CN107017395B - A carbon-coated sodium manganese pyrophosphate@reduced graphene oxide composite material with sandwich structure and its preparation method and application - Google Patents
A carbon-coated sodium manganese pyrophosphate@reduced graphene oxide composite material with sandwich structure and its preparation method and application Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 165
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 93
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 74
- 239000002131 composite material Substances 0.000 title claims abstract description 72
- UMZUVDAJYPZSCI-UHFFFAOYSA-K sodium [hydroxy(oxido)phosphoryl] phosphate manganese(2+) Chemical compound [O-]P([O-])(=O)OP(=O)([O-])O.[Mn+2].[Na+] UMZUVDAJYPZSCI-UHFFFAOYSA-K 0.000 title claims abstract description 68
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 44
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000011572 manganese Substances 0.000 claims abstract description 32
- 239000002245 particle Substances 0.000 claims abstract description 32
- 229910001415 sodium ion Inorganic materials 0.000 claims abstract description 32
- 239000011734 sodium Substances 0.000 claims abstract description 30
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 28
- 239000002243 precursor Substances 0.000 claims abstract description 26
- 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 claims abstract description 25
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 25
- 239000007788 liquid Substances 0.000 claims abstract description 22
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 22
- 238000009210 therapy by ultrasound Methods 0.000 claims abstract description 19
- 239000008139 complexing agent Substances 0.000 claims abstract description 14
- 238000010438 heat treatment Methods 0.000 claims abstract description 9
- 238000007710 freezing Methods 0.000 claims abstract description 8
- 230000008014 freezing Effects 0.000 claims abstract description 8
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 7
- 239000011574 phosphorus Substances 0.000 claims abstract description 7
- 238000004108 freeze drying Methods 0.000 claims abstract description 6
- 239000007864 aqueous solution Substances 0.000 claims abstract description 4
- 230000001681 protective effect Effects 0.000 claims abstract description 4
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 37
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 26
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 20
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 20
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 20
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 12
- 239000010406 cathode material Substances 0.000 claims description 8
- 229960005070 ascorbic acid Drugs 0.000 claims description 6
- 239000011668 ascorbic acid Substances 0.000 claims description 6
- 235000010323 ascorbic acid Nutrition 0.000 claims description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 5
- 229910001416 lithium ion Inorganic materials 0.000 claims description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- 229940071125 manganese acetate Drugs 0.000 claims description 4
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 4
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 3
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 2
- 229910000388 diammonium phosphate Inorganic materials 0.000 claims description 2
- 235000019838 diammonium phosphate Nutrition 0.000 claims description 2
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 2
- RGVLTEMOWXGQOS-UHFFFAOYSA-L manganese(2+);oxalate Chemical compound [Mn+2].[O-]C(=O)C([O-])=O RGVLTEMOWXGQOS-UHFFFAOYSA-L 0.000 claims description 2
- 235000011007 phosphoric acid Nutrition 0.000 claims description 2
- 239000001632 sodium acetate Substances 0.000 claims description 2
- 235000017281 sodium acetate Nutrition 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 235000017550 sodium carbonate Nutrition 0.000 claims description 2
- 239000001509 sodium citrate Substances 0.000 claims description 2
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 2
- ZNCPFRVNHGOPAG-UHFFFAOYSA-L sodium oxalate Chemical compound [Na+].[Na+].[O-]C(=O)C([O-])=O ZNCPFRVNHGOPAG-UHFFFAOYSA-L 0.000 claims description 2
- 229940039790 sodium oxalate Drugs 0.000 claims description 2
- 239000007774 positive electrode material Substances 0.000 abstract description 27
- 239000000243 solution Substances 0.000 description 55
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 34
- 239000000463 material Substances 0.000 description 23
- 238000005245 sintering Methods 0.000 description 18
- 239000008367 deionised water Substances 0.000 description 17
- 229910021641 deionized water Inorganic materials 0.000 description 17
- CESXSDZNZGSWSP-UHFFFAOYSA-L manganese(2+);diacetate;tetrahydrate Chemical compound O.O.O.O.[Mn+2].CC([O-])=O.CC([O-])=O CESXSDZNZGSWSP-UHFFFAOYSA-L 0.000 description 17
- 238000000034 method Methods 0.000 description 16
- 229960004543 anhydrous citric acid Drugs 0.000 description 14
- 239000010405 anode material Substances 0.000 description 10
- 239000012265 solid product Substances 0.000 description 10
- 238000002441 X-ray diffraction Methods 0.000 description 9
- 239000000047 product Substances 0.000 description 8
- 229940082328 manganese acetate tetrahydrate Drugs 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000012071 phase Substances 0.000 description 5
- 230000009286 beneficial effect Effects 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 239000013543 active substance Substances 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 229930006000 Sucrose Natural products 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 229960004106 citric acid Drugs 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000006258 conductive agent Substances 0.000 description 2
- XPPKVPWEQAFLFU-UHFFFAOYSA-J diphosphate(4-) Chemical compound [O-]P([O-])(=O)OP([O-])([O-])=O XPPKVPWEQAFLFU-UHFFFAOYSA-J 0.000 description 2
- 235000011180 diphosphates Nutrition 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 229940048084 pyrophosphate Drugs 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 239000005720 sucrose Substances 0.000 description 2
- 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 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 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 1
- 238000003763 carbonization Methods 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 235000015165 citric acid Nutrition 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 229960001031 glucose Drugs 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 150000002697 manganese compounds Chemical class 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 229940116315 oxalic acid Drugs 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 229910001488 sodium perchlorate Inorganic materials 0.000 description 1
- BYTVRGSKFNKHHE-UHFFFAOYSA-K sodium;[hydroxy(oxido)phosphoryl] phosphate;iron(2+) Chemical compound [Na+].[Fe+2].OP([O-])(=O)OP([O-])([O-])=O BYTVRGSKFNKHHE-UHFFFAOYSA-K 0.000 description 1
- XWQGIDJIEPIQBD-UHFFFAOYSA-J sodium;iron(3+);phosphonato phosphate Chemical compound [Na+].[Fe+3].[O-]P([O-])(=O)OP([O-])([O-])=O XWQGIDJIEPIQBD-UHFFFAOYSA-J 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229960004793 sucrose Drugs 0.000 description 1
- 230000001360 synchronised effect Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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- 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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
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Abstract
本发明公开了一种具有三明治结构的碳包覆焦磷酸锰钠@氧化石墨烯复合材料及其制备方法和应用，该复合材料由表面均匀分布有碳包覆焦磷酸锰钠颗粒的氧化石墨烯片堆叠构成。在溶有磷源、钠源、锰源及络合剂的水溶液中加入氧化石墨烯后，依次进行超声处理、液氮冷冻及冷冻干燥，得到前驱体；所述前驱体置于保护气氛下，进行热处理，即得具有三明治结构的碳包覆焦磷酸锰钠@氧化石墨烯复合材料，其作为钠离子电池正极材料具有优良的电化学性能，且“Na‑Mn‑P‑O”体系资源丰富，成本低廉，且该制备方法操作简单，商业应用前景广阔。
The invention discloses a carbon-coated sodium manganese pyrophosphate@graphene oxide composite material with a sandwich structure and a preparation method and application thereof. The composite material is composed of graphene oxide with carbon-coated sodium manganese pyrophosphate particles evenly distributed on the surface. Sheet stacking. After adding graphene oxide to the aqueous solution in which the phosphorus source, the sodium source, the manganese source and the complexing agent are dissolved, ultrasonic treatment, liquid nitrogen freezing and freeze-drying are carried out in sequence to obtain a precursor; the precursor is placed in a protective atmosphere, Heat treatment to obtain a carbon-coated sodium manganese pyrophosphate@graphene oxide composite material with a sandwich structure, which has excellent electrochemical performance as a positive electrode material for sodium-ion batteries, and the "Na-Mn-P-O" system is rich in resources , the cost is low, the preparation method is simple to operate, and the commercial application prospect is broad.
Description
Technical Field
The invention relates to a positive electrode material of a sodium-ion battery, in particular to a composite positive electrode material of carbon-coated sodium manganese pyrophosphate and graphene oxide with a sandwich structure, a preparation method thereof and application of the composite material as a sodium-ion battery, belonging to the field of sodium-ion batteries.
Background
Lithium ion batteries have rapidly occupied the market for portable electronic products (notebook computers, smart mobile devices, tablet computers, etc.) due to their advantages of high energy density, high stability, long life, etc., and have continuously permeated the field of electric vehicles. However, the reserve of lithium resources in the earth crust is low, and the regional distribution is uneven, so that the lithium price of the lithium ion battery is continuously increased in the process of large-scale popularization and application, and the price of the lithium ion battery is high. Therefore, the application of lithium ion batteries to the field of large-scale power storage is limited. Sodium ion batteries are considered to be an ideal large-scale electricity storage application technology due to abundant sodium resource and environmental friendliness, and therefore have attracted much attention in the world.
During the past decades, researchers have conducted extensive research into positive electrode materials for sodium ion batteries. Among the existing positive electrode material systems, the polyanion-type compound system is considered to be the most commercially promising sodium-electric positive electrode material system. Among polyanionic compound systems, pyrophosphate system materials have been receiving attention from researchers because of their advantages such as open three-dimensional channels and high structural stability and thermal stability. At present, more sodium ferric pyrophosphate is reported to have excellent electrochemical performance, and the reversible specific capacity is close to the theoretical specific capacity of 95mAh/g under the multiplying power of 0.1C. But Fe2+/Fe3+The redox potential of (a) is low, so that the sodium iron pyrophosphate discharge plateau is low, and therefore the energy density is not high. Sodium manganese pyrophosphate has a theoretical specific capacity of 97.5mAh/g, and 3.7V (vs Na/Na)+) The high voltage has better sodium storage performance and low cost. However, the sodium manganese pyrophosphate material has poor conductivity, so that the rate capability and the cycle performance of the material as an electrode material are poor. In addition, most of the existing methods for synthesizing the sodium manganese pyrophosphate material are traditional solid-phase sintering methods, and the obtained product has large particle size and poor material dynamic performance, so that the method is not beneficial to the exertion of material capacity. Therefore, how to improve the rate capability and the cycle performance of the sodium manganese pyrophosphate and improve the specific capacity of the material becomes the research on the sodium manganese pyrophosphate as the positive electrode material of the sodium ion batteryThe key problem is solved.
Disclosure of Invention
Aiming at the defects of the sodium ion anode material of the existing pyrophosphate system, the invention aims to provide the carbon-coated manganese pyrophosphate sodium @ reduced graphene oxide composite material which has good stability, good dispersibility of active substances, uniform appearance and a special sandwich structure.
The invention also aims to provide the method for preparing the carbon-coated sodium manganese pyrophosphate @ reduced graphene oxide composite material, which has the advantages of good repeatability, simplicity in operation, environmental friendliness and low cost and has an industrial application prospect.
The third purpose of the invention is to provide an application of the carbon-coated sodium manganese pyrophosphate @ reduced graphene oxide composite material as a sodium ion battery positive electrode material, and the prepared sodium ion battery has high charge-discharge specific capacity, good rate capability and cycling stability.
In order to achieve the technical purpose, the invention provides a carbon-coated manganese sodium pyrophosphate @ reduced graphene oxide composite material with a sandwich structure, which is formed by stacking reduced graphene oxide sheets with carbon-coated manganese sodium pyrophosphate particles uniformly distributed on the surface.
According to the technical scheme, the manganese sodium pyrophosphate particles are uniformly coated by the carbon layer, so that the conductivity of the manganese sodium pyrophosphate particles is improved, higher capacity exertion and rate capability can be obtained, and the thermal stability and chemical stability of the manganese sodium pyrophosphate are improved by the carbon layer coating, and the cycle performance of the manganese sodium pyrophosphate is favorably improved. Meanwhile, the carbon-coated sodium manganese pyrophosphate particles are uniformly loaded on the surface of the reduced graphene oxide sheet, so that the uniform dispersion of the carbon-coated sodium manganese pyrophosphate particles is improved, a higher specific surface is obtained, the electrochemical activity is improved, and the reduced graphene oxide sheet form a sandwich structure in a stacking form, so that the stability of the composite material is further improved.
According to the preferable scheme, the specific surface area of the carbon-coated manganese pyrophosphate sodium @ reduced graphene oxide composite material with the sandwich structure is 60-120 m2g-1(ii) a Carbon bagThe particle size of the sodium manganese pyrophosphate-coated particles is 300-1000 nm; preferably 300-700 nm; more preferably 300 to 500 nm.
In a more preferable scheme, the mass of the manganese sodium pyrophosphate is 85-99% of that of the carbon-coated manganese sodium pyrophosphate @ reduced graphene oxide composite material with a sandwich structure; more preferably 94% to 97%; most preferably 95% to 96%.
The invention also provides a preparation method of the carbon-coated sodium manganese pyrophosphate @ reduced graphene oxide composite material with the sandwich structure, which comprises the steps of adding graphene oxide into an aqueous solution in which a phosphorus source, a sodium source, a manganese source and a complexing agent are dissolved, and then sequentially carrying out ultrasonic treatment, liquid nitrogen freezing and freeze drying to obtain a precursor; and (3) placing the precursor in a protective atmosphere, and carrying out heat treatment at 500-800 ℃ to obtain the catalyst.
According to the technical scheme, the complexing agent is adopted, on one hand, the complexing agent can coordinate and complex metal ions, not only can promote the generation and uniform dispersion of the sodium manganese pyrophosphate crystals and be beneficial to the generation of uniform-appearance sodium manganese pyrophosphate particles, but also can be used as a carbon source, the complexing agent is adsorbed on the surfaces of the sodium manganese pyrophosphate particles and is converted into the conductive carbon coating layer through high-temperature carbonization, the conductivity of the sodium manganese pyrophosphate material can be effectively improved, and the stability of the sodium manganese pyrophosphate material is improved. According to the technical scheme, the graphene oxide is introduced and used as a dispersing carrier, so that the carbon-coated sodium manganese pyrophosphate particles are uniformly dispersed and form a sandwich structure, the specific surface area and the stability of the composite material are improved, and the graphene oxide provides a good conductive substrate for the composite material and effectively improves the conductivity of the sodium manganese pyrophosphate. The technical scheme of the invention also adopts the processes of liquid nitrogen freezing and freeze drying, can effectively maintain the morphology of the composite material, and avoids electrochemical performance reduction caused by serious agglomeration.
In the preferred scheme, the ratio of the phosphorus source, the sodium source and the manganese source is measured by the molar ratio of P to Na to Mn being 1.8-2.2: 0.8-1.2; the most preferred ratio is measured as a molar ratio of P to Na to Mn of 2:2: 1.
In a preferable scheme, the molar ratio of the complexing agent to manganese in the manganese source is 2-5: 1. More preferably 3 to 4: 1, most preferably 3: 1.
in a more preferred embodiment, the phosphorus source comprises at least one of diammonium hydrogen phosphate, ammonium dihydrogen phosphate, and phosphoric acid.
In a more preferred embodiment, the sodium source includes at least one of sodium carbonate, sodium bicarbonate, sodium acetate, sodium oxalate, and sodium citrate. The sodium source is preferably anhydrous sodium carbonate and/or sodium bicarbonate, most preferably anhydrous sodium carbonate.
More preferably, the manganese source is a water-soluble inorganic manganese compound known to those skilled in the art. Preferred manganese sources include at least one of manganese acetate, manganese nitrate, manganese oxalate. The most preferred manganese source is manganese acetate.
Mn in the aqueous solution in the technical scheme of the invention2+The concentration is 0.05-0.3 mol/L. Mn2+The concentration is preferably 0.1 to 0.2 mol/L.
In a more preferred embodiment, the complexing agent is at least one of citric acid, oxalic acid, ascorbic acid, sucrose and glucose. The complexing agent is more preferably citric acid and/or sucrose.
In a more preferable scheme, the heat treatment temperature is 600-700 ℃, and most preferably 600 ℃.
In a more preferable scheme, the heat treatment time is 6-12 h.
The protective gas in the solution according to the invention is preferably an inert gas, such as argon.
In the technical scheme of the invention, the mass of the added graphene oxide sheet is 1-10% of that of the carbon-coated manganese pyrophosphate sodium @ reduced graphene oxide composite material with a sandwich structure.
The invention also provides an application of the carbon-coated manganese sodium pyrophosphate @ reduced graphene oxide composite material with a sandwich structure, and the carbon-coated manganese sodium pyrophosphate @ reduced graphene oxide composite material is applied as a positive electrode material of a sodium ion battery.
The preparation method of the carbon-coated sodium manganese pyrophosphate @ reduced graphene oxide composite material with the sandwich structure comprises the following steps of:
step (1): push buttonWeighing manganese acetate tetrahydrate, ammonium dihydrogen phosphate and anhydrous sodium carbonate according to a stoichiometric ratio, and mixing the manganese acetate, the ammonium dihydrogen phosphate and the anhydrous sodium carbonate with the complexing agent and Mn2+The molar ratio of (A) to (B) is 2-5: 1, weighing anhydrous citric acid, dissolving the anhydrous citric acid in deionized water, and fully stirring to obtain a mixed solution; mn of the mixed solution2+The concentration is 0.05-0.3 mol/L;
step (2): adding graphene oxide accounting for 3% -6% of the mass of a theoretical product into the solution, carrying out ultrasonic treatment for 30min, carrying out water bath at 80 ℃ for 6h, freezing by using liquid nitrogen, placing the obtained precursor into a freeze dryer, carrying out freeze drying, sintering the obtained precursor in a tube furnace at 600-700 ℃ for 8-10 h under an inert atmosphere, and finally obtaining the carbon-coated manganese pyrophosphate sodium @ reduced graphene oxide composite material with a sandwich structure.
The invention also discloses a method for preparing the positive electrode of the sodium ion battery by using the carbon-coated manganese pyrophosphate sodium @ reduced graphene oxide composite positive electrode material with the sandwich structure, and testing the electrochemical performance of the positive electrode.
For example, the carbon-coated manganese sodium pyrophosphate @ reduced graphene oxide composite material is mixed with a conductive agent and a binder, and then coated on an aluminum foil to prepare the positive electrode of the sodium-ion battery. The conductive agent and the binder used may be those known to those skilled in the art. The method for assembling and preparing the positive electrode material of the sodium-ion battery can also refer to the existing method.
For example, the conductive carbon black of the carbon-coated manganese pyrophosphate sodium @ reduced graphene oxide composite material with the sandwich structure prepared by the invention and the PVDF binder are ground according to the mass ratio of 8:1:1, NMP is added after the materials are fully mixed to form uniform slurry, the slurry is coated on an aluminum foil to be used as a test electrode, metal sodium is used as a counter electrode, and the electrolyte is 1M NaClO 4100% PC, preparing a sodium half cell and testing the electrochemical performance of the sodium half cell.
Compared with the prior art, the technical scheme of the invention has the following beneficial effects:
the carbon-coated manganese sodium pyrophosphate @ reduced graphene oxide composite material has a special sandwich structure, reduced graphene oxide sheets are stacked, and carbon-coated manganese sodium pyrophosphate particles are uniformly dispersed and loaded on the surfaces of the reduced graphene oxide sheets and between two adjacent reduced graphene oxide sheets. The graphene can improve the dispersibility of the carbon-coated manganese sodium pyrophosphate particle active substance, improve the specific surface area of the carbon-coated manganese sodium pyrophosphate particle active substance, increase active sites and improve the electrochemical activity; the reduced graphene oxide sheets and the carbon-coated sodium manganese pyrophosphate particles form a sandwich structure, so that the physical and chemical stability of the composite material is improved; and the reduced graphene oxide is used as a good conductive matrix of the carbon-coated sodium manganese pyrophosphate particles, so that the conductivity of the reduced graphene oxide is improved, and the capacity exertion and rate capability of the composite anode material are greatly improved. The manganese sodium pyrophosphate particles are uniformly coated by the carbon layer, so that the conductivity of the manganese sodium pyrophosphate particles is improved, higher capacity exertion and rate performance can be obtained, and the thermal stability and chemical stability of the manganese sodium pyrophosphate are improved by the carbon layer coating, thereby being beneficial to improving the cycle performance of the manganese sodium pyrophosphate particles.
The carbon-coated sodium manganese pyrophosphate @ reduced graphene oxide composite material is synthesized by combining a solution method with high-temperature heat treatment. The precursor material is synthesized by a solution method, a complexing agent is adopted in the solution method, the complexing agent not only plays a complexing role, but also serves as a carbon source, on one hand, the generation and uniform dispersibility of the sodium manganese pyrophosphate crystal can be promoted, and in addition, the sodium manganese pyrophosphate crystal is converted into conductive carbon at high temperature, so that the conductivity of the sodium manganese pyrophosphate material can be effectively improved. Meanwhile, graphene oxide is used as a carrier material, reduced graphene oxide can promote dispersion of the sodium manganese pyrophosphate crystals by using polar groups contained on the surface of the reduced graphene oxide, the sodium manganese pyrophosphate crystals with uniform particle size and good appearance are easy to obtain, the reduced graphene oxide provides a good conductive substrate for the composite material, and the conductivity of the sodium manganese pyrophosphate is effectively improved. The precursor is frozen by liquid nitrogen and freeze-dried to effectively maintain the morphology of the material, and avoid the reduction of electrochemical performance caused by serious agglomeration. The high-temperature heat treatment process realizes the generation of the carbon coating and the synchronous realization of the in-situ coating of the sodium manganese pyrophosphate particles, and greatly simplifies the process steps.
The carbon-coated manganese sodium pyrophosphate @ reduced graphene oxide composite material with the sandwich structure has high electrochemical activity, high physicochemical stability and high safety, and shows excellent electrochemical performance when being used as a sodium ion positive electrode material for a sodium ion battery, the discharge specific capacity of 50 cycles of the sodium ion battery can reach 70mAh/g under the multiplying power of 0.2C, and the capacity retention rate can reach more than 90%.
The method for preparing the carbon-coated sodium manganese pyrophosphate @ reduced graphene oxide composite material with the sandwich structure is simple and reliable, environment-friendly, rich in 'Na-Mn-P-O' system resource, low in cost and wide in industrial application prospect.
Drawings
Fig. 1 is an X-ray diffraction pattern (XRD) of the carbon-coated sodium manganese pyrophosphate @ reduced graphene oxide composite positive electrode material with a sandwich structure prepared in example 1;
fig. 2 is a Scanning Electron Microscope (SEM) image of the carbon-coated sodium manganese pyrophosphate @ reduced graphene oxide composite positive electrode material with the sandwich structure prepared in example 1;
fig. 3 is a charge-discharge curve of the sodium ion battery assembled by the sandwich-structured carbon-coated manganese sodium pyrophosphate @ reduced graphene oxide composite positive electrode material prepared in example 1 at a magnification of 0.1C;
fig. 4 is a CV curve of the sodium ion battery assembled by the carbon-coated sodium manganese pyrophosphate @ reduced graphene oxide composite cathode material with the sandwich structure prepared in example 1 at a sweep rate of 0.1 mV/s.
Detailed Description
The following examples are intended to illustrate the invention in further detail; and the scope of the claims of the present invention is not limited by the examples.
Example 1
Firstly, 0.005mol of tetrahydrate manganese acetate, 0.01mol of ammonium dihydrogen phosphate, 0.005mol of anhydrous sodium carbonate and 2.88g (molar ratio to manganese is 3: 1) of anhydrous citric acid are dissolved in 50mL of deionized water and fully stirred to obtain a clear solution. Then 0.067g (5% of the mass of the sodium manganese pyrophosphate) of graphene oxide is added into the solution, and after 30min of ultrasonic treatment, the solution is subjected to water bath at 80 ℃ for 6 h. The solution was frozen with liquid nitrogen and then lyophilized in a lyophilizer. Placing the precursor into an inert atmosphere tube furnace, sintering for 9h at 600 ℃ to obtain a solid productThe carbon-coated manganese pyrophosphate sodium @ reduced graphene oxide composite cathode material has a sandwich structure. The X-ray diffraction pattern (XRD) of the prepared carbon-coated manganese pyrophosphate sodium @ reduced graphene oxide composite cathode material with the sandwich structure is shown in figure 1. The Scanning Electron Microscope (SEM) of the prepared carbon-coated sodium manganese pyrophosphate @ reduced graphene oxide composite cathode material with the sandwich structure is shown in figure 2, and as can be seen from figure 2, the material is prepared by uniformly compounding sodium manganese pyrophosphate and graphene, wherein the particle size of sodium manganese pyrophosphate particles is 300-500 nm, and the specific surface area is 110m2g-1。
The button cell is assembled by adopting the sodium ion battery composite positive electrode material prepared by the embodiment and a sodium sheet, and as can be seen from a 0.2C multiplying power cycle diagram, the discharge specific capacity of 50 cycles of the cycle reaches 73mAh/g, and the capacity retention rate reaches over 90 percent.
Example 2
Firstly, 0.005mol of tetrahydrate manganese acetate, 0.01mol of ammonium dihydrogen phosphate, 0.005mol of anhydrous sodium carbonate and 3.84g (molar ratio of the anhydrous sodium carbonate to the manganese is 4: 1) of anhydrous citric acid are dissolved in 50mL of deionized water and fully stirred to obtain a clear solution. Then 0.067g (5% of the mass of the sodium manganese pyrophosphate) of graphene oxide is added into the solution, after 30min of ultrasonic treatment, the solution is subjected to water bath at 80 ℃ for 6h, then liquid nitrogen freezing is carried out, and then the solution is freeze-dried in a freeze dryer. And placing the obtained precursor into an inert atmosphere tube furnace, and sintering for 9h at 600 ℃ to obtain a solid product, namely the carbon-coated sodium manganese pyrophosphate @ reduced graphene oxide composite anode material with a sandwich structure. The particle size of the sodium manganese pyrophosphate particles is 300-500 nm, and the specific surface area is 110m2g-1。
The sodium-ion battery composite positive electrode material prepared by the embodiment and a sodium sheet are assembled into a button battery, and the specific capacity is 65mAh/g after 50 cycles under the multiplying power of 0.2C. The excessive organic carbon with poor conductivity has no obvious effect on improving the material performance.
Example 3
Firstly, 0.005mol of tetrahydrate manganese acetate, 0.01mol of ammonium dihydrogen phosphate, 0.005mol of anhydrous sodium carbonate and 2.88g (molar ratio to manganese is 3: 1) of anhydrous citric acid are dissolved in 50mL of deionized water and fully stirred to obtain a clear solution. Then 0.134g (8% of the mass of the sodium manganese pyrophosphate) of graphene oxide is added into the solution, after 30min of ultrasonic treatment, the solution is subjected to water bath at 80 ℃ for 6h, frozen by liquid nitrogen and then freeze-dried in a freeze dryer. And placing the obtained precursor into an inert atmosphere tube furnace, and sintering for 9h at 600 ℃ to obtain a solid product, namely the carbon-coated sodium manganese pyrophosphate @ reduced graphene oxide composite anode material with a sandwich structure.
The button cell assembled by the sodium-ion battery composite positive electrode material prepared by the embodiment and the sodium sheet has a specific capacity of 70mAh/g after circulating for 50 circles under a multiplying power of 0.2C. The excessive graphene does not have obvious improvement effect on the material performance.
Example 4
Firstly, 0.005mol of tetrahydrate manganese acetate, 0.01mol of ammonium dihydrogen phosphate, 0.005mol of anhydrous sodium carbonate and 2.88g (molar ratio to manganese is 3: 1) of anhydrous citric acid are dissolved in 40mL of deionized water and fully stirred to obtain a clear solution. Then 0.067g (5% of the mass of the sodium manganese pyrophosphate) of graphene oxide is added into the solution, after 30min of ultrasonic treatment, the solution is subjected to water bath at 80 ℃ for 6h, frozen by liquid nitrogen and then freeze-dried in a freeze dryer. And placing the obtained precursor into an inert atmosphere tube furnace, and sintering for 9h at 600 ℃ to obtain a solid product, namely the carbon-coated sodium manganese pyrophosphate @ reduced graphene oxide composite anode material with a sandwich structure. The particle size of the sodium manganese pyrophosphate particles is 500-800 nm, and the specific surface area is 80m2g-1。
The sodium-ion battery composite positive electrode material prepared by the embodiment and a sodium sheet are assembled into a button battery, and the specific capacity is 62mAh/g after 50 cycles under the multiplying power of 0.2C. Illustrating that solution solubility affects the particle size of the material.
Example 5
Firstly, 0.005mol of manganese acetate tetrahydrate, 0.01mol of ammonium dihydrogen phosphate, 0.005mol of anhydrous sodium carbonate and 2.64g (molar ratio to manganese is 3: 1) of ascorbic acid are dissolved in 60mL of deionized water and fully stirred to obtain a clear solution. Then 0.067g (5% of the mass of the sodium manganese pyrophosphate) of graphene oxide is added into the solution, after 30min of ultrasonic treatment, the solution is subjected to water bath at 80 ℃ for 6h, frozen by liquid nitrogen and then freeze-dried in a freeze dryer. And placing the obtained precursor into an inert atmosphere tube furnace, and sintering at 600 ℃ for 12h to obtain a solid product, namely the carbon-coated sodium manganese pyrophosphate @ reduced graphene oxide composite anode material with a sandwich structure.
The sodium-ion battery composite positive electrode material prepared by the embodiment and a sodium sheet are assembled into a button battery, and the specific capacity is 62mAh/g after 50 cycles under the multiplying power of 0.2C. The electrochemical performance of the material sintered for 12 hours is obviously reduced.
Example 6
Firstly, 0.005mol of manganese acetate tetrahydrate, 0.01mol of ammonium dihydrogen phosphate, 0.005mol of anhydrous sodium carbonate and 2.64g (molar ratio to manganese is 3: 1) of ascorbic acid are dissolved in 60mL of deionized water and fully stirred to obtain a clear solution. Then 0.067g (5% of the mass of the sodium manganese pyrophosphate) of graphene oxide is added into the solution, after 30min of ultrasonic treatment, the solution is subjected to water bath at 80 ℃ for 6h, frozen by liquid nitrogen and then freeze-dried in a freeze dryer. And placing the obtained precursor into an inert atmosphere tube furnace, and sintering for 6h at 600 ℃ to obtain a solid product, namely the carbon-coated sodium manganese pyrophosphate @ reduced graphene oxide composite anode material with a sandwich structure.
The sodium-ion battery composite positive electrode material prepared by the embodiment and a sodium sheet are assembled into a button battery, and the specific capacity is 59mAh/g after circulation for 50 circles under the multiplying power of 0.2C. The electrochemical performance of the material sintered for 6h is obviously reduced.
Example 7
Firstly, 0.005mol of manganese acetate tetrahydrate, 0.01mol of ammonium dihydrogen phosphate, 0.005mol of anhydrous sodium carbonate and 2.64g (molar ratio to manganese is 3: 1) of ascorbic acid are dissolved in 60mL of deionized water and fully stirred to obtain a clear solution. Then 0.067g (5% of the mass of the sodium manganese pyrophosphate) of graphene oxide is added into the solution, after 30min of ultrasonic treatment, the solution is subjected to water bath at 80 ℃ for 6h, frozen by liquid nitrogen and then freeze-dried in a freeze dryer. And placing the obtained precursor into an inert atmosphere tube furnace, and sintering for 8h at 600 ℃ to obtain a solid product, namely the carbon-coated sodium manganese pyrophosphate @ reduced graphene oxide composite anode material with a sandwich structure.
The sodium-ion battery composite positive electrode material prepared by the embodiment and a sodium sheet are assembled into a button battery, and the specific capacity is 67mAh/g after 50 cycles under the multiplying power of 0.2C. The electrochemical performance of the sintered material for 8 hours is better.
Example 8
Firstly, 0.005mol of manganese acetate tetrahydrate, 0.01mol of ammonium dihydrogen phosphate, 0.005mol of anhydrous sodium carbonate and 2.64g (molar ratio to manganese is 3: 1) of ascorbic acid are dissolved in 60mL of deionized water and fully stirred to obtain a clear solution. Then 0.067g (5% of the mass of the sodium manganese pyrophosphate) of graphene oxide is added into the solution, after 30min of ultrasonic treatment, the solution is subjected to water bath at 80 ℃ for 6h, frozen by liquid nitrogen and then freeze-dried in a freeze dryer. And placing the obtained precursor into an inert atmosphere tube furnace, and sintering for 10h at 600 ℃ to obtain a solid product, namely the carbon-coated manganese sodium pyrophosphate @ reduced graphene oxide composite anode material with a sandwich structure.
The sodium-ion battery composite positive electrode material prepared by the embodiment and a sodium sheet are assembled into a button battery, and the specific capacity is 67mAh/g after 50 cycles under the multiplying power of 0.2C. The electrochemical performance of the material sintered for 10 hours is better.
Example 9
Firstly, 0.005mol of tetrahydrate manganese acetate, 0.01mol of ammonium dihydrogen phosphate, 0.005mol of anhydrous sodium carbonate and 2.88g (molar ratio to manganese is 3: 1) of anhydrous citric acid are dissolved in 60mL of deionized water and fully stirred to obtain a clear solution. Then 0.067g (5% of the mass of the sodium manganese pyrophosphate) of graphene oxide is added into the solution, after 30min of ultrasonic treatment, the solution is subjected to water bath at 80 ℃ for 6h, frozen by liquid nitrogen and then freeze-dried in a freeze dryer. And placing the obtained precursor into an inert atmosphere tube furnace, and sintering for 9h at 500 ℃ to obtain a solid product, namely the carbon-coated sodium manganese pyrophosphate @ reduced graphene oxide composite anode material with a sandwich structure.
The sodium-ion battery composite positive electrode material prepared by the embodiment and a sodium sheet are assembled into a button battery, and the specific capacity is 56mAh/g after 50 cycles under the multiplying power of 0.2C. The material sintered at 500 ℃ has obviously poor performance.
Example 10
Firstly, 0.005mol of tetrahydrate manganese acetate, 0.01mol of ammonium dihydrogen phosphate, 0.005mol of anhydrous sodium carbonate and 2.88g (molar ratio to manganese is 3: 1) of anhydrous citric acid are dissolved in 60mL of deionized water and fully stirred to obtain a clear solution. Then 0.067g (5% of the mass of the sodium manganese pyrophosphate) of graphene oxide is added into the solution, after 30min of ultrasonic treatment, the solution is subjected to water bath at 80 ℃ for 6h, frozen by liquid nitrogen and then freeze-dried in a freeze dryer. And placing the precursor into an inert atmosphere tube furnace, and sintering at 700 ℃ for 9h to obtain a solid product, namely the carbon-coated manganese sodium pyrophosphate @ reduced graphene oxide composite cathode material with a sandwich structure. The sodium-ion battery composite positive electrode material prepared by the embodiment and a sodium sheet are assembled into a button battery, and the specific capacity is 61mAh/g after circulation for 50 circles under the multiplying power of 0.2C.
Example 11
Firstly, 0.005mol of tetrahydrate manganese acetate, 0.01mol of ammonium dihydrogen phosphate, 0.005mol of anhydrous sodium carbonate and 2.88g (molar ratio to manganese is 3: 1) of anhydrous citric acid are dissolved in 60mL of deionized water and fully stirred to obtain a clear solution. Then 0.412g (5% of the mass of the sodium manganese pyrophosphate) of graphene oxide is added into the solution, after 30min of ultrasonic treatment, the solution is subjected to water bath at 80 ℃ for 6h, frozen by liquid nitrogen and then freeze-dried in a freeze dryer. And placing the obtained precursor into an inert atmosphere tube furnace, and sintering at 800 ℃ for 9h to obtain a solid product, namely the carbon-coated manganese pyrophosphate sodium @ reduced graphene oxide composite cathode material with a sandwich structure.
The sodium-ion battery composite positive electrode material prepared by the embodiment and a sodium sheet are assembled into a button battery, and the specific capacity is 52mAh/g after circulation for 50 circles under the multiplying power of 0.2C.
Comparative example 1
Firstly, 0.005mol of manganese acetate tetrahydrate, 0.01mol of ammonium dihydrogen phosphate, 0.005mol of anhydrous sodium carbonate and 0g of anhydrous citric acid are dissolved in 60mL of deionized water and fully stirred to obtain a clear solution. Then 0.067g (5%) of graphene oxide is added into the solution, after 30min of ultrasonic treatment, the solution is subjected to water bath at 80 ℃ for 6h, liquid nitrogen freezing is carried out, and then the solution is freeze-dried in a freeze dryer. And putting the obtained precursor into an inert atmosphere tube furnace, sintering for 9 hours at 600 ℃, and collecting a product. XRD did not detect a phase of sodium manganese pyrophosphate.
Comparative example 2
Firstly, 0.005mol of tetrahydrate manganese acetate, 0.01mol of ammonium dihydrogen phosphate, 0.005mol of anhydrous sodium carbonate and 2.88g (molar ratio to manganese is 3: 1) of anhydrous citric acid are dissolved in 60mL of deionized water and fully stirred to obtain a clear solution. And (3) performing water bath at 80 ℃ for 6h, performing liquid nitrogen freezing, and then freeze-drying in a freeze dryer. And putting the obtained precursor into an inert atmosphere tube furnace, sintering for 9 hours at 600 ℃, and collecting a product. XRD showed a phase of sodium manganese pyrophosphate. The button cell assembled by the sodium-ion battery composite positive electrode material prepared by the embodiment and the sodium sheet has obviously reduced electrochemical performance. The method shows that the graphene is important for improving the performance of the material.
Comparative example 3
Firstly, 0.005mol of tetrahydrate manganese acetate, 0.01mol of ammonium dihydrogen phosphate, 0.005mol of anhydrous sodium carbonate and 1.92g (molar ratio of the anhydrous sodium carbonate to the manganese is 1: 1) of anhydrous citric acid are dissolved in 60mL of deionized water and fully stirred to obtain a clear solution. Then 0.067g (5% of the mass of the sodium manganese pyrophosphate) of graphene oxide is added into the solution, after 30min of ultrasonic treatment, the solution is subjected to water bath at 80 ℃ for 6h, frozen by liquid nitrogen and then freeze-dried in a freeze dryer. And putting the obtained precursor into an inert atmosphere tube furnace, sintering for 9 hours at 600 ℃, and collecting a product. XRD showed no phase with sodium manganese pyrophosphate,
comparative example 4
Firstly, 0.03mol of tetrahydrate manganese acetate, 0.06mol of ammonium dihydrogen phosphate, 0.03mol of anhydrous sodium carbonate and 2.88g (molar ratio to manganese is 3: 1) of anhydrous citric acid are dissolved in 60mL of deionized water and fully stirred to obtain a clear solution. Then 0.067g (5% of the mass of the sodium manganese pyrophosphate) of graphene oxide is added into the solution, after 30min of ultrasonic treatment, the solution is subjected to water bath at 80 ℃ for 6h, frozen by liquid nitrogen and then freeze-dried in a freeze dryer. And putting the obtained precursor into an inert atmosphere tube furnace, sintering for 9h at 400 ℃, and collecting a product. XRD did not detect a phase of sodium manganese pyrophosphate.
Comparative example 5
Firstly, 0.005mol of tetrahydrate manganese acetate, 0.01mol of ammonium dihydrogen phosphate, 0.005mol of anhydrous sodium carbonate and 2.88g (molar ratio to manganese is 3: 1) of anhydrous citric acid are dissolved in 60mL of deionized water and fully stirred to obtain a clear solution. Then 0.067g (5% of the mass of the sodium manganese pyrophosphate) of graphene oxide is added into the solution, after 30min of ultrasonic treatment, the solution is subjected to water bath at 80 ℃ for 6h, frozen by liquid nitrogen and then freeze-dried in a freeze dryer. And placing the obtained precursor into an inert atmosphere tube furnace, sintering for 9h at 900 ℃, and collecting a product. XRD did not detect a phase of sodium manganese pyrophosphate.
Claims (6)
1. A preparation method of a carbon-coated sodium manganese pyrophosphate @ reduced graphene oxide composite material with a sandwich structure is characterized by comprising the following steps of: adding graphene oxide into an aqueous solution in which a phosphorus source, a sodium source, a manganese source and a complexing agent are dissolved, and then sequentially carrying out ultrasonic treatment, liquid nitrogen freezing and freeze drying to obtain a precursor; placing the precursor in a protective atmosphere, and carrying out heat treatment at 500-800 ℃ to obtain a carbon-coated manganese pyrophosphate sodium @ reduced graphene oxide composite material with a sandwich structure, wherein the carbon-coated manganese pyrophosphate sodium @ reduced graphene oxide composite material is formed by stacking reduced graphene oxide sheets with carbon-coated manganese pyrophosphate sodium particles uniformly distributed on the surfaces of the reduced graphene oxide sheets; the carbon-coated manganese pyrophosphate sodium @ reduced graphene oxide composite material with the sandwich structure has a specific surface area of 60-120 m2g-1(ii) a The particle size of the carbon-coated sodium manganese pyrophosphate particles is 300-1000 nm;
the molar ratio of the complexing agent to manganese in the manganese source is 2-5: 1;
the complexing agent is at least one of citric acid and ascorbic acid;
the phosphorus source comprises at least one of diammonium hydrogen phosphate, ammonium dihydrogen phosphate and phosphoric acid;
the sodium source comprises at least one of sodium carbonate, sodium bicarbonate, sodium acetate, sodium oxalate and sodium citrate;
the manganese source comprises at least one of manganese acetate, manganese nitrate and manganese oxalate.
2. The preparation method of the carbon-coated sodium manganese pyrophosphate @ reduced graphene oxide composite material with the sandwich structure according to claim 1 is characterized in that: the mass of the manganese sodium pyrophosphate is 85-99% of that of the carbon-coated manganese sodium pyrophosphate @ reduced graphene oxide composite material with the sandwich structure.
3. The preparation method of the carbon-coated sodium manganese pyrophosphate @ reduced graphene oxide composite material with the sandwich structure according to claim 1 is characterized in that:
the ratio of the phosphorus source, the sodium source and the manganese source is measured by the molar ratio of P to Na to Mn being 1.8-2.2: 0.8-1.2.
4. The preparation method of the carbon-coated sodium manganese pyrophosphate @ reduced graphene oxide composite material with the sandwich structure according to any one of claims 1 to 3, which is characterized in that: the heat treatment temperature is 600-700 ℃.
5. The preparation method of the carbon-coated sodium manganese pyrophosphate @ reduced graphene oxide composite material with the sandwich structure according to claim 4 is characterized in that: the heat treatment time is 6-12 h.
6. The application of the carbon-coated sodium manganese pyrophosphate @ reduced graphene oxide composite material with the sandwich structure prepared by the preparation method of any one of claims 1 to 5 is characterized in that: the lithium ion battery cathode material is applied as a cathode material of a sodium ion battery.
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| CN115626620B (en) * | 2022-12-08 | 2023-03-21 | 北京林立新能源有限公司 | Preparation method of manganese phosphate |
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