powder of stannide negative electrode materialsIn some embodiments, graphene and a metal cation precursor are heated and dissolved, then are subjected to hydrothermal reaction at 100-120 ℃ for 4-6 hours to synthesize the precursor, and are washed and dried, and then are burned at 400-550 ℃ for 4-6 hours under argon-hydrogen atmosphere to obtain the graphene nanosheet with SnP uniformly grown thereon2O7The final product of the granules. In other embodiments, the SnP is synthesized by using soluble starch and metallic tin powder as raw materials and adopting a microwave hydrothermal method2O7/C microsphere, wherein a large amount of SnP is dispersed in the microsphere2O7And (3) granules. In other embodiments, with SnCl4·5H2O、C2H8O7P2(etidronic acid), C12H22O11(sucrose) is used as raw material, and is calcined for 10 hours at 600 ℃ by adopting a sol-calcining method to synthesize the carbon-coated SnP2O7. Although the material synthesized by the method can relieve the volume expansion and pulverization phenomena of tin to a certain extent, the synthesized material shows poor cycle performance and rate performance when applied to a battery.
Disclosure of Invention
The invention mainly aims to provide a preparation method of a nano material, and aims to solve the problems of poor cycle stability, low rate capability and low coulombic efficiency caused by serious volume expansion and pulverization in the charging and discharging processes of the conventional tin-based negative electrode material.
The invention also aims to provide the nano material prepared by the preparation method.
It is still another object of the present invention to provide an electrode and a secondary electrode using the nanomaterial described above.
In order to achieve the purpose, the invention adopts the following technical scheme:
in one aspect, the invention provides a method for preparing a nano material, which comprises the following steps:
dissolving a metal precursor, a phosphorus source and a nitrogen-containing organic matter in a solvent to prepare a mixed solution;
heating the mixed solution for reaction to prepare a precursor;
and calcining the precursor in an inert gas atmosphere to prepare the nitrogen-doped carbon-coated pyrophosphate material.
According to the preparation method of the nano material, the nitrogen-containing organic matter is used as the raw material for synthesizing the nitrogen-doped carbon coating material, the carbon source required by synthesis is introduced while the nitrogen source is introduced, the synthesis of the nitrogen-doped carbon coating pyrophosphate material with the core-shell structure is promoted, the raw material source is wide and non-toxic, and the synthesis cost is reduced; and then, heating reaction and calcination treatment are sequentially carried out, so that the nitrogen-doped carbon-coated pyrophosphate material with the core-shell structure is prepared, and the method is simple and controllable and is suitable for large-scale preparation of the nitrogen-doped carbon-coated pyrophosphate material. According to the method, the nitrogen-doped carbon material is adopted to coat the pyrophosphate, so that on one hand, pyrophosphate particles are coated and fixed on a nitrogen-doped carbon material substrate, and the problems of poor cycle stability, low rate capability and low coulomb efficiency caused by the powdering of an alloyed volume expansion base can be effectively relieved in the charge and discharge processes; on the other hand, the nitrogen element is introduced, so that the electron transmission dynamic performance of the material is enhanced, and the specific capacity performance of the battery is improved; in another aspect, pyrophosphate is a spherical compound with a nanoscale size, can greatly shorten the transmission path of ions, has a unique three-dimensional structure, can provide a fast electronic channel in the reaction, and improves the reaction efficiency, so that the secondary battery, especially prepared from sodium, potassium, calcium ions and the like, has excellent electrochemical properties.
Accordingly, a nanomaterial comprising: the nitrogen-doped carbon-coated pyrophosphate material prepared by the preparation method.
The nano material provided by the invention is prepared by the preparation method, pyrophosphate is used as a core, and a nitrogen-doped carbon material is used as a shell layer, so that the problems of poor cycle stability, low rate performance and low coulombic efficiency caused by severe volume expansion and pulverization in the charging and discharging processes of the conventional negative electrode material are solved, and the nano material can be used as a negative electrode material to be applied to preparation of secondary batteries such as sodium, potassium and calcium ions and the like so as to improve the electrochemical performance of the batteries.
Accordingly, an anode, the material of the anode comprising: the nano material prepared by the preparation method or the nano material.
The cathode provided by the invention is made of the nano material prepared by the preparation method or the nano material, can effectively solve the problems of poor cycle stability, low rate capability and low coulombic efficiency caused by serious volume expansion and pulverization in the charging and discharging processes of the conventional cathode material, and can be applied to preparation of secondary batteries of sodium, potassium, calcium ions and the like so as to improve the electrochemical performance of the batteries.
Correspondingly, the negative electrode of the secondary battery is the negative electrode.
The secondary battery provided by the invention has the negative electrode, and has excellent electrochemical performance, such as high rate performance, high specific capacity performance and the like.
Drawings
FIG. 1 shows SnP obtained in example 12O7X-ray diffraction Pattern (XRD) of @ N-C;
FIG. 2 shows SnP obtained in example 12O7Scanning Electron Micrographs (SEM) of @ N-C;
FIG. 3 shows SnP obtained in example 12O7Transmission Electron Micrographs (TEM) of @ N-C;
FIG. 4 shows SnP obtained in example 12O7X-ray energy spectra (EDS) of @ N-C;
FIG. 5 shows SnP obtained in comparative example 12O7@ N-C and SnP prepared in example 12O7The detection result of the long-cycle performance of the sodium-ion half battery taking @ N-C as the negative electrode material under the condition of 1.5A g-1 current density;
FIG. 6 shows the product obtained in example 2 and SnP obtained in example 12O7The sodium ion half cell with @ N-C as the negative electrode material is 1.5A g-1A long cycle performance detection result under a current density condition;
FIG. 7 shows the product obtained in example 3 and SnP obtained in example 12O7The sodium ion half cell with @ N-C as the negative electrode material is 1.5A g-1Current densityAnd (5) detecting the long cycle performance under the condition.
Detailed Description
In order to make the technical problems, technical solutions and advantageous effects to be solved by the present invention more clearly apparent, the present invention is further described in detail below with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
A preparation method of a nano material comprises the following steps:
s01, dissolving the metal precursor, the phosphorus source and the nitrogen-containing organic matter in a solvent to prepare a mixed solution;
s02, heating the mixed solution for reaction to prepare a precursor;
and S03, calcining the precursor in an inert gas atmosphere to prepare the nitrogen-doped carbon-coated pyrophosphate material.
Specifically, in step S01, the metal precursor, the phosphorus source, and the nitrogen-containing organic substance are dissolved in a solvent to prepare a mixed solution. Wherein a metal precursor and a phosphorus source are used as pyrophosphate (e.g., SnP)2O7) The raw material of (1) is nitrogen-containing organic matter as the raw material for synthesizing the nitrogen-doped carbon-coated material, and the metal precursor, the phosphorus source and the nitrogen-containing organic matter are dissolved in a solvent to construct a reaction system for subsequently synthesizing the nitrogen-doped carbon-coated pyrophosphate material.
The phosphorus source contains phosphorus atoms, which upon reaction provide pyrophosphate. In one embodiment, the phosphorus source is at least one selected from the group consisting of phytic acid, phosphoric acid, ammonium dihydrogen phosphate, methylphosphonic acid and polyphosphoric acid, and the phosphorus source has good solubility and strong coordination ability. In some embodiments, the phosphorus source is selected from phytic acid, which has a fast reaction speed, a strong coordination capability and a low price, and at the same time, the phytic acid contains both phosphorus atoms and carbon atoms, and can provide a carbon source and a phosphorus source for the reaction and supplement a sufficient amount of carbon source for the reaction to promote the synthesis of the nitrogen-doped carbon-coated pyrophosphate material.
The metal precursor is used to provide metal atoms that react to form pyrophosphate in combination with pyrophosphate. In one embodiment, the metal precursor is at least one selected from the group consisting of a tin source, a lead source, a barium source, a calcium source, a zinc source, a cobalt source, and a bismuth source. In some embodiments, the metal precursor is selected to be a tin source, preferably at least one of stannous chloride, stannous sulfate, and stannous nitrate, which are relatively soluble in water. In a further embodiment, the metal precursor is stannous chloride, which can be rapidly dissolved in water and react with the phosphorus source to promote the synthesis of stannic pyrophosphate.
The nitrogen-containing organic matter refers to an organic matter containing nitrogen elements, contains nitrogen atoms and carbon atoms in molecules, can provide a carbon source and a nitrogen source for reaction at the same time, is a source for synthesizing the nitrogen-doped carbon-coated material, and promotes the synthesis of the nitrogen-doped carbon-coated pyrophosphate material. In one embodiment, the nitrogen-containing organic compound is at least one selected from urea, melamine, biuret, ethylenediaminetetraacetic acid and hexamethylenetetramine, and has a good reactivity with phytic acid. In some embodiments, the nitrogen-containing organic compound is selected from melamine, which has a relatively high nitrogen content and is inexpensive.
Different from the existing technology of introducing carbon sources to prepare carbon material-coated pyrophosphate, the embodiment of the invention adopts nitrogen-containing organic matters as raw materials for synthesizing the nitrogen-doped carbon-coated material, so that carbon sources required by synthesis are introduced while introducing the nitrogen source, the synthesis of the nitrogen-doped carbon-coated pyrophosphate material with the core-shell structure is promoted, the raw materials are wide in source and nontoxic, and the synthesis cost is reduced; meanwhile, due to the introduction of nitrogen elements, the electron transport kinetic performance of the material is further improved.
The solution is used as a reaction medium of the reaction volume, and water or a water-organic solvent system which can fully dissolve and disperse the metal precursor, the phosphorus source and the nitrogen-containing organic matter and does not influence the reaction is selected. In some embodiments, the solvent is selected from a mixture of equal volumes of deionized water and ethanol.
As an embodiment, in the step of dissolving the metal precursor, the phosphorus source and the nitrogen-containing organic compound in the solvent, the metal precursor, the phosphorus source and the nitrogen-containing organic compound are added to deionized water, and stirred at 40-95 ℃ for 1-8 hours, so that the metal precursor, the phosphorus source and the nitrogen-containing organic compound are completely dissolved.
In the mixed solution, the subsequent synthesis of the nitrogen-doped carbon-coated pyrophosphate material is influenced by the use amounts and concentrations of the metal precursor, the phosphorus source and the nitrogen-containing organic matter.
The dosage of the metal precursor and the phosphorus source is in accordance with the chemical dosage ratio of the metal precursor to the phosphorus source for synthesizing the corresponding pyrophosphate. As an embodiment, the molar ratio of the phosphorus source to the metal precursor is 1 (0.5-10) to ensure the synthesis of high purity tin pyrophosphate. In some embodiments, the phosphorus source is selected from at least one of phytic acid, phosphoric acid, ammonium dihydrogen phosphate, methyl phosphonic acid, and polyphosphoric acid, and the metal precursor is selected from a tin source. In a further embodiment, the phosphorus source is selected from phytic acid, the metal precursor is selected from a dihydrate of stannous chloride, the molar ratio of the phytic acid to the dihydrate of the stannous chloride is 2:10, and the prepared nitrogen-doped carbon-coated stannic pyrophosphate has a core-shell structure, is excellent in cycle performance and rate capability, high in dispersity and compact in material.
The dosage of the nitrogen-containing organic matter is enough to meet the basic requirement of synthesizing the nitrogen-doped carbon-coated pyrophosphate material, and as an implementation mode, the molar ratio of the nitrogen-containing organic matter to the metal precursor is (0.1-2):1, so that the synthesis of the nitrogen-doped carbon-coated tin pyrophosphate material with the core-shell structure is ensured. In some embodiments, the nitrogen-containing organic is selected from at least one of urea, melamine, biuret, ethylene diamine tetraacetic acid, and hexamethylenetetramine, and the metal precursor is selected as a tin source. In a further embodiment, the nitrogen-containing organic compound is selected from melamine, the metal precursor is selected from a dihydrate of stannous chloride, and the molar ratio of the dihydrate of stannous chloride to the melamine is 10:8, so that the prepared nitrogen-doped carbon-coated tin pyrophosphate has a core-shell structure and optimal electrochemical performance. In a further embodiment, the concentration of the nitrogen-containing organic compound in the mixed solution is 0.05-1 mol/L.
Furthermore, in the nitrogen-doped carbon-coated pyrophosphate material synthesized by the metal precursor, the phosphorus source and the nitrogen-containing organic matter with the limited dosage and concentration, the weight percentage content of carbon is 5-60%, and the weight percentage content of nitrogen is 2-30%. By doping 2-30% of nitrogen source in pyrophosphate coated with carbon material, the conductivity of the material can be obviously improved, active sites are introduced, and the specific capacitance of the material is obviously increased.
In step S02, the mixed solution is subjected to a heating reaction to prepare a precursor.
And heating the mixed solution for reaction, so that the metal precursor, the phosphorus source and the nitrogen-containing organic matter can perform preliminary reaction in a solvent to prepare the precursor. In the embodiment of the invention, nitrogen-containing organic matters, metal precursors and a phosphorus source are added to be mixed and reacted at the initial stage of the reaction, and basic groups are introduced for the reaction so as to promote the synthesis of the carbon material coated pyrophosphate material with a core-shell structure. As an example, a phosphorus source is phytic acid, a nitrogen-containing organic substance is melamine, a metal precursor is stannous chloride, during a heating reaction, part of pyrophosphate provided by the phytic acid reacts with the stannous chloride to generate stannic pyrophosphate, part of pyrophosphate distributed on the surface of the stannic pyrophosphate is combined with basic groups of the melamine to form an ammonium pyrophosphate shell material, and the nitrogen-doped carbon-coated stannic pyrophosphate material is prepared through subsequent calcination treatment.
In one embodiment, in the step of heating the mixed solution, the mixed solution is heated and refluxed at 70 ℃ to 95 ℃ for 8 to 20 hours, and the reaction is sufficiently performed by heating and refluxing, and the reaction at 70 ℃ to 95 ℃ accelerates the synthesis of the tin pyrophosphate core and the formation of the ammonium pyrophosphate shell material. In specific examples, the temperature of the heating reflux is 70 ℃, 78 ℃, 83 ℃, 90 ℃ and 95 ℃, and the time of the heating reflux is 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 and 20 hours.
As an embodiment, the mixed solution is heated, and then left to stand to fully precipitate the precursor obtained by the reaction, and then the precursor is washed and dried at a temperature of 40 ℃ to 95 ℃ for 1 to 20 hours in a vacuum environment to obtain a high-purity and dried precursor.
In step S03, the precursor is calcined in an inert gas atmosphere, and the precursor can be further reacted to synthesize the nitrogen-doped carbon-coated pyrophosphate material by the calcination.
Therefore, the prepared nitrogen-doped carbon-coated pyrophosphate material takes pyrophosphate as a core and a nitrogen-doped carbon material as a shell layer, and the nitrogen-doped carbon material is used for coating pyrophosphate, so that pyrophosphate particles are coated and fixed on a nitrogen-doped carbon material substrate, and the problems of poor cycle stability, low rate capability and low coulombic efficiency caused by the powdering of an alloyed volume expansion base can be effectively relieved in the charge and discharge processes; on the other hand, the nitrogen element is introduced, so that the electron transmission dynamic performance of the material is enhanced, and the specific capacity performance of the battery is improved; in another aspect, pyrophosphate is a spherical compound with a nanoscale size, can greatly shorten the transmission path of ions, improves the reaction efficiency, has a unique three-dimensional structure, and can provide a fast electron channel in the reaction, so that the secondary battery, especially the prepared sodium, potassium, calcium ions and the like, has excellent electrochemical properties.
The calcination treatment is performed under an inert gas atmosphere to prevent the air in the environment from affecting the synthesis of the target product. The inert gas atmosphere includes, but is not limited to, nitrogen, helium, argon, and the like, and in some embodiments, the inert gas atmosphere is an argon atmosphere.
As an embodiment, the precursor is calcined in an inert gas atmosphere, and the precursor is calcined at a high temperature of 500 ℃ to 800 ℃ for 1 to 5 hours in the inert gas atmosphere, so that the ammonium pyrophosphate shell material can be fully carbonized, nitrogen doping is facilitated, and a material with pyrophosphate as a core and nitrogen-doped carbon material as a shell is formed. In specific examples, the calcination temperature is 500 ℃, 550 ℃, 600 ℃, 640 ℃, 701 ℃, 765 ℃ and 800 ℃, and the calcination time is 1, 2, 3, 4 or 5 hours.
Through detection, the nitrogen-doped carbon-coated pyrophosphate material prepared by the preparation method is uniformly distributed in a material system, has a nanoscale spherical structure with the particle size of 50-500nm, thus greatly shortening the transmission path of ions and improving the reaction efficiency.
Compared with the prior art, the preparation method provided by the embodiment of the invention has the following advantages:
1) the nitrogen-containing organic matter is used as the raw material for synthesizing the nitrogen-doped carbon coating material, so that a carbon source required by synthesis is introduced while a nitrogen source is introduced, the charge transfer performance of the material is enhanced, the raw material source is wide and non-toxic, and the synthesis cost is reduced;
2) in the initial stage of the reaction, nitrogen-containing organic matter, a metal precursor and a phosphorus source are added for mixed reaction, for example, melamine is used for reaction to introduce an alkaline group, so that the synthesis of the carbon material coated pyrophosphate material with a core-shell structure is promoted;
3) dissolving a metal precursor, a phosphorus source and a nitrogen-containing organic matter in a solvent, and sequentially carrying out heating reaction and calcination treatment to obtain the nitrogen-doped carbon-coated pyrophosphate material with the core-shell structure, wherein the method is simple and controllable, and is suitable for large-scale preparation of the nitrogen-doped carbon-coated pyrophosphate material;
4) the method of coating the nitrogen-doped carbon material is adopted, so that the conductivity of the material is improved, and the pyrophosphate coated by the carbon material can effectively relieve the problem of volume expansion of alloying in the charging and discharging processes, so that the problems of poor rate capability and poor cycle stability of the material can be improved;
5) the synthesized nitrogen-doped carbon-coated pyrophosphate material has uniform particle distribution, and ensures that the material does not collapse due to local reaction, thereby further influencing the cycle performance and the rate performance of the material;
6) the synthesized nitrogen-doped carbon-coated pyrophosphate material effectively exerts the potential of pyrophosphate through the processes of conversion reaction and alloying reaction in the charge-discharge process, and presents higher specific capacity.
Accordingly, a nanomaterial comprising: the nitrogen-doped carbon-coated pyrophosphate material prepared by the preparation method.
The nanomaterial provided by the embodiment of the invention is prepared by the preparation method, pyrophosphate is used as a core, and a nitrogen-doped carbon material is used as a shell layer, so that the problems of poor cycle stability, low rate capability and low coulombic efficiency caused by severe volume expansion and pulverization in the charging and discharging processes of the conventional negative electrode material are solved, and the nanomaterial can be used as a negative electrode material to be applied to preparation of secondary batteries such as sodium, potassium and calcium ions and the like so as to improve the electrochemical performance of the batteries.
In one embodiment, the nitrogen-doped carbon-coated pyrophosphate material contains 5-60% by weight of carbon and 2-30% by weight of nitrogen.
In one embodiment, the particle size of the nitrogen-doped carbon-coated pyrophosphate material is 5 to 500nm, and the nitrogen-doped carbon-coated pyrophosphate material in the size range can greatly shorten the ion transmission path, improve the reaction efficiency, and alleviate the problem of poor cycle performance and rate capability caused by volume expansion during charge and discharge.
Based on the technical scheme described above, the embodiments of the present invention provide a negative electrode and a secondary battery.
Accordingly, an anode, the material of the anode comprising: the nano material prepared by the preparation method or the nano material.
The cathode provided by the embodiment of the invention is made of the nano material prepared by the preparation method or the nano material, can effectively solve the problems of poor cycle stability, low rate capability and low coulombic efficiency caused by serious volume expansion and pulverization in the charging and discharging processes of the conventional cathode material, and can be applied to preparation of secondary batteries of sodium, potassium, calcium ions and the like so as to improve the electrochemical performance of the batteries.
The existing negative electrode mainly comprises a current collector and a material layer coated above the current collector, wherein in the embodiment of the invention, the material layer is formed by mixing and solidifying a conductive agent, a binder and the nitrogen-doped carbon-coated pyrophosphate material in a solvent according to a mass ratio. Wherein, the current collector can refer to the current collector conventional in the field, such as in some embodiments, the current collector is selected from copper foil or aluminum foil; the conductive agent can refer to conductive agents conventional in the art, such as graphite, carbon black, carbon nanotubes, and the like in some embodiments; the binder may be referred to as a binder conventional in the art, such as in some embodiments, the binder is selected from at least one of polyvinyl alcohol, polytetrafluoroethylene, and sodium carboxymethylcellulose.
As an embodiment, the preparation of the anode includes: mixing the nitrogen-doped carbon-coated tin pyrophosphate, the conductive agent and the binder according to the mass ratio of 7:2:1, adding azomethyl pyrrolidone, grinding into slurry, coating on a copper foil, drying in vacuum at 70 ℃ after coating, and cutting into a negative plate.
Correspondingly, the negative electrode of the secondary battery is the negative electrode.
The secondary battery provided by the embodiment of the invention has the negative electrode, and has excellent electrochemical properties, such as high rate performance, high specific capacity performance and the like.
The secondary battery includes, but is not limited to, a lithium ion battery, a sodium ion battery, a potassium ion battery, a calcium ion battery, and the like. In some embodiments, the secondary battery is preferably a sodium ion battery or a potassium ion battery.
The structure of the secondary battery can refer to a battery which is conventional in the field and mainly consists of a positive electrode, a negative electrode, a diaphragm, an electrolyte and a shell, and the materials and the composition of the positive electrode, the diaphragm, the electrolyte and the shell can refer to the conventional positive electrode, the diaphragm, the electrolyte and the shell in the field.
In one embodiment, the secondary battery is a sodium ion battery, and the electrolyte in the electrolyte solution includes an organic salt of sodium and/or an inorganic salt of sodium. In some embodiments, the electrolyte is selected from at least one of sodium hexafluorophosphate, sodium sulfate, sodium hexafluoroarsenate, sodium tetrafluoroborate, sodium perchlorate, sodium trifluoromethanesulfonimide, and sodium trifluoromethanesulfonate, preferably sodium perchlorate. Sodium salt with abundant reserves and low price is used as electrolyte of the sodium ion half-cell, so that the cost of the cell can be reduced, and no dendrite can be generated to puncture a diaphragm in the reaction process, and the sodium salt has better safety performance.
The ion concentration of electrolyte in the electrolyte can affect the ion transmission performance of the electrolyte, and when the concentration of sodium salt in the electrolyte is too low, Na is taken as an example+And too little anion, poor ion transmission performance and low conductivity; when the concentration of sodium salt in the electrolyte is too high, Na+And too many anions, the viscosity of the electrolyte and the degree of ionic association also increase with increasing sodium salt concentration, which in turn reduces conductivity. In some embodiments, the concentration of the sodium salt in the electrolyte is preferably 0.5 to 3mol/L, more preferably 1 mol/L.
The electrolyte solution mainly includes an electrolyte and an organic solvent for dissolving the electrolyte, including, but not limited to, esters, sulfones, ethers, nitriles, and the like. In some embodiments, the organic solvent is selected from one of propylene carbonate, ethylene carbonate, diethyl carbonate, fluoroethylene carbonate, dimethyl carbonate, ethyl methyl carbonate, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, dimethyl sulfone, dimethyl ether. In a further embodiment, the electrolyte uses sodium perchlorate with the concentration of 1.0mol/L as an electrolyte and propylene carbonate and fluoroethylene carbonate as solvents, and the electrolyte composition and the negative electrode act synergistically to enable the electrochemical performance of the sodium-ion battery to be optimal.
The separator can refer to the conventional battery separator in the field, for example, in some embodiments, the material of the separator is glass microfiber, and the glass microfiber separator can be combined with the negative electrode and the sodium perchlorate-propylene carbonate-fluoroethylene carbonate electrolyte to exert the electrochemical performance of the sodium ion battery to the maximum extent.
In order that the above-described implementation details and operation of the present invention will be clearly understood by those skilled in the art, and the advanced performance of the nanomaterial and the preparation method thereof, the electrode and the secondary battery according to the embodiment of the present invention will be remarkably demonstrated, the implementation of the present invention will be exemplified by the following embodiments.
Example 1
The embodiment provides a nitrogen-doped carbon-coated tin pyrophosphate material, and a preparation method thereof specifically comprises the following steps:
(1) adding 10mmol of SnCl2·2H2Adding O into 50ml of deionized water, adding 2mmol of phytic acid and 8mmol of melamine, and violently stirring for 2h at 55 ℃ to obtain a mixed solution;
(2) transferring the mixed solution into a two-neck flask, adding 50ml of absolute ethyl alcohol, heating and refluxing at 85 ℃ for 12h, centrifuging to obtain a precipitate, washing with ethanol and water for several times, and drying at 70 ℃ in a vacuum drying oven for 12h to obtain a precursor;
(3) reacting the precursor at 600 ℃ for 2h under the argon atmosphere to obtain the nitrogen-doped carbon-coated tin pyrophosphate material SnP2O7@N-C。
Example 2
This example differs from example 1 in that: in the step (3), the precursor is reacted for 2 hours at 700 ℃; the rest of the process is basically the same as that of embodiment 1, and the description thereof is omitted.
Example 3
This comparative example differs from example 1 in that: in the step (1), the dosage of the phytic acid is adjusted to be 4 mmol; the rest of the process is basically the same as that of embodiment 1, and the description thereof is omitted.
Example 4
The embodiment provides a nitrogen-doped carbon-coated cobalt pyrophosphate material, and a preparation method thereof specifically comprises the following steps:
(1) adding 10mmol of CoCl2·6H2Adding O into 50ml of deionized water, adding 4mmol of phytic acid and 10mmol of urea, and violently stirring at 60 ℃ for 1h to obtain a mixed solution;
(2) transferring the mixed solution into a two-neck flask, adding 50ml of absolute ethyl alcohol, heating and refluxing at 85 ℃ for 12h, centrifuging to obtain a precipitate, washing with ethanol and water for several times, and drying in a vacuum drying oven at 70 ℃ for 10h to obtain a precursor;
(3) reacting the precursor at 700 ℃ for 2h under the argon atmosphere to obtain the nitrogen-doped carbon-coated tin pyrophosphate material Co2P2O7@N-C。
Example 5
The embodiment provides a nitrogen-doped carbon-coated lead pyrophosphate material, and a preparation method thereof specifically comprises the following steps:
(1) adding 5mmol of PbCl2Adding into 50ml deionized water, adding 3mmol phytic acid and 10mmol urea, and vigorously stirring at 70 deg.C for 1h to obtain mixed solution;
(2) transferring the mixed solution into a two-neck flask, adding 50ml of absolute ethyl alcohol, heating and refluxing at 85 ℃ for 12h, centrifuging to obtain a precipitate, washing with ethanol and water for several times, and drying in a vacuum drying oven at 70 ℃ for 10h to obtain a precursor;
(3) reacting the precursor at 700 ℃ for 2h under the atmosphere of argon to obtain the nitrogen-doped carbon-coated tin pyrophosphate material Pb2P2O7@N-C。
Example 6
The embodiment provides a nitrogen-doped carbon-coated barium pyrophosphate material, and a preparation method thereof specifically comprises the following steps:
(1) adding 8mmol of BaCl2Adding into 50ml deionized water, adding 2mmol phytic acid and 2mmol melamine, and stirring vigorously at 70 deg.C for 1h to obtain mixed solution;
(2) transferring the mixed solution into a two-neck flask, adding 50ml of absolute ethyl alcohol, heating and refluxing at 85 ℃ for 12h, centrifuging to obtain a precipitate, washing with ethanol and water for several times, and drying in a vacuum drying oven at 70 ℃ for 10h to obtain a precursor;
(3) reacting the precursor at 500 ℃ for 2h under the atmosphere of argon to obtain the nitrogen-doped carbon-coated tin pyrophosphate material Ba2P2O7@N-C。
Example 7
The embodiment prepares a sodium ion half-cell, and the preparation method comprises the following steps:
preparing a negative electrode: taking SnP prepared in example 12O7Mixing @ N-C, ketjen black and sodium alginate uniformly according to the mass ratio of 7:2:1, grinding for 30min, adding a proper amount of water to prepare pasty slurry, and then adding water to prepare the mixtureUniformly coating the slurry on a copper foil, and then drying the copper foil in vacuum at 70 ℃; rolling the dried copper foil to prepare a negative electrode, cutting the negative electrode into a wafer with the diameter of 10mm, and taking the wafer as the negative electrode for later use;
preparing a reference electrode and a counter electrode: cutting the sodium sheet into wafers with the diameter of 12mm, and using the wafers as reference electrodes and counter electrodes for later use;
preparing a diaphragm: cutting the glass fiber film into a wafer with the diameter of 16mm, and using the wafer as a diaphragm for later use;
preparing an electrolyte: weighing 0.6122g of sodium perchlorate, adding the sodium perchlorate into 5ml of propylene carbonate and 5 wt% of fluoroethylene carbonate solvent, stirring the sodium perchlorate to be completely dissolved, and fully and uniformly stirring the mixture to be used as electrolyte for later use;
assembling: and (3) in a glove box (the content of oxygen and water is less than 0.1ppm) protected by inert gas, tightly stacking the prepared anode, the diaphragm and the cathode in sequence, dripping electrolyte to completely soak the diaphragm, and then packaging the stacked part into a button type shell to finish the assembly of the sodium ion half cell.
Comparative example 1
The comparative example provides a carbon-coated tin pyrophosphate SnP material2O7@ C, the preparation of which differs from example 1 in that: in the step (1), melamine is omitted;
the rest of the process is basically the same as that of embodiment 1, and the description thereof is omitted.
Comparative example 2
This comparative example differs from example 1 in that: in step (3), in H2Reacting the precursor for 2 hours at 600 ℃ under the atmosphere of the/Ar mixed gas; the rest of the process is basically the same as that of embodiment 1, and the description thereof is omitted.
The nitrogen-doped carbon-coated tin pyrophosphate material with the core-shell structure could not be prepared by this comparative example.
Test example 1
For SnP obtained in example 12O7The XRD test is carried out on @ N-C, the diffraction pattern is shown in figure 1, and as can be seen from figure 1, all diffraction peaks can correspond to the JCPDS No.29-1352 of the XRD standard card. And alsoThe figure shows a clear carbon coating peak, and the carbon material coated tin pyrophosphate material can be seen.
For SnP obtained in example 12O7@ N-C for Scanning Electron Microscopy (SEM) and Transmission Electron Microscopy (TEM), the SEM is shown in FIG. 2, the TEM is shown in FIG. 3, and it can be seen from FIGS. 2 and 3 that SnP2O7@ N-C is a uniformly distributed particle.
For SnP obtained in example 12O7X-ray spectral analysis with @ N-C, SnP, FIG. 42O7The distribution of elements such as C, N, Sn, P, O and the like in @ N-C is very uniform.
Test example 2
In order to verify the SnP prepared by the embodiment of the invention2O7Electrochemical Properties of @ N-C the sodium ion half cell prepared in example 7 was tested for electrochemical properties. Meanwhile, SnP prepared in comparative example 1 was used2O7@ C A sodium ion half cell for control was prepared according to the procedure of example 7.
The charge and discharge test of the battery is carried out on a Xinwei test system, the working interval of the battery is 0.01-3V, and figure 5 shows that SnP prepared in comparative example 12O7@ N-C and SnP prepared in example 12O7The sodium ion half cell with @ N-C as the negative electrode material is 1.5A g-1Long cycle Performance at Current Density, as shown, SnP2O7@ N-C shows good cycle performance.
FIG. 6 shows the product obtained in example 2 and SnP obtained in example 12O7The sodium ion half cell with @ N-C as the negative electrode material is 1.5A g-1And (5) detecting the long-cycle performance under the current density condition.
FIG. 7 shows the product obtained in example 3 and SnP obtained in example 12O7The sodium ion half cell with @ N-C as the negative electrode material is 1.5A g-1The results of the long cycle performance measurements under current density conditions are shown.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (5)
1. The preparation method of the nano material is characterized by comprising the following steps of:
dissolving a metal precursor, a phosphorus source and a nitrogen-containing organic substance in a solvent to prepare a mixed solution, wherein the molar ratio of the phosphorus source to the metal precursor is 1 (0.5-10), the molar ratio of the nitrogen-containing organic substance to the metal precursor is (0.1-2) to 1, the phosphorus source is phytic acid, the nitrogen-containing organic substance is melamine, and the metal precursor is stannous chloride;
heating the mixed solution for reaction to prepare a precursor, wherein the mixed solution is heated and refluxed for 8-20 hours at the temperature of 70-95 ℃;
and calcining the precursor in an inert gas atmosphere to prepare the nitrogen-doped carbon-coated pyrophosphate material, wherein the precursor is calcined at a high temperature of 500-800 ℃ for 1-10 hours in the inert gas atmosphere.
2. The method according to claim 1, wherein the concentration of the nitrogen-containing organic substance in the mixed solution is 0.05 to 1 mol/L.
3. A nanomaterial, comprising: the nitrogen-doped carbon-coated pyrophosphate material produced by the production method according to any one of claims 1 to 2.
4. An anode, characterized in that the material of the anode comprises: nanomaterial produced by the production method according to any one of claims 1 to 2, or nanomaterial according to claim 3.
5. A secondary battery, wherein a negative electrode of the secondary battery is the negative electrode according to claim 4.
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| CN111063870B (en) * | 2019-11-27 | 2021-09-24 | 深圳先进技术研究院 | Nanomaterial and preparation method thereof, electrode and secondary battery |
| CN111747393A (en) * | 2020-07-13 | 2020-10-09 | 武汉科技大学 | A kind of preparation method of porous pyrophosphate and sodium ion battery |
| CN114597406A (en) * | 2020-12-04 | 2022-06-07 | 中国科学院大连化学物理研究所 | A kind of preparation method and application of carbon-coated tin pyrophosphate |
| CN113036101A (en) * | 2021-02-26 | 2021-06-25 | 中国科学院宁波材料技术与工程研究所 | Carbon-coated pyrophosphate and preparation method and application thereof |
| CN113479860B (en) * | 2021-07-01 | 2023-08-11 | 中国石油大学(华东) | A kind of preparation method of SbPO4/nitrogen-doped carbon composite material |
| CN113479858B (en) * | 2021-07-01 | 2023-08-11 | 中国石油大学(华东) | Composite material for high-performance alkali metal ion battery cathode |
| CN113488647B (en) * | 2021-07-01 | 2024-09-20 | 中国石油大学(华东) | Amorphous SnP containing oxygen vacancy2O7Application of nitrogen-doped carbon composite material |
| CN113772648B (en) * | 2021-09-24 | 2023-07-21 | 江南大学 | A homogeneous C, N co-doped phosphate material and its preparation method and application |
| CN114105149B (en) * | 2021-10-12 | 2023-09-22 | 湖南金硅科技有限公司 | Carbon-coated nitrogen-phosphorus double-doped silicon oxide composite material, preparation method thereof and application thereof in lithium ion battery |
| CN114349070B (en) * | 2021-12-14 | 2023-07-14 | 南通金通储能动力新材料有限公司 | Large-particle high-nickel quaternary precursor and preparation method thereof |
| CN114497510A (en) * | 2022-02-09 | 2022-05-13 | 北京理工大学 | Nitrogen-phosphorus doped carbon material with ultrahigh specific surface area and application thereof |
| CN114920222B (en) * | 2022-04-11 | 2023-09-12 | 齐鲁理工学院 | High-entropy metal phosphide FeCoNiCrMnP x Is prepared by the preparation method of (2) |
| CN115000425B (en) * | 2022-06-20 | 2024-05-14 | 巢湖学院 | Molybdenum nitride quantum dot\nitrogen-doped carbon composite material and preparation method thereof |
| CN115231534B (en) * | 2022-06-23 | 2024-04-09 | 西北工业大学深圳研究院 | Core-shell type nano metal phosphide material and preparation method and application thereof |
| CN115028216B (en) * | 2022-08-12 | 2022-10-28 | 宜宾锂宝新材料有限公司 | High-nickel ternary cathode material, preparation method thereof and lithium ion battery |
| CN115692692A (en) * | 2022-11-04 | 2023-02-03 | 惠州锂威新能源科技有限公司 | A kind of negative electrode active material and its preparation method and lithium ion battery |
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